GUIDELINE ON SAMPLING, HANDLING,

TRANSPORTING, AND ANALYZING LEGAL

WASTEWATER SAMPLES

Prepared for:

Canadian Water and Wastewater Association

Prepared by:

Goce Vasileski
Consultant
391 Wiffen Pvt.
Ottawa, ON K2H 1G4
Tel: 613-421-1023
E-mail: gocevasile@yahoo.com.au
Table of Contents

1. INTRODUCTION ........................................................................................................................................................ 3
1.1 OBJECTIVES ........................................................................................................................................................ 4
1.2 SCOPE .................................................................................................................................................................... 4
2. LEGAL, COURT OR EVIDENTARY SAMPLE....................................................................................................... 5
3. CHAIN OF CUSTODY ............................................................................................................................................... 5
3.1. CHAIN OF CUSTODY CONTINUITY............................................................................................................... 6
4. SAMPLING PROCEDURE......................................................................................................................................... 7
4.1 SAMPLING PLAN ................................................................................................................................................ 8
4.2. SAFETY CONSIDERATIONS ................................................................................................................................ 9
4.3 PRELIMINARY ASSESSMENT ........................................................................................................................ 10
4.4 PREPARATION ACTIVITIES ........................................................................................................................... 10
4.4.1 REAGENTS AND OTHER SUPPLIES ...................................................................................................... 10
4.5 SITE RECORDINGS ........................................................................................................................................... 11
4.5.1 PHOTOGRAPHIC DOCUMENTATION .................................................................................................. 13
4.5.2 VIDEO RECORDINGS ............................................................................................................................... 13
4.6 SAMPLING SITE SELECTION ......................................................................................................................... 13
4.7 SAMPLING CONTAINERS ............................................................................................................................... 14
4.8 SAMPLING APROACHES................................................................................................................................. 15
4.9 SAMPLE COLLECTION .................................................................................................................................... 16
4.9.1 TIME-PROPORTIONAL SAMPLING....................................................................................................... 17
4.9.2 AUTOSAMPLING....................................................................................................................................... 18
4.9.4 SAMPLING COMPLETION....................................................................................................................... 18
5. SAMPLE IDENTIFICATION - SEALING AND LABELING ............................................................................... 19
6. SAMPLE PRESERVATION, STORAGE AND HOLDING TIME ........................................................................ 20
6.1 PRESERVATION AND STORAGE ................................................................................................................... 20
6.2 HOLDING TIME ................................................................................................................................................. 20
7. SAMPLE TRANSPORTATION ............................................................................................................................... 21
8. SAMPLE CONTAMINATION ................................................................................................................................. 22
9. CLEANLINESS ......................................................................................................................................................... 23
9.1 CLEANING OF FIELD EQUIPMENT ............................................................................................................... 23
9.2 CLEANING OF CONTAINERS ......................................................................................................................... 23
10. LABORATORY SAMPLE SUBMISSION ............................................................................................................ 24
11. SAMPLE ANAYSIS ................................................................................................................................................ 25
12. SAMPLE DATA RECORDKEEPING AND ARCHIVING .................................................................................. 26
13. SAMPLE DISPOSAL .............................................................................................................................................. 27
14. POST SAMPLING CLEANING ............................................................................................................................. 27
15. QUALITY ASSURANCE /QUALITY CONTROL PROGRAM .......................................................................... 27
15.1 QUALITY ASSURANCE MANUAL............................................................................................................... 28
15.1.1 LABORATORY ORGANIZATION AND RESPONSIBILITY ............................................................. 28
15.1.2 FIELD SAMPLING PROCEDURES ........................................................................................................ 29

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 15.1.3 LABORATORY SAMPLE HANDLING PROCEDURES ...................................................................... 29
15.1.4 STANDARD OPERATING PROCEDURES ........................................................................................... 29
15.1.5 QUALITY CONTROL PROCEDURES ................................................................................................... 30
15.1.5.1 TRAVEL BLANKS ............................................................................................................................ 30
15.1.5.2 FIELD BLANKS ................................................................................................................................ 31
15.1.5.3 FIELD DUPLICATES ........................................................................................................................ 31
15.1.5.4 SPLIT SAMPLES ............................................................................................................................... 31
15.1.5.5 CALIBRATION STANDARDS ........................................................................................................ 31
15.1.5.6 BLANK SPIKES ................................................................................................................................ 32
15.1.5.7 MATRIX SPIKES .............................................................................................................................. 32 
15.1.6   DATA REDUCTION, VALIDATION AND VERIFICATION PROCEDURES ............................ 32 
15.1.7 PREVENTATIVE MAINTENANCE PROCEDURES ............................................................................ 32 
15.1.8 LABORATORY AUDITS ......................................................................................................................... 33 
15.1.9 CORRECTIVE ACTIONS ........................................................................................................................ 33 
15.1.10 RECORD KEEPING PROCEDURES .................................................................................................... 33 
15.1.11 PROFICIENCY TESTING ...................................................................................................................... 34 
16. ACRONYMS............................................................................................................................................................ 35 
17. GLOSSARY ............................................................................................................................................................. 36 
18. REFERENCES ......................................................................................................................................................... 39 
APPENDIX 1 - REAGENTS AND SUPPLIES SHEET .............................................................................................. 41 
APPENDIX 2 - FIELD SAMPLING DATA SHEET ................................................................................................... 42 
APPENDIX 3 - SAMPLE SHIPPING/RECEIVING SHEET ...................................................................................... 44 
APPENDIX 4 - SAMPLE RECEIPT AND RECORD LOG SHEET .......................................................................... 46 
APPENDIX 5 - SAMPLE CONTROL RECORD SHEET ........................................................................................... 47 
APPENDIX 6 - ANALYTICAL DATA SHEET .......................................................................................................... 48 
APPENDIX 7 - SAMPLE DATA ARCHIVING .......................................................................................................... 49 

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1. INTRODUCTION

The extent and complexity of natural processes and human activities manifested in the
environmental quality of the ecosystem require adherence to the principles of international best
practices. The development and implementation of universal operating procedures include the
best applicable technologies for sampling, laboratory analyses and providing evidence, as well
as, operational accountability, transparency in information, data exchange, and interpreting
sample results.

The Environment Ministers from each province/territory and the federal government through the
Canadian Council of Ministers of the Environment provide a perspective on environmental
issues to bring national strategies to deal with common issues. On February 17, 2009 The
Council of Ministers endorsed the Canada-Wide Strategy for the Management of Municipal
Wastewater Effluent (MWWE). The Strategy sets out a harmonized framework to manage
discharges from existing wastewater facilities and offers municipalities the Model Sewer Use
Bylaw, recommending its adoption and implementation, as a means of helping meet the quality
of effluent discharges. In order to achieve the aims of the MWWE Strategy, the approach,
components and methodologies of monitoring and assessment must be clearly elaborated and
scrupulously followed by those engaged at all levels of the process for providing reliable and
coherent environmental data.

The implementation of the Sewer Use Bylaw inevitably implies the possibility of enforcement
and prosecution in the case of violation. Successful prosecution depends on recording and
maintaining a reliable chain of evidence from sample taking through the verification of an
exceedance of the bylaw, confirmed through accredited laboratory analyses. Analytical results
of samples taken referred to as “legal”, “court” or “evidentiary” samples demand establishment
and adherence to a protocol that will demonstrate the particular results that were found are for
the sample taken.

This Guideline has been created to facilitate the achievement of the purposes set out in the
MWWE Strategy and serve as the basic reference for the work of the personnel involved in any
stage of the legal sampling. From the aspect of the existing policy and technical requirements
with respect to the environmental system protection, the document is designed to provide
essential documentation needed to fulfil the legal sampling requirements. It presents standards
and uniformity in undertaking legal sampling procedures for all those involved from sample
taking, through handling, transport and analysis, to storage and ultimate disposal.

The Guideline is based on national and international established standards, procedures and
protocols, legislative and regulatory requirements, scientific literature and the experience of
Environment Canada, provincial/territorial institutions and municipal laboratory staff, as well as
international environmental agencies and other associations.

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The Guideline alone cannot guarantee high quality results. It is not created to be a complete
document as it is written based on the analytical sampling and testing requirements associated
with the issues of current interest which may from time to time change. Therefore, it is to be
regularly reviewed and updated. Common sense steps to avoid contamination, ongoing programs
of staff training and proactive analytical method improvement procedures are also essential.

1.1 OBJECTIVES

The purpose of the guideline is to define standard operating procedures, methods and
considerations that are to be used and observed when collecting and handling wastewater (or
other) legal samples for field screening, laboratory analysis and evaluation for potential
enforcement and legal actions in court. The guideline is intended to supplement the various
sampling reference methods and clearly identify the points and requirements specific to the
legal sampling procedure. It can assist in ensuring that the legal sampling criteria are
established on a formal basis and accepted by all involved.

The development of the Guideline primarily is led by the ISO/IEC 17025 Standard
management requirements. The guideline promotes a set of appropriate forms of
documentation to support the legal samples as conclusive evidence in the case of
prosecution. Furthermore, it assists municipal laboratories in developing their own
continuity documentation during such activities as field sampling, sample receiving, sample
storage, sample analysis, sample disposal and chain of custody procedures.

