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Water and wastewater sampling

1. Australian and New Zealand Environment Conservation Council ANZECC amp Agriculture and Resource Management Council of Australia and New Zealand ARMCANZ 2000 Australian guidelines for water quality monitoring and reporting National water quality management strategy No 7 International Organisation for Standardisation ISO 10260 1992 Water quality measurement of biochemical parameters spectrometric determination of the chlorophyll a concentration National Association of Testing Authorities 1996 Technical Note 19 Liquid in glass thermometers selection use and calibration checks NATA New South Wales National Association of Testing Authorities 1995 Technical Note 21 Laboratory pH meters calibration and electrode performance checks NATA New South Wales Standards Australia 1996 AS NZS 1512 1996 Personal flotation devices type 1 Standards Australia Standards New Zealand New South Wales 1998a AS NZS 5667 1 1998 Water quality sampling guidance on the design of sampling programs sampling techniques and the preservation and handling of samples Standards Australia New South Wales 1998b AS NZS 5667 4 1998 Water quality sampling guidance on sampling from lakes natural and man made Standards Australia New South Wales 1998c AS NZS 5667 6 1998 Water quality sampling guidance on sampling of rivers and streams Standards Australia New South Wales 1998d AS N
2. A basic list of equipment required for sample transport and storage is listed in the Sampling Checklist see Appendix 3 and includes labels for sample containers if not already on containers snap lock bags or tubes if required esky or fridge ice bricks or crushed ice packing material eg foam packing packing tape consignment note for external courier and Chain of Custody forms 6 3 1 Preservation techniques Preservation techniques are vital to minimise changes to the sample following sampling Changes that may occur if poor or incorrect preservation occurs are summarised in Section 2 2 Required preservation techniques for specific analytes are detailed in Appendix 2 Some common preservatives are described below Refrigeration Keeping samples between 1 C and 4 C will preserve the majority of physical chemical and biological characteristics in the short term 24 hours and as such is recommended for all samples between collection and delivery to the laboratory It is recommended that microbiological samples be refrigerated between 2 C and 10 C as per AS NZS 2031 2001 Ice can be used to rapidly cool samples to 4 C before transport Ice bricks are preferred over loose ice or dry ice 25 EPA Guidelines Water and wastewater sampling Freezing In general freezing at lt 20 C will prolong the storage period However the freezing process significantly alters some nutrients and biological analytes such as chlorophyll
3. Reporting monitoring plan and in requirements accordance with sampling EPA 2006 guidelines EPA Guidelines Water and wastewater sampling 3 DEVELOPING A MONITORING PLAN To ensure that monitoring is specific targeted and cost effective a monitoring plan should be developed A monitoring plan is the document that details the actions responsibilities and timeframes that will deliver monitoring that meets monitoring objectives When developing a monitoring plan in response to a condition of authorisation the EPA guidelines Regulatory monitoring and testing Monitoring plan requirements EPA 2006b sets out what should be included in a monitoring plan i e the elements The monitoring plan guideline does not however provide guidance on how to design an effective monitoring plan i e the considerations Considerations Monitoring Variability of Spatial Precision Logistical Cost objective process and extent of accuracy and OHS amp W receiving impacts required issues environment v Monitoring plan Elements Duration of Sampling Frequency Analytes Method of Responsible sampling points and patterns parameters sampling eg persons campaign location and of sampling grab ongoing number automatic Figure 2 Designing a monitoring plan Issues that should be considered in designing monitoring for water and wastewater include e the objective of monitoring e variability
4. and the laboratory should be consulted before samples are frozen Filtering samples in the field before freezing may be required This is usually done for soluble nutrients particularly when same day delivery to the laboratory is not possible Chemical addition The appropriate chemical preservative and dose rate can vary between analytes and according to container size The analytical laboratory should always be consulted to establish which chemical preservative is appropriate for the analytical technique employed by that laboratory Preservatives include acidic and basic solutions and biocides It is important these are used in the form of concentrated solutions so that the volume of preservatives required is minimised This will minimise the dilution effect the preservative has on the sample Chemical additives are normally added by the laboratory and supplied pre prepared When sampling with pre prepared additives it is important that the bottle is not flushed during sampling It is also important to minimise the amount of spillage from the bottle during collection All preservation procedures employed should be recorded such as on the field sheet or chain of custody form Some preservatives need to be removed or negated before analysis eg pH corrections and are required to be considered by the laboratory before analysis It is crucial that a clear record of any sample treatments is available to the laboratory 6 3 2 Holding times While p
5. hosing down of floors and equipment filtration units rinsing of transfer lines laboratory wastewater stormwater diverted into or captured in the wastewater management system Wine production is seasonal and the characteristics of wastewater vary with the production period Up to six production periods can be defined these are summarised in the table below Description of winery wastewater production periods at wineries Typical months of Period the year Description Pre vintage J anuary February Bottling caustic washing of tanks non caustic washing of equipment in readiness for vintage Early vintage February March Wastewater production is rapidly rising to peak vintage flows and has reached 40 of the maximum weekly flow vintage operations dominated by white wine production Peak vintage March May Wastewater generation is at its peak vintage only operations are at a maximum Late vintage April J une Wastewater production has decreased to 40 of the maximum weekly flow vintage operations dominated by production of red wines distillation of ethanol spirit may coincide with this period Post vintage May September Pre fermentation operations have ceased effect of caustic cleaning ion exchange etc is at its greatest and wastewater quality may be poor Non vintage J une December Wastewater generation is at its lowest generally less than 3096 0f maximum weekly flows during vintage wastewater quality i
6. record of each sampling site and event is kept Other required paperwork includes Chain of Custody forms see Section 6 2 and Appendix 5 and labels Navigational aids It is important to be able to accurately locate the sampling site for future reference A modern Global Positioning System GPS can be a useful aid in accurately locating a sampling site Before attempting to navigate using GPS the sampler should be trained and competent in the use of these systems The sampling locations should also be recorded on site maps Field testing meters Some analytes are most reliably determined at the point of sampling See Section 5 2 for further information Sampling containers As the wrong sampling equipment can affect the integrity of the sample it is important to use appropriate sample containers for each of the various parameters Additionally treatments are applied to the sampling containers for some parameters to ensure sample integrity Appropriate sample containers and preservation methods are listed in Appendix 2 Your analytical laboratory should be able to provide appropriate containers with required treatments Other sampling equipment Other forms of sampling equipment may include sampling rods bucket and rope refer to Section 5 3 depth equipment Section 5 3 or filtration equipment Section 5 5 Decontamination of sampling equipment All sampling equipment presents a risk of cross contamination and should be thoroughly clean
7. waterbody Thus temperature should be measured in situ Temperature can be measured using a liquid in glass thermometer or a digital meter However multimeters pH meters conductivity meters and DO meters will also often measure temperature so it is unlikely you will need a separate device The probe or thermometer needs to be left fully immersed until a stable reading is obtained The time required for the thermometer to stabilise will vary according to the temperature of the water and the individual thermometer or probe Insufficient time can lead to inaccurate readings 5 2 3 pH Field testing of pH can be achieved using a calibrated electronic meter or pH test strips If pH strips are available with the range and resolution required for sampling they can give a robust and reliable measurement Meters have a higher resolution but require careful calibration and maintenance Traditional pH meters have potassium chloride KCI solutions that need to be topped up The newer electrodes including non glass ISFET gel or liquid filled are more robust and reliable for field use As pH is temperature dependent newer pH meters have been designed to automatically measure temperature and adjust to give a correct pH reading The user manual should be checked to determine if this is the case When calibrating a pH meter the temperature of standard solution should be as close as possible to the sample solution to minimise the possibility of temperature
8. Note that duplicate analyses should be targeted at the contaminants of concern and will not necessarily consist of a full set of analytes 31 EPA Guidelines Water and wastewater sampling 8 ANALYSIS AND REPORTING This guideline is intended primarily to provide guidance on the sampling process However some simple tips on analysis and reporting are provided in this section 8 1 Data review It is important that the data obtained is reviewed prior to assessment and interpretation Simple reviews can be undertaken that will highlight major issues in the quality of sampling or analysis and provide useful information on accuracy and precision of sampling and analytical methods The reviews should Compare duplicate samples results As duplicate samples are a sub sample of the same initial sample the variation between samples should be within the tolerances for the analytical procedure Differences between duplicates are often quantified as relative percentage difference RPD The relative percentage difference RPD of each field duplicate set can be calculated to assess the overall sample precision by using the formula RPD R R Passio where R result of sample Rz result of duplicate sample If an RPD is gt 20 or if the RPD of intra laboratory duplicates is much greater than the RPD of inter laboratory duplicates an investigation as to the cause should be investigated and documented Review spike recovery values
9. Spiked samples have a known amount of an analyte added to them This is generally done in the laboratory Laboratories should report the results of spiked samples As the actual concentration of the analyte is known spiked samples are used to check the analytical process Spike recovery values should be within the 80 120 range Consistently high or low spike recovery values indicate that there may be bias in the analytical process Review blank samples results Blank samples should have low or zero concentrations of the analytes of concern Should high concentrations of analytes be detected the monitoring should be thoroughly reviewed to determine whether there is a problem with contamination 8 2 Reporting When submitting a monitoring report to the EPA as a requirement of an authorisation the data must be reviewed and accompanied by appropriate supporting information Licensees are referred to the EPA guidelines Regulatory monitoring and testing Reporting requirements EPA 2006c with regard to the type and presentation of information 32 EPA Guidelines Water and wastewater sampling REFERENCES Artiola J F Pepper IL and Brusseau M 2004 Environmental Monitoring and Characterization Elsevier Academic Press Massachusetts American Public Health Association APHA American Water Works Association AWWA amp Water Environment Federation WEF 1999 Standard methods for the examination of water and wastewater 20th edition
10. analysis method In general there is not a great contamination risk from the actions of the sampler However preservation methods storage and transportation can affect the results and cross contamination between samples can occur In most cases follow the general sampling techniques described in Section 5 3 for surface or depth samples as required When collecting samples for live analysis leave an air gap in the container Marine samples should be kept at close to ambient temperature because marine flagellates will burst if subj ected to temperature shocks Freshwater phytoplankton is more robust and samples can be refrigerated for transport Both marine and freshwater samples for phytoplankton analysis should 20 EPA Guidelines Water and wastewater sampling be protected from exposure to direct sunlight Samples should be examined as soon as possible after collection within 48 hours If phytoplankton samples are to be counted much later fill the container completely preserve samples and transport and store in the dark The most suitable preservative for phytoplankton is Lugol s solution Formalin merthiolate and glutaraldehyde are not recommended preservatives because of their toxicity to humans Recommendations for preservation and holding times of samples for chlorophyll determination are included in Appendix 2 Sample containers can be wrapped in aluminium foil for protection from light Filter samples as soon as possible after c
11. and wastewater sampling For example e Organics have a tendency to adsorb to plastic including polyethylene polypropylene and polycarbonate Therefore stainless steel equipment such as buckets and sampling rods should be used Glass sample containers are preferred e When sampling for metal analytes the use of metal equipment and some glasses such as soda glass should be avoided Rubber can also cause contamination when sampling for trace concentrations Plastic equipment should be used when possible when analysing for metals e When sampling for analytes that are the major constituents of glass eg sodium potassium boron and silicon glass equipment and containers should be avoided Appendix 2 provides information on the type of sampling container eg glass plastic typical required volume filling technique and preservation requirements for common analytes The container type as listed in Appendix 2 is a useful guide to the most appropriate material for sample equipment Where uncertainty exists as to whether the sampling equipment may cause contamination or other effects an equipment blank as detailed in Section 7 should be collected and analysed 5 3 2 Surface samples grab sampling When the waterbody is shallow and well mixed sub surface water sampling is generally adequate Sub surface samples should be taken from approximately 30 cm depth with care taken to ensure no floating films or organic material are collecte
