December 2003 Sampling and Analysis Protocol for Ontario Regulation 267/03 Made under the Nutrient Management Act, 2002

Part 4 - Data Quality Requirements

Table of Contents

  1. Guidance on Selecting Laboratories for Analysis
  2. Analysis - Soil
  3. Analysis - Land Applied Materials

Data quality requirements for the analysis of soil and land applied material for the Nutrient Management Act are given in this section.

Laboratories may use the methods that are referenced under specific tests or other validated methods that meet data quality requirements as given under each test.

4.1 Guidance on Selecting Laboratories for Analysis

A listing of laboratories accredited under the OMAF Agronomic Test Accreditation Program is available from the Ontario Ministry of Agriculture and Food at any of its offices, in the crop production recommendation publications (e.g. OMAF publications 360, 363, 811), or from the OMAF website.

A directory of ISO/IEC 17025 accredited laboratories within Canada may be obtained from the Standards Council of Canada, 270 Albert Street, Suite 200, Ottawa ON, K1P 6N7. Telephone: (613) 238-3222 Fax: (613) 569-7808. This information may also be obtained from their website.

4.2 Soil Analysis

4.2.1 Soil pH

Matrix

Soil

Analysis

This analysis is required at least once within the five years prior to nutrients being applied. Soil pH is measured in a saturated paste.

Method Principle

Soil pH is determined with a standard glass electrode pH meter in a saturated soil-water paste.

Sample Preparation

Samples must be air dried and crushed to pass a 2 mm sieve. Add sufficient distilled water to air-dried, crushed soil to make a saturated paste. There should not be any free water on top of the soil sample. Hand mix the sample well using a glass rod, and allow to stand for 15-20 minutes.

Instrumentation

Standardize the pH meter with both pH 7.00 and pH 4.00 buffers. Insert the pH electrodes into the paste and determine the pH while slowly moving the electrodes within the paste.

Laboratory QC Samples per Run

Calibrate the pH meter, according to manufacturer's directions, before each set of analysis.

Method Performance Criteria

Inter- and intralab precision must be within ±0.3 pH units of the mean of samples from all accredited labs.

Reference Method

OMAF pH


4.2.2 Soil Buffer pH

Matrix

Soil

Analysis

This analysis is required to determine the lime requirement of soil samples with a soil pH below 6.0. Buffer pH is measured into a sample of previously dried, crushed soil mixed with a Shoemaker-McLean-Pratt (SMP) buffer solution.

Method Principle

The reduction in pH of a standard buffer solution is measured to determine the amount of lime required to bring the soil pH of an acid soil into an acceptable range for crop production.

Sample Preparation

Samples must be air dried and crushed to pass through a 2 mm sieve. Combine one part air dried crushed soil with two parts SMP buffer in a disposable beaker. Shake for 10-15 minutes, let stand 15 minutes then determine pH.

Instrumentation

Read the pH on a standardized pH meter, calibrated to both pH 4.00 and 7.00 buffer solutions, while electrodes are slowly moved within the suspension.

Laboratory QC Samples per Run

Method Blank, Matrix Matched In-House Control or CRM, Calibration Check and Sample Replicate.

Method Performance Criteria

Inter- and intra-lab precision must be within ±0.3 pH units of the mean of samples from all accredited labs.

Reference Method

OMAF BpH


4.2.3 Available Nutrients - Phosphorus

Matrix

Soil

Analysis

This analysis is required at least once within the five years prior to nutrients application. Plant available phosphorus is measured using the 0.5 M sodium bicarbonate method.

Method Principle

A portion of previously dried, crushed and sieved (< 2 mm), sample is extracted with a dilute alkaline solution, and P concentration is determined in the extract.

Sample Preparation

Samples must be air dried and crushed to pass a 2 mm sieve. Shake one part air-dried crushed soil for 30 minutes with 20 parts of 0.5 M sodium bicarbonate extracting solution, then let settle and filter. Determine P concentration in extract in autoanalyzer and calculate mg P/L of soil.

Instrumentation

Set up the Autoanalyzer to develop the colour reaction by the molybdate – ascorbic acid method. Read the sample absorbance at a wavelength of 820 nm.

Laboratory QC Samples per Run

Method Blank, Matrix Matched In-House Control or CRM, Calibration Check and Sample Replicate.

Method Performance Criteria

Inter- and intra-lab precision must be within ±15% of the mean of samples from all accredited labs.

Reference Method

OMAF P


4.2.4 Available Nutrients - K, Mg and Ca PLANT AVAILABLE NUTRIENTS Ø K, Mg and Ca

Matrix

Soil

Analysis

Analysis of available potassium is required at least once within the five years prior to nutrients application. Analysis of available magnesium is not required as part of a nutrient management plan, but is very useful in determining the requirement for magnesium fertilizers for crop production. Some labs may also determine the calcium content of the soil from the same extract. Plant available cations are measured using the 1 M ammonium acetate method.