The objectives also involve:

 Supporting the laboratories accredited to work with legal samples to produce
analytical data of the required quality and improve quality assurance management,
 Addressing the existing data and legal sampling management protocols to develop a
national standard approach,
 Ensuring and encouraging explicit acceptance and utilization of operating
procedures by the personnel involved,
 Consolidating the information on legal sampling to reinforce the positive effects
and aspects of its use for law enforcement and legal action in court,
 Encouraging and assisting municipalities to set a framework and develop programs
on their benefits to manage wastewater discharges as a means of helping meet the
quality of effluent discharges.

1.2 SCOPE

The Guideline describes both general and specific methods to be used by those involved
when collecting and handling samples from industrial, commercial and institutional

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 discharge points into a municipal sewer. It also demonstrates the manner of sample
transportation, analysis, storage and disposal.

The priority area of this Guideline is development of a legal sampling protocol and therefore
is to be viewed as a general guide to legal sampling. Additional sources are to be referenced
for detail protocols, equipment options and insights regarding the usefulness of a particular
analytical method.

Examples of the proposed documentary forms can be found in Appendices 1, 2, 3, 4, 5, 6,

and 7 respectively, while their contents are discussed under each section of the guideline.

2. LEGAL, COURT OR EVIDENTARY SAMPLE

Legal samples are samples collected and handled for court purposes and are intended to be used
as evidence for a possible prosecution concerning the sample origin, type and constituents. In
comparison to the non-legal samples, the legal sample should demonstrate more stringent proof
of custody from the time of collection to the time of analysis and disposal. The sample collection
procedure itself may be equivalent to the routine sampling, but the sample handling and
documentation requirements are more stringent. The legal samples must also confirm the
samples could not have been tampered with at any stage and therefore they require special care
due to the influence they may have on a court case.

Legal samples are needed when there is evidence an individual or company has not complied
with regulatory requirements and there is a potential for laying charges. Legal sampling is
conducted under the following circumstances:
 Any known or suspected violation,
 Spills or environmental accidents,
 Previous knowledge about compliance history does not exist or it is unknown.

From the standing point of objectivity, continuity of evidence and quality of the results, the
collection, handling, transport, analysis, storage and disposal of the legal samples must be
defensible.

3. CHAIN OF CUSTODY

Samples can be collected by the field sampler, wastewater laboratory technician or a bylaw
officer, labeled and sent to the laboratory for analysis. When legal litigation is indicated, an
accurate written record to trace possession and handling of samples from collection through
reporting is mandatory.

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Chain of custody is demonstrated when there is documented evidence confirming that a sample
has not been exchanged with another sample, contaminated, or tampered with in any manner.
The chain of custody shows how evidence was collected, who collected it, the location where it
was collected and who has had custody of the evidence throughout the various steps that
followed. The forms confirming the sample has been secure should be signed by each person that
had true possession of the sample.

A sample is considered to be in true possession or custody when it is:

 In actual physical possession of one person,
 In view of one person after being in their physical possession,
 In physical possession and then locked up so that no one can tamper with it,
 Kept in a secured area, restricted to authorized personnel only.

The chain of custody procedure is intended to ensure the sample is kept secure at all times and
stands up to the documentation requirements associated with a legal challenge. It is a written
record documenting continuity by tracing the transfer, security and possession of the sample
during all stages from collection, transportation, storage, laboratory analysis through to its
introduction into evidence and ultimately to disposal. Samples are not admissible as evidence
before the court in a case where their continuity has been interrupted for any reason.

The chain of custody documentation should include the following forms:

 Reagents and Supplies Sheet,
 Field Data Sampling Sheet,
 Sample Shipping/Receiving Sheet,
 Sample Receipt and Record Log Sheet,
 Sample Control Record Sheet,
 Analytical Data Sheet,
 Sample Data Archiving Sheet,

Three elements must be taken into consideration to achieve a full control of sample custody:
 Control at site is achieved by a member of the sampling team responsible for correct
labelling and storage of samples,
 Transport is controlled by completing a form with shipping notes including brief
descriptions of the samples,
 Within laboratories custody of samples is controlled by establishing detailed procedures,
as many samples must be tested and reported correctly.

3.1. CHAIN OF CUSTODY CONTINUITY

Legal sample continuity is ensured by taking the following steps:

 Sealing – proper techniques, such as custody seals; masking tape should be used to seal
the sample,

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  Permanent Marking – sample should be labelled by permanent water proof uniquely
numbered label and/or a diamond-tipped scribe, waterproof marker, or other means of
permanent identifications with sufficient information to enable sample identification,
 Information Transfer – all data from the label should be transferred into the Field
Sampling Data Sheet including the reference to unique identifier,
 Security and Safety – the sample must be locked in a secure container, refrigerator, etc.
or kept in the possession or view of the person dealing with the sample at all times until it
can be secured. The number of people handling the sample must be limited ensuring only
one person at a time has access to the sample,
 Chain of Custody Forms – the forms must be completed and included with the sample.
 Packing – the sample must be placed in an appropriate and secure shipping container.
 Delivery – during transportation to the laboratory and from the laboratory to the
sender/submitter or court, the sample must be sent by appropriate means and ensured it
arrives within the required holding period. Samples should be delivered to the laboratory
as soon as possible to minimize sample degradation,
 Analysis – laboratory personnel are responsible for maintaining the chain of custody. The
sample must be traced from the moment it was received to the time the final results are
reported,
 Court Use – to introduce sample results as evidence in court the chain of custody
procedure must be clear and complete, demonstrating the sample has not been
exchanged, contaminated, or tampered with at any stage,
 Note taking – detailed notes of sample collection methods, container markings,
packaging, shipping and details for sample analysis, storage and disposal must be
retained, and made available as required.

4. SAMPLING PROCEDURE

The accuracy of the final result of the legal sample analytical procedure begins with sample
collection. The primary aim of the sampling is to produce a set of samples representing the
source of interest and suitable for analysis to identify the compound(s) in question in a case of
legal investigation.

Going on-site and collecting a sample without first planning how to do so, may result in a
meaningless, contaminated, or unrepresentative sample. If the sample has been improperly
collected, stored, or preserved, the results can be incorrect no matter how precise the analyses are
or how thorough the quality assurance and quality control methods are.

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4.1 SAMPLING PLAN

To meet the objectives of legal sampling and ensure success of the whole procedure
thorough planning is crucial. The planning process of the legal sampling procedure begins
with a preparation of a detailed sampling plan.

At the very beginning, before the start of a sampling activity, it is important to perform a
thorough research of existing information. All involved in the process should get
familiarized with the case in a whole and understand what should be documented before,
during and after the sampling to fulfil all requirements and provide sufficient, reliable and
defensible data.

Since the legal sample is collected for enforcement purposes and/or to use in court, the
following questions and answers should be addressed during preparation of the sampling
plan:
1. What specific tests need to be run on the sample?
2. Where will the samples be collected?
3. How is sample going to be collected and what type of sample is to be obtained – is it
to be a grab sample or a composite sample?
4. When does the sample need to be collected and analyzed?

The legal sampling documentation includes a record of the planning process, field work and
laboratory activities. Keeping detailed notes provides much needed information and aids
getting successful results when such information is used in a court case and/or other
enforcement activities. For example, the raw notes, documents, notebooks and report can be
used in preparation of the court brief and may be taken as evidence into legal proceedings.

The sampling plan should explain the reason of choosing a particular approach and leaves
no doubt on the final results and evidence provided. A documented systematic sampling
approach can be used to recall important details while testifying in court.

A comprehensive legal sampling plan should include:

 Categories:
- Introduction and objectives,
- Scope,
- Sampling matrix and sampling site,
- Method of sampling,
- Administrative arrangements – health, safety and security provisions,
- Preliminary site inspection,
- Sampling equipment,
- Containers, preservatives, holding times and shipping and additional
information.

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  Further details:
- A summary of background information of the site,
- The issue and purpose of sampling,
- The breadth of coverage of a sampling plan,
- Investigation methods required to characterize the site – sample types,
sampling locations and field quality control,
- Sampling protocols,
- Personnel requirements,
- List of standard and non-standard equipment, list of containers needed,
- Method used to control contaminated materials including documentation
procedures, solutions to be used and storage or disposal obligations,
- Using a certified laboratory, ensuring the understanding of sample holding
times, special training required, the way how to be contacted with the
information.

 References
- Information sources,
- Sampling media background,
- Sampling protocols and procedures,
- Sampling tests and equipment protocols,
- Laboratory certifications.

4.2. SAFETY CONSIDERATIONS

Sampling related safety consideration should be brought into the planning process from the
beginning, especially for the following:
 Personal protective equipment,
 Fall protection equipment,
 Specialized air monitoring equipment for hazardous environments, and
 Specialized equipment for handling potentially harmful substances.

The field sampler should be thoroughly familiarized with existing safety guidelines and
follow the sampling procedure, guidelines and practices for any analyte of particular
interest. The sampler must always be alert to the possibility of danger, especially in dealing
with unknown sites, situations or possible contaminants.

