CE528 .

Environmental Chemistry &

Microbiology

Water & Wastewater Sampling

WHO Definition

Defines safe drinking water as water that “does not represent any
significant risk to health over the lifetime of consumption,
including different sensitivities that may occur between life
stages.”
Guidelines vs. Standards
• Guideline: a recommended limit that should not be
exceeded
• Standard: a mandatory limit that must not be exceeded
(often reflects legal duty or obligation)

• WHO Guidelines/IS:10500 for Drinking Water Quality

Guideline values to ensure safety of drinking water
• Standards vary among countries and regions
Why Do We Do
Water Quality Testing?
• Ensure safe drinking water
• Identify problems
• Adopt precautionary measures
• Raise awareness
• Determine the effectiveness of water treatment
technologies
• Select an appropriate water source
• Influence policies to supply safe water
Categories of Contaminants

Chemicals

Microbiological

Physical
Categories of Contaminants

Chemicals
Microbiological  Organic
Bacteria  Inorganic
Virus  pH
Protozoa
Helminths

Physical
 Turbidity
 Colour
 Odor
 Taste
Water Sampling
-Microbiological sampling
-Indicator organisms for pathogen presence

Physical sampling
-turbidity, conductivity, total dissolved solids etc

Chemical sampling
- pH, dissolved oxygen, phosphates, chemical oxygen
demand, biochemical oxygen demand, mineral impurities
(iron, manganese, chloride, lead, sodium etc)
Types of Testing
• Observation
• Advantages:
• Quick and easy
• Inexpensive
• Limitations:
• Qualitative – low precision and accuracy
• Field testing
• Advantages:
• Easy to use and portable
• Rapid results
• Less expensive
• Limitations:
• Less precision and accuracy
• Less quality assurance
Types of Testing
• Mobile laboratories
• Advantages:
• Controlled environment,
• High level of precision and accuracy
• Limitations:
• Relatively expensive
• Requires skilled laboratory technicians
• Laboratory testing
• Advantages:
• Controlled environment,
• High level of precision and accuracy
• Limitations:
• Expensive
• Lack of flexibility to conduct own testing
 Selecting Test Methods
Depends on:
• Objectives
• Range of concentration
• Required accuracy and precision
• Time period between sampling and analysis
• Technical skills and equipment required
• Familiarity with the method
• Availability of resources
Where Do We Sample?
• Source water
• Transport container (before treatment)
• Treated water
• Stored water (after treatment)
• Point of use
Important Terms
• Accuracy—combination of bias and precision of an analytical procedure, which reflects the closeness of
a measured value to a true value
• Bias—consistent deviation of measured values from the true value, caused by systematic errors in a
procedure
• Calibration check standard—standard used to determine the state of calibration of an instrument
between periodic recalibrations
• Confidence coefficient—the probability, %, that a measurement result will lie within the confidence
interval or between the confidence limits
• Confidence interval—set of possible values within which the true value will lie with a specified level of
probability
• Confidence limit—one of the boundary values defining the confidence interval
• Detection levels—Various levels in increasing order are
• Instrumental detection level (IDL)
• Lower level of detection (LLD)
• Method detection level (MDL)
• Level of quantitation (LOQ)/minimum quantitation level (MQL)
• Duplicate—usually the smallest number of replicates (two) but specifically herein refers to duplicate
samples, i.e., two samples taken at the same time from one location
• Internal standard—a pure compound added to a sample extract just before instrumental analysis to
permit correction for inefficiencies
• Precision—measure of the degree of agreement among replicate analyses of a sample, usually
expressed as the standard deviation
• Quality assessment, Quality assurance, Quality control
Collection and preservation of samples
• Obtain a sample that meets the requirements of the sampling program and handle it so that it does not
deteriorate or become contaminated or compromised before it is analyzed
• Ensure that all sampling equipment is clean and quality-assured before use. Use sample containers that
are clean and free of contaminants. Bake at 450°C all bottles to be used for organic-analysis sampling
• Fill sample containers without pre-rinsing with sample; pre-rinsing results in loss of any pre-added
preservative and sometimes can bias results high when certain components adhere to sides of container
• Sample carefully to ensure that analytical results represent the actual sample composition
• Carefully consider the technique for collecting a representative sample and define it in the sampling plan
• Make a record of every sample collected and identify every bottle with a unique sample number,
preferably by attaching an appropriately inscribed tag or label
• Document sufficient information to provide positive sample identification at a later date, including the
unique sample identification number, the name of the sample collector, the date, hour, exact location,
and, if possible, sample type (e.g., grab or composite), and any other data that may be needed for
correlation, such as water temperature, weather conditions, water level, stream flow, post-collection
conditions, etc.
• Before collecting samples from distribution systems, flush lines with three to five pipe volumes (or until
water is being drawn from the main source) to ensure that the sample is representative of the supply, taking
into account the volume of pipe to be flushed and the flow velocity
• Although well pumping protocols depend on the objectives of an investigation and other factors such as well
characteristics and available equipment, a general rule is to collect samples from wells only after the well
