United States	Office of Solid Waste and
Environmental Protection	Emergency Response	September 2001
Agency	(5201G)	www.ep3.gov/superfund
Superfund
4vEPA Chemistry for Environmental
Professionals - Applied
(165.21)
Student Manual
' \
A /.. Recycled/Recyclable
7~ \ \ \ Printed with Soy/Canola Ink on paper that
' / contains at least 50% recycled Fber

-------
Agenda
CHEMISTRY FOR ENVIRONMENTAL PROFESSIONALS - APPLIED
New York, New York
January 29 - 30, 2004
COURSE DIRECTOR: Tom Savin	Tetra Tech NUS, Inc.
INSTRUCTORS:	Steve Okulewicz Tetra Tech NUS, Inc.
Tom Bobowski Nobis Engineering Inc.
DAY and TIME	SUBJECT	SPEAKER
Thursday, January 29
8.00
- 8 10
a.m
Orientation/Introduction
T.
Savin
8.10
- 9 00
a.m.
Process Chemistry - Pesticide Formulation
S.
Okulewicz
9.10
- 10.00
a.m.
Process Chemistry - Municipal Landfills
T.
Bobowski
10*10
- 1100
a.m.
Process Chemistry - PCBs
S.
Okulewicz
11:10
- 12.00
p.m.
Process Chemistry - Wood Preserving
T.
Savin
12.00
- 1:00
p.m.
LUNCH


1:00
- 3.00
p.m.
Fate and Transport in the Vadose Zone
S.
Okulewicz
3:10
- 4:00
p.m.
Fate and Transport in Groundwater I
T.
Bobowski
4:10
- 5:00
p.m.
Fate and Transport in Groundwater II
T.
Bobowski
Friday,
January 30



8:00
- 1000
a m.
Data Usability
T.
Bobowski
10:10
- 11.30
a.m.
Data Quality Objectives
T.
Savin
11.30
- 12:00
p.m.
Closing Remarks/Evaluation
T.
Savin
1

-------
^t0 sr«v
UNITEO STATES ENVIRONMENTAL PROTECTION AGENCY
CINCINNATI, OHIO 45268
It is the policy of the U.S. Environmental Protection Agency's
Environmental Response Training Program to maintain a learning
environment that is mutually respectful.
Please refrain from any actions or comments, including jokes,
which might make another class participant feel uncomfortable.
The Course Director is prepared to take appropriate action to
ensure your full participation and benefit from our training.
Please present your concerns to the Course Director, or to the
U.S. EPA Project Officer, Bruce Potoka at (513) 569-7537.

-------

-------
FOREWORD
This manual is for reference use of students enrolled in scheduled training courses of the U.S.
Environmental Protection Agency (EPA). While it will be useful to anyone who needs information
on the subjects covered, it will have its greatest value as an adjunct to classroom presentations
involving discussions among the students and the instructional staff.
This manual has been developed to provide the best available current information; however,
individual instructors may provide additional material to cover special aspects of their presentations.
Because of the limited availability of the manual, it should not be cited in bibliographies or other
publications.
References to products and manufacturers are for illustration only; they do not imply endorsement
by EPA.
Constructive suggestions for improvement of the content and format of the Chemistry for
Environmental Professionals (165.21) manual are welcome.

-------
CHEMISTRY
FOR ENVIRONMENTAL
PROFESSIONALS -
APPLIED
presented by
Telra Tech NUS, Incorporated
for the
U.S. Environmental Protection Agency's
Environmental Response Center
(Contract #68-C-03-039)

Environmental Response

Training Program (ERTP)
.UisVepa
—p-™
U.S. Environmental Protection Agency
I
,OSw&S:
Office of Solid Waste and Emergency

Response (Superfund)
UOEftR1 .
Office of Emergency and Remedial
~'T~
Response
.y E.RG;>
Environmental Response Center
ERTP Training Courses
9 Are offered tuition-free for environmental
and response personnel from federal,
state, and local agencies
® Vary in length from one to five days
® Are conducted at EPA Training Centers
(Cincinnati, Ohio or Edison, New Jersey);
and at other locations throughout the
United States
CHEMISTRY FOR ENVIRONMENTAL PROFESSIONALS - APPLIED
PAGE 1

-------
Course Materials
®	Student Registration Card
®	Student Evaluation Form
©	Course Agenda
®	Student Manual
Course Focus
® Basic chemistry
-	Inorganic chemistry
-	Organic chemistry
® Analytical chemistry
o Chemical processes
® Chemical fate and transport
o Data evaluation
Process Chemistry
® Survey of four industries
-	Process overview
-	Key chemicals
-	Process details
-	Modes of release
-	Analytical considerations
PAGE 2		¦ ¦	CHEMISTRY FOR ENVIRONMENTAL PROFESSIONALS—APPLIEP
R02/03

-------
Chemical Fate and Transport
•	Vadosezone
•	Groundwater
Data Evaluation
•	Data usability
•	Data quality objectives
CHEMISTRY FOR ENVIRONMENTAL PROFESSIONALS - APPLIED ^- 1	PAGE3

-------
Section 1

-------
Wood Preserving
Ji

IW
WOOD
PRESERVINC
¦N

Wood Preserving
Objectives
•	List three major chemical preservative
systems
•	List key chemicals associated with
wood preserving
•	Describe the pressure treating
process
Wood Preserving
Objectives
•	List major modes of release to the
environment
•	Identify analytical methods useful for
detecting wood preservative
contaminants in the environment
CHEMISTRY FOR ENVIRONMENTAL PROFESSIONALS-APPLIED
PAGE 1

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PAGE 2	CHEMISTRY FOR ENVIRONMENTAL PROFESSIONALS- APPLIED

-------
Wood Preserving
a
Process Overview
•	SIG: 2491, NAICS 321114
•	Used by construction, railroad,
and utilities industries
•	6.5 billion board ft/yr (2000)
•	486 U.S. facilities (1992)
- 307 employ 20 or fewer
•	90% by pressure treating process
Process Overview
Major chemical preservative systems
•	Organic (oil-borne):
-	Creosote (15%)
-	Pentachlorophenol (PCP) (6%) systems
•	Inorganic (water-borne) 78%
-	Chromated copper arsenate
-	Ammoniacal copper-zinc-arsenate
(ACZA)
-	Ammoniacal copper arsenate (ACA)
CHEMISTRY FOR ENVIRONMENTAL PROFESSIONALS-APPLIED
PAGE 3

-------
Wood Preserving
Key Chemicals

1999

ATSDR Rank
Arsenic
1
Oil (BTEX)
5, 48, 62, 87
PAHs
8, 9, 10, etc.
Chromium
16, 73
Creosote
21
PCP
44 .
Zinc
70
Dioxins/furans
67, >100, etc.
Copper
>100
Diesel oil
>100
Standard Process Schematic
VACUUM & BQELER
EMISSIONS SLOWDOWN
VOCs AMMONIA,
-si'.': i::ir:-. :^R80R.Pi£:;
, arsb^ics rrc
UNTREATED LUMBER,
PCP, CREOSOTE, CCA, Q^jv£\
STEAM. DIESEL OIL 		0_-\
COAL TAR 1—JVv
PETROLEUM OIL, ETC,
CHROMIUM, PAHs,
ARSENIC, ZINC
P ^> TREATED LUMBER
B ~> PCP, CREOSOTE, CCA
(RECYCLED)
—'W^> CONTAMINATED DEBRIS
^ FILTERS, METAL-
BEARING SLUDGE.
ORGANIC SLUDGE,
SPENT CARBON
Pressure Treating Process Details
STORAGE
OF
FFtfiHLV.
TffitTFO
WOOD
• :


:'RerOf-.l
cnmf'SP.
HXH 1
: Wm M

mtmtm

P-vEO CONTfilMMEr/r area
CHARGING -PE»*
C P IP F -
*\ CURBS
^ CONCENT FATE
' PROCE>>
WAT ER
PAGE 4
CHEMISTRY FOR ENVIRONMENTAL PROFESSIONALS - APPLIED

-------
' 	: ' y	. ' .	- - _		¦ 	Wood Preserving
CCA Process Description
(Bethell or Full-cell Process) F 50-60% cca
WORklllG ^	-CONCENTRATE
SOLUTION	\/Cut'~ {
)^HT	":-TR0"'fEf
V .	J !
«[0+1	' »
tZZWte	*
9>M* :::	' *
>: ILINE
RETORr	JW •	' J
CVUNPER	•	f ;
WWK	."**'¦	¦
fit IPv.v,	
STORaGC	.
of •	mtmssm ¦¦
PSE3H.Y-	'	x :	k ¦
TREATED	::x
.s^-V "	P j.'EO CONTAINME'/T -RE a
..«•	s\«
./y.\>s	CHARGING AREA
\C'JR &i
CHEMISTRY FOR ENVIRONMENTAL PROFESSIONALS- APPLIED	PAGE 5 |

-------
Wood Preserving

-------
. , . :	 Wood Preserving
Stepl: Preparation
STGRXCE
Of
f Rl SHtY
TFf A te 0
WOOD
: V&trt
'& P£"0-T
: CVUWDER
WORKING
SOLUTION
HfcH ...
CONCENTRATE
pa#w**e- ^


PAVED CONTAINMENT AREA
s A
CHARGING APE A

DRIP PAD
^\CUR BS
CHEMISTRY FOR ENVIRONMENTAL PROFESSIONALS - APPLIED 	PAGET

-------
Wood Preserving
Step 2: Vacuum
SfQRAOS
Of
FRfFSHLr.
TpEATCO
WOOD

VACUUM
*u*r ^
4w»wsw*£:::
*"«*«!•
$*3R?$ V
V^exr&wo*:
PM/EO CONTAINMENT AREA
CONCENTRATE
TRANSFER
LIME
PROCESS
WATER .

