ENGI 9628 – Environmental

Laboratory

Lecture 3:
Environmental Sampling
and Chemical Analysis

Faculty of Engineering & Applied Science

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 Part One:
Fundamentals of
Environmental Sampling

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1. Objectives
The purpose of environmental sampling is:

 To determine the background, natural

concentrations of chemical constituents in the
environment
 To determine the concentrations of harmful
pollutants in the environment

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2. Environmental Sample Design
 Planning and sampling protocols
 Data quality objectives
 Sampling plan

 Environmental sampling strategies

 Where and when
 How many samples

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(1) Planning and sampling protocols

Project Manager

Sampling Data Data User

Lab Analysis
Analysis - - Client
- Field personnel -Chemist Statistician
- Field Engineer - Decision
maker
- Geologist
- Soil specialist QA/QC specialist

Modified from Zhang, 2007. “Fundamentals of Environmental Sampling & Analysis” Wiley

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 Data quality objectives

US EPA 1994 “Guidance for Data Qualitative Objectives” QA/G-4

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 Sampling plan

Samples must be “representative”.

(Zhang, 2007. “Fundamentals of Environmental Sampling & Analysis” Wiley)

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(2) Environmental sampling strategies
Where and When?

 Judgmental
 Simple random
 Stratified random
 Systematic
 Other
 Composite
 Transect

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Judgmental
 Selection of sampling locations based on professional
judgment using prior information on the sampling site,
visual inspection and/or personal knowledge and
experience
 Schedule and budget  tight, early stage when
objective is just screen the area
 Primary representative sampling approach for
groundwater assessment
 No randomization and does not support any statistical
interpretation of sampling results

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Simple random
 Arbitrary collection of samples by a
process that gives each sample unit in
the population the same probability of
being chosen
 Assumes variability of sampled
medium is insignificant – homogenous
population
 Applies for sites with little background
information
 Not applicable for heterogeneous
population
 Ignoring prior information leads to
more samples
 Statistical analysis of data  simple
and straight forward
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Stratified random
 Sampling population is
divided into several non
overlapping strata
 Each strata is more
homogenous than whole
population
 Strata could be temporal or
spatial
 Sample size can be
adjusted

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Systematic sampling
 Systematic random 
subdivides the area into grids
and collects samples using
simple random sampling
 Systematic Grid  easy to
implement
 Uniform distribution over the
space or time domain
 Critical part  choose right
grid spacing

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Other
 Composite sampling
 Sampling cost much less than analytical cost
 Average concentration rather than variability

e.g., Trace metal analysis

 Transect sampling
 Variation of systematic grid sampling  one or more
transect lines across a surface
 Regular intervals along the transect lines

 Parallel or non parallel to one another

e.g., characterizing waste piles and water flow

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Where and when: sampling contaminants
 In space domain  contaminant variations can be in 3
dimensions and hence sampling points can be designed by the
coordinates in 1-D, 2-D or 3-D
 In time domain  there is only one dimension and hence
sampling points can be designed in a time period such as days,
weeks, months or years
 Space and time are of interest – both spatial and temporal
patterns of a contamination
 Obtain representative samples
 Solids - contaminants accumulates at certain depth
 Air - wind velocity and direction
 Water – seasonal variations
 Biological – different species, size, sex
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Environmental sampling strategies
How many samples?
 Largest sample number possible
 Avoid taking too few samples
 No Universal formula
 Simple random sampling
n= 4* variability2 / acceptable error2

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3. Sampling Techniques
 General guidelines common to all
environmental sampling
- Sequence of sampling matrices
- Sample amount
- Sample preservation and storage
- Selection of sample containers
- Selection of sampling equipments

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(1) Sequence of sampling matrices
 Least to most contaminated sampling locations
 Sediment and water at same site  collect water first
 Sampling at different depths  collect surface water
samples first
(2) Sample amount
 Sufficient to perform all required laboratory analyses
and with an additional amount remaining for QA/QC
analysis
 Representativeness factor

