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STOPPING WATER POLLUTION AT ITS SOURCE

PROTOCOL FOR THE SAMPLING AND ANALYSIS OF INDUSTRIAL/MUNICIPAL WASTEWATER

January, 1999

 

TABLE OF CONTENTS

1.0 INTRODUCTION 1
1.1 PURPOSE 1
1.2 SCOPE 1
1.3 HISTORY OF REVISIONS AND CHANGES 2

2.0 FORMAT AND CONTENT 3

3.0 GUIDELINES FOR SAMPLING, PRESERVATION AND STORAGE 5
3.1 SAMPLE TYPES AND TECHNIQUES 5
3.1.1 Grab Samples 5
3.1.2 Composite Samples 6
3.1.3 On-line Analysers 7
3.1.4 Automated Sampler Considerations 8
3.1.5 Compositing Techniques 9
3.1.6 Recommended Sample Volume(s) 10
3.2 PRESERVATION 10
3.3 STORAGE 11
3.4 UNIQUE SAMPLING REQUIREMENTS FOR SOME ATGs 11
3.5 SAMPLING UNDER INDUSTRIAL EFFLUENT MONITORING AND
EFFLUENT LIMITS REGULATIONS 13
3.6 SAMPLING UNDER SEWAGE TREATMENT PLANT REGULATIONS 15

4.0 GUIDELINES FOR THE ANALYSIS OF SAMPLES 17
4.1 PRINCIPLES OF ANALYSIS 17
4.1.1 Recommended and Alternate Techniques 18
4.1.2 Container Pretreatment 18
4.1.3 Sample Preparation and Pretreatment 18
4.1.4 Instrumental Analysis 18
4.1.5 Calibration 19
4.2 ON-LINE ANALYSERS 19
4.2.1 Use, Operation and Maintenance 19
4.2.2 Recommendations for pH and Specific Conductance Analysers 20
4.2.3 Performance Check 20
4.2.4 Malfunction 20
4.3 ANALYTICAL PERFORMANCE CRITERIA 20
4.3.1 Method Detection Limits (MDL): 20
4.4 ADOPTION OF NEW METHODS 22
4.5 METHOD VALIDATION 22
4.6 SPECIAL CONSIDERATIONS AND PRECAUTIONS 23

5.0 QUALITY MANAGEMENT 27
5.1 QUALITY ASSURANCE AND QUALITY CONTROL (QA/QC) 27
5.2 DOCUMENTATION/RECORD KEEPING 28
5.2.1 Methods/Bench Procedures 28
5.2.2 Analytical Control Status 28
5.2.3 Sampling Records 29
5.2.4 Analytical Records 30
5.2.5 QC Sample Records 30
5.3 LABORATORY QC SAMPLES 31
5.3.1 Types and Frequency 31
5.3.2 Use of Laboratory QC Data 32
5.4 FIELD QC SAMPLES 34
5.4.1 Types and Frequency 34
5.4.2 Field QC Data Application 35
5.5 STANDARD AND CERTIFIED REFERENCE MATERIALS 36
FIGURE 1: PROPOSED QC SUMMARY TABLE 37

6.0 ANALYTICAL DATA RECORDING 39
6.1 ROUTINE DATA RECORDING - GENERAL 39
6.1.1 Method Codes 41
6.1.2 Laboratory Method Detection Limit (LMDL) 42
6.1.3 Routine Data Recording - Significant Digits 44
6.1.4 Routine Data Recording - Low-Level and “Less Than" Data 46
6.2 REMARK CODES - GENERAL 47
6.2.1 Low-Level Data - Remark codes 48
6.2.2 Missing Data and Attached Report 49
6.2.3 Sample Matrix Effects/Interference 49
6.2.4 Approximate/Unreliable Data 50
6.2.5 Miscellaneous 52
6.3 LABORATORY QUALITY CONTROL 53

7.0 ESTIMATION OF ANALYTICAL METHOD DETECTION LIMITS (MDL) 57
7.1 INTRODUCTION 57
7.2 DEFINITION 57
7.3 SCOPE AND APPLICATION 58
7.4 ORGANIC ANALYTES (Analytical Test Groups 16-24, 26 and 27) 58
7.5 CONVENTIONALS, METALS AND INORGANICS
(Analytical Test Groups 1-15 and 25) 59
7.6 PROCEDURE FOR LMDL DETERMINATION 60
7.7 Treatment of Outliers 62

8.0 GLOSSARY 65

9.0 APPENDIX 69
TABLE 1 - Analytical Test Groups 71
TABLE 2 - Checklist for Sampling, Preservation and Storage 87
TABLE 3 - Checklist for QC Samples 90
TABLE 4 - Suggested Spiking Materials 92
TABLE 5 - International Toxicity Equivalent (ITEF) Factors for PCDDs and PCDFs 94

10.0 GUIDELINES FOR INDIVIDUAL ANALYTICAL TEST GROUPS (ATG) 95

DISCLAIMER:

Throughout this document the use or reference to trade names, companies or trademarks is provided only for example purposes and does not constitute endorsement of the products by the Ministry of Environment. Some of the terms throughout this document are encountered elsewhere, in everyday use or in literature, in a usage which is sometimes inconsistent with the use in this document. The following text clarifies the usage of these terms for the purposes of the Ministry of Environment (MOE) requirements.

1.0 INTRODUCTION

This section provides the user with an overall view of the intent, scope and limitations of this document. Additionally, the user is provided an insight as to the format and content of the main body of the document (Section 10.0, Guidelines for Individual Analytical Test Groups - ATG).

1.1 PURPOSE

The purpose of this Protocol is to provide guidelines with respect to sampling, analysis and QA/QC procedures to be followed for MOE programs and to specify requirements for compliance with Effluent Monitoring and Effluent Limits Regulations. In all cases Sector Specific Regulatory Requirements take precedence over this Protocol. Reference must be made to the Regulations for specific requirements.

The MISA (Municipal and Industrial Strategy for Abatement) program was initiated with a series of sector specific monitoring regulations which referred to a common General Regulation (Effluent Monitoring Regulation, General: Ontario Regulation 695/88 as amended to 533/89). The General Regulation contained, among other things, the common requirements, guidelines, principles and protocols related to the sampling, preservation, storage and analysis of wastewater samples, the minimum numbers and types of field and laboratory quality control samples to be included and a general guideline for data recording and reporting.

1.2 SCOPE

This Protocol contains much of the same information originally presented in the General Regulation. It includes direction on techniques for sampling of industrial/municipal wastewater, preservation of samples and their storage requirements, maximum storage times allowed prior to analysis, the most appropriate and where applicable alternate preparation and instrumental analysis protocols and the type and frequencies of field and laboratory QC samples. This document represents a synthesis of best available information from organizations including the Ontario Ministry of Environment, Environment Canada, Standard Methods for the Examination of Water and Wastewater (Current edition, American Public Health Association), US Environmental Protection Agency (Federal Register CFR40 part 136). It also incorporates the recommendations and conclusions reached through collaborative efforts of government, industrial and private laboratory personnel.

This document also defines the principles and protocols which must be followed by all laboratories handling samples under Effluent Monitoring and Effluent Limits Regulations. In some cases it intentionally stops short of stipulating any detailed procedures, methods or control techniques. While this approach can leave room for interpretation and uncertainty resulting in slight differences in sampling or analytical procedures, it also leaves room for improvement, analyst discretion and modernization of techniques which can improve the quality of environmental analytical data being generated.

1.3 HISTORY OF REVISIONS AND CHANGES

This Protocol will be reviewed on a regular basis. Changes will be incorporated which represent an improvement, refinement or advancement in environmental science based on best scientific judgement and/or peer review.

1.3.1 Initial Publication:

August, 1994.

1.3.2 Revision #1:

January, 1999

1.3.3. Major Changes in Revision #1:

Additions: Sec.3.6 - Sampling Under Sewage Treatment Plant Regulations
ATG1b - Carbonaceous BOD
ATG12 - Mercury - Fluorescence detection added
ATG31 - Total Residual Oxidants: “(total residual chlorine)” added
ATG36 - NDMA, ( n-Nitrosodimethylamine )

Changes: Use of n-hexane for Solvent Extractables (ATG25)
(See pages 25, 26, Section 4.6)
Sec. 9 - Appendix - Table 1 - Analytical Test Groups
Changes to RMDL’s.

Clarifications: Sec. 5.3.1 - Laboratory QC Samples
Sec. 5.4.1 - Field QC Samples

2.0 FORMAT AND CONTENT

The information in this document is presented in ten sections providing background information and direction for the sampling and analysis of wastewaters.

Sections 1.0 and 2.0 contain introductory remarks, background information and an outline of the content of each section for quick reference.

Section 3.0 outlines requirements related to sampling techniques, containers, container pretreatment, preservation, storage, sample volume recommendations and any associated notes, precautions or remarks. The information is presented with recommended, alternate and in some cases, not recommended approaches and is also presented as a short checklist in Table 2.

Section 4.0 outlines the principles and protocols related to sample preparation/ pretreatment, analytical technique, instrumental measurement methods, reporting/ recording units and performance criteria as defined by the Method Detection Limit (MDL). As with the sampling section, this information is presented with recommended, alternate or in some cases, not recommended approaches for the analysis of wastewater samples.

Section 5.0 outlines the requirements for laboratory and field QC samples. Laboratory (or bench) QC samples include: blanks, spiked blanks, spiked samples and replicates and each is identified as to need and frequency for a given ATG. Field QC samples include: travelling blanks, travelling spiked blanks and duplicates. Again each is identified as to need and suggested frequency for a given ATG. A check list of QC requirements and recommendations is presented in Table 3.

Section 6.0 presents data recording requirements and recommendations. It addresses the determination of analytical repeatability, analytical method detection limit, smallest reporting increment and rounding-off of measurements.

Section 7.0 describes procedures to be followed for the determination of analytical method detection limits.

Section 8.0 is the Glossary which provides definitions of acronyms and technical terms listed in alphabetical order.

Section 9.0 the Appendix contains four tables which provide quick reference to summary information which should be used in conjunction with the relevant textual information in Sections 3.0 to 5.0. Table 1 provides specific information on Analytical Test Group’s (ATGs), numbers, parameter names, CAS numbers where applicable and method detection limits. Table 2 provides a checklist for recommended sampling, preservation and storage needs. Table 3 summarizes the requirements for laboratory QC and recommendations for field QC samples. Table 4 lists suggested spiking materials for each ATG. Table 5 lists the International Toxicity Equivalent Factors (ITEF) for calculating TEQ's (toxic equivalents) for PCDD's and PCDF's.

Section 10.0 Guidelines for Individual Analytical Test Groups, provides in summary form recommendations and general principles for each ATG with respect to sampling, container, material composition, sample volume, preservation, maximum storage time, analysis, laboratory and field QC.

3.0 GUIDELINES FOR SAMPLING, PRESERVATION AND STORAGE

See Section 10.0 for sampling, preservation and storage requirements for each ATG. Table 2 summarizes this information.

All samples obtained for analysis must be from a point in the wastewater stream that is representative of the whole stream composition. The volume of sample taken must be sufficient to allow for analysis of all required analytes plus associated quality control samples (e.g. field duplicate, laboratory replicate and spiked sample).

It is recommended that all automated and manual sampling devices and equipment, their containers and all tubing, valves and contact components be dedicated to a particular sampling site in order to minimize the possibility of cross contamination. As an alternate to this dedicated application it is the user's responsibility to demonstrate that the sampling equipment is clean, free from contamination and suited to the sampling and analysis needs at the next location. Generally, the cleaning and preparation of relocated equipment should include hot water, phosphate free detergent washing, hot and cold water rinsing, distilled water rinsing and, finally, multiple rinses with the actual wastewater being sampled. This is especially important where trace levels of contaminants are being analyzed.

3.1 SAMPLE TYPES AND TECHNIQUES

See Section 3.4 for some ATG specific sampling requirements.

Wastewater samples are often obtained by the use of automated equipment capable of either flow or time proportional sub-sampling of a wastewater stream. These autosamplers must be mechanically and electrically suited to the environment in which they will operate and, in consideration of safety and accessibility, be physically located to facilitate routine use, maintenance and inspection by field staff and Ministry officials.

Most sampling requirements for wastewater analysis can be fulfilled by manual sampling using simple field equipment including buckets, funnels and suitable lengths of chain or dip poles. This equipment must conform to the same materials composition as outlined for automated equipment in Section 3.1.4 (1) (i.e. Teflon®, stainless steel, glass, etc.). The equipment must be suited to the sampling and analysis being performed.

3.1.1 Grab Samples

A grab sample is meant to represent the wastewater stream at a given point in time as opposed to a composite sample which represents the wastewater stream over a longer time period (24 hours). Grab samples should be collected by dipping an appropriate container, bucket, bottle or vial, into the wastewater stream using an appropriate retrieval device, such as a chain or pole.

Grab samples may be taken from a slipstream and valve: after purging the sample line, the samples should be collected into appropriate laboratory containers.

Grab sampling may also be conducted using an automated sampler in manual mode when the automatic function fails. If necessary, a pump may be used to draw the sample.

There are several methods of obtaining grab samples:

GRAB 1: wastewater is collected in a bucket or other container and immediately transferred to the appropriate laboratory container(s), preserved as necessary and capped.

GRAB 2: the appropriate laboratory sample container is submerged in the wastewater stream on a chain or pole until it is full; it is retrieved, preserved as necessary and capped.

GRAB 3: the wastewater is collected in a bucket as for GRAB 1 and the appropriate clean (outside as well) laboratory container (e.g. volatiles vial) is held at an angle and submerged into the liquid until it is full and air bubbles have been expelled at which time it is carefully retrieved, preserved as necessary and capped. Care must be taken to avoid sample contamination from the outside of the laboratory container, label adhesives or the retrieval device.

Grab samples collected for analysis of compatible ATGs may be combined in a single large container and subdivided later, or they may be collected in several individual containers, each dedicated to a specific analysis.

3.1.2 Composite Samples

Composite samples can be collected either by automated or manual methods.

A manual composite sample consists of grab samples typically taken at equally spaced time intervals and combined (composited) once all sub-samples have been collected.

Automated composite samples can be taken either proportional to the wastewater stream flow (in which cases there must be flow sensing devices connected to the sampler) or on an equal volume/equal time basis. Both of these approaches require fully automated, programmable sampling devices.

Some sampling procedures specific to certain situations are described in Sections 3.4, 3.5 and 3.6, but severally composite samples are collected by the following techniques:

flow proportional:

AUTO 1 Automatic equipment collecting samples proportional to the wastewater stream flow at time intervals of 30 minutes or less over the sampling period, under typical flow conditions.

MANUAL 1 A minimum of 8 grab samples taken at equally spaced time intervals over the sampling period (e.g. every 3 hours in a 24 hour period) combined in proportion to the wastewater stream flow.

equal time/equal volume:

AUTO 2 Automatic equipment collecting samples of equal volume at equally spaced time intervals of 15 minutes or less over the sampling period.

MANUAL 2 A minimum of 8 grab samples taken at equally spaced time intervals over the sampling period (e.g. every 3 hours in a 24 hour period) combined in equal volumes.

MANUAL 3 See Section 3.4 for specific uses: A minimum of 3 grab samples taken at time intervals of at least 6 hours over the sampling period and combined prior to analysis, or analyzed individually and the mean reported.

MANUAL 4 Three grab samples taken at time intervals of at least 2 hours over an 8 hour sampling period.

3.1.3 On-line Analyzers

On-line analyzers offer an alternate approach to sampling and analysis for some parameters. See Section 4.2.

3.1.4 Automated Sampler Considerations

Three important characteristics of automated sampling devices are discussed in this section.

1) Materials Composition

All wettable surfaces that contact the wastewater sample must be inert (i.e. must not contaminate, absorb or adsorb chemicals required to be analyzed in the wastewater sample). This requirement can generally be met through consistent use of materials such as Teflon®, (see Section 8.0, Glossary, for alternate acceptable compositions), glass, stainless steel and, where dictated by sampler design and function (e.g. peristaltic type pumps, pinch valves, volume control tubes), short sections of surgical grade silicone rubber tubing. This type of tubing should be preferentially replaced by Teflon® or other chemically inert materials as far as possible without impairing the performance of the sampling device. Where surgical grade silicone rubber tubing is used the total length should be kept to an absolute minimum and it is generally accepted that this should be less than 2 metres. Particular care should be taken to ensure that this tubing and all other wettable parts are cleaned or replaced appropriately.

2) Temperature Stability

A requirement for autosamplers is that they maintain the sample storage environment at a temperature between the freezing point of the sample and 10oC. This will require cooling and/or heating capabilities depending on location and time of year. The temperature must be monitored daily during sample collection and storage and the readings documented. A min-max thermometer may be used for this purpose. Sampling records must be maintained such that all data including repair, inspection, use, maintenance and temperature records, be readily available for inspection.

3) Ability to Obtain a Representative Sample

Automated sampling devices can provide either a single large sample composite which can be further subdivided at the end of a predefined sampling period, as suitable, for the analysis to be performed or multiple individual composites each of which can be individually assigned to specific analytical test groups. The latter capability can provide better flexibility and accommodate a wider range of analysis requirements by providing the option of individual container preservation (e.g. phenolics) and multiple composite samples for specialty testing needs (e.g. solvent extractables analysis requires that the original container be submitted to the laboratory).

The choice of autosampler design and capability will be dictated by specific sampling and analysis requirements. It is, however, essential that the autosampler take the sample from a location in a wastewater stream that will provide a representative sample. This requirement will typically be met by sampling at a point of thorough mixing with no excessive turbulence (loss of volatiles may occur) and at a point away from walls or surfaces of a pipe or channel that may cause insufficient mixing due to currents and eddies. The sampling location must be determined by preliminary testing to evaluate the impact of any site specific turbulence and mixing phenomena.

The sampler must maintain the sample integrity when transferring effluent from the stream to the sample container, in particular by maintaining adequate velocities (1 metre/second) in the transport system to exceed the scour and settling velocities of the constituents of interest.

3.1.5 Compositing Techniques

Where a sample is collected in a large container and requires analysis for several groups of compounds, the wastewater must be transferred to appropriate laboratory containers. Teflon® or other suitable tubing and gravity suction is recommended for transfer of the wastewater to the individual laboratory container. A peristaltic pump may be used to transfer the aliquots into the appropriate laboratory containers, so long as the materials in contact with the sample conform to the requirements of Section 3.1.4, Materials Composition. The sample may also be poured into the individual laboratory containers. Sample transfer must be accompanied by continuous mixing of the composite sample by using a mechanical stirrer, manual swirling or other appropriate means. Use of magnetic stirring bars should be avoided since they may adsorb suspended solids containing metals, thus affecting the sample integrity.

Where grab samples are collected as part of a composite for volatiles or sulphide (ATGs 15-18 and 28a), i.e. by the MANUAL 3 technique, each individual sample container must be submitted to the laboratory for analysis. The laboratory has the option of analyzing each sample and recording the arithmetic mean or combining equal volumes of each grab and analyzing the resulting composite.

Where grab samples are collected as part of a composite for solvent extractables analysis (ATG 25), each sample container must be submitted to the laboratory as this analysis includes solvent rinsing of each container. The laboratory has the option of analyzing each sample and recording the arithmetic mean or combining the samples for a single analysis, ensuring adequate rinsing of the sample containers.

Another option for tests such as solvent extractables (ATG 25) or sulphide (ATG 15) is to collect three equal volumes of wastewater into a single pre-graduated laboratory container, which, for ATG 15, has been pre-charged with sufficient preservative to ensure alkalinity of the final solution.

3.1.6 Recommended Sample Volume(s)

See Section 10.0 for recommended minimum sample volumes for each ATG.

The minimum recommended sample size for a grab is 100 mL except where samples are collected directly in the septum-capped glass vials (ATGs 16-18 and 28a), when sample volumes may be 25 or 40 mL.

A smaller volume may be collected and submitted to a laboratory for analysis if it is sufficient to meet all the analytical requirements including lab and field QC obligations. The volume used for analysis must also be sufficient for the laboratory to achieve its analytical method detection limit (MDL).

3.2 PRESERVATION

See Section 10.0 for preservation requirements for each ATG.

Some samples require preservation to ensure stability of target compounds during transportation and storage or to eliminate substances which may interfere with the analysis. In some cases preservation of the sample is optional, and if selected, will allow for a longer storage period before analysis must be initiated.

Generally, samples requiring preservation must be preserved immediately upon collection, either at the end of the collection period for samples collected with an automated sampling device or after collection of each grab sample. See Section 3.4 for cases where the preservative must be pre-charged.

Where a composite sample is collected in a large container for analysis for several ATGs, some of which require preservation, the samples must be preserved immediately following their transfer into laboratory containers.

Where samples are to be preserved to a fixed set-point (pH, colour) care must be taken that the set point has been reached by using detection techniques such as confined range pH paper, pocket/portable pH metres, standard colour comparison charts etc. The use of these techniques and/or devices must not contaminate the sample.

It is recommended that the volume of preservative not exceed 1% of the total sample volume.

CAUTION: Acid preservation of samples suspected of containing cyanide or sulphide MUST be carried out in a well ventilated area.

3.3 STORAGE

See Section 10.0 for maximum storage times for each ATG.

Storage time is defined as the time interval between sample pick-up (typically at the end of the 24 hour composite sampling period) and the initiation of analysis.

All samples must be stored for as short a time interval as possible and under conditions that will minimize sample degradation.

Samples must be maintained at temperatures above the freezing point of the wastewater and under 10oC, with minimal exposure to light. See Section 3.1.4, Temperature Stability.

In the case of ATGs 19-24, 26, 27 and 28b where analysis is considered to be initiated by the sample extraction step, the extracts should be completely analyzed within 60 days.

Samples digested for metals analysis may be maintained in a sealed container and analyzed within 30 days for timeliness of analysis and data reporting.

3.4 UNIQUE SAMPLING REQUIREMENTS FOR SOME ATGs

See Section 10.0 for sampling requirements for each ATG.

The characteristics of sampler composition can be reviewed and adapted to suit the nature and sensitivity of the chemicals to be analyzed and the testing protocols to be used. For example, if an autosampler were applied only to the collection of samples for phosphorus analysis, then wettable surfaces could include materials of a similar composition to the containers for that test (e.g. polyethylene terephthalate or linear polyethylene as described in Section 10.0).

Cyanide (ATG 2)

Samples collected for cyanide analysis using an automated sampler require a separate container which must be pre-charged with the appropriate preservative as described in Section 10.0.

Samples containing strong oxidizing agents (e.g. chlorine) should be neutralized with sodium arsenite as soon as possible after sample collection to prevent oxidation/degradation.

Alternate: The MANUAL 3 technique may be used for cyanide, in lieu of AUTO 1 or 2, when an automated composite sampler cannot deliver sufficient sample volume for all required analyses.

pH (ATG 3)

Where the characteristics of the wastewater may lead to changes in pH over the sampling period, an on-line analyzer must be used or grab samples must be collected and analyzed as soon as reasonably possible.

Ammonia (ATG 4a)

Samples containing strong oxidizing agents (e.g. chlorine) should be neutralized as soon as possible after sample collection to prevent oxidation/degradation.

Phenolics (ATG 14)

It is recommended that MANUAL sampling techniques be used for phenolics to avoid contamination from silicone rubber parts in automated samplers. If an automated sampler is used, sample contamination may be avoided by using the last bottle in the collection sequence for the phenolics.

A sample collected for phenolics analysis using an automated sampler requires a separate container which must be pre-charged with the appropriate preservative. See Section 10.0.

Samples containing strong oxidizing agents (e.g. chlorine) should be neutralized as soon as possible after sample collection to prevent oxidation/degradation.

Alternate: The MANUAL 3 technique may be used for phenolics, in lieu of AUTO 1 or 2, when an automated composite sampler cannot deliver sufficient sample volume for all required analyses.

Volatiles: ATGs 15, 16, 17, 18, 28a

Grab samples must be collected for volatile organics and sulphide analysis and composite samples must be taken by manual sampling techniques.

Use of automated samplers in manual mode and of pumps for volatiles sampling (ATGs 15-18 and 28a) is not allowed unless there is no practicable alternative.

A volatiles sample should be obtained at a location of quiescence and uniform concentration upstream of turbulence which might strip volatile constituents from the wastewater.

To minimize losses of target parameters, the sample should be collected directly into the laboratory container with no headspace and the container sealed, refrigerated and analyzed as soon as possible. Where the water collected is below 4oC, some headspace may be needed to accommodate increasing pressure within the sealed containers.

Solvent Extractables (ATG 25)

Samples for ATG 25 (oil and grease) must be collected directly into the laboratory container (GRAB 2) to minimize losses during transfer, unless direct retrieval is not practicable.

Total Residual Oxidants (TRO): ATG 31

TRO must be sampled and analyzed using an on-line analyzer or by collecting a grab sample (GRAB 1, GRAB 2 or GRAB 3) and analyzing it as soon as reasonably possible.

E. Coli (ATG 35)

E. Coli samples must be collected by the GRAB 2 technique. Where disinfection is accomplished through the use of oxidizing agents (e.g. chlorine or sodium hypochlorite), sodium thiosulphate must be added to E.Coli samples as soon as possible after sample collection.

Changes in sampling techniques

Changes in sampling techniques should be kept to a minimum: once a valid mode of sampling has been selected, it must be maintained and changed only if necessary. Each change must be documented and reported to the MOE or to the municipality in the case of Sewer Use applications.

3.5 SAMPLING UNDER INDUSTRIAL EFFLUENT MONITORING AND EFFLUENT LIMITS REGULATIONS

Effluent Monitoring and Effluent Limits Regulations specify sampling requirements which are outlined below. Reference must be made to the regulations for specific requirements.

Process Effluent

Flow proportional composite samples must be collected from process effluents (AUTO 1, MANUAL 1 for most ATGs, except MANUAL 3 for ATGs 15-18 and 28a).

In cases of automated sampler malfunction, composite samples must be collected using the MANUAL 1 technique. If the malfunction affects only the flow proportional programming, the AUTO 2 sampling technique may be used.

The discharger must be able to demonstrate that the samples are being collected flow proportionally by recording the number and/or volume of samples, where possible.

In cases where the process effluent stream flow has been proven, to the Director's satisfaction, to be non-variable, equal volume/equal time composite samples may be collected (AUTO 2 or MANUAL 2 for most ATGs except MANUAL 3 for ATGs 15-18 and 28a). The discharger must record the number and/or volume of samples, where possible.

Variable flow means a flow rate within a day which varies by more than plus or minus 15 percent of the daily mean flow rate for more than 10% of the time (more than 150 minutes per operating day for more than 18 operating days in a six month period).

Sampling for pH

Where Effluent Monitoring and Effluent Limits Regulations require pH analysis, three grab samples must be collected over the sampling period at intervals of at least 4 hours and each GRAB analyzed as soon as reasonably possible. An on-line analyzer may be used and three readings taken at intervals of at least 4 hours must be recorded and reported.

Batch Discharges of Process Effluent

Where a process effluent is to be discharged in batches, a grab sample of the effluent must be collected. If the effluent is not representative of the process, e.g. thorough mixing is not possible or particulates are not completely re-suspended, a composite sample of the effluent must be collected using the AUTO 1 or 2 techniques (MANUAL 3 for ATGs 15-18 and 28a). If conditions prohibit use of an automated sampler, three grabs must be collected from the effluent: one at the beginning, one halfway through, and one at the end of the discharge.
Cooling Water

Composite samples must be collected from cooling water streams and the AUTO 1 or 2 techniques are preferred, although the MANUAL 3 technique may also be used. In case of automated sampler malfunction the MANUAL 3 technique may be used.

Storm Water

Sampling requirements for storm water streams are outlined in the MOE Protocol for Conducting a Storm Water Control Study, August 1994.

3.6 SAMPLING UNDER SEWAGE TREATMENT PLANT REGULATIONS

The following requirements do not apply to pH (ATG 3) and TRO (ATG 31 - total residual oxidants or total residual chlorine) which are best sampled and analyzed using on-line analyzers.

An alternate sampling method for these parameters is the collection of a grab sample which is then analyzed as soon as reasonably possible.

Process effluent, secondary treatment plants and primary treatment plants:

The following sampling procedures apply to limits monitoring and monitoring for assessment.