CHARGING AREA


Pressure = -3 in Hg absolute
Temperature = 70°F

Step 3: Pressurization
STORAGE
op
FRESHLY-
TREATED
WOOD

VACUUM /
• -PUMfcx.-v#
• -T
HIGH
PRESSURE '
«* *npump
V	i
V	r *
jcu --
;
v y '-y '

PAVEO CONTAINMENT AREA
CONCENT RATE
CHAPGING AREA

C'ftlP PAC-
*\ CURBS
Pressure = 175 psi (5-8 mm j
Temperature = 70°F
PAGE 8
CHEMISTRY FOR ENVIRONMENTAL PROFESSIONALS-APPLIED

-------
Wood Preserving
Step 4: Depressurization
WORKING
50 LIT ION -
STORAGE
SHkY-i.
TREATS Q:
sA/OGQ ': :

• - W?* -- -	¦¦¦J
>	1
***«*«. S,^ ,

PAVED CONTAINMENT AREA

•' CHARGING AREA
V y^Jssrj S
-CONCENTRATE
PROCE j'
WATER

DRIP PAD
\ CURBS
Pressure = 175 psi to 1 atm
(up to 2 hours)
Temperature = 70*F
Step 5: Final Vacuum
VENT^J'
WORKING
SOLUTION
STOftAOE ;
fPl iHLV.
T ftSft TC Cj
WOOD
VHtU 
-------
Wood Preserving
Step i:
$TOKAoe
OF
PPf jHLY-
Repeat of Cycle
PA'.eOCOMTAlfMEf/T AREA	WATER
DRIP PAD
Pressute - 1 atm
Temperature = 70eF
PAGE 10
CHEMISTRY FOR ENVIRONMENTAL PROFESSIONALS - APPLIED
-------
Composition of Commercial Grade and
Purified Grade Pentachlorophenol
ANALYTICAL RESULTS

Commercial
Purified
Component
(Dov.icide7)
(Dowicide EC-7)
Pentachlorophenol
88.4%
89.8%
Tefrachlorophenot
4.4%
10.1%
Trichlorophenol
0.1%
0.1%
Chlorinated phenoxyphenol
6.2%
-
Octachlorodioxin
2500 ppm
15 ppm
Heptachlorodioxin
125 ppm
6.5 ppm
Hexachlorodioxin
4 ppm
1.0 ppm
Octachlorod ibenzofuran
80 ppm
1.Q ppm
Heptachlorodibenzofuran
80 ppm
1.8 ppm
Hexachlorodibenzofuran
30 ppm
1.0 ppm.
Source: EPA 1978
Technical PCP Constituents
OH
a^SrCi
ci
Pentachlorophenol
OH
CI.^T\,CI
85-90%
4-8%
ci-^^-ci
2,3,5,6-T etrachlorophenol
CI
Higher chlorophenols
-0.1%
CI "V" o'"vr^"CI
CI CI
Dioxin
(octa-, traces of hepta, and
hexachlorodioxin)
Major Chemical Components of
Creosote Produced in the U.S.
Compourd or Component Percentage*
Compound or Component Percentage*
Naphthalene
3.0-17.0
Methyl fluorenes
3.0
Methyl naphthalene
2.1-10.0
Phenanthrene
21.0
Diphenyl

Anthracene
2.0
dimethylnaphthalene
-
Carbazole
2.0-5.1
Biphenyl
0.8-1.9
Methylphenanthrene
3.0
Acenaphthene
7.6-9.0
Methyl anthracenes
4.0
Dimethylnaphthalene
2.0
Fluoranthene
10.0-11.8
Diphenyloxide
—
Pyrene
8.5
Dibenzofuran
5.0
Benzofluorene
2.0
Fluorene-related

Chrysene
3.0
compounds
6.0-10.0




'Volume may vary significantly
Source: EPA 1990. 1992
CHEMISTRY
FOR ENVIRONMENTAL PROFESSIONALS - APPLIED
PAGE 11:
-------
Structure of the Major Components
of Creosote
Naphthalene
Fluoranthene
Pyrene
Physical Properties of Creosote
Compounds
Com Bound
Molecular
Weiaht
Solubility
Specific
Gravity
Vapor
Pressure (20 C)
Boiling
Point*
benzene
78.11
1780 mg/!@ 20:'C
0.88
76.0 mm
176 F
naphthalene
128.0
insol
1.10
0.5 mm
424 F
pyrene
202.26
0.16@ 26 C
1.27
1.0 mm
739 F
chrysene
228.20
0.06 mg/l @ 25'C
1.27
not available
488 C
benzo(a)
anthracene
252.30
0.003 mg/l
1.35
1.0 mm
590-594^
'condition
unspecified
Source: Verschueren, 1977 (Occupational Health Services)
CCA and ACZA Formulations

Compound (%)
Preservative
Chromium (VI)
as CrO,
Copper
as CuO
Zinc
as ZnO
Arsenic
as ASjO.
CCA
Type A
Standard
Range
Type B
Standard
Range
TypeC
Standard
Range
65 5
59.4-69	3
35 3
33.0-38 0
47 5
44.5-50.5
18.1
16 0-20.9
19.6
18.0-22.0
18.5
17.0-21.0

16.4
14.7-19 7
45 1
42.0-48.0
34.0
30.0-38.0
ACZA
Standard
Range

50.0
45.0-55.0
25.0
22.5-27.5
25 0
22.5-27.5
Source: American Wood Preservers' Association 1992
PAGE 12	CHEMISTRY FOR ENVIRONMENTAL PROFESSIONALS - APPLIED
R12/02
-------
Modes of Release
Continuous release
•	Wastewater (F032, F034, F035)
•	Oil/water separator sludge (K001)
•	Filtration sludge (D004, D007,
D037, etc.)
Modes of Release
Fugitive emissions
•	Retort outwash
•	Drip pad/storage pad drippage
•	Off-loading spills
•	Stormwater runoff
•	Discarded, unused commercial
products (F027, U051, P011, etc.)
CHEMISTRY FOR ENVIRONMENTAL PROFESSIONALS-APPLIED
PAGE 13
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Wood Preserving
-------
Wood Preserving
-------
Wood Preserving
-------
Modes of Release
Hazardous Waste Streams
• Wastewaters (ww), process residuals,
drippage
-	F032 - PCP processes
-	F034 - Creosote processes
-	F035 - Inorganic preservatives
-	K001 - Bottom sediment sludge from
ww processes for creosote
and/or PCP facilities
Modes of Release
	Hazardous Waste Streams
•	Characteristic wastes
-	D004 - Arsenic
-	D007 - Chromium
-	D018 - Benzene
-	D037- PCP
•	Discarded, unused commercial products
-	F027-PCP
-	U051 - Creosote
-	Inorganics, e.g., arsenic pentoxide
CHEMISTRY FOR ENVIRONMENTAL PROFESSIONALS -APPLIED
PAGE 17
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Wood Preserving
Modes of Release
Typical Hazardous Waste Composition
Waste

Description: K001-C (Creosote type)

Allied Chemical's Birmingham, Alabama Plant, Bottom,
Sediment Sludge

Analysis: Soil
30.0%
Water
20.0
Wood chips
10.0
Naphthalene
4.0
. Phenanthrene
3.5
Fluoranthene
2.5
Other active organics
30 0

100%
Ash content
12-51%
Heating value 10,000-11,000 BTU/lb
Volatile matter
57-81%
Modes of Release
Typical Hazardous Waste Composition
Waste


Description:
K001 Pentachlorophenol (PCP) Type

Allied Chemical's Richton Mississippi Plant, Bottom,

Sediment Sludge

Analysis:
Soil
40.0%

Water
30.0

Wood chips
10.0

Active organics*
30 0


100%

Ash content
12-51%

Heating value
3,800-8,300 BTU/lb

PCP
970-3,800 ppm
*Tetra-and pentachlorophenols, benzene, toulene, and PAHs
Analytical Considerations
Laboratory Methods
® Inorganic
-	Total metals: AA or ICP
-	TCLP for RCRA characteristic
• Creosote
-	Analyze for PAHs
-	HPLC orGC/MS
® PCP
-	SW-846 8250/8270
-	TCLP
PAGE18
CHEMISTRY FOR ENVIRONMENTAL PROFESSIONALS-APPLIED
-------
Wood Preserving
Analytical Considerations
Field Screening Methods
• Inorganic
-	X-ray fluorescence (XRF)
-	Organics
-	Immunoassay test kits (PCP, PAH,
TPH, etc.)
-	Portable GC or GC/MS
CrpM- hum ,^4	^
CHEMISTRY FOR ENVIRONMENTAL PROFESSIONALS-APPLIED
-------
Section 2
-------
Pesticide Formulation Manufacturing
CI
CI
°N	c
CH2 OH
PESTICIDE
FORMULATION
MANUFACTURING
H
CI -C-\"
i V
CI 1 CI
CI
/ - CI
Pesticide Overview
• Pesticide
-	Destroys or inhibits action of plant or
animal pests
-	Provides economic and health
benefits
-	Poses unintended threat to people
and environment
Process Overview
•	SIC: 2879; NAICS 32532
•	21,000 products
•	860 active ingredients
•	1.1 billion lb/year active
ingredient (1993)
Source EPA 1994
0
CHEMISTRY FOR ENVIRONMENTAL PROFESSIONALS-APPLIED
PAGE 1
-------
Pesticide Formulation Manufacturing
Pesticide Overview
• Formulation
-	Mixture of active ingredient(s) with
"inert" ingredient(s)
-	Optimize handling, effectiveness and
ease of use
Standard Process Schematic
SOLVENTS, WATER
ADJUVANTS, CARRIER
DUSTS. EMULSIFIERS.
SURFACTANTS ETC
PESTICIDES SOLVENTS.
RINSE WATERS
PESTICIDE FORMULATIONS
DISCARDED RAW
MATERIALS CONTAINERS,
OFF-SPEC PRODUCTS
SPENT FILTER CARTRIDGES.
SPENT SOLVENTS
(CONTAMINATED)
Key Chemicals
(Over 50 in Top 100)

1999

ATSDR Rank
Arsenic, lead, mercury, etc.
1,2,3	
BaP, etc. (PAHs)
8,9, 10, ...
Chloroform, TCE, cyanide, etc.
11, 15, 26, ...
DDT, DDE, DDD
12, 20, 27
Solvents
48, 62, 87
PAGE 2
CHEMISTRY FOR ENVIRONMENTAL PROFESSIONALS-APPLIED
-------
Pesticide Formulation Manufacturing
	Formulation Rationale	
•	Technical Pesticides (e.g., DDT)
-	Insoluble in water
-	Lumpy solid
-	Difficult to apply
•	Formulations
-	Easier to apply
-	Increases potency
-	Includes: powders, dusts, granules,
wettable powders emulsifiable concentrate,
aerosols, treated seed, bait pellets and
cubes
Formulation Types
•	Carrier solvent
•	Carrier dust (e.g., clay)
•	Adjuvants
•	Emulsifiers
•	Surfactants
Formulation Ingredients
• Dry formulations
- Organic flours, sulfur, silicon oxides,
lime, gypsum, talc, pyrophyllite,
bentonites, kaolins, attapulgite,
volcanic ash
Source EPA 1990
CHEMISTRY FOR ENVIRONMENTAL PROFESSIONALS-APPLIED
PAGE 3
-------
Pesticide Formulation Manufacturing
Dry Pesticide Formulation Process
Carrier
Formulation Operations
•	Mixing/blending
•	Particle size reduction
•	Packaging, labeling, storage
•	Very little chemical reaction
Formulation Ingredients
•	Solvents
-	Xylenes, kerosene, MIBK, amyl acetate,
chlorinated solvent
•	Propellents
-	Nitrogen, C02
•	Other
-	Wetting agents, dispersing agents,
masking agents, deodorants, emulsifiers
Source. EPA 1990
PAGE 4
CHEMiSTRY FOR ENVIRONMENTAL PROFESSIONALS- APPLIED
-------
Pesticide Formulation Manufacturing
Liquid Pesticide Formulation Process
Organochlorine Pesticides

