a guide to the sampling and analysis of waters, wastewaters, soils and wastes

A GUIDE TO THE SAMPLING AND ANALYSIS OF WATERS,WASTEWATERS, SOILS AND WASTES

Environment Protection AuthorityState Government of Victoria

March 2000

Environment Protection Authority

ii

A GUIDE TO THE SAMPLING AND ANALYSIS OF WATERS, WASTEWATERS,SOILS AND WASTES

Environment Protection Authority40 City RoadSouthbank Victoria 3006Australia

Printed on recycled paper

Publication 441

© Environment Protection Authority, 7th edition, March 2000

ISBN 0 7306 7577 7

A Guide to the Sampling and Analysis of Waters, Wastewaters, Soils and Wastes

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FOREWORD

To effectively reduce risks of environmental damage, a regular program of monitoring industrial andother activities should be undertaken in which wastes are characterised, and potentially contaminatedland is audited. This responsible approach should be taken whether or not it is a statutory requirement.

This publication significantly expands on the previous edition of A Guide to the Sampling and Analysisof Water and Wastewater by including soils, other non-gaseous environmental samples and wastes.

For quantified information, rigorous procedures, as outlined in this Guide, need to be followed to ensurethat laboratory analysis accurately and reliably measures a pollutant or quality of the receivingenvironment.

Providing accurate and reliable measurements of environmental quality depends on a number of steps.Program and sampling design must have statistical rigour and ensure that representative samples aretaken, with due consideration of the chemical behaviour and temporal and spatial distribution of thepollutant in situ. To maintain the integrity of the sample in the interval before it is analysed, mostpollutants need to be preserved in some way to inhibit physical, chemical and biological transformationswhich can alter their concentration.

It is necessary for both the sampler and laboratory staff to work closely together, within the frameworkprovided in this Guide. Any weak link between collection of the sample, its pre-treatment and storage,and the analysis, can jeopardise the integrity of the final result.

Laboratories need to establish a rigorous quality assurance system covering all their analyticalprocedures, as well as addressing field testing and sample collection.

This Guide establishes best practice procedures for collecting and analysing environmental samples. Itshould be used for statutory purposes under the Environment Protection Act 1970, and by anycompany or agency that wishes to obtain an accurate picture of the impact of its activities on theenvironment.


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CONTENTS

Foreword............................................................................................................................... iii

1. Introduction........................................................................................................................1

2. Planning a sampling program ..............................................................................................2

3. Sample collection and transport ..........................................................................................4

4. Analytical methods and quality assurance procedures ........................................................ 12

5. Reporting and review of results......................................................................................... 18

6. References........................................................................................................................ 20

Appendix A: Containers, preservation and holding periods for waters, groundwatersand wastewaters ................................................................................................................... 23

Appendix B: Containers, preservation and holding periods for soils and sediments ................ 40

Appendix C: Containers, preservation and holding periods for concentrated liquidwastes, sludges and solid wastes, other than soils and sediments ........................................... 43

Appendix D – Quality assurance systems .............................................................................. 49


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1. INTRODUCTION

Environmental samples are analysed for a rangeof purposes, such as to:

• determine ambient pollutantconcentrations

• assess potential and known contaminatedsites

• monitor effluents, trade wastes andprocess streams to manage performance

• identify the source and nature ofaccidental spills or pollution to assesstheir effects on the environment

• determine background levels of potentialcontaminants and pollutants, and

• meet statutory requirements of theEnvironment Protection Act 1970 and thePollution of Waters by Oils and NoxiousSubstances Act 1986.

The importance of obtaining representativesamples, which faithfully represent a waste orelement of the environment from which they aretaken, cannot be underestimated. Whereasquality assurance* systems are well developedfor laboratories, similar systems often do notencompass sample collection. Care needs to betaken in the field to ensure that samples are notcontaminated during collection, and that theconcentrations of analytical parameters ofinterest do not alter in the interval betweencollection and analysis.

Critical steps in any environmental monitoringprogram include, but are not limited to:

• determining the objectives of themonitoring program

• selecting chemical, physical or biologicalindicators which are relevant to theobjectives of the monitoring program

* According to the International Standards

Organisations (ISO), quality assurance isdefined as: ‘...all those planned and systematicactions necessary to provide adequate confidencethat a product, process or service will satisfyquality requirements.’

• selecting the appropriate samplingequipment

• obtaining a representative sample orsamples

• making and accurately recording siteobservations and measurements

• labelling, preserving, storing andtransporting the sample correctly foranalysis

• analysing the sample accurately andprecisely for appropriate indicators

• reporting the result accurately andcompletely, and

• providing informed interpretation.

Good communication between the sampler andanalyst is vital because they are mutuallydependent on each other in order to produce arelevant and accurate output.

It is not possible to address all the issues thatcould arise in the field, and specialist advicemay need to be called upon. Statisticians canprovide useful advice on developing a samplingstrategy to adequately represent a complexsituation, while chemists, microbiologists orhydrogeologists may need to be consulted toadvise on the behaviour of a pollutant indifferent elements of the environment.

This Guide aims to provide general direction onappropriate sampling, preservation, storage, andanalytical and quality assurance procedures. Itshould be used for environmental monitoringprograms, assessments, risk management,investigations and audits. The guidelines coverwaters (including groundwaters), wastewaters,wastes and soils, but not biota. They must beused for analyses produced for the purposes ofthe Environment Protection Act 1970 and thePollution of Waters by Oils and NoxiousSubstances Act 1986, unless other proceduresare approved by EPA.

This Guide is a companion publication to AGuide to the Sampling and Analysis of AirEmissions (EPA Publication 440).


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2. PLANNING A SAMPLING PROGRAM

Monitoring or assessment involves the collectionof observations and measurements from the fieldfor interpretation, in order to provide a reliablepicture of the condition or state of a particularelement of the environment.

There is no single methodology that is applicablefor all monitoring and assessment needs.Therefore the design of a successful samplingstrategy is dependent on firstly determining boththe objectives of the program and the hypothesisto be tested. Wherever possible, an objectiveshould be expressed as a statistically testablehypothesis.

In turn, the choice of indicators in mostmonitoring and assessment applications will bedictated by their capacity to reliably reflect anelement of the environment to be monitored.Where characterisation or identification ofpollutants is required, the choice of indicatorswill be dependent on the likelihood of theirpresence in the environment to be tested.

Any sampling program needs to be based on agood understanding of the spatial and temporaldistribution of the indicator and its physico-chemical behaviour in the element of theenvironment being investigated. Statisticalmethodology should be employed to ensure thatsampling locations and timing are representativeof both indicator behaviour and the discharge orstudy area. Spatial and temporal representivityshould be achieved.

Spatial representivity means that the wholestudy area is accurately characterised by a set ofdata. For elements of the environment where apollutant’s distribution is not homogeneous, agood understanding of the factors that affect thisdistribution will assist in developing a statisticalbasis for obtaining a representative picture. Forexample, the spatial distribution of a pollutantcould be affected by spot spills onto soils. In thecase of water bodies, understanding the verticalstratification in large water bodies, and the

effects of mixing in flowing streams, may beimportant in characterising them.

Temporal representivity means that variations intime are accurately characterised by thesampling strategy selected. Examples oftemporal variations include changes in industrialprocesses over a periodic cycle that affecteffluent quality and, storm events where shortterm, peak concentrations of pollutants instormwater enter natural waterways.

Composite sampling is a cost-effective means ofrepresenting study areas or flows that areheterogeneous in space or time, and is alsouseful as a screening tool. In compositesampling, collected samples are mixed to give an‘average’ concentration. Great care needs to betaken to ensure that composites are not biased.However, if the objective of a program is todetect a ‘hot spot’, then composite samplingmay be unsuitable because it dilutes pollutedsingle samples, which could result in the ‘hotspot’ going undetected.

Some pollutants do not mix with the surroundingmatrix. A good example is oil which floats onstill water. If the objective is to quantify itsconcentration, it may prove difficult taking arepresentative volume of the water body. In suchcases, the impact may be governed by the areacovered, which needs to be estimated in the field.If, however, the objective is to characterise thenature of the oil, then skimming the oil off thewater surface will suffice.

Sampling wastes stored in a drum or otherstorage container presents particular problems.It should not be assumed that the contents of thedrum are homogeneous; the sampling strategyshould take into account the nature andquantities of any distinct liquid or solid layers inthe container.

In situ measurement provides a rapid and directmeans of measuring certain qualities in theenvironment (see section 4). Where it providesrelevant and reliable information, it should beused in preference to laboratory testing.

If a program objective requires pollutant loadsto be calculated, accurate flow, volume or mass


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measurement will be required at the samplingpoint.

There are also practical issues that need to beaddressed in designing a sampling program.They are:

• access to the area and media beingsampled;

• the availability of relevant and sufficientlysensitive analytical methods; and

• the distance from, and capacity of, theanalytical laboratory.

The sampling design will need to ensure that thepracticalities of on-site pre-treatment andpreservation (where required) are in accordancewith section 3 of this Guide.

The choice of analytical methods needs to becompatible with the sampling program design.The choice should be made in full understandingof what characteristic of, or component in, thesample needs to be measured to meet theobjectives of the monitoring program.

Good design will assist in determining the limitof detection and precision required which will, inturn, determine the analytical method to be used.For example, ambient heavy metalconcentrations in seawater will be in the part perbillion range or lower, while determining heavymetals in polluted sludge will be many orders ofmagnitude higher. In some instances inexpensivescreening tests may be acceptable, while in otherprograms a high level of accuracy will berequired. Methods to be used should be chosenfrom those presented in section 4 of this Guide.

PROGRAM DESIGN CHECKLIST

q The key to good programdesign is to first determine theobjectives of the samplingprogram and proposehypotheses to be tested.

q Collect backgroundinformation, including:

• potential pollutants, their likelysources and transportmechanisms

• pollutant behaviour, fate andeffects in the environment

• the beneficial uses of thereceiving environment.

q Equipped with the program aimand background, a statisticallyrigorous testing program mustbe developed to meet the testhypotheses.

q Site locations, indicators,timing, frequency and analyticalmethods must be determined inaccordance with the programobjectives and hypotheses.


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3. SAMPLE COLLECTIONAND TRANSPORT

The objective of sampling is to collect andpresent for analysis a sample that properlyrepresents the element of the environment, wasteor waste discharge of interest.

There are physical, chemical and biologicalprocesses that can affect the sample from thetime it is collected to when it is analysed. Toavoid or minimise the effect of these processes,it is necessary to use the appropriate samplingequipment, select the appropriate container andapply preservation methods in order to maintainthe sample’s integrity. Samples must also beanalysed within stipulated holding time limits.

Care is required to avoid contamination of thesample during sampling, handling and transportto the laboratory.

Health and safetyprecautions Safety precautions need to be taken whensampling in the field, and when handlingcontaminated samples and preservativechemicals. The characteristics and features ofeach site and sampling point need to be assessedto ensure the safety of the sampler.

The following precautions and warnings must beobserved when sampling wastewaters, otherwastes or heavily polluted soils, sludges orwastes that may contain harmful chemicals orbacteriological contaminants.

