Protocol of accepted drinking water testing methods

Overview

This protocol of Accepted Drinking Water Testing Methods (Protocol) sets out testing methods that may be used to conduct tests of Ontario drinking water. Under the Safe Drinking Water Act, 2002 (SDWA), only licensed laboratories located in Ontario and eligible out-of-province laboratories are allowed to conduct tests on samples of drinking water.

This Protocol provides a compilation of reference methods that the ministry recognizes as acceptable for drinking water testing. It also provides information on the ministry’s review process for method licensing. The Protocol  includes chemical and microbiological parameters listed in the Ontario Regulation (Ontario Regulation) 169/03: Ontario Drinking Water Quality Standards and additional parameters specified in Ontario Regulation 170/03: Drinking Water Systems regulation . It is incorporated by reference in the Drinking Water Testing Services regulation (section 11(1)(a) of Ontario Regulation 248/03 made under the SDWA.

Laboratory licensing for drinking water testing in Ontario

Under Part VII of the SDWA, only licensed laboratories in Ontario and eligible out-of-province laboratories may conduct tests of samples of Ontario drinking water. Analytical methods must also be licensed so that they produce quality results that can be compared against regulatory standards. As a prerequisite for licensing, laboratories and their testing methods must be accredited to the current International Organization for Standardization/International Electrotechnical Commission (ISO/IEC)17025 international standard General Requirements for the Competence of Testing and Calibration Laboratories. Laboratory licensing requires that the laboratory properly document and validate its testing methods and that the laboratory demonstrate competence to perform the methods it employs.

The reference methods included in this Protocol meet the ministry requirements for drinking water testing. They contain detailed instructions to enable laboratories to test the target analytes and they can typically be performed without significant modification. Requirements of the SDWA and its regulations or conditions of the drinking water testing licence may supercede the reference methods listed in this Protocol.

The ministry uses this Protocol to determine the scope of the review process for its approval of laboratory licence applications:

• Appendix A provides a list of the documents that a laboratory must include with its drinking water testing licence application
• Appendix B provides general guidance on method modifications that a laboratory may make after the ministry has approved a testing method for licensing
• Appendix C provides a summary of the ministry’s requirements for sample collection and handling

Accepted reference methods

The accepted reference methods are listed by the type of parameter each method may be used in:

• Microbiological parametersas set out in the Ontario Regulation 169/03
• Chemical parameters as set out in Ontario Regulation 170/03

The required reporting detection limit (RDL) is also included in the parameter tables in this Protocol. These methods have well-documented performance characteristics and are compiled from recognized sources. Those specific references are listed in sections Microbiological parameters and Chemical parameters beneath the parameter tables to which they apply.

In general, laboratories should use the most recent revision of the relevant reference method. This Protocol only includes testing methods intended for use at a licensed laboratory. It does not include testing methods intended for operational parameters or in-line monitoring tests done at a drinking water system. Radiological testing methods have not been included in this Protocol.

For information on specific reference methods for radiological tests, contact the ministry’s Laboratory Licensing and Compliance Program at llcp@ontario.ca.

Sources for reference methods

Reference methods can be obtained from the following sources:

• Licensed methods used by the ministry Laboratory Services Branch (LaSB) for the testing of drinking water can be requested via email at LaboratoryServicesBranch@ontario.ca. These methods are identified in this Protocol as LaSB Methods.
• Methods described in the reference Standard Methods for the Examination of Water and Wastewater, American Public Health Association, American Water Works Association (AWWA) and Water Environmental Federation are available from Standard Methods. These methods are identified in this Protocol as AWWA Methods.
• Methods of the United States Environmental Protection Agency (US EPA) are available through the US EPA, the National Technical Information Service, Springfield, Virginia, or the National Environmental Methods Index. These methods are identified in this Protocol as US EPA Methods.
• Methods of ASTM International (formerly the American Society for Testing and Materials) (ASTM) areavailable from ASTM International. These methods are identified in this Protocol as ASTM Methods.
• Methods of the International Organization for Standardization (ISO) are available from ISO. These methods are identified in this Protocol as ISO Methods.

Alternate reference methods and in-house developed methods

Since new reference methods are constantly being developed, this Protocol does not include all existing reference methods. There may be alternative reference methods that can produce suitable results for the purposes of meeting licensing requirements. Laboratories can contact the ministry to request a review of a new or alternate method for inclusion in this Protocol.

A laboratory may apply for the licensing of a method based on either an alternate reference method not listed in this Protocol or a chemistry method developed in-house. Microbiology methods developed in-house are generally not accepted for licensing. To be considered for licensing, such alternate methods or techniques must not have been previously determined to be unacceptable for the target analytes. Methods based on alternate reference methods or in-house development must produce analytical data that is consistent with or superior to an accepted reference method. The proposed alternate methods must also have sample collection and handling procedures that are suitable for drinking water and consistent with an accepted test reference method listed in this Protocol.

Requirements for licensing

The laboratory’s licence application must include the items listed in Appendix A. Laboratories applying for licensing are required to include supporting validation data relating to the analyte’s specific performance requirements.

The ministry uses the following criteriawhen reviewing and approving licence applications:

• Methods based on an accepted reference method are reviewed based on the criteria outlined in the Criteria for licensing — accepted reference method section.
• Methods based on either an accepted reference method with modifications or an alternate reference or in-house developed method are reviewed based on the criteria outlined in the Licensing – methods modified from accepted reference methods section and the Additional criteria — alternate reference  or in house methods section.

The ministry may also have additional requirements depending on the known sources of error or limitations associated with the reference method in question. Reference methods such as the US EPA SW-846 series that are general guidance methods and not prescriptive procedures may require additional validation as described in the Additional criteria — alternate reference  or in house methods section.

Criteria for licensing — accepted reference method

1. Authorization that is is fit for purpose

The laboratory must have assessed and deemed the method validation as being “fit for the purpose.” The laboratory may document this in the method or in a method validation summary. The method must be reviewed, approved for adequacy and issued by laboratory as a controlled document. The method must include at a minimum

• a unique identifier
• indicate the current revision status
• date of issue
• revision number

2. Accreditation status

Accreditation is a prerequisite for licensing. All parameters in the licence application, except for calculated parameters, must be accredited and listed on the laboratory’s current scope of accreditation issued by its accreditation body.

3. Review of method

The laboratory must include a copy of its authorized analytical method with the application. The methodology must clearly document the instrumentation involved in the test’s analysis, sample preparation, and the analytical procedures. Additionally, it must include the test’s reporting detection limits and working range as follows:   

• The method or supporting procedures must ensure that there are no delays in the immediate processing and reporting of results as required by regulations. The laboratory may document its overall process for ensuring there are no undue delays in a policy or procedure that is separate from the analytical method material. Microbiology tests must not include delayed or extended overnight refrigerated incubation.
• The laboratory must document deviations from the reference methods in its method. The ministry will review methods that involve significant deviations from the accepted reference method as alternate reference methods or in house methods. A microbiology test should not deviate from the full incubation time specified in the reference method.
• The method’s working range should encompass the relevant concentration required by the Ontario Drinking Water Quality Standards (ODWQS).
• Where possible, the method must use proper techniques to assess and mitigate known interferences with the parameter.
• The laboratory must prepare calibration standards as frequently as, or more frequently than, prescribed by the reference method. For microbiology methods, a suitable daily positive control must be included.
• The volume of the sample required for analysis (test volume) must be properly documented in the method and must be suitable for drinking water analysis.