has been purged sufficiently (usually with three to ten well volumes) to ensure that the sample represents
the groundwater
• When samples are collected from a river or stream, observed results may vary with depth, stream flow, and
distance from each shore. Selection of the number and distribution of sites at which samples should be
collected depends on study objectives, stream characteristics, available equipment, and other factors
• If equipment is available, take an integrated sample from top to bottom in the middle of the main channel of
the stream or from side to side at mid-depth. If only grab or catch samples can be collected, preferably take
them at various points of equal distance across the stream; if only one sample can be collected, take it in the
middle of the main channel of the stream and at mid-depth
• Rivers, streams, lakes, and reservoirs are subject to considerable variations from normal causes such as
seasonal stratification, diurnal variations, rainfall, runoff, and wind. Choose location, depth, and frequency
of sampling depending on local conditions and the purpose of the investigation
Safety Considerations
• Because sample constituents may be toxic, take adequate precautions during sampling and sample
handling
• Toxic substances can enter through the skin and eyes and, in the case of vapors, also through the lungs
• Ingestion can occur via direct contact of toxic materials with foods or by adsorption of vapors onto
foods
• Always wear eye protection (e.g., safety glasses with side shields or goggles). When toxic vapors may be
present, sample only in well-ventilated areas, or use an appropriate respirator or self-contained
breathing apparatus
• In a laboratory, open sample containers in a fume hood. Never have food in the laboratory, near
samples, or near sampling locations; always wash hands thoroughly before handling food
• Always prohibit eating, drinking, or smoking near samples, sampling locations, and in the laboratory
• Collect samples safely, avoiding situations that may lead to accidents. When in doubt as to the level of
safety precautions needed, consult a knowledgeable industrial hygienist or safety professional
• Label adequately any sample known or suspected to be hazardous because of flammability, corrosivity,
toxicity, oxidizing chemicals, or radioactivity, so that appropriate precautions can be taken during
sample handling, storage, and disposal.
Sample Collections
1. Types of Samples
• Grab samples: Grab samples are single samples collected at a specific spot at a site over a short period
of time (typically seconds or minutes)
• Grab samples, represent a ‘‘snapshot’’ in both space and time of a sampling area
• Discrete grab samples are taken at a selected location, depth, and time
• Depth-integrated grab samples are collected over a predetermined part or the entire depth of a water
column, at a selected location and time in a given body of water
• A sample can represent only the composition of its source at the time and place of collection when a
source is known to be relatively constant in composition over an extended time or over substantial
distances in all directions, then the sample may represent a longer time period and/or a larger volume
than the specific time and place at which it was collected
• In such circumstances, a source may be represented adequately by single grab samples. Examples are
protected groundwater supplies, water supplies receiving conventional treatment, some well-mixed
surface waters, but rarely, wastewater streams, rivers, large lakes, shorelines, estuaries, and
groundwater plumes
• When a source is known to vary with time, grab samples collected at suitable intervals and analyzed
separately can document the extent, frequency, and duration of these variations
• Choose sampling intervals based on the expected frequency of changes, which may vary from as little as 5
min to as long as 1 h or more
• Seasonal variations in natural systems may necessitate sampling over months. When the source
composition varies in space (i.e., from location to location) rather than time, collect samples from
appropriate locations that will meet the objectives of the study (for example, upstream and downstream
from a point source, etc.)
• The same principles apply to sampling wastewater sludges, sludge banks, and muds, although these
matrices are not specifically addressed in this section
• Take every possible precaution to obtain a representative sample or one conforming to a sampling program
b. Composite samples
• Composite samples should provide a more representative sampling of heterogeneous matrices in which
the concentration of the analytes of interest may vary over short periods of time and/or space
• Composite samples can be obtained by combining portions of multiple grab samples or by using specially
designed automatic sampling devices
• Sequential (time) composite samples are collected by using continuous, constant sample pumping or by
mixing equal water volumes collected at regular time intervals
• Flow-proportional composites are collected by continuous pumping at a rate proportional to the flow, by
mixing equal volumes of water collected at time intervals that are inversely proportional to the volume of
flow, or by mixing volumes of water proportional to the flow collected during or at regular time intervals
• Advantages of composite samples include reduced costs of analyzing a large number of samples, more
representative samples of heterogeneous matrices, and larger sample sizes when amounts of test
samples are limited
• Disadvantages of composite samples include loss of analyte relationships in individual samples, potential
dilution of analytes below detection levels, increased potential analytical interferences, and increased