H
ci-OfOci

c'iQ


Cl ci Cl
u P.P'-DDT

c T^CI
Cl
HEPTACHLOR


CLy wci
Vv01
cA Ah
H ' 'Cl
Cl H
LINDANE (y-BHC)

Cl
ALDRIN

All in the Family
Acetylcholinesterase Inhibitors

c
i, /=. Organophosphate
C2H50-P-0-^ V N02 pesticides
OC2H5 e.g., parathion



II 0 	v
Carbamates nN.. 11 _ / \
' °~°\J
e.g., CARBARYL CH3 >=K
(Sevin) \ /

CHEMISTRY FOR ENVIRONMENTAL PROFESSIONALS -APPUED
PAGE 5
-------
Pesticide Formulation Manufacturing
All in the Family
Acetylcholinesterase Inhibitors
NAME THAT COMPOUND

0


(CH3)2CHOn||


/P-F


h3c


Dioxin-Forming Pesticides
PCP
octachlorodibenzo-p-dioxin
Dioxin-Forming Pesticides
2,4,5-T
(Agent Orange ingredient)
+ v3°
CI v CI	HO
—
minor	CI
reaction
2,3,7,8-tetrachlorodibenzo-p-dioxin
PAGE 6
£iCHEMISTRY FOR ENVIRONMENTAL PROFESSIONALS^ APPLIED^
-------
Pesticide Formulation Manufacturing
Modes of Release
• Continuous emission
-	Contaminated wastewater
-	Wastewater sludge
-	Spent rinsate solvent
-	Spent filter media/cartridges
-	Discarded chemicals
Modes of Release
• Fugitive emissions
-	VOC emissions
-	Loading and unloading spills
-	Process spills/leaks
-	Fugitive dusts
-	Floor sweepings/washwater
Where Did They Go?
® Relatively water insoluble
•	Soluble in fat tissue
-	Mechanism for bioaccumulation
® Adsorbs strongly to clays and NOM
(natural organic matter)
-	Sediments
-	Soil horizon
•	Many species hydrolyze
-	Organochlorines do not
CHEMISTRY FOR ENVIRONMENTAL PROFESSIONALS -APPLIED ' j¦ PAGE 7
-------
Pesticide Formulation Manufacturing
Analytical Considerations
• Field screening methods
-	Immunoassay
/ SW-846 4010, etc.
-	Biosensor detector tickets
/ppm to ppb range
-	Inorganics
/X-ray fluorescence
Analytical Considerations
• Laboratory methods
-	Organochlorine pesticides
/CLP (GC/ECD)
/SW-846 8080A, etc.
-	Organophosphorus pesticides
-/ SW-846 8140
-	Other methods
/ HPLC
/ AA or ICP (inorganics)
PAGE 8
CHEMISTRY FOR ENVIRONMENTAL PROFESSIONALS-APPLIED
-------
Section 3
-------
Municipal Landfills
MUNICIPAL
LANDFILLS
Process Overview
• Discarded material from homes and
businesses: includes product
packaging, newspaper, grass
clippings, clothing, furniture, bottles,
food scraps, appliances, paint,
batteries, etc.
Process Overview
• Municipal solid waste (MSW)
-	220 million ton/year (1998)
-	55% landfilled
-	Enough to fill the Superdome
twice each day
CHEMISTRY FOR ENVIRONMENTAL PROFESSIONALS - APPLIED		PAGE 1
-------
Municipal Landfills
Process Overview

• ' ,>¦
% SH
v»:>- , 1
1% : :
;n- V\-,7 		
r - 		
rJ £
•f'i \


V'

tr ¦ )-
¦ /


\ s-';
V
V	¦
"V
:!'T



figure lu'stvi
ocH(CiS\M»p
¦.

Garland Road Landfill
Process Overview
• Federal government-led reform
-	SWDA (1965), RCRA (1976), etc.
-	Set standards for operation (sanitary
landfill)
-	Classify/segregate waste streams
-	Contain/control/monitor off-site migration
-	Noncompliant facilities (open dumps)
closed
Process Overview
• Past practices
-	Open and burning
dumps
-	Failed to exclude
hazardous waste
-	Poor siting choices
-	Lack of environmental
protection
-	Other problems
PAGE 2		CHEMISTRY FOR ENVIRONMENTAL PROFESSIONALS - APPLIED
-------
Municipal Landfills
Key Chemicals
Lead
Mercury
Vinyl chloride
Benzene
PCB
Cadmium
1999
ATSDR Rank
2
3
4
5
6, 13, 14, etc.
7
CHEMISTRY FOR ENVIRONMENTAL PROFESSIONALS--APPLIED
R12/02
PAGE 3
-------
Municipal Landfills
Key Chemicals (cont.)

1999

ATSDR Rank
PAHs
8, 9, 10, 17, etc. ¦
Pesticides
12, 18, 20, etc.
TCE
15
Methane
65
Corrosives
>100
Petroleum
N/A
Process Details
1998 MSW Generation by Material Type
(before recycling)

Paper
38.2%
Yard Waste
12.6%
Plastic
10.2%
Food Waste
10.0%
Metals
7.6%
Rubber, leather, textiles
7.0%
Glass
5.7%
Wood
5.4%
Other
3.3%
PAGE 4	CHEMISTRY FOR ENVIRONMENTAL PROFESSIONALS - APPLIED
R12/02
-------
Municipal Landfills
Landfill Construction Methods
Sanitary Landfill
ORIGINAL GROUND
COMPACTED
SOLID WASTE
ihuJL-
~m\
	
m
Landfill Construction Methods
Modem MSW Landfill
ff^
LOW-PERMEABILITY
COVE R/GEO ME MBR ANI
VENT
LAYER
%
3?
PERFORATED PIPE
'-a? _ v• WASTE f':, &:'» ,>*	£
.^o ^ V> \
'J a m Sri) #/V
LOW-PERMEABILITY SOIL
"W"
GEOMEMBRANE
^-LEACHATE
COLLECTION SUMP
/^/t- ^
—-io^cm /Mis
Process Details
• Landfill gas
-	Produced by action of indigenous
microorganisms upon degradable
organic matter content of waste
-	May contain C02, CH4, H2S, VOCs
-	Production rates vary with waste
composition, temperature, water
content, air permeability, etc.
-	Potential explosion hazard

CHEMISTRY FOR ENVIRONMENTAL PROFESSIONALS-APPLIED
PAGE 5
-------
Municipal Landfills
	Process Details	
Leachate Generation Key Factors
•	Water infiltration rates
•	Waste composition and leachability
•	Underlying soil characteristics
•	Depth/distance to receptors
Process Details
Leachate Generation
Leachate: a solution containing dissolved
and finely suspended solid matter and
microbial waste products.

Process Details

Changes in Landfill Gas Composition Over Time

Aerobic Anaerobic

_ ICO
1 X
Pf.iM Phasa 1 ' P-:a«f ' PI aso
II 1 It' | IV

I *-
	1	!	

£ 7f
X tc


8 -
.. ^ ;Tr^:	:
55%
-o~4C
Q.
/
40%
C
/ '

(/)
< IC
C
( •- \H< ~ 1 - ¦-
5%

TIME AFTER PLACEMENT

PAGE 6 i ^ -CHEMISTRY FOR ENVIRONMENTAL PROFESSIONALS-APPLIED
-------
Municipal Landfills
Process Details
Leachate Generation with Time
Household Hazardous Wastes
•
Thermometers: Mercury
* Waste oil: BTEX
•
Batteries: Lead, cadmium, mercury
•
Plastics: Cadmium, lead, phthalates
•
Cleaning solvents: TCE, acetone
•
Others:

- Paints, appliances, pesticides, etc.
CHEMISTRY FOR ENVIRONMENTAL PROFESSIONALS-APPLIED				PAGE 7
-------
Municipal Landfijls
Modes of Release
•	Continuous release
-	Leach ate
-	Landfill gases
•	Fugitive emissions
-	Surface water runoff
-	Groundwater plume
-	Landfill gas migration
-	Construction incursion
Where Did They Go?
• Inorganic material
-	Relatively insoluble
-	Sorbs to soil particles (attenuates
migration)
-	Transport via colloids
-	Can be mobilized by pH or reducing
conditions
Where Did They Go?
• Organic material
-	Relatively insoluble
-	Electron donors (fuel) for biodegradation
-	May create reducing environment
-	Degradation byproducts may be more
mobile
PAGE 8
CHEMISTRY FOR ENVIRONMENTAL PROFESSIONALS-APPLIED
-------
Municipal Landfills
	Analytical Methods	
• Field Screening
-	Soil gas
-	Test kits
-	Specific conductivity
-	Eh, pH
-	Direct reading VOC meters (PID, FID)
-	Explosimeter
Analytical Methods
• Laboratory Methods
-	TCL/TAL
-	BOD,COD
-	TOC,TOX
-	TDS, TSS, specific conductance
-	Chlorides, iron, manganese, sodium, etc.
Presumptive Remedy Guidance
•
Assumes low threat, treatment impractical
•
Containment
9
Run-on/runoff control
9
Landfill gas collection or venting
•
Leachate collection/control
•
Remove "hot-spots"
0
Monitor/remediate off-site plumes
CHEMISTRY FOR ENVIRONMENTAL PROFESSIONALS-APPLIED	PAGE 9
-------
Municipal Landfills
uUtk<
Summary
Volume of MSW enormous
•	Thousands of closed landfills
•	Often contain industrial/hazardous waste
•	Generate leachate/landfill gas
•	Potential to degrade usable water supplies
•	Cover/contain/control/monitor
PAGE 10	CHEMISTRY FOR ENVIRONMENTAL PROFESSIONALS-APPLIED
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Section 4
-------
Petroleum Refining
PETROLEUM
REFINING
Petroleum Refining
Objectives
•	List key chemicals associated with
petroleum refining
•	Describe associated chemical and
physical processes
•	List modes of release
•	List laboratory and field screening
analytical methods
Process Overview
•
SIC 2911, NAICS 32411
•
15.7 million barrels per day processed
in U.S. (2000)
•
$194 billion per year U.S. sales (1999)
6
155 operating U.S. refineries (2000)
•
15% employ <20 persons (1992)
CHEMISTRY FOR ENVIRONMENTAL PROFESSIONALS - APPLIED
PAGE 1
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Petrojeum Refining
Process Overview
Petroleum or crude oil
•	Pumpable liquid natural resource
•	Primarily hydrocarbons (Cs-Cgo or
greater)
•	Derived from buried marine plants and
animals
Process Overview
Gasoline
•	Most valuable refined product
•	Primarily hydrocarbons (C5-C12)
•	Composition manipulated to optimize
internal combustion engine
performance while minimizing
pollutants
Refinery Unit Operations
Physical separation
•	Desalting
® Fractionation (distillation)
Conversion processes
•	Cracking, alkylation, reforming, etc.
Treating, purifying, blending, storage
CHEMISTRY FOR ENVIRONMENTAL PROFESSIONALS - APPLIED
-------
Process Overview
Conversion of Average Crude Oil Barrel
2.5%
8.5%
Noncondenslbles (100
BTX
CN
CD
CO
Ln
87
PAHs
8,9, 10..., 75,
>100
Acids/bases
>100