4. Sample collection, containers and holding time

The sample volume requirements of a method specify the amount of water that must be collected by the sampler. This volume must be sufficient to provide a representative sample to the laboratory. Additionally, the volume must be enough for the prescribed test volume, additional quality control tests (such as duplicates or matrix spikes) and the method’s RDL requirement. The sample collection volumes, containers and holding times are summarized in Appendix C: Sample collection and handling requirements table.

5. Proficiency testing

The applicant must demonstrate satisfactory proficiency testing by submitting the most recent set of results as part of the application. A minimum of 1 set of successful proficiency tests is required by the ministry. Where possible, proficiency tests should encompass the analyte concentration range suitable for drinking water. In some cases, proficiency tests may not be available for the parameter and the laboratory must provide validation of the accuracy of the test method.

6. Method detection limit (MDL)

The laboratory must demonstrate that the method detection limit (MDL) meets or is less than the ministry’s required reporting detection limit (RDL). The laboratory’s calculated MDL and RDL used for reporting purposes must meet the ministry’s requirements.

The ministry’s required RDLs are listed in the Microbiological parameters section and the Chemical parameters section of this Protocol. These are typically one tenth of the regulatory standard and are listed in the most commonly used units of measure. The laboratory may use alternate units of measure for the MDL determination.

The minimum validation data that the ministry requires for licensing is a summary of the calculation of the MDLL. The laboratory must validate the MDL and determine any impact of the matrix effects from drinking water and any preservatives. It is best practice to validate the MDL using a matrix representative of the drinking water to be tested (for example, chlorinated tap water with suitable preservative). The laboratory should calculate the MDLL in accordance with the laboratory’s policies and at a minimum it should follow the criteria in AWWA Method 1020B “Quality Control”. For microbiology methods, the test volume used and inter and intra analyst precision data must demonstrate that it is suitable to achieve the required RDL and that the method performance is consistent with the accepted reference method.

7. Data reporting

The laboratory’s test results reported must:

• be expressed in defensible significant figures
• be expressed by 2 to 3 significant figures for the expression of chemical data include 1 additional digit more than the ODWQS concentration where possible.

8. Reporting overgrown microbiology tests

The method must include a definition for overgrown “over-crowding,confluent or non-identifiable microbial growth” results so that overgrown results are reported as adverse test results where a standard exists.

9. Accuracy, precision and other requirements

If accuracy and precision validation data are not fully documented in the reference method, then the laboratory must submit a summary of this validation with its licence application. It is a best practice for a laboratory to include accuracy and precision validation data with its licence application submission.

Licensing — methods modified from accepted reference methods

A laboratory may request licensing for a method that is modified from an accepted reference method.

The ministry may approve a licensing application for a method modified from an accepted reference, if the modified method can produce analytical data that is equivalent or superior to the reference method.

In its licence application, the laboratory must identify the method as a modification of a reference method and the modifications must be detailed in the method. This includes general methods such as EPA SW-846 series methods. Modifications must remain consistent with the quality control (QC) procedures and any other aspects critical for drinking water analysis as specified in the reference method.  

For microbiology tests, the incubation time may not be modified. For all other microbiology modifications including media formulation modifications, the method developer must demonstrate that the modification produces consistent or superior data to the reference method. The laboratory should evaluate the modification following procedure in the international standard ISO 17994 “Water quality — Requirements for the comparison of the relative recovery of microorganisms by two quantitative methods”.

Unless specified in the following list, the ministry will review applications for methods modified from accepted reference methods according to the criteria in the Requirements for licensing section.

The following are accepted Method Modifications: 

1. Minor variations to instrumental or apparatus conditions

   The ministry may permit minor changes in instrumental or apparatus conditions to facilitate equivalent equipment or technology or improved analytical performance.

2. Modifying sample volume requirements

   The ministry will review changes to methods’ sample volume requirements according to the same criteria that apply to an accepted reference method if the volume requirements are supported by a secondary accepted reference method(s). Lower volumes than accepted reference methods may be accepted provided that the container is suitable for sample collection, the volume is greater than 40 mL and all other regulatory requirements, licence conditions and method requirements are met.

3. Modifying sample preservative requirements
   • May use an alternate suitable preservative that is in a different accepted reference method.
   • Other alternate preservatives consistent with the purpose of accepted reference preservative (meaning dechlorination in treated samples may use a different dechlorination agent or acidification for antimicrobial in untreated samples may use an alternate antimicrobial agent) may be accepted with sufficient validation.
4. Microbiological method modifications
   • Heterotrophic Plate Count may be modified not to test every sample in duplicate
   • Sample hold time may be increased to 48 hours for all microbiological samples

Additional criteria — alternate reference or in-house methods

1. Confirmation of identity

The analytical technique must establish confirmation of identity. The laboratory must demonstrate that the response produced by the method is attributable to the analyte of interest. Chemical analyte identity is often confirmed by analyzing a reference standard and or Certified Reference Material. For microbiology tests, a suitable type culture such as an American Type Culture Collection (ATCC) or equivalent should be used.

2. Selectivity

The selectivity of a method is its ability to measure analytes of interest in the presence of other chemicals.

Selectivity is often achieved by employing a variety of sample preparation and sample clean-up techniques and separatory techniques such as gas chromatography which isolate the analyte of interest when presenting it to the measurement device.

The effects of interferences between chemicals include co-eluting peaks and analyte degradation due to interaction with either injector port, transfer line or column (chromatographic methods), overlapping of spectral lines causing either positive or negative signal enhancement (spectroscopic methods) and more.

 Selectivity is demonstrated by analyzing samples containing various suspected interfering materials in the presence of the analytes of interest, and by using statistical techniques to confirm that there are no significant differences in test results between samples with and without interfering substances. Laboratories should choose such potentially interfering materials based on scientific judgment with consideration of the interference that could occur. Paired t-test and analysis of variance (ANOVA), factorial analysis are statistical tools that laboratories may employ to demonstrate selectivity. For selective microbiology methods, this can be demonstrated through testing target organisms for positive results and potentially interfering non-target micro-organisms for negative results.

3. Working and linear ranges

The laboratory must provide validation of the calibration linearity that supports the method’s working range.

The laboratory should evaluate the working range by visually examining the plot of response versus analyte concentration. If there is a linear relationship, the laboratory must apply statistical methods to check for linearity and calculate the regression line by the method of least squares. The lowest and highest result that can be reported must be established by analyzing suitable standards. To establish working linearity the laboratory must prepare, in triplicate, a minimum of 5 concentrations between upper and lower limit of the working range and analyze them.