A number of reagents (e.g. concentrated acid and alkalis, potassium dichromate and other
chemicals) should never be handled without wearing protective gloves and eyewear since
they may be corrosive or strong oxidants. Water should be never added to strong acid – it
may boil up. Concentrated chemical pellets, e.g., sodium hydroxide, may generate heat if
dissolved, whereas concentrated nitric acid, fumes freely. Consequently, only the amount of

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reagents needed to complete the field work should be taken and, while working with them,
the vessels must be handled with complete care.

4.3 PRELIMINARY ASSESSMENT

If the circumstances of the sampling event allow, a preliminary site visit should be
conducted to fully understand the legal sampling requirements. This examination assists in
obtaining background information on the location and facility, as well as to identify the
required equipment, safety and hazard considerations, and what will the technical approach
to the site sampling consist of. For this purpose, prior to sampling, the applicable legislation,
regulations, interim orders, guidelines, codes of practices and other legal or regulatory
documents should be reviewed.

4.4 PREPARATION ACTIVITIES

The sampling preparation activities should include, but are not limited to the following:
 Verifying mean(s) of transportation e.g., checking and traffic safety plan
completion, including completion of transportation vehicle inspection checklist,
if applicable,
 Creation of sampling plan and chain of custody forms,
 Preparing sample containers for the parameters of interest. The containers
should be inspected before taking and than placed in the lockbox,
 Obtaining additional required equipment (autosamplers along with an
autosampler numbered evidentiary lock and charged batteries, appropriate
tubing, strainers and any external devices such as flow loggers, flow meters, or
liquid level actuators),
 Filling the required number of empty containers with de-ionized water in case
travel blanks are to be collected and including them with the other sampling
equipment,
 Providing evidentiary seals and a numbered evidentiary lockbox with matching
lock and key,
 Prepare all the required equipment including personal protective equipment.

4.4.1 REAGENTS AND OTHER SUPPLIES

During preparations for sampling, the reagents and field supplies that will be used
should be prepared. Each laboratory is responsible for ensuring that all reagents and
equipment are suitably clean and free from contaminants and interfering substances.
Reagents can be used as calibration solutions to calibrate sampling equipment or may
be used as chemical preservatives and become part of the sample itself. Such reagents

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 should be of high purity with an expiration date, beyond which they should not be used.
All exchanges of reagents and supplies must be documented on the Reagents and
Supplies Sheet.

In a legal proceeding, both the methods of preparation and the competence of the
preparer may be questioned. It is essential to keep records, including the preparation
date, name of the preparer, and location of the reagents and supplies from preparation
through use.

Field supplies may include:

 Labelled sample containers,
 Labelled shipping containers,
 Buckets for grab sampling,
 Automatic samplers,
 Portable meters (thermometer, pH meter, spectrophotometer, turbidity
meter, colorimeter, dissolved oxygen meter, magnetic flow meter),
 Filtration or other preservation equipment used in sample collection,
 Ice packs and coolers,
 Personal gear (for all possible weather conditions, gloves, goggles,
protective footwear),
 Camera or video equipment, GPS,
 First aid kit.

An example of the Reagents and Supplies Sheet is found in Appendix 1.

4.5 SITE RECORDINGS

Proper documentation of all site activities is an integral part of legal sampling and field
investigation. In a written form, the field sampler keeps accurate notes as an inclusive
documentation of sampling operations including field data, observations, field equipment,
sample handling and chain of custody forms. All notes should be made at the time or as
soon as possible thereafter. Whenever possible, the notes should be written in waterproof
ink and kept by one person.

The chain of custody Field Sampling Data Sheet (also Field Logbook or Sample Journal) in
which all field measurements should be entered directly while in the field is mandatory in
the legal sampling procedure. The field sampler must note all unusual occurrences (e.g.
unusual colour or odour, surface films) and any deviations from standard protocols (e.g.
sample is taken from a different location due to safety or access considerations or sampling
procedures differ from the set protocol). Preservation of the sample consistent with the type
of analysis that will be performed as well as additional samples, if collected, and for what
purposes should also be recorded.

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The Field Sampling Data Sheet is the basis for later reports and therefore should contain
objective factual information, free of personal opinion and feelings or other terminology
which might prove inappropriate. Data that has been entered incorrectly should be corrected
by drawing the line through the incorrect entry and initialling or signing and dating the
lined-through entry. The incorrect material should not be erased, made illegible or obscured
so that it cannot be read.

The Field Sampling Data Sheet for each sampling program should include common site and
sample information:

A. Site Information
The site information could include, but is not limited to the following:
 Sample location description – site name and global positioning system (GPS)
coordinates including the type and number of sample point access (e.g. sewer access,
manhole), photo/video recordings
 Name of the sample collector and names and affiliation of the persons present on the
spot (e.g. business card) including all those attending the site and witnessing the
sample collection,
 Name and address of the facility, reason for visit and any other characteristics of the
sampling location,
 Date and time of sampling including the times of arrival and departure, details for
any stops made between departure and arrival at the sample location,
 General description of the area along with the land use and/or production practices
upstream and down-stream of the sampling location,
 Weather conditions on the day before and the day of sampling.

B. Sample Information
The sample information could include but is not limited to the following:
 Sample identification number,
 Numbers and natures of quality control samples and time of collection,
 Time and date and other details of collection (e.g. completion of evidentiary labels,
the time when labels and seals are affixed to the sample containers, seal number),
 Method of sample collection and any factors that may affect sample quality,
 Equipment used and work performed on site (equipment blanks, grab sample
collection, auto sampler, duplicate sample collection),
 Discharge characteristics along with all pertinent observation (e.g. discharge flow
rate, colour, clarity, any noticeable odours),
 Time when samples were sent/transported to the laboratory, including the times and
details for any stops made between departure and arrival, time of arrival at the
laboratory and details for relinquishment of the cooler and samples.

An example of the Field Sampling Data Sheet is found in Appendix 2.

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 4.5.1 PHOTOGRAPHIC DOCUMENTATION

Legal sampling procedure should be supported by photographic documentation as the

easiest, most accurate and convenient way to record and elaborate the observations and
provide accurate identification of sampling points. Photographs should be taken
showing the labels along with clearly visible sample numbers and linking the sample to
the source. Documenting the sampling locations by photographs should include two or
more references that will help to identify the point at a letter date. A series of
photographs should be taken at each sampling location looking upstream, downstream,
to the left, and to the right at the same time as the sampling is done. By using
specialized software digital images can be sent via internet to the central database and
documented in the Field Sampling Data Sheet notifying the following information:
 Date and time of the photograph,
 Name of the photographer,
 Name and coordinates of the site,
 Compass directions or GPS location and description of the subject taken,
 Photograph number and/or film roll number.

4.5.2 VIDEO RECORDINGS

Video coverage can be used to describe the sampling location and prove that samples
were taken properly. It gives an idea of the sampling circumstances to all involved in
the process that have not been present on-site. Complete and accurate perception is
ensured when a verbal documentary of the scene is included on the video camera’s
sound track. While choosing the camera angle, maximum care should be taken to get
valuable information. The video recording memory medium within a device (DVD,
USB flash drive, memory card) should be labelled with the name of the person who has
made it, location, date and time.

Video recordings and photography are included to assist the process of documentation,
but they can not be used to the exclusion of written documentation. Photographs and
video recordings have to be saved and kept for future reference (e.g. for planning of
sampling, future sampling trips, investigation, or for use in court as means of
consultations).

4.6 SAMPLING SITE SELECTION

Selection of a representative sampling site is one of the most important steps in

investigation, monitoring, or surveillance planning. A sampling site must be selected at the

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point which is sufficiently characteristic to reflect the objectives and meet the goals of the
legal sampling program. The reasons for choosing a particular sampling location should
always be documented.

The objective of legal sampling in most occasions is to find unknown sources of known
contamination. It has to match the strategy for choosing the sampling locations. Along with
the sampling objectives and the analyte of interest, the site selecting process depends on the
following factors and concerns:
 Sample quantity - what number and volume of the sample is required?
 Legislation - are regulatory requirements a factor?
 Method of sampling - what is the most appropriate method of sampling?
 Sample characteristics – for example do the substances mix with water, float on
it, or sink?
 Sample type - should the sampler collect a grab or composite sample?
 Sampling equipment - is the sample to be collected by an automatic sampler or
manually?
 Accessibility – is access to the site a problem?
 Location – can the location be found easily?
 Re-sampling – will it be easy to repeat the sampling if required?

The field sampler has the responsibility to locate all sampling locations accurately.
Satisfactory knowledge about on-site conditions prior the sampling is crucial. Physical site
inspection and research of available records (e.g. file information or previous reports or
consultation with others who may know the site) should be done before sampling.

Sampling location must be identified in a simple and unambiguous way. A detailed sewer
site map, when the sample is to be taken within the industrial premises, or a detailed area
map, when sample is taken outside industrial premises, can be helpful in selection and
description of the sampling location. A map describing the sample location should
accompany the Field Sampling Data Sheet.

