2015-16 Certified Reference Material Inter-Laboratory Study

August 15, 2017

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Any comments, questions, or suggestions regarding the content of this document may be

directed to:

Environmental Monitoring and Science Division

Alberta Environment and Parks

9888 Jasper Ave NW

Edmonton, Alberta T5K 2J6

Tel: 780-229-7200

Toll Free: 1-844-323-6372

Fax: 780-702-0169

Email: EMSD-Info@gov.ab.ca

Media Inquiries: AEP.Mediainquiries@gov.ab.ca

Website: http://environmentalmonitoring.alberta.ca/

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Table of Contents 1.0 Introduction ............................................................................................................................................. 3

2.0 Methodology ........................................................................................................................................... 4

2.1 Certified Reference Materials (CRMs) ............................................................................................... 4

2.2 Sample Handling ................................................................................................................................. 4

2.3 Sample Analysis .................................................................................................................................. 5

2.4 Data Analysis ...................................................................................................................................... 5

3.0 Results and Discussion ............................................................................................................................5

3.1 Certified reference materials ............................................................................................................... 6

3.1.1 Trace Metals ................................................................................................................................ 6

3.1.2 Major ions and nutrients ............................................................................................................. 7

3.1.3 Total phosphorus ......................................................................................................................... 9

4.0 Results from Commercial Laboratory Internal Investigations .............................................................. 10

4.1 Lab C investiggation ......................................................................................................................... 10

4.2 Lab A investigation ........................................................................................................................... 11

5.0 Summary ............................................................................................................................................... 12

Appendix ..................................................................................................................................................... 13

Appendix A: CRM Certificates .............................................................................................................. 13

Appendix B: VMV codes used by the three laboratories in the study. ................................................. 147

References ................................................................................................................................................. 255

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1.0 Introduction

The purpose of a certified reference material (CRM) study is to ensure confidence and

assurance in the measurement processes of the laboratories being examined. In general, for a

typical CRM comparison, materials with known specifications are sent to several laboratories for

analyses. The results are used to compare the performance of the laboratories both to the known

value of the material and also to each other [1].

The use of CRMs for inter-laboratory comparisons is an important component of the

quality assurance (QA) system [2]. In particular, CRMs are useful for assessing the accuracy and

precision of the laboratories providing service [3]. Since the CRMs submitted to the laboratories

have certified concentrations, the results obtained from the labs can be directly compared to the

certified values, providing confidence that the laboratory and analytical method can accurately

measure the parameters of interest. Also, since the laboratories may be using equivalent but

slightly different analytical methods and/or instrumentation for the analysis, the results can be

used to assess if the methods between labs are comparable [4]. Furthermore, when CRMs are

submitted in triplicates, this provides a way to assess the precision of the laboratory and

methods, by evaluating the percent relative standard deviation (%RSD) of the triplicates [3].

As discussed in the “Guidelines for Quality Assurance and Quality Control in Surface

Water Quality Programs in Alberta” document prepared by Patricia Mitchell in 2006, the %RSD

for triplicates in general should not exceed 18% and the percent error for duplicates should not

exceed 25% [5]. This is an Alberta and BC SWQ-specific recommendation. For more parameter

specific guidance, the draft Measurement Qualities Objectives document developed in 2014 can

be used [6]. In the literature, precision measurements for intra-laboratory and inter-laboratory

comparison have been reported to range from 13 to 22% and 8.4 to 29%, respectively [7]. Other

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studies for inter-laboratory comparisons have reported an RSD% range of 25 to 50% for standard

samples [6].

In 2015, CRMs for trace metals, ions and nutrients and total phosphorus were sent to

three laboratories in Alberta as part of the quality assurance (QA) program to assess the

performance of the commercial laboratories that generate data for the Alberta surface water

monitoring programs. This report summarizes these results and makes recommendations for the

SWQ monitoring program and future CRM studies.

2.0 Methodology

2.1 Certified Reference Materials (CRMs)

All CRMs were purchased from Environment and Climate Change Canada (ECCC)

(Appendix A). For trace metals, the CRM TM-26.4 was obtained from a filtered and diluted

sample from Lake Ontario, preserved with 0.2% nitric acid, while the nutrients and ions sample

was obtained from a river in Ontario.

ECCC certifies each parameter to a specific concentration +/- a certain interval. This

interval represents the 95% confidence interval for each individually measured parameter and is

the 2R-STD (robust standard deviation). The R-STD is calculated using the Algorithm A

technique described in Annex C of the ISO/IEC 13528 standard.

2.2 Sample Handling

Triplicate samples for trace metals, ions and nutrients, and total phosphorus were

purchased from ECCC and stored in the McIntyre Centre (Water) cold room upon receipt. The

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sample bottle labels were replaced with AEP-specific labels. The samples were shipped

unopened and in coolers to the three labs: Lab A, Lab B and Lab C.

2.3 Sample Analysis

Lists of the methods and applicable VMV codes used by the three laboratories can be

found in Appendix B.

2.4 Data Analysis

Laboratory results were averaged and compared to the certified values provided by the

CRM supplier. Acceptable ranges for trace metals, ions and nutrients, and total phosphorus were

within two standard deviations of the certified value. To evaluate precision, the percent relative

standard deviation (%RSD) was calculated for each parameter using Equation 1:

%RSD = s/mean*100 Eq. 1

where s is the standard deviation of the mean.