Sometimes it is difficult to establish deviations from linearity by visual inspection. In such cases, laboratories can plot the deviations from the regression line versus the concentrations. For linear ranges, negative and positive values must be approximately equally distributed.

While the shape of calibration curves can be modelled by quadratic equations or higher order mathematical functions, most analytical methods focus on a calibration range where the response is essentially a linear function of the concentration of the analyte. An advantage of linear calibration is that the response factor or calibration factor represents the slope of the calibration line and is relatively constant, simplifying the calculations and data interpretation.

If the calibration is not linear, as determined by the validation or the established characteristics of the analytical technique, then a non-linear calibration curve such as a quadratic or higher order equation may be used provided the following is demonstrated:

• there is established rationale (such as peer reviewed studies) to support the use of the type of calibration curve
• Relative Standard Deviation study of the calibration demonstrated the non-linearity
• the calibration curve equation is validated to be repeatable
• the calibration curve has sufficient calibration points to support the curve
• the method has sufficient calibration control checks that cover the working range

4. Bias, precision and recovery

The performance of laboratory methods, including, bias, precision and recovery, must align with the performance of one of the accepted reference methods for the target analyte. Laboratories should use the most similar accepted reference method to the alternate or in house developed method for the purpose of method performance comparison.

5. Ruggedness

Ruggedness is the ability of the method to be unaffected by slight changes in testing conditions including laboratory environmental conditions. Examples of testing conditions include chromatographic parameters including:

•  flow rate
• column temperature
• injection volume
• detection wavelength
• mobile phase composition and more

Other testing conditions include:

• digestion temperature
• pH of buffers
• normality of acids and more

Ideally, ruggedness is demonstrated by varying testing conditions and laboratory environmental conditions within previously specified tolerance and establishing that these changes do not significantly affect the measurement result, employing factorial analysis and or Youden Ruggedness Tests. At a minimum, inter and intra analyst precision must be evaluated.

6. Sample containers, preservative and holding times

The sample container, sample volume, preservative and holding requirements of the proposed alternate method must be supported by an accepted reference method. These details are summarized in Appendix C.  Alternative preservatives from non-accepted reference methods are discouraged but may be accepted provided it has suitable properties (including dechlorination, antimicrobial or pH control) and is supported with suitable references and a sample holding time validation study.

If the chemistry of an extract is different from an accepted reference method or ministry sample collection and holding time requirements, then the laboratory must prepare an extract holding time validation study.

In these cases, the laboratory must provide a validation summary that supports the sample and or extract hold time and storage conditions in the method. The hold time validation must include sufficient replicates and monitoring frequency of the analyte to confirm that the analyte is stable throughout the hold time. For guidance on how to validate holding times and determine the number of replicates, refer to Standard Practice for Estimation of Holding Time for Water Samples Containing Organic and Inorganic Constituents (ASTM D4841 — 88 ) as amended from time to time.

7. Comparison with an accepted reference — microbiology

Depending on the rigor of peer review and validation of the alternate reference method source, the applicant may be required to perform an additional method comparison. This should be done in accordance with ISO 17994 “Water quality — Requirements for the comparison of the relative recovery of microorganisms by two quantitative methods” to demonstrate, at a minimum, equivalence to an approved reference method.

Microbiological parameters

Total coliform and Escherichia coli

The ODWQS is “not detectable” for total coliforms and Escherichia coli (E. coli) respectively. 

The following table describes the methodology and results with required reporting units that are equivalent to “not detectable.”

Reporting units for total coliforms and E. coli are dependent on the methodology used. The ODWQS values provided in the table above include the appropriate reporting unit for each methodology.

Required RDL: The required RDL for total coliforms and E. coli is 0 CFU/100 mL, 0 MPN/100 mL or absent. MPN <1.1/100 mL is considered absent and is to be reported as 0 MPN/100 mL.

Methods for total coliforms and E. coli

LaSB methods:      

• Method E3407 — Membrane Filtration Method Using Differential Coliform (DC) Agar for the Simultaneous Detection and Enumeration of Total Coliforms and Escherichia coli in Drinking Water
• Method E3371 — A membrane Filtration Method for the Detection and Enumeration of Total Coliform, Escherichia coli, and Enterococci/Fecal Streptococci in Environmental Samples (Revision 5)
• Method E3561 — Presence-Absence Test for Coliform Bacteria, including Escherichia coli, in Drinking Water by Colilert^® Quanti-Tray^®
• Method E3571 — Quantitative Test for Total Coliform and/or Escherichia coli, in Water by Colilert^® Quanti-Tray^®

AWWA methods:   

• Method 9221B — Standard Total Coliform Fermentation Technique
• Method 9221C — Estimation of Bacterial Density
• Method 9221D — Presence — Absence Coliform Test
• Method 9221F — Escherichia coli Procedure using Fluorogenic Substrate
• Method 9222J — Simultaneous Detection of Total Coliform and E. coli by dual chromogen Membrane Filter Procedure
• Method 9222K — Simultaneous Detection of Total Coliforms and E. coli by Fluorogen/Chromogen Membrane Filter Procedure
• Method 9223 — Enzyme Substrate Coliform Test (Including Colilert^®, Colilert-18^® and Colisure^® media available from IDEXX Laboratories Inc.)

US EPA methods: 

• Method 1103.1 — Escherichia coli (E. coli) in Water by Membrane Filtration Using membrane-Thermotolerant Escherichia coli Agar (mTEC)
• Method 1603 — Escherichia coli (E. coli) in Water by Membrane Filtration Using Modified membrane — Thermotolerant Escherichia coli Agar (Modified mTEC)
• Method 1604 — Total Coliforms and Escherichia coli in Water by Membrane Filtration using a Simultaneous Detection Technique (MI Medium) Enzyme substrate methods as approved by the EPA — 40 CFR Part 122,136, et al., March 12, 2007

US EPA approved method:

• Tecta EC/TC, v.2.0 — Tecta^™ EC/TC medium and the Tecta^™ Instrument: A Presence/Absence Method for the Simultaneous Detection of Total Coliforms and Escherichia coli (E. coli) in Drinking Water, March 2017, Version 2.0

Methods for Total Coliforms

AWWA methods:   

• Method 9221B — Standard Total Coliform Fermentation Technique
• Method 9221C — Estimation of Bacterial Density
• Method 9221D — Presence — Absence Coliform Test
• Method 9221F — Escherichia coli Procedure using Fluorogenic Substrate
• Method 9222B — Standard Total Coliform Membrane Filter Procedure using Endo Media

US EPA method:   

• Enzyme substrate methods as approved by the EPA — 40 CFR Part 122,136, et al., March 12, 2007

US EPA approved method:

• Tecta EC/TC, version 2.0 — Tecta^™ EC/TC medium and the Tecta^™ Instrument: A Presence/Absence Method for the Simultaneous Detection of Total Coliforms and Escherichia coli (E. coli) in Drinking Water, March 2017, Version 2.0