• Skin contact and inhalation of gases fromthe effluents and polluted samples mustbe avoided. Wearing disposable plasticgloves is advisable, and if necessary,wearing suitable protective clothing.

• For sewage effluents, hands should bewashed with bactericidal soap aftersampling such effluent.

• If accidental contact occurs, then rinse theexposed area thoroughly and seek medicaladvice. If regularly sampling or handling

effluents containing sewage, appropriateinoculations should be obtained.

• For hazardous or heavily contaminatedsamples, the sample label should bear awarning to the analyst.

• Where necessary, designated samplingpoints, such as a suitable stable platformshould be provided. Locations should bereadily accessible, and where necessary,safety rails or roping points to whichsafety harnesses can be attached shouldbe available. The sampler should be eitheraccompanied by another person or makeknown their sampling location.

• When sampling wastes, care should betaken to avoid inhaling vapours that couldbe harmful. If necessary, appropriaterespiratory protection should be worn bypersonnel trained in its use. Unless theignition point of the contents orcontaminants is known, precautionsshould be taken on the assumption thatthey are flammable.

• Cuts and skin abrasions should becovered with waterproof dressings.

• A suitable change of clothing should beworn during work.

• Eye protection should be used when thereis a risk of material entering the eye.

• If dusts or aerosols are considered aproblem then masks, conforming toAustralian Standard AS 1715 (StandardsAustralia 1994), should be worn toprevent inhalation. Where possible, workupwind of the application process.

The degree of precaution taken and the type ofprotective equipment and clothing used shouldbe commensurate with the level of risk. When indoubt, assume the worst case outcome willoccur.


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When preserving samples in the field, thefollowing precautions should be observed:

• Familiarise yourself with the safetyprecautions relevant to the preservative(s)to be used.

• The preservation of samples should beperformed on a stable surface such as thelid of a portable cooler or a paved surfacein order to minimise the chances ofspillage.

• Avoid contact with acids, solvents andother preservatives by wearing disposableplastic gloves and safety glasses and byavoiding the inhalation of vapours.

• Addition of acid preservative may releasetoxic gases such as hydrogen sulphide andhydrogen cyanide. This should always bedone in a well-ventilated area, and withdue care. After the acid has been added tothe sample, time should be allowed for allevolved gas to be vented before placingthe lid on the container.

Sampling devicesSampling devices should be constructed ofmaterials that have minimum interaction with,and do not contaminate, the sample. They shouldbe designed in such a way as to minimisedisturbance to the sample.

Sampling devices need to be cleanedappropriately, using the same approach used forsampling containers, as recommended elsewherein this Guide. Sampling devices should be wellcleaned between samples*, particularly whenheavy contamination is suspected. In somecases, it may be necessary to collect the finalrinsate for analysis, in order to demonstrate thatthe sampling device has been sufficiently wellcleaned. Wherever possible, when samplingwaters and wastewaters rinse the container withsome of the material to be sampled.

It is not always possible to collect a liquidsample directly into a sample container. Where

* When this involves the use of detergents orsolvents, the cleaning liquid should be collected anddisposed of appropriately.

access is difficult, a scoop or bucket may beused. When a bucket is used, care must be takento ensure the contents of the bucket remain wellmixed while sub-samples are withdrawn. Fordeep waters, wastewaters and groundwaters, aspecial sampling device (for example, automaticsamplers, Van Dorn bottle) may be needed tocollect the sample, which is then transferred intothe sample container.

Sample containers

Selecting a sample container

Containers are usually glass, polyethylene orpolypropylene, and are selected based on theirlack of interaction with analytical parameters.For example, glass is suitable for samplescontaining trace organics as leaching andadsorption are minimal. However, glass isunsuitable for sampling most trace inorganicsbecause active sites on its surface are capable ofbinding inorganic ions. For some analyticalparameters, fluoropolymer (PTFE) lid linersshould be used.

Washing sample containers

To avoid contamination, sample containers needto be specially washed and pre-treated. Suitablecontainers and special instructions on washingthese containers are presented in Appendix A forwaters, wastewaters and groundwaters,Appendix B for soils and Appendix C forwastes. Even new containers should be washedand dried, unless specifically not recommendedin this Guide.

Containers should only be washed and rinsedwith high-grade reagents and solvents. Thesemay need to be retained and submitted to thelaboratory for analysis as a blank. Wherereagents are added during the preservation step,a sample of the added reagents must besubmitted to the laboratory for analysis as areagent blank.

For waters, wastewaters and groundwaters,rinsing the sampling container with the sample isusually advisable. This minimises anycontamination of the container that may have


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occurred between washing and sampling. Do notfollow this procedure when:

• the analytical parameters are associatedwith immiscible liquids or suspendedparticles that will adhere to the sides ofthe container and may result in higherconcentrations in the sample

• sampling for bacterial or othermicrobiological pollutants, because it isessential that the sterility of the containeris maintained before use and the removalof any de-chlorinating agent must beprevented

• containers already contain preservatives(for example solvent or acid).

In the case of waters, wastewaters and wastes, itis occasionally appropriate to overfill containers,particularly when the analytical parameter ispotentially oxidisable. For requirements forspecific analytical parameters see Appendices Band D.

Sampling watersSampling and analysis plans should be devisedin accordance with the requirements ofAustralian Standard 5667.1-12 (StandardsAustralia 1998a).

Where very low ambient concentrations areexpected, special precautions may need to betaken to ensure samples are not contaminated.The integrity of samples must be maintainedduring sampling, and sources of contaminationshould be avoided.

Precautions for avoiding or minimisingcontamination are suggested below.

• Never handle the insides of containers,lids and collection vessels.

• Where preservative is required for thesample, do not allow the device used toadd the preservative to make contact withthe inside of the container or sample.

• Isolate buffer solutions and preservativesthat could cross-contaminate samples. Forexample, buffer solutions can cross-

contaminate water samples beingcollected for phosphorus analysis.

• Sample containers and chemicalpreservatives may need to be speciallyprepared and purified to ensure no cross-contamination occurs. Specialistlaboratories have clean rooms to handlethe analysis of such samples.

When sampling for volatile species, care shouldbe taken to avoid losses. The sample vial orbottle should be filled gently to reduce agitationthat might drive off volatile compounds. Coolthe sample immediately on ice for transportationto the analysing laboratory.

Sampling surface waters

When waters are well mixed, a sample taken100 mm below the surface, well away from theedge, may be adequate. However, deep andstratified waters may require special devices(such as a Van Dorn sampler) and carefulhandling techniques if the chemical species ofinterest is unstable. A hand or power-drivenpump with an extended inlet tube may be usefulto draw water from selected depths.

When sampling shallow waters, contaminationof the sample from disturbed sediment should beavoided by using an extended inlet of thin tubeon the sample bottle and drawing water into thebottle by suction.

To collect a sample of the surface layer foranalysis, the container should be heldhorizontally in the water, half submerging it. Tocollect a sample of the water beneath a surfacelayer, a syringe or other device with an extendedinlet tube capable of piercing the surface layer,may be appropriate, depending on the thicknessof the surface layer.

In all cases, ensure that the sampling device ormethod does not contaminate the sample.


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Sampling groundwaters

Regular testing of groundwater quality isusually done from bores. Monitoring boresshould be constructed in accordance with theguidelines of the Agriculture and ResourceManagement Council of Australia and NewZealand (ARMCANZ 1997).

Groundwater sampling should be undertaken inaccordance with Groundwater SamplingGuidelines (EPA 2000).

Sampling groundwaters by pumping or bailingthe sample to the surface requires specialprecautions to avoid contamination. Allequipment that either enters a bore or carries thewater from the bore to the sampling containershould be cleaned before each sample is taken.Special care needs to be taken for certainanalytical parameters that can be affected by thepresence of dissolved gases.

Sampling a waste discharge

The most representative sample of a wastedischarge is from a point where the effluent isthoroughly mixed and close to the outlet fromthe discharging premises. For a licenseddischarge, a sampling point will normally bedescribed in the licence, and samples mustalways be taken from that point.

Use of automatic samplers

Automatic samplers are used to monitor diurnalvariations or to collect temporal compositesamples from a water body. The probe for thesesamplers should be placed sufficiently far fromboth the surface and bottom of the water bodyso that the sample is not affected by the presenceof the air/water or sediment/water interface.

Sampling soils Sampling and analysis plans should be devisedin accordance with the requirements of theAustralian and New Zealand Guidelines for theAssessment of Contaminated Sites(ANZECC/NH&MRC 1992) and AustralianStandard 4482.1 (Standards Australia 1997a) orAustralian Standard 4482.2 (Standards

Australia 1999). When sampling soils forvolatile contaminants, special precautionsshould be taken to prevent evaporative losses.

Collection of samples should be accomplishedwith minimal disturbance, using a coring device.The core soil sample should either be immersedinto methanol in the field; or the core should beplaced into a vial that will also act as a purgevessel in the laboratory. These methods havebeen shown to provide generally more accurateresults than placement of samples into jars(USEPA 1991).

If the soils to be sampled are suspected of beingacid sulfate soils or potential acid sulfate soils,the EPA Information Bulletin Acid Sulfate Soiland Rock (EPA 1999) provides guidance andfurther references on sampling and handling.

When sampling from a test pit, samples shouldbe taken from the lowest point first to preventcross contamination from other sampling points.

Before sampling, vegetation and other non-soilmaterial (including rocks and concrete) shouldbe removed by hand. Any material removedshould be weighed and its description recorded.

Sampling sediments The best locations for sampling sediments arewhere fine materials accumulate. These aregenerally confined to areas where there is littleor no flow.

Sediment samples can be collected using anumber of devices including grabs, scoops,corers, shovels and buckets. When sampling fororganic analysis, sampling devices should beconstructed from metal. Conversely, whensampling for metals, sampling devices should beconstructed from plastic.

Where there is a lack of fine sediment, morethan one scoop or grab sample may be necessaryto obtain a sufficient amount of material. Thesesamples should be combined and mixed wellbefore processing for analysis.


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Sampling wastes At all times it is important that sampling iscarried out so that representative samples areobtained. Sampling wastes can be difficult if thewastes are heterogeneous, contain manydifferent types of waste, or the contamination isnot evenly distributed. In these circumstances, itcan be useful to keep different types of wasteseparate (for example by separating the phasesin a multi-phase waste), or to separate differentportions that contain high levels ofcontaminants. General guidance on samplingcan be obtained from Pierre Gy’s SamplingTheory and Sampling Practice: Heterogeneity,Sample Correctness and Statistical ProcessControl (Pitard, 1989) particularly when thereare large amounts of waste to be sampled.

Liquid wastes should be handled according tothe methods for sampling waters describedabove. Waste soils should be treated accordingto the guidelines for soils above.

For solid wastes with particle sizes greater thansoils, or non-uniform particle sizes, AustralianStandard 1141.3:1996, (Standards Australia,1996) may be relevant in some cases. Wastescontaining biosolids should be handled andtreated according to the procedures listed inAppendix C for the individual parameters bywhich the wastes are to be characterised.

Preserving samples When biological, chemical or physical changesto the sample may occur between the time it iscollected and when it is analysed, it must beeither chemically or physically preserved toretard such processes.

