SURFACE WATER

SAMPLING
LECTURE CONTENT
1. Design for Water Sampling
2. Sampling strategies of water pollutants
3. Water sampling, equipment and storage
4. Field measurements – Field quality control and quality assurance
samples
5. Pretreatment and extraction technique for contaminants in water
sample
The Department of Environment (DOE) has classified the
water quality index based on 5 classifications (I, II, III, IV and
V) as shown in Table 1

Source: https://www.doe.gov.my/wp-content/uploads/2021/10/ii-Standard-Kualiti-Air-Kebangsaan.pdf
Design for Water Sampling

• Four types of typical Sampling program

• Rapid Assessment
• Establishing a Baseline
• Long-term Monitoring
• Problem Assessment
Design for Water Sampling

• Rapid Assessment
• simply wants to know the water quality
• generally good or bad.
• may not represent the actual condition of the water source.
• True at that specific time and place
• often used for creating awareness
• often inexpensive
• the objective is to illustrate concepts of water quality.
Design for Water Sampling

• Establishing a Baseline
• undertaken prior to establishing a Long Term Monitoring Program.
• established by sampling at least once per season at the same sampling
locations for a minimum of one year.
• Provides characteristics data for each season.
• From this information, future sampling can be targeted
• Useful when funds and/or time needed for sampling are limited.
Design for Water Sampling

• Long-Term Monitoring
• To overview of a system over time
• to monitor the characteristics on a continuous basis
• Repeated sampling at multiple designated sites
Design for Water Sampling

• Problem Assessment
• to identify sources of contamination
• to assess potential impacts to a system before or after a change
• requires several sampling points within the system
• Required statistics data
• to show target sites are significantly different from the rest of the system.
• The type, location, and number of samples taken to suit the intended
statistical analyses.
SAMPLING STRATEGIES
OF WATER POLLUTANTS
Water Characteristics
 Short-Term Variability
Different findings when sampled
moving upstream vs moving
downstream during the day

(moving downstream)

(moving upstream)
Surface Water Sampling Strategies
• Chronic standards
Sample at equal time intervals to obtain a 4-day mean
• Acute standards
Pick sample time to coincide with the daily maximum
• Temporal or spatial analysis
Always sample at same time or collect 24-hour samples
• Comparison of loads (temporally or spatially)
Collect samples and measure flows over at least 24 hours
Sequence of Sampling Matrices
Collect from the least to the most contaminated sampling locations in
order to minimize cross-contamination.
• Collect water first and then sediment.
• Collect surface water samples first and then proceed to a deeper
interval.
• For sampling at shallow stream, begin by standing downstream of the
collection point, and work upstream.
Sequence of Sampling for Analyte
1. VOCs
2. SVOCs
3. Total metals
4. Dissolved metals
5. Microbiological samples
6. Inorganic non-metals
Sample amount

• Sufficient to perform all required laboratory analyses and with

an additional amount remaining for QA/QC analysis
• Representativeness factor
• Water/waste water samples
• 100 ml for trace metals
• 1 L for total organics
• 20-40 L for an effluent acute toxicity test
WATER SAMPLING,
PRESERVATION &
STORAGE
 Equipment for Surface Water Sampling

Pond sampler (Grab sampler) Weighted bottle sampler Kemmerer bottle

van Dorn sampler
Equipment for Surface Water Sampling
• Pond sampler - near shore sampling
• weighted bottle sampler - collect samples in a water body at a
predetermined depth
• Kemmerer bottle – Teflon, acrylic or stainless-steel tube attached to a
rope and best used when access is from a boat or structure such as
bridge or pier
Preservation Methods for Sample Changes
Sample Refrigeration
• ‘‘Wet’’ ice (frozen water) in
insulated coolers is recommended.
• Samples should be double-bagged
to prevent water damage from
melting ice.
• Glycol-based ice packs are not cool
enough
• Dry ice is not recommended as it
freezes samples and causes the
containers to break.
Preservation Methods According to Analytes
Water Sample Containers
• Glass
• Plastic
• Teflon
• VOC vial with Teflon-lined septum
• Wide-mouth amber glass bottles
• BOD bottle
 23