For comparison purposes, all results were reported in µg/L for the trace metals results and

in mg/L for the major ions, nutrients and total phosphorus results. This required unit conversions

for the data from some labs.

3. Results and Discussion

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3.1 Certified reference materials

3.1.1Trace Metals

The trace metals results obtained from the three laboratories are presented in Table 1. The

triplicate values were averaged and the %RSD for each lab was determined. Values highlighted

in yellow represent data that were below the method detection limit (MDL) and values

highlighted in pink represent data that are outside two standard deviation of the certified value

obtained from the CRM supplier (ECCC).

Of the 29 metals that were present in the CRM, Lab B reported detection above MDL for

all the parameters, with the exception of gallium, which was not reported by any lab and is not

currently included in the surface water monitoring program, but was a constituent of the CRM.

Lab A and Lab C reported 26 and 22 parameters above detection, respectively.

Lab B reported all parameters within the certified range, while Lab A reported one value

outside of the two standard deviation range for zinc. Lab C reported eleven metals outside the

range of the certified value including arsenic, chromium, cobalt, copper, lead, nickel, silver,

thallium, titanium, uranium and vanadium. Lab C consistently returned results higher than the

certified range.

All %RSD were under 18%.

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Table 1: Results and statistical analyses on the results obtained for trace metals

Results and Statistical Analyses for Trace Metals (TM-26.4, lot 1115)

Parameter

Labs (ug/L)

Lab A RSD% Lab B RSD% Lab C RSD% Certified

value ±2σ

Aluminum, Total 73.9 0.3 73.3 3.3 78.0 1.3 74.0 7.0

Antimony, Total 2.7 1.1 2.9 2.1 3.0 5.0 2.80 0.32

Arsenic, Total 8.1 1.5 8.8 0.9 9.6 4.0 8.70 0.85

Barium, Total 26.3 0.6 27.3 2.1 26.0 0 26.0 1.9

Beryllium, Total 3.3 2.1 3.4 1.5 3.8 2.6 3.47 0.46

Bismuth, Total 3.0 1.5 2.7 0.6

2.97 1.02

Boron, Total 46.1 1.7 43.7 1.3 47.0 2.1 46.0 5.9

Cadmium, Total 6.7 1.1 7.2 0.3

7.10 0.59

Chromium, Total 12.4 1.2 11.8 1.0 14.7 3.9 12.4 1.0

Cobalt, Total 7.7 0.0 8.1 0.8 9.2 1.7 8.11 0.6

Copper, Total 14.0 1.5 14.9 1.4 16.7 3.5 15.0 1.3

Gallium, Total

5.49 0.37

Iron, Total 22.2 2.7 19.7 2.9 <60.0 0.0 21.3 3.4

Lead, Total 10.2 0.6 10.3 1.1 11.7 4.9 10.4 1.0

Lithium, Total 4.9 0.7 4.9 1.2 <20.0 0 4.96 0.59

Manganese, Total 10.2 0.6 10.7 0.5 10.7 5.4 10.9 0.9

Molybdenum, Total 7.5 0.9 6.9 2.1 8.7 2.4 7.70 1.06

Nickel, Total 10.7 0.5 11.2 1.0 12.7 4.6 11.2 1.0

Rubidium, Total

10.4 1.0

10.6 0.8

Selenium, Total 5.2 2.5 5.3 1.4 5.7 2.7 5.40 0.87

Silver, Total 6.5 0.4 7.3 2.4 7.5 2.8 6.85 0.65

Strontium,Total 105.3 0.5 106.3 1.4 103.3 5.6 106 7

Thallium, Total 5.3 1.7 5.3 1.0 5.8 1.0 5.22 0.45

Tin, Total 5.8 0.8 5.4 1.5 6.4 1.6 5.78 0.63

Titanium, Total 6.1 0.6 5.7 3.2 7.0 13.6 6.15 0.78

Tungsten, Total

5.8 2.4

6.52 0.83

Uranium, Total 7.4 0.3 7.5 1.7 8.7 2.4 7.40 0.57

Vanadium, Total 12.1 0.5 12.4 0.9 14.7 3.9 12.6 1.2

Zinc, Total 33.2 2.3 38.1 2.1 41.3 2.8 38.0 3.9

Yellow highlighting indicates all three samples are below the detection limit. Pink highlighting indicates

the mean value is not within 2 standard deviations.

3.1.2 Major ions and nutrients

The major ions and nutrients results obtained from the three laboratories are presented in

Table 2. Of the 18 certified parameters, Lab A, Lab B and Lab C reported 16, 15 and 16

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parameters, respectively. None of the labs reported boron or total nitrogen values, and both Lab

A and Lab B did not report a value for dissolved inorganic carbon. Lab B did not report a result

for silica. Nitrate and nitrite from Lab C was accidentally omitted from the Chain of Custody (or

analytical request). Lab A reported five values outside the certified range: for color, dissolved

organic carbon, nitrate and nitrite, silica and total Kjeldahl nitrogen (TKN). Lab B reported two

parameters outside the certified range (dissolved magnesium and dissolved potassium). Lab C

also reported two parameters outside the certified range (alkalinity and TKN).