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 Water/waste water samples
- 100 ml for trace metals
- 1 L for total organics
- 20~40 L for an effluent acute toxicity test
 Soil/sediment/solid waste samples

- 200 g per sample

 Air samples

- Trial and error method

- 10 m3 may be required per sample

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(3) Sample preservation and storage
 Purpose to minimize any physical, chemical and biological changes
from time of sample collection to the time of analysis

(Zhang, 2007. “Fundamentals of Environmental Sampling & Analysis” Wiley)

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 Analytical Change Preservation
 Cold storage  object during storage

reduce metal
Metals Adsorption to Use plastic
solubility glass wall bottles and
 Chemical addition or precipitation add HNO3 to
pH < 2
pH change  reduce
Oil Adsorption to Use glass
metal adsorption to plastics bottles
glass container walls
Organics Biodegradatio Low pH and
n temp; add
HgCl2 to kill
bacteria
Modified from Zhang, 2007. “Fundamentals of Environmental Sampling & Analysis” Wiley

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 ASAP 6 - 48 h 7 - 28 6 months
 No sample can be stored days
for an extended period of
time pH Color Oil and Metals
(48 h) grease (28
days)
 Maximum Holding Times
(MHTs) – Length of time Salinity Chlorophy Solids Hardness
ll (7 d)
a sample can be stored
(24 -48 h)
after collection and prior to
analysis without DO Turbidity Pesticide
significantly affecting the (24 h) (7 d)
analytical results Tempe Odor (6 h) Total P
rature (28 days)

Modified from Zhang, 2007. “Fundamentals of Environmental Sampling & Analysis” Wiley

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(4) 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

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(5) Selection of sampling equipments
 Made of plastic, glass, Teflon, stainless steel and other
materials for
 Surface water and waster water sampling
 Groundwater sampling
 Soil sampling
 Sediment sampling
 Hazardous waste sampling
 Biological sampling
 Air and stack emission sampling

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4. Environmental Sampling
(1) Soil sampling
 Soft surface soil samples
– scoop or trowel
 1~10 ft – tube sampler
 3 inches ~ 10 ft –auger
sampler
 Will disrupt and mix soil
horizons
 Hard soils – split spoon
sampler

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(2) Surface water and waste 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

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(3) Ground water sampling
 Collected from a well by a bailer
 Bailer – an open pipe with an open top and
a check valve at the bottom.
 Peristaltic pump – rotor with ball bearing
rollers
 Well – with a small diameter and has a
depth limitation of 25 ft

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(4) Sediment sampling
 Scoops and trowels – for sample sediments
around shoreline and slow moving waters
 Ekman dredge – small and light weight (10 lbs)
and collects soft sediments
 Petersen or Ponar dredges

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(5) Hazardous waste sampling
 Ponar or Ekman sampler – sludge
sampling
 Composite liquid waste sampler –
stratified liquid in drums and other similar
containers
 Thief – drum sampling device particularly
useful for grain like materials
 Trier – sampling sticky solids and
loosened soils

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(6) Biological sampling
 Unique and diverse equipments
 Mammals – trapping

 Fish – trawl nets gill nets

 Vegetation – harvested during growing season

 Benthic macro invertebrate samples – Petersen

and Ekman dredges can be used

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(7) Air and stack emission sampling
 Direct reading instruments and type of monitoring
instruments
 Expensive and complex techniques
 Professional stack – testing firms
 High volume, total suspended particle (TSP)
sampling system
 PM-10 sampling system

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5. Quality Assurance/Quality Control
 Standard Methods
- EPA Methods for Air, Water, Wastewater and Hazardous
waste
- SSSA for soil
Project point of view 
 Objectives for accuracy, precision
 Sampling & custody
 Analytical procedures
 Calibration (when, how)
 Data analysis & management
 Corrective action plan