The GPS is most frequently used to determine the latitude and longitude of each location
and confirm the exact sample collection location during subsequent sampling events,
particularly when a return to the same location is necessary. Nowadays, the most GPS
systems are accurate to within 3-5 meters and offer multiple station locations, data
recording, way marking and navigation capabilities. It is important to note that the locations
with a restricted view from the sky have reduced accuracies. GPS measurements should be
recorded on the Field Sampling Data Sheet.

4.7 SAMPLING CONTAINERS

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An equipment check list including sampling and safety equipment, sample containers,
reagents, shipping materials and other supplies should be prepared during the preparation
for the sampling event. When taken in the field, the field sampler takes possession of the
materials and accompanied documentation. When in the laboratory, the lab-sample
custodian should store the materials prepared by the lab technician in a locked storage with
limited-access until they are needed.

Most wastewater samples can be collected in either plastic or glass containers. Sample
containers that will not affect or react with the sample must be chosen. The sampler should
be aware of the composition of sampling containers when analyzing for trace contaminants.
Containers may decompose and release contaminants or sorb materials onto the walls of the
bottle. Cracked, chipped and etched glass bottles, as well as crazed plastic bottles and
bottles which are leaking should be discarded.

When choosing sampling containers, the field sampler should consider the following:
 Glass can be used for sampling hazardous materials,
 Amber glass is used to prevent photo degradation of the sample. If not available, the
sample should be protected from light by other appropriate means,
 Plastic or Teflon can be used for alkali solutions, hydrofluoric acid and mercury
samples,
 Teflon or glass can be used for organic samples and media,
 High-density polyethylene should be used for metals, except mercury, most
inorganic samples and media.

The field sampler should be also aware of the type of container lid used. Lids with metal foil
liners should not be used when collecting metal samples. Inappropriate lids or lid liners can
cause serious problems; for example, lid liners made of paper or cardboard are potential
source of contamination. Lids should be of the screw type to form a leak-proof seal and
should be lined with Teflon or Teflon-coated material. In certain situations, polyethylene
liners may be acceptable. Heat-treated aluminium foil can be used when sampling petroleum
products to cover the mouth of a container before the lid is screwed on to avoid
contamination from a plastic lid.

4.8 SAMPLING APROACHES

Selection of the sampling method for representative sample collection must account for the
unique characteristics of a specific sampling location, including the physical features of the
site and the discharge characteristics (e.g. floating debris, turbulence, flow velocity and
depth).

15
There are three sampling approaches: random, systematic, and judgmental. The random and
systematic approaches are used in routine sampling, whereas the judgemental sampling is
often the method of choice for regulatory and emergency response sampling.

The judgmental approach used in combination with one of other two may be useful in most
occasions. The validity of judgemental sampling depends on the accuracy of the knowledge
of distribution of the parameter(s) of interest, prior site history and visual assessment of
technical judgement. This knowledge is also critical in determining locations that will
provide the most representative samples.

4.9 SAMPLE COLLECTION

When collecting wastewater samples, minimum safety precautions such as gloves and
goggles should be required. Selecting sampling sites that present a hazard such as leaning
over railings, slippery decks, etc. should be avoided for the safety reason. It is very
important that maximum attention to be paid for the possible hazardous and infectious
materials.

Legal samples can be collected as grab samples or composite samples. Composite samples
can be collected manually or by using an auto sampler. When sampling involves more than
one staff member on-site at the sampling location, only one person should collect the
sample(s). The other person(s) may only observe the event without any active participation.

The following steps are recommended during the sample collection:

 Check in with security or company staff, if required; this should be done upon
arrival to gain an access to the sampling location,
 Survey for hazards (traffic, equipment, other) should be done on the sampling
location,
 Traffic safety set-up equipment and traffic safety plan should be implemented, if
required. Traffic cones for example can be used to make people more aware of the
sampling staff presence particularly when the sampling location is easily accessible
by the public,
 Precise sampling location should be selected,
 Gas detector and manhole lifter should be used to remove a manhole cover and gain
access to the sampling point, if applicable,
 The evidentiary lockbox should remain within the unobstructed view of the person
taking samples at all times unless it is securely locked in the transportation vehicle,
 Sampling equipment should be gathered, including:
- Stainless steel grab containers or sterilized steel grab container if collecting
bacteria samples,
- Sampling containers (amber glass jugs) with lab grade water if equipment
blanks are to be collected,

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 - Sample container - bottle carrier and required bottles, pre-labelled with
numbers, including sample containers with first or second part grab samples
from previous site visits, if applicable,
- Paper towels, sampling pole or rope, when collecting grab samples,
- Spotlight,
- Auto sampler with appropriate length of sample tubing, strainer, battery and
any required external connections as well as steel suspension ring for auto
sampler, only if an auto sampler is to be installed.

4.9.1 TIME-PROPORTIONAL SAMPLING

Samples of equal volume collected by hand grab method must be taken

sequentially at regular time intervals. When taking such samples certain
considerations for representative sampling collection should be acknowledged,
such as:
 The grab container should be made of material that has no possibility of
leaching a contaminant(s) of interest or to chemically react with the
sample,
 The grab container should be attached to the sampling pole or rope and
then lowered into the sampling point and into the discharge stream with
the opening facing the flow, where possible,
 The grab container should be filled by the discharge flow and after
being retrieved, it should be emptied back into the sample point to rinse
the container,
 The grab container should be lowered into the sampling point and
discharge stream again, filled by the discharge flow, retrieved and
emptied back into the sample point to rinse the container a second time,
 A sample should be taken after the grab container is lowered into the
sampling point and discharge stream for third time, filled by the
discharge flow and retrieved. The sample is kept for transfer to sample
containers/bottles,
 The cap(s) from the first bottle or set of bottles to be filled should be
removed by setting the outside surface of the cap(s) down on a clean
surface,
 Sufficient volume of the sample from the grab container should be
poured into the bottle(s) until they are filled. If necessary, the procedure
should be repeated until all the required bottles are filled.

In addition to the sample collection procedure, immediately after taking hand grab
sample(s) a separate evidentiary label should be completed and affixed to each
sample container. The corresponding legal custody seal should also be placed
across each container lid with each end affixed to the sides of the container. At the

17
 end, the samples should be placed in the cooler - lockbox and locked inside. The
key of the lockbox should be kept in possession of the field sampler.

4.9.2 AUTOSAMPLING

Anutosampler is used when a representative sample over a fixed time period is

required. Based on the standard installation procedure, an autosampler is installed when
a new sample and pump tubing are installed on the autosampler prior to use. For further
use manufacturer’s operating manuals and specifications for the operating details
should be consulted. Frozen gel packs should then be placed in the autosampler’s base
along with either glass or polyethylene plastic composite container. Prior to lowering the
autosampler into the sampling point, the autosampler lock should be attached to the
appropriate spot on the carrying handle and the key kept by the field sampler.

During the automated composite sampling that may take from few hours to several
days the sampling probe can be exposed to the environment and possible tampering. In
order to prevent such occurrences, the sampling location will need to have some degree
of security and the sampling device should be checked by the field sampler at random
intervals.

An autosampler used for legal sampling should be removed immediately after the
sample containers are filled and an evidentiary label is completed and affixed to each
container. The corresponding legal custody seal should be placed across each container
lid end affixed to the sides of the container. The samples should be then placed in the
cooler - lockbox, which should be locked and the key kept in the field sampler’s
possession.

4.9.3 WATER SUPPLY SYSTEM SAMPLING

A water sample from a distribution system entering the premises and/or water that is
discharged from a cooling or heating system could be taken to verify the possible presence
of a violating parameter. This is recommended when the contaminant in question is also
present in the water supply system and could influence the total concentration of the
violating parameter in wastewater sample.

4.9.4 SAMPLING COMPLETION

After the sampling procedure has been completed, the sampling equipment and cooler -
lockbox with collected samples are returned to the transportation vehicle. Dirty grab
containers, if any, should be placed into “dirty” plastic storage containers. The traffic
safety set-up, if applicable, need to be dissembled and all safety set-up equipment and
traffic cones returned to the transportation vehicle. Finally, protective gloves should be
removed and hands cleaned with a hand sanitizer. Unless it is securely locked in the

18
 transportation vehicle at all times, the cooler - lockbox along with the samples should
remain within unobstructed view of the field sampler or person authorized.

Collected samples and its chain of custody documentation are in the custody of the
field sampler until relinquished to the laboratory personnel.

5. SAMPLE IDENTIFICATION - SEALING AND LABELING

Once the legal sample is collected, the containers should immediately be properly sealed and
labelled. A legal custody seal is applied over the top of the lid and down the side of the container
showing the identification number of sample and the field sampler’s signature. To prevent
container mix-up each sample container must also be labelled with waterproof, permanent,
adhesive, polyester labels or equivalent.

Different labelling systems can be used, such as:

 Pre-printed and two-part labels with corresponding unique numbers. One part of the label
is attached on the container and the other one is kept for the sampling documentation,
 Another way of labelling is to etch the container with a glass etcher. The etchings should
be marked directly into glass, forming a permanent record,
 Evidentiary labels that match container identification numbers on three separate stickers
can also be used. In such a case, one of the stickers is used to seal the lid of the sample
container (the lid cannot be removed without damaging the seal), one is put on the
sample container and the last is placed in the Field Sampling Data Sheet along with the
sampler’s notes for the sampling event.