The %RSD for the major ions and nutrients at Lab B and Lab C were below 16% for all

parameters. The precision of Lab A for the major ions and nutrients were below 20% on all

parameters with the exception of DOC, ion balance and iron

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Table 2: Results and statistical analyses on the major ions and nutrients

Results and Statistical Analyses on the Major Ions and Nutrients (ION-96.4 River Water, lot 0815)

Parameter Units

Labs

Lab A RSD% Lab B RSD% Lab C RSD% Certified

value ±2σ

Alkalinity, Total (as CaCO3) mg/L 244.7 0.2 248.0 0.4 296.7 15.6 245.0 11.0

Boron mg/L

0.0 0.0

Calcium, Dissolved mg/L 101.6 8.9 91.8 4.3 94.0 1.8 95.5 7.6

Chloride (Cl) mg/L 76.1 1.0 75.6 0.4 77.3 1.5 74.0 3.7

Color, True C.U. 9.3 6.2 15.8 3.9 13.0 15.4 14.0 3.8

Conductivity uS/cm 821.0 0.2 836.7 0.1 820.0 0.0 829.0 28.0

Dissolved Inorganic Carbon mg/L

57.0 0.0 57.1 6.3

Dissolved Organic Carbon mg/L 10.1 56.2 5.5 4.6 4.5 3.4 4.7 0.7

Fluoride (F) mg/L 0.1 0.0 0.1 3.0 0.1 4.6 0.1 0.0

Hardness (as CaCO3) mg/L 365.3 5.6 325.3 3.4 336.7 1.7 343.0 26.0

Magnesium, Dissolved mg/L 27.1 2.0 23.3 1.3 25.7 4.5 25.5 2.0

Nitrate and Nitrite (as N) mg/L 2.5 1.4 2.8 0.2 * 2.9 0.3

pH pH 8.5 0.2 8.5 0.1 8.4 0.6 8.4 0.2

Potassium, Dissolved mg/L 3.6 2.2 3.9 0.6 3.3 4.6 3.5 0.3

Silica mg/L 0.36 7.5

0.25 10.5 0.29 0.04

Sodium, Dissolved mg/L 43.4 0.5 40.9 1.2 41.7 9.1 43.2 4.5

Sulfate (SO4) mg/L 77.0 1.3 77.6 0.4 76.7 1.5 76.3 4.1

TKN (Total Kjeldahl Nitrogen) mg/L 0.77 13.83 0.52 1.64 0.64 5.41 0.46 0.17

Total Nitrogen mg/L

3.2 1.7

Bicarbonate (HCO3) mg/L 275.0 0.4 285.3 0.7 336.7 15.0

Carbonate (CO3) mg/L 11.7 4.9 8.6 8.8 14.2 83.8

Ion Balance % 3.5 57.9 93.9 2.6 90.3 12.1

TDS (Calculated) mg/L

474.7 0.7

Total Dissolved Solids mg/L 494.3 2.0

496.7 5.8

Total Inorganic Carbon mg/L

57.0 0.0

Iron, Dissolved mg/L 6.95 21.8

<0.060

Manganese, Dissolved mg/L

<0.0040

Alkalinity (pH 8.3) mg/L 9.7 6.0

Yellow highlighting indicates all three samples are below the detection limit. Pink highlighting indicates

the mean value is not within 2 standard deviations. Blue highlighting indicates %RSD > 18%.

3.1.3 Total phosphorus

The total phosphorus results obtained from the three laboratories are presented in Table 3.

Lab B performed within the acceptance criteria for all three concentrations (high, medium and

low). Lab A returned values higher than the certified range for the medium and high

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concentration sample, while Lab C returned values below the certified range for the medium and

low TP concentrations. Re-running the total phosphorus samples at Lab A and Lab C did not

significantly change the results.

The %RSD for TP by Lab B, Lab C and Lab A were below 7% for all concentrations.

Table 3: Results and statistical analyses for total phosphorus

Labs (mg/L)

Lab A RSD% Lab B RSD% Lab C RSD% Certified value

TP106-7 0.021 5.4 0.016 0.7 0.013 4.3 0.014-0.021

TP107-1 0.072 6.8 0.061 0.5 0.056 1.0 0.059-0.069

TP107-8 0.119 0.5 0.104 1.7 0.102 0.0 0.102-0.118

Pink highlighting indicates the mean value is not within 2 standard deviations.

4.0 Results from Commercial Laboratory Internal Investigations

The results of the 2015 CRM study were communicated to Lab A and Lab C individually.

Both labs launched internal quality assurance investigations.

4.1 Lab C investigation

Lab C reran all the CRM samples (including re-digestions where appropriate) that were

still within hold times and did not find any significantly different results. As part of the

investigation, all laboratory quality control samples (blanks and spikes) were reviewed and were

found to be within the laboratory’s data quality objectives. Furthermore, the laboratory has

passed all CALA proficiency testing samples.

Rather, discussions with Lab C’s Quality Systems Specialist have suggested the issue

may be how the certified range of the CRMs was determined. In many cases, the CRMs are

gathered from previous CALA PTs and the passing range for the PTs are not determined from

fixed ranges, but from the mean and standard deviation of the participating laboratories [ref

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CALA]. This method of determining the CRM certified range may be subject to bias from the

true value. For example, inaccurately low consensus values may be obtained if multiple labs did

a partial digestion instead of a complete digestion.