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 Part Two:
Environmental Chemical Analysis

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1. Water Analysis
 Turbidity
 Color
 pH
 Acidity/Alkalinity
 Hardness
 Residual Chlorine and Chlorine
Demand
 Dissolved Oxygen
 Biochemical Oxygen Demand
 Chemical Oxygen Demand
 Solids
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(1) Turbidity

 Result of interference of passage of light through the

water containing suspended materials
 Turbidity determination
Nephelometer ==> scattering of light from particles
Turbidimeter ==> interference to light passage in a
straight line
 NTU is commonly used
 Samples with turbidities > 40 NTU must be diluted

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Schematic diagram of a turbidimeter and a nephelometer
(Zhang, 2005. “Chemistry for Environmental Engineering” )
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(2) Color
 Apparent color  caused by suspended matter 
determined on the sample “as is”
 True color  caused by colloidal vegetable or
organic extracts  remove suspended matter by
centrifugation then determine color of clarified liquid
 1 standard unit of color
= 1 mg/L of Pt (as K2PtCl6)
 Nessler tubes  0 ~ 70 color units
Color-comparison tubes 
(Nessler tubes)
(Zhang, 2005. “Chemistry for Environmental Engineering” )
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(3) pH and acidity/alkalinity
 pH  condition of a solution related to [H+]
pH = - log[H+]  determined by a pH meter
 Acidity/Alkalinity  the ability of natural water to
neutralize base/acid  determined from a titration
 Acidity = (Volume need to reach end point) ×
(concentration of the strong base)
 Mineral acidity = [H+] + [H2CO3] − [OH-] 
titration to pH = 3.7 (methyl orange end point)
 Total acidity = [H+] + 2[H2CO3] + [HCO3-] − [OH-]
 titration to pH = 8.3 (phenolphthalein end point)
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 Alkalinity = (Volume need to reach end point) ×
(concentration of the strong acid)  => titrated with 0.02 N
H2SO4
 Phenolphthalein alkalinity (mg/L) = [OH-] + [CO32-] − [H+] 
titration to pH = 8.3
 Total Alkalinity = Bromcresol-Green alkalinity (mg/L) = [HCO3-]
+ [OH-] + 2 [CO32-] − [H+]  titration to pH = 4.5

End points for Acidity/Alkalinity titration

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(Zhang, 2005. “Chemistry for Environmental Engineering” )
(4) Hardness
 Hardness  caused mainly by divalent metallic cations (e.g.
Ca2+ , Mg2+ , Sr2+ , Fe2+ , Mn2+)  determined by EDTA
titrimetric method
 EDTA = ethylenediaminetetraacetic acid (H4Y)
M2+ + EDTA ==> [M-EDTA]complex
 Total hardness = Ca hardness + Mg hardness (in most cases)

(Zhang, 2005. “Chemistry for Environmental Engineering” ) 44

(5) Residual chlorine
 Chlorine (Cl2)  used for disinfection of water supplies and
wastewater effluent to prevent water-borne diseases
 Free chlorine residuals  Cl2 + HOCl + OCl−
 Combined chlorine residuals  NH2Cl + NHCl2 + NCl3
 Total chlorine residuals = free chlorine residuals +
combined chlorine residuals
 Measurement of total chlorine residuals
Cl2 + 2 I− ==> I2 +2 Cl−
I2 + starch ==> blue color
I2 + 2Na2S2O3 ==> 2Na2S4O6 + 2NaI

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(6) Dissolved oxygen
 The concentration of DO in water is small and
therefore precarious from ecological point of view.
 The dissolution process

O 2 (gas) ⇔ O 2 (dissolved)

 The equilibrium constant is the Henry’s Law constant

KH O (dissolved)
KH = 2
Partial Pressure O2

 DO analysis  the Winkler Method

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DO: Thermal pollution

 River and lake water that has been artificially warmed

can be considered to have undergone Thermal
Pollution. Why?
 Gas solubility decreases with increasing temperature.
 Warm water contains less oxygen than cold water. To
sustain life, most fish species require at least 5 ppm of
DO.
 Consequently, their survival in warm water can be
problematic.