Preservation methods vary greatly in theireffectiveness and should only be employed whenthe sample cannot be analysed within a fewhours of collection. Preservation should becarried out as soon as possible after sampling.

Recommended preservation methods for waters,wastewaters and groundwaters are given inAppendix A, for soils and sediments inAppendix B, and for wastes in Appendix C.

Freezing

Water and soil samples are best frozen in smallamounts sufficient for the determination of oneparameter. This procedure avoids repeatedthawing and re-freezing if the total analysis isspread over a number of days. Quick freezingwith dry ice is recommended.

For water, wastewater and groundwater samplesprovide sufficient air gap in the container toallow expansion of the liquid.

Thawed samples must be mixed and allowed toreach ambient temperature before anymeasurements or analysis.

Cooling

Samples that need to be cooled to between 1°Cand 4°C should be placed in an insulatedcontainer or icebox containing a mixture ofwater and ice, and checked to ensure that someice always remains. Alternatively, amaximum/minimum thermometer can be used inthe icebox to check that the temperatureremained within this range during transport tothe laboratory.

Acidification

For water samples, acidification to below pH 2is used to preserve most trace metals. Thisreduces precipitation and sorption losses to thecontainer walls. A sample of the acid used,which should be of analytical grade and havelow metal content, must be retained for analysisas a blank by the laboratory and correction ofthe analytical results for any analyte present.For groundwaters, acidification should only beapplied to filtered samples.

Reagent addition

Reagents may be added to samples to chemicallyfix the analytical parameter. Reagents addedshould be of high grade, and blanks provided tothe laboratory so that contamination levels canbe checked.

When chemicals are added to a sample topreserve or fix an analytical parameter, it isimportant to separate procedures for sampling,


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sample handling and analysis for eachparameter, to minimise any risk of cross-contamination. For example, nitric acid used forcontainer preparation and as a preservative forheavy metals analysis can contaminate samplesto be analysed for nitrate. Similarly, coppersulfate used for preservation of phenols maycontaminate samples for metals analysis.

For heavily contaminated samples, care needs tobe taken when adding chemical preservativesthat could release hazardous gases. Forexample, when adding acid to preserve a samplecollected for a heavy metal analysis, care shouldbe taken to ensure that the sample does not alsocontain high concentrations of cyanide whichcould result in release of hydrogen cyanide gas.

Solvent extraction

A solvent may, at times, be added to extract theanalyte from its matrix. For analysis of organicpollutants such as hydrocarbons, PAHs andsome pesticides, an initial on-site solventextraction in the sample container may benecessary. Samples of the solvent and containersused should be submitted for analysis.

Field filtration

Filtration of water samples in the field may berequired in the following circumstances.

• Where organic and inorganiccontaminants adsorb onto suspendedmatter in water, wastewater andgroundwater samples.

• Where the concentration of dissolvedcontaminants or the contaminantsassociated with suspended matter need tobe determined.

Filtering should occur immediately aftercollection and the analysis conducted on thefiltered liquid, the particles, or both.

Filtration can be undertaken under gravity or byapplying vacuum or pump pressure.

Filters and filtering devices should be cleaned ina similar manner to sample containers, and caretaken that contamination is not introduced in thefield. Filters from the same batch as used in the

field, and the filtering device should be providedto the laboratory so that blank levels can bedetermined. On-site (between sample) finalrinses from filtration equipment should also besubmitted to the laboratory as ‘rinsate blanks’for analysis.

Preserving soil samples

Often soil samples are moist when collected.This moisture can accelerate microbial action,which can change the concentration of somecontaminants. In these circumstances, it isrecommended to store the soil at 4°C or below.

Labelling and logging Samples should be adequately described andsecurely labelled at the sampling site.

The sample container must be labelled touniquely identify the sample, and the time andlocation of sampling. Use a solvent basedmarking pen (preferably black) or similarwaterproof means of marking. Any changes to alabel should be initialled and dated.

The sample log must show all relevant information,including where (precise location and depth) andwhen (date and time of day) the sample was takenand other relevant information.

Details of preservatives added (the type,concentration before addition and quantityadded) and other pre-treatment applied to thesample must be noted on the label.

An example of a label used for samples is shownbelow:


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A submission sheet must accompany all sampleswhen handed to the laboratory. This containsrelevant information about the sample and thenature of the analyses required and is signed offby the person delivering the samples and theperson receiving them.

Transporting samples Transport of the sample to the laboratory shouldbe done as soon as possible after sampling, andwithin the stipulated holding times (AppendicesA, B and C).

Before and during transport, the followingprecautions must be taken to:

• check that container seals or caps aresecured tightly to prevent leakage

• ensure sample labels remain on containersand are not damaged during transit

• store all bottles upright, and

• prevent containers from unnecessarymovement during transport, and inparticular ensure glass bottles arecushioned to prevent breakage.

When collecting and transporting samples, allpossible sources of contamination must beavoided. A few examples are given below:

• vehicle exhausts (hydrocarbons or lead)

• airborne dusts

• ammonia solutions – including cleaningagents – must not be handled or stored inthe vicinity of sampling or analyticaloperations

• smoking during sampling and analyticaloperations must be avoided –cigarette ashand smoke contain contaminants such asphosphate, nitrate, hydrocarbons, andheavy metals.

If there is concern that contamination hasoccurred, the sample and container should bediscarded, and a fresh sample collected.

Approved samplers Sampling requires special expertise and must beundertaken by trained people.

Whenever sampling or field analysis isundertaken, it must done within the frameworkof a well-documented quality system. Thisapplies whether the analysing laboratory is alsoresponsible for the sampling, whether acompany monitoring its own wastes orwastewaters does it, or another organisation iscontracted to conduct the sampling.

Preferably, sampling should be undertaken bypeople operating within a laboratory systemaccredited by the National Association ofTesting Authorities (NATA) for sampling.Otherwise, people taking samples must meet thefollowing requirements.

• Samplers must have undertaken face-to-face training by an appropriate body withexperience in sampling, and be able todemonstrate that they have the knowledgeand ability to safely take, preserve, storeand transport samples within therequirements of this Guide. This wouldinclude programmed refresher training,with records to be kept on the nature andfrequency of training provided.

• The laboratory conducting the analysis isto provide appropriately prepared samplecontainers and preservatives, for theanalytes of interest.

• Sufficient records of the sampling are tobe prepared and maintained by thesamplers so that the results obtained bythe laboratory can be related back to thedate, time and location of sampling.

Evidence showing that the above requirementshave been satisfied shall be documented.


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SAMPLE HANDLING ANDPREPARATION CHECKLIST

qq Ensure that there is goodcommunication betweensampling staff and thelaboratory on precautions to betaken in the field.

qq Observe all safety precautionsduring sampling, in particulartaking care to avoid contactwith contaminated samples.

qq Ensure that the selection ofsample containers, thecontainer pre-treatmentprocedures (such as washing),the sample preservationprocedures and the sampleholding times stipulated in thisGuide are followed.

qq Ensure that, where reagents areadded to the sample or thesample is filtered, blanks arecollected and delivered to thelaboratory for analysis of blanks.

qq Take precautions to ensuresamples are not contaminatedby reagents, polluted samplesor environmental sources in thefield or during transport, andthat samples are securedduring transport to avoiddamage.

qq Complete the sampleidentification and descriptionon a label attached to thesample and on the submissionsheet, including any treatmentof the sample undertaken in thefield.


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4. ANALYTICAL METHODS AND QUALITY ASSURANCEPROCEDURES

Approved laboratories Laboratories performing analyses should beaccredited by NATA for all the tests conducted.In addition, the laboratory should be experiencedand proficient at testing the types of samples, atthe concentration ranges required, for theparticular program.

Where testing is being undertaken for statutorypurposes under the Environment Protection Act1970 or the Pollution or Waters by Oils andNoxious Substances Act 1986, NATAaccreditation of the laboratory is a requirement,unless permission is given by EPA to use a non-accredited laboratory.

Approved analyticalmethods Only analytical methods chosen from theapproved references listed for eachenvironmental matrix in this chapter should beused. Minor changes can be made to thesemethods, provided that the changes are of littleconsequence.

For all methods used, the laboratory needs todemonstrate that it can accurately analyse forthe relevant analytes, in the types ofenvironmental samples, and in the concentrationrange normally encountered. This can be doneby either:

• proficiency tests, or

• checking against standard referencematerials.

It is also necessary to determine the precision(both reproducibility and repeatability),selectivity, limits of detection, linearity andapplicable range of concentrations when usingthe method.

Procedures that should be followed for methodvalidation are available in Requirements for theFormat and Content of Test Methods andRecommended Procedures for the Validation ofChemical Test Methods [NATA Technical NoteNo. 17] (NATA 1997).

For statutory testing, methods not based on anyof the methods in the approved references canonly be used with prior approval of EPA.Validation of the proposed procedure must bedemonstrated before approval can be granted.

It is important that the analyst verifies thesuitability of the procedure used for theparticular sample type under investigation,before commencing the analysis.

Limits of detection andreportingIt is important that the limits of detection andreporting are reliably established beforesampling and analysis are undertaken. A methodfor estimating the limit of detection and the limitof reporting (also known as the ‘limit ofquantitation’) is provided in NATA TechnicalNote No. 17 (NATA 1997).

The limit of detection is defined as the lowestconcentration of analytical parameter in asample that can be detected, but not necessarilyquantitated. The limit of reporting is defined asthe lowest concentration of an analyticalparameter that can be determined withacceptable precision and accuracy. In practice,the limit of reporting is frequently taken to beten times the limit of detection (NATA, 1997).However, some laboratories may use limits ofreporting that are five times the limit ofdetection (APHA 1995).

The selected methods should have appropriatedetection limits for the objectives of theprogram. This is particularly relevant whentesting ambient waters, as dissolved species areinvariably at much lower concentrations thanwastewaters. For instance the detection limit forlead using flame atomic absorption spectroscopyis 50 µg/L, whereas using graphite furnaceatomic absorption spectroscopy it is 1 µg/L,


13

more suitable for pristine waters. Detectionlimits may also be affected by interferences.

Waters, wastewaters andgroundwatersFor waters, wastewaters and groundwatersmethods selected from the standard referenceslisted below* should be used.

1. American Public Health Association1995, Standard Methods for theExamination of Water and Wastewater.

2. US Environmental Protection Agency1979, Methods for Chemical Analysis ofWater and Wastes.

3. American Society for Testing andMaterials 1992, Water andEnvironmental Technology.

4. US Environment Protection Agency 1978,Microbiological Methods for Monitoringthe Environment, Water and Wastes.

5. Department of the Environment 1994,The Bacteriological Examination ofDrinking Water Supplies, Report onPublic Health and Medical Subjects, No.71, Method for the Examination ofWaters and Associated Material.

6. Relevant Australian Standards.

Trace analysis

For analysis at very low contractions (at µg/Land below) special precautions need to be taken.

Publications such as USEPA Method 1669(USEPA 1995) should be referred to for thespecifics of sampling at trace levels. For alltrace level work, sample container cleanlinessmust be established before sampling isundertaken. Treating a statistically significantnumber of containers from any batch by therelevant extraction method and analysing theextract for the analytical parameters of interestshould do this.