A plant with a design capacity exceeding 4,600 cubic metres per day must collect from each process effluent stream a composite sample over a 24 hour period using automated sampling equipment and the AUTO 1 or AUTO 2 technique.

In cases of autosampler malfunctioning, composite samples should be taken by the MANUAL 1 or MANUAL 2 technique.

A plant with a design capacity of less than 4,600 cubic metres per day may collect from each process effluent stream a composite sample consisting of three grab samples taken at intervals of at least two hours over an eight hour period (MANUAL 4). The grabs may be combined prior to analysis or the laboratory may analyze each individual sample and report the arithmetic mean. Samples should be collected during peak influent flow periods to be representative of average operating conditions.Lagoon Treatment Plants

A lagoon treatment plant which discharges continuously, must collect from the effluent stream a composite sample over a 24 hour period using automated equipment and the AUTO 1 or AUTO 2 technique. In cases of autosampler malfunctioning, composite samples should be taken by the MANUAL 1 or MANUAL 2 technique.

A lagoon treatment plant which discharges seasonally or annually over a period of one week or less, must collect three grabs, one at the beginning, one in the middle and one at the end of the discharge. When the seasonal or annual discharge period exceeds one week, the lagoon treatment plant must collect one sample for each week of discharge

Bypass Effluent

A sample may be collected from each bypass effluent stream as a single grab sample (GRAB1, 2 or 3) during each day of a bypass discharge. Each sample must be analyzed as soon as is reasonably possible after sample pick-up.

4.0 GUIDELINES FOR THE ANALYSIS OF SAMPLES

See Section 10.0 for analytical principles for each ATG.

4.1 PRINCIPLES OF ANALYSIS

This section describes and provides guidance on the general principles and protocols to be followed in sample preparation, clean-up and instrumental analysis.

The analysis of wastewater samples can be a very demanding and complex activity depending on the type of sample, matrix problems, the presence of co-extractive or interfering materials etc. In this regard it is necessary that laboratory analysis be performed according to tenets of good laboratory practice as well as regulatory requirements.

A few key requirements that must be met are:

• analysis must be carried out by competent laboratory personnel in a properly equipped and maintained laboratory environment;
• analytical procedures must meet generally accepted principles of good laboratory practice and quality control;
• analytical techniques must be appropriate for the sample matrix and must lead to adequate separation and accurate identification of the compounds to be analyzed;
• recovery of target parameters must be optimized;
• analytical procedures must comply with the principles and protocols of analysis listed in Section 10.0.

All wastewater samples must be analyzed according to the sample preparation and instrumental measurement principles listed for each ATG in Section 10.0. This includes elements related to container materials, container pretreatment and preservation.

Before an analytical procedure can be used under Effluent Monitoring and Effluent Limits Regulations, the method detection limit (MDL) must be determined for each target parameter according to the procedure described in Section 7.0 and must be equal to or less than the values listed in Table 1.

All analyses must be initiated within the time frames listed as maximum storage times for each ATG in Section 10.0, except in unavoidable circumstances, in which case analytical results must be qualified by the remark code "OLD" as described in Section 6.2.5. Results of analyses must be made available as soon as reasonably possible.

Sufficient and appropriate QC samples must be included with each set of samples being analyzed. Section 10.0 lists the types of QC samples which apply for each ATG. The types and frequency of QC samples are specified in Section 5.3.

4.1.1 Recommended and Alternate Techniques

Section 10.0 outlines recommended and any alternate principles of preservation and storage times, sample preparation and instrumental measurement.

The recommended instrumental measurement method principles are deemed to be the most suitable for a wide range of effluent matrices.

The alternate instrumental measurement method principles may be suitable for some effluent types.

4.1.2 Container Pre-treatment

Generally new containers do not need to be cleaned prior to use, but if they are re-used, recommended pre-treatment or washing procedures are identified in Section 10.0 for each ATG.

Each laboratory is responsible for ensuring that all glassware, reagents and equipment used for sampling and/or analysis are suitably clean and free from contaminants and interfering substances. The frequency and nature of cleanliness checks demonstrating acceptability of labware is the responsibility of the laboratory.

4.1.3 Sample Preparation and Pretreatment

The task of preparation and/or pretreatment of wastewater samples prior to instrumental analysis can represent the majority of time and effort in the overall analysis scheme. Where preparation or pretreatment is required, principles and protocols to be followed are listed in Section 10.0. for each ATG. With the range of preparation/pretreatment techniques available, the main consideration is to treat the sample so that it will be suitable for the instrumental technique being employed and for the matrix being analyzed. Containers should be rinsed with the matrix to be analyzed prior to sample collection.

4.1.4 Instrumental Analysis

Instrumental measurement methods must comply with the principles set out in Section 10.0 for each ATG. The recommended principles must be used for characterization while the alternate instrumental measurement principles may be used for routine analysis.

4.1.5 Calibration

All analytical instruments must be calibrated in accordance with good laboratory practice. This includes periodic multiple point calibration (full calibration series) to establish response factors and linearity range. Daily calibration checks using a subset of the full calibration series are required before each run and should be repeated at intervals during the run to verify system stability and control.

Calibration standards must be validated against a standard reference material, if available from a standards organization as described in Section 5.5.

A calibration curve must be established and confirmed periodically for each analytical procedure within the range normally encountered in samples of the type being analyzed.

4.2 ON-LINE ANALYZERS

On-line analyzers offer the capability to continuously monitor and report the presence and concentration of selected constituents in the wastewater stream. For an approved list of constituents (ATGs 3, 5a, 7, 16, 17, 18, and 31), these analyzers present an alternate approach to manual or automated sampling and subsequent laboratory analysis.

The sampling equipment and instrumentation used must satisfy the requirements which are identified in Section 3.1.4. These include sampling equipment materials of composition, the ability to obtain a representative sample and assurance of temperature stability. They must also meet the criteria set out in Sections 4.0 and 5.0 in the analytical principles used for the test in question which include QA/QC practices such as establishing control limits and calibrating against reference standards.

An on-line analyzer should continuously monitor the wastewater and produce a continuous record over the sampling period; the continuous record should be composed of minute by minute or more frequent monitoring data. In the case of on-line GC analysis, the continuous record should be composed of data monitored at not more than two hour interval frequencies.

4.2.1 Use, Operation and Maintenance

On-line analyzers must be properly installed and operated according to good laboratory practice principles. Initially, on-line analyzers should be inspected and calibrated daily to determine the time interval during which the instrument continues to operate within reasonable control limits. Subsequently the maintenance and calibration frequencies may be adjusted accordingly with a weekly interval as the minimum. These activities must be documented and be available upon request.

4.2.2 Recommendations for pH and Specific Conductance Analyzers

Electrodes must be cleaned regularly to maintain their accuracy and replaced when their performance becomes unacceptable. Experience has shown that the need for calibration tends to be less frequent when the electrodes are replaced at regular intervals.

4.2.3 Performance Check

At least once a month the performance of each on-line analyzer must be checked to verify its continued proper functioning by verifying the operating system using an appropriate certified reference material. ( see Glossary Sec. 8, for definition. )

The equipment used for these checks must meet the criteria set out in Sections 4.0 and 5.0 in the analytical principles used for the test in question including QA/QC practices such as establishing control limits and calibrating against reference standards.

4.2.4 Malfunction

When an on-line analyzer malfunctions samples may be collected by the AUTO 1 or 2 or the MANUAL 1 or 2 techniques.

4.3 ANALYTICAL PERFORMANCE CRITERIA

The requirements outlined in this section apply to analyses done under Effluent Monitoring and Effluent Limits Regulations but they should be followed for all the MOE programs.

4.3.1 Method Detection Limits (MDL):

Requirements under Effluent Monitoring and Effluent Limitations Regulations:

See Table 1 for RMDLs for each ATG.

To ensure that all laboratories performing analyses under the Effluent Monitoring and Effluent Limits Regulations have the capability to perform these analyses at appropriate levels, they are required to determine a laboratory specific method detection limit (LMDL) for each parameter to be analyzed.

These LMDLs must be determined according to the MOE protocol described in Section 7.0, using the sample volumes, preparation and instrumental analysis procedures which will be used for wastewater samples.

An analytical method must not be used for samples taken under Effluent Monitoring and Effluent Limits Regulations until all LMDLs have been demonstrated to fall at or below the higher of either 1/5th of the average level or limit typically found in the specific effluent stream being monitored, or the applicable Analytical Method Detection Limit (RMDL) values listed in Table 1.

The LMDLs are to be recorded using the number of significant digits used in recording subsequent sample data generated by that analytical method (usually 2 figures). This is further defined in Section 6.1.3.

It is recommended that LMDL determinations be repeated at least semi-annually for each parameter to be analyzed by a laboratory unless routine QC data demonstrate that no significant change has occurred in the sensitivity or the precision of the analytical procedure. The LMDLs must be re-determined whenever a significant change is made to a method.

LMDLs should be determined using the routine sample aliquot and dilution factor that will be applied to "real" samples because the size of sample analyzed and associated changes in dilution will affect the LMDL value proportionately.

If a dilution factor is applied to the LMDL, a sample where the measurement is near or below this adjusted LMDL must be re-analyzed using a larger aliquot to meet the requirement to measure down to a LMDL which is less than the RMDL listed in Table 1.

If matrix interferences preclude target parameter detection near the LMDL the protocol described in Section 6.2.3 must be used.

Where matrix effects cause co-elution of compounds, the analytical method used for LMDL determinations and sample analyses is expected to resolve all target parameters (exceptions are listed in Table 1), but it is understood that there may be cases where interferences render resolution impossible. However, it is expected that the laboratory will make every reasonable effort to resolve and quantitate every required parameter. In the case where an effluent is known to contain interferences, e.g. chloride, a different detection method or additional clean-up must be used where possible.

4.4 ADOPTION OF NEW METHODS

The method principles recommended in Section 10.0, ATG Guide reflect the best known methods of analyzing effluent at the time of printing. To facilitate the use of alternate methods of analysis, and to accommodate future analytical improvements, the MOE plans to move towards performance based methods. This plan entails the development of criteria for precision, accuracy, recovery, etc. for each ATG. The MOE plans to develop these data quality objectives in cooperation with private and municipal laboratories. The use of analytical criteria from a wide variety of sources should lead to the setting of the best achievable data quality objectives.

4.5 METHOD VALIDATION

Any new method must be validated by the user prior to use and all methods must be re-evaluated periodically to ensure their continued validity.

The following are some suggestions which may be of assistance to anyone wishing to validate a method.

The first step would involve verifying the calibration standards against appropriate standard reference materials, where available from a standards organization. The National Oceanic and Atmospheric Administration, U.S. Department of Commerce (NOAA) publishes a compendium of SRM/CRM available world wide, Standard and Reference Materials for Environmental Science (2 parts), November 1995, NOAA Technical Memorandum NOS ORCA94.

A comparison of data from samples analyzed by an already valid method and the new method should be carried out to indicate ability of the new method to analyze the particular matrix involved for the required parameter.

Criteria or control limits should be set and documented for acceptance or rejection of the calibration standards.

Within run and between run precision should be determined in reagent water and samples which approximate the matrix routinely analyzed. Control limits should be set for each sample type.

Documentation should be available demonstrating that the required QC samples are run with every batch of samples, that they are checked for conformance to predetermined performance levels (e.g. control limits) and that corrective action is taken when performance does not meet specifications.

The presence of a quality assurance system should also be demonstrated to ensure that the quality control procedures are continuously documented, monitored and controlled.

4.6 SPECIAL CONSIDERATIONS AND PRECAUTIONS

CAUTION: Acid preservation of samples suspected of containing cyanide or sulphide MUST be carried out in a well ventilated area.

Test Specific Precautions

The following include some of the more important precautions to be followed in the sampling and analysis of certain parameters.

COD (ATG 1)

High chloride content in samples may cause severe interference problems in the analysis of COD.

Biochemical Oxygen Demand (5 day) (ATG 1a)

Where the option to use an oxygen electrode is selected for BOD5 determination, the data must be verified by analyzing at least one sample or standard per run by both the Winkler and oxygen electrode methods (both results must be recorded). To avoid sample degradation samples must be analyzed immediately.

Carbonaceous Biochemical Oxygen Demand (5 day) (ATG-1b)

For the analysis of BOD5C, a nitrification inhibitor must be added to the sample before analysis, either in the field or in the laboratory.

pH (ATG 3)

Where the characteristics of the wastewater may lead to rapid changes in pH an on-line analyzer should be used or grab samples collected and analyzed as soon as reasonably possible.

DOC/TOC (ATG 5)

High chloride content in samples may cause severe interference problems in the analysis of DOC/TOC.

Total Phosphorus Analysis (ATG 6)

The stannous chloride procedure must not be used due to linearity problems: increases in phosphorus concentration beyond a method-specific point are detected as decreases. Consequently, unexpectedly high phosphorus concentrations may not be detected.

Metals Analysis (ATGs 9, 10, 12 and 29)

If the presence of cyanide or sulphide is suspected in the wastewater, care must be taken to ensure adequate ventilation while lowering the pH, and the sample container and submission sheets must contain adequate caution notes to alert laboratory staff to the presence of these chemicals.

When spiking samples, care must be taken to ensure that the presence of anions will not result in the formation of insoluble compounds.

Boron (ATG 9)

Glass containers must not be used when samples are to be analyzed for Boron due to the possibility of sample contamination from borosilicate.

Hydrides (ATG 10)

It is recommended that plastic bottles not be precharged with concentrated nitric acid to avoid false positives for antimony.

Mercury Analysis (ATG 12)

Samples containing coloured materials, reducing agents and highly alkaline substances may require larger volumes of potassium dichromate solution and nitric acid as preservatives. The amounts of preservatives to obtain coloured acidic samples should be determined and these volumes noted on the sample bottles so
that an appropriate blank compensation can be done.

Preservatives are likely to become contaminated if stored in plastic vials/bottles close to mercury and its compounds. It is recommended that preservatives be stored in glass containers and away from mercury and its salts. A periodic test for mercury should be made to ensure preservatives are uncontaminated.

Phenolics (4AAP) (ATG 14)

High chloride content in samples may cause severe interference problems in the analysis of phenolics (ATG 14).

Volatile Organics Analysis (ATGs 16-18 and 28a)

Grab samples composited in the laboratory must be handled carefully and quickly to avoid undue losses of target parameters.

Extractables, base-neutral (ATG 19)

Samples must not come into contact with any plastic or rubber material (such as disposable gloves) to avoid contamination by substances such as phthalate esters.

Extractables, acid (ATG 20)

Samples must not come into contact with phenolic resins, such as Bakelite® caps, to avoid sample contamination.

General Organics Analyses (ATGs 16-27, 28a and 28b)

Collection of duplicate samples is recommended for organics analyses (ATGs 16-27, 28a and 28b) in case problems are encountered necessitating re-analysis and to fulfil QC sample requirements including use as an alternate for laboratory replicate sample or spiked sample.

Dioxins/Furans (ATG 24)

Under the Effluent Monitoring and Effluent Limits Regulations, limits are set as total toxic equivalents (TEQ) in addition to individual limits on 2,3,7,8-TCDD and 2,3,7,8-TCDF. Analysis for the 17 most toxic congeners is now required, as opposed to the total congener group analysis. See Section 10.0.

Solvent Extractables (ATG 25)

It is possible that no other single analytical protocol has undergone as much review and evaluation as solvent extractables (also colloquially referred to as “oil and grease”).

Since the start of the MISA Program, the use of freon, chlorinated and non-chlorinated extraction solvents has been proposed or adopted for use.

In more recent years and largely due to the RIO Summit of 1995 and the signing of the Montreal Protocol, the disuse of freons, specifically, and chlorinated solvents generally has been recommended.

The current content of this MISA Protocol Document has been revised to reflect these recommendations and takes its direction from the work of many organizations including: the Laboratory Services Branch, MOE; Water Technology Institute, Burlington; and the USEPA, in establishing the use of n-hexane as the recommended solvent for extraction and residue characterization of industrial and municipal wastewaters. At this time, the use of dichloromethane as extraction solvent is assigned as the alternate procedure and freons, as a group, are assigned as not recommended.

It is noted that this can result in significant changes to the quantitative, gravimetric outcome of the test and may require the setting of new effluent limits where these are already established, based upon the use of freons or chlorinated solvents.

PCBs (ATG 27)

At present total PCB concentration calculated as an Aroclor or a mixture of Aroclors is required and laboratories doing congener-specific analysis should record these in addition to the required data. A trigger may be set requiring that PCB results above this concentration be confirmed by congener analysis to assist in determining the potential for toxic effects.

Fluoride (ATG 30)

High Chloride content in samples may cause severe interference in the analysis of Fluoride.

Some organic acids may interfere with Ion Chromatographic analysis of Fluoride.

5.0 QUALITY MANAGEMENT

See Section 10.0 for QC requirements for each ATG. Table 3 summarizes this information.

The requirements listed in this section apply to analyses done under Effluent Monitoring and Effluent Limits Regulations but they should be followed for all MOE programs.

"Quality Management: That aspect of the overall management function that determines and implements the quality policy" International Standards Organization, ISO8402-1986.

Environmental analysis requires a sound field and laboratory quality management program to ensure the quality of the analytical data produced. The laboratory management, in consultation with its customers, is responsible for ensuring that appropriate control activities and performance evaluation procedures are identified and performed, that the results are documented, and that appropriate action is taken in a dependable, timely and economic manner.

A good Quality Management (QM) program includes activities such as the development of a Quality Assurance Manual, regular use of external reference materials, participation in inter-laboratory (round-robin) comparison studies, and accreditation by an independent party (such as the Canadian Association for Environmental Analytical Laboratories - CAEAL). Accreditation does not preclude the possibility of inspections to evaluate compliance with regulatory requirements.

Parts of CSA standard Can/CSA Z753-95 (see Section 5.1), outlines the issues associated with documenting and implementing appropriate systems for managing staff, methods, equipment, samples and data.

5.1 QUALITY ASSURANCE AND QUALITY CONTROL (QA/QC)

"Quality Assurance: All those planned and systematic actions necessary to provide adequate confidence that a product or service will satisfy given requirements for quality" International Standards Organization, ISO8402-1986.

Quality assurance (QA) encompasses those activities which define the level of quality required, the critical system components which may impact quality, the procedures whereby quality status will be determined, and the nature and timing of any remedial action required. A comprehensive QA program will ensure that the quality of the process and its product is monitored, documented, and controlled on a continuing basis.

"Quality Control: The operational techniques and activities that are used to fulfil requirements for quality" International Standards Organization, ISO8402-1986.

Quality control (QC) encompasses those activities which specifically monitor and control discrete laboratory tasks or systems to produce the information that is required to verify and demonstrate that they meet predefined operating criteria or to substantiate the need for remedial action.

Performance Evaluation encompasses activities which evaluate and document the overall control status of the process and determine the need for long-term remedial action.

Good Laboratory Practice is a fundamental level of activities in the quality management of a laboratory. It encompasses elements of good housekeeping, cleanliness, quality and consistency of supplies, availability of standard operating procedures for all routine analysis activities, application of good technique based on proper education and training, as well as appropriate documentation of organizational and experimental purpose, tasks, procedures, observations, conclusions or results.

The establishment and maintenance of GLP and QM in a laboratory can be accomplished through the adoption of a standard code of practice such as those defined in Can/CSA Z753-95.

5.2 DOCUMENTATION/RECORD KEEPING

An essential element of QA/QC is documentation and record keeping for all facets of sample handling and analysis.

5.2.1 Methods / Bench Procedures

An authorized, formal written description of the method used to analyze samples is necessary. Bench procedures must be documented in sufficient detail to ensure proper uniform application and must be readily available to technical staff. When modifications are required because of sample matrix or other factors, they must be noted and appended to the appropriate analytical records. Bench procedures should include sample pretreatment/preparation, instrumental measurement methods and data reporting procedures. QC activities documented in the bench procedures should include instrument calibration standardization, standards preparation and validation, frequency of use of reference standards and materials, as well as the sources of all standards and standard solutions. Bench procedures and methods should be reviewed periodically to ensure their continued applicability to the matrices of interest.

5.2.2 Analytical Control Status

Protocols must be established to demonstrate that analytical systems are in control.

Control limits must be established and maintained for calibration and method blanks and should also be determined for replicate or duplicate precision, reference material accuracy and target parameter recovery.

Records must be kept of corrective actions taken when control elements are exceeded.

Control charting is a highly recommended method to demonstrate control status. The number of analytes being monitored and charted for control will depend on the individual behaviour of each analyte in a given laboratory setting. However, it is usual practice to demonstrate control of all analytes for a period of at least 1 year after which time a few selected, representative analytes can be monitored and charted for control of an entire group. The pertinent data for the remaining parameters must be recorded and stored for future use, if necessary.

Under Effluent Monitoring and Effluent Limits Regulations, limited parameters must be demonstrated to be under control; selection of other representative analytes for control charting is at the analyst's discretion.

The use, monitoring and charting of reference materials is an additional external verification of performance. The frequency of analysis and types of certified or standard reference materials will vary between laboratories depending on availability and analysis capabilities, but should generally represent 10% of routine in-house QC efforts.

5.2.3 Sampling Records

Records of sampling and sampler maintenance must be kept current and accessible for review.

Records must include:

• date and time of all sampling activity including grab and toxicity samples and performance check samples for on-line analyzers, etc;
• temperature stability records;
• sample identification, e.g. wastewater stream, control point etc.;
• sample collection method, e.g. autosampler, 24 hour composite, grab, etc.;
• identification of sampling staff;
• malfunctions and corrective action taken;
• maintenance log including frequency and type of maintenance performed, e.g. tubing changes, cleaning, reprogramming, programmer repairs etc.;
• calibration, cleaning, repair log for on-line analyzers;
• any other relevant information.

Any sampling malfunctions/problems which may impact sample analysis must be communicated to the laboratories performing the analysis.

5.2.4 Analytical Records

Formal data recording and reporting practices must be established to ensure that the quality of a reported result is known and that it is traceable back to the raw information on which it is based.

Analytical results must be recorded and archived along with the information required to ensure traceability to all associated procedural, quality control and performance evaluation records. An archiving policy should be established to ensure retention of analytical and QA/QC records for a minimum of 3 years.

An electronic database/spreadsheet format is recommended to enter, store and display data as tables or graphs.

5.2.5 QC Sample Records

Laboratories must maintain all records necessary to show that the analytical systems used were in control at the time of analysis. The results of these QC and performance monitoring checks should be separately tabulated and summarized for ready retrieval, evaluation and audit. They must be retained in a secure manner for review. A protocol should be established for data correction and any corrections should be made in such a manner that the original data is legible. QC records include results of all analyses of laboratory and field QC samples, as well as spiking concentrations for both the spiking solutions and spiked samples.

It is recommended that a protocol be established for the frequency and content of a statistical summary of QC sample data to facilitate data review by the analyst and clients. This summary should include all QC sample types and present a statistical review for each individual test such as number of samples, range of values observed, average or mean, standard deviation, plus any other relevant mathematical or statistical summary. A spreadsheet format is recommended for this documentation. Another suggested format is given in Section 5.5, Figure 1.5.3 LABORATORY QC SAMPLES

See Section 10.0 for laboratory QC samples which apply to each ATG.

Where the Effluent Monitoring and Effluent Limits Regulations refer to "sampling and analysis obligations" these include laboratory (or bench) QC as described below.

5.3.1 Types and Frequency

Four types of laboratory QC samples must be collected and/or prepared and analyzed with each analytical run. For a few special cases such as pH only one QC sample, ( duplicate or replicate ) need be analyzed. Section 10.0 lists the QC samples required for each ATG. An analytical run means a group of samples which are processed together through each step of an analytical procedure.

A set of laboratory QC samples comprises the following:

• a method blank sample which is an uncontaminated sample of reagent water which is free of the target parameters and of any substance which may interfere with that analysis;
• a replicate sample which is an additional or second aliquot of a randomly selected sample in the analytical run. If there is insufficient sample volume for replicate analysis for ATGs 19-23, 25, 26 and 27, a duplicate sample must be collected and analyzed.

Note: for ATG-16-18, the replicate sample requirement may be fulfilled by the collection and analysis of duplicate samples (defined in Section 5.4.1), unless the sample injection system allows for replicate analysis of the original sample.

Whether a replicate or a duplicate sample is analyzed must be specified when recording and reporting results.

• a spiked blank sample is a method blank sample to which known (and recorded) quantities of each target parameter have been added; the concentrations added should be 2-5 times the individual RMDLs.
• a spiked sample is a randomly selected sample in the analytical run to which known (and recorded) quantities of each target parameter have been added. Where there is insufficient sample volume, a duplicate sample must be collected, spiked and analyzed in lieu of a replicate. The recommended spiking concentration is two to three times the typical concentration in the effluent. The difference between the spiking concentration and the sample concentration should exceed the method precision. See Table 4 for suggested spiking materials.

Each of these QC samples must be processed through each step of the analytical procedure. The number of QC samples which must be analyzed depends on the number of samples in the analytical run.

Where a run consists of 14 samples or fewer, a single set of four QC samples must be analyzed at the beginning of the run. Where a run contains 15 to 27 samples, two sets of QC samples must be run, one at the beginning of the run and a second set after 14 samples. If there are 28 or more samples in a run, a minimum of three sets of QC samples must be run, one at the beginning, one in the middle and one at the end of the run.

When samples are analyzed for pH (ATG 3) the only QC sample required is a replicate. Where samples are analyzed for specific conductance, suspended solids, hexavalent chromium and solvent extractables (ATGs 7, 8, 11 and 25), the only QC samples required to be analyzed are the replicate ( or duplicate for ATG 25) and method blank samples.

For open characterization analysis (ATGs 28a, 28b and 29), the only QC sample required to be analyzed is a method blank. It is recommended that duplicate samples be collected for repeat analysis, if necessary.

5.3.2 Use of Laboratory QC Data

Laboratory QC sample analysis will serve to monitor the performance of the methods, the instrumentation and the analyst.

All QC activities must be documented and detailed records must be retained for review.

QC sample results are generally expected to fall within established control limits. If this is not the case, the impact and data quality of associated samples must be reported using appropriate remark codes or in a covering letter.

Replicate sample analysis will provide an indication of within-run precision.

Analysis of spiked blank samples will provide an indication of the efficiency of the method to recover and accurately quantify target parameters.

Results of spiked sample analysis will indicate the presence of matrix-specific interferences which may hinder accurate target parameter recovery and quantification.

Results for all QC samples must be closely monitored and reviewed periodically by responsible staff to ensure that out-of-control situations are identified and corrected. The protocols for definition and reaction to such situations must be documented and available to laboratory staff.

Method blank sample results will establish a baseline response and indicate the presence of contamination in glassware and equipment, and cross contamination from samples containing high concentrations of target parameters or interfering substances. Should method blank sample results fall outside the established control limits, results must be reviewed and validated or the samples in that particular run must be re-analyzed accompanied by method blank samples which fall within the established control limits.

It is recommended that sufficient sample volume be collected for repeat analysis if needed. However, if the sample volume is insufficient for re-analysis, a new set of samples must be collected and analyzed, accompanied by a controlled method blank sample.

Analytical results must be corrected to take into account any positive results of associated method blank sample analysis. A method blank result above the LMDL is normally considered to be a positive result. The criteria or control limits for blank corrections must be determined by the laboratories on the basis of historical data and they must be documented. Data are not normally corrected for method recovery (e.g. surrogates) except when isotope dilution is used as in dioxin analysis.
5.4 FIELD QC SAMPLES

Field QC samples indicate sampling variability and the presence of field contamination. This Section is especially relevant to Sewer-Use sampling where the risk of cross-contamination is often high.