Methods for Escherichia coli

AWWA methods:   

• Method 9221B — Standard Total Coliform Fermentation Technique
• Method 9221C — Estimation of Bacterial Density
• Method 9221D — Presence — Absence Coliform Test
• Method 9221F — Escherichia coli Procedure using Fluorogenic Substrate

US EPA methods: 

• Method 1103.1 — Escherichia coli (E. coli) in Water by Membrane Filtration Using membrane — Thermotolerant Escherichia coli Agar (mTEC)
• Method 1603 — Escherichia coli (E. coli) in Water by Membrane Filtration Using Modified membrane — Thermotolerant Escherichia coli Agar (Modified mTEC)

US EPA approved method:

• Tecta EC/TC, v. 2.0 — Tecta^™ EC/TC medium and the Tecta^™ Instrument: A Presence/Absence Method for the Simultaneous Detection of Total Coliforms and Escherichia coli (E. coli) in Drinking Water, March 2017, Version 2.0

Heterotrophic plate count

Heterotrophic bacteria (heterotrophic plate count) — technique and reporting units

Note: Certain drinking water systems are required to test for this parameter in accordance with Ontario Regulation 170/03, a ministry order or permission issued under the SDWA.

LaSB method:        

• Method E3408 — The Spread Plate Method for the Enumeration of Aerobic, Heterotrophic Bacteria in Drinking Water

AWWA methods:   

• Method 9215B — Pour Plate Method
• Method 9215C — Spread Plate Method
• Method 9215D — Membrane Filtration Method
• Method 9215E — Enzyme Substrate Method (SimPlate^® IDEXX Laboratories Inc.)

ASTM method:      

• D8516-23 — Standard Test Method for Quantification of Culturable Waterborne Bacteria using a Defined Culture Medium Coated Plate — EasyDisc PCA Method (EasyDisc^® IDEXX Laboratories Inc.)

Clostridium

ASTM method:       

• D5916-96 (2002) — Standard Test Method for Detection and Enumeration of Clostridium perfringens from Water and Extracted Sediments by Membrane Filtration (MF) (withdrawn 2011)

US EPA method:

• ICR Microbial Laboratory Manual Section XI — Membrane Filtration for C. perfringens

ISO method:  

• 14189 Water Quality — Enumeration of Clostridium perfringens Method using Membrane Filtration

Cryptosporidium and Giardia

AWWA method:     

• Method 9711B — Detection of Giardia and Cryptosporidium in Water

US EPA method:   

• Method 1623.1 — Cryptosporidium and Giardia in Water by Filtration/IMS/FA

Chemical parameters

The units shown for the ODWQS are standards listed in Schedule 2 of Ontario Regulation 169/03. The units shown for required RDLs are the units to be used when reporting to the ministry.

Some reference methods may indicate detection limits that do not meet the ministry required RDL for certain elements. To be acceptable to the ministry for the analysis of Ontario drinking water samples, the laboratory must demonstrate that the method used meets the applicable RDL listed.

Volatile organic compounds (VOCs)

LaSB method:        

• E3132 — The Determination of Volatile Organohalides and Hydrocarbons in Water, Leachates and Effluents by Purge and Trap Gas Chromatography (GC) Mass Spectrometry

AWWA methods:

• Method 6200B — Purge and Trap Capillary-Column Gas Chromatographic/Mass Spectrometric Method
• Method 6200C — Purge and Trap Capillary-Column Gas Chromatographic Method
• Method 6232 — Trihalomethanes and Chlorinated Organic Solvents

US EPA methods:

• Method 502.2 — Volatile Organic Compounds in Water by Purge and Trap Capillary Column Gas Chromatography with Photoionization and Electrolytic Conductivity Detectors in Series
• Method 524.2 — Measurement of Purgeable Organic Compounds in Water by Capillary Column Gas Chromatography/Mass Spectrometry
• Method 524.3 — Measurement of Purgeable Organic Compounds in Water by Capillary Column Gas Chromatography/Mass Spectrometry
• Method 524.40 — Measurement of Purgeable Organic Compounds in Water by Gas Chromatography/Mass Spectrometry Using Nitrogen Purge Gas
• SW-846 — Method 5030C, Purge-and-Trap for Aqueous Samples
• SW-846 — Method 5021A, Volatile Organic Compounds in Various Sample Matrices using Equilibrium Headspace Analysis
• SW-846 — Method 8021B, Aromatic and Halogenated Volatiles by Gas Chromatography using Photoionization and/or Electrolytic Conductivity Detectors
• SW-846 — Method 8260D, Volatile Organic Compounds by Gas Chromatography/Mass Spectrometry (GC/MS)

Trace metals

LaSB methods:      

• E3565 — The Determination of Trace Metals in Potable Waters by Inductively Coupled Plasma — Mass Spectrometry (ICP-MS)
• E3473 — The Determination of Trace Metals in Potable Waters by Dynamic Reaction Cell (DRC) Inductively Coupled Plasma — Mass Spectrometry (ICP-MS)

US EPA methods: 

• Method 200.5 — Determination of Trace Elements in Drinking Water by Axially Viewed Inductively Coupled Plasma — Atomic Emission Spectrometry
• Method 200.7 — Determination of Metals and Trace Elements in Water and Wastes by Inductively Coupled Plasma — Atomic Emission Spectrometry
• Method 200.8 — Determination of Trace Elements in Waters and Wastes by Inductively Coupled Plasma — Mass Spectrometry
• Method 200.15 — Determination of Metals and Trace Elements in Water by Ultrasonic Nebulization Inductively Coupled Plasma-Atomic Emission Spectrometry
• SW-846 — Method 6010D, Inductively Coupled Plasma-Optical Emission Spectrometry
• SW-846 — Method 6020B, Inductively Coupled Plasma-Mass Spectrometry

AWWA methods:

• Method 3120B — Metals by Plasma Emission Spectroscopy-Inductively Coupled Plasma (ICP) Method
• Method 3125B — Metals by Inductively Coupled Plasma-Mass Spectrometry (ICP-MS) Method

Mercury

LaSB method:        

• E3526 — The Determination of Mercury in Aqueous Samples by Cold Vapour Atomic Fluorescence Spectrometry (CV-AFS)

US EPA methods: 

• Method 245.1 — Determination of Mercury in Water by Cold Vapor Atomic Absorption Spectrometry — Manual
• Method 245.2 — Mercury (Automated Cold Vapor Technique)
• Method 200.8 — Determination of Trace Elements in Waters and Wastes by  Inductively Coupled Plasma — Mass Spectrometry
• Method 245.7 — Mercury in Water by Cold Vapor Atomic Fluorescence Spectrometry
• Method 1631E — Mercury in Water by Oxidation, Purge and Trap, and Cold Vapor Atomic Fluorescence Spectrometry
• SW-846 — Method 6020B, Inductively Coupled Plasma-Mass Spectrometry
• SW-846 — Method 7472, Mercury in Aqueous Samples and Extracts by Anodic Stripping Voltammetry (ASV)