* The latest editions of these references at the timeof publishing this Guide are referenced. Where theyare superseded, the most recent edition should beused.

For guidance on the installation and use of cleanrooms and clean workstations see AustralianStandards 1386.1–7 (Standards Australia 1989).

Trace level analysis methods for seawaters canbe obtained from either Methods of SeawaterAnalysis (Grasshoff 1983), A Manual ofChemical and Biological Methods for SeawaterAnalysis (Parsons 1989) or A PracticalHandbook of Seawater Analysis (Strickland1974).

During sampling of seawaters, extreme careshould be taken to avoid contamination of thesample by the sampling equipment or boat. Thepublications listed should be consulted forguidance on choice of equipment andprocedures.

In situ measurements

While most of the methods cited above relate tolaboratory analyses, they also include field or insitu measurements for selected environmentalindicators.

In situ measurement provides a rapid means toassess certain aspects of water quality. It has theadvantage of overcoming the possibility ofcontamination or change in sample compositionbetween collection and analysis.

Common in situ measurements include pH,temperature, turbidity, dissolved oxygen andconductivity. Some ions, such as fluoride andsulphide can also be determined using ionselective electrodes, although their determinationcan be subject to matrix interferences.

Ensure field instruments are robust and reliable,and that they are capable of measuring to theappropriate level of accuracy. They must becalibrated with fresh solutions before use. pHand dissolved oxygen meters need to becalibrated before every use. This can beperformed either in the laboratory or in the field.The manufacturer’s instructions are the bestguide for the use of any particular meter;however, meters must be calibrated according tothe NATA publications General Requirementsfor Registration: Supplementary Requirements:


14

Chemical Testing (NATA 1993) and TechnicalNote No. 19 (NATA 1994).

The meter must be calibrated over anappropriate range for the samples analysed. Ifthe meter is to be used over a period of severalhours, periodic readings of a reference solutionmust be made to ensure the calibration is stable.If excessive drift is observed, readings takenover the period of drift must be discarded.

While field meters are designed to take a certainlevel of harsh treatment (such as knocks,vibration, extreme temperature changes), goodmaintenance and calibration regimes ensure thatthey produce reliable and accurate data.

Secondary parameters such as temperaturesalinity, altitude and air pressure may affectcertain field measurements. For instance,dissolved oxygen readings are affected by all ofthe above parameters. If the field meter does notautomatically measure and compensate for thesecondary parameter, then this parameter mustbe measured, using the appropriate equipment,and a manual compensation performed. Themanufacturer’s instructions should be consultedfor correction factors.

Many factors may cause interference whentaking field measurements. These interferencescannot be compensated for; in particular, oilyfilms and high levels of suspended solids maycause problems. If the measurements are beingtaken in unusual situations, the manufacturer’sinstructions should be consulted to checkwhether interference could occur.

Where in situ measurements are incorporatedinto a process or effluent stream to providecontinuous monitoring, adequate levels of datavalidation through frequent calibration checksare required. The manufacturer’s instructionsfor the meter concerned should be consulted forthe appropriate calibration method. Anycalibration regime must be based on a soundknowledge of the process and the nature of theeffluent stream. Guidance may be obtained fromProcess Instruments and Controls Handbook(Considine 1985).

Radioactivity measurements

Some of the references cited above includemethods for the measurement of radioactivity.Other suitable methods for the measurement ofgross radioactivity can be found in theinternational standards ISO 9696:1992 (ISO1992a) and ISO 9697:1992 (ISO 1992b).

Soils and sedimentsFor the analysis of soils, Guidelines for theLaboratory Analysis of Contaminated Soils(ANZECC 1996) or Test Methods forEvaluating Solid Wastes: Chemical/ PhysicalMethods (USEPA 1997) should be followed.The procedures for quality control, described inthe latter document, should also be followed.

For measuring radioactivity in soils, use themethods included in Eastern EnvironmentalRadiation Facility Radiation ProceduresManual (Lieberman 1984).

For the analysis of acid sulfate soils or potentialacid sulfate soils, EPA Information BulletinAcid Sulfate Soil and Rock (EPA 1999) shouldbe consulted.

Depending on the objectives of the program, itmay be necessary to remove interstitial waterfrom the sample by filtration. This may need tobe done in the field if the contaminantequilibrium between the solid and liquid phasesis dynamic.

As the nature of the soil or sediment can have asignificant effect on the behaviour andenvironmental availability of contaminants, it isoften desirable to characterise the soil type,including other relevant information such as pH,ion exchange capacity, clay content, moisturecontent and permeability

Determination of contaminants in soils andsediments may entail measurement of the totalconcentration. Alternatively, a bio-available orleachable fraction may be determined.Therefore, the digestion step is of paramountimportance in determining the fraction of totalcontaminants present.

Often it is necessary to determine thepermeability or hydraulic conductivity of a soil.


15

The test methods to be used will vary dependingon the range of permeability values likely to beencountered and the purpose for which themeasurements are being made. Test methodswill, generally be applicable to either laboratorytests or field tests, but not both.

Relevant Codes of Practice, published as part ofthe EPA Best Practice EnvironmentalManagement Series*, contain details of tests tobe used to determine soil permeability. Forexample, the requirements for testing soilpercolation rates for septic tank installations aregiven in Code of Practice-Septic Tanks (EPA1996).

In the absence of a relevant Code of Practice,ASTM Standard D5126–90 (ASTM, 1998)contains references to a number of field tests forsoil permeability, and their applicable range ofpermeability values.

There are also American Society for Testing andMaterials (ASTM) Standards (ASTM 1990)and Australian Standards (Standards Australia1998b) which describe laboratory methods fortesting soil permeability. There is someuncertainty about the applicability to fieldconditions of the results obtained from testsaccording to these methods. As such, thesemethods should be treated with some caution iffield permeability is to be assessed.

In situ measurements

As for waters, a range of in situ measurementsmay be appropriate for characterising soils, forexample, field soil gas measurements using aphoto-ionisation analyser. Consult the section onin situ measurements above as similarrequirements regarding use and calibration applyto waters and to soil samples.

* This series of publications is updated from time totime, and only the latest editions should be used.

WastesProcedures to determine total concentrations of arange of contaminants in wastes are listed inTest Methods for Evaluating Solid Wastes.Chemical/ Physical Methods (USEPA 1997).

There are a number of other characteristics ofwastes that affect their environmental impact,and may need to be measured. They areleachability (the tendency for contaminants to beleached by rain or groundwater), flammability orignitability, corrosivity and the amount ofcontained free liquids. Some of the suitable testmethods are listed below.

Leachability and leachates

Leachable organics (volatile and semi-volatile),metals and anions (except cyanide) may bedetermined using the Toxicity CharacteristicLeaching Procedure (TCLP), which is method1311 in Test Methods for Evaluating SolidWastes. Chemical/ Physical Methods (USEPA,1997).

Alternatively, Australian Standard 4439.2(Standards Australia 1997b) can be used forvolatile organics, and Australian Standard4439.3 (Standards Australia 1997c) can be usedfor semi-volatile organics, metals and anions.

The methods in the Australian Standards aredifferent from the USEPA method in that awider range of leaching reagents is allowed. Allmethods are designed to simulate leachingconditions in the environment to determineavailable pollutants. The choice of leach reagentshould be based on the environmental conditionsto which the wastes are, or will be, exposed .

Leachable cyanide may be determined byMethod 1312, the Synthetic PrecipitationLeaching Procedure (USEPA 1997) or byleaching with distilled or de-ionised water only,using the methods in Australian Standard4439.2 (Standards Australia1997b).

Leachates collected from the environment shouldbe analysed using the methods listed for watersand wastewaters.


16

Flammability and ignitability

Flammability of liquid wastes may be assessedby determining whether a flash occurs onapplication of a flame to sample vapours. Asuitable procedure is described in ASTMMethod D327–96 (ASTM 1992). ‘Ignitability’is a characteristic of a waste that once ignited,burns. This characteristic can be measured usingMethod 1030 in Test Methods for EvaluatingSolid Wastes: Chemical/Physical Methods(USEPA, 1997).

Corrosivity

‘Corrosivity’ is defined as the ability of asubstance to attack human skin or plant andequipment. Often this is due to extreme acidityor alkalinity, and waste pH is normally tested.Liquid waste pH may be measured directlyusing a calibrated pH meter. The prescribed testfor soils and solid wastes is Method 103 inGuidelines for the Laboratory Analysis ofContaminated Soils (ANZECC 1996). Tomeasure corrosivity of a waste towards steel useMethod 1110, ‘Corrosivity Toward Steel’ fromTest Methods for Evaluating Solid Wastes:Chemical/Physical Methods (USEPA 1997).

Free liquid determination

To determine free liquid use Method 9095A:‘Paint Filter Liquids Test’ in Test Methods forEvaluating Solid Wastes. Chemical/PhysicalMethods (USEPA 1997).

Volatile contaminants insoils and wastesFor determination of volatile contaminants insoils and wastes, special precautions must betaken to avoid losses during sampling, transport,storage and analysis.

As samples for volatile analysis cannot be takenfrom thoroughly homogenised bulk samples,small samples should not necessarily beregarded as representative of the whole material.Therefore, a sufficient number of samplesshould be taken to confidently obtain anaccurate measure of average concentrations.

Samples taken for analysis of volatilecomponents should be separate from those takenfor other analytical parameters. This will allowfor volatile analysis to be repeated, if necessary,on samples that have not been homogenised orotherwise inappropriately treated.

Volatile components should be determined usingthe ‘purge and trap’, procedure. Methodsinvolving measurement of headspaceconcentrations may be less rigorous, and shouldonly be used for screening soil samples. Use themethods outlined in Test Methods forEvaluating Solid Wastes: Chemical/PhysicalMethods (USEPA 1997) for both theseprocedures.

Qualitative analysisSometimes, it is necessary to identifycomponents in a sample or confirm theirpresence prior to conducting a quantitativeanalysis. In such cases, a qualitative test may beused. Texts such as Spot Tests In OrganicAnalysis (Feigl and Anger 1966), Spot Tests inInorganic Analysis (Feigl and Anger 1972) andVogel’s Qualitative Inorganic Analysis (Vogel1996) are useful references.

Commercially available qualitative and semi-quantitative test kits may also be used. But, ineither instance, the analyst must be familiar withthe limitations of the method used, particularlypossible interferences and what factors are likelyto contribute to false positive or false negativeresults. Whenever qualitative tests are used,quality control should be incorporated, includinga blank, at least one standard or referencematerial, and a spike of standard into a sample.

For solid materials that have a limited solubility,x-ray diffraction analysis (XRD) may provideuseful information on the identity of compoundspresent in the sample. However, XRD doessuffer from some limitations. Only crystallinesubstances will give an XRD response.Components representing less that 5% of thesample cannot be identified with any reliability.Elements of X-ray Diffraction (Cullity 1978)and X-Ray Diffraction Procedures: ForPolycrystalline and Amorphous Materials


17

(Klug and Alexander 1974) are usefulreferences.