12. by propane or butane Methylated spirit burners do not produce a flame hot enough for sterilisation as per AS NZS 5667 1 e for plastic and glass or when unsafe to use a flame a solution of 10 sodium hypochlorite should be used Household bleach can range from 2 to 15 sodium hypochlorite and will degrade over time Flood the surface with the solution and wait approximately two minutes For pump lines and hoses trap bleach solution within the hose or equipment The hose doesn t need to be totally full as the gas from the solution does the work Wait for a minimum of 15 minutes e inan emergency scalding with boiling water for 10 minutes may disinfect a suitable glass or plastic container and equipment 5 4 7 Sampling for biological analytes Biological sampling can cover a broad spectrum of sampling of aquatic organisms from plankton to macroinvertebrates fish and other vertebrate aquatic animals If undertaking biological sampling it is recommended that other specific texts be referenced Wherever practical sampling should be undertaken by a trained biologist who will be better able to recognise signs of environmental changes through observations of conditions in the field This guideline only touches on sampling of phytoplankton Sample size depends on the concentration of plankton in the water being sampled the type of determination to be made eg phytoplankton count algal identification or chlorophyll concentration and the
13. dioxide and pH sensitive parameters such as dissolved heavy metals alkalinity and ammonium Total dissolved solids TDS and total organic carbon TOC are also affected and are likely to decrease in concentration due to degassing Chemical changes Precipitation is the formation of solids from dissolved constituents It can be caused by a change in conditions such as temperature pH chemical concentration or the presence of seed particles to begin the process For example where a groundwater sample experiences loss of carbon dioxide a rapid change in pH can occur causing precipitation of metals such as iron Oxidation is caused by the introduction of oxygen in air to the sample Oxidation results in increased dissolved oxygen pH and redox These changes can lead to decreases in concentrations of calcium ions magnesium ions heavy metals particularly iron and manganese hydrogen sulphide and ammonium Oxidation could also lower the concentrations of bulk organic parameters chemical oxygen demand COD biological oxygen demand BOD and TOC due to EPA Guidelines Water and wastewater sampling accelerating oxidation of organic constituents such as volatile fatty acids and semi volatile organic carbon Biological processes Biological activity in a sample may affect both its physical and chemical characteristics Parameters such as nitrite and nitrate can be affected by bacterial activity i e denitrification Biological activ
14. eg acidification and toxic gases such as hydrogen sulphide bacteria in wellhead or groundwater temperature hazards typically sunburn and heatstroke working in over or adjacent to water poisonous animals spiders snakes and plants e actions to be undertaken to remove reduce or control risk e emergency procedures and information such as location of nearest medical facility When conducting a sampling event the right safety equipment will make the task safer This equipment can be preventative or provide assistance in the case of an incident The sampling checklist see Appendix 3 provides an example list of the type of personal protective equipment PPE that may be required for sampling in the field Additional protective equipment may be necessary as required by the specialist nature of a particular sampling task or the OHS amp W policy of your employer 10 EPA Guidelines Water and wastewater sampling 5 SAMPLE COLLECTION AND FIELD TESTING PROCEDURES Samples should only be collected by personnel who have proper training and adequate experience 5 1 Field observations During every sampling event observations of field conditions that could assist in the interpretation of monitoring data are to be recorded This can provide useful information about the water being sampled which can help diagnose the source and potential impact of pollutants found by chemical analysis Examples of such field conditions are as follows e r
15. fill container none required 24 hours preferably carried out in field for 25 C glass completely to samples of low conductivity exclude air 20 uy cm fix oxygen in the field and oxygen dissolved glass 24 hours preferably determined in the field store in the dark as per method of analysis used pH plastic or 100 refrigerate 6 hours carry out test as soon as possible and glass preferably in situ solids dissolved plastic or 500 dissolved fill refrigerate 24 hours or suspended glass container completely to exclude air turbidity plastic or 100 fill container none required 24 hours preferable to analyse sample in field glass completely to or in situ exclude air A7 EPA Guidelines Water and wastewater sampling metals aluminium barium beryllium cadmium chromium cobalt copper lead manganese molybdenum nickel silver tin vanadium zinc antimony arsenic boron chromium VI acid washed plastic or glass acid washed plastic or glass acid washed plastic or glass plastic acid washed plastic or glass 100 100 500 100 100 Filling technique fill container completely to exclude air fill container completely to exclude air fill container completely to exclude air Filtration and acidify with nitric acid to acidify with nitric acid or hydrochloric acid to pH 1 to 2 acidify with nitric acid or hydrochloric acid to pH 1 to 2 none require
16. maximise a sample s integrity during transport from the sampling site to the laboratory nutrients such as ammonia nitrate and nitrite can have a short retention period in a sample and filtering can extend this significantly e to separate the total and the soluble portions of analytes eg dissolved metals he soluble portion of an analyte is generally more bio available and therefore can have greater impact upon the ecosystem e to extract filtered material for biological analytes such as chlorophyll and algae e to separate biomass when undertaking wastewater analysis There are various methods and equipment available for field filtration from simple gravity or syringe pressure systems to more complex pump operated pressure or vacuum systems The best method to use will depend upon the analysis to be performed Pressure filtration is preferable over vacuum filtration where the drawing off of volatiles may compromise results This is likely to be the case when analysing for nutrients and volatile organics Vacuum filtration is recommended for chlorophyll samples The pressure difference across the filter should not exceed 40 mmHg to prevent rupture of cells Vacuum filtration can be easier than pressure filtration when large sample volumes are required Always follow the operating instructions of your filtering equipment Factors to consider when filtering include 21 EPA Guidelines Water and wastewater sampling e filters may need
17. of process and receiving environment e the spatial extent of impacts e precision and accuracy required e logistical and OHS amp W issues e costs compared with benefits These considerations are discussed in Appendix 1 Further guidance on how to design water or wastewater monitoring plan is available within the Australian guidelines for water quality monitoring and reporting ANZECC 2000 The EPA has also developed industry specific guidelines such as Guidelines for wineries and distilleries EPA 2004 These industry specific guidelines primarily provide guidance on what specific industries may be required to monitor and why In the event of any inconsistency your licence and the Monitoring plan requirements guideline take precedent EPA Guidelines Water and wastewater sampling 4 PLANNING A SAMPLING EVENT Careful planning and preparation of a sampling event is important and will save time and reduce the number of difficulties that commonly occur during sampling 4 1 Logistics The basic steps for planning a sampling event are as follows 1 Review the monitoring plan including monitoring locations number of samples required sampling methods and Occupational Health Safety and Welfare OHS amp W issues 2 Inform the client or property owner of your intended schedule and be aware of any liabilities that you may incur 3 Co ordinate with the analytical laboratory Obtain appropriate sample containers i e containers of suit
18. possible Laboratory filtering is not appropriate where there is a risk of increased precipitation or mobilisation of metals prior to analysis Field filtering procedures are discussed in Section 5 5 Both vacuum and pressure filtration are suitable for metals 5 4 5 Sampling for organics Organics have a tendency to adsorb to plastic polyethylene polypropylene and polycarbonate Therefore stainless steel buckets and sampling rods and glass containers are recommended One of the most critical elements for organic analysis is the holding times and some analyses eg BOD having holding times of only 24 hours 5 4 6 Sampling for microbiological analytes Obtaining representative microbiological samples can take considerable care and timing Microbiological samples can often require large sample volumes and are easily contaminated as bacteria are present on most surfaces and in the air They also have short holding times preferably less than six hours Communication with the laboratory is necessary to confirm the sample volumes and to ensure that samples can be received and processed efficiently A laboratory may have to arrange staffing to meet processing needs as the processing capacity of a laboratory may be set by 19 EPA Guidelines Water and wastewater sampling NATA In particular laboratories should be warned of incoming samples that must be performed within 24 hours Specific precautions need to be taken to minimise the po
19. to be decontaminated or preconditioned through washing or soaking prior to use Check the requirements during planning of the sampling event as some decontamination soaking procedures can take up to 24 hours e the type and pore size of the filter will affect the results Select the right type and size of filter for the job A 0 45um filter should be used except where otherwise specified by criteria eg Water Quality Policy e be careful not to contaminate samples during the filtration process When filtering samples in the field minimise the chance of contamination with a clean work environment and by replacing caps on sample containers immediately A plastic sheet on the ground is a good method of defining and maintaining a clean work area e samples with lots of suspended material can be difficult to filter in the field Pre filters may be needed for pressure filtration For vacuum filtration it may be necessary to change the filters as they become clogged with sediment Excessive force may rupture clogged filters requiring recommencement of the sampling It is acknowledged that field filtering of very turbid samples may be problematic and it may be more practical for filtering to occur in the laboratory If samples are laboratory filtered this should be annotated on your results appropriately Contact your laboratory for instructions on collecting samples for laboratory filtration eg if sampling for dissolved metals analysis should not be aci
20. wastewater sampling As a minimum sampling the effects of a point source discharge should include the following sample locations e end of pipe samples to characterise the discharge e inthe receiving water upstream of the point of entry e inthe waterbody at the point of entry e multiple samples at progressive distances downstream from the point of entry Wastewater sampling The number of samples required to determine the composition of wastewater will depend upon the accuracy precision required from the study and the variability of the stream Generally grab samples can be used where the analyte of interest is not expected to vary greatly over time Sampling of wastewater may be undertaken in tanks drums pipes lagoons drains open channels and from taps or valves Wastewater in pipes will often exhibit laminar flow and samples taken from taps can be strongly influenced by boundary effects which may not produce a representative sample In the case of in pipe laminar flow the sampling location should be situated downstream of a restriction or obstacle which creates turbulence and mixing in the wastewater stream Profiling depth It is often sufficient to take discrete samples just below the surface at a given site particularly in shallow and well mixed environments such as adequately sized and designed lagoons In deeper or poorly mixed waters a surface sample may not accurately describe the characteristics of the entire
21. with nitric acid to 1 month pH 1to2 acidification allows the sample to be analysed for lithium as well as other metals samples with pH gt 8 or high carbonate content to be analysed solely for calcium magnesium or hardness should be acidified acidification permits determination of other metals from same sample particular care is needed to ensure that the sample containers are free from contamination acidification allows the sample to be analysed for potassium as well as other metals AQ EPA Guidelines Water and wastewater sampling Analyte ammonia chlorine cyanide total iodide fluoride nitrate plastic or glass 500 plastic or glass 500 plastic or glass 500 plastic or glass plastic or glass 250 Filtration and field filter through 0 45 um cellulose acetate membrane and refrigerate field filter and freeze keep out of direct sunlight analyse immediately if no interfering compounds are present then add sodium hydroxide to pH gt 12 refrigerate and store in the dark refrigerate 1 month none required field filter through 0 45um cellulose acetate membrane and freeze A10 Holding time 24 hours 1 month 5 minutes 24 hours Notes strict protocol required to reduce effects of contamination store in area free of contamination ammonia vapour may permeate the walls of even high density polyethylene containers pressure filtering is
22. 67 1 and requirement if type 2 monitoring as from ANZECC ARMCANZ Nes 2000 condition of authorisation Field and Contamination Select three identical sample Field blank open container in the 1 set of 3 Nil transport due to the field containers Fill all with distilled water field for a similar period of time as containers per blanks conditions or water of corresponding salinity to is required to take sample Re cap sampling tri p mple On mple is left in th ntainer and t rt t sample One sample is left i e container an ranspo Oo 1 blank per 10 laboratory as a control sample Two laboratory for analysis ampled samples are taken to the field one as a R Contamination Transport blank Carry a sealed Nil during transport FICHA dante os ANRE mpl ntainer in th ler with 9 P blank The actions in the field are then LAUD ES lt pua other samples No other action carried out necessary in the field Return to laboratory for analysis Container Contamination Fill a sample container with distilled None 1 per batch of Nil blanks due to the water do not rinse Apply the containers container reservation appropriate to samples i P pprop P 1 per 10 samples washing process taken in that container type The and sample is to be held in the laboratory preservatives for a similar period of time as the maj ority of samples are held before analysis Equipment Residue on Nil Wash sampling equipment as No specific 1 per sampling blan