Method Principle

A portion of previously dried, crushed and sieved (< 2 mm), sample is extracted with a dilute ammonia acetate solution, and analyzed using a spectrometric technique.

Sample Preparation

Samples must be air dried and crushed to pass a 2 mm sieve. Shake one part of air dried crushed soil with 10 parts of neutral 1 M ammonium acetate solution for 15 minutes. Let settle and then filter. Determine concentrations in extract on atomic absorption spectrophotometer.

Instrumentation

Potassium (K) is determined by atomic absorption spectrometry (AAS) in the emission mode at a wavelength of 766 nm. Magnesium (Mg) is determined on the same extract at a wavelength of 285.2 nm AAS. If the sample reads over 400 absorbance units, it is diluted 1:9 with ammonium acetate and the results multiplied by a factor of 10.Calcium (Ca) is read on same extract as Mg and K, but all samples are initially diluted 1:9 with ammonium acetate. Ca concentration is determined by AAS at a wavelength of 422.7 nm. ICP may also be used to measure the concentration of cations in the extract.

Laboratory QC Samples per Run

Method Blank, Matrix Matched In-House Control or CRM, Calibration Check and Sample Replicate.

Method Performance Criteria

Inter- and intralab precision of the K analysis must be within ±15% of the mean (±20% for Mg) of samples from all accredited labs.

Reference Method

OMAF Cations


4.2.5 Available Nutrients – Zn, Zn Index

Matrix

Soil

Analysis

This analysis is not required as part of a nutrient management plan, but can be useful in determining whether a zinc deficiency might occur in crops. Soil zinc content is measured using the DTPA method. Results from this analysis are combined with soil pH to produce an index of zinc availability in agricultural soil.

Method Principle

A portion of previously dried, crushed and sieved (< 2 mm), sample is extracted with a DTPA solution and the concentration of zinc is determined on an Atomic Absorption Spectrophotometer. Zinc content and soil pH are used in a formula to produce an index of Zn availability.

Sample Preparation

Samples must be air dried and crushed to pass a 2 mm sieve. Shake one part air dried crushed soil with 2 parts of DTPA extracting solution for 1 hour. Samples are allowed to settle and then filtered.

Instrumentation

Zinc is read by AAS in the emission mode at 213.9 nm. ICP may also be used to measure the concentration of ions in the extract. Zinc is reported by index using formula: 203 + 4.5 DPTA ext in mg/L - 50.7 soil pH + 3.33 (soil pH)2.

Note: A small error in pH will cause a major change in the zinc index. E.g. if you take values for soil A as 4.8 paste and 5.2 (25 mL water), the resulting values if the Zn reading is 2 mg/L, are 50.3 and 43.44 respectively – a rather large error.

Laboratory QC Samples per Run

Method Blank, Matrix Matched In-House Control or CRM, Calibration Check and Sample Replicate.

Method Performance Criteria

Inter- and intra-lab precision of the calculated index must be within ±15% of the mean of samples from all accredited labs

Reference Method

OMAF Zn


4.2.6 Available Nutrients – Mn, Mn Index

Matrix

Soil

Analysis

This analysis is not required as part of the nutrient management plan, but is useful in determining whether manganese deficiency may occur in crops. Soil manganese content is measured using the 0.5 M phosphoric acid method. Results from this test are combined with soil pH to produce an index of manganese availability.

Method Principle

A portion of previously dried, crushed and sieved (< 2 mm), sample is extracted with a dilute phosphoric acid solution, and analyzed using an atomic absorption spectrophotometer.

Sample Preparation

Samples must be air dried and crushed to pass a 2 mm sieve. Shake one part air dried crushed soil with 8 parts 0.5 M phosphoric acid extracting solution for 10 minutes. Let settle, and then filter.

Instrumentation

The manganese is read on an atomic absorption spectrophotometer at 279.5 manometers in the A.A. mode. ICP may also be used to measure the concentration of ions in the extract. Manganese index is reported using the formula: 498 - 137 soil pH + 0.248 extracted Mn + 9.64 (soil pH)2. A small change in pH affects the index greatly.

Laboratory QC Samples per Run

Method Blank, Matrix Matched In-House Control or CRM, Calibration Check and Sample Replicate.

Method Performance Criteria

Inter- and intra-lab precision of the calculated index must be within ±15% of the mean of samples from all accredited labs.

Reference Method

OMAF Mn


4.2.7 Available Nutrients – Nitrate N

Matrix

Soil

Analysis

This analysis is not required in a nutrient management plan, but can be used to refine the nitrogen fertilizer application rates on corn or barley. Nitrate nitrogen is measured using the 2 M potassium chloride extraction.

