On-Site Training Program
Industrial Wastewater Sampling
o Safety
o Sampling Procedures
o Required Events
o Sample Handling
o Sample Containers
o Documentation
o Collection Volume
o Labeling and Shipping
o Preservation & Hold Time
o QC/QA
o Sampling Equipment
Events can be customized for grab sampling, composite sampling,
low-level mercury , bioassay, and other specialized types of sampling
Alloway is an approved Ohio EPA contact hour provider.
Introduction

The most precise and
accurate analytical
measurements are
worthless and even
detrimental if performed
on a sample that was
improperly collected and
stored or was
contaminated in the
process (OEPA, 1978).
Introduction


Four factors that affect quality of environmental data
 Sample Collection
 Sample Preservation
 Analyses
 Data Documentation
Improper actions in any one area may result in:
 Poor data
 Leading to poor judgments
4
Introduction

A written sample-handling plan is essential before
initiating any program. It will answer the following:
 What parameters will be analyzed?
 Frequency of collection and sample type?
○ Grab
○ Composite
 What types of bottles?
 What type of chemical preservation?
 Is thermo preservation required (ice) ?
 What is the holding time for each parameter?
 What will be documented on the Chain of Custody?
 How will samples be delivered to the laboratory?
Frequency Definitions

Required frequency for sampling is listed in the
NPDES permit and shall be collected accordingly
 Daily, Weekly, Monthly, Semi-Annually, or
Annually
 Depending on plant conditions and continuous
monitoring, some of the analyses may be
required more frequently.
 All Samples taken according to proper
protocol must be reported to the respective
agency
Types of Samples:
NPDES Frequency Definitions

Weekly sample collection requirements
 OEPA defined weeks
○ Week 1 – days 1 thru 7
○ Week 2 – days 8 thru 14
○ Week 3 – days 15 thru 21
○ Week 4 – days 22 thru 28
7
Types of Samples:
NPDES Frequency Definitions cont’d

Quarterly (4 times per year)
 March, June, August, December

Semi-annual (2 times per year)
 June & December

Annual (1 time per year)
 September
Safety





Proper PPE at the terminal
 Safety Glasses
 Safety Shoes
 Hard Hat
 * Nomex
Positive Attitude
Maintain a Safe Work
Environment
Protect Yourself and Your
Colleagues
Use Chemicals Safely
Sampling Kits

Sampling Kits
 EPA-approved materials,
cap liners, and
acceptable preservatives
 Chain of Custody
 Custody seal(s)
 Samples on ice sticker
 Field log form
 Return shipping labels
 pH Buffers/Rinse solution
 Non-Powdered Gloves
 ICE
Sample Preservation



Reference 40 CFR 136 Table II – Required
Containers, Preservation Techniques, and Holding
Times
Complete preservation is impossible
Minimize the deceleration of the physical,
chemical, and biological changes by awareness
of nature of changes
 The effect of one will ultimately have an effect on all!
Sample Preservation

Nature of Changes (Physical):
 Physical: Sample Environment has been altered
○ Sampling Equipment
 Introduce contaminants from outside
○ Sample Containers
 Residue from previous samples
 Certain cations are subject to adsorption on, or
exchange with, cations in the walls of both glass
and plastic containers
- Plastic: Al, Cd, Cu, Cr, Fe, Pb, Mn, Zn and Ag
- Glass: Na, Bo, Si
Sample Preservation

Physical Changes (con’t)
 Temperature
○ Elevated
 Solubilize precipitated material
 Increase decomposition of organic materials
- Affect the NO3, NO2, NH3, BOD, Phenol, etc.
 Headspace
○ Zero headspace for volatile organic compounds
○ Microbiological samples should have air space for
aeration and mixing
Sample Preservation

Nature of Changes (Chemical):
 Chemical
○ Algae creates photosynthetic activity
 Affects DO, pH, and various other chemical equilibria
○ Metals can precipitate or solubilize, leach from
container walls, or be reduced or oxidized
 Affects the color, odor, or turbidity
Sample Preservation

Nature of Changes (Biological):
 Biological
○ Temperature
 Decreased
- Generally retard biological changes (ideal!)
 Increased
- Changes chemical composition
- Increased decomposition
Sample Preservation

Biological Changes (con’t)
 Changes in the dissolution of gases
 Consumption of organic material
 Production of cellular matter
 Formation of chemical byproducts (CO2,
NH3, and H2O)
Sample Preservation
3
primary methods of
preservation:
Refrigeration
pH Adjustments
Chemical Additions
Sample Preservation
Refrigeration
 pH Adjustment