Proper labelling of samples is also important for quality assurance purposes. Information on the
labels provides uniformity of sample records, assists the sampler and helps ensure that vital
information is not omitted. The label could contain, but is not limited to the following
information:
 Container identification number,
 Sampling date and time,
 Sampling location
 Field sampler’s name
 Name of the witness(es).

In a case the sample label is lost or was never prepared, a written statement should be made
detailing the sample collection and transportation from the field to the laboratory, description of
the known chain of custody data and references to any sample associated entries.

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6. SAMPLE PRESERVATION, STORAGE AND HOLDING TIME

Following, both the proper holding times and required preservation will help to retain the
integrity of the sample so that accurate, legally defensible results can be obtained.

6.1 PRESERVATION AND STORAGE

The purpose of sample preservation is to minimize any degradation until the samples can be
analyzed. Complete preservation of samples is practically impossible because complete
stability for every constituent can never be achieved. Sample that cannot be delivered to the
laboratory within 2 hours must be preserved to minimize changes in samples that begin
immediately after collection. It is the field sampler’s responsibility to preserve and store the
samples until delivered to the laboratory.

There are no absolute methods of preservation and no single method is entirely satisfactory.
The preservation methods are generally intended to retard biological action, retard
hydrolysis of chemical compounds and complexes and reduce volatility of organic
molecules. Between sampling and analysis samples should preferably be kept as cool as
possible. Using of dry ice should be avoided because it will freeze samples, may cause glass
containers to break and affect a pH change in samples.

Every parameter has a specific preservation technique. Chemical preservation should be

added to the sample where required to fix the analyte of interest from loss or breakdown.
The samples must be analyzed as quickly as possible on arrival at the laboratory. If
immediate analysis is not possible samples should be refrigerated at 4°C. It is the
responsibility of the laboratory to maintain the sample preservation and assure timely
analysis.

Some analyses are more affected by sample storage than others. Certain cations are subject
to loss by adsorption on, or ion exchange with the walls of sampling containers. Sample
collection using the proper containers, preservation, and analyzing method within the
required holding times lead to the accuracy of sample results. For samples that are not being
analyzed immediately after collection, analytical results cannot be accepted for reporting
purposes if samples have not been correctly preserved and stored.

6.2 HOLDING TIME

Holding time is the maximum time allowed between collection and the moment when
sample preparation or analysis on that sample must begin. Turnaround time in addition is
the length of time it takes from when a sample is received by the laboratory to the time
when a result of analysis is issued.

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 Correct handling of sample and prompt delivery is essential in order to obtain the best
quality of analytical results. The sample should be delivered to the laboratory immediately
after collection and analysis should start as soon as possible to ensure the results are
representative. Samples begin to change as soon as they are removed from their
environment. In a case when the holding times are exceeded the samples should be flagged
in the laboratory analytical report.

The samples that cannot be preserved should be analyzed either in-situ or on site
immediately after collection. For example, samples collected for parameters such as pH,
dissolved oxygen, chlorine residual and temperature have no acceptable holding times and
must be analyzed immediately. For composite samples, it is common practice to use the
time at the end of composite collection as the sample collection time.

7. SAMPLE TRANSPORTATION

Shipment of samples is time critical to ensure their integrity. The field sampler is responsible for
preserving and storing the samples until they are delivered to the laboratory. After collection all
samples should be handled as little as possible. They should be put on ice for transport to
laboratory but never frozen. Each collected sample stored in the cooler should have its own Field
Sampling Data Sheet that must accompany the sample at all times. The Field Sampling Data
Sheet should be placed in a waterproof bag, sealed and taped under the lid of the cooler along
with the samples to which it applies.

Samples can be hand delivered, delivered by mail, or private carrier. Samples that are expected
to be used for court purposes are preferably transported by the sampling personnel. They remain
in field sampler’s custody and must be secured until they are relinquished.

Samples transported by the postal service must be sent by registered mail with return receipt.
When sent by private carriers, samples require a description of the items on the bill of
lading. Either way the sample shipping bags or containers should be marked “deliver to
addressee only.”

The packages should be sealed with custody seal tape so the recipient can tell if the package has
been tampered with. This seal should not be broken until the samples arrive at the laboratory and
are checked in by laboratory staff. The seal label should include:
 Shipping and receiving facility name,
 Sampler’s name,
 Date the container is sealed for shipment, and
 It should read “Chain of Custody Sample – Authorization Required to Open”.

A copy of the Sample Shipping/Receiving Sheet should always accompany the transported
samples. The field sampler should keep a copy of this form and any other shipping documents

21
for the record and store them in a secure place. The original form should be sent with the sample
and signed by the sender and lab-sample custodian upon receipt. If the package is sent by private
carrier, the carrier needs to make sure the package tracking information is included on the form
so that samples can be tracked if necessary.

An example of the Sample Shipping/Receiving Sheet is found in Appendix 3.

8. SAMPLE CONTAMINATION

The possibility of a sample contamination is always present. A contaminated sample is

considered useless and contamination between containers, tools and equipment could become a
big issue during legal proceedings. Samples that do not require the addition of preservative must
be kept tightly capped and out of contact with anything that may cause contamination.

Samples may be contaminated by:

 Inappropriate containers or equipment,
 Dirty container caps,
 Containers that have not been properly cleaned,
 Loosely or improperly capped containers,
 Contaminated preservatives,
 Cross-contamination introduced by sampling equipment,
 Exposure to open air, which may contain various vapours,
 Sloppy sampling techniques.

As preventive measures, samples should not be stored in containers whose origin is not known to
the field sampler. The sample containers should be sealed tightly and stored in clean areas.
Sampling containers and other sampling equipment should never be stored near solvents,
gasoline, or other volatile substances that might cause contamination. Sampling equipment
should remain in wrapping material until it is used in the field. It must be decontaminated
according the appropriate protocol when transferred between sampling sites. Disposable gloves
should be worn at all times when handling preservative, sample containers and sampling
equipment.

Polyethylene and other kinds of plastic tubing can leach out phenolic compounds and phthalates,
which interfere with some organic analyses. All lengths of polyethylene, surgical and polyvinyl
chloride tubing should be as short as possible, thoroughly cleaned and replaced with Teflon
tubing where feasible.

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9. CLEANLINESS

Cleanliness is a high priority. To prevent contamination all sampling containers and equipment
must be kept clean and in a good condition, fit to be used at all times.

Pre-cleaned sample containers can be purchased from commercial suppliers and used for
sampling, only under condition that the laboratory is familiar with its cleaning protocol.

9.1 CLEANING OF FIELD EQUIPMENT

The equipment or its parts that come into contact with the sample should be cleaned to
avoid cross-contamination. The cleaning should be done before going into the field
whenever possible.

Prior to the trip all visible particulate matter and other residue should be removed by
washing the equipment accessible surfaces with phosphate-free laboratory grade detergent
and hot water. A steam or high-pressure water washer can be used if possible to remove dirt
or residue from the sampling equipment. In any case, an approved laboratory cleaning
methodology for analyte of interest must be followed.

While in the field, if washing is needed, the sampling equipment should be scrubbed with
detergent to remove all visible particulate matter and other residue, rinsed several times with
tap water and than few more times with de-ionized water to remove detergent.

9.2 CLEANING OF CONTAINERS

Sample containers must be properly cleaned prior to the sampling event. As a minimum, the
sample containers should be washed with phosphate-free laboratory detergent and hot water.
All surfaces should be scrubbed with a brush kept for this purpose only and then rinsed
thoroughly several times with tap water to remove all traces of detergent, followed by
several rinses with de-ionized water.

Sample containers should never be rinsed with the sample prior to collection. Pre-rinsing
may allow some contaminants to stick to the sides of the container or settle to the bottom
prior the final sample being collected. For example, pre-rinsing with wastewater sample
may cause extra oil and grease to stick to the sides or extra settle-able solids to remain in the
bottom of the bottle, causing a high bias to the sample answer.

Cleaning method is determined by the specific analyses to be performed on the sample:

 Metal Analyses - containers should be soaked in 10% - 20% nitric acid and rinsed
few times with de-ionized water before taking them into the field,

23
  Organic Analyses - cross-contamination with organic solvents or substances can be a
serious problem, therefore, the treatment of containers and equipment is frequently
recommended,
 Bacterial and Microbiological Analyses – bottles and equipment for microbiological
sampling and for any other samples requiring sterile conditions, must be sterilized
before being used.

10. LABORATORY SAMPLE SUBMISSION

Once the sample is received, the laboratory personnel are responsible for the care and custody of
the sample. The samples must be secured in the laboratory at all times. As they await analysis,
the samples should be put in locked and secured storage and stored in a way that satisfies
requirements for analyte stability, safety and ease of retrieval.

Few people as necessary should handle the sample. The laboratory usually designates one person
(lab-sample custodian) to be responsible for the custody of all samples. This person should be
able to testify that the sample was secured in the laboratory at all times from the moment it was
received until the time it was disposed.