23. ENVIRONMENT PROTECTION AUTHORITY EPA Guidelines Regulatory monitoring and testing Water and wastewater sampling J UNE 2007 EPA South Australia EPA Guidelines Regulatory monitoring and testing Water and wastewater sampling Authors David Duncan Fiona Harvey Michelle Walker and Australian Water Quality Centre The EPA would like to acknowledge the assistance of the Australian Water Quality Centre in preparation of this document For further information please contact Information Officer Environment Protection Authority GPO Box 2607 Adelaide SA 5001 Telephone 08 8204 2004 Facsimile 08 8204 9393 Free call country 1800 623 445 Email lt epainfo epa sa gov au gt Website lt www epa sa gov au gt ISBN 978 1 921125 47 8 J une 2007 Environment Protection Authority This document may be reproduced in whole or part for the purpose of study or training subject to the inclusion of an acknowledgment of the source and to its not being used for commercial purposes or sale Reproduction for purposes other than those given above requires the prior written permission of the Environment Protection Authority s Printed on recycled paper CONTENTS 1 INTRODUCTION 55 ioci ek ica i eins o c Ge RC n Y c eh n c a vedas 1 1 1 PUILTDIOSQ ihan a EE T E e E E aris Gee 1 iz SCOPE seh eet ke O dn E ok ha E E E 1 1 3 intended USES ansima a cdi ea oa EAEE ER 103 Aaa 1 L SCO a framework aed eie ott e pde
24. Hd e PERMET tea uh eee nd tue 1 15 iFurther dgidanegs A M scenes een cutee E EA eed E E age 2 2 AN OVERVIEW OF MONITORING enn nnm nnn nnn 3 2 1 Stepsin the monitoring process ssssssssse eeeeeeeeeeeeeeeeaeeeeaees 3 2 2 ntegrity of samples icto de e aded de eroe bet e dens cies aude 4 DEVELOPING A MONITORING PLAN nnnnn nnnm 7 PLANNING A SAMPLING EVENT nnnm nmn nnns 8 4l JEOUSeS ose EI REESE OM Do teeters eatin rete sets 8 42 DOmmuhlcablOolfscun wo tee ve rto n veto ecole eroe ad ea ies 8 AS EgUIDITGIIboodeuecccdier eere sae wed e eee eine e Rer o es 9 4 4 Occupational health safety and welfare sessssssssseeee 10 5 SAMPLE COLLECTION AND FIELD TESTING PROCEDURES 11 5 1 Field observations s ere eeeto deed e efto ait ie ARE p ener ENDE 11 Bie Freldumeasuremellsscsbuet eden t iere eel deep cate aiden ena ies 11 5 3 Collection of samples for analysis orem eure ce D Ede ee na e ect 14 5 4 Specific considerattole usos qeu EE eA X ESPERE RET RES IS Pe BOE ERN Rn 18 sn Feld gig ido OI ID LIU 21 5 6 DecontainifiatlOllos deem axo E RE RU e ERR Eee tp seen Exe d 22 6 SAMPLE IDENTIFICATION TRANSPORT AND STORAGE een 24 6 1 Labelling and IdentiTICablDDIssssa eoe ot oto tbe perta hx dico Ma GR aad osa n en cet 24 6 2 Chain of CUSEOU Versu ere re EpSs pr Ee REB DA Sen EN VERI ira Bi reo PERDRE dh 24 6 3 Transport and storage x exor edes ate eR ENSE ORITUR PETE
25. OD 5 Chemical oxygen demand The oxygen equivalent of the organic matter content of a sample that is susceptible to oxidation by a strong chemical oxidant A value numerical or relational set through a condition of licence that imposes a requirement on the licensee eg that the licensee must meet or that requires the licensee to report or take other action if exceeded Distilled water has been used throughout this guideline for decontamination and other purposes where water that will not impact upon the results of analysis is required The water should have no detectable concentration of the element to be analysed and be free of substances that interfere with the analytical method The most common types used for this purpose are distilled demineralised or deionised water Distilled or demineralised water is the most appropriate type of water except where dissolved ionised gases are under investigation Deionised water may not be suitable when investigating dissolved organics particulates or bacteria Spring water should not be used during sampling as in most cases no contaminants have been removed and high levels of some analytes such as metals and inorganic non metallics will be present Where uncertainty exists as to the suitability and impacts of the water used quality control blanks as described in Section 7 2 should be employed Dissolved oxygen Electrical conductivity The ability of water to conduct an electrical curr
26. OREEOTATG ec ie ue idees oa a eater usua eto ee redire eoo ER EM Ecrire 5 Summary of blank and duplicate samples sese 30 EPA Guidelines Water and wastewater sampling 1 INTRODUCTION 1 1 Purpose The purpose of this guideline is to set minimum standards and to provide practical guidance on water and wastewater sampling for regulatory purposes in South Australia 1 2 Scope This guideline applies to the sampling of waters and wastewaters including e receiving waters such as oceans rivers creeks and estuaries e end of pipe or channel effluents and industrial process waters cooling waters or wastewaters This guideline does not cover sampling of groundwaters The EPA guidelines Groundwater sampling 2006a should be consulted for advice on groundwater sampling For additional information not provided in the above guideline we recommend that the AS NZS 5667 series of standards be consulted This guideline does not provide detailed guidance on analysis methods or interpretation of data 1 3 Intended users This guideline is primarily aimed at e sampling to determine compliance with environmental regulatory requirements including authorisations under the Environment Protection Act 1993 EP Act e collecting and or analysing samples for comparison with the Environment Protection Water Quality Policy 2003 Water Quality Policy criteria However given suitable justification alternative methods may be appr
27. RS 25 7 C IRURE 27 7 1 Quality ASSUP ali edite entem ER t bti Si iur aloe iD UE tds 27 J2 Quality control acce esas terret ea e debes Een Up i 27 8 ANALYSIS AND REPORTING ssssssssnnnssnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnn 32 gb Data A EAV A ETE EPE AE A E E ae ec easel 32 Oa REDONO Areeni a S 32 REFERENCES iiaa aa Aa ar aAa 33 GLOSSARY ssssssssssnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnn 34 APPENDIX 1 GUIDANCE ON DEVELOPING AN EFFECTIVE MONITORING PLAN Al APPENDIX 2 CONTAINERS PRESERVATION METHODS AND HOLDING TIMES A7 APPENDIX 3 FIELD EQUIPMENT CHECKLIST EXAMPLE A17 APPENDIX 4 FIELD RECORD SHEET EXAMPLE ii xis pa pa erba excuse A18 APPENDIX 5 CHAIN OF CUSTODY FORM EXAMPLE 41 255 10 dy eda RA Rd sat A19 List of Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 Figure 7 Stages of MONMONNG 2 vie awe FO Se ar eter pase tpi ee Eben din tia 3 Designing a monitoring plan 227 d nante dea s beca teats ben re d12 tocdeneesdtsede Mies 7 Examples of the various types of field meters available sssssssse 12 Sampling by handi o3 vec o c oo ec cdd vtta ehe ier nete v pb dada 16 Using sampling rod e ia desee een is poete eee oe RO aid L obs Ev pra i dexs 16 Van Dorn samplers with cup ends set open sse 17 Quality assurance framework Puls amp Barcelona 1996 27 List of Tables Table 1 Table 2 Quality control in TT
28. ZS 5667 10 1998 Water quality sampling guidance on sampling of waste waters Standards Australia New South Wales 2001a AS NZS 2031 2001 Selection of containers and preservation of water samples for microbiological analysis Standards Australia New South Wales 2001b AS NZS 2865 2001 Safe working in a confined space Standards Australia New South Wales South Australian Environment Protection Authority EPA 2004 EPA guidelines for wineries and distilleries EPA Adelaide 2005 EPA manual Emission testing methodology for air pollution EPA Adelaide 2006a EPA guidelines Regulatory monitoring and testing Groundwater sampling EPA Adelaide 2006b EPA guidelines Regulatory monitoring and testing Monitoring plan requirements EPA Adelaide 2006c EPA guidelines Regulatory monitoring and testing Reporting requirements EPA Adelaide 33 EPA Guidelines Water and wastewater sampling GLOSSARY AS Analyte ANZECC BOD COD Criteria Distilled water DO EC Entrainment Environmental values EPA Filtrate Holding time Isokinetic LOR Monitoring plan Australian Standard Refers to any chemical compound element or other parameter as a subject for analysis Australian and New Zealand Environment Conservation Council Biochemical or biological oxygen demand A measure of the decrease in oxygen content in a sample of water usually over five days B
29. able material and volume that contain preservatives as listed in Appendix 2 Discuss any problems you foresee for example with procedures containers or limitations of reporting 4 Schedule the monitoring event including planning how and when you will transport the samples back to the laboratory The aim is to have all samples preserved and delivered to the laboratory as quickly as possible and within recommended holding times This is especially relevant for samples with holding times of 24 hours or less Holding times are listed in Appendix 2 5 Organise and review site maps and locations to determine logistics of sampling including sampling order Sampling order should be designed to avoid cross contamination i e as much as practical move from samples with lowest pollutant concentrations to highest concentrations 6 Check that you have all the equipment required for the sampling event Test that the equipment is operational and calibrated Ensure you are able to decontaminate equipment that is to be reused between samples 7 Fill out as much paperwork as practical before sampling such as preparation of labels 4 2 Communication It is strongly recommended that the analytical laboratory be consulted before implementing a sampling plan Each laboratory may use different analytical techniques that require specific sampling techniques preservatives or field treatments such as filtering and freezing It is important to inform the lab
30. aboratory often called secondary or QA laboratory these duplicates give an indication of the variability between laboratories which can provide a degree of confidence in the accuracy of the laboratories The duplicate samples should produce identical results within the specific tolerances of the analytical procedure 7 2 3 Spikes or sample spiking Spiked samples have a known amount of a particular analyte added to a sub sample This is generally done in the laboratory but can be undertaken in the field Spikes are used to determine the effectiveness of the overall sampling and analysis program including all of the QC samples described earlier as per AS NZS 5667 1 As the final concentration of that analyte is known spiked samples can be used to check the analytical process It is important that the person analysing the spiked samples is not aware of the spiked value to ensure they are treated in the same way as regular samples They are usually prepared in the analytical laboratory by trained personnel but can be prepared in the field if required If used the concentration of the spiked samples should be within the general range of the contaminant expected in the real water samples 29 EPA Guidelines Water and wastewater sampling Table 2 Summary of blank and duplicate samples Number i Minimum QC za s Quantifies i Lr P Recommended by contamination Action in the laboratory Action in field AS56
31. absorption of analytes and increases the risk of contamination between samples taken at different places or times The pumping rate may also affect the sample Ideally the velocity of the water in the inlet should be at the same velocity as the water being sampled i e isokinetic sampling conditions Where this is impractical the velocity of pumping should not be lower than 0 5 m s as this may reduce suspended solids within the sample or greater than 3 m s as high velocities may cause blockages by debris For dissolved gases and organics sealed immersion devices or open tube devices are preferred over pumping systems Sealed immersion devices These devices also called closed pipe or air displacement devices consist of sealed containers filled with air that are lowered to the correct depth A trigger mechanism then releases the end caps and the device is filled with water Open tube or cylinder devices Such devices are similar to sealed immersion devices with the exception that the ends are left open during the lowering of the device to the required depth A trigger mechanism such as weight water pressure or electromagnetic signal seals both ends of the device capturing the sample inside Van Dorn samplers shown in Figure 6 are an example of this type of device When sampling in fast flowing waters sampling devices that can be placed horizontally such as the Zukovsky are preferred over vertical devices as isokinetic samplin
32. aterbodies eg dissolved or suspended organically bound condensed or orthophosphates Phosphorus is further classified according to the analysis method used Reactive phosphorus relates to phosphates that respond to a particular colorimetric test and mainly consist of orthophosphate but also may contain a fraction of condensed phosphate Reactive phosphate occurs in both dissolved and suspended forms Criteria may be set as either total phosphorus or soluble phosphorus If monitoring to compare results against a set of criteria make sure that the sampling technique in particular the filter size and the nutrient form is the same as the criteria 5 4 4 Sampling for metals When sampling for metals care must be taken not to cause contamination during sampling Avoid metal including stainless steel sampling equipment using plastic wherever possible If analysing for trace metals deionised water is recommended for decontamination rather than distilled Distilled water may contain trace metals such as mercury When sampling for metals it is important to determine prior to collection whether total or just the soluble phase is required This will determine the preservation and filtration requirements When soluble metals are required samples may either be field filtered or sent to a laboratory for filtering If sending to the laboratory for filtering samples must not be acidified but be cooled to 4 C and filtered in the laboratory as soon as
33. ble in water It is important to take care when packing samples as samples are often subject to vibration during transport causing identification to rub off or become illegible It should be noted that xylene in permanent markers can contaminate samples intended for organic analysis Biro or pencil should be used for organic samples Labelling on samples should contain as much information as practical Sample labels must specify a clear and unique identifying code that can be cross referenced to the monitoring location and time of sampling eg via sampling record sheet see Appendix 4 Labels may also contain e date of sampling e time of sampling e location and name of sampling site include GPS coordinates if available e job or project number e name of sampler e container pre treatment and preservations added e other observations that may affect the method or results of the analysis The information above should be recorded on the Field Record Sheet and retained as a permanent record Hazardous or potentially hazardous samples such as solvents should be clearly marked as such Similarly any samples that could reasonably be expected to have particularly high concentrations of a particular analyte should be brought to the attention of the laboratory as this may affect the analytical technique 6 2 Chain of Custody Chain of Custody procedures and documentation demonstrate sample control This gives confidence that the sample integr