Method Principle

A portion of previously dried, crushed and sieved (< 2 mm), sample is extracted with a dilute potassium chloride solution, and the concentration of nitrate in the extract determined using a colourimetric technique.

Sample Preparation

Take frozen or air dried soil (if frozen allow to thaw approximately 2 hours at room temperature), and sieve through 2 or 4 mesh screen. Take smaller particles for nitrate analyses. Clay samples or extremely wet samples will not sieve properly, you may have to cut sample into smaller pieces, using a knife or spatula. Shake one part fresh or air dried soil with 5 parts of 2 N KC1 extracting solution for 30 minutes. Let settle and then filter. Take a sample of rest of soil (5-15 g) for moisture analyses. Dry at 105°C overnight and calculate soil moisture.

Instrumentation

Nitrate is determined on an autoanalyzer using the cadmium reduction technique to reduce the nitrate to nitrite, followed by reaction with a colour agent and measurement of the absorbance at 520 nm.

Laboratory QC Samples per Run

Method Blank, Matrix Matched In-House Control or CRM, Calibration Check and Sample Replicate.

Method Performance Criteria

Inter- and intra-lab precision must be within ±15% of the mean of samples from all accredited labs.

Reference Method

OMAF NO3


4.2.8 Total Metals - Cd, Cr, Co, Cu, Pb, Mo, Ni, and Zn

Matrix

Soil

Analysis

Soils in fields that will be receiving non-agricultural source material must be analyzed for each of the above metals. Sampling and analysis frequencies are given in Section 1.3.1. Non-agricultural source material may not be applied to soil where any of the metal concentrations in soil are equal to or greater than those given in Tables 1-1 and 1-2.

Method Principle

A portion of previously dried, ground and sieved (< 0.355mm), sample is extracted with a heated, strong mixed acid solution, brought to volume with pure deionized water and analyzed using a spectrometric technique.

Sample Preparation

    1. Air dry the sample, disaggregate and pass through a 2.0 mm sieve.
    2. Grind an aliquot of the above sample until the whole sample passes through a 0.355 mm sieve.
    3. Digest a portion of the sample (< 0.355 mm) with concentrated Nitric acid/ Hydrochloric acid mixture (1:3) by heating at 125 EC for a minimum of 2 hours.
Instrumentation

ICP/OES, DCP, ICP/MS, flame AAS and graphite furnace AAS with suitable matrix modifiers may be used.

Laboratory QC Samples per Run

Method Blank, Matrix Matched In-House Control or CRM, Calibration Check and Sample Replicate.

Method Performance Criteria
Analyte RDL
μg/g
Accuracy* (Recovery)
Acceptable Range (%)
Precision (Between-Run)
Acceptable Deviation (%)
Cadmium 1 80-120 ± 20
Chromium 12 80-120 ± 20
Cobalt 2.5 80-120 ± 20
Copper 10 80-120 ± 20
Lead 10 80-120 ± 20
Molybdenum 2.5 N/A N/A
Nickel 3.2 80-120 ± 20
Zinc 25 80-120 ± 20

* Accuracy is based upon the certified reference material, such as, EPA 287.

Reference Method

MOE/LSB - E3073


4.2.9 Mercury

Matrix

Soil

Analysis

Soils in fields that will be receiving non-agricultural source material must be analyzed for mercury. Sampling and analysis frequencies are given in Section 1.3.1. Non-agricultural source material may not be applied to soil where mercury concentration in soil is equal to or greater than that given in Tables 1-1 and 1-2.

Method Principle

Mercury in the sample is converted to the inorganic form by the acid digestion process. The inorganic mercury in aqueous solution is then reduced with stannous chloride, and analyzed by Cold Vapour Flameless Atomic Absorption (CV AAS.)

Sample Preparation

    1. Air dry the sample, disaggregate and pass through a 2.0 mm sieve.
    2. Grind an aliquot of above sample until the whole sample passes through a 0.355 mm sieve.
    3. Digest a portion of the sample (< 0.355 mm) with concentrated sulphuric acid/nitric acid (4:1) by heating within a temperature range of 215 °C to 235 °C for a minimum of 12 hours.
Instrumentation

CV-AAS

Laboratory QC Samples per Run

Method Blank, Matrix Matched In-House Control or CRM, Calibration Check and Sample Replicate.

 Method Performance Criteria
Analyte RDL
μg/g
Accuracy* (Recovery)
Acceptable Range (%)
Precision (Between-Run)
Acceptable Deviation (%)
Mercury 0.05 80 - 120 ±20

* Accuracy is based upon the certified reference material, such as, National Research Council Sediment - PACS-1 or NIST 1646 sediment.