Toxicity screening testingIf contaminated samples require screening teststo give an indication of their likely toxicity, theMicrotox® is the recommended technique. Theuse of this technique is described in EPAScientific series publication SRS 89/012(Hinwood 1990). Other toxicity screening testsmay be used if approval is obtained from EPA.

Quality assuranceA laboratory quality assurance system is arequirement of NATA accreditation, andlaboratories should seek to constantly assesstheir competence by participating, wheneverpossible, in inter-laboratory proficiencyprograms. Additional details on qualityassurance and quality control are presented inAppendix D.

Analysts receiving samples need to assurethemselves that they were collected inappropriate containers and they have beenpreserved in a manner recommended in thisGuide. A statement should be included in thereport on whether there have been anydepartures from the requirements outlined in thisGuide.

TEST METHODS CHECKLIST

qq Select the appropriate methodof analysis from thoseapproved in this Guide.

qq For field measurements, ensurethat meters are calibratedbeforehand.

qq Ensure that an adequate QualityAssurance regime is in place inthe laboratory and fieldprocedures.

qq Report analytical data on NATA-endorsed reports, whereappropriate.

qq Analysts should include astatement in their report thatsamples have been collected ina manner recommended in thisGuide.


18

5. REPORTING AND REVIEW OF RESULTS

Analytical reportsThe final product of sampling and analysis, theanalytical report, must have sufficientinformation for the end user to make a criticalevaluation of its contents. The analytical reportformat should comply with the NATArequirements.

The following information is usually reportedwith the analytical result for each parameterdetermined. This information is either providedby the person taking the sample or by thelaboratory and should include:

• identification of the sample (includesample description, location, samplenumber and unique laboratory number)

• date and time of sampling

• field observations and in situmeasurements

• field pre-treatment details, if any samplepreservation procedure

• reference to analytical method used.

• date of determination

• accurate description of the parameter

• results, in the appropriate units

• notations of any deviation from thesampling or analytical proceduresrecommended in this Guide.

Analysts should define the quality measured andensure reporting meets the formats required inthe standard method.

The limit of detection for each analyte should bequoted with quantitative test results.Concentrations below the limit of reportingshould be quoted as a ‘less than’ (<) figure.

Results are normally reported as mg/L or µg/Lfor concentrations in solutions, mg/kg or µg/kgfor concentrations in solids and organisms/100mL for concentrations of bacterial organisms inliquids. For radioactivity measurements, the

units are Bq/L for concentrations in solutionsand Bq/g for concentrations in solids.

It is preferable to report results that are notcorrected for spike recovery unless a test methodspecifically requires analytical results to bereported after correcting for recovery (NATA1997). A statement of the spike recoveryachieved provides the maximum information onthe quality of the test result to the recipient ofthe report.

Reviewing dataAll analytical results should be reviewed onreceipt by the person or organisation requestingthe analysis, and action taken if abnormal orunexpected levels are detected. When reviewingdata:

• compare results with those expected andquery unusual results

• as a general rule duplicates should agreewithin 10% and spike recovery valuesshould be between 80–120%. (If qualitycontrol results fall outside of this range,query the laboratory)

• identify problems, and

• take appropriate action to address theproblems identified.

If monitoring is being undertaken as a dischargelicence condition, then whenever the licenceemission limits are exceeded, the breach shouldbe reported immediately to EPA, in accordancewith the licence conditions. The reasons leadingto the breach and action taken to ensure futurelicence compliance should be included in thisreport.


19

REPORTING CHECKLIST

qq Analytical reports shouldinclude all relevant information

qq Analytical reports shouldinclude a statement thatsamples have been collected inaccordance with proceduresrecommended by this Guide.

qq Detection of abnormal orunexpected concentrations orpolluted samples should bereported quickly so that actioncan be taken to address theproblem.


20

6. REFERENCES

ANZECC/NH&MRC 1992, Australian andNew Zealand Guidelines for the Assessment ofContaminated Sites, Australian and NewZealand Environment and Conservation Council.

ANZECC 1996, Guidelines for the LaboratoryAnalysis of Contaminated Soils. Australian andNew Zealand Environment and ConservationCouncil.

APHA 1995, Standard Methods for theExamination of Water and Wastewater, 19th

Edition, American Public Health Association,Washington DC.

ARMCANZ 1997, Guidelines for MinimumConstruction Requirement for Water Bores inAustralia, Agriculture and ResourceManagement Council of Australia and NewZealand, Department of Resources, Brisbane.

ASTM 1990, Standard Test Method forMeasurement of Hydraulic Conductivity ofSaturated Porous Materials Using a FlexibleWall Permeameter, Standard D5084-90,American Society for Testing and Materials,Philadelphia.

ASTM 1992, Water and EnvironmentalTechnology, Volumes 11.01 to 11.04, AmericanSociety for Testing and Materials, Philadelphia.

ASTM 1998, Standard Guide for Comparisonof Field Methods for Determining HydraulicConductivity in the Vadose Zone, StandardD5126-90 (1998), American Society for Testingand Materials, Philadelphia.

Considine, D.M. and Considine, G.D. 1985.Process Instruments and Controls Handbook,McGraw-Hill, New York.

Cullity, B.D. 1978, Elements of X-rayDiffraction, Addison-Wesley, Reading, MA,USA.

Department of the Environment 1994, TheBacteriological Examination of Drinking WaterSupplies, Report on Public Health and MedicalSubjects, No. 71. Method for the Examination

of Waters and Associated Material. UKDepartment of the Environment.

EPA 1996, Code of Practice – Septic Tanks,EPA Best Practice Environmental ManagementSeries, EPA Publication 451, EnvironmentProtection Authority (Victoria).

EPA 1999, Acid Sulfate Soil and Rock EPAPublication 655, Environment ProtectionAuthority (Victoria).

EPA 2000, Groundwater Sampling Guidelines,EPA Publication 669, Environment ProtectionAuthority (Victoria).

Feigl, F. and Anger, V. 1966, Spot Tests inOrganic Analysis, Elsevier Science,Amsterdam, London, New York.

Feigl, F. and Anger, V. 1972, Spot Tests inInorganic Analysis, Elsevier Science:Amsterdam, London, New York.

Grasshoff, K., Erhardt, M. and Kremling, K.1983, Methods of Seawater Analysis, VerlagChemie, Weinheim, Deerfield Beach, Florida,Basel.

Hinwood, A., McCormick, M. and McCormick,R. 1990, Evaluation of the Microtox Techniquefor the Assessment of Toxicity in Waters andWastewaters, Scientific Series SRS 89/012,Environment Protection Authority (Victoria).

ISO 1992a, Water Quality-Measurement ofGross Alpha Activity in Non-saline Water-thickSource Method, International StandardsOrganisation.

ISO 1992b, Water Quality-Measurement ofGross Beta Activity in Non-saline Water,International Standards Organisation.

Juniper, I.R. 1995, ‘Method validation: Anessential element in quality assurance’, inQuality Assurance and TQM for AnalyticalLaboratories, Parkany, M. (Ed), Royal Societyof Chemistry, London.

Klug, H.P. and Alexander, LeR 1974, X-rayDiffraction Procedures: For Polycrystallineand Amorphous Materials, John Wiley & Sons,London.


21

Lieberman, R. 1984, Eastern EnvironmentalRadiation Facility Radiation ProceduresManual, NTIS Publication EPA520/5-84-006,National Technical Information Service,Springfield, VA, USA.

NATA 1993, General Requirements forRegistration: Supplementary Requirements:Chemical Testing, National Association ofTesting Authorities.

NATA 1994, Technical Note No. 19, Liquid-in-glass Thermometers – Selection, Use andCalibration, National Association of TestingAuthorities.

NATA 1995a, Guide to Development of aQuality System For a Laboratory, NationalAssociation of Testing Authorities.

NATA 1995b, Technical Note No. 23,Guidelines for Quality Control in theAnalytical Laboratory, National Association ofTesting Authorities.

NATA 1997, Technical Note No. 17, Formatand Content of Test Methods and Proceduresfor Validation and Verification of ChemicalTest Methods, National Association of TestingAuthorities.

Parsons, T. 1989, A Manual of Chemical andBiological Methods for Seawater Analysis,Pergamon Press, Oxford, New York.

Pitard, F.F. 1989, Pierre Gy’s Sampling Theoryand Sampling Practice: Heterogeneity, SampleCorrectness and Statistical Process Control,Books Britain, London.

Standards Australia 1989, AS 1386.1-1989 –1386.7-1989, Cleanrooms and CleanWorkstations, Standards Australia, NSW.

Standards Australia 1994, AS/NZS 1715: 1994,Selection, Use and Maintenance of RespiratoryProtective Devices, Standards Australia, NSW.

Standards Australia 1997a, AS 4482.1: 1997,Guide to the Sampling and Investigation ofPotentially Contaminated Soil, Part 1 Non-volatile and Semi-volatile Compounds,Standards Australia, NSW.

Standards Australia 1997b, AS 4439.2-1997,Wastes, Sediments and Contaminated Soils –Preparation of Leachates – Zero HeadspaceProcedure, Standards Australia, NSW.

Standards Australia 1997c, AS 4439.3-1997,Wastes, Sediments and Contaminated Soils –Preparation of Leachates – Bottle LeachingProcedure, Standards Australia, NSW.

Standards Australia 1998a, AS/NZS 5667.1-12:1998, Water Quality – Sampling, StandardsAustralia, NSW.

Standards Australia 1998b, AS 1289.6.7.3:1998, Soil Strength and Consolidation Tests –Determination of Permeability of a Soil –Constant Head Method Using a Flexible WallPermeameter, Standards Australia, NSW.

Standards Australia 1999, AS 4482.2: 1997,Guide to the Sampling and Investigation ofPotentially Contaminated Soil, Part 2: VolatileCompounds, Standards Australia, NSW.

Strickland, J.D.H. and Parsons, T.R. 1974. APractical Handbook of Seawater Analysis,Bulletin 167, Fisheries Research Board ofCanada.

USEPA 1978, Microbiological Methods forMonitoring the Environment Water andWastes, USEPA Publication No. EPA-600/8-78-017, United States Environmental ProtectionAgency.

USEPA 1979, Methods for Chemical Analysisof Water and Wastes, USEPA Publication No.EPA-600/4-79-020, United StatesEnvironmental Protection Agency.

USEPA 1991, Soil Sampling and Analysis forVolatile Organic Compounds, USEPAPublication No. EPA-540/4-91-001, UnitedStates Environmental Protection Agency.

USEPA 1995, Method 1669: Sampling AmbientWater for Trace Metals at EPA Water QualityCriteria Levels, USEPA Publication No. EPA-821/R-95-034, United States EnvironmentalProtection Agency.

USEPA 1997, Test Methods for EvaluatingSolid Wastes, USEPA Publication No. EPASW-


22

846, Third Edition, Final Update III, UnitedStates Environmental Protection Agency.

Vogel, A.I. 1996, Vogel’s Qualitative InorganicAnalysis, Longman Harlow, Essex, England.