5.4.1 Types and Frequency

• a duplicate sample is one of 2 separate samples collected at the same time in a manner that minimizes differences. When an autosampler is used, samples collected in separate bottles may be considered to be duplicates, otherwise duplicate samples must be collected using two automated samplers installed at the same sampling location. Samples collected by manual grab methods must be taken simultaneously or sequentially. The duplicate sample must be correctly identified and recorded so as to facilitate data evaluation.
• a travelling blank is a sample of uncontaminated reagent water free of the analytes of interest. It is prepared by the laboratory performing the analysis, brought to the sampling site, opened at least as long as the manual sampling interval, ( or while sampler bottles are being changed ), preserved as necessary, then returned to the lab for analysis. A travelling blank is not required where an on-line analyzer is used unless the monthly performance check sample is transported to a laboratory for analysis, then a travelling blank sample should be prepared and analyzed quarterly.
• a travelling spiked blank is a sample of uncontaminated reagent water free of any interfering substances to which a known amount of standard solution and appropriate preservative have been added by the laboratory performing the analysis. The travelling spiked blank must be prepared within 24 hours of accompanying the sample containers to the sampling location. The travelling spiked blank is brought to the field and returned, unopened, to the same laboratory for analysis. For a list of suggested spiking materials see Table 4. The travelling spiked blank must be spiked with solutions containing all the target parameters required to be analyzed.

It is required that at least once a year, a duplicate sample must be analyzed from at least one process effluent stream for which limits have been set, for which the frequency of monitoring is weekly or quarterly. As well, a travelling blank and a travelling spiked blank must be analyzed in accordance with this Protocol for each sample for which a duplicate is being analyzed,. These requirements do not apply to 2,3,7,8 - Tetrachlorodibenzo-para-dioxin, 2,3,7,8 - Tetrachlorodibenzofuran, or 2,3,7,8 - substituted dioxin and furan congeners.

It is recommended that a set of the above field QC samples be analyzed for every effluent stream once a month for parameters which are monitored daily, once a quarter for weekly parameters, semi-annually for monthly and quarterly parameters, and annually for semi-annual parameters, to ensure and demonstrate control of the sampling process, and effluent quality.

Duplicate samples should be collected for all ATGs. Travelling blank samples should be prepared and analyzed for all ATGs except ATGs 3, 8 24, and 25, at the frequencies listed above. When on-line analyzers are used, field QC samples need not be collected and analyzed. However, if the monthly performance checks are analyzed in a laboratory as opposed to using instantaneous field measurement, the performance check sample should be collected and analyzed in duplicate.

Travelling spiked blanks should be prepared and analyzed only for organics analyses, ATGs 16-23, 26, 27, and 33.

When recording field QC results, the proper sample type codes must be used to correctly identify the samples for data evaluation.

5.4.2 Field QC Data Application

Each of the field QC samples provides different information about the quality of the effluent samples collected and indicates possible field contamination.

A duplicate sample provides a measure of the reproducibility of the sampling, handling and analytical techniques used.

A travelling blank sample will provide an indication of any problems with sample contamination due to extraneous volatile fractions of contaminants in the atmosphere and any contaminants introduced by handling of the sample containers.

A travelling spiked blank sample should provide an indication of the degree of degradation of the target parameters from the time of sampling to analysis.

Field QC data is an integral part of the database. All records associated with the field QC analysis, as well as the associated laboratory QC samples must be accessible for review.

5.5 STANDARD AND CERTIFIED REFERENCE MATERIALS

Calibration standards must be validated against standard reference materials (SRM) if available from a standards organization. SRMs are used as an independent check of a system calibration. Frequency of SRM analysis will depend on the nature and historical data for the analytical system of interest. Well established, traditional, stable methods/standards may require use of SRMs on a less frequent basis, while experimental methods or highly variable or perishable standards may need more frequent SRM analysis.

SRMs are materials that have been certified by National Research Council of Canada, the United States Environmental Protection Agency, the National Institute of Standards and Technology, or international standards organizations. If an SRM is unavailable for a particular parameter, an additional external source of calibration material should be used for validation. Prepared standards are available whose concentrations have been verified by quality management practices.

Results of SRMs and the associated QC samples should be documented and summarized. Control limits for SRMs may be established and performance reports prepared indicating the accuracy of SRM analysis.

Certified reference materials (CRM) are samples that can be used to assess laboratory accuracy and precision, depending on method of usage. CRMs are typically matrix samples for which certain contaminants or analytes are given certified values or ranges of concentration based on multiple laboratory and method comparisons. While there are few, if any, CRMs available for wastewater analysis, a range of matrix spikes for some conventional and inorganics tests are available as an additional check on analytical performance.

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6.0 ANALYTICAL DATA RECORDING

This section presents guidelines and requirements with respect to data recording under the Effluent Monitoring and Effluent Limits Regulations. It describes the practices to be followed when recording results for all analytical test groups (ATGs). Whether or not there is a requirement to report data to the MOE, there is a requirement to record and maintain an appropriate data management system within any company subject to an Effluent Monitoring and Limits Regulations and within the laboratory providing the analytical services. This system must ensure that records are readily accessible for audit by the MOE upon request.

The requirements listed in this section are specific to the Effluent Monitoring and Effluent Limits Regulations but the data recording principles listed should be followed for sampling and analysis under all MOE programs.

The following sections address the determination of: analytical repeatability (Sw), method detection limit (MDL), the smallest reporting increment (SRI) and truncation or round-off of measurements. They describe the use of remark codes, particularly for indicating low-level results and the definition and use of method codes.

While this section defines the principles related to the recording of analytical data for safekeeping and for availability to the Ministry, except for a few clearly indicated situations (e.g. MDLs), it does NOT stipulate how that data must be developed, managed, or maintained within the company or laboratory record system. This approach leaves room for the use of systems and practices which best suit existing company practices.

Test codes and units of measure codes are discussed. But the actual codes to be used are to be found in the MISA Data Entry System (MIDES) software. Information on the use of MIDES for reporting data electronically to the MOE, is obtained in the MIDES User Manual which addresses the specific details (e.g. sample type codes) and procedures required for both effluent and field QA/QC data. The MISA Compliance Data Entry System Discharger Application Development Guideline and System Requirements provides guidelines for development of electronic data systems compatible with MIDES.

Each topic is addressed by the use of a brief background discussion or indication of concern, definitions, as well as, a statement of regulatory requirements and a proposed protocol where applicable. Additional notes are provided based on questions which have arisen in the past. Where alternative or optional protocols exist these will be indicated.

6.1 ROUTINE DATA RECORDING UNDER EFFLUENT MONITORING AND EFFLUENT LIMITS REGULATIONS - GENERAL

A laboratory's data management system will establish and maintain direct links between the sample information (such as source, field sample number/code, date/time sampled, tests required, etc.) and laboratory information (such as lab sample number/code, date/time analyzed, tests performed, analyst, etc.).

A properly recorded result will include the test/analyte name/code, the units of measure, the method used and appropriate qualifying remarks. The result will include an adequate number of significant digits (based on the analytical repeatability of the method used).

A key component of the Effluent Monitoring and Effluent Limits Regulations has been the specification of:

a) analytical principles, to ensure general data comparability; and,
b) analytical sensitivity, based on pre-determined criteria for analytical detection capability, to ensure a consistent ability to measure at the levels required to ensure achievement of the program's goals.

The imprecision (noise) associated with analytical measurements ultimately affects the analyst's ability to differentiate between a sample containing some small amount of the target analyte and a sample presumed to contain none of the target analyte (a blank). The imprecision of the analytical method also affects the ability to define `zero', and to discern bias (a systematic difference between results from different analysts and/or methods). It also impacts on the analytical operating range.

To enhance the comparability of data from different laboratories, the MOE established a target value for analytical performance based on a tabulated Regulation Method Detection Limit (RMDL) for each analyte. In general, laboratories can achieve this level of performance by making adjustments to the amount of sample analyzed and the relative dilution or concentration factors used within the selected method.

For general purposes analytical measurement results below RMDL are considered to be low-level values. The Ministry requires that all low-level measurements be recorded, and reported to the MOE as required. The interpretation of individual data at or below 2x MDL is considered problematical by most analysts. In fact, in some jurisdictions results below 4x to 5x MDL are not reported. Experience during the monitoring phase of the MISA regulations has demonstrated that such data can be very useful for assessing the presence or absence or low-level trends at trace levels over extended periods of time. The requirement to record and report such data also improved the overall quality of data through better blank and recovery control.

A variety of remark codes are provided to discriminate between various types of low-level and "less-than" data. Their use is described in Section 6.1.4 and their interpretation in Section 6.2.1.

For the purposes of the Effluent Monitoring and Effluent Limits Regulations program, an electronic data reporting system was developed to facilitate transfer of data from the laboratory, to the discharger and to the MOE. The MISA Data Entry System (MIDES) diskettes will be provided to each discharger for data transfer. In addition to various codes defining sample locations and sample types (including QC sample types), its reporting structure for each field sample test result depends on, a test code, a result field, a unit of measure code and a remark code. The actual codes available are tabulated in the MIDES User Manual. The following sections of this document provide detailed information on data recording practices and requirements.

Definitions:

Test Code: A six character alphanumeric field. The first two characters identify a chemical element (e.g. nitrogen = NN, lead = PB, etc.) or a group of related organic compounds often within the same chromatographic scan (e.g. halogenated compounds group 1 = X1). The remaining four characters clarify the type of test or the test name. They tend to be mnemonic. Thus PPO4FR is phosphate (a phosphorus compound) performed on a fractionated sample to recover whatever reacts under the test conditions. CUUT is copper performed on the entire (unfractionated) sample to recover the total amount (subject to the method used), B2BENZ is benzene.

Units of Measure: Used to identify the concentration units used (e.g. mg/L, µg/L, etc.) and how the result was calculated (e.g. report as N, as SO4, as P, as PO4, etc.). These are defined in the MIDES User Manual. The corresponding codes are "hard coded" in the customized MIDES diskettes for each discharger.

Remark Code: A three-character alphanumeric code, provided in the MIDES data reporting system. It is used for indicating low-level or less-than data, for qualifying results, or to explain the absence of a result.

6.1.1 Method Codes

This code was used under the Effluent Monitoring Regulations to identify laboratories and methods of analysis. Although it is not required under the Effluent Limits Regulations it remains a convenient tool for the identification of the lab doing the analysis and the method used.

The laboratory must list each of its methods for the analytical tests for which it is responsible and should assign a unique method code for each of the variations/combinations of sample preparation, analysis, detection, and measurement procedures it may use.

The documentation for the method code of an analytical method used to determine one or more test results might include:

CODE Brief Description

ID003A (sample prep).............entire sample
(analytical workup).....acid digestion
(detection system)......AAS

The forms used under the Effluent Monitoring and Effluent Limits Regulations provide a useful means for keeping records of method codes and LMDLs.

Required: The company must provide to the Ministry, on request, the names of its laboratories (including sub-contractors), contact information and the analytical method used with the corresponding LMDL for each test required.

The laboratory must follow the test methodologies it has selected, and must maintain a complete procedural description, including the associated control practices, for review by Ministry staff on request. Laboratories are required to apply the quality assurance and quality control practices specified under the regulation, as listed in Section 5.0.

Any significant changes to the method which might affect the precision, accuracy, or recovery of the method must be documented by the laboratory and be available to the Ministry, on request, along with new estimates of the LMDL.

6.1.2 Laboratory Method Detection Limit (LMDL)

Definitions:

Analytical repeatability: Ability to obtain a similar result for each of a sequence of replicate applications of a method carried out by the same analyst within the same analytical batch/run. It can be estimated at various concentration levels by the procedure provided for calculating the within-run standard deviation (Sw) in Section 7.6.5. This estimate does not include the effect of analytical biases/mistakes or unpredictable sample matrix effects.

Method detection limit (MDL): MDL is a statistically defined decision point. It marks the detection level above which one can conclude that a measured result indicates the probable presence of analyte in the sample, with a stated risk that this conclusion is false. This estimate is based on the analytical repeatability, within-batch standard deviation (Sw) for samples processed through the entire method with a risk of less than 1% that the conclusion is false.

Regulation MDL (RMDL): The upper limit permitted for the LMDL value for analytes required under Effluent Monitoring and Effluent Limits Regulations. RMDL values are listed in Table 1.

Laboratory MDL (LMDL): A laboratory specific estimate of the method detection limit calculated using the procedure described in Section 7.0.

The relatively low number of replicates (8) required to estimate MDL yields a highly variable estimate. It should be recognized that the LMDL estimate is typically uncertain by as much as a factor of two.

When different LMDL estimates (between-day, among analysts, between methods, or between sample types) agree within about a factor of two, they are not considered statistically different.

The fact that the LMDL is not greater than the RMDL must be demonstrated at least once. If the method is altered or significantly changed a new LMDL must be determined. It is recommended that the LMDL be redetermined approximately every 6 months unless routine QC data demonstrate that no significant change has occurred in the sensitivity or the precision of the analytical procedure.

To provide confidence that the actual LMDL on any given day will be below the RMDL, it is desirable that the LMDL estimate be about 1/2 of the RMDL. If the LMDL is much less than 1/10th RMDL, the analytical precision exceeds the requirements of the Effluent Monitoring and Effluent Limits Regulations and a smaller sample aliquot may provide a more appropriate operating range for the analytical method.

The analyst should demonstrate reliable precision before estimating the LMDL. The test samples must be processed individually through the entire method. The analytical method must be defined rigorously enough to ensure that replicate measurements will be more or less `normally distributed' e.g. clustered together. Anomalous values should not be included in the calculation of analytical repeatability.

The size of sample analyzed, and associated changes in dilution or concentration factors, will affect the LMDL value proportionately. Therefore the LMDL should be determined using the routine sample aliquot and dilution factor that will be applied when analyzing actual samples.

If the concentrations of analyte found in routine samples are typically off-scale, a smaller sample aliquot may be taken for routine measurement purposes. This dilution factor will cause a proportional change to the operational LMDL. BUT, when the measurement is near or below this adjusted LMDL, the sample must be re-analyzed using a larger aliquot to meet the requirement to measure down to an LMDL which is less than RMDL.

The statistical procedure and concepts on which the detection limit is based do NOT incorporate allowance for errors or bias in measurement due to sample matrix effects or otherwise. The analyst is expected to prevent or control errors. If the result for a specific sample is suspect because of sample matrix effects, the analyst may use one of several remark codes to indicate this. If these effects prevent measurement of an analyte, the analyst must estimate the level at which the interference prevents analysis. See Sections 6.2.3 and 6.2.4.

Required under the Effluent Monitoring and Effluent Limits Regulations: The LMDL must be calculated for each regulated analyte using the procedure described in Section 7.0.

The measured LMDL must not exceed the required value of the RMDL.

The value of the LMDL for each regulated analyte must be recorded, along with an identification of the test procedure used. See Section 6.1.1, Method Codes.

6.1.3 Routine Data Recording - Significant Digits

Definitions:

Significant Digits: Any digit/figure in a recorded value which is at, or to the left of the same decimal position as the left-most digit of the estimated within-run standard deviation (Sw) of the analytical method, excluding leading zeros.

Estimate the analytical repeatability by calculating the within-run standard deviation (Sw) by one of the alternatives provided in Section 7.0.

Smallest Reporting Increment (SRI): Describes the size of the interval between adjacent results. It is chosen to be smaller than Sw when Sw has been estimated at or near the MDL.

Procedure for SRI determination: The SRI value is based on Sw:

e.g. SRI = Sw rounded down to nearest 1, 2 or 5 with due regard for decimal position.

Thus, if the first (left most) digit of Sw is:
5 to 9; SRI = 5 (adjusted for decimal position)
2 to 4; SRI = 2
1; SRI = 1

Example:

Sw	SRI
570	500 **
293	200 **
134	100 **
8.9	5
0.93	0.5 (or 1) ***
0.038	0.02
0.013	0.01
0.0088	0.005

** Right hand zeros may not be `significant'.
They also indicate the inferred decimal position.

*** Borderline cases can be chosen to reflect the most typical SRI for other analytes in the scan.

Record results in multiples of SRI or to retain at least two significant digits. Three significant digits should be retained if the first digit on the left is "1".

e.g. if SRI = 0.2, then results are recorded in steps of 0.2, thus ...,
6.4, 6.6, 6.8, ...

e.g. the result 35.8 can be rounded off (to 36).
the result 13.4 should not be rounded off.

Ensure that the units of measure are correct. Add any remark codes considered appropriate.

For the purposes of the MOE reporting requirements, only two significant digits need be used, although three significant digits are preferable if the first digit on the left is a "1". This avoids introducing bias.

Results should be recorded in steps not larger than the SRI, unless at least two significant digits can be retained. The laboratory is free to record results in increments smaller than SRI.

Estimates of standard deviation, and therefore of LMDL and SRI, are affected by the size of the sample aliquot and any additional dilution or concentration factors. Thus, if SRI =0.002 and a 100x dilution of sample is taken, then the SRI becomes 0.2.

When several analytes are being measured together, SRI values can be adjusted slightly if the Sw value is just below a 1,2, or 5 boundary, and other similar analytes in the `scan' have Sw values just above the same boundary.

Required under Effluent Monitoring and Effluent Limits Regulations: Laboratories must record all results. A result must be recorded for all regulated analytes down to the level of SRI. Censoring of results below LMDL is not permitted. Results should be recorded with at least two significant digits.

6.1.4 Routine Data Recording - Low-Level and “Less Than” Data

Definitions:

In the following examples assume RMDL = 25, LMDL = 7.3, SRI = 2.

Low-Level: Below RMDL but not below LMDL - Results in this range should be qualified as low-level by use of the remark code <T. e.g. 12 <T

Very Low-Level: Below LMDL but not below SRI - Results in this range should be qualified as very low-level by using the remark code <DL. e.g. 3 <DL.

Less Than: Below SRI - Results below SRI represent `analytical zero'. Generally there will be no observable response. These are recorded by indicating the measured value, usually the value of SRI qualified by the remark code <W. e.g. 2 <W.

Less Than: Over-estimate (Interference) - When a result cannot be estimated due to gross sample matrix interference, etc., estimate the amount due to the effect of the interference. Record estimate and qualify it by the remark code <, e.g. 150 <.

The recorded value is usually a definite over-estimate. The actual amount present is unknown. It may, or may not be, a low-level data point. See also "Remark Codes - Approximate/Unreliable".

All results above RMDL may be accompanied by an appropriate explanatory remark code.

The use of the remark code <T for results at or above LMDL is entirely optional. It does serve to flag low-level trace/tentative values.

Results below 1/10th RMDL are considered to be very low and they will be considered as "analytical zeros" for the purpose of estimating loadings under the Effluent Monitoring and Effluent Limits Regulations. The company/laboratory must record such measurements by recording the measured value, usually of SRI qualified by the remark code <W.

When the analyte cannot be measured because of interference from other matrix constituents, the analyst should provide an estimate of the maximum amount (although it may be present at a much lower level) of analyte that might be present. This estimate is accompanied by the remark code <.

In the absence of a result the analyst must record an explanation for the lack of a result by an attached report, and/or by use of an accepted remark code. See Section 6.2.2.

6.2 REMARK CODES - GENERAL

While analysts make every effort to control and prevent analytical and measurement errors, certain samples may introduce analytical problems due to the presence of other matrix constituents. These may affect the quality and interpretation of the reported result. Remark codes provide a means to bring these concerns to the attention of the data user.

There are several classes of remark codes. Their codes and interpretation are discussed in the following sections.

low-level or less than codes <T, <DL, <W
missing result or textual report codes u, !, !IN, !NM, AR
sample matrix/interference codes I, IB, IC, IM, MP
possible approximate/unreliable data codes A, AIS, <, >, UCR, UNF, UQC, USD
miscellaneous codes OLD, SD, SID, SIP, Pxx, Txx

Many of the remark codes described above are optional. Their use does not preclude the acceptance and use of the reported value by the MOE.

Definitions:

Attached Reports: Written statements explaining the reason why a result has not been recorded for situations not adequately covered by a remark code.

For uniformity, it is recommended that all laboratories/companies use the same system for recording and qualifying data as described in this section and in the MIDES User Manual for reporting data to the MOE.

Required under the Effluent Monitoring and Effluent Limits Regulations: All analytical results must be recorded for all regulated analytes. When no result is available, a written explanation must be provided. 6.2.1 Low-Level Data - Remark codes

The interpretation of low-level data requires a consistent approach to the use of the < sign and the low-level remark codes. Section 6.1.4 discusses their application for the MOE requirements. This section describes their interpretation.

The remark codes < and > are discussed separately in the section "Remark Codes - Approximate/Unreliable"

Definitions:

<T A measurable trace amount, interpret with caution

Recorded value = measured value.
Value is at or greater than LMDL but below RMDL.
It is a tentative low-level result.

Such data requires verification against other related data. Even when results exceed the LMDL, other QA/QC information may indicate the presence of biases which will affect data interpretation.

<DL Recorded value = measured amount <LMDL (non-zero)

Recorded value = measured value.
The value is below the LMDL.
It is a very low-level result.

Sufficient data of this type may help distinguish between analytes which are consistently not present from those which tend to be found at low levels. This is important when evaluating the trace presence of analytes of concern, particularly when the levels are comparable to the blank. Conclusions are subject to evaluation of QA/QC blank and spike recovery data.

<W No measurable response (zero)

The recorded value is the smallest observable response.

Either no response was observed and the measured result was `analytically zero', or the response is negligible (below SRI).
Sufficient data of this type suggests the absence of analyte at levels above the recorded SRI value, subject to evaluation of QA/QC spike recovery data.

6.2.2 Missing Data and Attached Report

Missing results can occur because of sampling or analytical problems. An attached report is always required to explain missing results. The following codes are used when there is no result to report in the result field, or when the result is textual rather than numeric. Use of the following remark codes will assist data users who may not have ready access to the file of explanatory textual notes.

Definitions:

u Late data: data not yet available: see text

All available data must be recorded within the specified deadline in order to be in compliance. If some data is not yet available from the laboratory this must be explained.

! No data will be recorded: See textual report

Field or laboratory accidents may prevent analysis for one or more analytes. Whenever possible sufficient sample volume must be taken to allow for re-analysis.

!IN No data: insufficient volume due to inspection

When the MOE inspectors remove some or all of the routine sample, the company is not required to re-sample.

!NM No data: no effluent - no sample taken

If there is no effluent there can be no data.

AR Attached report

If there is need to explain data, or the lack of data, in more depth than permitted by the use of remark codes, an attached report can be useful.

6.2.3 Sample Matrix Effects/Interference

Sample matrix effects are often suspected, but can be difficult to confirm. Information from the analyst which flags suspect data may assist in the data interpretation.

Sample matrix problems (particulates, multi-phase, heterogeneity, etc.) can introduce analytical problems. Colour and the multiplicity of other sample constituents present in waste can interfere, increasing or decreasing the observed vs real concentrations of the target analytes. Certain types of interference are characteristic of specific methods. The analyst will often be able to explain the effect of the interference on data interpretation. If the effect is severe enough the analyst may elect not to report a result.

Definitions:

The following codes are used when the measured result is recorded but is considered to be somewhat suspect.

I Interference suspected

The nature of the sample, problems during sample preparation or analysis, etc. lead the analyst to question the result. Do not use indiscriminately.

IB Interference: background

Often relates to problems setting background correction, baseline, etc., due to noise or adjacent interfering peaks.

IC Interference: colour

Certain colourimetric tests may yield high results on coloured samples.

MP Multi phase sample: result may be suspect

The presence of fine and coarse particulates (or biomaterial, wood chips, etc.) and/or an oily phase may prevent the acquisition of a representative sample.

6.2.4 Approximate/Unreliable Data

The nature of waste samples (non-homogeneity or perishability) is such that a proper representative aliquot may be difficult to obtain for analysis. The ability of the analyst to flag this assists in the data interpretation. In some cases the estimate may still be adequate for determining compliance with an effluent limit.

Definitions:

A Approximate value

The nature of the sample prevents proper representative aliquotting. The result is less precise or less accurate than usual.

AIS Approximate value: Insufficient sample

Smaller than routine aliquots degrade the precision and reliability of measurements.

The following codes are used when the measured value is felt to represent an upper or lower limit for the amount of target analyte actually present in the sample. The value recorded may be the actual number obtained, or it may be an indication of a limitation of the method for this particular sample.

< Actual amount less than recorded value

This remark code indicates that the recorded value is an over-estimate. The analyst suspects that the response has been enhanced (e.g. by severe matrix interference) or has increased due to sample perishability effects.

The estimate is accompanied by the remark code <.

> Actual amount greater than recorded

The analyst suspects that the response is suppressed by severe interference effects, or has decreased due to sample perishability.

The estimate is accompanied by the remark code >.

The following codes indicate a larger than usual range of uncertainty for the accompanying result, often because of difficulty obtaining a representative aliquot, or because of related sample or QC problems. The result may be okay, but the analyst is unwilling to report an unqualified result.

UCR Data unreliable: could not confirm by re-analysis.

When a suspicious result is obtained, the analyst will often repeat the analysis when there is sufficient sample. This code indicates inability to perform the required re-analysis.

UNF Data unreliable: container not filled to top

Tests for many organics require a completely filled container to avoid target analyte losses into the headspace. Results will tend to be low.

UQC Data unreliable: possible lab QC problems

Tests for some analytes require use of the entire sample. Therefore a repeat analysis is not possible in the event that a QC problem was detected. A duplicate sample should be collected to allow for re-analysis when needed.

USD Data unreliable: sample decomposition noted

May be used when sample decomposition has occurred during transit which might affect the analytical result.

6.2.5 Miscellaneous

Certain codes are required to note sample problems related to field procedures, or inability to comply completely with the Effluent Monitoring and Effluent Limits Regulations. There is also a set of codes required to explain how PCB data has been quantified.

Definitions:

OLD Old: sample exceeds maximum storage time

Effluent Monitoring and Effluent Limits Regulations specify a maximum storage time before analysis. Exceeding this time may not affect results which must be recorded and reported, accompanied by the remark code "old".

SD Sample duplicates differ in appearance

Duplicates are required under Effluent Monitoring and Effluent Limits Regulations to monitor the variability and reliability of sampling. When the samples look different upon arrival at the laboratory, there may have been problems with sampling, transportation or sample preservation.

SID Sample identification questionable

The sample bottle labels don't match the submission form or the sample appears to be different than expected for the specified source.

SIP Sample improperly preserved

The regulation specifies the type of sample preservation required. Analyses may have been performed on an incorrectly preserved, or unpreserved sample, because of misadventure to the proper sample. Coding should be done where there is reason to believe that the result will be significantly affected.

Txx Time: xx hours between sampling and analysis

These codes are primarily used when recording microbiological data.

Pxx PCB resembled (mix of) AROCLOR ---- (& ----)

These codes are used to identify the chromatographic `fingerprint' as resembling an Aroclor type.
Tables for Txx and Pxx are included in the MIDES User Manual.

6.3 LABORATORY QUALITY CONTROL

The validity of analytical data depends on the application of a well-documented methodology by trained, expert staff, using an analytical detection system which has been properly calibrated and which is maintained in a state of statistical control. A competent laboratory will include a variety of check procedures and check samples.

Definitions:

Laboratory Quality Control: Activities are undertaken to evaluate the suitability of a process or component for its intended purpose. These may include pre-service checks of reagent quality, instrument stability, staff expertise, etc. They also include in-service checks of system performance to ensure performance criteria are being met and that the system is stable. Most analytical systems include `bench procedures' such as sample preparation, sample cleanup and analytical work-up. The system also includes some form of measurement device through which one or more `batches' of prepared samples are `run'.

Quality control: Implies the existence of an expected value and predetermined, statistically defined criteria for determining acceptability. Bench QC includes: method blank(s), certified reference materials (in natural matrix), `spiked samples', and `replicate samples', etc. Run QC includes: calibration checks, standard reference materials (in laboratory solvent), baseline checks, sensitivity checks, curvature checks, etc.

QC Summaries: A table or chart showing expected value, limits, observed values, and notes concerning action taken when observed values exceeded the predetermined limits.

Standard Reference Materials (SRMs): Pure materials obtained from a recognized agency (such as EPA, NIST, NRC, or others delegated by them) and certified for the purpose of making standard solutions of known purity and concentration, or prepared and certified solutions of one or more analytes in a laboratory solvent prepared by such agencies. These are used for validating in-house standards prepared from commercial or other sources of materials.

Certified Reference Materials (CRMs): Naturally occurring materials (biota, vegetation, soil, etc.) which have been certified by a recognized agency (as listed above) to contain specified levels of selected constituents, when measured by specified standard procedures. These are used for validating the performance of a method (recovery, specificity, selectivity, repeatability).