Reference Method

MOE/LSB - E3059


4.2.10 Arsenic and Selenium

Matrix

Soil

Analysis

Soils in fields that will be receiving non-agricultural source material must be analyzed for arsenic and selenium. The sampling and analysis frequencies are given in Section 1.3.1. Non-agricultural source material may not be applied to soil where concentrations of arsenic and selenium in soil are equal to or greater than those given in Tables 1-1 and 1-2.

Method Principle

A portion of sample is digested in an oxidizing acid mixture to convert all forms of arsenic and selenium to arsenate (AsO4)3- and selenate (SeO4)2- respectively. The arsenate and selenate are then reduced with sodium borohydride to arsine and hydrogen selenide which are then analyzed by flameless AAS.

Sample Preparation
    1. Air dry the sample, disaggregate and pass through a 2.0 mm sieve.
    2. Grind an aliquot of above sample until the whole sample passes through 0.355 mm sieve.
    3. Digest a portion of the sample (< 0.355 mm) with concentrated Nitric acid/Sulphuric acid/Perchloric acid (6:3:1) at 200°C for 16 hours.
Instrumentation

Hydride - Flameless Atomic Absorption Spectrophotometry (HYD-FAAS). ICP/MS and graphite furnace AAS with suitable matrix modifiersmay be used.

Laboratory QC Samples per Run

Method Blank, Matrix Matched In-House Control or CRM, Calibration Check and Sample Replicate.

Method Performance Criteria
Analyte RDL
μg/g
Accuracy* (Recovery)
Acceptable Range (%)
Precision (Between-Run)
Acceptable Deviation (%)
Arsenic 1.4 80 - 120 ± 20
Selenium 1 80 - 120 ± 20

*Accuracy is based upon the certified reference material, such as, NIST 2709 San Joaquin soil.

Reference Method

MOE/LSB - E3245


4.2.11 Boron - Hot Water Extraction

Matrix

Soil

Analysis

The ministry may require analysis of soils where application of materials high in boron is planned, on a case-by-case basis

Method Principle

A 25 g portion of previously dried, ground (< 2 mm) sample is extracted with a weak calcium chloride solution and analyzed using a spectrometric technique.

Sample Preparation
    1. Air dry the sample, disaggregate and pass through a 2.0 mm sieve.
    2. Combine a 25 g portion of the air dried sample with 50 mL 0.01 M CaCl2 solution. Boil for 5 minutes, then cool and filter.
Instrumentation

ICP (AAS or DCP may be used)

Laboratory QC Samples per Run

Method Blank, Matrix Matched In-House Control, Calibration Check and Sample Replicate.

Method Performance Criteria

Accuracy and precision data are under review.

Reference Method

MOE/LSB - E3073

Note: This method can identify contaminated sites, but is not sensitive enough to identify potentially deficient sites for crop production.


4.3 Analysis - Land Applied Materials

4.3.1 Hydrogen Ion (pH)

Matrix

Land Applied Materials (Non-agricultural source materials)

Analysis

Non-agricultural source materials with pH less than 6.0 unit or pH greater than 8.5 units, should not be applied to crops when they are being grown.

Method Principle

pH is determined with a standard glass electrode pH meter.

Sample Preparation

Solid: Prepare aqueous slurry in the ratio of 1g sample:9 mL water. Stir or shake for approximately 20 minutes, allow suspension to settle and then determine pH of liquid fraction.

Liquid/Slurry: Decant, filter or centrifuge a portion of sample, then determine the pH of the liquid fraction.

Instrumentation

pH electrode and pH meter compensated to 25°C. Accuracy and reproducibility to 0.2 pH unit with a range of 0 - 14 and equipped with temperature compensation.

Laboratory QC Samples per Run

3 Buffer Checks, Sample Replicate and In-House Matrix Check.

Method Performance Criteria

Accuracy: ± 0.2 pH units

Precision: ± 0.2 pH units

Reference Method

MOE/LSB - E3137 (solid), MOE/LSB - E 3218 (liquid/slurry)

Notes
  1. Sample preservation - store samples in refrigerator (4 - 10°C).
  2. Maximum sample storage time: 14 days

4.3.2 Electrical Conductivity

Matrix

Land Applied Materials (Non-agricultural source materials)

Analysis

Method Principle

Conductivity, a measure of the capacity of a liquid to convey an electric current at a specific temperature, is defined as the reciprocal of a water's electrical resistance, measured between two electrodes one square centimeter in area and one centimeter apart. The conductivity test requires introducing the sample to the conductivity cell and recording the conductivity.

Sample Preparation

Solid (low organic matter): Prepare aqueous slurry in the ratio of 10g sample:20 mL water. Stir or shake for approximately 30 minutes, allow suspension to settle for 30 minutes then determine conductivity on the material.

Liquid/Slurry: Decant, filter or centrifuge a portion of sample and then perform conductivity determination on the liquid fraction.

Instrumentation

Conductivity meter compensated to 25°C.