The lab-sample custodian that receives incoming samples verifies the received package and its
content by checking the following:
 The integrity and condition of all sample cooler-lockboxes,
 The integrity and condition of all sample containers,
 Checks for leakage, cracked or broken closures or containers, evidence of grossly
contaminated container exteriors or shipping cooler-lockbox interiors and obvious
odours,
 Verifies the receipt of complete Field Sampling Data Sheet for each container,
 Verifies that each sample container identification number on the Field Sampling Data
Sheet and Shipping/Receiving Sheet corresponds to sample container identification
number on the container label,
 Verifies that each sample container seal number on the Field Sampling Data Sheet and
Shipping/Receiving Form corresponds to sample container seal number on the container
itself,
 Verifies proper field preservation of each sample has been done. There must be clear
note of any chemical preservation of the sample on the Field-Sampling Data Sheet done
in accordance with approved preservation protocols,
 For samples that require thermal preservation, lab-sample custodian will verify proper
storage temperature by determining that sample containers are in adequate contact with
wet ice in the shipping chest and by documenting sample temperatures.

The acceptance of the package is confirmed by lab-sample custodian signing the

Shipping/Receiving Sheet and the Field Sampling Data Sheet for each container.

24
All information from the Reagents and Supplies Sheet, Field Sampling Data Sheets and
Shipping/Receiving Sheet should be entered into laboratory’s master log. The lab-sample
custodian assigns to each sample a laboratory unique identification number and records it in the
Sample Receipt and Record Log Sheet. The unique identification numbers are used to track the
sample through the laboratory and should also be written on the sample container labels. In
addition, bar coding technology may be used to help reduce transcription errors.

All transfers of samples within the laboratory and all procedures performed on the sample should
be documented. The lab-sample custodian should maintain the chain of custody procedures and
indicate on the Sample Control Record Sheet who removed the sample from the storage area and
when it was removed and/or destroyed. After analysis, the sample should be returned to its
original location in the storage. A label should be placed on a container signifying that it has
been analyzed.

Examples of the Sample Receipt and Record Log Sheet and the Sample Control Record Sheet
are found in Appendices 4 and 5.

11. SAMPLE ANAYSIS

Laboratories dealing with legal sample analysis have to have appropriate accreditation to carry
out specific tests. The recognition of the laboratory competence requires ongoing demonstration
of performance through proficiency testing and laboratory audits to maintain capabilities.

According to the ISO/IEC 17025 Standard requirements and Canadian Association for
Laboratory Accreditation’s (CALA) accredited procedures and methodologies, samples should
be analyzed in a timely manner to ensure the integrity of the results. Laboratories should develop
chain of custody procedures in order to verify the sample information is tracked from its
reception through analysis, storage and disposal and the results obtained are related to the
respective samples. Developing and maintaining of such procedures is extremely important for
laboratories required to present evidence and testify in court.

The laboratory analyst is responsible for maintaining the chain of custody procedures during
sample analysis. The laboratory analyst should record the sample into the Laboratory Sample
Journal and assign the sample a unique laboratory analytical number. The Laboratory Sample
Journal contains the information recorded in the Field Sampling Data Sheet as well as any other
pertinent information.

The laboratory analyst should sign the Sample Control Record Sheet every time the sample is
removed from and returned to the secured storage. A record should be made in the Laboratory
Sample Journal whenever the container seal is broken and sample aliquots are taken for sample
analysis. The sample container should be sealed with a new numbered seal each time it is

25
returned to the secured storage and the new seal number should be noted in the Laboratory
Sample Journal. Sample aliquots taken should be kept locked in the refrigerator locked container
or incubator awaiting the analysis. If the sample is given to another analyst or person, the
exchange should be recorded and signed in the Laboratory Sample Journal. After analysis
samples must be returned to the lab-sample custodian for secure storage.

Each analytical method used for sample analysis should have its own Analytical Data Sheet
where obtained readings are recorded. The readings are copied to the Laboratory Sample Journal
where final sampling results are calculated and together with other relevant information
transcribed to the Report.

All written records must be documented in permanent ink. Any errors during the analytical
process should be corrected by drawing a single line through the error. The correct value is then
entered beside the incorrect entry with the initials and date of the individual making the
correction. The laboratory analyst has the primary responsibility of assuring the data is correct
and complete.

An example of the Analytical Data Sheet is found in Appendix 6.

12. SAMPLE DATA RECORDKEEPING AND ARCHIVING

The lab-sample custodian is responsible for maintaining the chain of custody procedures during
sample data recordkeeping. This involves documenting the entire sampling and analysis
procedures and placing all related forms, notes, calculations, test reports, and chain of custody
records in limited-access locked storage. The Sample Data Archiving Sheet should identify
where the data will be stored, what form it will be stored in, and how long it will be stored.

Records may be preserved in hardcopy or electronic format. Hard copies should be kept in
folders and filed using the following guidelines:
 By year,
 By analytical parameter,
 By assigned lab number.

If stored electronically there should be written procedure where the copies will be stored, how
many copies will be made, and how the database will be secured. For example, photographs and
video recordings can be stored in special photo/video storage-vault or USB stick with security
encryption/password protection. All records should be linked to internal records via laboratory
identification number. If samples are expected to be part of a legal action all laboratory
information must be easily accessed and defensible.

Documents and records must have designated minimum retention times, which must comply
with applicable legislated requirements. Some storage times are legislated, while other storage

26
times may be set by the municipality. Minimum storage time will depend on internal policies and
procedures developed pertaining to record retention.

An example of the Sample Data Archiving Sheet is found in Appendix 7.

13. SAMPLE DISPOSAL

After sample analyses were done and the test report has been issued, the authorized person
should dispose of the sample in a safe and convenient manner according to the laboratory
practice following appropriate federal, provincial and municipal health and safety requirements.

The sample will be disposed when it is certain that the information is no longer required, or the
sample has deteriorated. Samples can be stored for reuse for the maximum holding time, after
which it is considered to have deteriorated.

14. POST SAMPLING CLEANING

After sampling, used equipment should be properly cleaned and a label should be attached
indicating when and how it was cleaned and who cleaned it. An equipment log should be kept on
pertaining information.

Reusable collection containers should be washed and rinsed according to the proper cleaning
procedure and then labelled with the information of the person who cleaned the container, how
and when it was cleaned.

Dirty grab containers should be thoroughly cleaned, rinsed and returned to the “clean” storage
container. Autosamplers should be cleaned and repaired following the equipment manual. The
sampling vehicle and other sampling equipment should be cleaned and restocked as per future
sampling requirements.

15. QUALITY ASSURANCE /QUALITY CONTROL PROGRAM

Quality Assurance (QA)/Quality Control (QC) is a program designed by the laboratory that
specifies the methods and procedures required to produce measurement-based, technically valid,
legally defensible and known quality information. The QA/QC activities are designed to
evaluate precision and accuracy of the sample collection and analysis and to ensure that any
problems that may occur are quickly identified and rectified.

27
The QA/QC Program has two components:
1. Quality Assurance (QA) - describes the overall measures that a laboratory uses to ensure
the quality of its operations. It is designed to evaluate the precision and accuracy of the
sample collection, laboratory analysis and potential sources of contamination
encountered during sample collection and delivery to the laboratory.
2. Quality Control (QC) – is part of the overall QA. It consists of operational techniques and
activities that are used to fulfil requirements for quality.

An effective QA/QC Program is essential for any laboratory seeking accreditation according to
ISO/IEC 17025 Standard and CALA accreditation program.

15.1 QUALITY ASSURANCE MANUAL

The QA/QC Program should be defined in a written document called Quality Assurance
(QA) Manual as a top tier of the document hierarchy. The manual should describe the
approaches to achieve quality data and address any differences in handling between process
control samples, compliance samples and samples headed to court. It should also include
policy statements describing the intent and goal of the laboratory to conform to ISO/IEC
17025 Standard requirements. The quality policy statement should be written by senior
management. The QA Manual which is to be reviewed and updated regularly should include
the following topics:
 Laboratory organization and responsibility,
 Field sampling procedures,
 Laboratory sample handling procedures,
 Standard Operating Procedures for each analytical method used,
 Quality control procedures,
 Data reduction, validation, and verification,
 Preventative maintenance procedures,
 Laboratory audits,
 Corrective actions,
 Recordkeeping procedures,
 Proficiency testing.

For more detailed structure of documentation to be used in implementation of QA/QC Program,

the ISO/IEC 17025 Standard and CALA accreditation program should be referenced.

15.1.1 LABORATORY ORGANIZATION AND RESPONSIBILITY

An organizational chart should be created showing the laboratory organization and

lines of responsibility. For small systems the organizational chart is simpler. As the

28
system gets larger, the organizational chart will expand and the lines of communication
become more complex.

Each position in the laboratory should have a well defined job description including
training requirements to assure the laboratory personnel are updated on regulations and
methodology. Each person in the organizational chart should know well their job duties
and the job duties of all other personnel. A clear job description will minimize
laboratory communication problems and provide an efficient movement of samples
through the laboratory.

15.1.2 FIELD SAMPLING PROCEDURES

The field sampling procedures should be part of the Sampling Plan that describes
required sample preservation, proper containers, correct sample container cleaning
procedures, sample holding times from collection to analysis and sample shipping and
storage conditions. The Plan should also provide copies of appropriate chain of custody
forms.