In the US, environmental PT is standardized through the NELAC Institute and fixed

limits are used for the PT studies. In Canada, CALA is planning to switch to a fix limit system of

± 15% for the upcoming scheduled CALA PT in 2016 for metals. If the US fixed limit system

was applied to the CRMs in this study, Lab C would have passed all the total metals parameters

with the exception of two parameters.

4.2 Lab A investigation

Lab A reviewed all laboratory quality control samples (blanks and spikes) and everything

was found to be within the laboratory’s data quality objectives. Lab A has passed all CALA

proficiency testing samples. Furthermore, Lab A purchased equivalent CRMs from ECCC and

all parameters were found to be within specified criteria with the exception of silica. Thus, Lab A

attributes the non-compliance parameters to be among the one-in-twenty statistically valid

measurements outside the 95% confidence interval. This means that 95% of the time the

concentration intervals listed would contain the true value; however, 5% of the time the true

value may be outside the concentration interval range. Lab A suggested that their measurements

were in the 5% of valid measurements outside the 95% confidence interval.

However, due to financial reasons, Lab A retired the Technicon units and began

subcontracting chemical oxygen demand, ammonia, total phosphorus, dissolved phosphorus,

Kjeldahl nitrogen, dissolved organic carbon to Lab B beginning on August 8, 2016 and

continuing until further notice.

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5.0 Summary

Certified reference materials were sent to three laboratories to determine their accuracy

and precision as part of the QA assessment program. The results from the lab were assessed by

determining if they exceeded the acceptance limits, as prescribed by the supplier (in this case

ECCC), and also by reviewing the labs’ %RSD for each parameter (to assess precision).

In general, for total metals, both Lab A and Lab B performed well, meeting the CRM

acceptance criteria in most cases. For the major ions and nutrients, both Lab B and Lab C

performed well, meeting the highest number of the CRM parameters. For total phosphorus, Lab

B performed the best, meeting all three acceptance values for high, medium and low level

phosphorus samples.

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Appendix

Appendix A: CRM Certificates

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Appendix B: VMV codes

Table B1: VMV codes for total metals analyses

Parameter Lab A

VMV codes Narratives

Aluminum 103999 Elements, Total Recoverable by ICP-MS: Samples preserved and analysed

Antimony 80043 Elements, Total Recoverable by ICP-MS: Samples preserved and analysed

Arsenic 80020 Elements, Total Recoverable by ICP-MS: Samples preserved and analysed

Barium 80022 Elements, Total Recoverable by ICP-MS: Samples preserved and analysed

Beryllium 80023 Elements, Total Recoverable by ICP-MS: Samples preserved and analysed

Bismuth 80024 Elements, Total Recoverable by ICP-MS: Samples preserved and analysed

Boron 80021 Elements, Total Recoverable by ICP-MS: Samples preserved and analysed

Cadmium 80026 Elements, Total Recoverable by ICP-MS: Samples preserved and analysed

Calcium 80025 Elements, Total Recoverable by ICP-MS: Samples preserved and analysed

Chlorine 80027 Elements, Total Recoverable by ICP-MS: Samples preserved and analysed

Chromium 80029 Elements, Total Recoverable by ICP-MS: Samples preserved and analysed

Cobalt 80028 Elements, Total Recoverable by ICP-MS: Samples preserved and analysed

Copper 80030 Elements, Total Recoverable by ICP-MS: Samples preserved and analysed

Iron 80031 Elements, Total Recoverable by ICP-MS: Samples preserved and analysed

Lead 80041 Elements, Total Recoverable by ICP-MS: Samples preserved and analysed

Lithium 80034 Elements, Total Recoverable by ICP-MS: Samples preserved and analysed

Magnesium not reported

Manganese 80036 Elements, Total Recoverable by ICP-MS: Samples preserved and analysed

Molybdenum 80037 Elements, Total Recoverable by ICP-MS: Samples preserved and analysed

Nickel 80039 Elements, Total Recoverable by ICP-MS: Samples preserved and analysed

Phosphorus not reported

Potassium not reported

Selenium 80044 Elements, Total Recoverable by ICP-MS: Samples preserved and analysed

Silicon not reported

Silver 103998 Elements, Total Recoverable by ICP-MS: Samples preserved and analysed

Sodium not reported

Strontium 80047 Elements, Total Recoverable by ICP-MS: Samples preserved and analysed

Sulfur not reported

Thallium 80053 Elements, Total Recoverable by ICP-MS: Samples preserved and analysed

Thorium 80048 Elements, Total Recoverable by ICP-MS: Samples preserved and analysed

Tin 80046 Elements, Total Recoverable by ICP-MS: Samples preserved and analysed

Titanium 80049 Elements, Total Recoverable by ICP-MS: Samples preserved and analysed

Uranium 80054 Elements, Total Recoverable by ICP-MS: Samples preserved and analysed

Vanadium 80055 Elements, Total Recoverable by ICP-MS: Samples preserved and analysed