MTBE, ethanol, etc.
>100

PCBs, asbestos,


degreasers
6, 13, 14, 15..
-90
Standard Process Schematic
CRUDE OIL
CONDENSATE
WATER CATALYSTS
ACID SOLVENTS
ADDITIVES
GASOLINE. JET FUEL. LPG,
DIESEL FUEL OIL LUBE
OIL. COKE WAX. ASPHALT.
BTX, etc.
SPENT CATALrSTS,
SULFUR SPENT ACIDS
API SEPARATOR SLUDGE.
DAF FLOAT TANK BOTTOM
SLUDGE SPENT
CATALYSTS etc
SALT OIL ANDGREASE
HYDROCARBON EMULSION. H S.
PHENOL MERCAPTANS
CHEMISTRY FOR ENVIRONMENTAL PROFESSIONALS - APPLIED	PAGE 3
	
-------
Petroleum Refining
Conversion Processes:
Cracking
•	Makes smaller, lighter
molecules from larger, heavier
ones
® Increases gasoline yield
•	Requires thermal energy
•	Sometimes uses catalyst
or hydrogen
a
j
Atmospheric Distillation
General Refinery Process Flow Diagram
	,	»|h -r £-7E- 	
Sourze Consdine
PAGE 4
CHEMISTRY FOR ENVIRONMENTAL PROFESSIONALS - APPLIED
-------
Petroleum Refining
Conversion Processes
Fluid
Catalyic
Cracking
Unit (FCCU)
Conversion Processes:
Alkylation
•	Makes gasoline ingredient
from propylene, butylenes,
and isobutane
•	Strong acid catalyst
-	Hydrofluoric acid (HF)
-	Sulfuric acid (H2S04)
Conversion Processes:
Isomerization
•	Boosts octane by increasing
molecular branching
•	Uses platinum catalyst

J
if

f m
' ii
CHEMISTRY FOR ENVIRONMENTAL PROFESSIONALS - APPLIED
PAGE 5
-------
Petroleum Refining
Conversion Processes:
Delayed
Coking
Unit
Conversion Processes:
Coking
•	Extreme thermal cracking
•	Produces solid
carbonaceous products
•	Produces hydrogen and \ fjr
cracked gas ( [
byproduct : ~Jjj||: S



Conversion Processes
Catalytic Reforming
Increases octane by
increasing ring and
aromatic content
Uses platinum
catalyst
Produces hydrogen.
PAGE 6	CHEMISTRY FOR ENVIRONMENTAL PROFESSIONALS - APPLIED
-------
Petroleum Refining
Treating, Purifying, etc.
•	Propane deasphalting
•	"Sweetening"
•	Sulfur recovery
•	Lube oil extraction and dewaxing
Treating, Purifying, etc.
• Blending
-	Antiknock additive
-	Oxygenates
/ MTBE, ethanol
-	Others
/ Antioxidants, corrosion inhibitors,
deicers, others
Wastewater Streams
m
SANITARY
WASTEWATER
OILY WASTEWATER FROM
RUNOFF CRUDE DESALTER.
DEASPHALTING
COOUNG WATER. STORAGE
TANKS
GRAVITY
OH/WATER DISOLVEDAIR !
SEPARATION FLOTATION .]
BIOLOGICAL
TREAT VENTS
	 SEDIMENTATION

T
TERTIARY
TREATMENT
NF
OILY SOURWATER FROM
ATMOS. DISTILLATION.
VACUUM DISTILLATION.
CATALYTIC CRACKING.
HYDROCRACKING.
ALKYLATION. COKJNG
THERMAL CRACKING.
HYDRO TREATING
m
NONOILY WASTEWATER FROM
STEAM GENERATION. RUNOFF.
COOLING WATER
I SOLIDS I
—> jDEWATERING "
V SLUDGE DISPOSAL
Source EPA 1995
CHEMISTRY FOR ENVIRONMENTAL PROFESSIONALS - APPLIED
p
r i
-------
Petroleum Refining
Floating Roof Storage Tank
FLOATING ROOF
—	PROCESS WATER
—	CRAIN
COMBINED SEWER
; DfTCH (to WWTP)
Modes of Release
Air emissions
-	Furnace vents
-	Vacuum pumps or ejectors
-	Compressor engines
-	Utility and vapor recovery boilers/flares
-	Wastewater ponds
-	Fugitive emissions, (valves, pumps,
flanges, tank seals, etc.)
Modes of Release
• Water emissions
-	Desalting water
-	API separator
-	Coke drum cutting water
-	Storage tank drain
CHEMISTRY FOR ENVIRONMENTAL PROFESSIONALS — APPLIED
-------
Petroleum Refining
Modes of Release
• Water emissions (cont.)
-	Stormwater
-	Heat exchanger bundle cleaning water
-	Cooling water blowdown
-	-Sour-water
-	Vacuum pump/ejector water
Modes of Release
• Solid/land emissions (cont.)
-	Process tank farm cleanout sludge
-	Spent catalysts
-	Filter clays
Modes of Release
• Environmental/legacy
-	Lagoon sludges
-	Tank bottoms
-	AST LNAPL plume
-	Process area spills
-	Degreasing solvent spills
-	PCBs/asbestos
CHEMISTRY FOR ENVIRONMENTAL PROFESSIONALS -'APPLIED
PAGE 9;
-------
Petroleum Refining
Where Did They Go?
• Hydrocarbons
-	Volatility variable
/ VOCs: VP > 1mm Hg
-	Relatively water insoluble (NAPL)
s (Even substituted HCsJose
miscibility >C4 or C5)
Where Did They Go?
• Hydrocarbons (cont.)
-	Specific gravity <1 (LNAPL)
-	Generally biodegradable
/ Electron donor
/ Dissolved phase only
	Weathering	
Weathering: Change in contaminant
composition over time due to relatively
higher rates of mobility and biodegradability
of lighter HC components
•	Solubility, volatility, and biodegradability
generally decrease with increasing carbon
number (molecular weight)
•	Sorption (retardation) increases with
carbon number
PAGE 10
CHEMISTRY FOR ENVIRONMENTAL PROFESSIONALS- APPLIED
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Petroleum Refining
Weathering
Structural Effect on Volatility
Isoparaffins (branched alkanes)
N-paraffins (straight chain alkanes) most VOiatiie
Naphthenes (cyclic alkanes)
Aromatics
least volatile
Example: Boiling points of C12 aromatics, C13 naphthenes,
C14 n-paraffins, and C15 isoparaffins are about the same
Analytical Considerations
Laboratory methods
- Gasoline
/ Analyze for BTX
/ GC, GC/MS, IR
/ Purge and trap, headspace, etc.
Analytical Considerations
• Diesel and heavier
-	Analyze for PAHs
-	GC, GC/MS, HPLC
-	Solvent extraction
9 Inorganics
-	Total metals by AA or ICP
-	TCLP for RCRA characteristics
CHEMISTRY FOR ENVIRONMENTAL PROFESSIONALS - APPLIED
PAGE 11
-------
Petroleum Refining
Analytical Considerations
• Field screening methods
- Organic contaminants
/ Immunoassay
/ Friedel-Krafts reaction
/ Portable GC, GC/MS
/ Soil gas
/ Laser-induced fluorescence (LI F)
Analytical Considerations
• Field screening methods (cont.)
- Inorganic contaminants
/ X-ray fluorescence (XRF)
/ Test kit
	Summary	
•	Petroleum refiners employ physical and
chemical processes to produce gasoline
and other products
•	Although refineries are very efficient,
contamination accumulates over time due
to the tremendous volume processed
•	Refining operations produce LNAPL
plumes, oily-sludges, and tarry residue
often containing heavy metals and sulfur
PAGE 12'
CHEMISTRY FOR ENVIRONMENTAL PROFESSIONALS - APPLIED
-------
Section 5
-------
PCBs


IN INDUSTRY
f=-
y

-
1
PCBs i



f
<»


PCBs In Industry
	Objectives	
o Describe the chemical structure of
polychlorinated biphenyls (PCBs)
© List major industries that formerly
utilized PCBs
® List common trade names for PCBs
© List major modes of release to the
environment
j ® Identify analytical methods useful for
detecting PCBs in the environment
PCB Overview
Volume and Scope of PCB Use
® Polychlorinated biphenyls (PCBs)
-	Class of industrially useful chemicals
-	Clear to yellow oily liquid or solid
® 1.4 billion lbs produced or imported
from 1920s to 1977
-	99% by Monsanto Corp
CHEMISTRY FOR ENVIRONMENTAL PROFESSiONALS^APPUEb
R12/02
PAGE*
-------
PCBs in Industry
PCB Overview
Industrially Useful Properties of PCBs
®	Chemically and thermally stable
©	Nonvolatile
©	Nonflammable
®	Dielectric (electrical insulator)
®	Nonpolar (behaves like oil)
©	Dense (sinks in water)
PCB Overview
Chemical Structure of PCBs
•	1-10 chlorine atoms attached to a
biphenyl molecule
•	209 combinations (congeners)
® Molecular weight 189-499 g/mole

¦to
lMH
¦ZI0
it?