15.1.3 LABORATORY SAMPLE HANDLING PROCEDURES

The QA Manual should address the way how samples are processed within the
laboratory from the moment of receiving, through the storage, to analysis and disposal.
It should describe:
 How unprocessed and processed samples are stored at the proper temperature,
isolated from laboratory contaminants,
 Practices to ensure that holding times will not be exceeded,
 How personnel maintain integrity of samples, by tracking them from receipt by
laboratory through analysis to disposal,
 Chain of custody forms.

15.1.4 STANDARD OPERATING PROCEDURES

Standard operating procedures (SOPs) describe the analytical procedures used by the
laboratory in sufficient detail that an experienced analyst, unfamiliar with the specific
test procedure should be able to perform the analysis. SOPs should list or describe the:
 Method title and referenced documents,
 Scope of method and application,
 Method summary,
 Materials and instruments needed,

29
  Operating instructions for instrumentation as a supplement to the
manufacturer’s operating manuals,
 Health and safety precautions, including personal protective equipment,
 Personnel qualifications,
 Calibration or standardization methods,
 Detailed analytical procedure,
 Calculations and data reduction,
 Chain of custody forms,
 Quality control parameters, frequency, corrective actions and trouble-shooting.

SOPs should be reviewed on an annual basis or whenever there is new equipment being
introduced. All revisions must be dated and signed. Test methods that are new to the
laboratory, methods that have been developed in-house, and changes and modifications
to existing methods must be validated.

15.1.5 QUALITY CONTROL PROCEDURES

The laboratory QA Manual should identify procedures used by the laboratory to

demonstrate the laboratory data is valid and defensible. It should define control samples
used and their frequency of use.

Control samples include:

 Method blanks to monitor possible contamination,
 Duplicates and split samples to monitor precision,
 Certified reference samples to monitor accuracy,
 Internal reference samples to monitor accuracy,
 Blank and matrix spikes to monitor recoveries.

15.1.5.1 TRAVEL BLANKS

A travel blank (also called trip blank or transport blank) is an aliquot of analyte-
free reagent water used to determine if airborne factors present during the handling
and transport of samples to the laboratory may have affected sample quality.
Travel blanks are prepared in the laboratory by filling containers with de-ionized
water and transported to the field with the regular sample containers and then
returned in the same condition together with the field samples to the laboratory.
They must not be opened in the field and the seal remains unbroken.

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15.1.5.2 FIELD BLANKS

A field blank is prepared in the field by filling containers with de-ionized water
during the sample collection process. Field blanks are treated exactly the same way
as the samples are treated using the same preservative, if any being used. During
the transport and shipping, the field blank is packed labelled and sent to the
laboratory with the field samples. This way it is exposed to the same
environmental conditions as the sample of interest.

Field blanks can be used to verify the sampling equipment, collection

environment, storage, transport and sample preparation as well as correct ambient
conditions. An appropriate number of extra field blanks should be treated at each
sampling point when conditions vary significantly between sampling points at a
facility or sampling points are more than a kilometre in distance. The laboratory
should report both the trip and field blank results along with the genuine sample
results.

15.1.5.3 FIELD DUPLICATES

Field duplicates also called replicates are multiple (two or more separate samples)
collected by the same person using the same equipment and procedures, at
approximately the same time and location under identical circumstances. They are
treated exactly the same way through the field and laboratory procedures. The
results of the duplicates give a measure of the precision for each analyte associated
with the collection and analytical processes.

15.1.5.4 SPLIT SAMPLES

Split samples are two or more portions taken from the same sample container that
are processed and analyzed separately. They can be split either in the field or in the
laboratory. They are analyzed separately and used to calculate test method
precision. Legal samples should not be split under any circumstances.

15.1.5.5 CALIBRATION STANDARDS

Primary calibration standards are prepared from traceable stock solutions which
can be purchased (certified reference samples) or prepared in-house (internal
reference samples) from reagent grade chemicals. These standards are used to
calibrate instruments, prepare standard curves, and verify method of analysis.

31
 15.1.5.6 BLANK SPIKES

Blank spikes are prepared by adding known quantities of a standard to a volume of

de-ionized water. The concentration prepared should be typically mid-range for the
method used.

15.1.5.7 MATRIX SPIKES

Matrix spikes are prepared by adding known quantities of a standard (blank spike)
to a sample prior to analysis. The results of the matrix spike should be reported as
percent recovery. In a case when the percent recovery is outside the established
acceptable range, interferences with the method may be present.

15.1.6 DATA REDUCTION, VALIDATION AND VERIFICATION

PROCEDURES

Data reduction is the process of transforming the raw analytical data printouts into
reportable units. It should be specified by formula for each parameter tested and is
specific to the laboratory used. Quality controls obtained must be within the control
range. If data is outside the acceptable control limits, the sample must be either re-
analyzed or invalidated. If the data is invalidated, it should not be reported.

The QA Manual should describe how invalidated samples are handled and the procedures
used to prevent the release of incorrect data, as well as identify what corrective actions
are to be performed when data cannot be validated.

15.1.7 PREVENTATIVE MAINTENANCE PROCEDURES

Laboratory and field instruments must be properly maintained to ensure they continue to
work properly. The QA Manual should describe preventative maintenance procedures
needed to assure proper operation. Effective preventative maintenance will reduce
downtime, poor performance and interruption of analysis. Consumable materials such as
batteries and membranes should be readily available. Replacement and repair of
laboratory equipment must be planned. Routine maintenance performed by laboratory
personnel should be recorded. Service contracts on major equipment should also be
documented.

32
15.1.8 LABORATORY AUDITS

Laboratory internal and external audits should be conducted as part of the routine QA
Program. The internal audits check that the quality procedures are in place and fully
implemented and ensure the quality system is effective and achieves objectives. The
review is carried out by senior management with responsibility. The internal audits are
useful in preparation for external audits.

QA Manual should contain internal auditing predetermined schedule covering all

activities over a reasonable period of time. Since it is inconvenient to audit all activities
in a single audit, it should be spread over several quarterly or monthly audits.

External audits are carried out by an independent external body as part of the
accreditation process. It verifies that the laboratory is operating in compliance with
ISO/IEC 17025.

Audits may be carried out in two basic ways:

 Horizontal audit - the auditor will examine in detail single aspects of the quality
system, for example calibration or reports, and
 Vertical audit - the auditor will select a sample and follow its progress from
receipt to disposal, examining all aspects of the quality system relating to its
testing.

15.1.9 CORRECTIVE ACTIONS

Any quality control tests that are suspect require the laboratory to evaluate the analytical
process for errors. The errors could be from the method used, the instrument used, or
personal errors by the analyst. The QA Manual should discuss what corrective actions the
laboratory will take to remedy errors, such as:
 Identify and define the problem,
 Assign responsibility for investigating the problem,
 Determine the cause of the problem,
 Determine actions needed to correct the problem,
 Implement the corrective action,
 Establish the corrective action is effective,
 Management verifies the corrective action effectiveness.

15.1.10 RECORD KEEPING PROCEDURES

The QA Manual should describe recordkeeping for all aspects of the laboratory activities.
Record keeping not only includes tracking sample and analytical information but also QC

33
information, equipment maintenance, calibrations, reagent purchase/preparation, etc. The
QA Manual should identify where all data, reports and chain of custody forms must be
stored, what form they will be stored in, and how long they will be stored.

15.1.11 PROFICIENCY TESTING

One of the best ways for an analytical laboratory to monitor its performance against both
its own requirements and the norm of other laboratories is to participate regularly in
proficiency testing schemes. Proficiency testing helps to highlight not only repeatability
and reproducibility performance between laboratories, but also systematic errors, i.e.
bias. Proficiency testing and other types of inter-comparisons are accepted as being an
important means of monitoring quality at national and international levels. Accredited
laboratories are normally required to participate in proficiency testing as an integral part
of their QA Program. It is important to monitor proficiency testing results and to take
corrective action as necessary.

34
16. ACRONYMS

CALA Canadian Association for Laboratory Accreditation

GPS Global Positioning System
ISO/IEC International Organization for Standardization/International Electrotechnical
Commission
MWWE Canada-Wide Strategy for the Management of Municipal Wastewater
Effluent
QA Quality Assurance
QC Quality Control
SOP Standard Operating Procedure
VOC Volatile Organic Compounds

35
17. GLOSSARY

Accreditation Procedure by which an authoritative body gives formal

recognition that a body or person is competent to carry out
specific tasks

Aliquot Any representative portion of the sample regardless of

whether a remainder is left or not

Analyst Person responsible for the chemical analysis of samples

according to the appropriate method

Autosampler Device used to collect samples automatically, either in

proportion to the wastewater flow, or as equal volumes at
equal time intervals

Calibration Procedure that checks or adjusts an instrument’s accuracy

by comparison with a standard or reference

Certification Procedure by which a third party gives written assurance

that a process or service conforms to specified requirements

Chain of Custody A legal term that refers to the ability to guarantee the
identity and integrity of the sample (or data) from
collection through reporting of the test results. It is a
process used to maintain and document the chronological
history of the sample (or data)

Composite Sample Combination of a number of smaller samples collected over

a period of time and/or locations. This sampling method
will produce an average sample composition when
pollutant concentrations vary over time or when the
frequency of individual samples containing the analytes of
interest is low.