Guide to the Sampling and Analysis of Waters, Wastewaters, Soils and Wastes

23

APPENDIX A: CONTAINERS, PRESERVATION AND HOLDING PERIODS FOR WATERS,GROUNDWATERS AND WASTEWATERS

Sample containers and their preparationSelection and preparation of containers, sample pre-treatment, preservation and holding periods must comply with this Appendix, which is based, in part, onAS/NZS 5667.1:1998*. The third column lists typical volumes for a single determination, and should only be used as a guide. To determine very lowconcentrations that may be present in uncontaminated samples, larger volumes may be required. Typical volumes are dependent on the analytical method used,and the analyst should be consulted prior to sampling on his or her requirements. Unless otherwise stated, the requirements listed are those for quantitativedetermination. The analyst should always be consulted for advice on the actual sample volumes required when a choice of preservation methods exists in theTable.

Container types, preservation and maximum sample holding timesAnalyticalparameter

Container Typical volume(mL)

Preservation procedure Maximumholdingperiod

Comments

Acidity andalkalinity

Polyethylene orborosilicate glass

500 Fill bottle to exclude air.Immediately store between 1°Cand 4°C.

24 hours Samples should preferably be analysed in the field, particularlyif they contain high levels of dissolved gases.

Aluminium Acid washed glass oracid washedpolyethylene

500 Acidify with nitric acid to pH 1to 2.

28 days

* EPA is grateful to Standards Australia for the permission to reproduce information presented in AS/NZS 5667.1:1998 on which this Table is, in part, based.


24

Analyticalparameter



Comments

Ammonia Polyethylene or glass 500 Store between 1°C and 4°C. 6 hours When samples containing low levels of ammonia areencountered, special care should be taken to avoidcontamination.

Filter sample on site (0.45 µmcellulose acetate membranefilter) and store between 1°Cand 4°C.

24 hours Pressure filtering is preferred.

Filter sample on site (0.45 µmcellulose acetate membranefilter) and freeze sampleimmediately upon collection.

28 days

Antimony Acid washedpolyethylene or acidwashed glass

500 Acidify with nitric orhydrochloric acid to pH 1 to 2.

28 days Hydrochloric acid should be used for acidification if the hydridegeneration technique is used for analysis.

Acid washed polyethylene, polycarbonate or fluoropolymercontainers should be used for determinations at very lowconcentrations, such as encountered in uncontaminated streamsand seawater.

Arsenic Acid washedpolyethylene


28 days Hydrochloric acid should be used for acidification if the hydridegeneration technique is used for analysis.

Acid washed polyethylene, polycarbonate or fluoropolymercontainers should be used for determinations at very lowconcentrations, such as encountered in uncontaminated streamsand seawater.

Barium Acid washedpolyethylene or acidwashed glass


28 days

Beryllium Acid washedpolyethylene or acidwashed glass


28 days


25

Analyticalparameter



Comments

Biochemicaloxygen demand(BOD) andCarbonaceousBiologicalOxygen Demand(CBOD)

Plastic or glass 1000 Fill bottle to exclude air. Storebetween 1°C and 4°C in thedark.

24 hours Do not pre-rinse container with sample.

Glass containers should be used for samples with low BOD(<5 mg/L).

Nitrification inhibition is not to be implemented whenperforming the BOD test unless carbonaceous biologicaloxygen demand (CBOD) is required.

Boron Polyethylene 100 Fill bottle to exclude air. 28 days

Bromate Polyethylene or glass 100 Store between 1°C and 4°C. 7 days

Bromide Polyethylene or glass 500 Store between 1°C and 4°C inthe dark.

28 days

Bromine(residual)

Polyethylene or glass 500 Store between 1°C and 4°C inthe dark.

24 hours Samples should be kept out of direct sunlight.

Cadmium Acid washedpolyethylene


28 days Acid washed polyethylene, polycarbonate or fluoropolymercontainers should be used for determinations at very lowconcentrations, such as encountered in uncontaminated streamsand seawater.

Calcium Polyethylene 500 Fill bottle to exclude air. 7 days

Fill container completely toexclude air, acidify with nitricacid to pH 1 to 2 and storebetween 1°C and 4°C.

28 days Samples of water of pH > 8 or high total carbonate, taken solelyfor the determination of calcium, magnesium or hardnessshould be acidified with nitric acid.

Acidification permits the determination of calcium and theother metals in the sample.

Carbamates Solvent washed amberglass

1000 Store between 1°C and 4°C. 28 days Extract the sample in the container as part of the sampleextraction procedure.

If the sample is chlorinated, for each 1000 mL of sample, add80 mg of sodium thiosulfate to the container prior to collection.


26

Analyticalparameter



Comments

Carbon dioxide Polyethylene or glass 500 Fill container completely toexclude air. Store between 1°Cand 4°C.

24 hours Determination preferably carried out in the field.

Carbon, totalorganic (TOC)

Amber glass with PTFEcap liner

100 Acidify with sulphuric acid topH 1 to 2, store between 1°Cand 4°C in the dark.

7 days

Chemical oxygendemand (COD)

Glass or polyethylene 100 Fill container completely toexclude air. Acidify withsulphuric acid to pH 1 to 2 andstore between 1°C and 4°C inthe dark.

7 days Glass containers are preferable for samples with lowCOD (<5 mg/L).

Freeze (only if polyethylenecontainers are used).

28 days

Chloramine Polyethylene or glass 500 Keep sample out of directsunlight.

Beginanalysiswithin fiveminutes ofsamplecollection.

Analysis should be carried out in the field.

Chlorate Polyethylene or glass 500 Store between 1°C and 4°C. 7 days

Chloride Polyethylene or glass 100 None required. 28 days

Chlorine(residual)

Polyethylene or glass 500 Keep sample out of directsunlight.




27

Analyticalparameter



Comments

Chlorine dioxide Polyethylene or glass 500 Keep sample out of directsunlight.



Chlorite Polyethylene or glass 500 Store between 1°C and 4°C. 24 hours

Chlorophyll Polyethylene or amberglass

Filter on site Filter and snap freeze filterpaper in the dark.

28 days Samples should be filtered at the time of collection. Thevolume filtered will depend largely on the amount of particulatematter present and expected chlorophyll concentrations. Filtersmust not be touched with fingers and all sample handlingapparatus must be kept free of acids, as this causes degradationof chlorophylls to phaeophytins.

Filter and process promptly upon reception at the laboratoryand ensure minimum exposure to light.

Use polyethylene containers only when snap freezing samplefilters.

Store in the dark between 1°Cand 4°C.

24 hours

Chromium (total) Acid washedpolyethylene or acidwashed glass



Chromium (VI) Acid washedpolyethylene or acidwashed glass

500 Store between 1°C and 4°C. 24 hours Acid washed polyethylene, polycarbonate or fluoropolymercontainers should be used for determinations at very lowconcentrations, such as encountered in uncontaminated streamsand seawater. Sample containers should be thoroughly rinsedafter acid washing to ensure there is no residual nitric acidpresent.


28

Analyticalparameter



Comments

Cobalt Acid washedpolyethylene or acidwashed glass



Coliforms (total) Polyethylene or glass,sterile and containingpre-sterilised sodiumthiosulfate solutionsufficient to give100 mg/L in preservedsample

500 Store between 1°C and 4°C. 6 hours Do not rinse container before taking sample. Leaveapproximately 2 cm head space.

In exceptional circumstances, such as sampling in a remotelocation, a holding period of up to 24 hours is acceptable.

Colour Polyethylene or glass 500 Store between 1°C and 4°C andin the dark.

48 hours

Conductivity Polyethylene or glass 100 Fill container completely toexclude air. None required.

24 hours Preferably on site or in situ. The meter must be calibrated priorto use.

Fill container completely toexclude air. Store between 1°Cand 4°C.

28 days

Copper Acid washedpolyethylene or acidwashed glass



Cyanide Polyethylene or glass 500 If no interfering compounds arepresent, then add sodiumhydroxide solution to pH ≥ 12.Store between 1°C and 4°C inthe dark.

24 hours If hydrogen sulphide is present it can be removed by adding

cadmium nitrate after adjusting the pH of the sample to pH ≥12. If oxidising agents are present, add ascorbic acid. Excessascorbic acid has been added when a starch iodide paper failsto turn blue on contact with the sample.


29

Analyticalparameter



Comments

E. coli Plastic or glass, sterileand containing pre-sterilised sodiumthiosulfate solutionsufficient to give100 mg/L in preservedsample

500 Store between 1°C and 4°C. 6 hours Do not rinse container before taking sample. Leaveapproximately 2 cm head space.

In exceptional circumstances, such as sampling in a remotelocation, a holding period of up to 24 hours is acceptable.

Fluoride Polyethylene 500 None required. 28 days

Hardness Polyethylene 200 Fill bottle to exclude air.Immediately store between 1°Cand 4°C or acidify with nitricacid to pH 1 to 2.

7 days Water samples of high pH (pH > 8) or high total carbonatetaken solely for the determination of hardness, calcium ormagnesium should be acidified with nitric acid.

Herbicides(acidic)

Glass with PTFE capliner

1000 Acidify with hydrochloric acidto pH 1 to 2 and store between1°C and 4°C. Do notcompletely fill container.

14 days If residual chlorine is present, add 80 mg sodium thiosulfateper 1000mL of sample.

Herbicides (non-acidic)

Amber glass with PTFEcap liner

1000 Store between 1°C and 4°C. 7 days If residual chlorine is present, add 80 mg sodium thiosulfateper 1000mL of sample.

Herbicides(glyphosate)

Polypropylene 1000 Store between 1°C and 4°C inthe dark.

14 days If residual chlorine is present, add 80 mg of sodium thiosulfateper litre of sample.

Hydrazine Glass 500 Acidify with 100 mL ofconcentrated hydrochloric acidfor every litre of sample andstore in the dark.

24 hours


30

Analyticalparameter



Comments

Hydrocarbons, Solvent rinsed glasswith PTFE faced liner

500 Solvent extract on site with theappropriate solvent wherepractical.

Analyse assoon aspossible butwithin 7days

If residual chlorine is present, add 80 mg sodium thiosulfateper 1000mL of sample. Store in an area free of solvent fumes..

For purge and trap analysis collect samples in duplicate in40 mL vials with PFTE faced septum Store in an area free ofsolvent fumes.

80 Fill container to completelyexclude air and store between1°C and 4°C.

Analyse assoon aspossible butwithin 24hours

80 Fill container to completelyexclude air and acidify to pH 1to 2 with hydrochloric acid andstore between 1°C and 4°C.


. .

Hydrocarbons(qualitativeidentification)

Solvent washed glasswith PTFE cap liner

500 Do not completely fillcontainer. Acidify withsulphuric or hydrochloric acidto pH 1-2. Store between 1°Cand 4°C.

7 days Do not pre-rinse container with sample.

This procedure may also be suitable for unreactive hydrocarbonderivatives.

Hydrocarbons(halogenated)

Solvent rinsed glasswith PTFE cap liner

250 Fill container to completelyexclude air and acidify to pH 1to 2 with hydrochloric acid andstore between 1°C and 4°C.


If residual chlorine is present, add 80 mg sodium thiosulfateper 1000mL of sample.

For purge and trap analysis collect samples in duplicate in40 mL vials with PFTE faced septum Store in an area free ofsolvent fumes.