possibility of analyte interactions
• Do not use composite samples with components or characteristics subject to significant and unavoidable
changes during storage
• Automatic sampling devices are available; however, do not use them unless the sample is preserved as
described below. Composite samplers running for extended periods (weeks to months) should undergo
routine cleaning of containers and sample lines to minimize sample growth and deposits.
C. Integrated (discharge-weighted) samples
• For certain purposes, the information needed is best provided by analyzing mixtures of grab samples
collected from different points simultaneously, or as nearly so as possible, using discharge-weighted
methods such as equal-width increment (EWI) or equal discharge-increment (EDI) procedures and
equipment
• An example of the need for integrated sampling occurs in a river or stream that varies in composition
across its width and depth
• To evaluate average composition or total loading, use a mixture of samples representing various points in
the cross-section, in proportion to their relative flows
• The need for integrated samples also may exist if combined treatment is proposed for several separate
wastewater streams, the interaction of which may have a significant effect on treatability or even on
composition
• Both lakes and reservoirs show spatial variations of composition (depth and horizontal location). However,
there are conditions under which neither total nor average results are especially useful, but local
variations are more important. In such cases, examine samples separately (i.e., do not integrate them)
• Preparation of integrated samples usually requires equipment designed to collect a sample water
uniformly across the depth profile. Knowledge of the volume, movement, and composition of the various
parts of the water being sampled usually is required. Collecting integrated samples is a complicated and
specialized process that must be described adequately in a sampling plan
Chain-of-Custody Procedures
• Properly designed and executed chain-of-custody forms will ensure sample
integrity from collection to data reporting
1. Sample labels (including bar-code labels) - a unique sample number, sample type, name of
collector, date and time of collection, place of collection, and sample preservative
2. Sample seals - Use self-adhesive paper seals that include at least the following information:
sample number (identical with number on sample label), collector’s name, and date and time of
sampling
3. Field log book: As a minimum, include the following in the log book: purpose of sampling;
location of sampling point; name and address of field contact; producer of material being
sampled and address, if different from location; type of sample; and method, date, and time of
preservation
4. Chain-of-custody record: Fill out a chain-of-custody record to accompany each sample or group of
samples, record includes the following information: sample number; signature of collector; date,
time, and address of collection; sample type; sample preservation requirements; signatures of
persons involved in the chain of possession; and inclusive dates and times of possession
5. Sample analysis request sheet - laboratory portion of such a form is to be completed by laboratory
personnel and includes: name of person receiving the sample, laboratory sample number, date of sample
receipt, condition of each sample (i.e., if it is cold or warm, whether the container is full or not, color, if
more than one phase is present, etc.), and determinations to be performed
6. Sample delivery to the laboratory
7. Receipt and logging of sample
8. Assignment of sample for analysis
9. Disposal
Sampling Methods
1. Manual sampling: Manual sampling involves minimal equipment but may be unduly
costly and time-consuming for routine or large-scale sampling programs. It requires
trained field technicians and is often necessary for regulatory and research
investigations for which critical appraisal of field conditions and complex sample
collection techniques are essential
2. Automatic sampling: Automatic samplers can eliminate human errors in manual
sampling, can reduce labor costs, may provide the means for more frequent
sampling, and are used increasingly
3. Sorbent sampling: Use of solid sorbents, particularly membrane-type disks, is
becoming more frequent. These methods offer advantages of rapid, inexpensive
sampling if the analytes of interest can be adsorbed and desorbed efficiently and
the water matrix is free of particulates that plug the sorbent
Sample Containers
• Test sample containers and document that they are free of analytes of interest,
especially when sampling and analyzing for very low analyte levels
• Containers typically are made of plastic or glass, but one material may be preferred
over the other
• Silica, sodium, and boron may be leached from soft glass but not plastic, and trace
levels of some pesticides and metals may sorb onto the walls of glass containers
• For samples containing organic compounds, do not use plastic containers except
those made of fluorinated polymers such as polytetrafluoroethylene
• Use glass containers for all organics analyses such as volatile organics, semivolatile
organics, pesticides, PCBs, and oil and grease
 Number of samples & Sample volume

• Collect a 1-L sample for most physical and chemical analyses. For certain determinations,
larger samples may be necessary
• Do not use samples from the same container for multiple testing requirements (e.g.,
organic, inorganic, radiological, bacteriological, and microscopic examinations) because
methods of collecting and handling are different for each type of test
• Always collect enough sample volume in the appropriate container in order to comply with
sample handling, storage, and preservation requirements