Laboratory QC Samples per Run

2 Conductivity Standards, Blank and Sample Replicate.

Method - Performance Criteria

Accuracy: 100 ± 10%

Precision: ± 10 %

Reference Method

MOE/LSB - E3218 (liquid/slurry), MOE/LSB - E3138 (solid)

Notes
    1. Sample preservation - store samples in refrigerator (4 – 10°C).
    2. Maximum sample storage time: 14 days.

4.3.3 Total Dry Matter

Matrix

Land Applied Materials

Analysis

Accurate determination of the dry matter content of land-applied materials is necessary to calculate application rates on a moist basis.

Method Principle

A portion of sample is weighed as received, dried for 16 hours at 105 ± 5°C, cooled and reweighed. The per cent total solid is determined.

Sample Preparation

Disaggregate the sample and pass through a 2 mm sieve. Take sub-samples (10 - 25 g) of this mixture, and dry in an oven at 105 ± 5°C for 16 hours to a constant weight. Cool and reweigh sample to determine total solids as a per cent of the fresh weight.

Instrumentation

Balance, capable of weighing ± 0.01 g.

Laboratory QC Samples per Run

Calibration Check and Sample Replicate.

Method - Performance Criteria

Accuracy: 100 ±10%

Precision: ±10%

Reference Method

MOE/LSB-3139


4.3.4 Total Volatile Solids (Organic Matter)

Matrix

Solid or Liquid Land Applied Materials

Analysis
Method Principle

A portion of ground sample is dried for 16 hours at 105°C ± 5°C, then muffled at 475°C ± 25°C for 4 hours. The weight loss, and per cent ash are determined.

Sample Preparation

  1. Disaggregate the sample and pass through a 2 mm sieve, then take and grind a sub-sample to pass through a 0.355 mm sieve.
  2. Heat the sub-sample in a muffler oven at 475°C ± 25°C for 4 hours.
  3. Determine the weight loss, and per cent ash.
Instrumentation

Muffle furnace; Balance, capable of weighing ± 0.01 g.

Laboratory QC Samples per Run

Calibration Check and Sample Replicate.

Method - Performance Criteria

Accuracy: 100±10%

Precision: ±10%

Reference Method

MOE/LSB-3139


4.3.5 Total Kjeldahl Nitrogen

Matrix

Land Applied Materials

Analysis

Total nitrogen in land applied materials is determined to provide a basis for calculating the organic nitrogen portion of the material (by subtracting the ammonium N from the total). The required sampling frequency is specified in Sections 1.3.2 and 1.3.3.

Method Principle

Amino nitrogen in organic materials is converted to ammonium by digestion in the presence of strong acid, salt and a catalyst. Ammonium content, which will also include ammonia and ammonium in the sample before digestion, is determined by colourimetry, ammonia selective electrode or titration.

Sample Preparation

Test the samples as received. Determine the dry matter content of the material separately. Sample is mixed with H2SO4, K2SO4, and cupric sulphate (catalyst), and heated to 400°C to convert organically bound nitrogen to NH4.

Instrumentation

Autoanalyzer, colourimeter

Laboratory QC Samples per Run

Method Blank, Matrix Matched In-House Control or CRM, Calibration Check and Sample Replicate.

Method Performance Criteria

Inter- and intra-lab precision must be within ±10% of the mean of samples from all accredited labs.

Reference Method

AOAC 978.02

Notes
  1. Sample Preservation - Store samples in refrigerator (4 - 10°C). If extended storage is required (>10 days), freeze the samples.
  2. Method does not completely account for oxidized forms of nitrogen such as nitrate, nitrite, or nitrogen in heterocyclic ring compounds. Nitrogen determination by combustion (Dumas method) may give better results in materials with significant contents of these forms of nitrogen.

4.3.6 Ammonia and Ammonium - Nitrogen

Matrix

Land Applied Materials

Analysis

Ammonium nitrogen in land applied materials (which includes both ammonium and ammonia nitrogen) is determined to provide an estimate of plant available nitrogen, as well as a basis for calculating the organic nitrogen portion of the material (by subtracting the ammonium N from the total). The required sampling frequency is specified in Sections 1.3.2 and 1.3.3.

Method Principle

Ammonium plus ammonia nitrogen is extracted from the sample in a KCl solution. Ammonium content in the extract is determined by colourimetry, using a modified Berthelot reaction.

Sample Preparation

Test the samples as received. Determine the dry matter content of the material separately. Sample is mixed with 2M KCl solution, shaken, and then centrifuged or filtered.

Instrumentation

Autoanalyzer, colourimeter

Laboratory QC Samples per Run

Method Blank, Matrix Matched In-House Control or CRM, Calibration Check and Sample Replicate.

Method Performance Criteria

Inter- and intra-lab precision must be within ±10% of the mean of samples from all accredited labs.