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(7) Biochemical oxygen demand (BOD)
 BOD: amount of O2 required by bacteria to stabilize
decomposable organic matter under aerobic
conditions
 High BOD value = high organic-matter concentration
= poor water quality
 Decomposition of organic matter is a slow process
20 daysdecompose 95 to 99%
of organic matter
5 days  decompose 60 to 70%
of organic matter
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 Measurement of BOD  BOD5
 BOD5 = DO5-DO0

where DO0 = DO before incubation (day 0)

DO5 = DO after 5 days of incubation at 20ºC
(day 5)
 BOD5 for domestic sewage = several hundreds mg/L

 BOD5 for industrial sewage = several thousands

mg/L
 when the sewage is discharged to water  quick
depletion of oxygen

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 initial stage (Zhang, 2005. “Chemistry for Environmental Engineering” )

==> DO curve drops (i.e. rate of O2 consumption by

bacteria > rate of reaeration with atmosphere)
 at the point where [DO] = minimum
==> rate of consumption = rate of reaeration
 beyond minimum point
==> rate of consumption < rate of reaeration (DO level
eventually returns to normal)

This sequence is called "natural self-purification of water"

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(8) Chemical oxygen demand (COD)
 COD  a measure of total organic strength of wastes
 The basis for the COD test  nearly all organic compounds can
be fully oxidized to carbon dioxide with a strong oxidizing agent
under acidic conditions.
 COD determination  potassium permanganate (KMnO4) was
used for years  potassium dichromate (K2Cr2O7) becomes the
most effective oxidant now (it is relatively cheap, easy to purify,
and is able to nearly completely oxidize almost all organic
compounds)

CnHaObNc + d Cr2O72− + (8d+c) H+ 

n CO2 + [(a + 8d − 3c)/2] H2O + c NH4+ + 2d Cr3+
where d = 2n/3 + a/6 − c/2
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(9) Residue (Solids)
 Usual definition of solids = residue upon evaporation and
drying at 103 ~105 ºC

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2. Soil Analysis
 Physical properties  Chemical analysis
 Particle size  Soil pH
 Density  Soil organic matter
 Porosity  Cation exchange capacity
 Texture
 Soil contaminants
 Heavy metals (e.g. Pb, Cd, Cr)
 Organic pollutants (e.g. Pesticides, Petroleum
hydrocarbons)

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(1) Soil particle size

Sand

Clay Silt Fine Coarse Gravel

2 µm 20 µm 200 µm 2.0 mm
Soil Non-soil

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(2) Soil density

 Soil particle density

< 1 g/mL for organic matter, > 5 g/mL for
some metals oxides; average 2.5 ~ 2.8 g/mL
 Soil bulk density
 Include the pore spaces between particles
 Smaller than particle density; average 1.2
~1.8 g/mL

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(3) Porosity and texture
 Porosity
Pore space (%) = 100 -
(bulk density/particle
density)*100
 Texture
 Clay
 Sand
 Silt

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(Zhang, 2005. “Chemistry for Environmental Engineering” )
(4) Soil pH
 How acidic or alkaline the
soil is
 0 to 14
 pH = -log [H+]
 At pH 6 there are 10x
more H+ than at pH 7
 At pH 5 there are 100x
more H+ than at pH 7

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 (5) Soil organic matter
 Soil organic matter includes
 Humic substances (humic Soil Type Organic Mater
acid, fulvic acid, and humin) Content
 Fats, resin, and waxes
Agriculture 1–5%
 Polysaccharides soils
 Amino acids
Forest soils > 10 %
 Main constituents
C (52 - 58 %), O (34 – 39 %),
H (3.3 – 4.8 %) and N (3.7 – Peat Soils > 20 %
4.1 %) with other prominent
elements being P and S