SRM, CRM: Are acronyms used by NIST and NRC respectively to describe either type of material provided by them, irrespective of function.
Required under the Effluent Monitoring and Effluent Limits Regulations: Every laboratory must be able to demonstrate regular use of SRM's and CRM's as appropriate and as available from a standards organization, and must maintain a record of results obtained for inspection by the MOE regional or laboratory staff.

Also the MOE must be able to readily access bench level and run QC data for the purpose of database evaluation, and to ensure appropriate response to effluent data variability.

Every laboratory providing results under Effluent Monitoring and Effluent Limits Regulations must prepare a summary report of its bench and run QC data on a quarterly basis (every 3 months) with a final annual summary report every 12 months. All reports and the supporting original QC data must be available for review by the MOE regional or laboratory staff. This summary should include at least the following information for each of the QC sample types (blank, spiked blank, spiked sample, replicate sample) required under the regulation:

• number of actual samples analyzed
• concentration of test analyte found routinely
• minimum, maximum, average, standard deviation
• number of QC samples (of each type) analyzed
• for spiked blank and spiked sample, the design (expected) value
• minimum, maximum, average recovery
• for replicate samples, data should be segregated by concentration level, e.g.bottom 10% of operating range, 10 to 50% of range, 50 to 100% of range, off- scale
• the standard deviation and mean for each interval should be calculated from the differences (D) between replicates as follows:
  

where: i varies from 1 to n
n is the number of samples in the interval

An example of data tabulation/presentation is shown in Section 5.5, Figure 1.

The process for setting statistical limits should avoid data which indicates chronic drifting or sudden changes in the observed values. Control charts provide a particularly useful mechanism for demonstrating control status over an extended period of time and assist in assessing long-term performance (trends, sudden changes, bias, etc.). A well-controlled system will approach a `normal' or `Gaussian' distribution.

Analysts should participate in relevant inter-laboratory comparison studies, as available, to substantiate the overall validity of their method.

7.0 ESTIMATION OF ANALYTICAL METHOD DETECTION LIMITS (MDL)

The requirements listed in this section are specific to the Effluent Monitoring and Effluent Limits Regulations, but the principles listed here should be applied to all MOE programs involving low-level data.

7.1 INTRODUCTION

This protocol has been established to ensure a consistent approach to the development of method detection limit (MDL) estimates for the MISA program based on the use of fortified reagent (blank) water or evaluation of available routine within-run duplicate analyses. The Effluent Monitoring and Effluent Limits Regulations have established criteria for maximum permitted laboratory MDLs (LMDLs), which are referred to as Regulation MDLs (RMDLs) and are shown in Table 1.

It should be noted that when MDL estimates are developed using clean samples (e.g. reagent (blank) water) they represent an optimum achievable value. MDLs obtained in this fashion are very useful for establishing performance criteria and allowing comparison of inter-laboratory method capabilities, but may not be applicable in defining the quantitation capability for other samples which introduce matrix effects.

The following protocol represents a modification to that documented in the Federal Register/Vol. 49, No. 209/Friday, October 26, 1984/Appendix B to Part 136 - Revision 1.11.

This modification restricts the options listed in the original document and gives more direct instructions at other option points.

7.2 DEFINITION

The method detection limit (MDL) is a statistically defined decision point such that measured results falling at or above this point are interpreted to indicate the presence of analyte in the sample with a specified probability, and assumes that there are no known sources of error in identification or biases in measurement.

For the purposes of this protocol, the MDL is defined as having a confidence limit of 99%. This confidence limit defines the multiplication factor used from Student's t-tables relating MDL to the analytical precision. This Student's t-value depends on the amount of data used to calculate the analytical precision. In general, analytical precision will depend on the analytical conditions and the sample matrix. When possible, precision will be determined by replicate analysis of typical low-level samples, with sufficient replication to provide a reasonable estimate.

7.3 SCOPE AND APPLICATION

This protocol is designed for application to a wide variety of sample types ranging from reagent (blank) water fortified with a known concentration of analyte to wastewater containing analyte. The MDL for an analytical procedure may vary as a function of sample type. The protocol requires a complete, specific, and well defined analytical method. It is essential that all sample processing steps of the analytical method be included in the determination of the method detection limit.

Since the MDL procedure was designed for application to a broad variety of physical and chemical methods, it was made device or instrument independent.

There are four options available for estimating the analytical precision:

a) accumulation of a large number of in-run replicate analyses of typical samples at levels not exceeding 10 times the estimated MDL;

b) accumulation of in-run replicate analyses of laboratory reagent quality water spiked with a known amount of the target analyte(s) at levels not exceeding 10 times the estimated MDL;

c) analysis of eight replicate aliquots of a typical low level sample at levels not exceeding 10 times the estimated MDL;

d) analysis of a series of eight replicate aliquots of laboratory reagent quality water spiked with a known amount of the target analyte(s) at a level not exceeding 10 times the estimated MDL.

When applied for the Effluent Monitoring and Effluent Limits Regulations, the appropriate RMDL shall be used in place of the 'estimated MDL' in the above options.

7.4 ORGANIC ANALYTES (Analytical Test Groups 16-24, 26 and 27)

This protocol requires that option d) in Section 7.3 be used. The fortification of laboratory reagent (blank) water with a known level of analyte is required to standardize the protocol for all laboratories and minimize the problems associated with analyzing duplicate or replicate samples or finding a standard “matrix” for organics analysis. The analytical precision is established based on eight replicate analyses and the estimated MDL is derived from a combination of these measurements and the appropriate value from t-test tables. This option is not intended to assess the effect of the matrix on the values obtained but rather to define a standardized approach in the development and application of inter-laboratory performance criteria for the program.

7.4.1 To determine the MDL, proceed as follows:

Make an estimate of the MDL using one of the following:

• the concentration value that corresponds to an instrument signal/noise ratio of 3:1;
• the concentration equivalent of three times the standard deviation of replicate instrumental measurements of the analyte in reagent water;
• that region of the standard curve where there is a significant change in sensitivity, e.g., a break in the slope of the standard curve;
• instrumental limitations.

It is recognized that the experience of the analyst is important to this process. However, the analyst must include the above considerations in the initial estimate of the detection limit.

7.4.2 Prepare reagent (blank) water that is as free of analyte as possible.

Reagent or interference-free water is defined as a water sample in which analyte and interferent concentrations are not detected at the method detection limit of each analyte of interest. Interferences are defined as systematic errors in the measured analytical signal of an established procedure caused by the presence of interfering species (interferent). The interferent concentration is presupposed to be normally distributed in representative samples of a given matrix. The use of commercially obtained or laboratory prepared organic free water is acceptable but clearly indicate what was used.

7.4.3 Prepare a laboratory standard (analyte in reagent water) at a concentration which is at least 5 times, but not to exceed 10 times the estimated method detection limit.

Proceed to Section 7.6.1.

7.5 CONVENTIONALS, METALS AND INORGANICS

(Analytical Test Groups 1-15 and 25)

This protocol allows any of the options a), b), c) or d) in Section 7.3 to be used. For options a) and b) the laboratory should review recent data on in-run replicates (data accumulated within the preceding 12-month period or less) and apply the formula as outlined in Section 7.6.3 to at least 40 data pairs.

7.5.1 For Option c) proceed as follows:

7.5.1 a) When a "real" sample is being used for the MDL determination analyze the sample. If the measured level of the analyte is in the recommended range of one to five times the estimated method detection limit proceed to Section 7.6.

7.5.1 b) If the measured level of analyte is less than the estimated method detection limit, add a known amount of analyte to bring the level of analyte between five and ten times the estimated method detection limit.

7.5.1 c) If the measured level of analyte is greater than 5 times the estimated method detection limit, there are two options:

• Obtain another sample with a lower level of analyte in the same matrix if possible;
• The sample may be used as is for determining the method detection limit if the analyte level does not exceed 10 times the MDL of the analyte in reagent water. The variance of the analytical method changes as the analyte concentration increases from the MDL, hence the MDL determined under these circumstances may not truly reflect method variance at lower analyte concentrations.

Proceed to Section 7.6.1.

7.5.2 For option d) proceed as in Section 7.4.

7.6 PROCEDURE FOR LMDL DETERMINATION

7.6.1

Take eight aliquots of the sample to be used to calculate the method detection limit and process each through the entire analytical method. Make all computations according to the defined method with final results in the method reporting units.

If a blank measurement is required to calculate the measured level of analyte, obtain a separate blank measurement for each sample aliquot analyzed. Calculate a result (x) for each sample/blank pair.

7.6.2

For option c) and d), 8 replicates of a typical low level sample or spiked reagent water, calculate the standard deviation (S) of the replicate measurements as follows:

where:
xi = the analytical results in the final method reporting units for the eight replicate aliquots (i = 1 to 8)
x = the average of the eight replicate measurements

7.6.3

For option a) and b), assessment of historic within run replicate analysis data, calculate the standard deviation (S) of the replicate measurements as follows:

where:

x1, x2 = the two replicate results for each of the n replicate pairs
(minimum n = 40)

7.6.4 Compute the MDL as follows:

MDL = t( n-1, a = 0.01 ) S

where:

t( n-1, a = 0.01 ) is the Student's value appropriate for a 99% confidence level given the degrees of freedom n-1.

S = the standard deviation as determined above.

Tables of Student's t Values at the 99 Percent Confidence Level

Number of Replicates	Degree of Freedom (n-1)	t (n-1)
7	6	3.143
8	7	2.998
9	8	2.897
10	9	2.821
11	10	2.764
16	15	2.603
21	20	2.528
26	25	2.485
31	30	2.457
infinity	infinity	2.369

7.6.5 Recording

Record the calculated MDL to two significant figures (e.g. 0.032). The analytical method used must be specifically identified by number or title and the MDL for each analyte expressed in the appropriate method reporting units. If the analytical method permits options which affect the method detection limit, these conditions must be specified with the MDL value. Report the mean analyte level with the MDL and indicate if the MDL procedure was iterated. If a laboratory standard or a sample that contained a known amount of analyte was used for this determination, also record the mean recovery.

7.7 TREATMENT OF OUTLIERS

Single Analyte Methods:

If one of the results can be shown to be an 'Outlier' by the Dixon test (described below), AND the LMDL calculated for the remaining seven replicates (3.143 times S) is less than RMDL, this latter estimate of LMDL will be accepted.

Scans:

Certain methods permit analysis of several analytes within a single 'scan'. The MDL for each analyte in the scan must be less than the corresponding RMDL. When the LMDLs tend to bracket the RMDLs, the overall method is not sensitive enough and the LMDLs will not be considered acceptable.

However, if only a few of the LMDLs in a 'scan' exceed their respective RMDLs, there may be outliers within the set of eight replicates for these non-complying analytes. If this can be confirmed, as described above, for each of the non-complying analytes, then the LMDL based on seven replicates (3.143 times S) will be accepted for those few analytes.

To forestall the possibility that one replicate sample may be an outlier for all or most analytes in the scan, and that the calculated LMDLs therefore will be greater than RMDL for several analytes, the analyst may choose the following option:

- perform eleven replicates (rather than eight);
- for each analyte, note which replicate gives the highest and the lowest results;
- reject the sample replicate containing the greatest number of high results;
- reject the sample replicate containing the greatest number of low results;
- reject the sample with the greatest number of high and low results; and
- calculate LMDLs for each analyte using the remaining eight replicate samples.

If this procedure fails to indicate an LMDL for each analyte which is below the respective RMDL, redefine the method (for example, larger sample aliquot, different range expansion, etc.), retrain staff, and repeat the entire procedure for estimating RMDL for all analytes in the scan. Discard all previous replicate data.

Outlier procedure: Dixon's Test for sample size; n = 8 to 10.

i) sort the replicate values from lowest to highest r1, r2,.........r(n-1), rn;

ii) determine the difference between the suspect value and its nearest neighbour r1 - r2 (or rn - r(n-1),);

iii) determine the difference between the suspect value and the next to last value at the opposite end of the sorted list of values r1 - r(n-1), (or rn - r2);

iv) calculate the ratio of ii) divided by iii);

v) if the ratio is greater than 0.55 the value r1 (or rn) is considered to be an outlier (<5% risk of error).

Natrella, M.G. "Experimental Statistics", NBS Handbook 91, (1966) USGPO, Washington, D.C.

8.0 GLOSSARY

Analytical run: a group of samples processed together through each step of an analytical procedure;

AA: atomic absorption;

AUTO: refers to sampling technique where an automated sampling device is used;

ATG: analytical test group as listed in Table 1;

Autosampler: device to collect samples automatically either in proportion to the wastewater flow or as equal volumes at equal time intervals; automated sampler; automatic sampling device;

Bakelite®: registered trademark of Union Carbide Canada Ltd for phenol formaldehyde resin;

Blank: same as method blanks;

Composite sample: volume of waste water made up of sub-samples or aliquots which have been combined automatically or manually or obtained from a slip-stream by an on-line analyser;

CRM: certified reference material; matrix sample containing analytes at concentration values which have been certified by multiple laboratory analysis;

CSA Canadian Standards Association;

Duplicate: duplicate sample: one of two samples collected at a sampling point at the same time in a manner that minimizes differences between the samples;

DCP: direct current plasma;

ECD: electron capture detector;

FID: flame ionization detector;

Freon®: chlorofluorocarbon, trademark of E.I. Du Pont de Nemours & Company;

GC: gas chromatography;

GC/MS: gas chromatography/mass spectrometry;

GLP: good laboratory practice, see Section 5.1.;

GRAB sample: volume of effluent of at least 100 mL (except for volatiles), collected over a period not exceeding 15 minutes and immediately transferred to an appropriate laboratory sample container, see Section 3.1.1;

IC: ion chromatography;

ICP: inductively coupled plasma;

ICP/MS: inductively coupled plasma / mass spectrometry;

Inspection sample: sample collected by a provincial officer from a sampling point of a discharger;

HPLC: high performance liquid chromatography;

LSB: Laboratory Services Branch, the MOE;

LMDL: analytical method detection limit calculated by the laboratory performing the analysis;

LOC: Limit of characterization: value above which organic compounds or elements must be identified and their approximate concentration determined in open characterization analyses (ATGs 28a, 28b and 29);

MANUAL: refers to sampling technique where a number of grab samples are collected then combined either in proportion to flow or in equal volumes to form a composite sample;

MDL: analytical method detection limit or minimum concentration of a parameter necessary to infer its presence in a sample with a level of confidence greater than 99 percent;

MIDES: MISA Data Entry System;

MISA: Municipal and Industrial Strategy for Abatement of the MOE;

MOE: Ontario Ministry of Environment;

MOH: Ontario Ministry of Health;

NIST: National Institute for Standards and Technology;

NRC: National Research Council of Canada;

On-line analyser: device directly connected to a sampling point which can sample and analyze water automatically;

Parameter: refers to a compound listed in an ATG;

PID: photo ionization detector;

Pre-charged: refers to the addition of preservative to an autosampler container prior to sample collection;

QA: quality assurance; see Section 5.0;

QC: quality control; see Section 5.0;

QM: quality management; see Section 5.0;

Recording: refers to record keeping and documentation of information and data pertaining to sampling, analysis, QA/QC procedures, equipment maintenance and any other relevant information;

Replicate: one of two aliquots taken from a sample;

Reporting: submission to the MOE, as required, of analytical data and other information (with the exception of the technical term "smallest reporting increment");

RMDL: analytical method detection limit listed in Table 1. The RMDL is the maximum allowable value for a LMDL under the Effluent Monitoring and Effluent Limits Regulations

Routine: refers to analyses performed frequently (e.g. daily, thrice-weekly or weekly), as opposed to characterization, open characterization or other analyses performed at less frequent time intervals;

Run: same as analytical run: a group of samples processed together through each step of an analytical procedure;Sample storage period of time between sample collection (e.g. end of twenty four time: hour time:sample collection period) and initiation of sample analysis; maximum allowable sample storage times are listed for each ATG in Section 10.0;

SRI: Smallest reporting increment; see Section 6.1.3.

SRM: standard reference material: which has been certified by the NRC, NIST, USEPA or other agency of equal reliability;

Target parameter: compound of interest to be analyzed individually or as part of an analytical test group;

Teflon®: registered trademark of E.I.Du Pont de Nemours & Company. Where Teflon® is specified other chemically inert fluorocarbon resins may be used such as polytetrafluoroethylene (PTFE), fluorinated ethylene propylene (FEP), perfluoroalkoxy (PFA) resins, chlorotrifluoroethylene (CTFE), co-polymers of ethylene with tetrafluoroethylene (ETFE) or chlorotrifluoroethylene (TCTFE);

USEPA: US Environmental Protection Agency.

 

9.0 APPENDIX

TABLE 1 - Analytical Test Groups

ANALYTICAL TEST GROUP NUMBERS, PARAMETERS,
ANALYTICAL METHOD DETECTION LIMITS AND LIMITS OF CHARACTERIZATION

ANALYTICAL TEST GROUP NUMBER & NAME		PARAMETERS	CAS #	RMDL/LOC	UNITS
1	Chemical Oxygen Demand	Chemical Oxygen Demand (COD)	N/A *	10	mg/L
1a	Biochemical Oxygen Demand (5 day)	Biochemical Oxygen Demand (5 day)	N/A *	2	mg/L
1b	Carbonaceous Biochemical Oxygen
Demand (5 day)	Carbonaceous Biochemical Oxygen Demand (5 day)	N/A *	2	mg/L
2	Total cyanide	Total cyanide	1957/12/05	0.005 as HCN	mg/L
2a	Weak Acid Dissociable Cyanide	Free Cyanide	N/A *	0.005	mg/L
2b	Cyanate	Cyanate	N/A *	5	mg/L
2c	Thiocyanate	Thiocyanate	N/A *	5	mg/L
3	Hydrogen ion (pH)	Hydrogen ion (pH)	N/A *	N/A	pH units
4a	Nitrogen	Ammonia plus Ammonium	N/A *	0.25 as Nitrogen	mg/L
4a	Nitrogen	Total Kjeldahl Nitrogen	N/A *	0.25 as Nitrogen	mg/L
4b	Nitrogen	Nitrate + Nitrite	N/A *	0.25 as Nitrogen	mg/L
5a	Organic Carbon	Dissolved Organic Carbon (DOC)	N/A *	0.5 as Carbon	mg/L
5b	Organic Carbon	Total Organic Carbon (TOC)	N/A *	2 as Carbon	mg/L
6	Total Phosphorus	Total Phosphorus	N/A *	0.1 as Phosphorus	mg/L
7	Specific Conductance	Specific Conductance at 25°C	N/A *	5	uS/cm
8	Suspended Solids	Total Suspended Solids (TSS)	N/A *	3	mg/L
		Volatile Suspended Solids (VSS)	N/A *	3	mg/L
8a	Dissolved Solids	Dissolved Solids	N/A *	10	mg/L
9	Total Metals	Aluminum	7429-90-5	0.03	mg/L
		Beryllium	7440-41-7	0.01	mg/L
		Boron	7440-42-8	0.05	mg/L
		Cadmium	7440-43-9	0.002	mg/L
		Chromium	7440-47-3	0.01	mg/L
		Cobalt	7440-48-4	0.01	mg/L
9	Total Metals (cont’d)	Copper	7440-50-8	0.01	mg/L
		Lead	7439-92-1	0.02	mg/L
		Lithium	7439-93-2	0.05	mg/L
		Molybdenum	7439-98-7	0.01	mg/L
		Nickel	7440-02-0	0.02	mg/L
		Silver	7440-22-4	0.01	mg/L
		Strontium	7440-24-6	0.02	mg/L
		Thallium	7440-28-0	0.03	mg/L
		Vanadium	7440-62-2	0.02	mg/L
		Zinc	7440-66-6	0.01	mg/L
9a	Metals	Iron	7439-89-6	0.02	mg/L
		Uranium	7440-61-1	0.02	mg/L
		Magnesium	7439-95-4	0.02	mg/L
10	Hydrides	Antimony	7440-36-0	0.005	mg/L
10	Hydrides (con’td)	Arsenic	7440-38-2	0.005	mg/L
		Selenium	7782-49-2	0.005	mg/L
11	Chromium (Hexavalent)	Chromium (Hexavalent) (NOTE 1)	7440-47-3	0.01	mg/L
12	Mercury	Mercury	7439-97-6	0.0001	mg/L
13	Total Alkyl Lead	Tetra-alkyl Lead (NOTE 2)	N/A *	0.005 as Lead	mg/L
		Tri-alkyl Lead (NOTE 2)	N/A *	0.005 as Lead	mg/L
14	Phenolics (4AAP)	Phenolics (4AAP)	N/A *	0.002 as Phenol	mg/L
15	Sulphide	Sulphide as H2S	N/A *	0.02 as H2S	mg/L
16	Volatiles, Halogenated	1,1,2,2-Tetrachloroethane	79-34-5	1	ug/L
		1,1,2-Trichloroethane	79-00-5	0.6	ug/L
		1,1-Dichloroethane	75-34-3	0.4	ug/L
		1,1-Dichloroethylene	75-35-4	1	ug/L
		1,2-Dichlorobenzene	95-50-1	0.5	ug/L
		1,2-Dichloroethane (Ethylene Dichloride)	107-06-2	0.5	ug/L
		1,2-Dichloropropane	78-87-5	0.5	ug/L
		1,3-Dichlorobenzene	541-73-1	0.5	ug/L
		1,4-Dichlorobenzene	106-46-7	0.5	ug/L
		Bromodichloromethane	75-27-4	0.8	ug/L
		Bromoform	75-25-2	2	ug/L
		Bromomethane	74-83-9	3	ug/L
		Carbon Tetrachloride	56-23-5	0.8	ug/L
		Chlorobenzene	108-90-7	0.5	ug/L
		Chloroform	67-66-3	0.5	ug/L
16	Volatiles, Halogenated (cont’d)	Chlormethane	74-87-3	2	ug/L
		Cis-1,3-Dichloropropylene	10061-01-5	0.5	ug/L
		Dibromochloromethane	124-48-1	0.8	ug/L
		Ethylene Dibromide	106-93-4	0.5	ug/L
		Methylene Chloride (Dichloromethane)	1975/09/02	1.3	ug/L
		Tetrachloroethylene (Perchloroethylene)	127-18-4	0.5	ug/L
		Trans-1,2-Dichloroethylene	156-60-5	0.5	ug/L
		Trans-1,3-Dichloropropylene	10061-02-6	0.5	ug/L
		Trichloroethylene	1979/01/06	0.5	ug/L
		Trichlorofluoromethane	75-69-4	1	ug/L
		Vinyl Chloride (Chloroethylene)	1975/01/04	2	ug/L
17	Volatiles, Non-Halogenated	Benzene	71-43-2	0.5	ug/L
		Ethylbenzene	100-41-4	0.5	ug/L
		Styrene	100-42-5	0.5	ug/L
		Toluene	108-88-3	0.5	ug/L
		o-Xylene	95-47-6	0.5	ug/L
		m-Xylene and p-Xylene (NOTE 3)	108-38-3
& 106-42-3
0.5
ug/L
18	Volatiles, Water Soluble	Acrolein	107-02-8	4	ug/L
		Acrylonitrile	107-13-1	4	ug/L
19	Extractables, Base Neutral	Acenaphthene	83-32-9	1	ug/L
		5-nitro Acenaphthene	602-87-9	3	ug/L
		Acenaphthylene	208-96-8	1	ug/L
		Anthracene	120-12-7	0.6	ug/L
		Benz(a)anthracene	56-55-3	0.5	ug/L
		Benzo(a)pyrene	50-32-8	0.6	ug/L
		Benzo(b)fluoranthene	205-99-2	0.7	ug/L
		Benzo(g,h,i)perylene	191-24-2	0.7	ug/L
		Benzo(k)fluoranthene	207-08-9	0.7	ug/L
		Biphenyl	92-52-4	0.6	ug/L
		Camphene	79-92-5	2	ug/L
		1-Chloronaphthalene	90-13-1	1	ug/L
		2-Chloronaphthalene	91-58-7	1	ug/L
		Chrysene	218-01-9	0.3	ug/L
		Dibenz(a,h)anthracene	53-70-3	1.3	ug/L
		Fluoranthene	206-44-0	0.4	ug/L
		Fluorene	86-73-7	1	ug/L
		Indeno(1,2,3-cd)pyrene	193-39-5	1.3	ug/L
		Indole	120-72-9	1.5	ug/L
		1-Methylnaphthalene	90-12-0	2.2	ug/L
		2-Methylnaphthalene	91-57-6	1.5	ug/L
		Naphthalene	91-20-3	1	ug/L
19	Extractables, Base Neutral (cont’d)	Perylene	198-55-0	1	ug/L
		Phenanthrene	1985/01/08	0.4	ug/L
		Pyrene	129-00-0	0.4	ug/L
		Benzylbutylphthalate	85-68-7	0.6	ug/L
		Bis(2-ethylhexyl)phthalate	117-81-7	2.2	ug/L
		Di-n-butylphthalate	84-74-2	1	ug/L
		Di-n-octylphthalate	117-84-0	1	ug/L
		4-Bromophenyl Phenyl Ether	101-55-3	0.3	ug/L
		4-Chlorophenyl Phenyl Ether	7005-72-3	0.9	ug/L
		Bis(2-chloroisopropyl)ether	108-60-1	1	ug/L
		Bis(2-chloroethyl)ether	111-44-4	2	ug/L
		Diphenylether	101-84-8	0.4	ug/L
		2,4-Dinitrotoluene	121-14-2	0.8	ug/L
		2,6-Dinitrotoluene	606-20-2	0.7	ug/L
		Bis(2-chloroethoxy)methane	111-91-1	1	ug/L
		Diphenylamine (NOTE 4)	122-39-4	10	ug/L
		N-Nitrosodiphenylamine (NOTE 4)	86-30-6	10	ug/L
		N-Nitrosodi-n-propylamine	621-64-7	1.5	ug/L
20	Extractables, Acid (Phenolics)	2,3,4,5-Tetrachlorophenol	4901-51-3	0.4	ug/L
		2,3,4,6-Tetrachlorophenol	58-90-2	1.5	ug/L
		2,3,5,6-Tetrachlorophenol	935-95-5	1	ug/L
20	Extractables, Acid (Phenolics) (cont’d)	2,3,4-Trichlorophenol	15950-66-0	0.6	ug/L
		2,3,5-Trichlorophenol	933-78-8	1	ug/L
		2,4,5-Trichlorophenol	95-95-4	1	ug/L
		2,4,6-Trichlorophenol	1988/06/02	1	ug/L
		2,4-Dimethylphenol	105-67-9	5	ug/L
		2,4-Dinitrophenol	51-28-5	42	ug/L
		2,4-Dichlorophenol	120-83-2	1	ug/L
		2,6-Dichlorophenol	87-65-0	1	ug/L
		4,6-Dinitro-o-cresol	534-52-1	24	ug/L
		2-Chlorophenol	95-57-8	2	ug/L
		4-Chloro-3-methylphenol	59-50-7	1	ug/L
		4-Nitrophenol	100-02-7	1.4	ug/L
		m-Cresol	108-39-4	2	ug/L
		o-Cresol	95-48-7	2	ug/L
		p-Cresol	106-44-5	2	ug/L
		Pentachlorophenol	87-86-5	1	ug/L
		Phenol	108-95-2	1.5	ug/L
23	Extractables, Neutral-Chlorinated	1,2,3,4-Tetrachlorobenzene	634-66-2	0.01	ug/L
		1,2,3,5–Tetrachlorobenzene	634-90-2	0.01	ug/L
		1,2,4,5-Tetrachlorobenzene	95-94-3	0.01	ug/L
		1,2,3-Trichlorobenzene	87-61-6	0.01	ug/L
23	Extractables, Neutral-Chlorinated (cont’d)	1,2,4-Trichlorobenzene	120-82-1	0.01	ug/L
		2,4,5-Trichlorotoluene	6639-30-1	0.01	ug/L
		Hexachlorobenzene	118-74-1	0.01	ug/L
		Hexachlorobutadiene	87-68-3	0.01	ug/L
		Hexachlorocyclopentadiene	77-47-4	0.01	ug/L
		Hexachloroethane	67-72-1	0.01	ug/L
		Octachlorostyrene	29082-74-4	0.01	ug/L
		Pentachlorobenzene	608-93-5	0.01	ug/L
24	Chlorinated Dibenzo-p-dioxins
and Dibenzofurans	2,3,7,8-Tetrachlorodibenzo-p-dioxin	1746-01-6	3.9	pg/L
		1,2,3,7,8-Pentachlorodibenzo-p-dioxin	40321-76-4	14	pg/L
		1,2,3,4,7,8-Hexachlorodibenzo-p-dioxin	39227-28-6	7	pg/L
		1,2,3,7,8,9-Hexachlorodibenzo-p-dioxin	19408-74-3	27	pg/L
		1,2,3,6,7,8-Hexachlorodibenzo-p-dioxin	57653-85-7	6	pg/L
		1,2,3,4,6,7,8-Heptachlorodibenzo-p-dioxin	35822-46-9	8	pg/L
		Octachlorodibenzo-p-dioxin	3268-87-9	70	pg/L
		2,3,7,8-Tetrachlorodibenzofuran	51207-31-9	6	pg/L
		2,3,4,7,8-Pentachlorodibenzofuran	57117-31-4	5	pg/L
		1,2,3,7,8-Pentachlorodibenzofuran	57117-41-6	10	pg/L
		1,2,3,4,7,8-Hexachlorodibenzofuran	70648-26-9	6	pg/L
24	Chlorinated Dibenzo-p-dioxins and Dibenzofurans (cont’d)	1,2,3,7,8,9-Hexachlorodibenzofuran	72918-21-9	12	pg/L
		1,2,3,6,7,8-Hexachlorodibenzofuran	57117-44-9	11	pg/L
		2,3,4,6,7,8-Hexachlorodibenzofuran	60851-34-5	9	pg/L
		1,2,3,4,6,7,8-Heptachlorodibenzofuran	67562-39-4	23	pg/L
		1,2,3,4,7,8,9-Heptachlorodibenzofuran	5567-89-7	10	pg/L
		Octachlorodibenzofuran	39001-02-0	30	pg/L
		Total Heptachlorinated Dibenzo-p-dioxins	37871-00-4	10	pg/L
		Total Heptachlorinated Dibenzofurans	38998-75-3	28	pg/L
		Total Hexachlorinated Dibenzo-p-dioxins	34465-46-8	28	pg/L
		Total Hexachlorinated Dibenzofurans	55684-94-1	17	pg/L
		Total Pentachlorinated Dibenzo-p-dioxins	36088-22-9	8	pg/L
		Total Pentachlorinated Dibenzofurans	30402-15-4	7	pg/L
		Total Tetrachlorinated Dibenzo-p-dioxins	41903-57-5	3.9	pg/L
		Total Tetrachlorinated Dibenzofurans	55722-27-5	6	pg/L
25	Solvent Extractables	Oil and Grease	N/A *	1	mg/L
26	Fatty and Resin Acids	Abietic Acid	514-10-3	5	ug/L
		Chlorodehydroabietic Acid	57055-38-6	5	ug/L
		Dehydroabietic Acid	1740-19-8	5	ug/L
		Dichlorodehydroabietic Acid	N/A *	5	ug/L
26	Fatty and Resin Acids (cont’d)	Isopimaric Acid	5835-26-7	5	ug/L
		Levopimaric Acid	79-54-9	5	ug/L
		Neoabietic Acid	471-77-2	5	ug/L
		Oleic Acid	112-80-1	5	ug/L
		Pimaric Acid	127-27-5	5	ug/L
27	Polychlorinated Biphenyls (PCBs)	PCBs (Total)	N/A *	0.05	ug/L
28a	Open Characterization - Volatiles		N/A *	101 against 1,3-Dichlorobutane	ug/L
28b	Open Characterization - Extractables		N/A *	101against D10 Phenanthrene	ug/L
29	Open Characterization - Elemental	Aluminum	7429-90-5	0.051	mg/L
		Antimony	7440-36-0	0.051	mg/L
		Arsenic	7440-38-2	0.051	mg/L
		Barium	7440-39-3	0.051	mg/L
		Beryllium	7440-41-7	0.051	mg/L
		Bismuth	7440-69-9	0.051	mg/L
		Boron	7440-42-8	0.051	mg/L
		Cadmium	7440-43-9	0.051	mg/L
		Calcium	7440-70-2	0.051	mg/L
29	Open Characterization - Elemental (cont’d)	Cerium	7440-45-1	0.051	mg/L
		Cesium	7440-46-2	0.051	mg/L
		Chromium	7440-47-3	0.051	mg/L
		Cobalt	7440-48-4	0.051	mg/L
		Copper	7440-50-8	0.051	mg/L
		Dysprosium	7429-91-6	0.051	mg/L
		Erbium	7440-52-0	0.051	mg/L
		Europium	7440-53-1	0.051	mg/L
		Gadolinium	7440-54-2	0.051	mg/L
		Gallium	7440-55-3	0.051	mg/L
		Germanium	7440-56-4	0.051	mg/L
		Gold	7440-57-5	0.051	mg/L
		Hafnium	7440-58-6	0.051	mg/L
		Holmium	7440-60-0	0.051	mg/L
		Indium	7440-74-6	0.051	mg/L
		Iridium	7439-88-5	0.051	mg/L
		Iron	7439-89-6	0.051	mg/L
		Lanthanum	7439-91-0	0.051	mg/L
		Lead	7439-92-1	0.051	mg/L
		Lithium	7439-93-2	0.051	mg/L
		Lutetium	7439-94-3	0.051	mg/L
29	Open Characterization - Elemental (cont’d)	Magnesium	7439-95-4	0.051	mg/L
		Manganese	7439-96-5	0.051	mg/L
		Mercury	7439-97-6	0.051	mg/L
		Molybdenum	7439-98-7	0.051	mg/L
		Neodymium	7440-00-8	0.051	mg/L
		Nickel	7440-02-0	0.051	mg/L
		Niobium	7440/03/01	0.051	mg/L
		Osmium	7440/04/02	0.101	mg/L
		Palladium	7440/05/03	0.051	mg/L
		Phosphorus	7723-14-0	0.051	mg/L
		Platinum	7440/06/04	0.051	mg/L
		Potassium	7440/09/07	0.051	mg/L
		Praseodymium	7440-10-0	0.051	mg/L
		Rhenium	7440-15-0	0.051	mg/L
		Rhodium	7440-16-6	0.051	mg/L
		Rubidium	7440-17-7	0.051	mg/L
		Ruthenium	7440-18-8	0.051	mg/L
		Samarium	7440-19-9	0.051	mg/L
		Scandium	7440-20-2	0.051	mg/L
		Selenium	7782-49-2	0.051	mg/L
		Silicon	7440-21-3	0.051	mg/L
29	Open Characterization - Elemental (cont’d)	Silver	7440-22-4	0.051	mg/L
		Sodium	N/A *	0.051	mg/L
		Strontium	7440-24-6	0.051	mg/L
		Sulphur	7704-34-9	0.051	mg/L
		Tantalum	7440-25-7	0.151	mg/L
		Tellurium	13494-80-9	0.051	mg/L
		Terbium	7440-27-9	0.051	mg/L
		Thallium	7440-28-0	0.051	mg/L
		Thorium	7440-29-1	0.051	mg/L
		Thulium	7440-30-4	0.051	mg/L
		Tin	7440-31-5	0.051	mg/L
		Titanium	7440-32-6	0.051	mg/L
		Tungsten	7440-33-7	0.051	mg/L
		Uranium	7440-61-1	0.051	mg/L
		Vanadium	7440-62-2	0.051	mg/L
		Ytterbium	7440-64-4	0.051	mg/L
		Yttrium	7440-65-5	0.051	mg/L
		Zinc	7440-66-6	0.051	mg/L
		Zirconium	7440-67-7	0.051	mg/L
30	Anions	Chloride	N/A *	2	mg/L
30	Anions (cont’d)	Fluoride	N/A *	0.1	mg/L
		Sulphate	N/A *	5.0 as Sulphate	mg/L
31	Total Residual Oxidants	Total Residual Oxidants	N/A *	0.01 as Chlorine	mg/L
32	Fibrous Chrysotile Asbestos	Fibrous Chrysotile Asbestos	N/A *	0.04	million
fibres per L
33	Adsorbable Organic Halide	Adsorbable Organic Halide	N/A *	0.05
based on 2,4,6-michlorophenol	mg/L
34	Diethanolamine	Diethanolamine	111-42-2	0.1	mg/L
35	Escherichia Coli	E.Coli	N/A	1	CFU/100ml
36	NDMA	n-Nitrosodimethylamine	62-75-9	1	ng/L