Field Sampler Person authorized to collect the environmental sample in

the field

Grab Sample Single sample of water collected at a particular time and

place and represents the composition of the water only at
that time and place. It is a valid and often used sampling
method in regulatory sampling of industrial wastewater
effluent. Sometimes it can be the only method available to
the sampler.

36
 Grab samples are considered simpler in maintaining the
sample continuity in legal sampling situations. They are
best collected directly in a sample container either by hand
or by using simple field equipment such as buckets or other
containers.

Holding Time Elapsed time between sample collection and sample

analyses

Identification Number Unique number assigned to a test sample

In-Situ Testing Testing of occurring substances in their found state

Laboratory Facility that conducts scientific tests using established

methodology

Lab-Sample Custodian Person with responsibility for overseeing the possession,

exchange, and storage of reagents, sample(s), records, and
data as they are transferred between authorized personnel
or stored within the laboratory

Laboratory Sample Journal Book kept in the laboratory containing information on

sample collection, analyses and other pertinent information

Laboratory Technician Person with responsibility for preparing reagents and

supplies used in the laboratory and in the field

Legal Sample Sample taken and handled in such a manner that evidence
may be given in court concerning its origin, type and
constituents

Method Body of procedures and techniques for performing a task

(e.g. sampling) systematically presented in the order in
which they are to be executed

Procedure Set of systematic instructions for performing an operation

Proficiency testing Process, procedures, and activities for standardizing a given

measurement system to ensure that laboratories
participating in the same program can produce comparable
data

37
Protocol Detailed written procedure for a field and/or laboratory
operation (e.g. sampling, analysis)

Quality Assurance Overall measures that a laboratory uses to ensure the

quality of its operations

Quality Control Consists of operational techniques and activities used to

control and assess the quality of the measurements, product
and services

Sample Portion of material that is taken for testing

Sample Analyses All procedures carried out on samples including any

chemical alteration to sample

Sample Collection All procedures carried out on a sample at the time of

sample collection, including addition of chemical
preservatives

Sample Handling Manipulation to which samples are exposed during the

sampling process, from the selection from the original
material through to the disposal of all samples and test
portions

Site Area within boundaries established for a defined activity

Standard Operating Procedures Established analytical procedures used by the laboratory

Volatile Organic Compounds Organic chemical compounds that have high enough
vapour pressures under normal conditions to significantly
vaporize and enter the earth's atmosphere

38
18. REFERENCES

1. Practices for the Collection and Handling of Drinking Water Samples, Ontario Ministry
of the Environment, Version 2.0, 2009

2. British Columbia Environmental Laboratory Manual, British Columbia Ministry of

Environment, 2009

3. Water and Wastewater Sample Collection and Analysis, Prince Edward Island
Environment, Energy and Forestry, 2008

4. Example Small Wastewater Treatment Plant Laboratory Quality Manual - Fourth Edition,
Wisconsin Department of Natural Resources, 2008

5. Implementing Quality Management: A Guide for Ontario’s Drinking Water Systems,

Ontario Ministry of the Environment, 2007

6. Operational Guidelines for Monitoring and Reporting Public and Semi-Public Water
Systems, Manitoba Water Stewardship, 2007

7. USEPA Science and Ecosystem Support Division Operating Procedure - Wastewater

Sampling, 2007

8. USEPA Science and Ecosystem Support Division Operating Procedure - Logbooks, 2007

9. New Mexico Laboratory Certification Study Guide, Version I, 2007

10. Training Manual for Supervised Persons Conducting Operational Checks, Ontario
Ministry of the Environment, 2006

11. Atlantic Canada Wastewater Guidelines Manual for Collection, Treatment and Disposal,
2006

12. Laboratory Procedures Manual – 4.0 Edition, National Wild Fish Health Survey, US Fish
and Wildlife Service, 2006

13. ISO/IEC 17025, General Requirements for the Competence of Testing and Calibration
Laboratories, 2005

14. The Inspector’s Field Sampling Manual – Second Edition, Environment Canada, 2005

15. Sample Submission Guidance Document, North Carolina Division of Water Quality
Laboratory Section, 2005

16. Alberta Environment Laboratory Data Quality Assurance Policy Procedures and
Guidelines, Alberta Environment, 2004

39
17. Code of Practice for Wastewater Systems Consisting Solely of a Wastewater Collection
System, Alberta Environment, 2004

18. British Columbia Field Sampling Manual, British Columbia Ministry of Water, Land and
Air Protection, 2003

19. T. Loftus: Sample Handling for USEPA National Pollutant Discharge Elimination
System, 2003

20. Guide to Quality in Analytical Chemistry - An Aid to Accreditation, CITAC/Eurachem

Guide, 2002

21. Protocol for the Sampling and Analysis of Industrial/Municipal Wastewater, Ontario
Ministry of the Environment, 1999

22. Standard Procedures for Field Sampling, Measurement and Sample Preparation,
Gulfwatch Project, 1991-1992

23. City of Greeley, USA, Industrial Pretreatment Program, Wastewater Sampling

Procedures, 1984

24. Chain of Custody Procedures, USEPA Training Course

25. S J Couper, F McInnes and R Dexter: Wastewater Characterization. Comparison of

Conventional With Real Time Techniques

40
APPENDIX 1 - REAGENTS AND SUPPLIES SHEET
(Section 4. Sampling Procedure)

Reagent or Preparation Prepared by Quantity Comments

Supplies date

Relinquished by: ________________________

Received by: __________________________

Time: __________________________

Date: __________________________

Are any seals used: yes no

Seal No.: __________________________

Date sealed: __________________________

Name (print): __________________________

Signature: __________________________

Seal broken: __________________________

Date broken: __________________________

Name (print): __________________________

Signature: __________________________

41
APPENDIX 2 - FIELD SAMPLING DATA SHEET
(Section 4. Sampling Procedure)

Industry: __________________________

Sampler (print): _________________________

Witness(es) (print): ______________________

Location (Site Name or Number): __________

Sample Date: __________________________

GPS Coordinates: ________________________

Photo/Video: yes no

Sample container identification number: ______ Duplicate sample: yes no

Seal number: __________________________

Sample Time: __________________________

Sample Method: composite grab

Weather Conditions: Sampling Day Previous Day

Dry ______________ ___________________
Precipitation ______________ ___________________

Air Temperature: ________________________

Water Temperature: ______________________

Discharge Flow Rate: ____________________

Colour: without or _____________________

Foam: yes no

Clarity: yes no

Immiscible Matter: none fecal paper

oil/grease branches/foliage other (describe)

42
Odour: none faecal earthy mouldy
slurry ammonia chlorine hydrogen sulphide
mineral oil organic aromatic compounds other (describe)

Sample preservation description and other remarks:

Sample Relinquished by: _________________

Date and Time of Laboratory Custody: ________________

Laboratory Personnel Taking Custody: ________________________

43
APPENDIX 3 - SAMPLE SHIPPING/RECEIVING SHEET
(Section 7. Sample Transportation)

Sender

Name (print): ________________________

Signature: __________________________

Date: __________________________

Sent from: __________________________

Carrier

Company: __________________________

Signature: __________________________

Date: __________________________

Bill of Landing No.: __________________

Tracking No.: _______________________

Receiver

Lab-sample custodian name (print): ______

Signature: __________________________

Date: __________________________

Shipment condition upon receipt: ________

Comments: _________________________

Shipment Description

Number of packages: _________________

44
Package Sealed Seal intact Seal No. Condition prior to shipment
No. (yes or no) (yes or no)

Shipment contents
Type of Sample Sealed Seal intact Seal No. Condition:
container container (yes or no) (yes or no)
ID no.

45
APPENDIX 4 - SAMPLE RECEIPT AND RECORD LOG SHEET
(Section 10. Laboratory Sample Submission)

Sample Sample Lab ID Date Received Date Analyzed Date Reported

Container ID No.
No.

46
APPENDIX 5 - SAMPLE CONTROL RECORD SHEET
(Section 10. Laboratory Sample Submission)

Sample Sample Date and Time Released to: Reason Sample Date and Returned Sample Date and
container Lab ID Removed from Name (print) Location Time by: Name Destruction Time Sample
ID No. No. Storage and Signature Returned to (print) and Destroyed
Storage Signature

Lab-sample custodian name (print): _________________

Signature: _____________________

47
APPENDIX 6 - ANALYTICAL DATA SHEET
(Section 11. Sample Analysis)

DETERMINATION OF THE CHEMICAL OXYGEN DEMAND (COD)

Readings Analysis done by:

Sample Lab Sample (ml)
Date ml FAS ml FAS Result (mgO2/l) Remarks Name (print) and
ID No. (dilution)
(0,12 M) (0,005 M) Signature

48
APPENDIX 7 - SAMPLE DATA ARCHIVING
(Section 12. Sample Data Recordkeeping and Archiving)

Minimal Form of
Archive Place of
Document Storage Storage
No. storage
Time

Lab-sample custodian name (print): __________________

49