34. causing erroneous readings Electrodes used for measuring pH are usually calibrated using a two or three point calibration with standard buffers of known pH The buffers are commonly of around pH 4 and 9 while the third would fall between the two to represent a neutral reading Buffer solutions for calibration should be either side of the range anticipated in the sampled waters This means that if it is anticipated that the sample will be strongly acidic or basic calibration standards that match the pH range to be worked within should be used 5 2 4 Conductivity Conductivity is easily measured in the field using a portable meter and electrode This provides a measure of the total ionic concentration of the sample solution in units of electrical conductivity EC which can then be converted into total dissolved solids TDS by calculation EC can be converted to TDS using the equation TDS 2 0 548 x EC 2 2 x 10 x EC where TDS Total Dissolved Solids mg L EC Electrical conductivity uS cm 13 EPA Guidelines Water and wastewater sampling Many conductivity meters will automatically calculate TDS from EC However the equation above was developed for a wide range of South Australian waters and is applicable for samples within the conductivity range from 20 uS cm to 60 000 uS cm This range covers the majority of waters except for hypersaline environments Any TDS calculated from conductivity measurements outside this range sho
35. d refrigerate A8 1 month 1 month 1 month 1 month 1 day hydrochloric acid should be used if hydride technique is used for anal ysis consult laboratory hydrochloric acid should be used if hydride technique is used for anal ysis consult laboratory sample container should be rinsed thoroughly EPA Guidelines Water and wastewater sampling Typical Analyte pide mL Filling technique 500 iron II acid washed fill container plastic or glass completely to exclude air iron total acid washed 500 plastic or glass lithium plastic 100 magnesium acid washed 100 fill container plastic or glass completely to exclude air mercury acid washed 500 glass potassium acid washed 100 plastic or glass selenium acid washed 500 plastic or glass uranium acid washed 200 plastic or glass inorganic non metallic Filtration and E Holding time preservation acidify with hydrochloric 24 hours acid to pH 1 to 2 acidify with nitric acid to 1 month pH 1to2 none required but may 1 month acidify with nitric acid to pH 1 to 2 and refrigerate none required 1 week acidify with nitric acid to 1 month pH 1to 2 acidify with nitric acid to 1 month pH 1 to 2 and add potassium dichromate to give a 0 05 n v final concentration none required acidify 1 month with nitric acid to pH 1 to 2 1 month acidify with nitric or hydrochloric acid to pH 1 to 2 acidify
36. d unless they are of specific interest Stirring up and collection of bottom sediments will also compromise sample integrity Try and collect the sample a reasonable distance from the edge unless specifically trying to determine the water quality at the edge as edge water quality is generally not typical of the majority of the waterbody When practical collect the sample directly into the sample container Where this is not practical such as when a sample cannot be collected without loss of preservative an intermediate container may be used When sampling by hand surface films can be avoided by removing the cap inserting the container into the water vertically with the neck facing down Once at the required depth the container can then be inverted allowing the sample to flow in The mouth of the container should be faced into the current while keeping the hands sampler and any other equipment eg boat downstream to minimise the chance of contamination Figure 4 When sampling still water move the container slowly forward to obtain a continuous uncontaminated sample Refer to Appendix 2 to determine whether the sample container should be filled to the top to exclude air or whether an air gap 1 2 cm at top of container should be left 15 EPA Guidelines Water and wastewater sampling Figure 4 Sampling by hand Where it is impractical or unsafe to sample by hand a sampling rod can be used Figure 5 Sampling rods are polycarbona
37. design of sampling programs sampling techniques and the preservation and handling of samples Standards Australia 1998a e AS NZS 5667 6 1998 Water quality sampling guidance on sampling of rivers and streams Standards Australia 1998c e AS NZS 5667 10 1998 Water quality sampling guidance on sampling of waste waters Standards Australia 1998d e Australian guidelines for water quality monitoring and reporting ANZECC 2000 If this guideline does not provide enough direction or detail the above references should be consulted for further guidance The methods in this guideline were consistent with the requirements of the AS NZS 5667 series at the time of writing These standards are reviewed and updated regularly and it is possible that there will be discrepancies between future standards and this guideline For the purposes of regulatory monitoring and testing this guideline takes precedence to the extent of the inconsistency EPA Guidelines Water and wastewater sampling 2 AN OVERVIEW OF MONITORING 2 1 Steps in the monitoring process The main steps associated with monitoring are presented in Figure 1 below Develop monitoring plan why what how when where who See section 3 of this guideline Prepare for sampling Review logistical issues organise sampling equipment See section 4 Record site conditions Decontaminate equipment Collect samples for laboratory analysis Collect and label samples
38. design stage through to delivery at the laboratory Table 1 outlines typical quality assurance protocols for monitoring 7 2 Quality control Quality control QC is a sample or procedure intended to verify performance characteristics of a system Water sampling quality control ensures that the monitoring data sufficiently represents the condition of the target waters when the sample was collected That is that any significant change in or contamination to the sample due to containers handling and transportation is identified through the incorporation of QC samples The type and number of QC samples collected should be based on data quality objectives The required confidence in results will be reflected in the quantity of QC samples The greater the number of QC samples the greater the degree of confidence in the reliability of results The most common types of QC samples are blanks spikes and duplicates which are described in the following section Table 2 states the minimum type and number of sample blanks and duplicates that must be taken for monitoring and testing required by the EPA i e regulatory monitoring and testing RMT When stricter or less stringent requirements are appropriate the requirements may be modified through licence conditions EPA or by approval of monitoring plan Discussions must be held with your licence coordinator prior to developing a monitoring plan with QC that does not conform to the requirements within thi
39. dified as required in Appendix 2 For analysis of parameters such as chlorophyll and suspended solids retain the filter paper not the filtrate Record the volume of sample filtered as this will be used later to calculate the concentration of the sample When retaining the filter papers fold the filters so the residue surfaces are against themselves and place them in a sample tube or opaque bottle Appropriate preservation techniques must also be followed for filter paper such as dark storage or refrigeration 5 6 Decontamination Decontamination is the cleaning of sampling equipment to remove trace analytes and avoid cross contamination of samples Reliance should not be placed solely on decontamination procedures Minimise the chance and consequence of contamination with good sampling design and equipment When planning sampling consider e eliminating the need of multiple use equipment eg collect sample directly into container rather than using a bucket to collect and then transfer e using disposable equipment instead of multiple use equipment eg disposable syringes for field filtration e undertaking tasks within a sterile laboratory rather than in the field eg requesting that a laboratory undertake filtration rather than attempt field filtration e reducing the risk of contamination by as much as practical sampling from locations with lowest concentration of analyte to highest concentrations e dedicating a set of sampling equipment to differen
40. easily contaminated samples such as microbiological sampling There are two basic types of composite samples in water sampling e time weighted samples e flow weighted samples Time weighted samples are sub samples of equal volume taken at constant intervals during the sampling period For example four samples are taken six hours apart to create a 24 hour composite sample In flow weighted sampling the sub samples are proportional to the effluent flow or volume during the sampling period A flow weighted sample can be created by taking samples at constant intervals but with varying sample volumes that are proportional to the flow at the sampling time or by taking samples of equal volume that are taken at the time when fixed amounts of effluent have passed the sampling point For both types of composites the volume of the sub samples should be able to be accurately measured to 45 and the smallest sub sample should be at least 50 mL in volume When undertaking composite samples it is important that holding times and preservation requirements refer Appendix 2 are adhered to The holding time should be measured from the collection of the first sub sample The composite sample needs to be appropriately preserved between additions of the sub samples 5 4 Specific considerations This section provides further guidance on issues associated with the sampling of different types of analytes 5 4 1 Sampling for physical characteristics Many
41. ecent rain can wash potential pollutants from surrounding land into waterways e winds may drive some constituents toward one side of the waterbody or create mixing which might help dissipate them more quickly e shading from cloud and vegetation can influence the level of dissolved oxygen Any abnormalities that may indicate pollution or affect water quality such as absence of flow presence of surface scum water colour or odours excessive algal or plant growth dead fish or invertebrates should also be noted 5 2 Field measurements Analytes that quickly degrade after they are sampled must be tested in the field Field testing may also be used for other samples that can be reliably and cheaply measured in the field Where possible field measurements should be undertaken in situ AS NZS 5667 1 recommends the following analytes be measured in the field as concentrations of these analytes can be significantly changed during transport and storage e dissolved oxygen DO e temperature e pH e conductivity e redox reduction oxidation potential e turbidity e chlorine Many of these analytes can be reliably measured using multi parameter meters usually with an electrode for each analyte Figure 3 Field meters will not provide accurate results unless they are calibrated before use In particular dissolved oxygen pH and turbidity often drift from day to day Calibration requirements will vary between meters and manufacturers so it
42. ed between samples Further information on decontamination is outlined in Section 5 6 Decontamination equipment may include detergents ethanol scrubbing brushes tap water distilled water and a receptacle for collecting waste rinse A burner or 10 sodium hypochlorite solution may be required for microbiological samples Esky or refrigerator Most types of sample require chilling as a means of preservation Samples can be stored on ice in an esky or in a car refrigerator and the temperature should be maintained between 1 C and 4 C Camera Photographs can show where the sample was taken and illustrate observations recorded on the field datasheet It is good practice to take photographs on the first visit to a sampling location and when there are any unusual conditions at the site that may affect the sample EPA Guidelines Water and wastewater sampling 4 4 Occupational health safety and welfare There are many hazards to be aware of when working in any field environment It is recommended that a specific safety plan be developed for each monitoring plan The safety plan should be developed to address risks and may include such things as e hazard identification risk assessment and hazard control measures Typical hazards in sampling include vehicle breakdown or accident bogging in wet conditions exposure to hazardous substances eg decontamination chemicals analytes toxic products formed from sample preparation or stabilisation
43. ent commonly used as a measure of salinity or total dissolved salts Of a current or fluid incorporating and sweeping along in its flow Particular values or uses of the environment that are important such as ecosystem health or amenity that merit protection from the effects of contaminants waste discharges and deposits Several environmental values may be designated for a specific waterbody South Australian Environment Protection Authority The liquid portion of a sample after filtration After taking a sample the time by which the sample should be analysed Exceeding the recommended holding time is likely to cause deterioration of the sample Same velocity eg isokinetic sampling conditions occur when velocity of water at sample inlet is the same velocity as the water being sampled The laboratory limit of reporting also often referred to as limits of detection A documented plan detailing the actions responsibilities and timeframes that will deliver monitoring that meets the defined objectives 34 EPA Guidelines Water and wastewater sampling Monitoring program NATA NEPM Orthophosphate Plankton Protected environmental value Pollutant QA QC RMT RPD Spike recovery value Titration Water quality criteria A system developed to achieve the monitoring objectives National Association of Testing Authorities of Australia www nata com au National Environment Protection Measure Form of phosphoru
44. ent with acetone then solvent such as methylated spirits for metal analysis acid washing is recommended Rinse equipment with 10 nitric acid followed by distilled or deionised water rinse microbiological samples should be further sterilised as per Section 5 4 6 e f contamination is suspected the wastewater resulting from the decontamination process may require containment and disposal to a treatment facility If this is the case the water must not be disposed to groundwater or local drainage The effectiveness of the decontamination procedure should be checked following determination of the protocol and when concern or uncertainty about the effectiveness exists Section 7 2 provides guidance on collection of an equipment blank to check the decontamination process Except for determination of silicon boron and surfactants where detergent should not be used 23 EPA Guidelines Water and wastewater sampling 6 SAMPLE IDENTIFICATION TRANSPORT AND STORAGE 6 1 Labelling and identification Samples need to be labelled so they can be readily identified at all times Sample containers should be marked in such a way that they can be clearly identified and distinguished from other samples in the laboratory Without appropriate labelling all samples may look alike Labels will need to be durable Most samples will be preserved in ice so labels which will not come off when wet need to be used and the ink used will need to be insolu
