Reference:

Title 40 Code of Federal Regulations Part 136 (40 CFR 136)

Sampling and Preservation
The primary objective of a sampling program is to collect a small portion of a material so that analyses can be
made which will accurately represent the entire body of the material. Proper sampling and preservation
techniques are important in order to maintain the integrity of the sample. Improper sample handling can
invalidate the results of any analysis that a laboratory performs. In other words, the results are only as good
as the sample. A table with the sampling, preservation, and holding times for various analytical parameters
can be found in Appendix D.
This will be an overview of various topics concerning sampling and preservation. For further information,
consult the reference listed at the beginning of this section.
Sample Log
Standard Conditions for NPDES Permits, an attachment to the NPDES permit, Part 1 General Conditions
Section A Monitoring and Reporting Paragraph 5 requires sampling records. This is a log of all the daily
samples collected in the treatment plant. Regulations vary regarding how long these records must be kept,
but the permit requiring the sampling log will also identify how long these records must be retained. Items to
record are:

The date, exact place, and time of sampling or measurements;

The individual(s) who performed the sampling or measurements.

Include a spot to record any remarks concerning the sample collection that may have an effect on test results
(e.g. heavy rain, unusual color or odor, heavy recycle stream to head of plant, refrigeration of sampler off,
etc.).
Types of Samples
There are two types of samples based upon their method of collection: grab samples and composite samples.
The choice of method depends upon the analysis that is required on the sample.
A grab sample is an individual sample collected at a selected time.
A composite sample is composed of one of the following three:

Several grab samples, mixed together from various points in a waste stream, all samples are
collected within a short period of time.
Grab samples of the same volume, taken from one source over a specific period at regulated times.

Grab samples taken from one source over a specific period at irregular intervals in irregular volumes
that proportion the flow.

Items that Influence Grab and Composite Samples

Does every worker collect the sample in the same spot and manner each time?

Are the correct holding times observed?

Are preservatives used correctly when needed?

Is the correct type of sample bottle being used?

Is the correct amount of sample collected?

Is the sampler clean?

Is the sample mixed properly before pouring aliquot for testing?

Is the grab collected during appropriate flow conditions?

Are grabs collected at the same time, every time?

Grab Samples
A grab sample is one discrete sample where all of the material is collected at once and can only represent the
conditions at a particular time. It can be taken manually by using a pump or scoop or by dipping the container
directly into the water to be sampled.
Certain tests require the use of grab samples and are to be analyzed immediately upon collection. These tests
include pH, temperature, dissolved oxygen, chlorine residual and fecal coliform. Sometimes it is necessary to
collect a grab sample for tests that usually require composite samples. This can include instances when an
unusual discharge occurs and an operator must determine if appropriate action needs to be taken
immediately. A grab sample may also be necessary if there is an intermittent discharge, as in industrial
monitoring situations.
Composite Samples
A composite sample is made up of a number of grab samples collected over a period of time and mixed
together. It represents the average conditions of a site over a specific period of time. For most purposes, a
twenty-four hour time period is considered standard. Aliquots are usually collected at one site, but can be
collected at multiple sites, such as in soil analyses, and then mixed together. Composite samples are used
only when the parameters to be determined are shown to remain unchanged during collection and
preservation.
Composite samples can be collected either manually or with an automatic sampler. Manual compositing of
samples can present some problems. They are timeconsuming and too dependent on the person(s) collecting
the samples, especially if more than one person is collecting them. The margin of error increases due to the
differences between the methods of collecting the sample that is, the depth where the sample is collected,
how well it is stirred or shaken, the length of time between samples, etc.
A better way to collect composite samples is by using an automatic sampler. The automatic sampler
eliminates many of the errors associated with manual collection. Advantages include more consistent
sampling, less sample handling and the ability to collect samples in various modes time proportional or flow
proportional with either fixed or variable volumes. Disadvantages include increased maintenance, the
possibility of lines or probes becoming clogged or frozen and possible sample contamination. Problems in
collection from an automatic sampler can still arise if the sample is not thoroughly mixed before pouring into
smaller containers and if the sampler jug and hoses are not kept clean.
A time proportional sample with a fixed volume is probably the most common kind of composite sample. Both
the time interval and the size of the sample remain constant. This is used when the flow is fairly constant
throughout the entire sampling period. To calculate the volume for each sample, the time interval and the
final volume need to be established. For example, if one wishes to collect six liters of a sample in half hour
increments during a 24-hour sampling period, first calculate the number of samples needed per day: 24/0.5 =
48 samples/day. Then, calculate the volume of each sample.