Reference Method

USEPA 352.2

Notes: Ammonia specific electrode may be used as an alternate method, and will be less subject to interference from discolouration of the extract.


4.3.7 Nitrate And Nitrite - Nitrogen

Matrix

Land Applied Materials

Analysis

Samples are analyzed for nitrate nitrogen and nitrite nitrogen to assess the nitrogen immediately available to plants. Some non-agricultural source materials may contain significant amounts of nitrate and nitrite nitrogen.

Method Principle

Samples are analyzed using an automated colourimetric procedure which entails converting nitrate to nitrite, and then analyzing the sample for nitrite.

Nitrate is reduced to nitrite by heating an aliquot of sample with hydrazine in alkaline media; this reaction is catalyzed by the addition of cupric ion. Subsequently, an azo dye is formed in acid media by diazotizing sulphanilamide with nitrite and coupling the product with N (1-naphthyl) ethylenediamine dihydrochloride. The absorbance of the light red azo dye is measured at 520 nm and the concentration of nitrate nitrogen plus nitrite nitrogen is determined by comparison with a similarly treated series of mixed Standards.

Sample Preparation

Liquid/Slurry: A supernatant of the settled sample is used for this analysis. Samples (if frozen) are thawed to room temperature prior to analysis. Highly turbid samples should be filtered to prevent clogging of the analyser fittings. Sewage sludge samples should be centrifuged prior to analysis.

Solid: Under Development

Instrumentation

Colourimeter

Laboratory QC Samples per Run

Method Blank, In-House Standard, Calibration Check and Sample Replicate.

Method Performance Criteria

Accuracy: 100 ± 10%, Precision: 10%

Reference Method

MOE/LSB - E3366

Notes
  1. Store samples in a refrigerator (4 – 10°C).
  2. Maximum storage time, 7 days.

4.3.8 Organic Nitrogen

Matrix

Land Applied Materials

Analysis

The organic nitrogen portion of the material is calculated by subtracting the ammonium N from the total N contents of the sample. The required sampling frequency is laid out in Sections 1.3.2 and 1.3.3.

Method Principle

Ammonium plus ammonia nitrogen, as determined in a KCl extract of the manure sample, is subtracted from the Total Kjeldahl Nitrogen in the sample. The difference is the organic N.

Sample Preparation

Extraction as defined for ammonium and total N.

Instrumentation

As defined for ammonium and total N.

Laboratory QC Samples per Run

As defined for ammonium and total N.

Method Performance Criteria

As defined for ammonium and total N.

Method Reference

N/A

Notes: If the total N content of the material has been determined by combustion (dumas method) rather than wet digestion, the nitrate content of the material should also be determined and the nitrate as well as the ammonium content should be deducted from the total N to determine the organic N.


4.3.9 Metals - Cd, Cr, Co, Cu, Pb, Mo, Ni, and Zn

Matrix

Land Applied Materials (Non-agricultural source materials)

Analysis

This analysis is required for non-agricultural source material only. The sampling and analysis frequencies are given in table 1-3. Non-agricultural source material may not be applied to soil where any of the metal concentrations in such material are equal to or greater than those given in Tables 1-1 and 1-2.

Method Principle

A portion of sample is extracted with a heated, strong mixed acid solution, brought to volume with pure deionized water and analyzed using a spectrometric technique.

Sample Preparation

Solid (i.e. dewatered sludge, filter cake - Method E3071): Digest a portion of previously air dried, ground and sieved sample with concentrated Nitric acid/Hydrochloric acid mixture (1:3) by heating at 50°C for 1 hour and then at 95°C for another 3 hours. Adjust volume with pure deionized water, decant/filter and then analyze.

Liquid/slurry (i.e. liquid sludge, likely 1% to 10% solids - Method E3071): Weigh an aliquot of homogenized sample. Digest with concentrated Nitric acid/Hydrochloric acid mixture (1:3) by heating at 50°C for 1 hour and then at 95°C for another 3 hours. Adjust volume with pure deionized water, decant/filter and then analyze. Report results on dry weight basis.

Clear Liquid (i.e. supernatant, less than 1% solids - Method E3094): Digest an aliquot of sample with concentrated Nitric acid/Hydrochloric acid mixture (1:3) by heating at 50°C for 1 hour and then at 95°C for another 3 hours. Adjust volume with pure deionized water, decant/filter and then analyze.

Instrumentation

ICP/AES, DCP, ICP/MS, flame AAS and graphite furnace AAS with suitable matrix modifiers may be used.

Laboratory QC Samples per Run: Method Blank, Matrix Matched In-House Control or CRM, Calibration Check and Sample Replicate.