Zinc 80056 Elements, Total Recoverable by ICP-MS: Samples preserved and analysed

Parameter Lab C

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VMV codes Narratives

Aluminum 101996 Metals, Total: Nitric Acid Digestion Of Sample And Analyzed By ICP-MS

Antimony 102011 Metals, Total: Nitric Acid Digestion Of Sample And Analyzed By ICP-MS

Arsenic 101993 Metals, Total: Nitric Acid Digestion Of Sample And Analyzed By ICP-MS

Barium 100753 Metals, Total: Nitric Acid Digestion Of Sample And Analyzed By ICP-MS

Beryllium 101997 Metals, Total: Nitric Acid Digestion Of Sample And Analyzed By ICP-MS

Bismuth not reported

Boron 100773 Metals, Total: Nitric Acid Digestion Of Sample And Analyzed By ICP-MS

Cadmium 100852 Metals, Total: Nitric Acid Digestion Of Sample And Analyzed By ICP-MS

Calcium 20005 Plasma Emission Spectroscopy

Chlorine not reported

Chromium 102010 Metals, Total: Nitric Acid Digestion Of Sample And Analyzed By ICP-MS

Cobalt 102005 Metals, Total: Nitric Acid Digestion Of Sample And Analyzed By ICP-MS

Copper 101999 Metals, Total: Nitric Acid Digestion Of Sample And Analyzed By ICP-MS

Iron 100776 Metals, Total: Nitric Acid Digestion Of Sample And Analyzed By ICP-MS

Lead 102001 Metals, Total: Nitric Acid Digestion Of Sample And Analyzed By ICP-MS

Lithium 100768 Metals, Total: Nitric Acid Digestion Of Sample And Analyzed By ICP-MS

Magnesium 12005 Plasma Emission Spectroscopy

Manganese 100775 Metals, Total: Nitric Acid Digestion Of Sample And Analyzed By ICP-MS

Molybdenum 101995 Metals, Total: Nitric Acid Digestion Of Sample And Analyzed By ICP-MS

Nickel 102006 Metals, Total: Nitric Acid Digestion Of Sample And Analyzed By ICP-MS

Phosphorus 100754 Metals, Total: Nitric Acid Digestion Of Sample And Analyzed By ICP-MS

Potassium 100774 Metals, Total: Nitric Acid Digestion Of Sample And Analyzed By ICP-MS

Selenium 102009 Metals, Total: Nitric Acid Digestion Of Sample And Analyzed By ICP-MS

Silicon 100757 Metals, Total: Nitric Acid Digestion Of Sample And Analyzed By ICP-MS

Silver 102000 Metals, Total: Nitric Acid Digestion Of Sample And Analyzed By ICP-MS

Sodium 11005 Plasma Emission Spectroscopy

Strontium 100752 Metals, Total: Nitric Acid Digestion Of Sample And Analyzed By ICP-MS

Sulfur 100755 Metals, Total: Nitric Acid Digestion Of Sample And Analyzed By ICP-MS

Thallium 102015 Metals, Total: Nitric Acid Digestion Of Sample And Analyzed By ICP-MS

Thorium not reported

Tin 102012 Metals, Total: Nitric Acid Digestion Of Sample And Analyzed By ICP-MS

Titanium 102003 Metals, Total: Nitric Acid Digestion Of Sample And Analyzed By ICP-MS

Uranium 101990 Metals, Total: Nitric Acid Digestion Of Sample And Analyzed By ICP-MS

Vanadium 101994 Metals, Total: Nitric Acid Digestion Of Sample And Analyzed By ICP-MS

Zinc 101998 Metals, Total: Nitric Acid Digestion Of Sample And Analyzed By ICP-MS

Parameters Lab B

VMV codes Narratives

Aluminum n/a Metals in Water by CRC ICP-MS (No Digest)

Antimony n/a Metals in Water by CRC ICP-MS (No Digest)

Arsenic n/a Metals in Water by CRC ICP-MS (No Digest)

Barium n/a Metals in Water by CRC ICP-MS (No Digest)

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Beryllium n/a Metals in Water by CRC ICP-MS (No Digest)

Bismuth not reported

Boron n/a Metals in Water by CRC ICP-MS (No Digest)

Cadmium n/a Metals in Water by CRC ICP-MS (No Digest)

Calcium n/a Metals in Water by CRC ICP-MS (No Digest)

Chlorine not reported

Chromium n/a Metals in Water by CRC ICP-MS (No Digest)

Cobalt n/a Metals in Water by CRC ICP-MS (No Digest)

Copper n/a Metals in Water by CRC ICP-MS (No Digest)

Iron n/a Metals in Water by CRC ICP-MS (No Digest)

Lead n/a Metals in Water by CRC ICP-MS (No Digest)

Lithium n/a Metals in Water by CRC ICP-MS (No Digest)

Magnesium n/a Metals in Water by CRC ICP-MS (No Digest)

Manganese n/a Metals in Water by CRC ICP-MS (No Digest)

Molybdenum n/a Metals in Water by CRC ICP-MS (No Digest)

Nickel n/a Metals in Water by CRC ICP-MS (No Digest)

Phosphorus not reported

Potassium n/a Metals in Water by CRC ICP-MS (No Digest)

Selenium n/a Metals in Water by CRC ICP-MS (No Digest)