45. equency and pattern of sampling as well as sampling points A1 3 Precision required It is important when developing a monitoring plan that the amount and frequency of sampling is sufficient to provide confidence in the interpretation of results Most of the sampling undertaken for regulatory purposes is a form of hypothesis testing e testing the hypothesis that environmental harm has not occurred In hypothesis testing there are two types of errors to aim at avoiding falsely detecting environmental harm when it has not occurred and not detecting environmental harm when it has occurred The probability of a false positive is called the level of significance The probability of a false negative Type Il error is related to the power of the test Further information on determining the probabilities is provided in texts such as Australian guidelines for water quality monitoring and reporting ANZECC 2000 For regulatory purposes it is important to minimise both of these probabilities This information has been taken from the EPA Winery and Distillery guideline that outlines the monitoring requirements for the winery industry A2 EPA Guidelines Water and wastewater sampling Case Study Excerpt from EPA guidelines for wineries and distilleries J anuary 2004 Wastewater quality Winery wastewater comes from a number of sources that include cleaning of tanks spent wine and product losses ion exchange columns bottling facilities
46. erate filter and freeze residue acidify with nitric acid to pH1to2 filter for soluble analysis immediately add 20 1 ml of 5096 v v nitric acid per litre of sample the pH should be lt refrigerate and store in the dark see endnote b A15 24 hrs preferably 6 hrs 24 hours 1 month analyse as Soon as possible depends on the half life of the radionuclide from AS NZS 2031 2001 refrigerate in dark safety precautions and shielding are dependent on the activity of this sample it is imperative that radioactive dust is not inhaled or left on clothing safety precautions and shielding are dependent on the activity of this sample it is imperative that radioactive dust is not inhaled or left on clothing EPA Guidelines Water and wastewater sampling Notes from AS NZS 5667 1 1998 Samples for oil and grease analysis should be collected in glass containers with teflon coated equipment as these analytes will stick to the rubber tubing of automated sampling equipment resulting in an unrepresentative sample If there is suspended matter and a separate measurement is required or the solids are not readily dissolved filter the sample and treat as two separate samples Add quantitatively to the sample a known amount of solution containing non radioactive isotopes of interest For samples containing metals the solution is usually acidified to a pH of less than 2 the acid used should not prec
47. erference from other substances Therefore the results produced by these field meters may not be comparable to those produced in the laboratory Additionally some colorimetric methods are becoming available particularly for online applications To apply these methods in a regulatory monitoring plan the EPA must be consulted prior to field testing 5 2 1 Dissolved oxygen Dissolved oxygen DO is a measure of the amount of oxygen available within a waterbody and is measured on a scale of 0 mg L 20 mg L or as percentage saturation It can be determined using portable electronic meters Figure 3 or by titration Electronic meters are by far the most convenient method and should be used wherever possible In waterbodies DO usually varies due to depth and time of day Photosynthesis by plants and algae adds oxygen to the water This means as the day proceeds DO often increases reaching a peak in late afternoon As night falls photosynthesis stops and respiration decreases DO The solubility of oxygen also decreases at higher temperatures and salinities DO is highly unstable and should always be measured in situ as the process of taking a sample can influence the amount of dissolved oxygen in the sample A DO measurement of a sample taken in a bucket is not ideal An electronic meter should be immersed directly in the water column at a depth appropriate to the sample being taken For measurements in the surface layer as is most common when grab samplin
48. es quickly in solution and should be tested in the field It is important to determine what form of chlorine is required to be reported Total chlorine consists of free chlorine chlorine gas hypochlorite ion and hypochlorous acid and combined chlorine eg chloramines The most common forms required are total chlorine or free residual chlorine Free residual refers to the residual chlorine remaining at a certain location eg outlet of settling tank Chlorine can be tested in the field using a meter a field titration or a pre prepared chlorine kit Most of these methods are based upon colorimetry where the reagent diethyl p phenylene diamine DPD changes colour upon reaction with chlorine Where tablets are provided it is important that the tablets are current not expired and that contamination of the tablets prior to use is avoided Where total chlorine is required to be measured chlorine meters or chlorine kits are recommended rather than field titrations Field titrations can provide an accurate result and differentiate between the different species of chlorine However they require specialised equipment are more easily contaminated and often impractical 5 3 Collection of samples for analysis 5 3 1 Sampling equipment It is important when undertaking sampling particularly for trace analytes that the sampling equipment is inert that is it does not cause contamination or interference with the sample 14 EPA Guidelines Water
49. g the DO electrode should be placed within the top 30 cm of the water column For depth stratification the electrode should be lowered to the depth of interest It is important to know the specific procedures for the meter being used For example e f using traditional membrane type DO meters the electrode needs to be placed in an area with flow or continually moved through the water to obtain an accurate reading 12 EPA Guidelines Water and wastewater sampling The reason for this is that membrane type DO electrodes consume oxygen at the water membrane interface causing the DO reading to drift downwards Care should be taken to ensure that the movement is not rigorous enough to introduce more oxygen into the water However some DO meters have mechanisms such as an inbuilt stirrer a vibrating probe or take short pulsed readings rather than continuous These can deliver a correct reading without the need to have water moving over the probe e Salinity and atmospheric pressure and therefore altitude can affect oxygen readings Many modern meters automatically correct for these variables and therefore the manual should be checked to ensure this is the case Meters without automatic correction may require manual entry of this information 5 2 2 Temperature Temperature of a waterbody will vary throughout the day and at different depths Water temperature will move towards ambient temperature as soon as a sample is removed from the
50. g is more closely obtained Figure 6 Van Dorn samplers with cup ends set open Photo courtesy of AWQC 5 3 4 Automatic samplers Automatic samplers can be used to take discrete continuous or composite samples Issues that need to be considered when using automatic samplers include e where discrete samples are taken the sampling lines should be decontaminated or purged between samples e preservation filling technique and holding times Appendix 2 must be observed It may be necessary for the sampler to be able to keep samples cooled to 4 C to store the samples in the dark and or to add or maintain preservative in the sample containers e the inlet velocity of the sampler may affect the sample Ideal sampling conditions are isokinetic the velocity of the water in the inlet should be the same velocity as the water 17 EPA Guidelines Water and wastewater sampling being sampled The inlet velocity should be a minimum of 0 5 m s and maximum of 3 m s e the materials of an automatic sampler may affect the sample eg organics can adhere to plastic inlet tubing 5 3 5 Composite samples A composite sample is a sample consisting of two or more sub samples mixed together in known proportions Composite samples may be collected manually by combining grab samples or by an automatic sampler Composite samples are not appropriate for analytes that degrade during sampling or transport eg dissolved oxygen chlorine or for
51. ill have a direct effect on the integrity of the sample As many results are reported in fractions of grams even extremely small volumes of contaminants can significantly affect results Contamination can be very costly especially if decisions are based on unrepresentative data Physical changes Any process that changes the physical nature of a sample may affect the integrity of that sample Examples of physical changes are listed below Temperature of water varies throughout the day and year A change in temperature can alter the chemical properties of a wide range of many parameters Volatilisation is the loss of dissolved compounds by evaporation It is controlled by the vapour pressure of the solute or solvent Compounds most susceptible to volatilisation include volatile organic compounds such as chlorinated hydrocarbons eg TCE and monocyclic aromatic hydrocarbons eg benzene Sorption is the attraction of dissolved substances to the surface of solid particles sampling equipment and sampling bottles Any process or activity that increases suspended solids in samples can change the measured concentrations of dissolved major ions heavy metals and hydrophobic organic compounds eg organochlorinated pesticides Degassing is the loss of dissolved gas from a solution and can result from either an increase in temperature or a decrease in pressure Parameters potentially affected by degassing are pH likely to increase through loss of carbon
52. including QC See section 5 samples Lusieseeede e lal beni andes dei ce ee a Ete dem Ms E ESI Decontaminate equipment See section 5 6 Undertake field tests Filter sample Calibrate equipment where required Record results See section 5 2 Preserve sample Transport samples See section 6 3 Laboratory analysis See sections 7 amp 8 Review results and report See section 8 Figure 1 Stages of monitoring EPA Guidelines Water and wastewater sampling 2 2 Integrity of samples To ensure that sampling is consistent and of good quality and traceability samples need to be representative of the body from which they were taken If the sample integrity is altered the information gained from analysis could be misleading and ultimately result in mismanagement of water resources and or polluting of the resource The main processes that have the potential to affect the integrity of a sample are listed below These processes are interlinked and a change in one thing may have a flow on effect that will influence another eg a change in temperature can cause chemical changes Contamination Contamination of a sample occurs when foreign substances are introduced into it This will lead to the sample having characteristics that are not representative of the in situ conditions Contamination of a sample can occur at any stage of the sampling process from the collection of samples through to the final analysis and w
53. ion management plan IMP approved by the EPA or the wastewater management system is equipped with in line monitoring devices for dissolved oxygen DO and pH or EC to indicate irregularities that may indicate a need for further testing The parameters to be monitored in wastewater are listed in Table 5 in EPA Guideline for wineries and distilleries J anuary 2004 The winery may need to consult its EPA licence coordinator to confirm whether the optional parameters listed in the table need to be monitored If a winery generates less than 1 ML of wastewater per year the EPA may permit the omission of some minor wastewater parameters from the monitoring regime if it can be demonstrated that the risk to the environment is low and the wastewater management system has been working effectively for the past two years The EPA recommends that winery effluent not be combined with wastewater generated from cellar door and food preparation activities This is due to health concerns If separation is not possible the winery must seek advice from the Department of Human Services A2 Elements of a monitoring plan A2 1 Duration of sampling For regulatory monitoring sampling will generally be ongoing to show continued compliance with criteria or to monitor the ongoing influence of discharges on the receiving environment Campaign monitoring or pilot studies should be considered when the variability of a wastewater stream or receiving environment is unce
54. ion of contamination from the filtering process This can be from dust and atmospheric fallout during the filtration process or from the filter and filtration equipment After the filtration equipment has been decontaminated in the usual manner process a blank of high purity water through the filtration apparatus in the same way that the sample would be The filtrate should then be collected in a normal sample container preserved as appropriate and transported to the laboratory with the other samples 28 EPA Guidelines Water and wastewater sampling 7 2 2 Duplicates Field duplicate samples are obtained by dividing a sample collected from a sampling point They can be used to measure the precision or repeatability of the analytical process in the laboratory Duplicate samples should be blind coded so that the laboratory cannot tell which primary samples they correspond to Remember the corresponding sample to the duplicate needs to be recorded on the field sheet Note that duplicate analysis is generally targeted at the contaminants of concern and will not necessarily consist of a full set of analytes There are two types of duplicate samples e intra lab duplicates where the duplicate sample is transported to the same laboratory primary laboratory as the bulk of the samples these duplicates measure the precision variation of the primary laboratory s analytical methods e inter lab duplicates where samples are sent to a different l
55. ipitate or volatilise the elements of interest Refrigerate and store in the dark Plastic plastic containers eg polyethylene PTFE polypropylene PET and similar Glass borosilicate glass container Vials are flat bottomed borosilicate glass vials typically 30 50 mL capacity with screw caps The caps should have PTFE faced septa or liner The preservation technique will depend on the method of analysis to be used Other methods of preservation may be suitable and prior liaison with the analytical laboratory is required Refrigerate cool to between 1 C and 4 C see clause 11 2 2 of AS Freeze freeze to 20 C see clause 11 2 3 of AS A16 EPA Guidelines Water and wastewater sampling APPENDIX 3 FIELD EQUIPMENT CHECKLIST EXAMPLE Equipment list Check Equipment list Check Documentation Quality control samples Monitoring plan including site plan Field blanks Appropriate area maps Transport equipment blanks Field notebook record sheets Sample storage and transport Chain of Custody Eskies and ice Pens and textas Packing material Sampling equipment Ice packs blocks Sampling rod Packing tape Depth sampler Address Labels blanks Field meters Courier information Disposable gloves Safety equipment Sample containers including containers for duplicates and First aid kit Labels for samples Sunscreen sunglasses Dec