AWWA method:

• Method 3112B — Metals by Cold-Vapor Atomic Absorption Spectrometry

Nitrite and nitrate

LaSB method:        

• E3364 — The Determination of Ammonia Nitrogen, Nitrite Nitrogen, Nitrite plus Nitrate Nitrogen and Reactive Ortho-Phosphate in Waters by Colourimetry

US EPA methods:

• Method 300.0 — Determination of Inorganic Anions by Ion Chromatography
• Method 300.1 — Determination of Inorganic Anions in Drinking Water by Ion Chromatography
• Method 353.1 — Nitrogen, Nitrate-Nitrite (Colorimetric, Automated, Hydrazine Reduction)
• Method 353.2 — Determination of Nitrate-Nitrite Nitrogen by Automated Colorimetry
• SW-846 — Method 9056A, Determination of Inorganic Anions by Ion Chromatography

AWWA methods:   

• Method 4110B — Determination of Anions by Ion Chromatography with Chemical Suppression of Eluent Conductivity
• Method 4110C — Single-Column Ion Chromatography with Direct Conductivity Detection
• Method 4500-NO₂- B — Colorimetric Method
• Method 4500-NO₃- D — Nitrate Electrode Method
• Method 4500-NO₃- E — Cadmium Reduction Method
• Method 4500-NO₃- F — Automated Cadmium Reduction Method
• Method 4500-NO₃- H — Automated Hydrazine Reduction Method
• Method 4500-NO₃- I — Cadmium Reduction Flow Injection Method

Triazines (N-containing herbicides)

LaSB methods:      

• E3553 — The Determination of Organophosphate and Triazine Pesticides in Water by Direct Aqueous Injection Liquid Chromatography-Tandem Mass Spectrometry (LC-MS/MS) Analysis
• E3435 — The Determination of Triazine Pesticides in Water by Gas Chromatography/Time of Flight — Mass Spectrometry
• OWTRI-E3121 — The Determination of Triazine Herbicides in Water, Soils, Vegetation, and TCLP Leachate by Gas Chromatography-Mass Spectrometry (GC/MS) (2002)

US EPA methods:

• Method 505 — Analysis of Organohalide Pesticides and Commercial Polychlorinated Biphenyl (PCB) Products in Water by Microextraction and Gas Chromatography
• Method 508.1 — Determination of Chlorinated Pesticides, Herbicides and Organohalides by Liquid-Solid Extraction and Electron Capture Gas Chromatography
• Method 523 — Determination of Triazine Pesticides and their Degradates in Drinking Water by Gas Chromatography/Mass Spectrometry (GC/MS)
• Method 525.2 — Determination of Organic Compounds in Drinking Water by Liquid-Solid Extraction and Capillary Column Gas Chromatography/Mass Spectrometry
• Method 525.3 — Determination of Semivolatile Organic Chemicals in Drinking Water by Solid Phase Extraction and Capillary Column Gas Chromatography/Mass Spectrometry (GC/MS)
• Method 527 — Determination of Selected Pesticides and Flame Retardants in Drinking Water by Solid Phase Extraction and Capillary Column Gas Chromatography/Mass Spectrometry (GC/MS)
• Method 536 — Determination of Triazine Pesticides and Their Degradates in Drinking Water by Liquid Chromatography Electrospray Ionization Tandem Mass Spectrometry (LC/ESI-MS/MS)
• Method 551.1 — Determination of Chlorinated Disinfection Byproducts, Chlorinated Solvents and Halogenated Pesticides/Herbicides in Drinking Water by Liquid-Liquid Extraction and Gas Chromatography with Electron-Capture Detection
• SW-846 — Method 3510C, Separatory Funnel Liquid-Liquid Extraction
• SW-846 — Method 3520C, Continuous Liquid-Liquid Extraction
• SW-846 — Method 3535A, Solid-Phase Extraction (SPE)
• SW-846 — Method 8000D, Determinative Chromatographic Separations
• SW-846 — Method 8270E, Semivolatile Organic Compounds by Gas Chromatography/Mass Spectrometry

Carbamates

LaSB method:        

• E3501 — The Determination of Carbamates and Phenyl Ureas in Water by Direct Aqueous Injection Liquid Chromatography-Tandem Mass Spectrometry (LC-MS/MS) Analysis

US EPA methods:

• Method 531.1 — Measurement of N-Methylcarbamoyloximes and N-Methylcarbamates in Water by Direct Aqueous Injection HPLC with Post Column Derivatization [Excluding Triallate]
• Method 531.2 — Measurement of N-Methylcarbamoyloximes and N-Methylcarbamates in Water by Direct Aqueous Injection HPLC with Post Column Derivatization [Excluding Triallate]
• SW-846 — Method 3510C, Separatory Funnel Liquid-Liquid Extraction
• SW-846 — Method 3520C, Continuous Liquid-Liquid Extraction
• SW-846 — Method 3535A, Solid-Phase Extraction (SPE)
• SW-846 — Method 8000D, Determinative Chromatographic Separations
• SW-846 — Method 8318A, N-Methylcarbamates by High Performance Liquid Chromatography (HPLC) [Excluding Triallate]
• SW-846 — Method 8321B, Solvent-Extractable Nonvolatile Compounds by High-Performance Liquid Chromatography/Thermospray/Mass Spectrometry (HPLC/TS/MS) or Ultraviolet Detection

AWWA method:

• Method 6610B — Carbamate Pesticides, High-Performance Liquid Chromatographic Method [Excluding Triallate]

Polychlorinated biphenyls and trifluralin

LaSB methods:

• E3488 — The Determination of Polychlorinated Biphenyl Congeners (PCBs), Organohalogenated Pesticides and Chlorobenzenes (CB) in Water by Two-Dimensional Gas Chromatography Micro-Electron Capture Detection (GCxGC-μECD)
• E3400 — The Determination of Trifluralin in Water by Hexane Microextraction and Gas Chromatography-Mass Spectrometry (GC-MS)

US EPA methods:

• Method 505 — Analysis of Organohalide Pesticides and Commercial Polychlorinated Biphenyl (PCB) Products in Water by Microextraction and Gas Chromatography
• Method 508 — Rev 3.1, Determination of Chlorinated Pesticides in Water by Gas Chromatography with an Electron Capture Detector
• Method 508.1 — Chlorinated Pesticides, Herbicides, and Organohalides by Liquid-Solid Extraction and Electron Capture Gas Chromatography
• Method 525.2 — Determination of Organic Compounds in Drinking Water by Liquid-Solid Extraction and Capillary Column Gas Chromatography/Mass Spectrometry
• Method 525.3 — Determination of Semivolatile Organic Chemicals in Drinking Water by Solid Phase Extraction and Capillary Column Gas Chromatography/Mass Spectrometry (GC/MS)
• Method 551.1 — Determination of Chlorinated Disinfection Byproducts, Chlorinated Solvents and Halogenated Pesticides/Herbicides in Drinking Water by Liquid-Liquid Extraction and Gas Chromatography with an Electron-Capture Detection (Trifluralin only)
• SW-846 — Method 3510C, Separatory Funnel Liquid-Liquid Extraction
• SW-846 — Method 3511, Organic Compounds in Water by Microextraction
• SW-846 — Method 3520C, Continuous Liquid-Liquid Extraction
• SW-846 — Method 3535A, Solid-Phase Extraction (SPE)
• SW-846 — Method 8000D, Determinative Chromatographic Separations
• SW-846 — Method 8081B, Organochlorine Pesticides by Gas Chromatography
• SW-846 — Method 8082A, Polychlorinated Biphenyls (PCBs) by Gas Chromatography
• SW-846 — Method 8270E, Semivolatile Organic Compounds by Gas Chromatography/Mass Spectrometry