Iodide Polyethylene or glass 500 Store between 1°C and 4°C. 28 days

Iodine Glass 500 Store between 1°C and 4°C inthe dark.

24 hours


31

Analyticalparameter



Comments

Iron (II) Acid washedpolyethylene or acidwashed glass

500 Fill container completely toexclude air. Acidify withhydrochloric acid to pH 1 to 2.

24 hours Do not use nitric acid to wash sample containers.

Iron (total) Acid washedpolyethylene or acidwashed glass


28 days

Lead Acid washedpolyethylene or acidwashed glass



Lignins andtannins

Glass 250 Store between 1°C and 4°C. 7 days

Lithium Polyethylene 500 None required. 28 days If samples for lithium are also to be determined for other metalsthey can be acidified without effecting the analysis.

Magnesium Polyethylene 500 Fill bottle to exclude air. 7 days

Fill bottle to exclude air.Acidify with nitric acid to pH 1to 2 and store between 1°C and4°C.

28 days Water samples of high pH (pH > 8) or high total carbonatetaken solely for the determination of magnesium, calcium orhardness should be acidified with nitric acid.

Manganese Acid washedpolyethylene or acidwashed glass


28 days Acid washed polyethylene, polycarbonate or fluoropolymercontainers should be used for determinations at very lowconcentrations, such as encountered in uncontaminated streamsand seawater

Mercury Acid washedborosilicate glass

500 Immediately acidify theunfiltered sample to pH <2with nitric acid and addpotassium dichromate to give0.05% m/V final concentration.

28 days For contaminated waters more oxidant may be required.Reference should be made to the analyst for further instruction.

Acid washed fluoropolymer or borosilicate containers with afluoropolymer lined lid should be used for determinations atvery low concentrations, such as encountered inuncontaminated streams and seawater.


32

Analyticalparameter



Comments

Molybdenum Acid washedpolyethylene or acidwashed glass



Monocyclicaromatichydrocarbons(MAHs)

Solvent rinsed glasswith PTFE faced liner

500 Fill container to completelyexclude air. Acidify to pH 1 to2 with hydrochloric acid andstore between 1°C and 4°C.


If residual chlorine is present, add 80 mg sodium thiosulfateper 1000mL of sample. Store in an area free of solvent fumes.

For purge and trap analysis collect samples in duplicate in40 mL vials with PFTE faced septum. If the sample ischlorinated, for each 40 mL of sample add 3 mg of sodiumthiosulfate. Store in an area free of solvent fumes.

Nickel Acid washedpolyethylene or acidwashed glass



Nitrate Polyethylene or glass 500 Store between 1°C and 4°C. 24 hours

Filter on site (0.45 µmcellulose acetate membranefilter) and freeze sampleimmediately upon collection.

28 days

Nitrite Polyethylene or glass 200 None required. Analyse inthe field

Freeze sample immediatelyupon collection.

48 hours

Nitrogen (allforms)

See individual entries under Ammonia, Nitrogen (Kjeldahl),Nitrate and Nitrite.

Nitrogen(Kjeldahl)

Polyethylene or glass 500 Store between 1°C and 4°C. 24 hours The sample may be acidified with sulphuric acid to pH <2 ifrequired for other analyses.


28 days


33

Analyticalparameter



Comments

Nitrogen (total) Polyethylene or glass 500 Store between 1°C and 4°C. 24 hours


28 days

Odour Polyethylene or glass 500 Store between 1°C and 4°C. 6 hours

Organic carbon(total)

See Carbon, total organic (TOC)

Oxygen,dissolved (DO)

Polyethylene or glass 300 None required. On site or insitu

Excessive turbulence should be avoided to minimise oxygenentrainment. The meter must be calibrated on the day of useand preferably checked after measurements.

Pesticides(carbamates)

See entry under Carbamates

Pesticides(nitrogen-containing,organo-chlorineand organo-phosphate)


1000 to 3000 Do not completely fillcontainer. Store between 1°Cand 4°C.

7 days Solvent extract on-site with the appropriate solvent wherepractical.

Extract the sample in the container as part of the sampleextraction procedure.


pH Polyethylene orborosilicate glass

100 None. Determinein situ

The meter must be calibrated on the day of use and preferablychecked after measurements.

Phenoliccompounds

Solvent washed glass(amber) with PTFE capliner

1000 Store between 1°C and 4°C inthe dark. Do not completely fillsample container.

24 hours Do not pre-rinse container with sample.

Oxidising agents such as chlorine may be neutralised by theaddition of excess sodium arsenite or iron (II) sulfate prior toacidification.


Sulphur dioxide or hydrogen sulphide may be removed bybriefly aerating the acidified sample.


34

Analyticalparameter



Comments

Acidify to pH 1 to 2 withorthophosphoric acid,hydrochloric acid or sulphuricacid. Store between 1°C and4°C and store in dark.

21 days

Phosphate (orthoor dissolved)

Polyethylene or glass 50 to 300 Filter on site (0.45 µmcellulose acetate membranefilter). Store between 1°C and4°C.

24 hours

Filter on site (0.45 µmcellulose acetate membranefilter) and freeze uponcollection.

28 days


35

Analyticalparameter



Comments

Phosphate (total) Polyethylene or glass 300 Store between 1°C and 4°C. 24 hours

Freeze immediately uponcollection.

28 days

Acidify with sulphuric orhydrochloric acid to pH 1 to 2and store between 1°C and 4°Cin the dark.

28 days The use of the acid preservation method should not be used forthe persulfate oxidation method of analysis.

Polychlorinatedbiphenyls (PCBs)


1000 to 3000 Store between 1°C and 4°C inthe dark. Do not completely fillsample container.


Extract on-site, where practical, in the container as part of thesample extraction procedure.


Polycyclicaromatichydrocarbons(PAHs)


1000 Store between 1°C and 4°C inthe dark. Do not completely fillsample container.


Extract on-site, where practical, in the container as part of thesample extraction procedure.


Potassium Polyethylene 500 None required. 28 days

Acidify with nitric acid to pH 1to 2.

28 days Acidification permits the determination other metals in thesample.

Radioactivity(specific forms)

See Table 2 in AS/NZS 5667.1:1998.

Radioactivity, αand β activity(gross)

Polyethylene or glass 1000 Acidify with nitric acid to pH 1to 2. Fill container to excludeair.

28 days


36

Analyticalparameter



Comments

Selenium Acid washedpolyethylene or acidwashed glass



Silica (reactive) Polyethylene 200 Store between 1°C and 4°C. 24 hours

Filter in the field (0.45 µmcellulose acetate membranefilter) and store between 1°Cand 4°C.

28 days Turbid river samples should be filtered in the field (0.45 µmcellulose acetate membrane filter).

Silver Acid washedpolyethylene (wrappedin foil) or acid washedamber glass



Sodium Polyethylene 500 None required. 28 days

Acidify with nitric acid to pH 1to 2.

28 days Acidification permits the determination of other metals in thesample.

Solids(dissolved)

Polyethylene or glass 500 Store between 1°C and 4°C.Fill container to exclude air.

24 hours Also known as ‘filtrable residues’ and ‘total dissolved solids’or TDS.

Solids(suspended)

Polyethylene or glass 500 Store between 1°C and 4°C. 24 hours Also known as ‘non-filtrable residues’ and ‘suspended solids’or SS.

Solids (total) Polyethylene or glass 500 Store between 1°C and 4°C. 24 hours

Sulfate Polyethylene or glass 200 Store between 1°C and 4°C. 7 days

Sulphide(dissolved)

Polyethylene 50 by pipette Add 10 mL copper-DMPreagent.

12 hours

Sulphide (total) Polyethylene or glass 500 None required. Completely fillbottle without aeration.

Determineon site


37

Analyticalparameter



Comments

Fix samples immediately onsite by adding 2 mL of 10%(m/v) zinc acetate solution per500 mL of sample. Storebetween 1°C and 4°C.

7 days

Sulfite Polyethylene 1000 Fix in the field by addition of10 mL of 2.5% EDTA solutionper 1 L.

7 days

Surfactants(anionic)

Glass rinsed withmethanol

500 Acidify with sulphuric acid topH 1 to 2, fill container toexclude air and store between1°C and4°C.

48 hours Glassware should not previously have been washed withdetergent.

Add 40% formaldehydesolution to give 1% (v/v) finalconcentration and storebetween1°C and 4°C.

96 hours

Surfactants(cationic)


500 Fill container to exclude airand store between 1°C and4°C.

48 hours Glassware should not previously have been washed withcationic detergent.

Surfactants (non-ionic)


500 Fill container to exclude air.Add 40% formaldehydesolution to give 1% (v/v) finalconcentration and storebetween 1°C and 4°C.

28 days Glassware should not previously have been washed withdetergent.

Temperature None required Not applicable. Determinein situ


38

Analyticalparameter



Comments

Tin Acid washedpolyethylene or acidwashed glass



TOC See entry for Carbon, total organic

Total dissolvedsolids (TDS)

See entry for Solids (dissolved)

Total solids See entry for Solids (total)

Total suspendedsolids (TSS)

See entry for Solids (suspended)

Toxicity(by Microtox)

As for the suspectedtoxicant

200 Store between 1°C and 4°C. As for thesuspectedtoxicant

Trihalomethanes Solvent washed glassvial with PTFE facedseptum

100 Fill container to exclude air. 14 days If residual chlorine is present, for each 40 mL of sample add3 mg of sodium thiosulfate.

Turbidity Polyethylene 100 None required. On site

Store between 1°C and 4°C inthe dark.

24 hours

Uranium Acid washedpolyethylene or glass



Vanadium Acid washedpolyethylene or glass




39

Analyticalparameter



Comments

Zinc Acid washedpolyethylene or glass




40

APPENDIX B: CONTAINERS, PRESERVATION AND HOLDING PERIODS FOR SOILS ANDSEDIMENTS

Sample containers and their preparationThe requirements are taken from Table 3.1 of ANZECC Guidelines for the Laboratory Analysis of Contaminated Soils (1996)*. Unless otherwisespecified, samples should be stored refrigerated between 1°C and 4°C.

The analyst should always be consulted for advice on the actual sample sizes required.

Container types, preservation and maximum sample holding timesAnalyticalparameter

Container Preservation procedure Maximum holding period Comments

Acid sulfate soils Plastic bag Exclude as much air as ispossible from the bag andseal. Freeze the samplein the field using dry iceor a portable freezer.

24 hours for submission to the laboratory

14 days for analysis

Drying of the sample at 80°C – 85°C mustcommence as soon as possible after reception atthe laboratory. If the presence of monosulphidesis suspected, the sample must be freeze-dried.

Asbestos Glass or LDPE Store between 1°C and4°C.

48 hours Polypropylene containers are unsuitable.

Bromide (watersoluble)

Polyethylene or glass None. 7 days Air dry

Carbon, organic Glass Store between 1°C and4°C in the dark.

7 days Air dry

Cation exchangecapacity andexchangeablecations

Acid washedpolyethylene

None. 6 months Air dry

Chloride (watersoluble)

Polyethylene or glass If field moist, storebetween 1°C and 4°C.

7 days Field moist or air dry


41

Analyticalparameter


Cyanide Polyethylene or glass Store between 1°C and4°C in the dark.