56. is important to follow the instructions supplied with the equipment It is recommended that meters be calibrated prior to every sampling event as a minimum Most electrodes are calibrated using standard solutions of known properties These can be purchased from various laboratory supply companies or sourced from a National Association of Testing Authorities NATA accredited analytical laboratory Standard solutions have a limited shelf life and can deteriorate if not stored correctly away from light at 20 C for most solutions is acceptable The quality of standard solutions will directly influence the performance of the meter so it is important that if there is any doubt fresh standard solutions be obtained Calibration of all meters should be routinely recorded on a standard sheet including dates 11 EPA Guidelines Water and wastewater sampling temperatures and calibration readings This will provide a record of the performance of each meter and provide evidence that quality procedures are being employed Figure 3 Examples of the various types of field meters available From left to right a dissolved oxygen meter a multi parameter meter and a redox meter Some manufacturers are producing ion specific probes that measure analytes such as nitrite calcium sulphide bromide fluoride ammonium and chloride in the field They may be suitable for situations where parameters are present in high concentrations but may be subject to int
57. ity has not been compromised and imperative if the samples are to be used in legal proceedings or if there is any suspicion that the samples might be tampered with at any stage of the process The Chain of Custody documentation is a record used to trace possession and handling of a sample from the time of collection through analysis reporting and disposal The basis of Chain of Custody control is that a sample is always in someone s custody and as such they are responsible for it It is important to realise that couriers will often not recognise the contents of a sample container but only take responsibility for the container itself As such the item eg esky should be secured with tape so that it would be obvious if the items had been tampered with 24 EPA Guidelines Water and wastewater sampling The sampler should complete the Chain of Custody forms prior to packing the samples The original Chain of Custody form must remain with the sample at all times to enable the completion of custody details at each stage of progression through transportation analysis and reporting see Appendix 5 for an example Chain of Custody form A copy of the final completed Chain of Custody form should be sought from the laboratory to confirm receipt and appropriate transfer and handling The analytical laboratory should also include a copy of the completed chain of custody form as part of the analytical report 6 3 Transport and storage During sample
58. ity may change the amount of dissolved oxygen the pH and or redox Factors influencing the biological activity of a sample may in turn be influenced by temperature available oxygen pH and exposure to UV light The collection equipment and preservation methods used for sampling should be chosen to minimise the impacts of the above mentioned factors To minimise and to quantify the impact of these processes on sample integrity quality control protocols and procedures must be developed and implemented at all stages of monitoring Quality control QC protocols that are typically used in monitoring are shown in Table 1 This table also states the minimum quality control that is required for licensees undertaking regulatory monitoring and testing RMT i e monitoring required as a condition of authorisation Table 1 Quality control in monitoring TN Compulsory Monitoring Step QC protocols Purpose Refer to for RMT Various including Ensure sample collected is Section 3 of this If specified control sites multiple representative of body from guideline sample locations which it was taken duplicate samples Develop sampling times monitoring plan Review of monitoring To ensure that monitoring Monitoring plan Yes plan by EPA plan is in compliance with requirements authorisation and meets EPA 2006 monitoring objective Appropriate containers Minimise changes to sample Section 5 and Yes filling and preservation ph
59. ks sampling required Collect final rinse water as recommendation event if equipment equipment the blank is used 30 EPA Guidelines Water and wastewater sampling Number QC sample Quantifies a Recommended by sienna if type contamination Action in the laboratory Action in field AS5667 1 and sturpiciin L fromt ANZECC ARMCANz Monitoringas 2000 condition of authorisation Filtration Contamination Nil After washing the filtration No specific 1 per sampling blanks or changes equipment as required filter recommendation event if sample is during field distilled water using filtration field filtered filtration apparatus as for a normal sample Collect filtrate for analysis Duplicate Variability of Nil Split a sample into two sub samples 1 per 20 samples 1 per year or 1 per samples to analysis within and preserve as required Ensure 5960f samples 20 samples primary laboratory samples are labelled uniquely whichever is laboratory Transport to laboratory as required greater Duplicate Variability of Nil Split a sample into two sub samples No specific 1 per year or 1 per samples to analysis and preserve as required Transport recommendation 20 samples secondary between one sample to primary laboratory whichever is QA laboratories and one sample to secondary greater laboratory laboratory Recommendations sourced from a AJ NZS 5667 1 1998 ANZECCARMCANZ 2000
60. ment Temperature Dissolved oxygen Turbidity Conductivity pH Chlorine Sample collection Sample No Notes eg collection method filter method duplicate decontamination method Record in the order taken including duplicates and blanks A18 EPA Guidelines Water and wastewater sampling APPENDIX 5 CHAIN OF CUSTODY FORM EXAMPLE Cot feos me O em Phone jemasg oJ o O Analysis required Notes 0 05 5 Filter vivos 11 05 2 30pm Filter paper Agreed condition temp Sample relinquished by Sample received by intact poe Nome organisation_ i ET Time Sample Condition condition O
61. n the influent and effluent from sewage treatment plants varies after a rainfall event due to the infiltration and inflow into the sewage system diluting the concentration but increasing the volume of wastewater How process variability considerations are taken into account in the design of a monitoring plan will depend upon the objective of monitoring eg to determine the maximum concentrations of a pollutant the variability of discharge or the average concentration Receiving environment variability Variation in water quality can occur at different frequencies for varying reasons including but not limited to e diurnal variation changes in dissolved oxygen and pH throughout the day due to respiration and photosynthesis changes in water temperature e depth variation stratification effects can occur in lagoons and lakes as well as in rivers creeks marine water and estuaries e seasonal and event variation variations in flow and salinity due to rainfall and temperature e tidal variations variation in flow direction and volume due to tide in rivers and estuaries as well as marine environment e Spatial variation occurs in the receiving environment due to a range of factors from natural biological variability wave action and turbulence through to flow and concentration modifications around structures such as jetties and weirs Knowledge of the variations likely to affect monitoring results are important in selecting the fr
62. olding ti TKN total plastic or glass 500 acidify with sulfuric acid 24 hours Kj eldahl nitrogen or hydrochloric acid to pH 1to 2 refrigerate Organics biochemical plastic or glass do not pre rinse refrigerate and store in glass containers are preferable for oxygen demand container with the dark samples with low BOD lt 5 mg L BOD sample fill container completely to exclude air chemical oxygen plastic or glass fill container acidify with sulfuric acid glass containers are preferable for demand COD completely to to pH 1 to 2 refrigerate samples with low COD lt 5 mg L exclude air and store in dark Hydrocarbons oil glass solvent do not pre rinse refrigerate extract on site where practical and grease washed container with sample extract sample container as part of ET the sample extraction procedure acidify with sulfuric acid or hydrochloric acid to pH 1 to 2 and refrigerate do not completely fill container A12 EPA Guidelines Water and wastewater sampling Analyte MAH monocyclic aromatic hydrocarbons PAH polycyclic aromatic hydrocarbons PCBs polychlorinated biphenyls Tvpi glass vials 500 with PFTE fill container completely to exclude air lined septum glass solvent 500 do not completely washed fill container do not pre rinse glass solvent 1000 3000 do not completely washed with fill container PTFE cap liner do not pre rinse Filtration and No
63. ollection Guidance on field filtration including for chlorophylls is given in Section 5 5 Once filtered opaque bottles are recommended for storage of pigment extracts as even brief exposure to light can alter chlorophyll concentrations Labelling should identify the sampling technique to allow laboratory staff to better interpret results 5 4 8 Sampling for radiochemical analytes For background radioactivity in surface waters the procedures and techniques for sampling for radiochemical analysis are the same as for general sampling Sample storage transport and pre treatment requirements vary depending on the type of radioactivity of interest although most require acidification with nitric acid to pH 1 2 See Appendix 2 for details regarding sample holding times minimum volumes and other requirements of sampling for radiochemical analysis Radioactivity at background levels does not normally present a hazard to the sampler There are no additional decontamination procedures or personal protective equipment required when sampling surface waters for radiochemical analyses at low levels While it is unlikely that high levels of radioactivity will be encountered in current or foreseeable situations in South Australia if the sampler has concerns advice should be sought from a suitably qualified person with experience in dealing with radioactive substances 5 5 Field filtration Field filtration can be undertaken for a number of purposes e to
64. ontainer sample do not completely fill container Filtration and Notes preservation Holding time refrigerate 7 days extract on site where practical extract sample container as part of the sample extraction procedure if sample is chlorinated add 80 mg of sodium thiosulfate for every 1000 mL of sample to container prior to sampling refrigerate and store in 24 hours the dark acidify to pH 1to 2 3 weeks refrigerate and store in dark if sample is chlorinated add sodium thiosulfate to container prior to sample collection acidify with sulfuric acid 1 week to pH 1 2 refrigerate and store in the dark analyse as soon as possible phosphoric acid can be used instead of sulfuric if necessary freeze 1 month inorganic carbon needs to be purged before analysis so volatile organic compounds will be lost A14 EPA Guidelines Water and wastewater sampling Analyte faecal coliforms or E coli etc chlorophylls radiochenical analysis alpha and beta activity gross alpha and beta activity except radio iodine gamma activity Endnotes Filling technique glass or plastic Confirm with do not completely sterilised laboratory fill container plastic or glass man i consult laboratory Filtration and preservation for chlorinated chloraminated water add sodium thiosulfate to concentration 100 mg L for samples with high heavy metals add EDTA refrigerate refrig
65. ontamination Drinking water Clean work area eg plastic groundsheet Mobile phone communication equipment Buckets PPE wide brimmed hat wet weather gear waders rubber boots disposable overalls Demineralised deionised water Antiseptic hand wash Detergent solution Lifej ackets EPIRB Ethanol in wash bottle Other Sponges scrubbing brush Tools spanner shifter etc Gas burner sodium hypochlorite for microbiological Digital camera and batteries charger Field filtration GPS and batteries Filtration pump Keys for gates Filtration apparatus syringe etc Other equipment for site specific or remote area requirements Filters Note No claim is made that this list is comprehensive It is a suggestion for consideration and requires tailoring to individual needs Al7 EPA Guidelines Water and wastewater sampling APPENDIX 4 Sampling summary Sampler Date Site information Site ID Location Field observations FIELD RECORD SHEET EXAMPLE Project number Time begin and end GPS Photo numbers Weather Temperature Wind and direction Cloud cover rain Water Tide depth Flow Choppy mixed calm Observations examples Surface film Algae phytoplankton Debris Odour Other additional Field measurements Analyte Result s Instru
66. or in addition to a requirement of an authorisation or order the Australian guidelines for water quality monitoring and reporting ANZECC 2000 can provide further advice and assistance in setting monitoring plan objectives Water and wastewater monitoring can be undertaken to meet many objectives from gaining an understanding of an aquatic ecosystem and the physical chemical and biological processes that operate within it to the review of water quality within a specified criteria A1 2 Variability considerations Variability in time and space is probably the most significant aspect to be considered in the design of sampling plans Variability will determine the number of sites number of replicates and the frequency of sample collection High variability in the environment or the industrial discharge combined with poor sampling design or too few samples can result in data that is too variable to reveal an impact disturbance or trend Al EPA Guidelines Water and wastewater sampling Industrial process variability Examples of variation in wastewater due to process variability include e daily and weekly variation particular processes such as scheduled cleaning might always occur on the same day of the week leading to a consistent pattern of variation in the quality of the discharge e seasonal variation such as that experienced in the wine industry as shown in the case study presented later in this section e event variatio