Method Performance Criteria
Analyte RDL
μg/g
Accuracy* (Recovery)
Acceptable Range (%)
Precision(Between-Run)
Acceptable Deviation(%)
Cadmium 2.0 80 - 120 ± 20
Chromium 106 80 - 120 ± 20
Cobalt 15 N/A N/A
Copper 76 80 - 120 ± 20
Lead 50 80 - 120 ± 20
Molybdenum 2.5 N/A N/A
Nickel 18 80 - 120 ± 20
Zinc 185 80 - 120 ± 20

* Accuracy is based upon the certified reference material, such as, WWS-26 from Environmental Resource Associate or EPA Quality Control Sample, municipal digested sludge (SPL # 2900).

Reference Method

MOE/LSB - E3071 for liquid/slurry and solid; MOE/LSB - 3094 for Clear Liquid.

Notes
  1. Sample Preservation:
    • Clear Liquid Samples - Preserved with nitric acid to less than pH 2.
    • Solid/Slurry/Solid Sample - Store samples in refrigerator (4 - 10°C).
  2. Maximum Sample Storage Time: 60 days

4.3.10 Mercury

Matrix

Land Applied Materials (Non-agricultural source materials)

Analysis

This analysis is required for non-agricultural source material only. The sampling and analysis frequencies are given in table 1-3. Non-agricultural source material may not be applied to soil where mercury concentration in such material is equal to or greater than that given in Tables 1-1 and 1-2.

Method Principle

Mercury in the sample is converted to the inorganic form by acid digestion process. The inorganic mercury is aqueous solution is then reduced with stannous chloride, and analyzed by CV AAS.

Sample Preparation

Solid (e.g. dewatered sludge, filter cake - Method E3058): Digest a portion of previously air dried ground and sieved sample with 50% v/v Aqua Regia (hydrochloric acid/Nitric acid - v/v 3:1) in the presence of potassium permanganate by heating within a temperature range of 90°C to 110°C for 1 hour and 15 minutes. Treat excess permanganate with hydroxylamine sulphate. Reduce inorganic mercury with stannous chloride prior to analysis. Adjust volume with pure deionized water, decant/filter and then analyze. Report results on dry weight basis.

Liquid/Slurry (e.g. liquid sludge, likely 1% to 10% solids - Method E3058): Digest weighed aliquot of homogenized (well mixed) sample with 50% v/v Aqua Regia (hydrochloric acid/Nitric acid - v/v 3:1) in the presence of potassium permanganate by heating within a temperature range of 90°C to 110°C for 1 hour and 15 minutes. Treat excess permanganate with hydroxylamine sulphate. Reduce inorganic mercury with stannous chloride prior to analysis. Adjust volume with pure deionized water, decant/filter and then analyze. Report results on dry weight basis.

Clear Liquid (e.g. supernatant, less than 1% solids - Method E 3301): Digest an aliquot of homogenized (well mixed) sample with concentrated sulphuric acid/nitric acid (1.2:0.5) in the presence of potassium persulphate and potassium dichromate for 2 hours at 87°C ± 3°C. Adjust volume with pure deionized water, decant/filter and then analyze.

Instrumentation

Cold Vapour Flameless Atomic Absorption (CV-FAAS)

Laboratory QC Samples per Run

Method Blank, Matrix Matched In-House Control or CRM, Calibration Check and Sample Replicate.

Method Performance Criteria
Analyte RDL
μg/g
Accuracy* (Recovery)
Acceptable Range (%)
Precision(Between-Run)
Acceptable Deviation (%)
Mercury 0.5 80 - 120 ±20

* Accuracy is based upon the certified reference material, such as, CRM 145R (sewage sludge mixed origin) or BE - 1 (sewage sludge).

Reference Method

MOE/LSB - E3301 (clear liquid), MOE/LSB E3058 (slurry and solid)

Notes
  1. Sample Preservation
    • Clear Liquid Sample - Preserve 250 mL sample with 0.5 - 1.0 mL concentrated nitric acid and 5 - 10 drops of 5% potassium dichromate solution. This should lower pH to below 2.0 and give the sample a permanent yellow colour.
    • Liquid Slurry/Solid Sample - Store samples in refrigerator (4 - 10°C).
  2. Maximum Sample Storage Time: 15 days.

4.3.11 Arsenic and Selenium

Matrix

Land Applied Materials (Non-agricultural source materials)

Analysis

This analysis is required for non-agricultural source material only. The sampling and analysis frequencies are given in table 1-3. Non-agricultural source material may not be applied to soil where arsenic and selenium concentrations in such material are equal to or greater than that given in Tables 1-1 and 1-2.

Method Principle

A portion of sample is digested in oxidizing acid mixture to convert all forms of arsenic and selenium to arsenate (AsO4)3- and selenate (SeO4)2- respectively. The arsenate and selenate are then reduced with sodium borohydride to arsine and hydrogen selenide which are then analyzed by flameless AAS.