 Decreases biological and chemical activity
○ i.e. H2SO4
 Combined with refrigeration it preserves and
pretreats oil & grease
 Retards bacterial action
- COD, TOC, etc.
Sample Containers

Reference 40 CFR 136 Table II – Required Containers, Preservation
Techniques, and Holding Times
• “P” for
polyethylene
• “G” for Glass
• Polypropylene or
other
autoclavable
plastic
• “LDPE” for low
density
polyethylene
• “PA” for any
plastic that is
made of a
sterilizable
material
• “FP” for
fluoropolymer
• PTFE; Teflon®
polytetrafluoroet
hylene
Sample Containers

New or used
 New
○ Most manufacturers certify that their
containers are “clean” and may be used
without washing or sterilizing
 Recycled (Used) sampling containers
○ At a minimum, sampling containers and caps
must be
 Washed with non-ionic and nonphosphate detergent
 Rinsed with hot tap water
 Rinsed with distilled water
Sample Containers

Specific to parameters:
 Oil & Grease
○ Easily adheres to a number of materials
 Shall be collected in a 1-L, wide-mouth glass jar with a
polytetrafluoroethylene (Teflon®) screw lid liner
- Wide mouth allows analyst to rinse the inside walls of the
jar with solvent during analysis
○ Containers shall not be pre-rinsed with the sample
 Adherence of oil & grease to sampling container
Sample Containers and Volume

Container requirements should be
specified in the sampling program and
may depend on:
○ Volume
○ Interference problems anticipated
○ Type of test being performed
○ Cost
○ Availability
○ Resistance to breakage
Sample Volume
Fill appropriate
container completely,
allowing necessary
headspace when
mixing is required
Volatile Organic Compounds
and Toxicity samples must be
collected at zero headspace
Provide sufficient sample appropriate to the
analytical method and detection level desired
Sampling Equipment

The most accurate data
on a waste stream
would be obtained by
collecting and
analyzing the entire
flow from a discharge
point.
Sampling Equipment
Sample Collected Shall Be:
 Representative to the total discharge
 Sufficient volume to represent the source but small enough to be
handled in the laboratory
 Collected in accordance to the defined sampling plan
○ Quality of sampling is ensured by trained sampling personnel
 Two types of sampling equipment:
 Manual Collection
 Automatic Collection
○ Uniformity ensures samples collected were consistently and
accurately collected
 Collected by same method
 From same point
 Programmed time intervals
○ Reflect the condition in the source

Sampling Equipment

Manual
 Versatile, inexpensive, and simple to
use
○ Bottle Samplers
 Dippers
 “Jar on a Rope”
 Swing Samplers®
- Allows collection at various
angles, including 90°
(Nasco)
 Weighted Bottle Samplers
- Glass bottle, weighted
sinker, bottle stopper, line to
lower and raise the container
Sampling Equipment QA/QC

Equipment and Maintenance SOPs
 Composite Sampler Cleaning
○ How to perform it?
 What kind of soap?
- Phosphorus based not good idea for samples
being collected for phosphorus analysis
- Alconox/ Liquinox
○ How often to perform?
○ Where to document it was performed?
Sampling Equipment QA/QC

Equipment and Maintenance SOPs
 Specify the frequency of composite sampler




calibrations
Specify the calibration procedures
○ Timer calibrations
○ Flow calibrations (volume)
Specify how to document calibrations
Specify how to charge sampler batteries
Specify how to ensure batteries have charge
Sampling Equipment QA/QC

Parameter
General
Automatic*
Samplers
Enter make, model,
and serial or
identification
number for each
sampler in a log
book
Daily
Quarterly
Portable samplers:
check volume
setting; stationary
samplers on a
weekly basis
Sampler timer
check, checking
clock time setting
versus actual time
interval;
Contamination
Check
Equipment Calibration
 Calibration Checks
○ *Quality Assurance procedures on sampling equipment according to U.S.
EPA, 1982
 Blank Checks
○ Contamination checks shall be performed using distilled water through the
sampler and sampler equipment.
 Blank contamination check sampling shall be performed identical to the sampling method
used in the field.
Sample Documentation –
Bottle Labeling
Sampling containers should be prepared and
labeled prior to sample collection
 Labels shall be written on using indelible ink
 Sampling information to be documented on bottle
labels shall include:







Predetermined location ID
Date of sample collection
Time of collection
Sampler initials
Type of sample collected
Preservative(s) added
Sample Documentation –
Bottle Labeling
Writing directly on sample bottles may result in ink
leaching through the sampling container and could
result in contamination
 Sample labels shall:

 Adhere to sample container properly
 Removable
○ If sample container is to be reused
 User friendly
○ Allows enough space for documentation
○ Works well in inclement weather
Sampling Procedure
Sampling Procedure
ALWAYS CHECK SAMPLING
SPECIFICS IN YOUR PERMIT
 Grab Samples
 Discreet
○ Collection not to exceed
15 minutes
 Obtained during the first 30
minutes of a discharge
○ To determine max.
concentration of a
pollutant
 Must be conducted for pH,
temperature, cyanide, total
phenols, residual chlorine,
oil & grease, fecal coliform

Sampling Procedure Guidelines
SOP
Specify
Location
Representative
• Proper Sampling Techniques and
Guidelines shall be established prior
to sample collection
• Defined Sampling Site
• Sampling must represent the actual
process or true flow stream
Sampling Procedure

VOC Sampling Guidelines
 Samples collected for the analysis of
volatile organic compounds (VOC)
should be taken from areas of low
turbulence to reduce the amount of
entrapped air in the sample.
 VOCs could be driven off to the
atmosphere (as outgas) in turbulent
sections of the flow stream
 The “no head space” requirement for
VOC sample containers, meaning no air
space in the container, is important to
ensure that all VOCs are kept in solution
for proper analysis
Sampling Guidelines

Avoid taking samples at points where
solids settling occurs or floating debris is
present.
 These situations occur normally in quiescent
areas where the velocity of the flow has
decreased.

Avoid sampling non-representative
deposits or solids accumulated on channel
or tank walls.
Sampling Guidelines
Where samples are to be collected from
flowing pipes, keep the sample lines as
short as possible and with a minimum
number of bends
 To ensure that the sample is
representative, prevent settling by keeping
samples thoroughly mixed throughout the
collection and measurement procedure

Sample Hold Times

Composite
 Set of grab samples composited in the field or
laboratory
○ Holding time begins at the time the last grab
was collected
 Sample collected with an automated sampler
○ Holding time begins at the time the last

sample was collected
Grab
 Begins at the time of collection
Sample Hold Times
Analyte
pH
DO
Fecal
Coliform
Total
Coliform
BOD
(CBOD)
Hold
Time
Immediately
Immediately
6 Hours
30 Hours
48 Hours
• What is the hold time for:
•Cyanide?
•Total Suspended Solids?
•Volatile Organic Compounds?
•Semi-Volatile Organic Compounds?
Sample Handling
 Specified in 40 CFR 136.3 for NPDES
Analyte
Bottle
Type
pH
Preservation
Temp
Holding
Time
BOD or CBOD
Plastic or Glass
NONE
Cool, 6˚C
48 Hours
TSS
Plastic or Glass
NONE
Cool, 6˚C
7 days
Metals (Except
Hg and Cr6)
Plastic or Glass
HNO3
pH < 2
NONE
6 months
NH3
Plastic or Glass
H2SO4
pH < 2
Cool, 6˚C
28 Days
NO3/NO2
Plastic or Glass
H2SO4
pH < 2
Cool, 6˚C
28 Days
Sample Handling

Chain of Custody
 A sample is under custody if:
○ It is in your possession, or
○ It is in your view, after being in your possession, or
○ It was in your possession and then you locked it up to prevent
tampering, or
○ It is in a designated secure area
 The field sampler is personally responsible for the care and custody of the
samples collected until they are transferred
 During transfer of possession of samples the involved persons
relinquishing and receiving must:
○ Sign
○ Date
○ Note time of transfer on chain of custody
Sample Handling

Sample Acceptance Policy
 Chain of Custody Review for:
○ Client name
○ Contact name
○ Sample identification
○ Project identification
○ Sample location
○ Date & Time of Collection
○ Identification of collector
○ Preservations
○ Sample type (grab or composite)
○ Proper documentation of time line and custody
Chain of Custody Example
Reporting Quality Data

Verifying Quality of Data
 Representative sample
collection
 Sample Handling
 Document Control
 Laboratory Analysis
○ MDL Studies
○ Calibrations
○ QC Activities for
Accuracy and Precision
 ICV, CCV, Blank, MS/
MSD
 Reporting to required
Agency
Conclusion

Planning
 Observe the outfall/discharge
 Obtain samples first week of month
 Know the parameters

Correct sampling procedures
 Calibration
 Obtain sample

Documentation
 Field Log
 Chain-of-custody

Shipping of samples
 Shipping label
 Ice
800-436-1243
[email protected]
www.alloway.com