PCB Overview
Industrial Uses of PCBs
o Capacitors and transformers (77%)
e Hydraulic systems (6%)
© Heat transfer systems (2%)
® Other uses (15%)
PAGE 2
CHEMISTRY FOR ENVIRONMENTAL PROFESSIONALS - APPLIED
R12/02
-------
PCBs in
Industry
Industrial Uses of PCBs
Transformers and Capacitors
© 5-10% of transformers
-	Electric power utilities
-	Heavy industry (steel making, foundries,
die casting, etc.)
-	Railroad engines
© Nearly all capacitors
-	Fluorescent light ballast
-	Phone connectors
Industrial Uses of PCBs
117-f-
OLsiai&f
fte/b* cttMj
udajrf' '
© Hydraulic and heat transfer systems
- High temperature applications
Industrial Uses of PCBs (cont.)
• Other uses
-	Natural gas pipeline compression stations
-	Mining equipment (Joy Mfg.)
-	Carbonless paper (NCR Corp.)
-	Electromagnets (prior to 1970s)
-	Chemical processes
• Phthalocyanine pigments
-	Investment casting	—
-	Electric cable insulation
lAs
-------
PCBs in industry
/2 -
(eff-
laCahlHJ
°/0 uri-a
o cakl^
°/0vd'tt
Key Chemicals
1999
ATSDR Rank
Polychlorinated biphenyls (PCBs)
6
Arnnlnr 1 ?fi 0
13
1254
14
1248
25
1242
28
qo|J100
Trichlorobenzene
>100
V
Aroclors are Mixtures
Example; Aroclor 1016
"5,
c
<13
O
JZ
O
03
'
-------
PCBs in Industry
Trade Names for PCBs
Monsanto
-	Aroclor
-	Pydraul (hydraulic systems)
-	Askarel
/ Transformer fluid
/ 30-40% trichlorobenzene
Imports and repackaged products

Modes of Release
•	PCB-contaminated soil
-	Drain and fill residual
-	TSCA and RCRA limit is 50 ppm
•	Salvage operations
-	Break open and recover copper
-	Burn pits/PCDDs and PCDFs
	Modes of Release	
•	Transformer, capacitor, and switch gear
container leak or failure
-	Lightning strike, corrosion, struck by
accident
-	Fire may produce PCDDs and PCDFs
•	Fill and drain spills
-	Manufacturing and maintenance facilities
-	Electrical substations
-	Hydraulic systems
CHEMISTRY FOR ENVIRONMENTAL PROFESSIONALS - APPLIED
PAGE 5
-------
PCBs in Industry
Where Did They Go?
•	Relatively water insoluble
•	Soluble in fat tissue
-	Mechanism for bioaccumulation
•	Adsorb strongly to clays and NOM
(natural organic matter)
-	Sediments
-	Soil horizon
•	Resistant to biodegradation
-	Half-life -50 years
Modes of Release
•	Manufacturing outfalls
-	Wastewater outfalls and sludges
-	Stormwater
•	Demolition debris
-	Inadequately cleaned spills
-	Fluorescent lighting ballast
•	Disposal sites
-	Direct disposal allowed until 1979
i -0/P* JtH
luArtd
Analytical Considerations
Laboratory methods
•	CLP, SW-846 8080, etc. (GC/ECD)
-	Intended for intact aroclors
•	Method 680 (GC/MS)
-	Identifies congener homologues
® Other
PAGE 6	CHEMISTRY FOR ENVIRONMENTAL PROFESSIONALS-APPLIED
-------
PCBs in Industry
Analytical Considerations
Field screening methods
•	Immunoassay
-	Quantitation extrapolated from
assumed distribution
•	Sodium reagent-based l , ,
-	Measures chlorides < lA^JL^P>.
1

CHEMISTRY FOR ENVIRONMENTAL PROFESSIONALS-APPLIED
PAGE 7
-------
Section 6
-------
IL Ptk*CM -Leu) hhMaalA.
qQc/ff	T
-------
Metal Finishing
0,
p,R<
METAL
FINISHING
PROCESS

Process Overview
•	SIC: 347; NAICS: 332813
•	$10 billion per year ^[Q ^
•	5,600 businesses
•	50% have fewer than nine employees
hjVUtU 4	- 'sjheA lAuWi^
rJ^jJb !/HM H ^/gcuvti ft
Key Chemicals
Solvents
1999 ATSDR Rank
Benzene
5
TCE
15
etc.

Coatinqs

Cadmium
7
Chromium
16, 73
etc.

Acids and Bases

HCI
>100
Caustic
>100

40 C&L
CHEMISTRY FOR ENVIRONMENTAL PROFESSIONALS-APPLIED
PAGE 1
-------
Metal Finishing
V
Standard Process Schematic
SOLVENT
VAPORS
R cluJ N[tx
JNr WISHED METAL r-
PRODUCTS '—™K'
Cyanide, metal [	
SALTS SOLVENTS.
BASES, AC ICS
NEUTRALIZED SALTS
METALS SOLVENTS,
EMULSIONS
FINISHED METAL
'a'~\ RECYCLED
' ^ SOLVENTS
METAL S-UDGE,
SCALE

7
V	Process Details
Metal Finishing Process Overview
A-KALINE

RINSE

ACID DIP

RINSE

CLEANER




1

- - SURFACE PREPARATION -

1
-1

V
PLATING
—»
DRAG-OUT
TANKS
—>
¦ RINSE

FINISHING
TREATMENT

RINSE

1
1	SURFACE TREATMENT	
Source cdap'ea from EPA "S95

i
1
-\Uu kuifs
l/ljlfriM "s&My
U iMPM
PAGE 2	CHEMISTRY FOR ENVIRONMENTAL PROFESSIONALS-APPLIED
-------
Metal Finishing
Process Details
Surface Preparation Overview
Source: adapted from EPA 1995
0eCi
Process Details
Surface Treatment Overview
Chemical/electrochemical processes
a High temperature: case hardening,
nitriding
® Ambient temperature: anodizing,
chemical conversion, electroplating, etc.
• Utilize metal salts, phosphates,
cyanides, etc.
Process Details
Surface Treatment Overview
Physical processes
• Polish, cut, shape, grind
® Cutting fluids (organic and water-
based)
CHEMISTRY FOR ENVIRONMENTAL PROFESSIONALS - APPLIED
R12/02
PAGE 3
-------
Metal Finishing
Process Details
Surface Treatment Overview
Anodizing
•	Electrochemical process
•	Converts surface metal to insoluble
oxide
•	Uses chromic, sulfuric, or boric acids
Process Details
Surface Treatment Overview
Chemical conversion coating
© Conditions surface for painting or
coating
® Uses chromates, phosphates,
phosphoric acid, and hexavalent
chromium

l/ Process Details
Surface Treatment Overview

Electroplating
© Electrochemical process
© Acid, alkaline, or neutral pH
® Uses metal salts, cyanides, brighteners,
solid metal anodes
-	Cyanides keep metal ions in solution
-	Brighteners make surface more
reflective


CHEMISTRY FOR ENVIRONMENTAL PROFESSIONALS - APPLIED |
R12/02
-------
Metal Finishing
V
Process Details
Electroplating Process
GENERATOR OR
RECTIFIER
ANODE BUS BAR
cathode eus ear
Source adapted from EPA 1995
CHEMISTRY FOR ENVIRONMENTAL PROFESSIONALS -APPLIED	PAGE 5
-------
Metal Finishing
1 Process Details
Common Electroplating Bath Compositions
Bath Name
Composition
Brass and bronze
Copper cyanide, zinc cyanide,
sodium cyanide, sodium carbonate,
ammonia, Rochelle salt 		
Chromium
Chromic acid, sulfuric acid
Cadmium cyanide
Cadmium cyanide, cadmium oxide,
sodium cyanide, sodium hydroxide
Cadmium fiuoroborate
Source EPA 1990
Cadmium fiuoroborate, fluoroboric
acid, boric acid, ammonium
fiuoroborate, licorice
-Scdl- /W -
Process Details
Solvent Degreasing
•	Chlorinated solvents
-	Trichloroethylene (TCE), 1,1,1,-
trichloroethane (TCA), methylene
chloride, perchlorethylene, CFC-113
•	Methods
-	Vapor degreasing
-	Cold cleaning
-	Spot cleaning
Modes of Release
Air emissions
•	Solvent vapors
•	Acid mists
Water releases
•	Rinse water
•	Spent plating bath treatment
•	Washdown liquids
fiX) 1'
< 0 6 %
I


PAGE 6
CHEMISTRY FOR ENVIRONMENTAL PROFESSIONALS - APPLIED
-------
Metal Finishing
Modes of Release
Soil
•	Washdown liquids
•	Solvent spills
Groundwater
•	Hexavalent chromium (more mobile)
•	Chlorinated solvents (DNAPL)
1/OlcHMjl
T
Modes of Release
Solid and hazardous wastes
•	TCLP metals (D006,. D007, etc.)
•	Wastewater (F006)
•	Spent plating baths (F007, F008,
F009)
•	Quenching baths, etc. (F010, F012,
F019)
(/ Analytical Considerations
Laboratory methods j , // /
• Metals: AA, ICP
•	Solvents: GC/MS
Field screening methods
•	Metals: XRF
•	Solvents: Portable GC, Portable
GC/MS



CHEMISTRY FOR ENVIRONMENTAL PROFESSIONALS-APPLIED
PAGE 7
-------
Summary
•	Mostly small businesses with limited
environmental control programs
•	Use a wide variety of chemicals:
-	Organic solvents
-	Metals, metal salts, and cyanide
^-Corrosives
•	Metal finishing wastes can affect all four
media: soil, surface water and sediment,
air, and groundwater
PAGE 8			CHEMISTRY FOR ENVIRONMENTAL PROFESSIONALS-APPLIED
-------
Section 7
-------
Secondary Lead Smelting
SECONDARY
LEAD
SMELTING
vvxv...
s
Secondary Lead Smelting
	Objectives
•	Describe the basic smelting process
terms: smelting, refining, and alloying
•	List key chemicals associated with
secondary lead smelting
® Define volatility temperature, volatile
metals, and metals partitioning
Secondary Lead Smelting
	Objectives	
•	List major modes of release to the
environment
•	Identify analytical methods useful for
detecting secondary lead smelting
contaminants in the environment
CHEMISTRY FOR ENVIRONMENTAL PROFESSIONALS - APPLIED
	PAGE 1
-------
Secondary Lead Smelting
Process Overview
•	Total employment: 2300 (1993)
- 1700 by secondary smelters and
refiners
•	53 active secondary lead smelters in
U.S. (1991)
Process Overview
•	SIC: 3341; NAICS: 331492
•	U.S. lead consumption is 1.4 million
metric tons per year (1993)
•	72% of demand is met by secondary
lead industry
PAGE 2	CHEMISTRY FOR ENVIRONMENTAL PROFESSIONALS - APPLIED
-------
Secondary Lead Smelting
Process Overview
-• Smelting: Conversion of oxidized
metai species into metallic (zero
valence) form
• Process requires:
_^_High_temperatures (1.260°C)
-	Reducing agents
-	Exclusion of oxygen
Process Overview
•	Refining: Separation of
impurities from primary metal
•	Process requires:
-	Melting temperatures (327.5°C)
-	Refining agents
-	Physical separation of insoluble
layers
Process Overview
•	Alloying: Addition of ingredients to
obtain desirable product properties
•	Process requires:
-	Melting temperatures
-	Alloying agents
-	May occur during refining step
CHEMISTRY FOR ENVIRONMENTAL PROFESSIONALS - APPLIED
/PAGE 3
-------
Secondary Lead Smelting

Key Chemicals
Arsenic
Lead
Cadmium
Zinc
Antimony
Copper
Tin
1999
ATSDR Rank
1
2
7
70
>100
>100
>100
Standard Process Schematic
LEAD PARTICULATE
¦ SULFUR DtOXIDE
LEAD-CONTAINING
SCAP AND SLAGS
LIMESTONE COKE
SCRAP IRON AIR
ALLOYING AGENTS
r^RM~r,