Silicon not reported

Silver n/a Metals in Water by CRC ICP-MS (No Digest)

Sodium n/a Metals in Water by CRC ICP-MS (No Digest)

Strontium n/a Metals in Water by CRC ICP-MS (No Digest)

Sulfur not reported

Thallium not reported

Thorium not reported

Tin not reported

Titanium not reported

Uranium n/a Metals in Water by CRC ICP-MS (No Digest)

Vanadium n/a Metals in Water by CRC ICP-MS (No Digest)

Zinc n/a Metals in Water by CRC ICP-MS (No Digest)

Table B2: VMV codes for dissolved metals analyses

Parameter Lab A

VMV codes Narratives

Aluminum 103927 Dissolved Elements by ICP-MS: Samples filtered and then analysed

Antimony 103951 Dissolved Elements by ICP-MS: Samples filtered and then analysed

Arsenic 103928 Dissolved Elements by ICP-MS: Samples filtered and then analysed

Barium 103930 Dissolved Elements by ICP-MS: Samples filtered and then analysed

Beryllium 103931 Dissolved Elements by ICP-MS: Samples filtered and then analysed

Bismuth 103932 Dissolved Elements by ICP-MS: Samples filtered and then analysed

Boron 103929 Dissolved Elements by ICP-MS: Samples filtered and then analysed

Cadmium 103934 Dissolved Elements by ICP-MS: Samples filtered and then analysed

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Calcium 103933 Dissolved Elements by ICP-MS: Samples filtered and then analysed

Chlorine 103935 Dissolved Elements by ICP-MS: Samples filtered and then analysed

Chromium 103937 Dissolved Elements by ICP-MS: Samples filtered and then analysed

Cobalt 103936 Dissolved Elements by ICP-MS: Samples filtered and then analysed

Copper 103938 Dissolved Elements by ICP-MS: Samples filtered and then analysed

Iron 103939 Dissolved Elements by ICP-MS: Samples filtered and then analysed

Lead 103949 Dissolved Elements by ICP-MS: Samples filtered and then analysed

Lithium 103942 Dissolved Elements by ICP-MS: Samples filtered and then analysed

Magnesium not reported

Manganese 103944 Dissolved Elements by ICP-MS: Samples filtered and then analysed

Molybdenum 103945 Dissolved Elements by ICP-MS: Samples filtered and then analysed

Nickel 103947 Dissolved Elements by ICP-MS: Samples filtered and then analysed

Phosphorus not reported

Potassium not reported

Selenium 103952 Dissolved Elements by ICP-MS: Samples filtered and then analysed

Silicon not reported

Silver 103926 Dissolved Elements by ICP-MS: Samples filtered and then analysed

Sodium not reported

Strontium 103955 Dissolved Elements by ICP-MS: Samples filtered and then analysed

Sulfur not reported

Thallium 103958 Dissolved Elements by ICP-MS: Samples filtered and then analysed

Thorium 103956 Dissolved Elements by ICP-MS: Samples filtered and then analysed

Tin 103954 Dissolved Elements by ICP-MS: Samples filtered and then analysed

Titanium 103957 Dissolved Elements by ICP-MS: Samples filtered and then analysed

Uranium 103959 Dissolved Elements by ICP-MS: Samples filtered and then analysed

Vanadium 103960 Dissolved Elements by ICP-MS: Samples filtered and then analysed

Zinc 103961 Dissolved Elements by ICP-MS: Samples filtered and then analysed

Parameter Lab C

VMV codes Narratives

Aluminum 102024 Metals, Dissolved: Filtered And Preserved Samples Analyzed By ICP-MS

Antimony 102039 Metals, Dissolved: Filtered And Preserved Samples Analyzed By ICP-MS

Arsenic 102021 Metals, Dissolved: Filtered And Preserved Samples Analyzed By ICP-MS

Barium 100782 Metals, Dissolved: Filtered And Preserved Samples Analyzed By ICP-MS

Beryllium 102025 Metals, Dissolved: Filtered And Preserved Samples Analyzed By ICP-MS

Bismuth not reported

Boron 100802 Metals, Dissolved: Filtered And Preserved Samples Analyzed By ICP-MS

Cadmium 100880 Metals, Dissolved: Filtered And Preserved Samples Analyzed By ICP-MS

Calcium 20111 Inductively Coupled Argon Plasma Emission Spectroscopy

Chlorine not reported

Chromium 102038 Metals, Dissolved: Filtered And Preserved Samples Analyzed By ICP-MS

Cobalt 102033 Metals, Dissolved: Filtered And Preserved Samples Analyzed By ICP-MS

21

Copper 102027 Metals, Dissolved: Filtered And Preserved Samples Analyzed By ICP-MS

Iron 102090 Metals, Dissolved: Filtered And Preserved Samples Analyzed By ICP-MS

Lead 102029 Metals, Dissolved: Filtered And Preserved Samples Analyzed By ICP-MS

Lithium 100797 Metals, Dissolved: Filtered And Preserved Samples Analyzed By ICP-MS

Magnesium 12111 Inductively Coupled Argon Plasma Emission Spectroscopy

Manganese 102089 Metals, Dissolved: Filtered And Preserved Samples Analyzed By ICP-MS