AWWA methods:   

• Method 6630C — Organochlorine Pesticides, Liquid-Liquid Extraction Gas Chromatographic Method II
• Method 6410B — Extractable Base/Neutrals and Acids, Liquid-Liquid Extraction Gas Chromatographic/Mass Spectrometric Method

Organophosphorus pesticides

LaSB methods:      

• E3553 — The Determination of Organophosphate and Triazine Pesticides in Water by Direct Aqueous Injection Liquid Chromatography-Tandem Mass Spectrometry (LC-MS/MS) Analysis
• E3502 — The Determination of Organophosphorus Pesticides in Water by Direct Aqueous Injection Liquid Chromatography-Tandem Mass Spectrometry (LC/MS/MS) Analysis

US EPA methods:

• Method 526 — Determination of Selected Semivolatile Organic Compounds in Drinking Water by Solid Phase Extraction and Capillary Column Gas Chromatography/Mass Spectrometry (GC/MS)
• Method 527 — Determination of Selected Pesticides and Flame Retardants in Drinking Water by Solid Phase Extraction and Capillary Column Gas Chromatography/Mass Spectrometry (GC/MS)
• SW-846 — Method 3510C, Separatory Funnel Liquid-Liquid Extraction
• SW-846 — Method 3520C, Continuous Liquid-Liquid Extraction
• SW-846 — Method 3535A, Solid-Phase Extraction (SPE)
• SW-846 — Method 8000D, Determinative Chromatographic Separations
• SW-846 — Method 8270E, Semivolatile Organic Compounds by Gas Chromatography/Mass Spectrometry

Chlorophenols and phenoxy acids

LaSB methods:      

• E3552 — The Determination of Chlorophenols (CPs) and Chloro-Phenoxyacid Herbicides (PAs) in Aqueous Environmental Matrices by Liquid Chromatography — Tandem Mass Spectrometric (LC-MS/MS) Analysis
• E3119 — The Determination of Chlorophenols (CPs) and Phenoxyacid Herbicides (PAs) in Aqueous Environmental Matrices by Gas Chromatography-Mass Spectrometric (GC-MS) Analysis

US EPA methods: 

• Method 515.2 — Determination of Chlorinated Acids in Water using Liquid-Solid Extraction and Gas Chromatography with an Electron Capture Detector
• Method 515.1 — Determination of Chlorinated Acids in Water by Gas Chromatography with an Electron Capture Detector
• Method 515.3 — Determination of Chlorinated Acids in Drinking Water by Liquid-Liquid Extraction, Derivatization and Gas Chromatography with Electron Capture Detection
• Method 515.4 — Determination of Chlorinated Acids in Drinking Water by Liquid-Liquid Microextraction, Derivatization, and Fast Gas Chromatography with Electron Capture Detection
• Method 525.2 — Determination of Organic Compounds in Drinking Water by Liquid-Solid Extraction and Capillary Column Gas Chromatography/Mass Spectrometry
• Method 555 — Rev 1.0. Determination of Chlorinated Acids in Water By High Performance Liquid Chromatography with a Photodiode Array Ultraviolet Detector
• SW-846 — Method 3510C, Separatory Funnel Liquid-Liquid Extraction
• SW-846 — Method 3520C, Continuous Liquid-Liquid Extraction
• SW-846 — Method 3535A, Solid-Phase Extraction (SPE)
• SW-846 — Method 8000D, Determinative Chromatographic Separations
• SW-846 — Method 8041A, Phenols by Gas Chromatography
• SW-846 — Method 8151A, Chlorinated Herbicides by GC using Methylation or Pentafluorobenzylation Derivatization
• SW-846 — Method 8321B, Solvent-Extractable Nonvolatile Compounds by High-Performance Liquid Chromatography/Thermospray/Mass Spectrometry (HPLC/TS/MS) or Ultraviolet Detection
• SW-846 — Method 8270E, Semivolatile Organic Compounds by Gas Chromatography/Mass Spectrometry

AWWA method:     

• Method 6640B — Acidic Herbicide Compounds, Micro Liquid-Liquid Extraction Gas Chromatographic Method

Quaternary ammonium compounds

LaSB methods:      

• E3503 — The Determination of Quaternary Ammonium Pesticides (QUATS) in Water by Direct Aqueous Injection Liquid Chromatography-Tandem Mass Spectrometry (LC-MS/MS) Analysis
• E3417 — The Determination of Diquat and Paraquat in Water and Environmental Matrices by Liquid Chromatography-(Electrospray Ionization) Mass Spectrometry (LC-(ESI)MS) (2010)

US EPA method:   

• Method 549.2 — Determination of Diquat and Paraquat in Drinking Water by Liquid-Solid Extraction and HPLC with Ultraviolet Detection

Urea derivative

LaSB methods:      

• E3501 — The Determination of Carbamates and Phenyl Ureas in Water by Direct Aqueous Injection Liquid Chromatography-Tandem Mass Spectrometry (LC-MS/MS) Analysis
• E3436 — The Determination of Phenyl Ureas in Environmental Matrices by High Performance Liquid Chromatography and Mass Spectrometry-Mass Spectrometry (LC/MS-MS) Analysis (2010)

US EPA methods: 

• Method 532 — Determination of Phenylurea Compounds in Drinking Water by Solid Phase Extraction and High Performance Liquid Chromatography with Ultraviolet Detection
• Method 553 — Determination of Benzidines and Nitrogen-Containing Pesticides in Water by Liquid-Liquid Extraction or Liquid-Solid Extraction and Reverse Phase High Performance Liquid Chromatography/Particle Beam/Mass Spectrometry
• SW-846 — Method 3510C, Separatory Funnel Liquid-Liquid Extraction
• SW-846 — Method 8321B, Solvent-Extractable Nonvolatile Compounds by High-Performance Liquid Chromatography/Thermospray/Mass Spectrometry (HPLC/TS/MS) or Ultraviolet Detection
• SW-846 — Method 8325, Solvent Extractable Nonvolatile Compounds by High Performance Liquid Chromatography/Particle Beam/Mass Spectrometry (HPLC/PB/MS)

Glyphosate

LaSB methods:      

• E3500 — The Determination Glyphosate, Glufosinate and Aminomethyl-Phosphonic Acid in Water by Direct Aqueous Injection Liquid Chromatography-Tandem Mass Spectrometry (LC-MS/MS) Analysis
• GLYMS-E3415 — The Determination of Glyphosate and Aminomethylphosphonic Acid in Environmental Matrices by High Performance Liquid Chromatography — Electrospray Ionization — Mass Spectrometry (HPLC-ESI-MS) (2010)

US EPA method:   

• Method 547 — Determination of Glyphosate in Drinking Water by Direct-Aqueous-Injection HPLC, Post-Column Derivatization, and Fluorescence Detection

AWWA method:     

• Method 6651 — Glyphosate Herbicide by Liquid Chromatographic Post-Column Fluorescence Method.