CAS # - Chemical Abstracts Service Number
* N/A - Not Applicable
1 - Semi-quantitative
NOTE 1 - Analyze for hexavalent chromium only if total chromium is greater than 1.0 milligram per litre.
NOTE 2 - Analyze for alkyl leads only if total lead is greater than 1.0 milligram per litre, unless required by the MOE.
NOTE 3 - m-Xylene and p-Xylene often co-elute in the analysis. A single combined result may be reported as m-Xylene.
NOTE 4 - Diphenylamine & N-Nitrosodiphenylamine often co-elute in the Gas Chromatography/Mass Spectrometry (GC/MS) analysis.
A single combined result may be reported as Diphenylamine.
RMDL: The MDL values listed are the maximum allowable values for a LMDLs under the Effluent Monitoring and Effluent Limits Regulations.

TABLE 2 - Checklist for Sampling, Preservation and Storage under Industrial Effluent Regulations

MISA ATG #	Sample Type			Preservation (Y/N)	Storage Time (Days)	On-line Analyzer
	AUTO 1 MANUAL 1	AUTO 2 MANUAL 2	MANUAL 3
1	R	A		N or Y*	4 or 30
1a	R	A		N	4 **
1b	R	A		N	4 **
2	R	A		Y precharge	7
2a	R	A		Y precharge	7
2b	R	A		Y	7
2c	R	A		N	7
3	R	A		N	4	R
4a	R	A		N or Y*	3 or10
4b	R	A		N	5
5a	R	A		N or Y*	3 or 10	R
5b	R	A		N or Y*	3 or 10
6	R	A		N or Y*	14 or 30
7	R	A		N	4	R
8	R	A		N	7
8a	R	A		N	7
9	R	A		Y	30
9a	R	A		Y	30
10 Y30	R	A		Y	30
11	R	A		N	5
12	R	A		Y	7
13	R	A		N	4
14	R	A		Y precharge	30
15			M	Y	7

** Analysis within 6 hours is recommended
R = Recommended; A = Alternate sampling procedure; M = Mandatory

Note: Where Preservation indicates N or Y* the unpreserved sample (N) always has the shorter storage time requirement. Refer to specific ATG’s, Section 10.0, for specific requirements.
Samples must be maintained at temperature above freezing point of the wastewater and under 10 o C, with minimal exposure to light. See Section 3.1.4, Temperature Stability.

CAUTION: Acid preservation of samples suspected of containing cyanide or sulphide MUST be carried out in a well ventilated area

Table 2 Cont:

MISA ATG #	Sample Type			Preservation (Y/N)	Storage Time (Days)	On-line Analyzer
	AUTO 1 MANUAL 1	AUTO 2 MANUAL 2	MANUAL 3
16			R	Y+	7	A
17			R	Y+	7	A
18			R	Y+	7	A
19	R	A		N	30
20	R	A		N	30
23	R	A		N	30
24	R	A		N	30
25	A	A	R	N or Y*	7 or 30
26	R	A		N	7
27	R	A		N	30
28a			R		7	A
28b	R	A		N	30
29	R	A		Y	30
30	R	A		N	30
31			A	N	<1 hour	R
32	R	A		N	2
33	R	A		N	14
34	R	A		N	30
36	R	A		N	14*

R = Recommended
A = Alternate sampling procedure
M = Mandatory

Note: Where Preservation indicates N or Y* the unpreserved sample
(N) always has the shorter storage time requirement.

† = Applicable in specific cases: when samples contain residual chlorine, preserve with 80 mg Na 2 S 2 O 3 per 1L and store in the dark. See specific ATG for additional information or alternatives, Section 10.0.
*: Analysis must be initiated within 2 days for “Reactive” samples which contain precursors to NDMA and, upon chlorination, form NDMA during storage.
Storage temperature: samples must be maintained at temperatures above the freezing point of the wastewater and under 10 0C, with minimal exposure to light.

CAUTION: Acid preservation of samples suspected of containing cyanide or sulphide MUST be carried out in a well ventilated area.

TABLE 2A Checklist for Sampling, Preservation and Storage under Sewage Treatment Plant Regulation

MISA ATG #	Sample Type				Preservation (Y/N)	Storage Time (Days)
	AUTO 2	MANUAL 2	MANUAL 4	GRAB 2
1b	R	A	S	G	N	4 **
3	R	A	S	G	N	4
4a	R	A	S	G	N or Y*	3 or 10
4b	R	A	S	G	N	5
6	R	A	S	G	N or Y*	14 or 30
35				R	N or Y*	2 or 36 hours

** = Analysis within 6 hours is recommended
R = Recommended
A = Alternate Sampling Procedure
S = Alternate sampling procedure for plants with design capacity less than 4,600 cubic metres per day
G = Single grab per day of bypass discharge (GRAB1 or 3 techniques are alternates)

NOTE: Where Preservation indicates N or Y* the unpreserved sample (N) always has the shorter storage time requirement.

Refer to specific ATG’s in Section 10.0 for specific requirements.

Storage temperature: samples must be maintained at temperatures above the freezing point of the wastewater and under 10 o C, with minimal exposure to light.

CAUTION: Acid preservation of samples suspected of containing cyanide or sulphide MUST be carried out in a well ventilated area.

TABLE 3 - Checklist for QC Samples

MISA ATG #	Laboratory QC Required (*)				Recommended Field QC (+)
	Blank	Spiked Blank	Spiked Sample	Replicate	Travel. Blank	Travel. Spiked Blank	Duplicate
1	*	*	*	*	+		+
1a	*	*	*	*	+		+
1b	*	*	*	*	+		+
2	*	*	*	*	+		+
2a	*	*	*	*	+		+
2b	*	*	*	*	+		+
2c	*	*	*	*	+		+
3				*			+
4a	*	*	*	*	+		+
4b	*	*	*	*	+		+
5a	*	*	*	*	+		+
5b	*	*	*	*	+		+
6	*	*	*	*	+		+
7	*			*	+		+
8	*			*			+
8a	*			*			+
9	*	*	*	*	+		+
9a	*	*	*	*	+		+
10	*	*	*	*	+		+
11	*	*	*	*	+		+
12	*	*	*	*	+		+
13	*	*	*	*	+		+
14	*	*	*	*	+		+
15	*	*	*	*	+		+
16	*	*	*	**	+	+	R
17	*	*	*	**	+	+	R
18	*	*	*	**	+	+	R
19	*	*	*	**	+	+	R
20	*	*	*	**	+	+	R
23	*	*	*	**	+	+	R
24	*						R
25	*			**			R
26	*	*	*	**	+	+	R
27	*	*	*	**	+	+	R
28a	*				+		R
28b	*				+		R
29	*				+
30	*	*	*	*	+		+
31	*	*	*	*	+		+
32				*	+		+
33	*	*	*	*	+	+	+
34	*	*	*	*	+		+
35	See ATG35 for specific requirements
36	*	*		*	+		R

R = Recommended in case re-analysis needed
Refer to Section 5.0 for QA/QC requirements.
** : duplicates may be used as alternative.

TABLE 4 - Suggested Spiking Materials

View Table 4 in PDF Format

TABLE 5 - International Toxicity Equivalent (ITEF) Factors for PCDDs and PCDFs

PCDD/DF Congener	International Toxicity Equivalent Factors (ITEF)
2,3,7,8-tetrachlorodibenzo-p-dioxin	1
1,2,3,7,8-pentachlorodibenzo-p-dioxin	0.5
1,2,3,4,7,8-hexachlorodibenzo-p-dioxin	0.1
1,2,3,7,8,9-hexachlorodibenzo-p-dioxin	0.1
1,2,3,6,7,8-hexachlorodibenzo-p-dioxin	0.1
1,2,3,4,6,7,8-heptachlorodibenzo-p-dioxin	0.01
octachlorodibenzo-p-dioxin	0.001
2,3,7,8-tetrachlorodibenzofuran	0.1
2,3,4,7,8-pentachlorodibenzofuran	0.5
1,2,3,7,8-pentachlorodibenzofuran	0.05
1,2,3,4,7,8-hexachlorodibenzofuran	0.1
1,2,3,7,8,9-hexachlorodibenzofuran	0.1
1,2,3,6,7,8-hexachlorodibenzofuran	0.1
2,3,4,6,7,8-hexachlorodibenzofuran	0.1
1,2,3,4,6,7,8-heptachlorodibenzofuran	0.01
1,2,3,4,7,8,9-heptachlorodibenzofuran	0.01
octachlorodibenzofuran	0.001

10.0 GUIDELINES FOR INDIVIDUAL ANALYTICAL TEST GROUPS (ATG)

This section is presented as a series of tables which contain all the information related to sampling, analysis and QC for each ATG.

In all cases Sector Specific Regulatory requirements take precedence over this Protocol. Reference must be made to these for specific requirements.

The information is presented in the form of guiding principles and protocols related to each component of sampling, analysis and quality control. While there are no specific methods identified, there are recommended and alternate techniques clearly listed. Every effort should be made to apply the recommended techniques with adherence to good laboratory and sound quality control practices. There is sufficient latitude in the principles and protocols provided to allow for the customization of any specific sampling and analysis method to best suit the wastewater being assessed. All applied methods of sampling and analysis must however embody the principles and protocols listed.

In some rare cases, there may be an entry indicating that a sampling or analysis approach is not recommended. This is based on best available information on sampling and analysis techniques that suggest the sampling and analysis techniques are either not cost effective or not sufficiently sensitive or rugged enough to provide useful samples or analytical data. This does not absolutely exclude the use of the identified technique but serves more as a precaution or warning that these procedures ought to be reserved for "special cases" since they are not necessarily applicable to all types of wastewaters.

These tables provide all the information on a given ATG in an easy to read, comprehensive fashion. The reader should also be familiar with Sections 3.0 to 5.0 which present detailed information on the sampling and analytical principles to be followed.

The following types of composite samples are defined (see Section 3.1):

AUTO 1: Automatic equipment collecting samples proportional to wastewater stream flow at time intervals of 30 minutes or less over a 24 hour period.

MANUAL 1: A minimum of 8 grab samples taken at equally spaced time intervals over a 24 hour period (i.e. every 3 hours) combined in proportion to wastewater stream flow.

AUTO 2: Automatic equipment collecting samples of equal volume at equally spaced time intervals of 15 minutes or less over a 24 hour period.

MANUAL 2: A minimum of 8 grab samples taken at equally spaced time intervals over a 24 hour period (i.e. every 3 hours) combined in equal volumes.

MANUAL 3: A minimum of 3 grab samples taken at time intervals of at least 6 hours over the sampling period.

MANUAL 4: Three grab samples taken at time intervals of at least 2 hours over an 8 hour sampling period.The following types of grab samples are defined (see Section 3.1):

GRAB 1: Wastewater is collected in a bucket or other container and immediately transferred to the appropriate laboratory container(s), preserved as necessary and capped.

GRAB 2: The appropriate laboratory sample container is submerged in the wastewater stream on a chain or pole until it is full; retrieved, preserved as necessary and capped.

GRAB 3: Wastewater is collected in a bucket as for GRAB 1 and the appropriate clean (outside as well) laboratory container (e.g. vocatives vial) is held at an angle and submerged into the liquid until it is full and air bubbles have been expelled at which time it is carefully retrieved, preserved as necessary and capped. Care must be taken to avoid sample contamination from the outside of the laboratory container, label adhesives or the retrieval device.

NOTE: Samples must be maintained at temperature above the freezing point of the wastewater and under 10 0 C, with minimal exposure to light. See Section 3.1.4, Temperature Stability.

Please see Table 2 for additional details for each ATG.

 

ATG #1- CHEMICAL OXYGEN DEMAND (COD)

SAMPLING

Type Recommended: AUTO 1 or 2

Alternate: MANUAL 1 or 2

Container Recommended: Glass or polyethylene terephthalate

Alternate: Teflon®, polypropylene, high or low density polyethylene, polystyrene

Not Recommended: contact with metallic foil

Container Pretreatment Recommended: generally none for new containers

Alternate: wash with detergent if necessary, distilled water rinses

Sample Volume Recommended: 25 mL

Alternate: volume required to meet MDLs and analyze all applicable QC samples

Preservation Recommended: none; protect from light

Alternate: H2SO4 to pH between 1.5 and 2 after samplingMaximum Sample Storage Time

Unpreserved: 4 days

Preserved: 30 days

Precautions/Notes: If sample is expected to have high (>5%) hydrocarbon or organic solvent content, use glass or Teflon® container only and Teflon® lined caps.

ANALYSIS

Sample Preparation

Recommended: Preparation for measurement system as appropriate followed by reflux

Alternate: Oven digestion at 150°C in presence of oxidizing reagents

Not Recommended: N/A

Instrumental Measurement Recommended: Colourimetric measurement of trivalent chromium or back titration

Alternate: N/A

Method Detection Limit

Required: 10 mg/L

Precautions/Notes: High chloride content in samples may cause severe interference problems in the analysis of COD.

QUALITY CONTROL SAMPLES

Laboratory QC Samples

Blank: APPLICABLE

Spiked Blank: APPLICABLE

Spiked Sample: APPLICABLE

Replicate: APPLICABLE

Field QC Samples

Travelling Blank: APPLICABLE

Travelling Spiked Blank: N/A

Duplicate: APPLICABLE

ATG # 1a- BIOCHEMICAL OXYGEN DEMAND(5 DAY)

SAMPLING

Type

Recommended: AUTO 1 or 2

Alternate: MANUAL 1 or 2

Container

Recommended: Glass or polyethylene terephthalate

Alternate: Teflon®, polypropylene, high or low density polyethylene, polystyrene

Not Recommended: contact with metallic foil

Container Pretreatment

Recommended: generally none for new containers

Alternate: wash with detergent if necessary, distilled water rinses

Sample Volume

Recommended: 500 mL

Alternate: volume required to meet MDLs and analyze all applicable QC samples

Preservation

Recommended: none; protect from light

Alternate: N/A

Maximum Sample Storage Time

4 days *

Precautions/Notes: If sample is expected to have high (>5%) hydrocarbon or organic solvent content, use glass or Teflon® container only and Teflon® lined caps.

* Analysis should be initiated as soon as possible after sample collection: preferably within six hours.

ANALYSIS

Sample Preparation

Recommended: Preparation for measurement system as appropriate; i.e. destruction of chlorine, neutralization of pH, stabilization of sample to 20o C. Preparation of seed and dilution water as appropriate. Dilution of sample to provide adequate oxygen depletion during 5 day period

Alternate: N/A

Not Recommended: N/A

Instrumental Measurement

Recommended: Dissolved oxygen determination by Winkler method or by oxygen electrode verified by Winkler method for one sample or standard per analytical run on days of analysis

Alternate: N/A

Method Detection Limit

Required: 2 mg/L

Precautions/Notes: If carbonaceous BOD5 is required, a nitrification inhibitor is necessary and the test is called BODC. (See ATG 1b)

QUALITY CONTROL SAMPLES

Laboratory QC Samples

Blank: APPLICABLE

Spiked Blank: APPLICABLE, see note below

Spiked Sample: APPLICABLE, see note below

Replicate: APPLICABLE

Field QC Samples

Travelling Blank: APPLICABLE

Travelling Spiked Blank: N/A

Duplicate: APPLICABLE

NOTES/REMARKS/TIPS: For each analytical run perform a BOD5 test on seeded dilution water, and a BOD5 test on the seeded dilution water spiked with one or more organic compounds; i.e. glucose and glutamic acid. It is recommended that the results of the seeded dilution water be used to correct seeded sample results and that the spiked seeded dilution water be used as a recovery check against established control limits.

ATG # 1b- CARBONACEOUS BIOCHEMICAL OXYGEN DEMAND (5 DAY)

SAMPLING

Type

Recommended: AUTO 1 or 2

Alternate: MANUAL 1 or 2

Container

Recommended: Glass or polyethylene terephthalate

Alternate: Teflon®, polypropylene, high or low density polyethylene, polystyrene

Not Recommended: contact with metallic foil

Container Pretreatment

Recommended: generally none for new containers

Alternate: wash with detergent if necessary, distilled water rinses

Sample Volume

Recommended: 500 mL

Alternate: volume required to meet MDLs and analyze all applicable QC samples

Preservation

Recommended: none; protect from light

Alternate: N/A

Maximum Sample Storage Time

4 days *

Precautions/Notes: If sample is expected to have high (>5%) hydrocarbon or organic solvent content, use glass or Teflon® container only and Teflon® lined caps.

* Analysis should be initiated as soon as possible after sample collection.

ANALYSIS

Sample Preparation

Recommended: Preparation for measurement system as appropriate; i.e. destruction of chlorine, neutralization of pH, stabilization of sample to 20 o C. Preparation of seed and dilution water as appropriate. Dilution of sample to provide adequate oxygen depletion during 5 day period. Addition of an appropriate amount of nitrification inhibitor to the BOD bottle prior to taking dissolved oxygen (DO) reading on day one.

Alternate: N/A

Not Recommended: N/A

Instrumental Measurement

Recommended: Dissolved oxygen determination by Winkler method or by oxygen electrode verified by Winkler method for one sample or standard per analytical run on days of analysis

Alternate: N/A

Method Detection Limit

Required: 2 mg/L

QUALITY CONTROL SAMPLES

Laboratory QC Samples

Blank: APPLICABLE

Spiked Blank: APPLICABLE, see note below

Spiked Sample: APPLICABLE, see note below

Replicate: APPLICABLE

Field QC Samples

Travelling Blank: APPLICABLE

Travelling Spiked Blank: N/A

Duplicate: APPLICABLE

NOTES/REMARKS/TIPS: For each analytical run perform a BOD5C test on seeded dilution water, and a BOD5C test on the seeded dilution water spiked with one or more organic compounds; e.g. glucose and glutamic acid. It is recommended that the results of the seeded dilution water be used to correct seeded sample results and that the spiked seeded dilution water be used as a recovery check against established control limits.

ATG #2- TOTAL CYANIDE

SAMPLING

Type
Recommended: AUTO 1 or 2

Alternate: MANUAL 1 or 2 or 3, ( see sec. 3.4, Pg. 12 )

Container
Recommended: Glass or polyethylene terephthalate

Alternate: Teflon®, polypropylene, high or low density polyethylene, polystyrene

Not Recommended: Contact with metallic foil

Container Pretreatment
Recommended: generally none for new containers

Alternate: wash with detergent if necessary, distilled water rinses

Sample Volume
Recommended: 500 mL

Alternate: volume required to meet MDLs and analyze all applicable QC samples

Preservation
Recommended: NaOH (cyanide free) to raise pH to 12. For AUTO 1 or 2, sampler bottles must be pre-charged with preservative

Alternate: N/A

Maximum Sample Storage Time

7 days

Precautions/Notes: If sample is expected to have high (>5%) hydrocarbons or organic solvent content, use glass or Teflon® container only and Teflon® lined caps.For AUTO 1 or 2, sampler bottles must be pre-charged with preservative. The volume of preservative may be estimated based on the expected cyanide concentration.

If high cyanide is suspected, sample containers must be labelled "HAZARDOUS".

Samples containing strong oxidizing agents (e.g. chlorine) should be neutralized with sodium arsenite, as soon as possible after sample collection to prevent oxidation/degradation.

ANALYSIS

Sample Preparation
Recommended: Acid Distillation/Ultraviolet digestion.

Alternate: N/A

Not Recommended: N/A

Instrumental Measurement
Recommended: Colourimetry

Alternate: Specific ion electrode; or polarography via the method of standard addition in the presence of suitable electrolyte

Method Detection Limit
Required: 0.005 mg/L as HCN

Precautions/Notes: Manual distillation must be used where the sample contains significant thiocyanate levels unless the lab can demonstrate that the method used effectively removes thiocyanate. The presence of strong oxidizing agents (e.g. chloride) may affect the result.