Molybdenum 102023 Metals, Dissolved: Filtered And Preserved Samples Analyzed By ICP-MS

Nickel 102034 Metals, Dissolved: Filtered And Preserved Samples Analyzed By ICP-MS

Phosphorus 100783 Metals, Dissolved: Filtered And Preserved Samples Analyzed By ICP-MS

Potassium 19111 Inductively Coupled Argon Plasma Emission Spectroscopy

Selenium 102037 Metals, Dissolved: Filtered And Preserved Samples Analyzed By ICP-MS

Silicon 100786 Metals, Dissolved: Filtered And Preserved Samples Analyzed By ICP-MS

Silver 102028 Metals, Dissolved: Filtered And Preserved Samples Analyzed By ICP-MS

Sodium 11111 Inductively Coupled Argon Plasma Emission Spectroscopy

Strontium 100781 Metals, Dissolved: Filtered And Preserved Samples Analyzed By ICP-MS

Sulfur 100784 Metals, Dissolved: Filtered And Preserved Samples Analyzed By ICP-MS

Thallium 102043 Metals, Dissolved: Filtered And Preserved Samples Analyzed By ICP-MS

Thorium not reported

Tin 102040 Metals, Dissolved: Filtered And Preserved Samples Analyzed By ICP-MS

Titanium 102031 Metals, Dissolved: Filtered And Preserved Samples Analyzed By ICP-MS

Uranium 102018 Metals, Dissolved: Filtered And Preserved Samples Analyzed By ICP-MS

Vanadium 102022 Metals, Dissolved: Filtered And Preserved Samples Analyzed By ICP-MS

Zinc 102026 Metals, Dissolved: Filtered And Preserved Samples Analyzed By ICP-MS

Parameter Lab B

VMV codes Narratives

Aluminum n/a Dissolved Metals in Water by CRC ICP-MS (Ult)

Antimony n/a Dissolved Metals in Water by CRC ICP-MS (Ult)

Arsenic n/a Dissolved Metals in Water by CRC ICP-MS (Ult)

Barium n/a Dissolved Metals in Water by CRC ICP-MS (Ult)

Beryllium n/a Dissolved Metals in Water by CRC ICP-MS (Ult)

Bismuth not reported

Boron n/a Dissolved Metals in Water by CRC ICP-MS (Ult)

Cadmium n/a Dissolved Metals in Water by CRC ICP-MS (Ult)

Calcium n/a Dissolved Metals in Water by CRC ICP-MS (Ult)

Chlorine not reported

Chromium n/a Dissolved Metals in Water by CRC ICP-MS (Ult)

Cobalt n/a Dissolved Metals in Water by CRC ICP-MS (Ult)

Copper n/a Dissolved Metals in Water by CRC ICP-MS (Ult)

Iron n/a Dissolved Metals in Water by CRC ICP-MS (Ult)

Lead n/a Dissolved Metals in Water by CRC ICP-MS (Ult)

Lithium not reported

22

Magnesium n/a Dissolved Metals in Water by CRC ICP-MS (Ult)

Manganese n/a Dissolved Metals in Water by CRC ICP-MS (Ult)

Molybdenum n/a Dissolved Metals in Water by CRC ICP-MS (Ult)

Nickel n/a Dissolved Metals in Water by CRC ICP-MS (Ult)

Phosphorus not reported

Potassium n/a Dissolved Metals in Water by CRC ICP-MS (Ult)

Selenium n/a Dissolved Metals in Water by CRC ICP-MS (Ult)

Silicon not reported

Silver n/a Dissolved Metals in Water by CRC ICP-MS (Ult)

Sodium n/a Dissolved Metals in Water by CRC ICP-MS (Ult)

Strontium n/a Dissolved Metals in Water by CRC ICP-MS (Ult)

Sulfur not reported

Thallium not reported

Thorium not reported

Tin not reported

Titanium not reported

Uranium n/a Dissolved Metals in Water by CRC ICP-MS (Ult)

Vanadium n/a Dissolved Metals in Water by CRC ICP-MS (Ult)

Zinc n/a Dissolved Metals in Water by CRC ICP-MS (Ult)

Table B3: VMV codes for routine and nutrients

Parameters

Lab A

VMV

codes Narratives

Alkalinity, Phenolphthalein (as

CaCO3) 10151L Potentiometric Titration

Alkalinity, Total (as CaCO3) 10101L Potentiometric Titration

Ammonia (as N) 7562L Colorimetrically (Berthelot Method)

Bicarbonate 6201L Calculated Value

Calcium 103969 Extractable Elements by ICP-MS: Samples Preserved in Acid &

Analysed

Carbonate 6301L Calculated Value

Chloride 102087 Analysis Of Chloride By Flame Photometry (Flow Injection

Analysis)

Conductivity (μS/cm, 25°C) 2041L Conductivity Meter; Platinum Electrodes

Fluoride 9107L Automated Potentiometric Method

Hardness, Total (as CaCO3) 10602L Calculated Method

Iron 103975 Extractable Elements by ICP-MS: Samples Preserved in Acid &

Analysed

Magnesium 103979 Extractable Elements by ICP-MS: Samples Preserved in Acid &

Analysed

Manganese not

reported

Nitrate + Nitrite (as N) 7105L Colourimetry On An Autoanalyzer. The Sample; After Filtration