Sample Preparation

Solid (e.g. dewatered sludge, filter cake - Method E3091): Digest a portion of previously air dried ground and sieved sample and sample with concentrated Nitric acid/Sulphuric acid/Perchloric acid (6:3:1) at 200°C for minimum of 16 hours. Adjust volume with pure deionized water, decant/filter and then analyze.

Liquid/Slurry (e.g. liquid sludge, likely 1% to 10% solids - Method E3091): Digest a weighed aliquot of sample with concentrated Nitric acid/Sulphuric acid/Perchloric acid (6:3:1) at 200°C for minimum of 16 hours. Adjust volume with pure deionized water, decant/filter and then analyze. Report results on dry weight basis.

Clear Liquid (e.g. supernatant, less than 1% solids) (Method E 3302): Digest an aliquot of liquid with a 6:3:1 mixture of Nitric:sulphuric:perchloric acids at 140 ° C for about 16 hours. Adjust volume with pure deionized water, decant/filter and then analyze

Instrumentation

Hydride - Flameless Atomic Absorption Spectrophotometry (HYD-FAAS)

Laboratory QC Samples per Run

Method Blank, Matrix Matched In-House Control or CRM, Calibration Check and Sample Replicate.

Method Performance Criteria
Analyte RDL
μg/g
Accuracy* (Recovery)
Acceptable Range (%)
Precision(Between-Run)
Acceptable Deviation (%)
Arsenic 7.5 80 - 120 ± 20
Selenium 1.4 80 - 120 ± 20

* Accuracy is based upon the certified reference material, such as, CRM 145R (sewage sludge mixed origin) or BE - 1 (sewage sludge).

Reference Method

MOE/LSB - E3302 (clear liquid), MOE/LSB E3091 (liquid/slurry and solid)

Notes
  1. Sample Preservation
    • Clear Liquid Sample - Preserve sample with nitric acid.
    • Liquid/Slurry/Solid Sample - Store samples in refrigerator (4 - 10°C).
  2. Maximum Sample Storage Time: 30 days.

4.3.12 Total Phosphorus, Potassium, Sodium and Boron

Matrix

Land Applied Materials

Analysis

Total phosphorus and potassium content of land applied materials are determined to estimate the amount of plant available nutrient being applied to land. The required sampling frequency is laid out in Sections 1.3.2 and 1.3.3. Sodium or boron content may need to be determined for land applied materials suspected of containing high concentrations of these elements, on a case by case basis.

Method Principle

A portion of sample is extracted with a heated, strong mixed acid solution, brought to volume with pure deionized water and analyzed using a spectrometric technique.

Sample Preparation

Solid: Digest a portion of previously dried and homogenized sample with concentrated Nitric acid/Hydrochloric acid mixture (1:3) by heating at 50°C for 1 hour and then at 95°C for another 3 hours. Adjust volume with pure deionized water, decant/filter and then analyze.

Liquid/slurry: Weigh an aliquot of homogenized (well mixed) sample and then digest with concentrated Nitric acid/Hydrochloric acid mixture (1:3) by heating at 50°C for 1 hour and then at 95°C for another 3 hours. Adjust volume with pure deionized water, decant/filter and then analyze.

Instrumentation

ICP/AES

Laboratory QC Samples per Run

Method Blank, Matrix Matched In-House Control or CRM, Calibration Check and Sample Replicate.

Method Performance Criteria

Inter- and intra- lab precision must be within ±10% of the mean of samples from all accredited labs.

Reference Method

Under development


4.3.13 E. coli (Only Sewage Biosolids)

Matrix

Sewage Biosolids

Analysis

Municipal sewage sludge is required to be sampled and analyzed at least as frequently as set out in Table 1.2. Such material may not be applied to soil where concentrations of E-coli exceeds 2 x 106 CFU/g of total solid (dry wt.).

Method Principle

A volume of buffered dilution water is added to a weighed amount of biosolids and processed with a Stomacher™ or equivalent. Serial dilutions are then prepared using the supernatant. Serial dilutions are then plated out on mFC-BCIG agar (or other selective agar) and incubated.

Sample Preparation

Add an amount of buffered dilution water to a weighed mass of biosolids material. Process in the Stomacher™ for 2 minutes. Decant off supernatant.

Instrumentation

Classical microbiological techniques - selective agar, biochemicals for confirmation.

Laboratory QC Samples per Run

Positive and negative controls run with each set of samples, plus spiked samples for recovery.

Method Performance Criteria

Under development

Reference Method

MOE/LSB - E3433

Notes
  1. Sample storage - ice bath/temperature.
  2. Analysis must be performed within 48 hours.

For more information:
Toll Free: 1-877-424-1300
E-mail: ag.info.omafra@ontario.ca
Author: OMAFRA Staff
Creation Date: 10 December 2003
Last Reviewed: 10 December 2003