Selection of sample containers

• Glass vs. plastic
• Headspace vs. no headspace
• Special containers
• Biological samples - aluminum foil and closed
glass containers with inert seals or cap liners
• Aluminum foils should not be used if mercury
is the target
Water Sampling Containers & Methods
Water Sampling Containers & Methods
Maximum Holding Times (MHT)
• Even with the proper preservation, no samples can be stored for an extended
period of time without significant degradation of the analyte.
• The maximum holding times (MHTs) are the length of time a sample can be
stored after collection and prior to analysis (or pretreatment) without
significantly affecting the analytical results.
• MHTs start with the moment of sampling and end with the beginning of the
analytical procedure.
• Samples that have exceeded their MHTs should be discarded in order to not
jeopardize data quality.
• The MHT designated by U.S. EPA, ASTM, USGS, APHA, etc. are mainly
consistent.
MHTs (APHA, 1998) for Water Quality Parameters
FIELD QUALITY CONTROL
AND QUALITY
ASSURANCE
Greater that 50% of all errors
found in environmental analysis
can be directly attributed to
incorrect sampling
• Contamination
• Improper preservation
• Lacking representativeness
 What is Quality Control (QC)?
• The overall system of technical activities designed to
measure quality and limit error in a product or service.
• A QC program manages quality so that data meets the
needs of the user as expressed in a Quality Assurance
Program Plan (QAPP).
- US EPA (1996)

• QC samples are a way to evaluate the PARCC parameters.

QC is used to provide QUALITY DATA

PARCC Parameters
The PARCC parameters help evaluate sources of variability
and error
• Precision
• Accuracy
• Representativeness
• Completeness
• Comparability

“PARCC” parameters increase the level of confidence in

our data
QC methods: Representativeness
• Representativeness -
• extent to which measurements actually represent the true
environmental condition or population at the time a sample
was collected.
• Representative data should result in repeatable data

 Does this represent

this?? 

http://pubs.usgs.gov/fs/fs-0058-99
Key concepts of QA/QC: Completeness
• Completeness -
• % comparison between the amount of data intended to be
collected vs. actual amount of valid (usable) data collected.
• In the QAPP design – do the goals of the plan meet assessment
needs?
• Will sufficient data be collected?

Would this give usable data ?? 

Key concepts of QA/QC: Completeness
• Valid
Sampledata
design
• Will
Wouldsamples
data becollected
sufficient
at ifanhigh
outhumidity
flow characterize
resulted in
conditions
“error” readings?
in the entire
• lake?
Is data valid if the readings are outside the measurement range of the
• Statistically relevant number of data points
instrument?
• Will analysis in ppm address analytes toxic at ppb?
Key concepts of QA/QC: Comparability
• Comparability -
• the extent to which data generated by different methods and
data sets are comparable
• Variations in the sensitivity of the instruments and analysis
used to collect and assess data will have an effect upon
comparability with other data sets.

 Will similar data from

these instruments be
Comparable ?? 

Hach DR2400 portable spectrophotometer

QC for Environmental Measurement
• Sensitivity
• Ability to discriminate between measurement responses
• Detection limit
• Lowest concentration accurately detectable
• Instrument detection limit
• Method detection limit (MDL)
• Measurement range
• Extent of reliability for instrument readings
• Provided by the manufacturer
QC - Field
 Provide a table listing the QC samples for water samples
and environmental parameter (pH, phosphorus, etc.). The
table should include:
- Type of QC sample (field duplicates, split samples,
Performance Evaluation Samples, and trip, equipment
and cooler temperature blanks)
- Frequency
- Acceptance criteria (control limits)
- Corrective actions that will be done when acceptance
criteria are exceeded
 Include procedures and formulas for calculating QC data.
QC – Field Measurement/Laboratory
 Provide a table listing the QC samples for each analytical
method, for each matrix and for each measurement
parameter. The table should include:
- Type of QC sample (lab duplicates, matrix spikes,
Performance Evaluation Samples, method blanks,
surrogates, etc.)
-Frequency
-Acceptance criteria (control limits)
- Corrective actions that will be done when acceptance
criteria are exceeded.
 Describe procedures and formulas for calculating QC data.
Quality Control Samples