Through

Nitrate Nitrogen not

reported

23

Nitrite Nitrogen 7205L Colourimetry On An Autoanalyzer. The Sample; After Filtration

Through

pH 10301L Electrometric Method

Potassium 102086 Analysis Of Na & K By Flame Photometry (Flow Injection

Analysis)

Silica (as Si) 102616 Reactive Silica By Flow Injection Analysis

Sodium 102085 Analysis Of Na & K By Flame Photometry (Flow Injection

Analysis)

Sulfate (as SO4) 16306L Colourimetry On Autoanalyzer With Bacl2 & Methylthymol Blue

Total Kjeldahl Nitrogen 7021L Colorimetry On Autoanalyzer

Parameters

Lab C

VMV

codes Narratives

Alkalinity, Phenolphthalein (as

CaCO3) 10151 Potentiometric Titration

Alkalinity, Total (as CaCO3) 10111 Titro Processor

Ammonia (as N) 7505 Colorimetrically (Berthelot Method)

Bicarbonate 6201 Calculated Value

Calcium not

reported

Carbonate 6301 Calculated Value

Chloride 17206 Colourimetry On Autoanalyzer With Fe(NO3)3 & HgSCN

Conductivity (μS/cm, 25°C) 2041 Conductivity Meter;Platinum Electrodes

Fluoride 9105 Specific Ion Electrode

Hardness, Total (as CaCO3) 10602 Calculated Method

Iron not

reported

Magnesium not

reported

Manganese not

reported

Nitrate + Nitrite (as N) 102649 Nitrate, Nitrite And NO2-NO3 By Ion Chromatography

Nitrate Nitrogen 102647 Nitrate, Nitrite And NO2-NO3 By Ion Chromatography

Nitrite Nitrogen 102648 Nitrate, Nitrite And NO2-NO3 By Ion Chromatography

pH 10301 Electrometric Method

Potassium not

reported

Silica (as Si) not

reported

Sodium not

reported

Sulfate (as SO4) 106150 Dissolved Sulphate In Water: BaSO4 Suspension, Automated

Photometric Method

Total Kjeldahl Nitrogen 7015 Colorimetrically (Berthelot Method)

Parameters ALS

24

VMV

codes Narratives

Alkalinity, Phenolphthalein (as

CaCO3)

not

reported

Alkalinity, Total (as CaCO3) 10165 Automated Titration Method

Ammonia (as N) 107447 Ammonia Is Measured By Means Of The Berthelot Reaction On

An

Bicarbonate 6201 Calculated Value

Calcium 104394 Dissolved Metals In Water By ICP-OES

Carbonate 6301 Calculated Value

Chloride 99494 Anions In Water By Ion Chromatography

Conductivity (μS/cm, 25°C) 2041 Conductivity Meter; Platinum Electrodes

Fluoride 99493 Anions In Water By Ion Chromatography

Hardness, Total (as CaCO3) 10602 Calculated Method

Iron 104402 Dissolved Metals In Water By ICP-OES

Magnesium 104407 Dissolved Metals In Water By ICP-OES

Manganese 104410 Dissolved Metals In Water By ICP-OES

Nitrate + Nitrite (as N) 7110 Colorimetry On Autoanalyzer

Nitrate Nitrogen 443 Ion Chromatography

Nitrite Nitrogen 7206 Colorimetry On Autoanalyzer

pH 10301 Electrometric Method

Potassium 104416 Dissolved Metals In Water By ICP-OES

Silica (as Si) 103469 Inductively Coupled Argon Plasma Emission Spectroscopy

Sodium 104423 Dissolved Metals In Water By ICP-OES

Sulfate (as SO4) 98228 Sulphate By Chromatography Analysis

Total Kjeldahl Nitrogen 7021 Colorimetry On Autoanalyzer

Table B4: VMV codes for total phosphorus

Parameter

Lab A

VMV

code Narratives

Total phosphorus 15421L Colourimetry With Ammon. Molyb.; Antimony; Ascorbic Acid

Parameter

Lab C

VMV

code Narratives

Total phosphorus 15406 Colourimetry With Ammonium Molybdate; Etc.

Parameter

Lab B

VMV

code Narratives

Total phosphorus n/a Total Phosphorus in Water by Colour

25

References

1 Toman, B., Possolo, A. Accred Qual Assur, 2009, 14, 553-563.

2 Ellison, S. L. R., Burke, S., Walker, R. E., Heydorn, K., Mansson, M., Pauwels, J.,

Wegscheider, W., te Nijenhuis, B. Accred Qual Assur, 2001, 6, 274-277. 3 Taverniers, I., De Loose, M., Van Bockstaele, E. Trends in Analytical Chemistry, 2004, 23,

535-662. 4 Uriano, G. A., Gravatt, C. C., Morrison, G. H. CRC Critical Reviews in Analytical Chemistry,

1977, 6, 361-412. 5 Mitchell, P. ESRD document Guidelines for Quality Assurance and Quality Control in Surface

Water Quality Programs in Alberta, 2006. P 1-67. 6 Measurement Qualities Objectives, AEP internal document.

7 Standard Methods for the Examination of Water and Wastewater, Part 1000, Introduction,

Section 8.