QUALITY CONTROL SAMPLES

Laboratory QC Samples
Blank: APPLICABLE

Spiked Blank: APPLICABLE

Spiked Sample: APPLICABLE

Replicate: APPLICABLE

Field QC Samples
Travelling Blank: APPLICABLE

Travelling Spiked Blank: N/A

Duplicate: APPLICABLE

ATG # 2a- WEAK ACID DISSOCIABLE CYANIDES

SAMPLING

Type
Recommended: AUTO 1 or 2

Alternate: MANUAL 1 or 2 or 3, ( see sec. 3.4, Pg. 12 )

Container
Recommended: Glass or polyethylene terephthalate

Alternate: Teflon®, polypropylene, high or low density polyethylene, polystyrene

Not Recommended: contact with metallic foil

Container Pretreatment
Recommended: generally none for new containers

Alternate: wash with detergent if necessary, distilled water rinses

Sample Volume
Recommended: 500 mL

Alternate: volume required to meet MDLs and analyze all applicable QC samples
Preservation
Recommended: NaOH (cyanide free) to raise pH to 12. For AUTO 1 or 2, sampler bottles must be pre-charged with preservative

Alternate: N/A

Maximum Sample Storage Time
7 days

Precautions/Notes: If sample is expected to have high (>5%) hydrocarbon or organic solvent content, use glass or Teflon® container only and Teflon® lined caps.

If high cyanide is suspected, sample containers must be labelled "HAZARDOUS". ANALYSIS

Sample Preparation
Recommended: Preparation for measurement system as appropriate

Alternate: N/A

Not Recommended: N/A

Instrumental Measurement
Recommended: Colourimetry

Alternate: Ion chromatography with electro-chemical detection

Method Detection Limit
Required: 0.005 mg/L

Precautions/Notes: Presence of strong oxidizing agents (e.g. chloride) may affect the result.

QUALITY CONTROL SAMPLES:

Laboratory QC Samples
Blank: APPLICABLE

Spiked Blank: APPLICABLE

Spiked Sample: APPLICABLE

Replicate: APPLICABLE

Field QC Samples
Travelling Blank: APPLICABLE

Travelling Spiked Blank: N/A

Duplicate: APPLICABLEATG #2b- CYANATES

SAMPLING

Type
Recommended: AUTO 1 or 2

Alternate: MANUAL 1 or 2, or 3, ( see sec. 3.4 Pg. 12 )

Container
Recommended: Glass or polyethylene terephthalate

Alternate: Teflon®, polypropylene, high or low density polyethylene, polystyrene

Not Recommended: contact with metallic foil

Container Pretreatment
Recommended: generally none for new containers

Alternate: wash with detergent if necessary, distilled water rinses

Sample Volume
Recommended: 100 mL

Alternate: volume required to meet MDLs and analyze all applicable QC samples

Preservation
Recommended: add 2 drops of 10 N NaOH (cyanide free) per litre of sample for IC analysis. Add NaOH (cyanide free) to pH 12 for colourimetric analysis.

Alternate: N/A

Maximum Sample Storage Time
7 days

Precautions/Notes: If sample is expected to have high (>5%) hydrocarbon or organic solvent content, use glass or Teflon® container only and Teflon® lined caps.

ANALYSIS

Sample Preparation
Recommended: Preparation for measurement system as appropriate

Alternate: N/A

Not Recommended: N/A

Instrumental Measurement
Recommended: Ion chromatography

Alternate: Colourimetry

Method Detection Limit
Required: 5 mg/L

Precautions/Notes: Special care must be taken to minimize chloride interferences during IC analysis.

QUALITY CONTROL SAMPLES

Laboratory QC Samples
Blank: APPLICABLE

Spiked Blank: APPLICABLE

Spiked Sample: APPLICABLE

Replicate: APPLICABLE
Field QC Samples
Travelling Blank: APPLICABLE

Travelling Spiked Blank: N/A

Duplicate: APPLICABLE

ATG #2c- THIOCYANATES

SAMPLING

Type
Recommended: AUTO 1 or 2

Alternate: MANUAL 1 or 2 or 3, ( see sec. 3.4, Pg. 12 )

Container
Recommended: Glass or polyethylene terephthalate

Alternate: Teflon®, polypropylene, high or low density polyethylene, polystyrene

Not Recommended: contact with metallic foil

Container Pretreatment
Recommended: generally none for new containers

Alternate: wash with detergent, if necessary, distilled water rinses

Sample Volume
Recommended: 100 mL

Alternate: volume required to meet MDLs and analyze all applicable QC samples

Preservation
Recommended: none, when both cyanates and thiocyanates are being analyzed, then preserve as for cyanates (ATG 2b).

Alternate: N/A

Maximum Sample Storage Time
7 days

Precautions/Notes: If sample is expected to have high (>5%) hydrocarbon or organic solvent content, use glass or Teflon® container only and Teflon® lined caps.ANALYSIS

Sample Preparation
Recommended: Preparation for measurement system as appropriate

Alternate: N/A

Not Recommended: N/A

Instrumental Measurement
Recommended: Ion chromatography

Alternate: Colourimetry

Method Detection Limit
Required: 5 mg/L

Precautions/Notes:

QUALITY CONTROL SAMPLES

Laboratory QC Samples
Blank: APPLICABLE

Spiked Blank: APPLICABLE

Spiked Sample: APPLICABLE

Replicate: APPLICABLE

Field QC Samples
Travelling Blank: APPLICABLE

Travelling Spiked Blank: N/A

Duplicate: APPLICABLE

ATG #3- HYDROGEN ION (pH)

SAMPLING

Type
Recommended: On-line analyser, AUTO 1 or 2

Alternate: MANUAL 1 or 2
See sec. 3.5 for Sampling Under Industrial
Effluent Monitoring and Effluent Limits Regulations

Container
Recommended: Glass or polyethylene terephthalate

Alternate: Teflon®, polypropylene, high or low density polyethylene, polystyrene

Not Recommended: contact with metallic foil

Container Pretreatment
Recommended: generally none for new containers

Alternate: wash with detergent if necessary, distilled water rinses

Sample Volume
Recommended: 50 mL

Alternate: volume required to analyze all applicable QC samples

Preservation
Recommended: none

Alternate: N/A

Maximum Sample Storage Time
4 days*

Precautions/Notes: If sample is expected to have high (>5%) hydrocarbon or organic solvent content, use glass or Teflon® container only and Teflon® lined caps.

When the characteristics of the wastewater may lead to rapid changes in pH, an on-line analyser must be used or grab samples must be collected and analyzed as soon as reasonably possible.

* Analysis should be initiated as soon as possible after sample collection.

ANALYSIS

Sample Preparation
Recommended: Preparation for measurement system as appropriate

Alternate: N/A

Not Recommended: N/A

Instrumental Measurement
Recommended: On-line analyser, pH electrode and pH meter

Alternate: N/A

Method Detection Limit
Required: N/A

QUALITY CONTROL SAMPLES

Laboratory QC Samples
Blank: N/A

Spiked Blank: N/A

Spiked Sample: N/A

Replicate: APPLICABLE *

Field QC Samples
Travelling Blank: N/A

Travelling Spiked Blank: N/A

Duplicate: APPLICABLE *

NOTES/REMARKS/TIPS: pH may be analyzed from the same sample bottle as ATG 7 (specific conductance) and ATG 8 (TSS or VSS).

When an on-line analyser malfunctions, samples may be collected by AUTO 1 or 2 or MANUAL 1 or 2 techniques.

* When on-line analysers are used, duplicate and replicate samples need not be analyzed.

ATG #4a- AMMONIA PLUS AMMONIUM - TOTAL KJELDAHL NITROGEN (TKN)

SAMPLING

Type
Recommended: AUTO 1 or 2

Alternate: MANUAL 1 or 2

Container
Recommended: Glass or polyethylene terephthalate

Alternate: Teflon®, polypropylene, high or low density polyethylene, polystyrene

Not Recommended: contact with metallic foil

Container Pretreatment
Recommended: generally none for new containers

Alternate: wash with detergent if necessary, distilled water rinses

Sample Volume
Recommended: 100 mL

Alternate: volume required to meet MDLs and analyze all applicable QC samples

Preservation
Recommended: none

Alternate: H2SO4 to pH between 1.5 and 2

Maximum Sample Storage Time
Unpreserved: 3 days*

Preserved: 10 days

Precautions/Notes: If sample is expected to have high (>5%) hydrocarbon or organic solvent content, use glass or Teflon® container only and Teflon® lined caps.

Samples containing strong oxidizing agents (e.g. chlorine) should be neutralized as soon as possible after sample collection to prevent oxidation/degradation.

Chlorinated STP samples must be neutralized prior to analysis, by use of an appropriate chlorine buffer.

* Analysis should be initiated as soon as possible after sample collection.

ANALYSIS

Sample Preparation
Recommended: Preparation for measurement system as appropriate e.g. distillation (Ammonia plus Ammonium), Kjeldahl Type digestion (TKN)

Alternate: N/A

Not Recommended: N/A

Instrumental Measurement
Recommended: Colourimetry or ion selective electrode or titration or ion chromatography

Alternate: N/A

Method Detection Limit
Required: 0.25 mg/L as Nitrogen (Ammonia plus Ammonium)
0.25 mg/L as Nitrogen (TKN)

Precautions/Notes: High chloride content in samples may cause severe interference problems in the analysis of Ammonia plus Ammonium.QUALITY CONTROL SAMPLES

Laboratory QC Samples
Blank: APPLICABLE

Spiked Blank: APPLICABLE

Spiked Sample: APPLICABLE

Replicate: APPLICABLE

Field QC Samples
Travelling Blank: APPLICABLE

Travelling Spiked Blank: N/A

Duplicate: APPLICABLE
ATG #4b- NITRATE PLUS NITRITE

SAMPLING

Type
Recommended: AUTO 1 or 2

Alternate: MANUAL 1 or 2

Container
Recommended: Glass or polyethylene terephthalate

Alternate: Teflon®, polypropylene, high or low density polyethylene, polystyrene

Not Recommended: contact with metallic foil

Container Pretreatment
Recommended: generally none for new containers

Alternate: wash with detergent if necessary, distilled water rinses

Sample Volume
Recommended: 50 mL

Alternate: volume required to meet MDLs and analyze all applicable QC samples

Preservation
Recommended: none

Alternate: N/A

Maximum Sample Storage Time
5 days

Precautions/Notes: If sample is expected to have high (>5%) hydrocarbon or organic solvent content, use glass or Teflon® container only and Teflon® lined caps.ANALYSIS

Sample Preparation
Recommended: Preparation for measurement system as appropriate

Alternate: N/A

Not Recommended: N/A

Instrumental Measurement
Recommended: Colourimetry, Ion Chromatography or Ion Selective Electrode

Alternate: N/A

Method Detection Limit
Required: 0.25 mg/L as Nitrogen

Precautions/Notes: Results and MDLs to be reported as the sum of Nitrate plus Nitrite.

QUALITY CONTROL SAMPLES

Laboratory QC Samples
Blank: APPLICABLE

Spiked Blank: APPLICABLE

Spiked Sample: APPLICABLE

Replicate: APPLICABLE

Field QC Samples
Travelling Blank: APPLICABLE

Travelling Spiked Blank: N/A

Duplicate: APPLICABLE

ATG #5a- DISSOLVED ORGANIC CARBON (DOC)

SAMPLING

Type
Recommended: AUTO 1 or 2; on-line analyser

Alternate: MANUAL 1 or 2

Container
Recommended: Glass or polyethylene terephthalate

Alternate: Teflon®, polypropylene, high or low density polyethylene, polystyrene

Not Recommended: contact with metallic foil

Container Pretreatment
Recommended: generally none for new containers

Alternate: wash with detergent if necessary, distilled water rinses

Sample Volume
Recommended: 100 mL

Alternate: volume required to meet MDLs and analyze all applicable QC samples

Preservation
Recommended: none; protect from light

Alternate: filter then add H2SO4 to pH between 1.5 and 2

Maximum Sample Storage Time

Unpreserved: 3 days

Preserved: 10 days

Precautions/Notes: If sample is expected to have high (>5%) hydrocarbon or organic solvent content, use glass or Teflon® container only and Teflon® lined caps.

ANALYSIS

Sample Preparation
Recommended: Preparation for measurement system as appropriate, followed by filtration through glass fibre filter or analysis of the supernatant of a settled sample. Where volatile/purgeable organic carbon may represent a major portion of the DOC (i.e. more than 25%) use preparation and measurement techniques which favour inclusion of this portion in DOC results.

Alternate: N/A

Not Recommended: N/A

Instrumental Measurement
Recommended: Quantitative conversion of carbon to CO2 by one of:

i) ultraviolet/persulfate digestion
ii) combustion at >800 o C with a catalyst
iii) combustion at >1100 o C, catalyst optional, followed by infrared or colourimetric detection

Alternate: N/A

Method Detection Limit
Required: 0.5 mg/L as carbon

Precautions/Notes: DOC may be determined directly following filtration by using a sample free of inorganic carbon or as the difference between total carbon and inorganic carbon following filtration. If a filter is used for dissolved organic carbon, use a 0.45 micron size filter as per Standard Methods. High chloride content in samples may cause severe interference problems in the analysis of DOC/TOC.

QUALITY CONTROL SAMPLES

Laboratory QC Samples
Blank: APPLICABLE *

Spiked Blank: APPLICABLE *

Spiked Sample: APPLICABLE *

Replicate: APPLICABLE *

Field QC Samples
Travelling Blank: APPLICABLE *

Travelling Spiked Blank: N/A

Duplicate: APPLICABLE *

NOTES/REMARKS/TIPS: When an on-line analyser malfunctions, samples may be collected by AUTO 1 or 2 or MANUAL 1 or 2 techniques.

* When on-line analysers are used QC samples need not be analyzed. ATG #5b- TOTAL ORGANIC CARBON (TOC)

SAMPLING

Type
Recommended: AUTO 1 or 2

Alternate: MANUAL 1 or 2

Container
Recommended: Glass or polyethylene terephthalate

Alternate: Polypropylene, high or low density polyethylene, polystyrene

Not Recommended: contact with metallic foil

Container Pretreatment
Recommended: generally none for new containers

Alternate: wash with detergent if necessary, distilled water rinses

Sample Volume
Recommended: 100 mL

Alternate: volume required to meet MDLs and analyze all applicable QC samples

Preservation
Recommended: none; protect from light

Alternate: H2SO4 to pH between 1.5 and 2

Maximum Sample Storage Time
Unpreserved: 3 days

Preserved: 10 days

Precautions/Notes: If sample is expected to have high (>5%) hydrocarbon or organic solvent content, use glass or Teflon® container only and Teflon® lined caps.

ANALYSIS

Sample Preparation
Recommended: Preparation for measurement system as appropriate. A representative sample including particles must be introduced into the measurement system in a form (i.e. homogenized) which ensures effective processing by the measurement system. Particles may be separated from the liquid with subsequent exclusive analysis of both phases. Where volatile/purgeable organic carbon may represent a major portion of the TOC (i.e. more than 25%), use preparation and measurement techniques which favour inclusion of this portion in TOC results.

Alternate: N/A

Not Recommended: N/A

Instrumental Measurement
Recommended: Quantitative conversion of carbon to carbon dioxide (CO2) by one of:

i) ultra violet/persulfate digestion
ii) combustion at =800°C with a catalyst
iii) combustion at =1100°C, catalyst optional followed by infrared or colourimetric detection

Alternate: N/A

Method Detection Limit
Required: 2 mg/L as Carbon

Precautions/Notes: TOC may be determined directly using a sample free of inorganic carbon or as the difference between total carbon and inorganic carbon. Confirm effective processing of samples using option i) UV/persulfate digestion, by comparing results from the analyses of samples with TOC levels and concentrations of particles close to the maximum expected for the effluent/matrix, to results from the analysis of the same samples using an appropriate combustion technique. Repeat comparison whenever higher TOC levels or particle concentrations are expected.

High chloride content in samples may cause severe interference problems in the analysis of DOC/TOC.

QUALITY CONTROL SAMPLES

Laboratory QC Samples
Blank: APPLICABLE

Spiked Blank: APPLICABLE

Spiked Sample: APPLICABLE

Replicate: APPLICABLE

Field QC Samples
Travelling Blank: APPLICABLE

Travelling Spiked Blank: N/A

Duplicate: APPLICABLE

NOTES/REMARKS/TIPS: When on-line analysers are used, the monthly performance check sample should be taken as a single grab and the result compared to the on-linereading at the time of sampling (see Section 4.2.3). When such an on-line analyser malfunctions, samples may be collected by AUTO 1 or 2 or MANUAL 1 or 2 techniques.

ATG #6- TOTAL PHOSPHORUS

SAMPLING

Type
Recommended: AUTO 1 or 2

Alternate: MANUAL 1 or 2

Container
Recommended: Glass or polyethylene terephthalate Glass or Teflon, with Teflon lined cap

Alternate: Teflon®, polypropylene, high or low density polyethylene, polystyrene

Not Recommended: contact with metallic foil

Container Pretreatment
Recommended: generally none for new containers

Alternate: wash with phosphate free detergent if necessary, distilled water rinses

Sample Volume
Recommended: 75 mL

Alternate: volume required to meet MDLs and analyze all applicable QC samples

Preservation
Recommended: none

Alternate: H2SO4 to pH between 1.5 and 2

Maximum Sample Storage Time

Unpreserved: 14 days

Preserved: 30 days

Precautions/Notes: If sample is expected to have high (>5%) hydrocarbon or organic solvent content, use glass or Teflon® container only and Teflon® lined caps.

ANALYSIS

Sample Preparation
Recommended: Preparation for measurement system as appropriate followed by digestion with 5:1 ratio of nitric acid to sulphuric acid or Kjeldahl equivalent mixture

Alternate: perchloric acid digestion, persulphate digestion
or aqua regia digestion;

Instrumental Measurement
Recommended: Colourimetry or ICP

Alternate: N/A

Not Recommended: Stannous Chloride procedure not recommended.
( see sec. 4.6, Pg. 23 )

Method Detection Limit
Required: 0.1 mg/L as phosphorus

QUALITY CONTROL SAMPLES

Laboratory QC Samples
Blank: APPLICABLE

Spiked Blank: APPLICABLE

Spiked Sample: APPLICABLE

Replicate: APPLICABLE

Field QC Samples
Travelling Blank: APPLICABLE

Travelling Spiked Blank: N/A

Duplicate: APPLICABLE

ATG #7- SPECIFIC CONDUCTANCE

SAMPLING

Type
Recommended: on-line analyser; AUTO 1 or 2

Alternate: MANUAL 1 or 2
Refer to Effluent Monitoring and Effluent Limits Regulations for specific sampling requirements.

Container
Recommended: Glass or polyethylene terephthalate

Alternate: polypropylene, high or low density polyethylene, polystyrene

Not Recommended: contact with metallic foil

Container Pretreatment
Recommended: generally none for new containers

Alternate: wash with detergent if necessary, distilled water rinses

Sample Volume
Recommended: 75 mL

Alternate: volume required to meet MDLs and analyze all applicable QC samples

Preservation
Recommended: none

Alternate: N/A

Maximum Sample Storage Time
4 days

Precautions/Notes: If sample is expected to have high (>5%) hydrocarbtent, use glass or Teflon® container only and Teflon® lined caps.

ANALYSIS

Sample Preparation
Recommended: Preparation for measurement system as appropriate

Alternate: N/A

Not Recommended: N/A

Instrumental Measurement
Recommended: On-line analyser; conductivity meter and cell measured at 25°C or conductivity meter with temperature compensation

Alternate: N/A

Method Detection Limit

Required: 5 µS/cm

Precautions/Notes: Measurement at 25°C may be achieved by use of a jacketed cell, a water bath for samples, or the preparation of a curve comparing measured conductivity with temperature (to establish a correction factor if required) for each sample matrix.

QUALITY CONTROL SAMPLES

Laboratory QC Samples
Blank: APPLICABLE

Spiked Blank: N/A

Spiked Sample: N/A

Replicate: APPLICABLE

Field QC Samples
Travelling Blank: APPLICABLE

Travelling Spiked Blank: N/A

Duplicate: APPLICABLE

NOTES/REMARKS/TIPS: When on-line analysers are used, the monthly performance check sample should be taken as a single grab and the result compared to the on-line analyser reading at the time of sampling (see Section 4.2.3).

ATG #8- TOTAL SUSPENDED SOLIDS

SAMPLING

Type
Recommended: AUTO 1 or 2

Alternate: MANUAL 1 or 2

Container
Recommended: Glass or polyethylene terephthalate

Alternate: Teflon®, polypropylene, high or low density polyethylene, polystyrene

Not Recommended: contact with metallic foil

Container Pretreatment
Recommended: generally none for new containers

Alternate: wash with detergent if necessary, distilled water rinses

Sample Volume
Recommended: 500 mL

Alternate: volume required to meet MDLs and analyze all applicable QC samples

Preservation
Recommended: none

Alternate: N/A

Maximum Sample Storage Time
7 days

Precautions/Notes: If sample is expected to have high (>5%) hydrocarbon or organic solvent content, use glass or Teflon® container only and Teflon® lined caps.

ANALYSIS

Sample Preparation
Recommended: Preparation for measurement system as appropriate and filtration using a glass fibre filter with approximately 2 micrometers particle retention (934 AH or equivalent)

Alternate: N/A

Not Recommended: N/A

Instrumental Measurement
Recommended: Drying of filter and particulates at 103 o C ± 3 o C followed by gravimetry

Alternate: N/A

Method Detection Limit
Required: 3 mg/L

Precautions/Notes: Use of a filter having particle retention less than the nominal 1.5 - 2 micrometers of the recommended 934AH filter may lead to elevated results. The same filter size/model must be used for suspended solids and dissolved solids (ATG 8 and 8a) .

QUALITY CONTROL SAMPLES

Laboratory QC Samples
Blank: APPLICABLE

Spiked Blank: N/A

Spiked Sample: N/A

Replicate: APPLICABLE

Field QC Samples
Travelling Blank: N/A

Travelling Spiked Blank: N/A

Duplicate: APPLICABLE

NOTES/REMARKS/TIPS: Balance accuracy should be confirmed by frequent checks with standard weights. All results of weight checks should be recorded and retained for the MOE review. Weights should cover the entire analytical sample range (ie. include crucible weight if applicable).

ATG #8- VOLATILE SUSPENDED SOLIDS (VSS)

SAMPLING

Type
Recommended: AUTO 1 or 2

Alternate: MANUAL 1 or 2

Container
Recommended: glass or polyethylene terephthalate

Alternate: Teflon®, polypropylene, high or low density polyethylene, polystyrene

Not Recommended: contact with metallic foil

Container Pretreatment
Recommended: generally none for new containers

Alternate: wash with detergent if necessary, distilled water rinses

Sample Volume
Recommended: 500 mL

Alternate: volume required to meet MDLs and analyze all applicable QC samples

Preservation
Recommended: none

Alternate: N/A

Maximum Sample Storage Time
7 days

Precautions/Notes: If sample is expected to have high (>5%) hydrocarbon or organic solvent content, use glass or Teflon® container only and Teflon® lined caps.

ANALYSIS

Sample Preparation
Recommended: Perform TSS analysis

Alternate: N/A

Not Recommended: N/A

Instrumental Measurement
Recommended: Ignite filter at 600°C ±50°C for 1 hr. gravimetry

Alternate: N/A

Method Detection Limit
Required: 3 mg/L

QUALITY CONTROL SAMPLES

Laboratory QC Samples
Blank: APPLICABLE

Spiked Blank: N/A

Spiked Sample: N/A

Replicate: APPLICABLE

Field QC Samples
Travelling Blank: N/A

Travelling Spiked Blank: N/A

Duplicate: APPLICABLE

NOTES/REMARKS/TIPS: Balance accuracy should be confirmed by frequent checks with standard weights. All results of weight checks should be recorded and retained for the MOE review. Weights should cover the entire analytical sample range (ie. include crucible weight if applicable).

ATG # 8a- DISSOLVED SOLIDS

SAMPLING

Type
Recommended: AUTO 1 or 2

Alternate: MANUAL 1 or 2

Container
Recommended: glass or polyethylene terephthalate

Alternate: Teflon®, polypropylene, high or low density polyethylene, polystyrene

Not Recommended: contact with metallic foil

Container Pretreatment
Recommended: generally none for new containers

Alternate: wash with detergent if necessary, distilled water rinses

Sample Volume
Recommended: 100 mL

Alternate: volume required to meet MDLs and analyze all applicable QC samples

Preservation
Recommended: none

Alternate: N/A

Maximum Sample Storage Time
7 days

Precautions/Notes: If sample is expected to have high (>5%) hydrocarbon or organic solvent content, use glass or Teflon® container only and Teflon® lined caps.ANALYSIS

Sample Preparation
Recommended: Preparation for measurement system as appropriate and filtration using a glass fibre filter with approximately 2 micrometers particle retention (934AH) or equivalent.

Alternate: N/A

Not Recommended: N/A

Instrumental Measurement
Recommended: Gravimetry after drying at 103 o C ± 3 o C

Alternate: N/A

Method Detection Limit
Required: 10 mg/L

Precautions/Notes: Use of a filter having particle retention less than the nominal 1.5 - 2 micrometers of the recommended 934AH filter may lead to elevated results. The same filter Type must be used for suspended solids and dissolved solids (ATG 8 and 8a) .

QUALITY CONTROL SAMPLES

Laboratory QC Samples
Blank: APPLICABLE

Spiked Blank: N/A

Spiked Sample: N/A

Replicate: APPLICABLE

Field QC Samples
Travelling Blank: N/A

Travelling Spiked Blank: N/A

Duplicate: APPLICABLE

ATG #9- TOTAL METALS

SAMPLING

Type
Recommended: AUTO 1 or 2

Alternate: MANUAL 1 or 2

Container
Recommended: polyethylene terephthalate

Alternate: Teflon®, polypropylene, high or low density polyethylene, polystyrene, glass

Not Recommended: contact with metallic foil

Container Pretreatment
Recommended: soak overnight in 5% HNO3 followed by distilled water rinse, if necessary

Alternate: use new containers

Sample Volume
Recommended: 500 mL

Alternate: volume required to meet MDLs and analyze all applicable QC samples

Preservation
Recommended: HNO3 (containing <1 mg/L of total metals) to pH <2

Alternate: N/A

Maximum Sample Storage Time
30 days*

Precautions/Notes: If sample is expected to have high (>5%) hydrocarbons or organic solvent content, use glass or Teflon® container only and Teflon® lined caps. If boron analysis is required, glass containers must not be used due to the potential for sample contamination.If the laboratory can demonstrate that no target parameters are lost, preserved samples may be stored at an ambient temperature of 20°C or less.

ANALYSIS

Sample Preparation
Recommended: Nitric evaporation

Alternate: other acid digestion as appropriate

Not Recommended: N/A

Instrumental Measurement
Recommended: Flame AA or ICP or DCP or ICP/MS

Alternate: graphite furnace AAS or polarography by method of standard addition in the presence of a suitable electrolyte

Method Detection Limit
Required: See Table 1

Precautions/Notes: Some sector specific additional tests may appear as additions to this group (ATG 9a).

QUALITY CONTROL SAMPLES

Laboratory QC Samples

Blank: APPLICABLE

Spiked Blank: APPLICABLE

Spiked Sample: APPLICABLE

Replicate: APPLICABLE

Field QC Samples
Travelling Blank: APPLICABLE

Travelling Spiked Blank: N/A

Duplicate: APPLICABLE

NOTES/REMARKS/TIPS: Spiked blank analysis must include the entire analytical procedure, including evaporation or digestion.

ATG #9a- IRON, URANIUM, MAGNESIUM

SAMPLING

Type
Recommended: AUTO 1 or 2

Alternate: MANUAL 1 or 2

Container
Recommended: polyethylene terephthalate

Alternate: Teflon®, polypropylene, high or low density polyethylene, polystyrene, glass

Not Recommended: contact with aluminum foil

Container Pretreatment
Recommended: in 5% soak overnight HNO3 followed distilled water rinses, if necessary

Alternate: N/A

Sample Volume
Recommended: 100 mL

Alternate: volume required to meet MDLs and analyze all applicable QC samples

Preservation
Recommended: HNO3 (containing < 1 mg/L of total metals) to pH<2

Alternate: N/A

Maximum Sample Storage Time

Unpreserved: N/A

Preserved: 30 days*

Precautions/Notes: If sample is expected to have high (>5%) hydrocarbon or organic solvent content, use glass or Teflon® container only and Teflon® lined caps.