PARTICULATE
METALS DISSOLVED
METALS
SOFT LEAD ANTIMONIAL
LEAD LEAD ALLOYS
SLAG. DROSS,
EMISSION CONTROL
DUSTS (REUSED)
SLAG. DROSS,
EMISSION CONTROL
DUSTS (K069)
PAGE 4
CHEMISTRY FOR ENVIRONMENTAL PROFESSIONALS - APPLIED
					• -~ • 	;	;	:	:	:	;	
-------
.y.		. ,.y._ ;			¦¦¦¦¦¦	 Secondary Lead Smelting
Process Details
Reverberatory Furnace Schematic
Fire bridge
Coke (or
natural gas)
Air, 02 ———>
Flue gas
Ventilation
Process Details
Blast Furnace Schematic
Flue to
cooling
f Bucket
elevator
Tuyeres
Process Details
Reverberatory or blast furnace
® 1260°C
•	Burnout
•	Sweating
•	Slagging
CHEMISTRY FOR ENVIRONMENTAL PROFESSIONALS - APPUED	PAGES
-------
Secondary Lead Smelting
Environmental Chemistry
Metals partitioning
•	Volatility temperature (VT)
•	Vapor pressure >10~6 atm
•	Chlorine effect
•	Volatile metals ~ VT <900°C
PAGE 6	CHEMISTRY FOR ENVIRONMENTAL PROFESSIONALS-APPLIED
-------
Secondary Lead S netting
Modes of Release
Continuous emissions
•	Stack emissions
•	Emission control dusts/sludges
•	Slag, dross (K069)
Fugitive emissions
•	Fugitive dust
•	Seal leakage
•	Washdown dust and water
Predicted Metals Volatility Temperatures

With 0% Chlorine
With 10% Chlorine

Volatility
Principal
| Volatility
Principal
Metal
Temperature ( C)
Species
. Temperature ( C)
Species
Chromium
1613
CrO /CrO.
i 1610
CrO./CrO.
Nickel
1210
Ni(OH)
; 693
NiCI
Beryllium
1054
Be(OH)
1054
Be(OH)
Silver
904
Ag
627
AgCI
Barium
849
Ba(OH)
' 904
BaCI
Thallium
721
Tl O.
138
TIOH
Antimony
660
SbO
66'0
SbO
Lead
	627
PbO.
!	=15	
PbCI.
Selenium
318
SeO
318
SeO
Cadmium
214
Cd
214
Cd
Osmium
41
OsO.
41
OsO,
Arsenic
32
As O.
32
As.O
Mercury
14
Hg
14
Hg
Source EPA 1992




CHEMISTRY FOR ENVIRONMENTAL PROFESSIONALS - APPLIED
PAGE 7
-------
Secondary Lead Smelting
Modes of Release
Soils
•	Direct placement or burial
•	Air deposition
Groundwater
•	Limited migration potential
Surface wateT
•	Mobilized particulate
•	Limited solubility
Analytical Considerations
Laboratory Methods for Lead
Medium Method
Detection Limit
Water
Atomic absorption, ICP
0.001-0.1 mg/l
Soil
Atomic absorption, ICP
0.1-1.0 mg/kg
TCLP
Atomic absorption, ICP
0.001-0.1 mg/l
Analytical Considerations
Field Screening Methods for Lead
Medium Method
Detection Limit
Soil X-ray fluorescence (XRF)
-10 mg/kg
Water Photometric, Colorimetric
1 ppm
test kits
PAGE 8
CHEMISTRY FOR ENVIRONMENTAL PROFESSIONALS- APPLIED
-------
Secondary Lead Smelting
Summary
•	Secondary smelting uses "secondary"
resources to convert or recover lead metal
•	Smelting furnaces and refining kettles are
employed to reduce metallic species and
to separate impurities
•	Air-emissions-of-volatile-metals and
particulate dusts
•	Soils and surface water are primarily
environmental receptors
CHEMISTRY FOR ENVIRONMENTAL PROFESSIONALS - APPLIED
PAGE 9
-------
Section 8
-------
Lead-Acid Battery Breaking Sites
LEAD-ACID
BATTERY
BREAKING
SITES
Process Overview
Lead Recycling Demand
•	U.S. consumes 1.36 million metric tons
of lead per year
•	60% is consumed by automobile storage
battery industry
•	70% is supplied from reclaimed sources
Process Overview
Lead Recycling Demand
•	Sources
-	Lead solder
-	Pipe, sheet scrap
-	Terne-bearing metal scrap
-	Lead-acid storage batteries
•	Demand equivalent to 150,000
car batteries per day!
CHEMISTRY FOR ENVIRONMENTAL PROFESSIONALS-APPLIED
PAGti 1
-------
Lead-Acid Battery Breaking Sites
Process Overview
Remediation of Battery Breaking Sites
•	Batteries broken open
•	Acid removed
•	Physical separation of components
•	Recovery of lead-bearing materials
Source EPA 1991
Process Overview
Remediation of Battery Breaking Sites
•	Often associated with secondary smelters
•	Small operations to 50,000 batteries per
week
•	Disposal of residuals tends to be
"haphazard"
Source EPA 1991
PAGE2	CHEMISTRY FOFR Iff ftlVIR^^NiyjEI^T^XVL
JBI
-------
Lead-Acid Battery Breaking Sites
'in

ifM|

;fMS|p
$:H:. < V V"* °









{SBi

CHEMISTRY FOR ENVIRONMENTAL PROFESSIONALS- APPLIED	PAGE 3
-------
Lead-Acid Battery Breaking Sites
-------
Lead-Acid Battery Breaking Sites
¦
Key Chemicals

1999

ATSDR Rank
Arsenic
1
Lead
2
Cadmium
7
Antimony
>100
Sulfuric Acid
>100
Rubber/ebonite
>100
Polyproplyene
>100
Standard Process Schematic
LEAD SULFATE. LEAD
PLATE. LEAD OXIDE
POLYPROPYLENE
CASING SCRAP,
BATTERY ACID
RUBBER CASING
SCRAP. PVC,
FIBROUS PAPER
SODIUM SULFATE
CHEMISTRY FOR ENVIRONMENTAL PROFESSIONALS-APPLIED			PAGE 5
DISCARDED ,—Q—\
BATTERIES L#V
LIME NaOH |—^ *
-------
Lead-Acid Battery Breaking Sites
Process Details
Lead-acid Battery Cutaway
Post strap
Plate lugs
Positive plate
(cathode)
J	Envelope
] separators
Negative plate
(anode)
Terminal posts
Vent plugs
Cover	
Container —
Through-the-
partition
connectors
Sediment space —
Process Details
Lead-acid Battery Reactions	
At cathode:
Pb02(s) + 4H(aq) + S04(aq)+ 2e PbS04(s) + 2H20(L)
At anode:
Pb(s) + S04(2aq) PbS04(s) + 2e~
Overall:
Pb(S) + Pb02(S) + 4H(aq) + 2S04(aq) ^
2PbS04(S) + 2H20(L)
Reaction is reversible by reversing current flow
Source EPA 1991
Process Details
Lead-acid Battery Components

Weight (lb.)
Lead plating
19-20
Sulfuric Acid
6
Plastic casing
3
Posts, strap, lugs, etc.
9-10

~38 lb.
PAGE 6	CHEMISTRY FOR ENVIRONMENTAL PROFESSIONALS - APPLIED
-------
Lead-Acid Battery Breaking Sites
Process Details
Hammer Mill Schematic
Process Details
Methods of Battery Breaking
•	Shear
•	Saw
•	Hammer mill
•	Crushing
•	Dropping
•	Axe
Process Details
Flow Diagram of Lead-acid Battery Breaking
BATTERIES
RUBBER/
EBONITE
aASTIC.
RUBBER/
EBONITE
BATTERY
BREAKING
(Primarily hammer
mtfl or saw-type
breaker)	
	'DIRECT
DISCHARGE TO
ENVIRONMENT
SEPARATION
FLOTATION
PLASTIC
c
c
DISPOSAL
REUSE
Fuel
Other
LEAD PLATE
POSTS.
SLUDGE
DISPOSAL
RECYCLING
•	Battery cases
•	Other
«¦ SPILLAGE
~	Recycle
•	Wastewater treatment
SECONDARY
LEAD SMELTERS
COLLECTION
FACIUTY
ACID RECYCLE
TREATMENT >> DISCHARGE
. t
LIME/NaOH
CHEMISTRY FOR ENVIRONMENTAL PROFESSIONALS^- APPLIED
-------
Lead-Acid Battery Breaking Sites
Environmental Chemistry
Typical Metals Concentrations in
Lead- acid Battery Acid
Metal Concentration (ma/!)
Particulate lead (as lead sulfate >0.45 urn size) 60-240
Lead
1-6
Arsenic
1-6
Antimony
20-175
Zinc
1-13.5
Tin
1-6
Cadmium
5-20
Calcium
2-150
Iron
112
Selenium
Analysis not available
Source: EPA 1991
Environmental Chemistry
Lead Solubility vs. pH

10.COO


b
1,000
Q

<
UJ
100
_j

a
10
UJ
>

_j

o

V)

C/)
0 01
Q

_l
0.001
h-

O
h-
0 0001
i i i i i i

J	!	1	L
Equilibrium
solubility of lead at
25"C and 1 atm
Source EPA 1991
4.0 50 6.0 7 0 80 9.0 10.0 11.0
pH
PAGE 8
CHEMISTRY FOR ENVIRONMENTAL PROFESSIONALS—APPLIED
-------

Environmental Chemistry
Elemental Additives in Anode Grid
of Lead-acid Storage Battery
I Element
Concentration Range (•/»)
Purpose
I Cadmium
0.1-0.14
Grid-hardening agent - no longer used as an additK'e |
| Antimony
2.5-7.5
Grid-hardening agent - high concentrations of
antimony tend to poison the electrolytic process
! Arsenc
.015
Grid-hardening agent - used as substitute for
antimony
j Tin
0 10-0.5
Grid-hardening agent
| Copper
0 05
Smelting impurity which aids in electrolyte
conductivity
Calcium/lead alloy
.015-0 1 (Ca)
Prevents hydrogen degassing in maintenance-free j
batteries
Selenium/lead altoy

Prevents hydrogen degassing in maintenance-free
batteries
Source. EPA 1991
Environmental Chemistry
Lead-acid Battery Casing Compositions
Ebonite (hard rubber) cases
•	Styrene-butadiene rubber
•	Cross-linked sulfur (30-50%)
•	Carbon black or anthracite (1-3%)
•	Zinc oxide (2-4%)
Maintenance-free batteries
•	Polyproplyene
CHEMISTRYFOR ENVIRONMENTAL PROFESSIONALS—APPLIED
PAGE 9
-------
Lead-Acid Battery Breaking Sites
Environmental Chemistry
Lead Species at Battery Breaking Sites
Predominant
Source
• Lead metal and alloys
(Pb(0))
anode plate, posts,
lugs, grid
• Lead sulfate (PbS04)
product
battery reaction
• Lead oxide (Pb02)-
cathode, acid
Source EPA 1991