Fluoride

LaSB method:        

• E3172 — The Determination of Fluoride and Sulphate in Water, Leachates and Effluents by Automated Ion Chromatography

US EPA methods: 

• Method 300.0 — Determination of Inorganic Anions by Ion Chromatography
• Method 300.1 — Determination of Inorganic Anions in Drinking Water by Ion Chromatography
• Method 340.1 — Fluoride, Total (Colorimetric, SPADNS with Bellack Distillation)
• Method 340.2 — Fluoride (Potentiometric, Ion Selective Electrode)
• SW-846 — Method 9056A, Determination of Inorganic Anions by Ion Chromatography

AWWA methods:   

• Method 4500-F- B — Preliminary Distillation Step
• Method 4500-F- C — Ion-Selective Electrode Method
• Method 4500-F- G — Ion-Selective Electrode Flow Injection Analysis
• Method 4110B — Determination of Anions by Ion Chromatography with Chemical Suppression of Eluent Conductivity
• Method 4110C — Determination of Anions by Single-Column Ion Chromatography with Direct Conductivity Detection

Benzo(a)pyrene

LaSB method:        

• E3480 — The Determination of Polycyclic Aromatic Hydrocarbons (PAHs) in Water by Isotope-Dilution Gas Chromatography-Mass Spectrometry (GC-MS) 

US EPA methods: 

• Method 525.2 — Determination of Organic Compounds in Drinking Water by Liquid-Solid Extraction and Capillary Column Gas Chromatography/Mass Spectrometry.
• Method 550 — Determination of Polycyclic Aromatic Hydrocarbons in Drinking Water by Liquid-Liquid Extraction and HPLC with Coupled Ultraviolet and Fluorescence Detection
• Method 550.1 — Determination of Polycyclic Aromatic Hydrocarbons in Drinking Water by Liquid-Solid Extraction and HPLC with Coupled Ultraviolet and Fluorescence Detection
• Method 525.3 — Determination of Semivolatile Organic Chemicals in Drinking Water by Solid Phase Extraction and Capillary Column Gas Chromatography/ Mass Spectrometry (GC/MS)
• SW-846 — Method 8270E — Semivolatile Organic Compounds by Gas Chromatography/Mass Spectrometry

Cyanide

The cyanide standard in Ontario Regulation 169/03 is based on the toxicity of free cyanide. A laboratory may choose to be licensed for total cyanide, free cyanide, or both. The licence must specify either cyanide, total or cyanide, free. Strong acid dissociable is considered to be total cyanide and weak acid dissociable is considered to be free cyanide. In order to provide test results for the purpose of the SDWA the laboratory must be licensed for free cyanide.

LaSB method:        

• E3015 — The Determination of Total and Week Acid Dissociable Cyanide in Environmental Samples by Flow Injection Analysis

US EPA methods: 

• SW-846 — Method 9010C, Total and Amenable Cyanide: Distillation
• SW-846 — Method 9012B, Total and Amenable Cyanide (Automated Colorimetric, with Off-Line Distillation)
• SW-846 — Method 9014, Cyanide in Waters and Extracts Using Titrimetric and Manual Spectrophotometric Procedures [Spectrophotometric method only]

AWWA methods:   

• Method 4500 CN-E — Colorimetric method
• Method 4500 CN-G — Cyanides Amenable to Chlorination after Distillation
• Method 4500 CN-H — Cyanides Amenable to Chlorination without Distillation (Short-Cut Method)

Dioxins and furans — toxic equivalent quantity

LaSB method:        

• E3418 — The Determination of Polychlorinated Dibenzo-p-dioxins, Polychlorinated Dibenzofurans  and Dioxin-like Polychlorinated Biphenyls (DLPCBs) in Water by Gas Chromatography-High Resolution Mass Spectrometry (GC-HRMS).

US EPA method:   

• Method 1613 — Tetra — Through Octa-Chlorinated Dioxins and Furans by Isotope Dilution HRGC/HRMS

Dioxins and furans — calculation of toxic equivalent quantity (TEQ)

There are a total of 210 dioxins and furans. Only 17 are toxic (2,3,7,8-substituted congeners) and their toxicity is normalized to 2378-TCDD (the most toxic). The TEQ is determined (as shown in the following example) by multiplying the concentration of each detected 2,3,7,8-substituted congener by its respective toxic equivalent factor (TEF) to determine its toxic equivalence (TE). The TEFs in the following table are those provided by the World Health Organization (WHO), 2005, as amended from time to time. Laboratories must identify the source of the TEFs used for their calculations. For the 2,3,7,8-substituted congeners that are not detected, half of the detection limit is multiplied by the TEF to determine the TE for that congener. This converts each of the congeners to 2378-TCDD toxic equivalents. The sum of the 17 toxic equivalents (TEs) gives the TEQ for the sample normalized to 2378-TCDD. In this example, the result is 1.65 pg/L, which is well below the 15 pg/L ODWQS.

TEQ = Toxic equivalent quantity = sum of individual TE/congener
EDL = Estimated detection limit
TEF = Toxic equivalent factor (WHO, 2005)
TE/congener = Toxic equivalence / congener

Nitrilotriacetic acid (NTA)

LaSB method:        

• E3406 — The Determination of Nitrilotriacetic Acid (NTA) in Aqueous Samples by Automated Ion Chromatography (IC).

US EPA methods: 

• Method 430.2, NTA (Colorimetric, Automated, Zinc-Zincon)  
• Method 430.1, NTA (Colorimetric, manual, Zinc-Zincon)

Note: Both EPA 430.1 and 430.2 require modifications (calibration concentrations, cell size) to meet the required RDL. These methods also require additional quality controls which are not listed in the method.