ANALYSIS

Sample Preparation
Recommended: nitric acid evaporation or other as appropriate

Alternate: N/A

Not Recommended: N/A

Instrumental Measurement
Recommended: Iron and Magnesium: AA or ICP or DCP or ICP/MS
Uranium: Fluorescence Spectroscopy, ICP or ICP/MS

Alternate: Magnesium: EDTA Titration

Method Detection Limit
Required: See Table 1

Precautions/Notes:

QUALITY CONTROL SAMPLES

Laboratory QC Samples
Blank: APPLICABLE

Spiked Blank: APPLICABLE

Spiked Sample: APPLICABLE

Replicate: APPLICABLE

Field QC Samples
Travelling Blank: APPLICABLE

Travelling Spiked Blank: N/A

Duplicate: APPLICABLE

ATG #10- HYDRIDES

SAMPLING

Type
Recommended: AUTO 1 or 2

Alternate: MANUAL 1 or 2

Container
Recommended: glass or polyethylene terephthalate

Alternate: Teflon®, polypropylene, high or low density polyethylene, polystyrene

Not Recommended: contact with metallic foil

Container Pretreatment
Recommended: soak overnight in 5% HNO3 followed by distilled water rinse if necessary

Alternate: use new containers

Sample Volume
Recommended: 50 mL

Alternate: volume required to meet MDLs and analyze all applicable QC samples

Preservation
Recommended: HNO3 (containing <1 mg/L of total metals) to pH <2

Alternate: none

Maximum Sample Storage Time
30 days

Precautions/Notes: If sample is expected to have high (>5%) hydrocarbons or organic solvent content, use glass or Teflon® container only and Teflon® lined caps. It is recommended that plastic bottles not be precharged with concentrated nitric acid to avoid false positives for antimony.

ANALYSIS

Sample Preparation
Recommended: Acid digestion

Alternate: N/A

Not Recommended: N/A

Instrumental Measurement
Recommended: Hydride generation in conjunction with atomic absorption or ICP;
ICP/MS

Alternate: Graphite furnace AAS or polarography via the method of standard additions in the presence of a suitable electrolyte

Method Detection Limit
Required: 0.005 mg/L

Precautions/Notes:

QUALITY CONTROL SAMPLES

Laboratory QC Samples
Blank: APPLICABLE

Spiked Blank: APPLICABLE

Spiked Sample: APPLICABLE

Replicate: APPLICABLE

Field QC Samples
Travelling Blank: APPLICABLE

Travelling Spiked Blank: N/A

Duplicate: APPLICABLE

ATG #11- CHROMIUM (HEXAVALENT)

SAMPLING

Type
Recommended: AUTO 1 or 2

Alternate: MANUAL 1 or 2

Container
Recommended: Glass with plastic lined cap

Alternate: Teflon®, with plastic lined cap

Not Recommended: contact with metallic foil, paper or cardboard

Container Pretreatment
Recommended: soak overnight in 5% HNO3 followed by distilled water rinse if necessary

Alternate: new container

Sample Volume
Recommended: 200 mL

Alternate: volume required to meet MDLs and analyze all applicable QC samples

Preservation
Recommended: none

Alternate: N/A

Maximum Sample Storage Time:

5 days

Precautions/Notes: Unless ATG 11 analysis is specifically required, analyze for ATG 11 only if total chromium is >1 mg/L and ensure adherence with the 5 day storage time specified for ATG 11. If sample is expected to have high (>5%) hydrocarbons or organic solvent content, use glass or Teflon® container only and Teflon® lined caps.

ANALYSIS

Sample Preparation
Recommended: none

Alternate: Solvent extraction

Not Recommended: N/A

Instrumental Measurement
Recommended: Colourimetry or AA

Alternate: Polarography by method of standard additions in the presence of suitable electrolyte.

Method Detection Limit
Required: 0.01 mg/L

Precautions/Notes: Unless ATG 11 is specifically required, analyze for ATG 11 only if total chromium is >1 mg/L and ensure adherence with the 5 day storage time specified for ATG 11.

QUALITY CONTROL SAMPLES

Laboratory QC Samples
Blank: APPLICABLE

Spiked Blank: APPLICABLE

Spiked Sample: APPLICABLE

Replicate: APPLICABLE

Field QC Samples
Travelling Blank: APPLICABLE

Travelling Spiked Blank: N/A

Duplicate: APPLICABLE

ATG #12- MERCURY

SAMPLING

Type
Recommended: AUTO 1 or 2

Alternate: MANUAL 1 or 2

Container
Recommended: glass with plastic-lined cap

Alternate: Teflon® with plastic-lined cap

Not Recommended: contact with metallic foil

Container Pretreatment
Recommended: soak overnight in 5% HNO3 followed by distilled water rinse if necessary

Alternate: use new containers

Sample Volume
Recommended: 200 mL

Alternate: volume required to meet MDLs and analyze all applicable QC samples

Preservation
Recommended: add 1-2 mL HNO3 per 250 mL sample followed by at least 0.5 mL K2Cr2O7 solution to produce definite, lasting yellow colour

Alternate: add KMnO4 solution until pink or HNO3 to pH<2
HNO3 alone: ( use with caution since there is no colour indication of proper preservation )

Maximum Sample Storage Time
7 days

Precautions/Notes: No sample contact with metal except carbon steel or stainless steel. It is recommended that preservatives be stored in glass containers and away from mercury and its salts. A periodic test for mercury should be made to ensure preservatives are uncontaminated.

Samples containing coloured materials, reducing agents and highly alkaline substances may require larger volumes of potassium dichromate solution and nitric acid as preservatives. The amounts of preservatives to obtain coloured acidic samples should be determined and these volumes noted on the sample bottles so that an appropriate blank compensation can be done.

Preserved samples may be stored at an ambient temperature of 20°C or less.

ANALYSIS

Sample Preparation
Recommended: Oxidative acid digestion

Alternate: none

Not Recommended: N/A

Instrumental Measurement
Recommended: Cold vapour generation in conjunction with AA, ICP, ICP/MS, or Fluorescence detector

Alternate: Hydride generation in conjunction with AA, ICP, ICP/MS, or Fluorescence detector

Method Detection Limit
Required: 0.0001 mg/L

Precautions/Notes:

QUALITY CONTROL SAMPLES

Laboratory QC Samples
Blank: APPLICABLE

Spiked Blank: APPLICABLE

Spiked Sample: APPLICABLE

Replicate: APPLICABLE

Field QC Samples
Travelling Blank: APPLICABLE

Travelling Spiked Blank: N/A

Duplicate: APPLICABLE

ATG #13- TOTAL ALKYL LEAD: TETRA-ALKYL and TRI-ALKYL LEAD (INORGANIC LIGAND)

SAMPLING

Type
Recommended: AUTO 1 or 2

Alternate: MANUAL 1 or 2

Container
Recommended: glass amber with plastic- lined cap

Alternate: Teflon®

Not Recommended: contact with metallic foil

Container Pretreatment
Recommended: soak overnight in 5% HNO3 followed by distilled water rinse

Alternate: N/A

Sample Volume
Recommended: 1 L

Alternate: volume required to meet MDLs and analyze all applicable QC samples

Preservation
Recommended: none

Alternate: N/A

Maximum Sample Storage Time
4 days at < 4°C

Precautions/Notes: Fill slowly to the top, no air space, avoid turbulence. Unless ATG 13 analysis is specifically required analyze for ATG 13 only if total lead is > 1mg/L and ensure adherence with the 4 day storage time specified for ATG 13.

ANALYSIS

Sample Preparation
Recommended: Liquid/liquid extraction

Alternate: Derivatization

Not Recommended: N/A

Instrumental Measurement
Recommended: Colourimetry, using dithizone reagent or GC/AA

Alternate: N/A

Method Detection Limit
Required: .005 mg/L as lead

Precautions/Notes: Unless ATG 13 analysis is specifically required, analyze for ATG 13 only if total lead is >1 mg/L, and ensure adherence with the 4 day storage time specified for ATG 13.

QUALITY CONTROL SAMPLES

Laboratory QC Samples
Blank: APPLICABLE

Spiked Blank: APPLICABLE

Spiked Sample: APPLICABLE

Replicate: APPLICABLE

Field QC Samples
Travelling Blank: APPLICABLE

Travelling Spiked Blank: N/A

Duplicate: APPLICABLE

ATG #14- PHENOLICS (4AAP)

SAMPLING

Type
Recommended: MANUAL 1 or 2

Alternate: AUTO 1 or 2 or MANUAL 3, ( see sec. 3.4, Pg.12)

Container
Recommended: glass with phenolic-free cap

Alternate: Teflon® with phenolic-free cap

Not Recommended: Contact with metallic foil

Container Pretreatment
Recommended: generally none for new containers

Alternate: wash with detergent if necessary, distilled water rinses

Sample Volume
Recommended: 250 mL

Alternate: volume required to meet MDLs and analyze all applicable QC samples

Preservation
Recommended: H2SO4 to pH between 1.5 and 2

Alternate: 1 mL of (3N H3PO4 + 120 g/L CuSO4*5H2O) solution for each 250 mL sample, especially where high chloride is suspected, to prevent interference

Maximum Sample Storage Time
30 days

Precautions/Notes: It is recommended that Manual sampling techniques be used for phenolics to avoid contamination from silicone rubber parts in automated samplers. If an automated sampler is used, sample contamination may be avoided by using the last bottle in the sequence for the phenolics (ATG 14) sample. For AUTO 1 or 2, sampler bottles must be precharged with preservative. Remove any oxidizing agents as soon as possible after sampling, but no later than 48 hours after sampling, by adding ferrous sulphate or sodium arsenite.

ANALYSIS

Sample Preparation
Recommended: Preparation for measurement system as appropriate followed by distillation of acidified sample.

Alternate: N/A

Not Recommended: N/A

Instrumental Measurement
Recommended: Colourimetry of buffered sample

Alternate: Colourimetry of chloroform extract

Method Detection Limit
Required: 0.002 mg/L as phenol

Precautions/Notes: High chloride content in samples may cause severe interference problems in the analysis of phenolics.

QUALITY CONTROL SAMPLES

Laboratory QC Samples
Blank: APPLICABLE

Spiked Blank: APPLICABLE

Spiked Sample: APPLICABLE

Replicate: APPLICABLE

Field QC Samples
Travelling Blank: APPLICABLE

Travelling Spiked Blank: N/A

Duplicate: APPLICABLE

ATG #15- SULPHIDE

SAMPLING

Type
Recommended: Manual 3 collected as Grab 2

Alternate: Manual 3 collected as Grab 1

Container
Recommended: glass or polyethylene terephthalate

Alternate: Teflon®, polypropylene, high or low density polyethylene, polystyrene

Container Pretreatment
Recommended: generally none for new containers

Alternate: wash with detergent if necessary, distilled water rinses

Sample Volume
Recommended: 250 mL

Alternate: volume required to meet MDLs and analyze all applicable QC samples

Preservation
Recommended: 0.5 mL per 250 mL sample of 2N zinc acetate followed by dropwise addition of 5% sodium carbonate to pH 10

Alternate: N/A

Maximum Sample Storage Time
7 days

Precautions/Notes: Fill slowly, avoid excessive air space and turbulence prior to preservation. All sample contact surfaces should be Teflon®, glass, metallic foil, or stainless steel only. If sampling by MANUAL 3 technique, preservative should be added after each fraction is collected.

If the sample does not contain metals, sodium hydroxide may be used instead of sodium carbonate in the preservation reagent.

ANALYSIS

Sample Preparation
Recommended: Dissolution of precipitate

Alternate: Decantation if needed

Not Recommended: N/A

Instrumental Measurement
Recommended: Methylene blue colourimetry or specific ion electrode or ion chromatography

Alternate: Polarography by method of standard additions in the presence of a suitable electrolyte

Method Detection Limit
Required: 0.02 mg/L

Precautions/Notes: The three grab samples may be combined in the lab immediately prior to analysis, or the three samples may be analyzed separately and an arithmetic mean reported.

QUALITY CONTROL SAMPLES

Laboratory QC Samples
Blank: APPLICABLE

Spiked Blank: APPLICABLE

Spiked Sample: APPLICABLE

Replicate: APPLICABLE

Field QC Samples
Travelling Blank: APPLICABLE

Travelling Spiked Blank: N/A

Duplicate: APPLICABLE

ATG #16- VOLATILES, HALOGENATED

SAMPLING

Type
Recommended: Manual 3 collected as Grab 2

Alternate: Manual 3 collected as Grab 1 or On-Line Analyzer

Container
Recommended: glass vial with Teflon®-lined septum cap

Alternate: glass with foil-lined cap

Not Recommended: N/A

Container Pretreatment
Recommended: If needed, wash bottle in hot water, detergent, water, distilled water rinse. Heat at 105 o C for 1 hour. Cap - no pretreatment

Alternate:

Sample Volume
Recommended: 25 or 40 mL

Alternate: volume required to meet MDLs and analyze all applicable QC samples

Preservation
Recommended: when samples contain residual chlorine preserve with 80 mg Na2S2O3 per 1L and store in the dark.

Alternate: 2 to 4 drops HCl

Maximum Sample Storage Time

Unpreserved: 7 days

Preserved: 14 days

Precautions/Notes: Fill slowly to the top, no air space, avoid turbulence. All sample contact surfaces should be Teflon®, glass, metallic foil, or stainless steel only. Avoid contact with plastics.

Collection of duplicate samples is recommended to fulfill QA/QC requirements and for re-analysis if needed.

ANALYSIS

Sample Preparation
Recommended: Purge and trap

Alternate: N/A

Not Recommended: N/A

Instrumental Measurement
Recommended: GC/MS, capillary column

Alternate: GC/ECD or ELCD and GC/FID or PID, Capillary Column, Headspace - GC/MS

Method Detection Limit
Required: see Table 1

Precautions/Notes: The three grab samples should be analyzed separately and an arithmetic mean reported or they may be combined in the lab immediately prior to analysis.

QUALITY CONTROL SAMPLES

Laboratory QC Samples
Blank: APPLICABLE

Spiked Blank: APPLICABLE

Spiked Sample: APPLICABLE

Replicate: APPLICABLE, may use duplicate sample

Field QC Samples
Travelling Blank: APPLICABLE

Travelling Spiked Blank: APPLICABLE

Duplicate: APPLICABLE

ATG #17- VOLATILES, NON-HALOGENATED

SAMPLING

Type
Recommended: MANUAL 3 collected as Grab 2

Alternate: MANUAL 3 collected as Grab 1 or On-Line Analyzer

Container
Recommended: glass vial with Teflon®-lined septum caps

Alternate: glass with foil-lined caps

Not Recommended: N/A

Container Pretreatment
Recommended: If needed, wash bottle in hot water, detergent, water, distilled water rinse. Heat at 105 o C for 1 hour. Cap-no pretreatment.

Alternate:

Sample Volume
Recommended: 25 or 40 mL

Alternate: volume required to meet MDLs and analyze all applicable QC samples

Preservation
Recommended: when samples suspected to contain residual chlorine preserve with 80 mg Na2S2O3 per 1L and store in the dark.

Alternate: 2 to 4 drops HCl

Maximum Sample Storage Time

Unpreserved: 7 days

Preserved: 14 days

Precautions/Notes: Fill slowly to the top, no air space, avoid turbulence. All sample contact surfaces should be Teflon®, glass, metallic foil, or stainless steel only. Avoid contact with plastics.

Collection of duplicate samples is recommended to fulfill QA/QC requirements and for re-analysis if needed.

ANALYSIS

Sample Preparation
Recommended: Purge and trap

Alternate: N/A

Not Recommended: N/A

Instrumental Measurement
Recommended: GC/MS, Capillary column

Alternate: GC/FID or PID, Capillary column, Headspace - GC/MS

Method Detection Limit
Required: see Table 1

Precautions/Notes: The three grab samples should be analyzed separately and an arithmetic mean reported or they may be combined in the lab immediately prior to analysis. Certain sector-specific tests may appear as additions to this test group.

QUALITY CONTROL SAMPLES

Laboratory QC Samples
Blank: APPLICABLE

Spiked Blank: APPLICABLE

Spiked Sample: APPLICABLE

Replicate: APPLICABLE, may use duplicate sample

Field QC Samples
Travelling Blank: APPLICABLE

Travelling Spiked Blank: APPLICABLE

Duplicate: APPLICABLE

NOTES/REMARKS/TIPS: m-Xylene and p-Xylene often co-elute in the analysis; a single result may be reported as m-Xylene.

ATG #18- VOLATILES, WATER SOLUBLE

SAMPLING

Type
Recommended: Manual 3 collected as Grab 2

Alternate: Manual 3 collected as Grab 1 or On-Line Analyzer

Container
Recommended: glass vial with Teflon®-lined septum caps

Alternate: glass with foil-lined caps

Not Recommended: N/A

Container Pretreatment
Recommended: if needed, wash bottle in hot water, detergent, water, distilled water rinse. Heat at 105 o C for 1 hour. Cap - no pre-treatment.

Alternate:

Sample Volume
Recommended: 25 or 40 mL

Alternate: volume required to meet MDLs and analyze all applicable QC samples

Preservation
Recommended: none; when samples suspected to contain residual chlorine preserve with 80 mg Na2S2O3 per 1L and store in the dark.

Alternate: 2 to 4 drops HCl

Maximum Sample Storage Time

Unpreserved: 7 days

Preserved: 14 days

Precautions/Notes: Fill slowly to the top, no air space, avoid turbulence. All sample contact surfaces should be Teflon®, glass, metallic foil, or stainless steel only. Avoid contact with plastics.

Collection of duplicate samples is recommended to fulfill QA/QC requirements and for re-analysis if needed.

ANALYSIS

Sample Preparation
Recommended: Purge and trap

Alternate: N/A

Not Recommended: N/A

Instrumental Measurement
Recommended: GC/MS, Capillary column

Alternate: GCFID//PID, capillary column

Method Detection Limit
Required: see Table 1

Precautions/Notes: The three grab samples should be analyzed separately and an arithmetic mean reported or they may be combined in the lab immediately prior to analysis.

QUALITY CONTROL SAMPLES

Laboratory QC Samples
Blank: APPLICABLE

Spiked Blank: APPLICABLE

Spiked Sample: APPLICABLE

Replicate: APPLICABLE, may use duplicate sample

Field QC Samples
Travelling Blank: APPLICABLE

Travelling Spiked Blank: APPLICABLE

Duplicate: APPLICABLE

ATG #19- EXTRACTABLES, BASE NEUTRAL

SAMPLING

Type
Recommended: AUTO 1 or 2

Alternate: MANUAL 1 or 2

Container
Recommended: amber glass with Teflon®-lined caps

Alternate: Teflon® with Teflon®-lined caps

Not Recommended: N/A

Container Pretreatment
Recommended: If needed, wash bottle in hot water, detergent, water, distilled water rinse. Heat at 105°C for 1 hour. Cap - no pretreatment.

Alternate: instead of baking, rinse with acetone (or other water soluble solvent), distilled-in-glass hexane and/or dichloromethane, air dry.

Sample Volume
Recommended: 800 mL

Alternate: volume required to meet MDLs and analyze all applicable QC samples

Preservation
Recommended: none

Alternate: add first aliquot of extraction solvent on arrival at lab, prior to storage

Maximum Sample Storage Time
30 days

Precautions/Notes: All sample contact surfaces should be Teflon®, glass, or stainless steel only. Avoid contact with plastics.

Collection of duplicate samples is recommended to fulfill QA/QC requirements and for re-analysis of needed.

ANALYSIS

Sample Preparation
Recommended: Liquid/liquid extraction; clean-up if necessary.

Alternate: N/A

Not Recommended: N/A

Instrumental Measurement
Recommended: GC/MS, Capillary column

Alternate: High Performance Liquid Chromatography (HPLC), Ultraviolet or Fluorescence Detection for PAH's and biphenyl

Method Detection Limit
Required: see Table 1

Precautions/Notes:

QUALITY CONTROL SAMPLES

Laboratory QC Samples
Blank: APPLICABLE

Spiked Blank: APPLICABLE

Spiked Sample: APPLICABLE

Replicate: APPLICABLE, may use duplicate sample

Field QC Samples
Travelling Blank: APPLICABLE

Travelling Spiked Blank: APPLICABLE

Duplicate: APPLICABLE

NOTES/REMARKS/TIPS: N-Nitrosodiphenylamine breaks down to Diphenylamine in the injector. A single result is reported as Diphenylamine.

ATG #20- EXTRACTABLES, ACID (PHENOLICS)

SAMPLING

Type
Recommended: AUTO 1 or 2

Alternate: MANUAL 1 or 2

Container
Recommended: amber glass with Teflon®-lined caps

Alternate: Teflon® with Teflon®-lined caps

Not Recommended: foil lined caps

Container Pretreatment
Recommended: If needed, wash bottle in hot water, detergent, water, distilled water rinse. Heat at 1050C for 1 hour. Cap - no pretreatment.

Alternate: Instead of baking, rinse with acetone (or other water soluble solvent), distilled-in-glass hexane and/or dichloromethane, air dry.

Sample Volume
Recommended: 800 mL

Alternate: volume required to meet MDLs and analyze all applicable QC samples

Preservation
Recommended: none

Alternate: N/A

Maximum Sample Storage Time
30 days

Precautions/Notes: All sample contact surfaces should be Teflon®, glass, or stainless steel only. Avoid contact with plastics and phenolic resins (e.g. Bakelite®, caps).

Collection of duplicate samples is recommended to fulfill QA/QC requirements and for re-analysis of needed.ANALYSIS

Sample Preparation
Recommended: Liquid/liquid extraction, pH adjusted to <2; derivatization if appropriate; cleanup.

Alternate: N/A

Not Recommended: N/A

Instrumental Measurement
Recommended: GC/MS, Capillary column

Alternate: N/A

Method Detection Limit
Required: see Table 1

QUALITY CONTROL SAMPLES

Laboratory QC Samples
Blank: APPLICABLE

Spiked Blank: APPLICABLE

Spiked Sample: APPLICABLE

Replicate: APPLICABLE, may use duplicate sample

Field QC Samples
Travelling Blank: APPLICABLE

Travelling Spiked Blank: APPLICABLE

Duplicate: APPLICABLE

ATG #23- EXTRACTABLES, NEUTRAL CHLORINATED

SAMPLING

Type
Recommended: AUTO 1 or 2

Alternate: MANUAL 1 or 2

Container
Recommended: amber glass with Teflon®-lined caps

Alternate: Teflon® with Teflon®-lined caps

Not Recommended: N/A

Container Pretreatment
Recommended: If needed, wash bottle in hot water, detergent, water, distilled water rinse. Heat at 105°C for 1 hour. Cap - no pretreatment.

Alternate: instead of baking, rinse with acetone (or other water soluble solvent), distilled-in-glass hexane and/or dichloromethane, air dry.

Sample Volume
Recommended: 800 mL

Alternate: volume required to meet MDLs and analyze all applicable QC samples

Preservation
Recommended: none

Alternate: N/A

Maximum Sample Storage Time
30 daysPrecautions/Notes: All sample contact surfaces should be Teflon®, glass, or stainless steel only. Avoid contact with plastics. Foil-lined caps may be used if sample pH is between 6.5 and 8.5.

Collection of duplicate samples is recommended to fulfill QA/QC requirements and for re-analysis of needed.

ANALYSIS

Sample Preparation
Recommended: Liquid/liquid extraction, neutral pH.
Cleanup if necessary.

Alternate: N/A

Not Recommended: N/A

Instrumental Measurement
Recommended: GC/ECD, dual capillary column or GC/MS capillary column

Alternate: N/A

Method Detection Limit
Required: see Table 1

QUALITY CONTROL SAMPLES

Laboratory QC Samples
Blank: APPLICABLE

Spiked Blank: APPLICABLE

Spiked Sample: APPLICABLE

Replicate: APPLICABLE, may use duplicate sample

Field QC Samples
Travelling Blank: APPLICABLE

Travelling Spiked Blank: APPLICABLE

Duplicate: APPLICABLE

ATG #24- CHLORINATED DIBENZO-P-DIOXINS and FURANS

SAMPLING

Type
Recommended: AUTO 1 or 2

Alternate: MANUAL 1 or 2

Container
Recommended: amber glass with Teflon®-lined caps

Alternate: clear glass with Teflon®-lined caps

Not Recommended:

Container Pretreatment
Recommended: If needed, wash bottle in hot water, detergent, water, distilled water rinse. Heat at 105°C for 1 hour.

Alternate: If needed, 3 rinses with distilled-in-glass methanol and/or dichloromethane, air dry.
Cap-no pretreatment.

Sample Volume
Recommended: 4 L, to allow for repeat analysis, if needed

Alternate: volume required to meet MDLs and analyze all applicable QC samples

Preservation
Recommended: none

Alternate: N/A

Maximum Sample Storage Time
30 days

Precautions/Notes: All sample contact surfaces should be Teflon®, glass, or stainless steel only. Avoid contact with plastics. Collection of duplicate samples is recommended to fulfill QA/QC requirements and for re-analysis if needed.

ANALYSIS

Sample Preparation
Recommended: Liquid/liquid extraction and cleanup. Sample container must be rinsed with extraction solvent. If TSS >15 mg/L: filter sample, extract solids by Soxhlet using toluene, extract filtrate normally, combine both extracts prior to clean-up

Not Recommended: N/A

Instrumental Measurement
Recommended: GC/high resolution MS, capillary column; low resolution MS acceptable with effective clean-up if MDL achieved

Alternate: other GC-MS techniques, GC-MS/MS

Method Detection Limit
Required: See Table 1; MDL must be calculated for each congener listed in Table 5.

Precautions/Notes: The laboratory must be able to demonstrate that all glassware and equipment is free of contamination. The method requires that all samples be spiked with 13C labelled surrogates of the congeners listed in Table 5 and with labelled internal standards to aid recovery checks. The spikes must include at least one representative from each congener group, preferably one for each congener.

Analysis must be done for the 17 dioxin and furan congeners listed in Table 5 and results recorded for each individual congener. Highest possible concentration assumptions are to be made where full chromatographic resolution does not occur.

Analysis may be done in accordance with USEPA method 1613: Tetra- through Octa- Chlorinated Dioxins and Furans by Isotope Dilution HRGC/HRMS, the Environment Canada Reference Method for the Determination of Polychlorinated Dibenzo-para-Dioxins (PCDDs) and Polychlorinated Dibenzofurans (PCDFs) in Pulp and Paper Mill Effluents or the MOE method.The presence/concentration of 2,3,7,8-TCDF need not be confirmed on a second column unless:

i) its concentration is at or above the limit for this congener or
ii) the 2,3,7,8-TCDF contribution pushes the total TEQ value above the limit.

In addition, it is recommended that total congener group concentrations be recorded to ensure continuity/comparability with any historical data.

For the purpose of calculating a toxic equivalent concentration (TEQ) for a congener listed in Table 5, the positive concentration value obtained for that congener shall be multiplied by the respective International Toxicity Equivalent Factor listed in Table 5 for that congener with suitable adjustments to yield a result in pg/L. The total TEQ concentration is the sum of the TEQ concentrations for each congener listed in Table 5.

QUALITY CONTROL SAMPLES

Laboratory QC Samples
Blank: APPLICABLE*

Spiked Blank: N/A**

Spiked Sample: N/A***

Replicate: N/A

Field QC Samples
Travelling Blank: N/A

Travelling Spiked Blank: N/A

Duplicate: Recommended in case re-analysis is needed

NOTES/REMARKS/TIPS:

* Blank sample (method blank) need not be analyzed if 13C labelled compounds are used for spiked blank analysis.

** A separate method blank must be analyzed if native dioxins and furans are used for spiked blank analysis.

*** A separate spiked sample need not be analyzed because method requires that 13C labelled standards representing each congener group be added to each sample prior to extraction.