Environmental Chemistry
Lead Species at Battery Breaking Sites
Less Common
Source
• Lead carbonates
may be produced
(PbC03), etc.
in carbonaceous soils
• Lead hydroxide
wastewater
(Pb(OH)2)
neutralization product
Source EPA 1991

Environmental Chemistry
Some Physiochemical Properties of Selected Lead
Compounds
ComDOund
Formula
Molecular
Weight
(o/mole)
Solubility

Vapor
Pressure
mm -Ha
Lead
Pb
207 20
Insoluble

1 0 (900 C)
Lead dioxide
PbO.
239 19
Insoluble

NA
Lead carbonate
PbCO.
267 20
1 1 mg/l (j
% 20 C
NA
Lead hydro*
cerrusite
Pb.(CO.).(OH).
775 60
Insoluble

NA
Lead hydroxide
Pb(OH)
241 20
155 mg/l (
§20AC.
NA
Lead sulfide
PbS
239 25
0 9 mg/l <(
3 18'C
NA
Lead oxide
PbO
223 20
17 mg @
20 C
NA
Lead sulfate
PbSO_
303 25
41 mg/l <§
I 20 *C
NA
fM 'W pftiWJw
Source EPA 1991
PAGE10
CHEMISTRY FDR ENVIRONMENTAL PROFESSIONALS^-APPLIED
-------
Modes of Release by Source
•	Process Areas
-	Acid mist
-	Acid spills (RCRA)
-	Debris/particulate accumulation
-	Process area washdown and runoff
•	Material Handling, Storage, and Disposal
-	Spills and dust
-	Waste piles runoff or dust
-	Waste burial and dumping (on- or offsite)
»>APPITED		PAGE 11
-------
Modes of Release by Source
Wastewater T reatment
-	Spills
-	Tank/pond overflow/percolation
-	Discharge (NPDES)
Modes of Release by Media
Soil
-	Spilled acid runoff
-	Rainwater runoff or process area
washdown
-	Pond or tank overflow
-	Waste pile runoff or dust
-	Waste dumping or burial
CHEMISTRYFOR ENVIRONMENTAL PROFESSIONALS- APPLIED
-------
Modes of Release by Media
• Air
-	No regulated emissions (unless
linked with smelter or melter)
-	Dust and particulate transport
-	Acid mist emissions (short
range)
Modes of Release by Media
• Groundwater
-	Buried waste leaching
-	Limited migration potential
-	Acid mobilizes
CHEMISTRY FDR ENVIRONMENTAL PROFESSIONALS- APPLIED
1Z333EI
-------
Modes of Release by Media
• Surface Water
-	Runoff from process areas
and waste piles
-	Spills
-	Wastewater discharge
Analytical Considerations
•	Abundance of lead in the earth's
crust
-Average: 15ppm
- Range <10-700 ppm
•	Over 200 lead-containing minerals
PAGE 14	CHEMISTRY FORENVIRONMENTAL PROFESSIONALS- APPLIED
-------
Lead-Acid Battery Breaking Sites
Analytical Considerations
Laboratory Methods for Lead
Medium Method
Detection Limit
Water Atomic absorption, ICP
0.001-0.1 mg/L
Soil Atomic absorption, ICP
0.1-1.0 mg/kg
TCLP Atomic absorption, ICP
0.001-0.1 mg/l
Analytical Considerations
Field Screening Methods for Lead
Medium Method
Detection Limit
Soil X-ray fluorescence (XRF)
-10 mg/kg
Water Photometric, Colorimetric
1 ppm
test kits
pH Ion-specific electrodes
±0.01 units
Hydrion paper
±0.5 units
CHEMISTRY FOR ENVIRONMENTAL PROFESSIONALS - APPLIED	PAGEiS
-------
Lcad-Acid Battery Breaking Sites
Summary
•	Low-tech small businesses
•	Primary contaminant: lead
•	Secondary contaminants: corrosivity
arsenic, etc.
•	Key sources: breaking pad, waste piles,
treatment tanks and ponds
•	Affected media: soil, surface water, and
sediment
PAGE 16
CHEMISTRY FDR ENVIRONMENTAL PROFESSIONALS- APPLIED
-------
Section 9
-------
IRON and STEEL
MANUFACTURING
iron and Steel Manufacturing
Objectives
® Describe processes for coke, iron, and
steel manufacturing
® List key chemicals and reactions
associated with these processes
® List byproducts and wastes produced
and their modes of release
® Identify analytical methods for detecting
contaminants in environmental media
Industry Overview


© SIC 3312, NAICS 33111
© Approximately 800 million metric tons
per year, world (-100 million metric
tons/year in USA)
® Approximately $40 billion in sales/year
(USA)
® More than 150,000 employees (USA)








Rev. 09/03
-------
Process Chemistry: iron & Steel Manufacturing
General Process Schematic


/ DUST, AMMONIA,
/ SULFUR COMPOUNDS, f
/ VOCft, ete
COKE UMESTONE.
{RON ORE. SCRAP
STEEL ADDITIVES
|=#0>


iRON ANO STEEL
PRODUCTS SLAB WIRE.
PUTES SHEETS. TUBING,
etc
ACIDS ALKAUS
-WATER
ELECTRICITY. GAS

7^
^C>
TRAPPED DUSTS SCALE,
SLAG 00.

OILS. GREASES SLUDGES TARS.
CONTAMINATED WATER, etc

Coking Process Schematic

AMORPHOUS
CRYSTALLIZED CARBON
(COKE)
COAL TAR (PITCH
BITUMEN. CREOSOTE,
REFINED TAR.
NAPHTHALENE), LIGHT OIL
V }	STILL 80TTOMS. EMISSION
ACONTROL DUSTS. LIME
SLUDGE. AMMONIA.
WASTEWATER
QUENCH WATER
; >; . Chemistryfor Environmental Professionals - Applied
Rev. 09/03
-------
Process Chemistry : Iron A Steel Maiiiifacturing
Key Chemicals - Coking
1999
ATSDR Rank
Benzene	5
PAHs	8, etc.
Cyanide	26
Naphthalene	75
Phenol, coal, ammonia	>100
Coking Process
A Batch Process



Coal. 1600-2300°F Coke


(1 ton) no 02, 14-36 hours (o g+1um)
Byproducts
(Useful, toxic,
and hazardous)





Coking Byproducts


® Volatiles
-	"Breeze" particulates
-	Coke oven gas
® Liquids
-	Coal tar liquids
-	Flushing liquors
© Solids
-	Still bottoms, sludges
-	Other








"^Appliea;;S74
Rev. 09/03
-------
Process Chemistry: Iron & Steel Manufacturin

Coke Oven Volatiles


« Cooled from 1700° to 176°F
® Breeze particulate
-	Electrostatically separated
• Non-condensibles
-	H2S, HCN, CH4i CO, C02, NH3
® Condensibles







Ammonia
e
nh3 + h2so4
-»(NH4)2S04 (fertilizer)
«
nh3 + h2o
NH4OH (sold)
0
NH3,catalytically


cracked 	
—> N2 + H2
•
NH3, incinerate, but..
»
9
NH3 + H2(NH4)P04 —^Anhydrous NH3

(United States Steel's PHOSAM process)
Condensibles
• Light oil
-	Contains BTX (LNAPL)
® Naphthalene
-	Partially dissolves in oil
-	Partially solidifies (sublimes)
o Phenolics
-	Many constituents water soluble
jPAGE4
i ChemistryforEnvironmental Professionals—Applied
Rev. 09/03
-------
Process Chemistry: Iron &Steel Manufacturing
Light Oil and Naphthalene


CH3
CH,
| »



A
Ach'


0
0
0 i
00

Benzene
Toluene
Xylenes
V \/
Naphthalene



(o.m.p)

m.p., °C
5.5
-95
-48-13.3
80.2
b.p.,-C.
80.1
111
138-144
218
sp.gr.
.88
.87
.8 6-. 88
1.0
sol., mg/l
1750
526
161-185
31
OH
m.p, °C	43
b.p., °C	182
sp.gr.	1.06
sol., mg/l	8.3%
Phenolics
Cresols	Catechol,
(o;m,p) et al.
12-35 105-173
191-202	245-285
-1.03	1.15-1.35
-2%	7%—infinite
OH
Xylenols
27-75
210-225
<1.0
"slight"
Coal Tar Liquids


® Aromatics, including PAHs
« Creosote oil
« Refined tar
• Pitch, bitumen
« "Dumped" coal tar most environmentally
damaging








'Eherhishy JorEhvirbnmehtalPro^	1	A ,	..PAGE5
Rev. 09/03
-------
Process Chemistry: Iron & Steel Manufacturin
PAHs
(Polycyclic Aromatic Hydrocarbons)

Other Coking Byproducts


• Flushing liquors, wastewater
-	Recirculated
-	Treated, purified, discharged
® Solid hazardous wastes
-	Sludges
-	Distillation and other residues
-	Captured dusts








Iron Making - Blast Furnace


/DUST SO,
/ OTHER GASIFIED f
/ IMPURITIES i\j-J

IRON ORE. COKE
{COAL}
UMESTONE.
ADDITIVES
~7/pmT—7
IRON • PRODUCTS
OXIDES. ETC. (IMPURITIES)



LSLAG

Old, continuous process
SPAGEfi	i	"i 4 Chemistry for Environmental Professionals f-Applied,
Rev. 09/03
-------
¦:i',	.. Process Chemistry: Iron & Steel Manufacturing
Reactions in Blast Furnace
® C (coke) + 02 —
	> C02
• C02 + C
	~ CO
• CaC03 —
	> CaO + C02
• Fe304 + CO —
	> Fe203 + C02
• Fe203 + CO t—
	»• FeO + C02
© FeO + CO —
	*¦ Fe~+ C02
® FeO + C
	>• Fe + CO
Slag from Blast Furnace
© P removed early at high FeO and basicity
o S removed as sulfide:
— FeS + CaO + C =4) CaS + FeO + CO
• Other metals/metalloids removed as
oxides: Si02, Al203, MnO, MgO, CaO
Slag is used as road fill and railroad ballast, etc.
Iron to Steel - Basic Oxygen Furnace


irnn Carbon c+ooi



iron 	^ bteei
Other additives, e.g.
Cr or Cr+Ni — stainless steel





'CherfiistivforEhyirbi^enblPrbfessipnals^	:.-'V^;"PAGE7-
Rev. 09/03
-------
Process Chemistrv: Iron & Steel Mariufacturin