QC sample types include:

• Trip / field blank
• equipment or rinsate blank
• duplicate/replicate samples
• spiked samples
• split samples http://ma.water.usgs.gov/CapeCodToxics/photo-gallery/wq-sampling.htm

• blind samples
Trip Blank
• This is a sample container is filled at the laboratory with
deionized water.
• The blank(s) follows the same handling and transport
procedures as the samples collected during the event.
• The trip blank vial(s), to the same environmental
conditions (i.e., light, temperature, etc.) of the sample
vial(s) but do not open until it is time for analysis.
• The blank(s) functions as a check on sample contamination
originating from sample transport, shipping and from site
conditions.
Field Blank
• Field blank sample collection
• In the field, using a sample container supplied by the analytical
laboratory, collect a sample of analyte free water (e.g. distilled
water)
• Use preservative if required for other samples
• Treat the sample the same as all other samples collected during
the designated sampling period
• Submit the blank for analysis with the other samples from that
field operation.

• Field blanks determine representativeness

Equipment or Rinsate Blank
• Rinse the equipment to be used in sampling with distilled
water immediately prior to collecting the sample
• Treat the sample the same as all others, use preservative if
required for analysis of the batch
• Submit the collected rinsate for analysis, along with
samples from that sample batch
• Rinsate blanks determine representativeness
Duplicate or Replicate sample
• Two separate samples are collected at the same time,
location, and using the same method
• The samples are to be carried through all assessment and
analytical procedures in an identical but independent
manner
• More that two duplicate samples are called replicate
samples.
• Replicates determine representativeness
Split and Blind Samples
• A sample is collected and mixed thoroughly
• The sample is divided equally into 2 or more sub-
samples and submitted to different analysts or
laboratories.
• Field split
• Lab split
• Blinds - submitted without analysts knowledge
• Split and blind samples determine precision
Spiked Sample
• A known concentration of the analyte is added to the
sample
• Field preparation
• Lab preparation
• The sample is treated the same as others for all
assessment and analytical procedures.
• Spiked samples determine accuracy
• % recovery of the spiked material is used to calculate
accuracy
Some things to consider when reviewing QC sample
results:
• What will you do if contaminants are found in a “blank” sample?
• What will you do with sample results that do not compare with previously
collected data and appear to be incorrect?
• What will you do with sample results if the instrument was not calibrated
correctly?
• What will you do when duplicate sample results aren’t comparable?
• What will you consider the range of comparable results to be?
• What will you do with sample results when a spiked compound is not
recovered? Or the results of a performance evaluation sample are inaccurate?
Instrument/Equipment Testing, Inspection,
Maintenance and Calibration
• Identify equipment and instrumentation (both field and laboratory) requiring
calibration and periodic maintenance, inspection and testing.
• Describe how often the instrument needs to be calibrated and maintained and who
will perform and document these tasks.
• Describe the calibration and testing procedures and acceptance criteria (control
limits) for operation.
• List the spare parts needed to be kept on hand to keep the instrument operational.
• Describe how problems (e.g., instrument doesn’t hold calibration) will be resolved
and documented.
• Attach applicable SOPs.
Review: Quality Assurance Project Plans
• QAPP
The QAPP
guides:
is a project-specific QA document.
• the
• The selection
QAPP of parameters
outlines and procedures
the QC measures to be taken for the project.
• data management and analysis
• steps taken to determine the validity of specific sampling or analysis
procedures
Review: Elements of a QAPP
• The QAPP governs work conducted in the field, laboratory, and the
office.

• The QAPP consists of 24 elements generally grouped into four project

areas:
• Project management (office)
• Measurement and data acquisition (field and lab)
• Assessment and oversight (field, lab, and office)
• Data validation and usability (field, lab, and office)
PRE-LECTURE MOVIE
• Drinking water sampling
• Wastewater sampling from wastewater treatment plant