7 days Field moist

Electricalconductivity

Polyethylene or glass None. 7 days Air dry

Fluoride Polyethylene If moist, store between1°C and 4°C.


Leachable metalsand semi-volatileorganics

As for the analyticalparameter of interest(see below)

As for the analyticalparameter of interest.

No preservatives to be added prior to leaching. As for the analytical parameter of interest (seebelow).

MetalsAnionsHydrocarbons (including TotalPetroleum Hydrocarbons and PAHs)Pesticides, organochlorinePesticides, otherPhenolicsPolychlorinated biphenylsOther

6 months7 days

14 days14 days14 days14 days28 days14 days

Leachablevolatile organics

As for the analyticalparameter of interest

Store between 1°C and 4°C in the dark.

7 days

Mercury Acid washedpolyethylene

Store between 1°C and 4°C in the dark.

28 days Field moist

Metals (exceptmercury)

Acid washedpolyethylene

If moist, store between1°C and 4°C.

6 months Field moist or air dry

Moisture content Polyethylene or glass(As for the analyticalparameter of interest)

Store between 1°C and4°C.

7 days, and on the same day as sample extraction forother analytical parameters.

Field moist

Net acidgeneratingpotential

See entry for acid sulfate soils


42

Analyticalparameter


Organics, semi-volatile

Solvent rinsed glass Store between 1°C and4°C in the dark.

14 days Field moist

Organics, volatile Solvent rinsed glass Store between 1°C and4°C in the dark.

14 days Field moist

pH Polyethylene or glass None. 7 days Air dry

Sulfate Polyethylene or glass If moist, store between1°C and 4°C.


Sulphide Polyethylene or glass Add sufficient 1 molarzinc acetate to fully coversoil surface and allowminimal headspace.

Store between 1°C and4°C.

7 days Field moist

Sulphur – total Polyethylene or glass If moist, store between1°C and 4°C.



43

APPENDIX C: CONTAINERS, PRESERVATION AND HOLDING PERIODS FORCONCENTRATED LIQUID WASTES, SLUDGES AND SOLID WASTES, OTHER THAN SOILSAND SEDIMENTS

Where the sample is being collected to determine a specific component, the following containers and sample handling procedures should be followed. Otherprocedures apply when the sample is being collected for a general identification (See the second Table, at the end of this Appendix).

Additional details on sampling for soils and sediments can be obtained from USEPA Publication: Test Methods for Evaluating Solid Waste: Volume 1ALaboratory Manual Physical/Chemical Methods, USEPA Publication No SW-846, Third Edition, Final Update III (1997)), or its latest update.

Aqueous trade wastes should be handled in accordance with the requirements set out in Appendix A.

Analytical parameter Container Preservation procedure Maximum holding period

Antimony Acid washed polyethylene or acidwashed glass

For solid samples, store between 1°C and4°C.

6 months

For liquid samples, acidify to pH<2 withnitric acid.

6 months

Arsenic Acid washed polyethylene or acidwashed glass


6 months


6 months

Asbestos Glass or LDPE Store between 1°C and 4°C. 6 months

Barium Acid washed polyethylene or acidwashed glass


6 months


6 months

Cadmium Acid washed polyethylene or acidwashed glass


6 months


6 months


44


Carbon, total organic(TOC)

Polyethylene or glass (glass ispreferable)

For liquid samples, acidify to pH < 2 usingsulphuric acid or hydrochloric acid. Storebetween 1°C and 4°C in the dark.

28 days

Chloride Polyethylene or glass None. 28 days

Chromium (total) Acid washed polyethylene or acidwashed glass


6 months


6 months

Chromium (VI) Polyethylene or glass For solid samples, store between 1°C and4°C.

28 days until extraction and 4 days after extraction.

For liquid samples, store between 1°C and4°C.

24 hours

Copper Acid washed polyethylene or acidwashed glass


6 months


6 months

Cyanide Polyethylene or glass For solid samples, store between 1°C and4°C in the dark.

7 days

For liquid samples, if oxidising agents arepresent add an excess of 0.6 g ascorbic acidper litre (excess ascorbic acid has beenadded when a starch iodide paper fails toturn blue on contact with the sample) andadjust pH>12 with 50% sodium hydroxide.Store between 1°C and 4°C in the dark.

14 days

Dioxins and furans Solvent washed glass with PTFE-lined cap


14 days until extraction and 40 days after extraction


45


Solvent washed amber glass withPTFE-lined cap

For liquid samples, store between 1°C and4°C. If residual chlorine is present, add 80mg sodium thiosulfate per 1000mL ofsample.


Hydrocarbons(halogenated)

Solvent washed glass with PTFE-lined cap






Lead Acid washed polyethylene or acidwashed glass


6 months


6 months

Mercury Acid washed polyethylene or acidwashed glass


28 days


28 days

Metals (except mercuryand chromium (VI))

Acid washed polyethylene or acidwashed glass


6 months


6 months

Nitrate Polyethylene or glass For liquid samples, store between 1°C and4°C.

48 hours

Polychlorinatedbiphenyls (PCBs)







Pesticides and herbicides(organochlorine)





46





Pesticides and herbicides(organophosphate)





For liquid samples, adjust the samples to pH5-8 using sodium hydroxide or sulphuricacid.


pH Polyethylene or glass None. For solid samples 7 days

Polyethylene or glass None. For liquid samples 6 hours

Phenols Solvent washed glass with PTFE-lined cap






Phthalate esters Solvent washed glass with PTFE-lined cap






Polycyclic aromatichydrocarbons (PAHs)







Residues, volatile Polyethylene or glass Store between 1°C and 4°C. 7 days


47


Selenium Acid washed polyethylene or acidwashed glass


6 months


6 months

Sulfate Polyethylene or glass For solid samples, store between 1°C and4°C.

6 months


28 days

Sulphide Polyethylene or glass For solid samples, fill the surface of the solidwith 1 M zinc acetate until moistened. Storebetween 1°C and 4°C and store headspacefree.

6 months

For liquid samples, add 4 drops 1 M zincacetate per 100 mL, adjust pH to >9 using6 M sodium hydroxide. Fill bottle completelyand stopper with minimum aeration. Storebetween 1°C and 4°C.

7 days

Zinc Acid washed polyethylene or acidwashed glass


6 months


6 months

Where the sample is being collected for a general identification, then the following procedures should be followed.

Analyticalparameter

Container Preservation procedure Maximum holding period

Concentrated wastes Glass with afluoropolymer cap

Store at 1°C and 4°C. 14 days

Aqueous samples Glass with afluoropolymer cap

Store at 1°C and 4°C and adjustpH <2 with hydrochloric acid.

7 days


48

Analyticalparameter

Container Preservation procedure Maximum holding period

Solids and sludges Glass with afluoropolymer cap

Store at 1°C and 4°C. 7 days


49

APPENDIX D: QUALITYASSURANCE SYSTEMS

Quality assurance procedures are mandatory forNATA accreditation. The recommendedmethods (see Chapter 4) contain detailedguidance on appropriate QA/QC systems, andthese should be followed.

The terms ‘quality assurance’ (QA) and ‘qualitycontrol’ (QC) are often confused. In terms oflaboratory analysis activities, they are definedbelow.

Quality assuranceQuality assurance (QA) is all of the actions,procedures, checks and decisions undertaken toensure the accuracy and reliability of analysisresults. For example: routine procedures ensureproper sample control, data transfer, instrumentcalibration; proper decisions are required toselect and properly train staff, select equipmentand analytical methods; and day-to-dayjudgments result from regular scrutiny andmaintenance of the laboratory system.

Any of the following publications could be usedin developing a QA program:

1. Australian and New Zealand Environmentand Conservation Council, Guidelines forthe Laboratory Analysis of ContaminatedSoils, Chapter 2 (ANZECC 1996).

2. American Public Health Association,Standard Methods for the Examination ofWater and Wastewater, Method 1020(APHA 1995).

3 US Environment Protection Agency, TestMethods for Evaluating Solid Waste, SW-846, Chapter 2 (USEPA 1997).

4 National Association of TestingAuthorities, Guide to Development of aQuality System For a Laboratory (NATA1995a).

Quality controlQuality control (QC) is those parts of QA whichserve to monitor and measure the effectivenessof other QA procedures compared withpreviously decided objectives. These mayinclude measurement of the quality of reagents,cleanliness of apparatus, accuracy and precisionof methods and instrumentation, and reliabilityas implemented daily in the laboratory.

For more information, readers are referred todocumentation available from NATA. Inparticular, Technical Note No. 23 (NATA,1995b).

QC proceduresAnalysts should implement the following QCsteps with each analytical batch, or with eachtwenty samples, whichever is the smaller.

Analysis blank – determination of thecontribution to the analytical signal by reagents,glassware, etc. The contribution measuredshould be subtracted from the gross analyticalsignal for each analysis, before calculation ofeach sample’s measured concentration.

Replicate Analysis – repeated analysis of atleast one sample from the batch.

Laboratory Control Samples – comprise acontrol matrix (for example deionised or tapwater) or a replicate portion of a sample underanalysis, fortified with componentsrepresentative of the analytical parameter class.Recovery check portions should be fortified atconcentrations that are easily quantified, butwithin the range of concentrations expected forreal samples.


50

Surrogate Spikes – known additions to eachsample, blank and matrix spike or referencesample of compounds that are similar to theanalytical parameters of interest in terms of:

• extraction,

• recovery through clean-up procedures,

and

• response to chromatographic or otherdetermination,

but which:

• are not expected to be found in realsamples,

• will not interfere with quantification ofany analytical parameter of interest,

and

• may be separately and independentlyquantified.

Surrogate spikes are added to the analysisportion before extraction. The purpose ofsurrogates is to provide a means of checking thatno gross errors leading to significant analyticalparameter losses have occurred at any stage ofthe procedure.

In the case of organic analyses, the surrogatespike compounds may be deuterated, alkylatedor halogenated analogues, or structural isomersof compounds under analysis. They should beadded for each analysis by chromatographicanalysis.

Internal Standards – are added to samples afterall extraction, clean-up and concentration steps.The addition is a constant amount of one ormore compounds with similar qualities tosurrogate compounds.

The purpose of internal standards is to check theconsistency of the analytical step (for example,injection volumes, instrument sensitivity andretention times for chromatographic systems)and provide a reference against which resultsmay be adjusted in case of variation.

Use of internal standards is required forchromatographic analysis of organics.

Reference Materials – are homogeneousmaterials that have been rigorouslycharacterised by several different procedures.They may be prepared in-house or obtainedfrom commercial suppliers. Reference materialsshould be certified and traceable to a recognisedauthority. A reference material of comparablematrix should be analysed with each batch ofsamples.

QC recordsRecords of the results of QC procedures shouldbe maintained to establish method reliability,confidence intervals for analysis results, andtrends in precision and accuracy. NATAaccreditation means that analytical methods andQA systems are regularly reviewed. However,no QA system is perfect. As the user of theservice, any organisation having analysesperformed is entitled to question the analyticalservice regarding methods and QA procedures.

a guide to the sampling and analysis of waters, wastewaters, soils and wastes

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