N-nitrosodimethylamine

LaSB method:        

• E3388 — The Determination of N-nitrosamines in Water by Gas Chromatography-Tandem Mass Spectrometry (GC-MS/MS)

US EPA method:   

• Method 521 — Determination of Nitrosamines in Drinking Water by Solid Phase Extraction and Capillary Column Gas Chromatography with Large Volume Injection and Chemical Ionization Tandem Mass Spectrometry (MS/MS)

AWWA methods:   

• Method 6450B — Carbonaceous-Resin Solid-Phase Extraction GC/MS Method [Nitrosamines]
• Method 6450C — Micro Liquid-Liquid Extraction GC/MS Method [Nitrosamines]

Bromate, chlorate and chlorite

LaSB method:

• E3462 — Determination of Bromide and Inorganic Oxyhalide Disinfection By-Products by Ion Chromatography Mass Spectrometry

US EPA methods:

• Method 317.0 — Determination of Inorganic Oxyhalide Disinfection By-Products in Drinking Water Using Ion Chromatography with the Addition of a Post column Reagent for Trace Bromate Analysis
• Method 326.0 — Determination of Inorganic Oxyhalide Disinfection By-Products in Drinking Water Using Ion Chromatography Incorporating the Addition of a Suppressor Acidified Post Column Reagent for Trace Bromate Analysis
• Method 300.1 — Determination of Inorganic Anions in Drinking Water by Ion Chromatography
• Method 302.0 — Determination of Bromate in Drinking Water Using Two-Dimensional Ion Chromatography with Suppressed Conductivity Detection (Bromate only)

AWWA method:     

• Method 4110D — Ion Chromatographic Determination of Oxyhalides and Bromide

Microcystin LR

LaSB method:

• E3450 — The Determination of Microcystins and Anatoxins in Water by On-Line SPE Liquid Chromatography — (Electrospray Ionization)-High Resolution Quadrupole Time of Flight Mass Spectrometry [On-Line SPE-LC-(ESI)-HRQTFMS]

Screening tests for total microcystins

LaSB method:    

• E3469 — The Screening and Semi-Quantitative Analysis of Water Samples for Microcystins by Enzyme-Linked Immunosorbent Assay (ELISA)

US EPA methods:

• Method 546 — Determination of Total Microcystins and Nodularins in Drinking Water and Ambient Water by Adda Enzyme-Linked Immunosorbent Assay

Haloacetic acids

The ODWQS is expressed as a running annual average of quarterly results. The RDL applies to the sum of MCAA, DCAA, TCAA, MBAA and DBAA to determine Haloacetic Acids (HAA5).

LaSB method:        

• E3478 — The Determination of Haloacetic Acids (HAAs) and 2,2-Dichloropropionic Acid (2,2-DCPA) in Raw and Treated Water by Direct Aqueous Injection Liquid Chromatography-Tandem Mass Spectrometry (LC-MS/MS)

US EPA methods: 

• Method 552 — Determination of Haloacetic Acids in Drinking Water by Liquid-Liquid Extraction, Derivatization, and Gas Chromatography with Electron Capture Detection (GC/ECD)
• Method 552.1 — Determination of Haloacetic Acids and Dalapon in Drinking Water by Ion-Exchange Liquid-Solid Extraction and Gas Chromatography with an Electron Capture Detector
• Method 552.2 — Determination of Haloacetic Acids and Dalapon in Drinking Water by Liquid-Liquid Extraction, Derivatization and Gas Chromatography with an Electron Capture Detector
• Method 552.3 — Determination of Haloacetic Acids and Dalapon in Drinking Water by Liquid-Liquid Microextraction, Derivatization, and Gas chromatography with Electron Capture Detection
• Method 557 — Determination of Haloacetic Acids, Bromate, and Dalapon in Drinking Water by Ion Chromatography Electrospray Ionization Tandem Mass Spectrometry (IC-ESI-MS/MS)

AWWA method:     

• Method 6251B — Micro Liquid-Liquid Extraction Gas Chromatographic Method

Sodium

LaSB methods:      

• E3171 — The Determination of Cations in Aqueous Samples by Atomic Absorption Spectrophotometry (AAS)
• E3497 — The Determination of Metals in Water by Inductively Coupled Plasma-Optical Emission Spectroscopy (ICP-OES) Using an Apex Desolvation System

US EPA methods: 

• Method 200.7 — Determination of Metals and Trace Elements in Water and Wastes by Inductively Coupled Plasma-Atomic Emission Spectrometry
• SW-846 — Method 6010C, Inductively Coupled Plasma — Atomic Emission Spectrometry
• SW-846 — Method 7000B, Flame Atomic Absorption Spectrophotometry

AWWA methods:   

• Method 3111 B — Metals by Flame Atomic Absorption Spectrometry — Direct Air-Acetylene Flame Method
• Method 3500-Na B — Sodium by Flame Emission Photometric Method
• Method 3120 B — Metals by Plasma Emission Spectroscopy — Inductively Coupled Plasma (ICP) Method

ASTM method:       

• Method D6919-17 — Standard Test Method for Determination of Dissolved Alkali and Alkaline Earth Cations and Ammonium in Water and Wastewater by Ion Chromatography Method

For more information

If you have questions or would like more information about drinking water:

• The ministry’s Laboratory Licensing and Compliance Program llcp@ontario.ca
• Drinking water

Appendix A Licence application checklist

• Licence Amendment Application Form
• Current Scope of Accreditation
• Method and any relevant supporting procedures
• Successful Proficiency Test Results
• Method Validation Summary (Raw validation data does not need to be submitted with the application, but must be available for ministry review upon request)

Accepted Reference Method

• Validation summary of the MDL

Alternate Reference/In-house Methods

Full method validation summary including:

• Confirmation of Identity
• Selectivity
• Working and Linear Ranges
• Accuracy and Precision
• Ruggedness
• Sample/Extract Hold Time
• Copy of the alternate reference method and relevant supporting references

Appendix B Modifications to methods after licensing

In cases where a laboratory is planning method changes after a method has been licensed, it must determine the impact of such changes. Where the changes are found to affect the original validation, the laboratory must perform a new method validation. It must receive a licence amendment application approval from the ministry prior to implementing the modified method. The laboratory testing licence terms and conditions provide details on changes that are permitted and what changes require licence amendment approval by the ministry prior to implementation.

Any of the following changes require a laboratory to submit a licence amendment application and receive approval by the ministry prior to implementation:

• changes to sample preservation requirements
• increasing maximum hold time requirements
• decreasing minimum sample volume requirements
• changes in either the front end or determinative technique
• changes that remove or reduce method Quality Control (QC) requirements
• any change inconsistent with the analytical technique described in the laboratory’s licence or the applicable reference method
• any change specifically prohibited by the applicable reference method
• changes to the reference method except for reference method revision updates
• changes to microbiology media formulation and incubation conditions
• changes to any critical components of the analysis that are integral to the technique

The laboratory is permitted to make changes that optimize analytical conditions provided that the changes remain suitable and consistent with the reference method and the changes do not negatively impact method performance. All revisions must be documented in the method and must be done in accordance with the terms and conditions in the laboratory’s drinking water testing licence.

Appendix C Ministry sample collection and handling requirements

For this appendix, cool means storage at the laboratory at any temperature range between > 0°C (above freezing point of water) and ≤ 8°C. For example, 5 ± 3°C; 4 ± 3 °C or > 0°C (above freezing point of water) to ≤ 6°C would all be acceptable temperature ranges.

Hold times are based on the reference methods at the time of publication of this Protocol  Refer directly to the current revision of the reference methods for the most current information.