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 (6) Cation exchange capacity
 Capacity of a soil exchange of
positively charged ions between the
soil and the soil solution
Soil Texture CEC
 Clay particles and organic matter
have negatively charged sites that (meq/100g soil)
can hold positively charged ions on Sands 3 - 20
their surfaces
Loams 10-15
 Expressed in meq/100g of soil
 1 m eq of CEC has 6.02 × 1020 Silt loams 15 - 25
adsorption sites Clay and clay 20 - 50
 CEC of most soils increases with an loams
increase in soil pH Organic soils 50 - 100
 Highly dependent upon soil texture
and organic matter content
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(7) Soil contaminants

 Inorganic contaminants
(e.g. heavy metals) 
AAS or AES analysis
 Organic contaminants
(e.g. Petroleum
hydrocarbons and
pesticides)  GC
analysis

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 Part Three:
Information Sources on
Environmental Sampling and
Analysis

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 Water/Soil /Sediments Sampling and
Analysis
 US EPA Office of Water Analytical Methods online
 US EPA's SW-846 Online Test Methods for Evaluating Solid Waste Physical/Chemical Methods
- all approved methods and draft update IV are available
 US EPA Technical Support Centre for Monitoring and Site Characterisation and National
Laboratory Accreditation Programme
 FAQ's on Oil & Grease analysis from US EPA
 Canadian sampling strategy for Sediments, Fresh Water and Effluent, Lake Sediments,
Stormwater
 USFDA Pesticides, Metals, Chemical Contaminants & Natural Toxins
 Guidelines for Soil Sampling
 FAQ's about Soil and Plant Analysis
 DOE Methods for Evaluating Environmental and Waste Management Samples
 Environmental analysis techniques from the Association of Official Analytical Chemists
 Free software for Environmental Sampling from American Chemical Society
 US source on Bethnic Macroinvertebrate Identification
 US EPA on Biological Indicators and Bethnic Macroinvertebrate identification
 Canadian information on Biological Sampling, Invertebrate Sampling, Fish and Fish Tissue,
Algae, Microbiology, Aquatic Pathogens, Aquatic Plants and Weeds
 Canadian Water Sampling Manuals
 US Source on Environmental SOPs
 How to carry out ecological sampling
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Air Sampling and Analysis
 US based OSHA Manual on Personal Air Sampling, Sampling for Surface
Contaminants, Sample Shipping and Handling, indoor air quality
investigations
 NIOSH Manual of Analytical Methods
 Air sampling information on the SKC Website with Sampling Guides
 US EPA Ambient Air Monitoring Information, air toxics methods,
inorganics methods, open path analysers, air pollution training institute,
index to EPA test methods
 Fast Analysis of Hazardous Organics in Fire and Chemical Accidents
by Mobile GC/MS
 WORKPLACE ATMOSPHERES - GENERAL REQUIREMENTS FOR
THE PERFORMANCE OF PROCEDURES FOR THE MEASUREMENT
OF CHEMICAL AGENTS INTERNET AND OTHER SOURCES OF
METHODS FOR THE ASSESSMENT OF WORKPLACE AIR
QUALITY

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Laboratory Quality Control
 OECD Series on Principles of Good
Laboratory Practice and Compliance
Monitoring
 UK based Aqua check International
Proficiency Testing for Chemical Analytical
Laboratories

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Environmental Quality Standards

 US EPA Water Quality Criteria

 US EPA Air information including Ambient Air
Quality Standards
 Netherlands - Contaminated Land at the Ministry of
Housing, Spatial Planning & Environment,
Contaminated Land Guidance and Contaminated
Land Tables of Values
 US EPA soil screening guidelines
 US survey of Soil and Groundwater Clean-up
Standards
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