A container marked at 125 mL can then be used for manual collection or, following the manufacturers
instructions, an automatic sampler can be programmed for a 125 mL sample every 30 minutes.
A flow-proportional composite can be collected two ways. One way is to keep the sample volume constant and
vary the time interval. As the flow increases, the time interval between samples decreases. The other way is
to keep the time interval constant and vary the sample volume with the flow. With either method, a sampling
chart listing flow rates and their corresponding sample volumes must be established and closely followed for
manual collection. It is far easier to use an automatic sampler which is tied into a flow measuring device so
that it will collect a fixed volume of sample that is flow-proportional. A signal from the flowmeter starts the
sample pump and a sample is taken. In this way, the sample is dependent upon flow rather than time.
There are also automatic samplers, known as sequential samplers, available that can collect a series of
discrete samples in individual containers, which can then be composited at a later time. These are useful
when one wishes to analyze different portions during the sampling period based on color, shift time, etc.
Some industries are required to be monitored this way in order to separate the discharges between
operational and non-operational hours.
Techniques
The techniques for collecting representative samples are as varied as their sampling locations. In general, the
samples should be collected in an accessible location in an area of high turbulence to insure good mixing. The
sampling site should be kept constant so that results from repeated testing can be compared. If possible,
collect the sample in the center of the flow, about halfway from the bottom in order to avoid the debris on the
bottom and any large amounts of floating materials. When sampling manually with a bottle, place the mouth
of the container below the liquid surface and facing the flow, keeping ones hand from blocking the mouth of
the bottle. It is a good practice to wear waterproof gloves while sampling by hand so as to lessen the chance
of infection by pathogenic organisms, especially if one has cuts or abrasions on the hand.
Collect enough sample to allow sufficient volume for analysis and for any duplicate testing. Some analyses,
such as for volatile organics, dissolved oxygen, etc., require the containers to be completely full with no air
trapped in them. Other analyses, such as fecal coliform and total suspended solids, need airspace to allow
adequate mixing before analysis. Consult the individual analytical methods for proper collection techniques.
If samples are to be taken from a closed pipe through a valve or faucet, the valve should be opened and
allowed to flush thoroughly before the sample is collected. The time needed for the flushing will depend upon
the diameter and length of the pipe and the velocity of the flow.
For solid samples such as soils and filter cakes, several small portions are collected from over the entire area,
placed in a wide mouth container, and mixed thoroughly before taking subsamples for analysis.
As each sample is collected, it must be clearly identified so there is no chance of confusing it with any other
sample. Samples should be tagged or labeled with the following information:

Sample location

Date and time of collection.

Type of sample (either grab or composite)

Name of collector

Preservatives added

Any unusual conditions at the time of sampling

Other information deemed pertinent (an identifying sample number, a list of analyses to be
performed, type of container, etc.)

Fill in the information on the tag with waterproof ink and attach to the container immediately after collection.
This is important when more than one sample is taken or when a composite sample is divided into different
containers at one sampling location.
At the same time the samples are being tagged, a chain-of-custody document needs to be filled out and kept
with the samples. This is used to trace the possession and handling of a sample from the point of collection
through the final reporting of data. A chain-of-custody is a record that shows the samples are collected,
transferred, stored and analyzed properly, thereby ensuring the validity of the resulting data, and that
documentation exists for the samples if the resulting data is ever used in enforcement cases. The information
on the chain-of-custody needs to include all of the items listed above that are on the sample tag, along with
the signature of the collector, the signatures of all involved with the possession of the sample and dates and
times of each possession. The samples should then be taken to the laboratory as soon as possible.