67. oratory of any analytes that may be in particularly high or low concentrations Some analytical methods need to be modified for the extremes in concentration ranges and prior knowledge of the expected range can speed up the turnaround Some instruments may be affected if exceptionally high concentrations of certain analytes are introduced without prior dilution Factors such as salinity of a sample can also influence the choice of analytical methods and some sample characteristics can cause interference with procedures for other analytes During the implementation of a monitoring program it is useful to stay in communication with the laboratory so they know when to expect the samples and whether there are any problems with sample collection This is especially important with microbiological samples EPA Guidelines Water and wastewater sampling 4 3 Equipment An example of an equipment checklist is included in Appendix 3 Major items of equipment likely to be needed are discussed as follows Paper work and record keeping Good planning and record keeping is imperative The sampling plan or concise sampling schedule and map should provide all the required information such as location of monitoring points the number and type of samples that need to be collected and container types Records of observations and actions can be critical for future reference A sampling data sheet similar to that in Appendix 4 is recommended to ensure that a complete
68. ot provide the information desired Grab samples Grab samples are discrete samples that are taken at a location to provide a snapshot of the water quality characteristics at that time For the purposes of quantifying water or wastewater constituents grab samples will show the concentrations at that location and time of sampling They will not provide any information about the concentrations outside that point in time As such if grab samples are employed a high number of samples high sampling frequency may be required to show the nature of change over time A sampling plan using grab samples could show the dispersal of discharge constituents in the receiving environment at the time of day when the discharge is present They can also be used to show worst case scenario situations eg in the case of surface scums of algae or oil and greases However taking manual grab samples is labour intensive and often impractical for long intensive sampling plans Composite samples Composite samples are those collected through mixing multiple grab samples to obtain a single mixed sample Compositing samples can increase the temporal and spatial extent of sampling without increasing the number of samples or sampling and analysis costs These types of samples are used when the average water quality characteristics are of interest over a given period of time or volume of flow They may be more appropriate than grab samples when the distribution of consti
69. otected environmental value means the maximum concentrations of certain substances permitted by the Environment Protection Water Quality Policy 2003 to be in water or the minimum or maximum levels permitted for certain characteristics of water 35 EPA Guidelines Water and wastewater sampling APPENDIX 1 GUIDANCE ON DEVELOPING AN EFFECTIVE MONITORING PLAN The following appendix provides general guidance on issues to be considered when developing a monitoring plan for water or wastewater sampling Consideration of these issues will assist in designing a monitoring plan that is specific targeted and cost effective Monitoring Variability of Spatial Precision Logistical Cost obj ective process and extent of accuracy and receiving impacts required OHS amp W environment issues Monitoring plan Duration of sampling campaign ongoing Sampling points location and number Frequency and patterns of sampling Analytes parameters Method of sampling grab automatic Responsibilities Al Key considerations Al 1 Monitoring objective The first step in developing a monitoring plan is to clearly identify the objectives of the monitoring For licensees required to undertake regulatory monitoring and testing RMT the EPA intends to specify objectives of the monitoring as a condition of authorisation or order Where monitoring is being undertaken for purposes other than
70. oved for unique circumstances upon written application to the Environment Protection Authority EPA This guideline may also provide guidance for water sampling for non regulatory reasons such as collecting samples for ambient or hot spot monitoring Any monitoring submitted to the EPA for these purposes should also meet the requirements of this guideline 1 4 Legal framework The principal legislation dealing with pollution in South Australia is the EP Act The EPA may impose conditions on person s required to hold a licence or authorisation In particular under Section 52 of the Act the EPA can require holders of an authorisation to carry out specified tests and environmental monitoring relating to the activity undertaken pursuant to the authorisation or activities previously undertaken at the place to which the authorisation relates and to make specified reports to the Authority on the results of such tests and monitoring in Section 52 The requirement to undertake monitoring and testing can also be imposed under clause 44 of the Water Quality Policy on any person granted an exemption under the Policy Monitoring and testing that is required under these powers is termed regulatory monitoring and testing RMT EPA Guidelines Water and wastewater sampling 1 5 Further guidance The principles in this guideline are based on the following standards e AS NZS 5667 1 1998 Water quality sampling guidance on the
71. physical properties are best determined in situ by field measurements If unable to determine in this way ensure that a representative sample is taken and that recommended filling preservation and holding times as listed in Appendix 2 are met 5 4 2 Sampling for dissolved gases When collecting samples for dissolved gases care should be taken to minimise aeration and retain the gases within the sample Gases are maintained within the sample by displacing water rather than air when collecting the sample eg by using open tube devices when sampling depths If sampling from a tap insert a flexible inert tube from the tap to the bottom of the sample container with water exiting within the container rather than to air 18 EPA Guidelines Water and wastewater sampling 5 4 3 Sampling for nutrients When sampling for nutrients it is important to determine the nutrient form that is required and to determine how that form is to be reported Forms of nitrogen in order of decreasing oxidation state include nitrate nitrite ammonia and organic nitrogen Oxidised nitrogen or total oxidised nitrogen includes nitrate and nitrite Kjeldahl nitrogen is a term that refers to ammonia and organic nitrogen and a specific analytical method that is used to determine the concentrations All forms are generally reported as nitrogen There are also many forms of phosphorus and classifications of phosphorus according to how they naturally occur in w
72. preferred this analysis should be carried out in the field within 5 minutes of sample collection the preservation technique will depend on the interfering compounds present sulfides and oxidising agents potentially cause large errors in the determination of different cyanide forms refer to the analytical method for suitable preservation techniques PTFE containers are not suitable EPA Guidelines Water and wastewater sampling Holding time Notes volume preservation refrigerate 24 hours unfiltered sample nitrite uu or al immediate analysis analyse as soon as possible after collection field filter through 1 month O 45um cellulose acetate es and freeze phosphorus total plastic or glass s 24 hours acidification not recommended for persulfate oxidation method freeze o 1 month acidify with sulfuric acid 1 month or hydrochloric acid to pH 1 to 2 refrigerate and store in dark phosphorus plastic or glass field filter through dissolved cellulose acetate membrane and refrigerate or field filter and freeze sulfide total Peso se or glass fill container none required for field 1 week completely to measurement Preserve preserved exclude air with zinc acetate for laboratory analysis nitrogen total plastic or glass refrigerate or freeze 24 hours 1 month 24 hours 1 month All EPA Guidelines Water and wastewater sampling Typical Filtration and Anal Contai Filling techni H
73. reservation techniques can reduce degradation rates they may not completely halt such changes All analytes therefore have a holding time which is the maximum time that can elapse between sampling and analysis and where the sample is unlikely to be significantly modified under the recommended preservation conditions Holding times for each analyte are included in Appendix 2 Samples must be delivered to the laboratory within the required holding times 26 EPA Guidelines Water and wastewater sampling 7 QUALITY 7 1 Quality assurance Quality assurance QA is the policies procedures and actions established to provide and maintain a degree of confidence in data integrity and accuracy For a monitoring program to successfully meet its objectives a rigorous and thorough program of checks comparisons and communication must be implemented In order to achieve consistent data collection a QA system must be followed Figure 7 outlines a systematic approach to the development of a QA program for sampling Define program objective Establish data quality requirements Define sampling and analytical f protocols Continuous improvement Apply protocols fo Refine protocols ____________ Site decisions Figure 7 Quality assurance framework Puls amp Barcelona 1996 To control errors in field sampling to a level acceptable to the data user various aspects of a QA program should be implemented from the monitoring program
74. rtain A pilot study of high frequency discrete and or composite sampling will provide information regarding the variability in the wastewater stream due to random and systematic influences Based on an understanding of the results of the pilot study a more targeted cost effective ongoing monitoring plan that will adequately characterise the water can be developed A2 2 Sampling locations The design of a sampling plan to monitor water or wastewater composition should ensure samples are collected at sites and times that provide a representative sample thus providing an accurate description of the overall quality of the wastewater stream Additionally sampling sites should be located in areas that are safe to access accessible under all conditions of flow and discharge be well mixed to ensure a homogenous sample is collected and be easily identifiable for later sampling Permanent sampling locations should be established in any sampling environment to ensure that representative samples can be compared over time Determine impacts on receiving waters In the case of examining the effect of a point source discharge sites should be arranged in such a way that the end of pipe and upstream and downstream of the discharge water is sampled The degree of mixing within the waterbody will determine the proximity of sites to each other where mixing is strong the water is homogenous sites may be spread further apart A4 EPA Guidelines Water and
75. s guideline 27 EPA Guidelines Water and wastewater sampling 7 2 1 Blanks QC blank samples are typically made from high purity water The extremely low level of all analytes in high purity water enables identification of any contamination If an elevated result of a particular analyte is found in a blank it is reasonable to assume that similar contamination may have occurred in other samples Each type of blank is designed to assess the contamination from a particular part of the process and together a system of blanks isolates contamination from the sampling transport and analytical process If elevated concentrations of target analytes are detected during the analysis of a blank sample a thorough review of the areas of the sampling plan that may be introducing the contamination must be undertaken to determine the effect on the results and corresponding conclusions Field and transport blanks Field blanks are designed to illustrate the effect of handling on sample integrity They detect contamination from sources such as dust and atmospheric fallout To collect field and transport blanks high purity water is poured into three sample containers prior to going on site If the water to be sampled is known to be saline the blanks should be of corresponding salinity Two of the sample containers are taken to the site and one is sent to the laboratory At the site the cap of the field blanks should be removed and replaced at the end of
76. s highly dependent on day by day activities To accurately determine the pollutant load that is discharged to the environment sampling must reflect wastewater quality during the production period It must be performed at a suitable location before it is disposed of to land or re used for irrigation Monitoring plans submitted to the EPA to comply with licence requirements must be accompanied by a schematic diagram This must indicate the sequence of wastewater treatment processes employed and where the wastewater sampling is to be performed to enable the EPA to advise on the suitability of the monitoring point The table below shows the EPA monitoring frequency requirements for differing volumes of wastewater generated by wineries For facilities that do not have distinct production periods a suitable frequency must be discussed with the EPA Wastewater produced per year ML Frequency gt 10 Once per production period 10 20 Twice per production period gt 20 Three times per production period A3 EPA Guidelines Water and wastewater sampling Case Study cont Excerpt from EPA guidelines for wineries and distilleries 2004 For a winery that generates more than 10 ML of wastewater per year the EPA may permit a reduction in wastewater monitoring frequency if an adequate treatment system approved by the EPA to treat wastewater before application to land has been installed the facility fully implements an irrigat
77. s that is immediately accessible for plants and animals to use Microscopic plants phytoplankton or animals zooplankton found in the water column of aquatic ecosystems In relation to waters or a particular body of water means the beneficial aspects or uses of water as are designated by the Environment Protection Water Quality Policy 2003 in respect of those waters or that body of water for protection from pollution Something that pollutes such as sewage or mine waste exhaust gases etc Quality assurance The implementation of checks on the success of quality control Quality control The implementation of procedures to maximise the integrity of samples and data eg cleaning procedures contamination avoidance sample preservation methods Regulatory monitoring and testing Monitoring undertaken as a condition of authorisation or in order to enable an environmental risk to be assessed or to assess the effectiveness of risk controls and management within the scope of the EP Act Relative percentage difference Refer to Section 8 for equation and description A percentage indicating the detected concentration of a known volume of analyte over the known value A measured amount of a solution of unknown concentration is added to a known volume of a second solution until the reaction between them is just complete the concentration of the unknown solution the titer can then be calculated In relation to protecting a particular pr