ATG #25- SOLVENT EXTRACTABLES

SAMPLING

Type
Recommended: Manual 3 collected as Grab 2

Alternate: Manual 3 collected as Grab 1 or 3
AUTO 1 or 2

Container
Recommended: clear glass, Teflon® or foil lined cap

Alternate: N/A

Not Recommended: amber glass, plastic

Container Pretreatment
Recommended: generally none for new containers

Alternate: wash with detergent if necessary, distilled water and solvent rinses

Sample Volume
Recommended: 800 mL

Alternate: volume required to meet MDLs and analyze all applicable QC samples

Preservation
Recommended: none

Alternate: acidification with HCl to approximately pH 2

Maximum Sample Storage Time

Unpreserved: 7 days

Preserved: 30 days

Precautions/Notes: Sample should be collected directly into the laboratory container. All sample contact surfaces should be Teflon®, glass, metallic foil, or stainless steel only. Avoid contact with plastics.Collection of duplicate samples is recommended to fulfill QA/QC requirements and for re-analysis if needed.

ANALYSIS

Sample Preparation
Recommended: Acidify with a mineral acid to approximately pH 2. Liquid/liquid extraction with n-hexane, plus solvent rinsings of sample containers. Silica gel chromatography when speciation into animal/ vegetable and mineral/synthetic materials is needed.

Alternate: Same as above except that dichloromethane used instead of n-hexane.

Not Recommended: Use of freons

Instrumental Measurement
Recommended: Gravimetric. Infrared spectroscopy is recommended to confirm the nature of the extracted materials

Alternate: N/A

Method Detection Limit
Required: 1 mg/L

Precautions/Notes: Entire sample must be analyzed; method requires that sample container be rinsed with extraction solvent.

Other methods of analysis are being investigated, including solid phase extraction.

QUALITY CONTROL SAMPLES

Laboratory QC Samples
Blank: APPLICABLE

Spiked Blank: N/A

Spiked Sample: N/A

Replicate: Applicable, may use duplicate sample

Field QC Samples
Travelling Blank: N/A

Travelling Spiked Blank: N/A

Duplicate: Recommended in case re-analysis is needed

ATG #26- FATTY AND RESIN ACIDS

SAMPLING

Type
Recommended: AUTO 1 or 2

Alternate: MANUAL 1 or 2

Container
Recommended: amber glass with Teflon®-lined caps

Alternate: Teflon® with Teflon®-lined caps

Not Recommended: foil lined caps

Container Pretreatment
Recommended: If needed, wash bottle in hot water, detergent, water, distilled water rinse. Bake at 300°C for 4 hours. Cap - no pretreatment

Alternate: Instead of baking, rinse with acetone (or other water soluble solvent), distilled-in-glass hexane and/or dichloromethane, air dry. Cap - no pretreatment.

Sample Volume
Recommended: 800 mL

Alternate: volume required to meet MDLs and analyze all applicable QC samples

Preservation
Recommended: none

Alternate: N/A

Maximum Sample Storage Time
7 days

Precautions/Notes: All sample contact surfaces should be Teflon®, glass, or stainless steel only. Avoid contact with plastics. Collection of duplicate samples is recommended to fulfill QA/QC requirements and for re-analysis if needed.

ANALYSIS

Sample Preparation
Recommended: pH adjusted to 9. Liquid/liquid extraction with t-butyl ether, methylation.

Alternate: N/A

Not Recommended: N/A

Instrumental Measurement
Recommended: GC/FID, Capillary column

Alternate: GC/MS*

Method Detection Limit
Required: see Table 1

Precautions/Notes: Recommended methodology is the MOE Method for Resin and Fatty Acids, November 1989 which is a consensus validated method.

* Quantitation should be done relative to the response of dehydroabietic acid. The total Ion Count of the chromatographic peaks should be used for quantitation. Compound identity should be confirmed against the mass spectrum of the methylated acid with a match > 80%.

QUALITY CONTROL SAMPLES

Laboratory QC Samples
Blank: APPLICABLE

Spiked Blank: APPLICABLE

Spiked Sample: APPLICABLE

Replicate: APPLICABLE; may use duplicate

Field QC Samples
Travelling Blank: APPLICABLE

Travelling Spiked Blank: APPLICABLE, to contain dehydroabietic acid only

Duplicate: APPLICABLE

ATG #27- POLYCHLORINATED BIPHENYLS (PCBs) TOTAL

SAMPLING

Type
Recommended: AUTO 1 or 2

Alternate: MANUAL 1 or 2

Container
Recommended: amber glass with Teflon®-lined caps

Alternate: Teflon® with Teflon®-lined caps

Not Recommended: N/A

Container Pretreatment
Recommended: If needed, wash bottle in hot water, detergent, water, distilled water rinse. Bake at 300°C for 4 hours. Cap - no pretreatment

Alternate: Instead of baking, rinse with distilled-in-glass hexane and/or dichloromethane, air dry

Sample Volume
Recommended: 800 mL

Alternate: volume required to meet MDLs and analyze all applicable QC samples

Preservation
Recommended: none

Alternate: N/A

Maximum Sample Storage Time
30 days

Precautions/Notes: All sample contact surfaces should be Teflon®, glass, metallic foil or stainless steel only. Avoid contact with plastics.Collection of duplicate samples is recommended to fulfill QA/QC requirements and for re-analysis if needed.

ANALYSIS

Sample Preparation
Recommended: Liquid/liquid extraction

Alternate: Cleanup if necessary

Not Recommended: N/A

Instrumental Measurement
Recommended: GC/ECD, single capillary column or GC/MS, capillary column

Alternate: N/A

Method Detection Limit
Required: 0.05 µg/L

Precautions/Notes: Report as individual Aroclors or as a mixture of Aroclors, as appropriate.

QUALITY CONTROL SAMPLES

Laboratory QC Samples
Blank: APPLICABLE

Spiked Blank: APPLICABLE

Spiked Sample: APPLICABLE

Replicate: APPLICABLE, may use duplicate sample

Field QC Samples
Travelling Blank: APPLICABLE

Travelling Spiked Blank: APPLICABLE

Duplicate: APPLICABLE

ATG #28a - OPEN CHARACTERIZATION - VOLATILES

SAMPLING

Type
Recommended: Manual 3 collected as grab 2

Alternate: Manual 3 collected as grab 1 or On-Line Analyzer

Container
Recommended: Glass with Teflon® - lined septum caps

Alternate: N/A

Not Recommended:

Container Pretreatment
Recommended: If needed, wash bottle in hot water, detergent, water, distilled water rinse. Bake at 3000C for 4 hours. Cap - no pretreatment

Alternate: Instead of baking rinse with acetone (or other water soluble solvent), distilled-in-glass hexane and/or dichloromethane. Air dry

Sample Volume
Recommended: 100 mL

Alternate: Volume required to meet MDLs and analyze all applicable QC samples

Preservation
Recommended: none

Alternate:

Maximum Sample Storage Time
7 days

Precautions/Notes: Fill slowly to the top, no air space, avoid turbulence. All sample contact surfaces should be Teflon® , glass, metallic foil or stainless steel only. Avoid contact with plastics.

Collection of duplicate samples is recommended to fulfill QA/QC requirements and for re-analysis if needed.

ANALYSIS

Sample Preparation
Recommended: Purge and trap

Alternate: N/A

Not Recommended: N/A

Instrumental Measurement
Recommended: GC/MS, capillary column

Alternate: N/A

Limit of Characterization
Required: 10 µg/L against 1,3-Dichlorobutane

Precautions/Notes: Three grab samples may be combined in the lab immediately prior to analysis, or the three samples may be analyzed separately and an arithmetic mean reported. Analysis must be performed according to the MOE publication Techniques for the Gas Chromatography - Mass Spectrometry Identification of Organic Compounds in Effluents, dated July 1989, revised December 1990, reprinted June 1991.

QUALITY CONTROL SAMPLES

Laboratory QC Samples
Blank: APPLICABLE

Spiked Blank: N/A

Spiked Sample: N/A

Replicate: N/A

Field QC Samples
Travelling Blank: APPLICABLE

Travelling Spiked Blank: N/A

Duplicate: Recommended, in case re-analysis is needed

NOTES/REMARKS/TIPS: Results must be recorded and reported as required in a format acceptable to the Director, such as MOCHA, available from LSB.

ATG #28b - OPEN CHARACTERIZATION - EXTRACTABLES

SAMPLING

Type
Recommended: AUTO 1 or 2

Alternate: MANUAL 1 or 2

Container
Recommended: Amber glass with Teflon® - lined caps

Alternate: Glass with Teflon® - lined caps

Not Recommended: N/A

Container Pretreatment
Recommended: If needed, wash bottle in hot water, detergent, water, distilled water rinse. Bake at 3000C for 4 hours. Cap - no pretreatment

Alternate: Instead of baking rinse with acetone (or other water soluble solvent), distilled-in-glass hexane and/or dichloromethane. Air dry

Sample Volume
Recommended: 800 mL

Alternate: Volume required to meet MDLs and analyze all applicable QC samples

Preservation
Recommended: none

Alternate: N/A

Maximum Sample Storage Time
30 days

Precautions/Notes: All sample contact surfaces should be Teflon® , glass or stainless steel only. Avoid contact with plastics and metallic foil..

Collection of duplicate samples is recommended to fulfill QA/QC requirements and for re-analysis if needed.

ANALYSIS

Sample Preparation
Recommended: Liquid/liquid extraction at pH > 12 (base/neutral) followed by liquid/liquid extraction at pH < 2 (acid)

Alternate: N/A

Not Recommended: N/A

Instrumental Measurement
Recommended: GC/MS, capillary column; co-injection of base/neutral and acid fractions

Alternate: N/A

Limit of Characterization
Required: 10 µg/L against D10 -Phenanthrene

Precautions/Notes: Analysis must be performed according to the MOE publication Techniques for the Gas Chromatography - Mass Spectrometry Identification of Organic Compounds in Effluents, July 1989 - revised March 1990, reprinted June 1991.

QUALITY CONTROL SAMPLES

Laboratory QC Samples
Blank: APPLICABLE

Spiked Blank: N/A

Spiked Sample: N/A

Replicate: N/A

Field QC Samples
Travelling Blank: APPLICABLE

Travelling Spiked Blank: N/A

Duplicate: Recommended, in case re-analysis is needed

NOTES/REMARKS/TIPS: Results must be recorded and reported as required in a format acceptable to the Director, such as MOCHA, available from LSB.

ATG #29 - ELEMENTAL CHARACTERIZATION

SAMPLING

Type
Recommended: AUTO 1 or 2

Alternate: MANUAL 1 or 2

Container
Recommended: Glass or Teflon®

Alternate: polypropylene, high or low density polyethylene, polystyrene, polyethylene terephthalate.

Not Recommended: contact with metallic foil

Container Pretreatment
Recommended: Soak overnight in 5% HNO3 followed by distilled water rinse, if necessary

Sample Volume
Alternate: N/A

Recommended: 500 mL

Alternate: Volume required to meet MDLs and analyze all applicable QC samples

Preservation
Recommended: HNO3 (containing < 1 mg/L of total metals) to
PH <2

Alternate: N/A

Maximum Sample Storage Time
30 days

Precautions/Notes: If sample is expected to have high (>5%) hydrocarbon or organic solvent content, use glass or Teflon® lined caps.

If boron analysis is required, glass containers must not be used due to the potential for sample contamination.

ANALYSIS

Sample Preparation
Recommended: nitric acid evaporation or other acid digestion, as appropriate

Alternate: N/A

Not Recommended: N/A

Instrumental Measurement
Recommended: AA and/or ICP, DCP or ICP/MS

Alternate: N/A

Limit of Characterization
Required: 50 µg/L

Precautions/Notes: Analysis to be performed in accordance with the MOE publication Guidance Document for the Elemental Characterization of Liquid Waste Samples, dated July 1989, second revision March 1991, reprinted June 1991.

QUALITY CONTROL SAMPLES

Laboratory QC Samples
Blank: APPLICABLE

Spiked Blank: N/A

Spiked Sample: N/A

Replicate: N/A

Field QC Samples
Travelling Blank: APPLICABLE

Travelling Spiked Blank: N/A

Duplicate: N/A

NOTES/REMARKS/TIPS: Results must be reported using MIDES, or in a format acceptable to the Director.

ATG #30- ANIONS: CHLORIDE

SAMPLING

Type
Recommended: AUTO 1 or 2

Alternate: MANUAL 1 or 2

Container
Recommended: Glass or polyethylene terephthalate

Alternate: Teflon®, polypropylene, high or low density polyethylene, polystyrene

Not Recommended: contact with metallic foil

Container Pretreatment
Recommended: generally none for new containers

Alternate: wash with detergent if necessary, distilled water rinses

Sample Volume
Recommended: 50 mL

Alternate: volume required to meet MDLs and analyze all applicable QC samples

Preservation
Recommended: none

Alternate: N/A

Maximum Sample Storage Time
30 days

Precautions/Notes: If sample is expected to have high (>5%) hydrocarbon or organic solvent content, use glass or Teflon® container only and Teflon® lined caps.

ANALYSIS

Sample Preparation
Recommended: Preparation for measurement system as appropriate

Alternate: N/A

Not Recommended: N/A

Instrumental Measurement
Recommended: Ion chromatography, colourimetry or titration

Alternate: N/A

Method Detection Limit
Required: 2 mg/L

QUALITY CONTROL SAMPLES

Laboratory QC Samples
Blank: APPLICABLE

Spiked Blank: APPLICABLE

Spiked Sample: APPLICABLE

Replicate: APPLICABLE

Field QC Samples
Travelling Blank: APPLICABLE

Travelling Spiked Blank: N/A

Duplicate: APPLICABLE

ATG #30- ANIONS: SULPHATE

SAMPLING

Type
Recommended: AUTO 1 or 2

Alternate: MANUAL 1 or 2

Container
Recommended: Glass or polyethylene terephthalate

Alternate: Teflon®, polypropylene, high or low density polyethylene, polystyrene

Not Recommended: contact with metallic foil

Container Pretreatment
Recommended: generally none for new containers

Alternate: wash with detergent if necessary, distilled water rinses

Sample Volume
Recommended: 50 mL

Alternate: volume required to meet MDLs and analyze all applicable QC samples

Preservation
Recommended: none

Alternate: N/A

Maximum Sample Storage Time
30 days

Precautions/Notes: If sample is expected to have high (>5%) hydrocarbon or organic solvent content, use glass or Teflon® container only and Teflon® lined caps.

ANALYSIS

Sample Preparation
Recommended: Preparation for measurement system as appropriate

Alternate: N/A

Not Recommended: N/A

Instrumental Measurement
Recommended: Ion chromatography

Alternate: N/A

Method Detection Limit
Required: 5 mg/L as Sulphate

QUALITY CONTROL SAMPLES

Laboratory QC Samples
Blank: APPLICABLE

Spiked Blank: APPLICABLE

Spiked Sample: APPLICABLE

Replicate: APPLICABLE

Field QC Samples
Travelling Blank: APPLICABLE

Travelling Spiked Blank: N/A

Duplicate: APPLICABLE

ATG #30- ANIONS: FLUORIDE

SAMPLING

Type
Recommended: AUTO 1 or 2

Alternate: MANUAL 1 or 2

Container
Recommended: Glass or polyethylene terephthalate

Alternate: Teflon®, polypropylene, high or low density polyethylene, polystyrene

Not Recommended: contact with metallic foil

Container Pretreatment
Recommended: generally none for new containers

Alternate: wash with detergent if necessary, distilled water rinses

Sample Volume
Recommended: 50 mL

Alternate: volume required to meet MDLs and analyze all applicable QC samples

Preservation
Recommended: none

Alternate: N/A

Maximum Sample Storage Time
30 days

Precautions/Notes: If sample is expected to have high (>5%) hydrocarbon or organic solvent content, use glass or Teflon® container only and Teflon® lined caps.

ANALYSIS

Sample Preparation
Recommended: Preparation for measurement system as appropriate

Alternate: N/A

Not Recommended: N/A

Instrumental Measurement
Recommended: Colourimetry, ion selective electrode or ion chromatography

Alternate: N/A

Method Detection Limit
Required: 0.1 mg/L

Precautions/Notes: High chloride content in samples may cause severe interference problems in the analysis of Fluoride.

QUALITY CONTROL SAMPLES

Laboratory QC Samples
Blank: APPLICABLE

Spiked Blank: APPLICABLE

Spiked Sample: APPLICABLE

Replicate: APPLICABLE

Field QC Samples
Travelling Blank: APPLICABLE

Travelling Spiked Blank: N/A

Duplicate: APPLICABLE

ATG #31- TOTAL RESIDUAL OXIDANTS (total residual chlorine)

SAMPLING

Type
Recommended: on-line analyser

Alternate: GRAB 1, 2 or 3

Container
Recommended: Amber Glass with ground-glass stopper

Alternate: Stopper or cap that will ensure headspace is eliminated.

Not Recommended: N/A

Container Pretreatment
Recommended: none

Alternate: N/A

Sample Volume
Recommended: 1000 mL

Alternate: volume required to meet MDLs and analyze all applicable QC samples

Preservation
Recommended: none, protect from light

Alternate: N/A

Maximum Sample Storage Time
<1 hour

Precautions/Notes: Fill container completely, mount stopper to eliminate headspace. Analysis of each grab sample should be initiated as soon as possible after sample collection.

ANALYSIS

Sample Preparation
Recommended: N/A

Alternate: N/A

Not Recommended: N/A

Instrumental Measurement
Recommended: Amperometry or potentiometry

Alternate: N/A

Method Detection Limit
Required: 0.01 mg/L as chlorine

Precautions/Notes: Each sample must be analyzed within the 1 hour storage time specified above.

QUALITY CONTROL SAMPLES

Laboratory QC Samples
Blank: APPLICABLE

Spiked Blank: APPLICABLE

Spiked Sample: APPLICABLE

Replicate: APPLICABLE

Field QC Samples
Travelling Blank: APPLICABLE, see note below

Travelling Spiked Blank: N/A

Duplicate: APPLICABLE

NOTES/REMARKS/TIPS: Travelling blank need not be analyzed if sample analysis occurs immediately after sampling at the sampling point.

ATG #32- FIBROUS CHRYSOTILE (ASBESTOS)

SAMPLING

Type
Recommended: AUTO 1 or 2

Alternate: MANUAL 1 or 2

Container
Recommended: plastic container, never before used

Alternate: N/A

Not Recommended: N/A

Container Pretreatment
Recommended: none, container must be new

Alternate: N/A

Sample Volume
Recommended: 1000 mL

Alternate: volume required to meet MDLs and analyze all applicable QC samples

Preservation
Recommended: none

Alternate: N/A

Maximum Sample Storage Time
2 days before filtration, unlimited after, dependent on reporting time requirement

Precautions/Notes: Wide-mouth sample containers are preferable. Do not agitate to avoid breaking clusters into fibres.

ANALYSIS

Sample Preparation
Recommended: Filtration onto membrane filter

Alternate: N/A

Not Recommended: N/A

Instrumental Measurement
Recommended: Transmission Electron Microscopy with electron diffraction

Alternate: N/A

Method Detection Limit
Required: 0.04 million fibres/L

QUALITY CONTROL SAMPLES

Laboratory QC Samples
Blank: N/A

Spiked Blank: N/A

Spiked Sample: N/A

Replicate: APPLICABLE

Field QC Samples
Travelling Blank: APPLICABLE

Travelling Spiked Blank: N/A

Duplicate: APPLICABLE

ATG #33- ADSORBABLE ORGANIC HALIDE (AOX)

SAMPLING

Type
Recommended: AUTO 1 or 2

Alternate: MANUAL 1 or 2

Container
Recommended: amber glass with Teflon® lined cap

Alternate: Teflon® with Teflon® lined cap

Not Recommended: N/A

Container Pretreatment
Recommended: generally none for new containers

Alternate: wash with detergent if necessary, distilled water rinses

Sample Volume
Recommended: 1000 mL

Alternate: volume required to meet MDLs and analyze all applicable QC samples

Preservation
Recommended: none

Alternate: If analysis cannot be performed immediately upon arrival at laboratory, to 1 L of sample, add nitric acid to pH 2 then 1 mL of 0.1M sodium sulphite solution

Maximum Sample Storage Time
14 days

ANALYSIS

Sample Preparation
Recommended: Carbon adsorption (column or shaker) at pH 2 followed by nitrate wash. Dohrmann 100-200 mesh charcoal, granular activated carbon or equivalent

Alternate: N/A

Not Recommended: N/A

Instrumental Measurement
Recommended: Pyrolysis in an oxygen rich atmosphere followed by microcoulometric analysis

Alternate: N/A

Method Detection Limit
Required: 0.05 mg/L, based on 2,4,6-Trichlorophenol

Precautions/Notes: Analysis should be carried out in an environment free of chlorinated solvents.

QUALITY CONTROL SAMPLES

Laboratory QC Samples
Blank: APPLICABLE

Spiked Blank: APPLICABLE

Spiked Sample: APPLICABLE

Replicate: APPLICABLE

Field QC Samples
Travelling Blank: APPLICABLE

Travelling Spiked Blank: APPLICABLE

Duplicate: APPLICABLE

ATG #34- ORGANICS: DIETHANOLAMINE

SAMPLING

Type
Recommended: AUTO 1 or 2

Alternate: MANUAL 1 or 2

Container
Recommended: Amber glass bottle

Alternate: N/A

Not Recommended: N/A

Container Pretreatment
Recommended: none

Alternate: N/A

Sample Volume
Recommended: 100 mL

Alternate: volume required to meet MDLs and analyze all applicable QC samples

Preservation
Recommended: none

Alternate: N/A

Maximum Sample Storage Time
30 days

ANALYSIS

Sample Preparation
Recommended: none

Alternate: liquid/liquid extraction, clean-up if necessary

Not Recommended: N/A

Instrumental Measurement
Recommended: Ion Chromatography

Alternate: GC/MS

Method Detection Limit
Required: 0.1 mg/L

QUALITY CONTROL SAMPLES

Laboratory QC Samples
Blank: APPLICABLE

Spiked Blank: APPLICABLE

Spiked Sample: APPLICABLE

Replicate: APPLICABLE

Field QC Samples
Travelling Blank: APPLICABLE

Travelling Spiked Blank: N/A

Duplicate: APPLICABLE

ATG #35- E.COLI

SAMPLING

Type
Recommended: Grab 2

Alternate: N/A

Container
Recommended: Sterile, glass or polyethylene terephthalate. MOH containers should be generally described.

Alternate:

Not Recommended: All non sterile container not specifically prepared for bacterial analysis

Container Pretreatment
Recommended: Containers should be sterile and contain sufficient sterile sodium thiosulphate to provide a concentration of 100 mg/L in the Sample Volume collected.

Alternate: N/A

Sample Volume
Recommended: 250 mL

Alternate: N/A

Preservation
Recommended: Chill on ice during transport to laboratory. Samples should never be frozen.

Alternate: N/A

Maximum Sample Storage Time
Unpreserved: 2 hours

Preserved: 36 hours, maximum
(under certain circumstances, this may be extended to a maximum of 48 hours)

Precautions/Notes: Sodium thiosulphate must be added as soon as possible after sample collection when chlorine or sodium hypochlorite has been used as a disinfectant. It is strongly recommended that suitable containers be used which are pre-charged with the preservative.

ANALYSIS

Sample Preparation
Recommended: none

Alternate: N/A

Not Recommended: N/A

Method summary (E.coli)
Culture medium: mFCBCIG agar

Technique: Membrane filtration

Use vacuum to draw sufficient volume of sample through a white, gridded, 47 mm diameter, 0.45 micron cellulose acetate/nitrate membrane filter to obtain between 20 - 80 target colonies per filter. Aseptically transfer the filter to the surface of mFCBCIG agar.

Incubation: Place culture plates in a plastic container with 2 jars each containing 50 mL ice. Incubate the closed container at 44.5°C ± 0.2°C for 21 ± 1 hours.Reading: Use a binocular, stereomicroscope set at 10 x magnification to read and record the E.coli colony counts per filter. Count all blue colonies as E.coli regardless of the intensity or location of the blue colour within the colony.

Reporting: Report levels of E.coli as colony forming units (CFU) per 100 mL. Use the following formula.

Count/100 mL = 100 x the number of colonies per filter divided by the millilitres of sample filtered.

Alternate: Other methods for determining the level of E.coli in water are available including the mTEC agar method followed by a urease test, the Idexx Colilert Quanti-tray system and ColiPlate.

Method Detection Limit
Required: 1 CFU per 100 mL

Precautions/Notes: Among coliform bacteria, Escherichia coli (E.coli) are considered the most specific bacterial indicators of fecal contamination. Tests for fecal coliforms are unnecessary if sewage effluent is tested for levels of E.coli. Sewage treatment plants which have certificates of approval requiring fecal coliform tests should seek an amendment to the certificate and replace tests for fecal coliforms by tests for E.coli.

The mTEC agar plus urease method is usually acceptable for determining levels E.coli in water except in areas where there is pulp and paper waste. Thermotolerant, urease negative Klebsiella pheumoniae found in pulp and paper waste may produce false positive E.coli results when the mTEC agar plus urease method is used.

Membrane filtration (MF) methods which employ agar culture media and an incubation temperature of 44.5°C are used to test for the presence of thermotolerant E.coli. They are usually less sensitive for determining the overall level of E.coli in water than most probable number (MPN) methods, such as Colilert Quantitray or ColiPlate, which employ liquid culture media and a 35°C incubation temperature. MF methods will indicate lower levels of E.coli than the above mentioned MPN methods when used to test the same sample. However, objectives for the level of E.coli in surface water and sewage effluent are currently based upon the use of MF methods which employ 44.5°C incubation.

QUALITY CONTROL

Laboratory QC Media: Test random samples of culture media and dilution blanks for sterility before using media or blanks from the batch.

Test random samples of culture media with bacteria known to produce positive and negative reactions before using media from the batch.

Incubator: Check and record incubator temperatures daily

Blank: Filter about 30 mL of sterile rinse water and place the filter onto the culture medium as a blank control before each sample in a series is tested. The filter should remain blank after incubation unless cross contamination between samples has occurred.

Spiked Blank: N/A

Spiked Sample: N/A

Replicate: Run 5% of samples in duplicate to check within analyst and between analyst precision.

Field QC Samples
Travelling Blank: N/A

Travelling Spiked Blank: N/A

Duplicate: N/A

ATG #36- ORGANICS: NDMA

SAMPLING

Type
Recommended: AUTO 1 or 2

Alternate: MANUAL 1 or 2

Container
Recommended: amber glass with Teflon®-lined caps

Alternate: Teflon® with Teflon®-lined caps

Not Recommended: foil lined caps

Container Pretreatment
Recommended: If needed, wash bottle in hot water, detergent, water, distilled water rinse. Heat at 105°C for 1 hour. Cap - no pretreatment.

Alternate: instead of baking, rinse with methanol, air dry.

Sample Volume
Recommended: 500 mL

Alternate: volume required to meet MDLs and analyze all applicable QC samples

Preservation
Recommended: none

Alternate: N/A

Maximum Sample Storage Time
14 days*Precautions/Notes: All sample contact surfaces should be Teflon®, glass, or stainless steel only.

Collection of duplicate samples is recommended to fulfill QA/QC requirements and for re-analysis of needed.

* Analysis must be initiated within 2 days for "Reactive" samples which contain precursors to NDMA and, upon chlorination, form NDMA during storage.

ANALYSIS

Sample Preparation
Recommended: Adsorption on Ambersorb® 572; desorption into dichloromethane.

Alternate: Liquid/liquid extraction with dichloromethane

Not Recommended: N/A

Instrumental Measurement
Recommended: GC/High resolution MS, Capillary column;
GC/low resolution MS acceptable with effective clean-up if MDL is achieved.
Quantitation by isotope dilution.

Alternate: N/A

Method Detection Limit
Required: 1 ng/L

QUALITY CONTROL SAMPLES

Laboratory QC Samples
Blank: APPLICABLE

Spiked Blank: APPLICABLE

Spiked Sample: N/A

Replicate: APPLICABLE

Field QC Samples
Travelling Blank: APPLICABLE, with each set of samples collected.

Travelling Spiked Blank: N/A

Duplicate: Recommended, in case re-analysis is needed.

 



 

 

 

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