Sampling and Preservation; the Tips for Techs version

Determine the analysis parameter(s) to be sampled at a given site

Determine the volume of sample needed

Collect sample containers for the samples

Obtain the proper preservatives for sample preservation

Tag or label samples as they are collected

Fill out appropriate chain-of-custody forms as needed

Lesson 3:
Sampling
Types of Samples
Introduction
There are two main types of samples which are used in water and wastewater treatment - grab
samples and composite samples. The type of sample taken in a given instance will depend on the
type of test to be performed, the frequency of testing, and on permit requirements. We will
explain each test procedure below.

Grab Samples

A grab sample, also known as a catch sample, consists of a single sample taken at a specific
time. This is the most common type of sample and is the sampling technique you will use for
most of your labs. For example, you took a grab sample when you collected a beaker of raw
water and tested it for pH.
A grab sample has certain limitations. In essence, a grab sample takes a snapshot of the
characteristics of the water at a specific point and time, so it may not be completely
representative of the entire flow. Grab samples are most appropriate to small plants with low
flows and limited staffs who cannot perform continual sampling.
On the other hand, grab samples do provide an immediate sample, and are thus to be preferred
for some tests. Specifically, pH, dissolved oxygen, and total residual chlorine can change very
rapidly in water once the sample is removed from the flow, so grab samples are preferred for
these tests.
Grab samples must be collected carefully to make them as representative as possible of the water
as a whole. They should be taken at a time of day when the plant is operating near its average
daily flow rate. If grab samples are used to determine plant efficiency by collecting a raw water
sample and a treated water sample, then the collection of the effluent should be delayed long
enough after collection of the influent sample to allow for the raw water to pass completely
through the treatment process.
Finally, be aware that mixing two or more grab samples may not result in a result which averages
the characteristics of the samples. Chemical reactions can take place in mixed samples which
alter pH and chlorine residual values. The next section will give you more information on
combining samples.

Composite Samples

A composite sample, also known as an integrated sample, is a sample which consists of a

mixture of several individual grab samples collected at regular and specified time periods, each
sample taken in proportion to the amount of flow at that time. Composite samples give a more
representative sample of the characteristics of water at the plant over a longer period of time.
Like grab samples, composite samples have both strengths and weaknesses and are not
acceptable for all tests. The greatest strength of composite samples is their ability to take into
account changes in flow and other characteristics of the water over time. This helps the operator
gain an overall picture of the total effects that the influent will have on the treatment process and
that the effluent will have on the receiving water. However, composite samples cannot be used
for tests of water characteristics which change during storage (such as dissolved gases) or of
water characteristics which change when samples are mixed together (such as pH.) Table 1060:I
in Standard Methods lists whether grab or composite samples are most appropriate for a variety
of tests.
Composite samples are often taken using automatic sampling devices. These may be set to take
a sample every 8, 12, or 24 hours, with the frequency depending on test requirements, on the size
of the treatment plant, and on permit requirements.

Sample Volumes for Composite Samples

One of the most important aspects of a composite sample is that each individual grab sample
must be proportional to the amount of flow at the time the sample was collected. Most automatic
equipment used to take composite samples will make these calculations for you and will collect a
correctly sized grab sample during each time period. This section presents a calculation you can
use to determine the size of the grab sample at a given time when producing a composite sample
manually.
The volume of sample collected at any given time depends on the volume of flow at that time,
the total flow for the day, the total composite sample volume, and the number of individual grab
samples to be taken. The following equation can be used to calculate a grab sample's volume:

For example, the average daily flow at your plant is 11.3 MGD and the total volume of your
composite sample is to be 4,000 mL made up of 24 grab samples. At the time you take your first
sample, the plant's flow is 5.2 MGD, so you can calculate the volume of the grab sample to take
as follows:

So you should take a 77 mL grab sample during your first sampling of the day.

Part 3: Storage