78. sampling During transport and storage the containers should be treated as if they hold a real sample The transport blank need not be opened but should be carried with the rest of the samples Container blanks Container blanks show if there has been any contamination of the sample from the container itself the washing process or any preservation techniques Containers are selected randomly filled with distilled water in the laboratory and the appropriate preservation applied These blanks should be held in the laboratory for the same time as the samples before analysis They are particularly important when the holding time is in the order of several days or weeks Equipment rinsate blanks Contamination introduced into the sample through contact with sampling equipment is measured using an equipment blank Ideally an equipment blank is prepared before sampling to show contaminants have not been introduced and at the conclusion of sampling to show the effectiveness of the decontamination procedure The equipment should be decontaminated in the usual manner The final rinse with distilled water or similar in the decontamination process has completed preparation of the equipment blank If the washing process is cleaning the equipment sufficiently the equipment blanks should show no change in composition from the rinse water Filtration blanks Some parameters require a sample to be filtered in the field A filtration blank allows determinat
79. ssibility of sample contamination Prior to and between collection of samples hands should be washed then disinfected with an alcohol based hand disinfectant eg 70 ethanol or hexifoam Wearing latex gloves will help avoid contamination of samples during collection Gloves should be changed between samples Whenever possible collect the sample directly into the sample container ensuring that the inside of the cap and the neck of the container are not touched or exposed to the air for longer than necessary For samples of chlorinated or chloraminated water the container should contain sufficient sodium thiosulphate to neutralise the disinfectant Care should be taken not to overdose excessively as this may cause changes in dissolved oxygen and pH Analytical laboratories should be able to supply suitably treated bottles The hierarchy with regard to sampling equipment for microbiological analytes is e minimise usage of sampling equipment where possible thus avoiding risk of contamination e use disposable pre sterilised equipment as per AS NZS 2031 2001 for each sample e use metal sampling equipment eg stainless steel bucket sterilised stainless steel jug as intermediary container metal sampling rod Equipment should be sterilised prior to and between samples by flaming with a gas burner All sections of the sampling equipment that may come in contact with the container and the waterbody should be flamed The burner should be fuelled
80. t uses eg equipment used for wastewater sampling should not be used for receiving environment sampling Multiple use equipment must be decontaminated prior to sampling and between collection of samples Equipment should also be decontaminated at the end of each sampling trip optional in terms of sample integrity but good practice to ensure contamination is not transported off site Refer to operating manuals for specific decontamination instructions for equipment such as field meters and automatic samplers The following methods should be used when decontaminating sampling equipment 22 EPA Guidelines Water and wastewater sampling e Decontaminate equipment away from sampling site Use plastic sheets to prevent contamination from ground material e It is advisable to wear clean sterile gloves and protective clothing when performing the decontamination process e Prepare detergent solution in large container or bucket place equipment into container and scrub clean Detergents should be phosphate free To clean hoses pumps pump decontamination solution through lines e Rinse equipment thoroughly preferably triple rinse Distilled or deionised water should be used for rinsing e Clean equipment with further decontamination solutions if required The cleaning solution will depend on the contaminants being investigated as follows for oil and grease hydrocarbons pesticides PCBs or PAHs a solvent should be used Rinse equipm
81. te or stainless steel poles with a large clamp or cage on one end designed to securely hold various sizes of sample container Containers are placed in the cage while sampling to provide extra reach or to prevent the hands from contaminating the sample or contacting wastes The container should be gently but quickly lowered into the water to minimise the contribution of surface films to the sample Figure 5 Using sampling rod The sample may also be collected using a bucket and rope in situations where access to the water is limited eg when the sampling point is a high bridge In this case a sub sample is immediately taken from the bucket using the techniques above for sampling directly from the watercourse 5 3 3 Sampling at depths When samples are required from particular depths such as for depth profiling specific equipment is required The equipment falls into three general categories as follows Pumping systems These can be used for depths up to 10 m Water is sucked to the surface through PVC or PTFE tubing around 10 mm diameter The inlet of the tube should face the direction of water flow At least one volume of water should be pumped through the tubing before collecting a sample to minimise the effects of pumping including entrainment of suspended solids by dissolved gases 16 EPA Guidelines Water and wastewater sampling Issues with pumping include the large surface area to volume of tubing that increases the chance of
82. tes preservation Holding time 2 x 40mL vials are recommended for purge and trap analysis 1 week Acidify with hydrochloric acid to pH 1 to 2 and refrigerate If residual chlorine is present for each 40ml of sample add a 25 mg of ascorbic acid b 3 mg of sodium thiosulfate or c 3 mg of sodium sulfite refrigerate and store in 1 week extract on site where practical the dark E extract sample container as part of if sample is chlorinated the sample extraction procedure add 80 mg of sodium thiosulfate for every 1000 mL of sample to container prior to sampling if sample is chlorinated 1 week extract on site where practical add 80 mg of sodium thiosulfate for every 1000 mL of sample to container prior to sampling extract sample container as part of the sample extraction procedure a 40 mL vial with PTFE lined septum is recommended for micro extraction A13 EPA Guidelines Water and wastewater sampling Typical pesticides glass solvent 1000 3000 organochlorine washed with organophosphorus PTFE cap liner and nitrogen containing phenolic amber glass 1000 compounds solvent washed including with PTFE cap chlorinated liner phenols TOC total organic carbon amber glass with PTFE cap liner I E Microbiological biological Filling technique do not pre rinse container with sample do not completely fill sample container with air do not pre rinse c
83. transport and storage it is vital that all procedures are followed to ensure that samples are not significantly altered in condition and are in a state fit for analysis at the laboratory Contamination of samples can easily occur during transport due to container cross contamination packaging material or chilling products During sample storage degradation can occur due to lack of appropriate preservation inappropriate storage conditions excessive storage times and sample cross contamination The key aspects of effective transport and storage are to e ensure samples are appropriately packed to avoid breakage and cross contamination e reduce sample degradation through appropriate preservation e ensure time between sampling and analysing does not exceed holding time e sample containers should be sealed carefully packed with an appropriate packing material chilled or frozen as required and transported in an appropriate cooler esky or fridge It is sometimes necessary to take further action to prevent cross contamination either between samples or from ice during transport This could include placing sample containers in snap lock bags or airtight plastic tubes with screw caps before transport If a courier is to be employed sample security Chain of Custody and refrigeration issues need to be considered prior to transporting the samples If a courier is not able to meet all the requirements an alternative form of transport should be found
84. tuents within the waste stream is random or when the variability within that stream is low Composite samples are also useful when the determination of loads of constituents is required However compositing does have its limitations Prior knowledge of the stream is required to determine if composite samples are appropriate i e random distribution of contaminants and low variability This may require a pilot study of discrete grab samples Additionally compositing may mask variability within the waste stream by hiding peak and trough concentrations A6 EPA Guidelines Water and wastewater sampling APPENDIX 2 CONTAINERS PRESERVATION METHODS AND HOLDING TIMES The information in this appendix is sourced from the AS NZS 5667 1 1998 unless otherwise noted This table is not comprehensive but provides an overview of the most common analytes sampled Where analytes are not listed in this table please refer to Australian Standards International Standards ASTM or APHA This information is reproduced with the permission of Australian Standards Filtration and Anal Filling techni yte illing ique ion Notes physical and aggregate samples acidity and plastic or 500 fill container refrigerate 24 hours preferable to analyse sample in field alkalinity glass completely to exclude air colour true plastic or 500 fill container refrigerate and store in 2 days glass completely to the dark exclude air conductivity at plastic or 100
85. uld be treated with caution The conductivity of waters increases with temperature Most modern portable conductivity meters automatically compensate for small temperature variations from the calibration temperature However if there is a large difference between the temperature of standard solutions at the time of calibration and the sample solution at the time of measurement a new calibration may be required For example if a conductivity meter is calibrated early in the morning and the temperature rises significantly through the course of the day it is preferable to recalibrate during the day Similarly standard solutions that have been refrigerated overnight should be returned to room temperature before calibration 5 2 5 Redox Direct redox potential or oxidation reduction potential measurements determine the oxidising or reducing capacity of waters Redox must be measured in situ and it often varies substantially in a waterbody especially with depth Redox potential can be measured using an electronic meter or multimeter 5 2 6 Turbidity Turbidity meters are generally based on light attenuation principles There is a large variation in the reliability and accuracy of turbidity meters It is therefore essential that turbidity meters are regularly calibrated When a reliable turbidity meter is not available a representative sample may be collected and turbidity measurement undertaken in a laboratory 5 2 7 Chlorine Chlorine dissipat
86. water column and other sampling techniques should be employed These can include integrated vertical column samples or discrete samples at given depths A2 3 Sampling frequency and patterns of sampling There are no strict rules regarding how frequently sampling should occur but the sampling frequency will be dictated by the variability of the discharge and the objectives of the plan During the planning stages consider the aims of the study and choose a sampling frequency that has the best chance of providing the information required to meet the objectives of the plan It is important to consider the frequency carefully If samples are not taken frequently enough the characteristics of the waters or wastewaters might not be adequately described resulting in a poor understanding of the system and potentially inaccurate reporting of compliance or non compliance Alternatively overly frequent sampling may be a waste of time and resources In general if a measurement parameter has a predictable pattern which has been shown statistically or through a pilot study eg discharge at a certain time of day the sampling plan can be tailored to sample at regular intervals Alternatively if the system or processes are highly variable or unpredictable the sampling should be undertaken more regularly over several time scales Sampling to determine loads Determination of loads should be undertaken using a flow meter mechanical or magnetic in combination
87. with sampling If the flow rate of the wastewater is variable flow weighted composite sampling is most appropriate This can be done either discretely with knowledge of flow or using an automatic sampler where sampling is triggered after a predetermined volume of flow has passed a given point A2 4 Analytes A5 EPA Guidelines Water and wastewater sampling Choice of analytes will depend on the contaminants from the process under consideration and the criteria against which the monitoring is to be evaluated The environmental values of the waters must be considered and the relevant criteria that are common to the discharge and the values should be considered Environmental values and criteria to be considered in South Australia are set out in the Environment Protection Water Quality Policy 2003 Key considerations when choosing analytes include the form of analyte eg total metals dissolved metals chemical speciation and the confounding factors eg faecal coliforms are often used to indicate contamination from human faeces however in lagoons faecal coliforms may be the result of the presence of birds A2 5 Sampling procedures Various types of samples can be taken according to the requirements of the specific monitoring plan Thorough consideration of the objectives of the sampling plan should occur before deciding on the types of samples to be taken If an inappropriate type of sample is collected the water quality data gained may n
88. ysical and chemical Appendix 3 techniques Sample collection Sample blanks field Quantify contamination of Section 7 2 Equipment transport equipment samples during sampling blanks only and container process Decontamination of Minimise contamination Section 5 6 Yes sampling equipment Filtration procedures Minimise physical and Section 5 5 If field chemical changes to sample filtration f performed Sample filtration Filtration blanks Quantify physical changes Section 7 2 1 If field and contamination during filtration blanks filtration filtration performed Equipment calibration Minimise and quantify bias Section 5 2 Yes Field testing and error in field equipment Transport and Appropriate preservation Minimise physical and Section 6 3 and Yes storage techniques chemical changes to sample Appendix 2 EPA Guidelines Water and wastewater sampling T Compulsory Refer t Monitoring Step QC protocols Purpose efer to for RMT NATA lab accredited for Ensure laboratory Section 8 Yes required analysis undertakes appropriate QC including spikes calibration of equipment Analysis Duplicate samples intra Check variability in lab Section 7 2 2 Yes within lab analysis Duplicate samples inter Quantify differences Section 7 2 2 Yes between lab between laboratories analysis methods Peer review Validate that sampling is Independent When stated validation undertaken as per verification in licence

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