Iron to Steel -
Electric Arc Furnace (EAF)


Electricity



Fe from Other additives
direct and/or alloying
reduction agents (Cr.-Cr+Ni)




Key Chemicals - Steelmaking
Lead
Cadmium
PCBs
Chromium
Zinc
Acids, alkalis, iron, etc.
1999
ATSDR Rank
2
7
8, etc.
16, 73
70
>100
Raw Steel to Products
Sheets &
Slabs
Plates, pipe
Hot rolled sheets and
coil stock
Blooms &
Billets
""Seamless tube
-~Structural shapes (I-beams, etc.)
-~Bars, rods, etc.
Chemistry for£nvironmentaj Professionals--: Applied
Rev. 09/03
-------
Process Chemistry: Iron & Steel Manufacturing
Surface Treatment- Cleaning


® Physical
-	Air/water blasting
-	Abrasive
-	Vapor cleaning
• Chemical
Acid, base
-	Electrochemical








Surface Treatment - Protecting


o Oiling
• Pickling
o Coatings - metal/metal oxide, etc.
® Coatings - organic (vinyls)








Wastes from Surface Treating


•	Volatiles - from cleaning
- from organic coatings
•	Liquids - mostly aqueous
® Solids - mostly oxides








- Apptjicd
.PAGE9
Rev. 09/03
-------
Process Chemistry: Iron &Steel Marnifacturirii

Modes of Release - Overall


•	Air-borne - gases, "dusts"
•	Liquids - used up, recovered, "lost" to
environment
•	Solids - metals and oxides, etc., still
bottoms, slag, captured
"dusts," etc.
(Many wastes, classifiable under 40 CFR 261
and its amendments and appendices)








Analytical Considerations


•	Metals -AA.ICP.XRF
•	Solvents - GC, GC/MS
•	Tars/solids - Wet chem extraction,
separation
- HPLC, IR, MS







PAGE 10
; Chemistry forEnvironmental Professionals—Applied
Rev. 09/03
-------
Section 10
-------
Con taminant Fate and Transport jn the JAadpseZone
FATE AND
TRANSPORT
PROCESSES IN THE
ENVIRONMENT

VilUf 1
)oltLu\ I I ^ M

CHEMICAL FATE AND
TRANSPORT
IN THE
VADOSE ZONE
dr&y £oU. j M/vH
fa, \v4M-
CHEMISTRY FORENVIRDNMENTAL PROFESSIONALS- APPLIED ; ' ,	~ 3PAGE 1
*12/02
-------
Contaminant Fate and Transport in the Vadose Zone
Fate and Transport in the Vadose Zone
Objectives
« Define terms: Vadose zone, capillary fringe,
and matric potential
® Define volatilization, solubility, and adsorption,
processes which distribute contaminants
within the vadose zone
® Define advection, diffusion, and dispersion,
processes which describe the movement
and/or dilution of a contaminant plume
IUdMs)^
6

Vadose Zone


So)Iftoffeon . o-&\



Capillary fringe
Unsaturated
(vBtfose)

GW Fiow
	~
Saturated |
(unconfined aquifer) |

ib cmUamj (j ftkiuMx
fzMJtt-x -jjjbuGkMi
rWd
VoJMju-nd
q~qMx ffA'
Vadose Zone
Capillary Fringe
JSmJj
-------
Contaminant Fate and Transport in the VadoseZonc
u *
9v$~
Distribution of Water and Other Fluids
in Vadose Zone
• Matric potential
- Adhesive^nd cohesive forces ^ ^
•	Wilting point
•	Field capacity
•	Horizontal and vertical distribution
Matric Potential
Adhesive
forces
Cohesive
forces
Free water

Saturated
GVV ffow
_ . 1 oo 
-------
Contaminant Fate and Transport in the VadoseZone
Soil Peds or Particles Wetting
•	Water wet peds
•	Contaminant wet peds
Contaminants Considered
•	Metal ions
•	LNAPLs
•	DNAPLs
•	Landfill/sewage leachate
Partitioning of Contaminant in
Vadose Zone
•	Solubility
•	Volatilization
•	Henry's Law
•	Adsorption
PAGE 4,

-------
Contaminant Fate andTransport :n the VadoseZone
Solubility
•	Free-phase - 100% liquid contaminant
•	Dissolved phase - contaminant soluble
in H20
CHEMISTRY FDR ENVIRONMENTAL PROFESSIONALS-^ APPLIED		PAGES
-------
Contaminant Fate and Transport in the VadoseZone
Volatilization
•	Vapor pressure
•	Transport of contaminant vapor
"v-r	^
.......
•- .. *•:•••• • *¦
• • •. . • • 7; •:: •
Vapor
"P t ' f %.

"...,

A;
¦¦-'r	%
%'

/) ir
[M) td
Mb
Yvfk
Vapor Pressure
Chemical
VP (mm Hg)
MW (g)
Acetone
180
58.08
Benzene
75
78.12
TCE
65
131.39
Phenanthrene
«1.0
178.24
PCB
«1.0
296.00
all values reported at 20 C


CHEMISTRYFORENVIRONMENTALPROFESSIONALS—APPLIED
-------
Contaminant Fate and Transport in the Vadose Zone
CD
L_
W
ifl
(1)
O
Cl
CD
>
Vapor Pressure
' Acetone
Benzene
TCE
Phenanthrene
Tpcb
Molecular weight
X
E
> 200
Vapor Pressure Curves
<1.0 Atm (760 mm Hg)
i .1
700
I
j

600


500


400
. f
i	1 i i
10 20 30 40 50 60 70 80 50 100
Temperature (°C)
Vapor Pressure
Triple Point for Water
218



§
Ice

Water
-------
Contaminant Fate and Transport in the VadoseZone
Vapor Pressure
Conditions that affect volatilization:
•	Concentration of contaminant vapor in
soil-air
•	Soil moisture content
•	Soil matric potential
•	Soil temperature
•	Atmospheric pressure
Henry's Law Constant
•	Describes the partitioning of a
contaminant between air (vapor phase)
and water (liquid phase)
•	Vapor is non-reactive in water

Henry's Law


1, _ VP
nL Solubility

Compound
VP (mmHg)
Sol.(mg/L)
u , atm-m3*
nL ( mor )
VC
2,300
1,100
6.9 x 10 ~1
Benzene
76
1,780
5.4 * 10~3
TCE
58
1,100
8.9 * 10 "3
MEK
71.2
268,000
2.7 x 10 "5
PCP
0.00011
1
2.8 x 10"*
/-y-

-------
Contaminant Fate and Transport in the VadoseZone
Henry's Law Constant

' v.
".V
% C,
••••• .•••" fifth

'W
¦¦¦¦ •

ca 	
a-..
		*,
¦,;S'
U**'
Contaminant partitioning
between soil-air and soil-liquid
Henry's Law Constant
How to quantify this process?
Example C02
,, _ Ca _ Vapor pressure
H -
H =
Cw Solubility
VPco2lg, (in atm)
Molar cone. C02(aq) /liter
atm-L
mole
Adsorption
@ Soil's adsorbent materials
• Retards liquid contaminant transport in
vadose
CHEMISTRY FOR ENVIRONMENTAL PROFESSIONALS— APPLIED
PAGES
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Contaminant Fate and Transport in the VadoseZone
Adsorbent Materials
•	NOM - natural organic matter
-	Nonpolar organic compounds
-	Low solubility in soil-water with high
surface areas
•	Clays and metal ion complexes
•	Adsorptive forces
Natural Organic Matter
•	Fulvicacid
•	Humin and humic acid
•	Biopolymers
-	Lignin
-	Cellulose
-	Proteins
Clays and Other Minerals
•	Clays
-	Montmorillonite
-	Illite
-	Kaolinite
•	Metallic complexes
® Colloids
PAGE 10 "	CHEMISTRY FOR ENVIRONMENTAL PROFESSIONALS^ APPLIED:
-------
Contaminant FateandTransport in the VadoseZone
Other Adsorbent Environments
•	Van der Waal's forces
•	Chemisorption
-	Sorption to NOM
-	Sorption to metal complexes
ijA-
- CM
-------
Contaminant Fate and Transport in the VadoscZone
Cation Exchange Capacity (CEC)
[soil] e 2H+ + Cu+2 ^ [soil] = Cu+2 + 2H+
CEC units:
-	meq /100 g of soil
-	centimoles of positive charge/kg soil
	Quantifying CEC	
One equivalent (eq) of an ion is the weight
which will completely react with an
equivalent of another species
^	weight of 1 mol of ion
0C' valence charge of the ion
Example:
. n +2 63.546 g -.
1 eq Cu 2 = —^— = 31.773 g
Quantifying CEC
Defining milliequivalent (meq):
-------
Contaminant Fate and Transport in the Vadose Zone
	CEC
Examples:
•	Clays: 2-150 meq/100 g of soil
•	Soil organic matter: >200 meq /100g of
soil
•	Sand: 2-7 meq/100 g of soil
Transport Processes of a
Contaminant's Vapor
•	Advection
•	Gravity-driven
•	Diffusion
•	Dispersion - tortuosity of pathways

Transport Processes
•	Primary porosity pathways
•	Secondary porosity pathways


Mulgujcr [idf-Q
CHEMISTRY FOR ENVIRONMENTALPROFESSIQNALS—APPLIED
PAGE 13
-------
Contaminant Fate and! Transport in the Vadose Zone
Secondary Porosity Pathways
•	Faults
•	Fractures and joints
•	Bedding plane partings
•	Exfoliation
-------
Contaminant Fate and Transport in the Vadosc Zone
Gravity-driven
Vapor Density
Pure air	1200 g/m3
DCE	1949 g/m3
o-Dichlorobenzene	1211 g/m3
Benzene	1409 g/m3
DCM	2274 g/m3
Gravity-driven
•	Vapor density of pure air - 1200 g/m3
@ 20°C
•	Density of contaminant vapors
•	Source of information - NIOSH Pocket
Guide
Advection
•	Vapor movement by pressure gradient
•	Causes of gradient
•	Gas velocity
CHEMISTRY FOR ENVIRONMENTAL PROFESSIONALS-^ APPLIED	• ' • V'"'' ;	. PAGE "15
-------
Contaminant Fate and Transport in the VadoseZone
Diffusion of Vapors
Concentration vs. Distance from Source
Concentration gradient = ^
Diffusion of Vapors
•	Solubility of contaminant in air spaces
•	How large are the spaces?
•	How continuous are the spaces?
Dispersion
Process which results in dilution of
contaminant plume's concentration
PAGE16

-------
Contaminant Fate and Transport in the VadoseZone
The Real World

^ - hv ¦''











flQORE y'f^

Case Study
Dispersion
.v.VKss
Dispersion - Tendency for a
} solute to spread from the
|| path that it would be
f| expected to follow under
f advective transport
v^.j.v.v.v.v.v. ¦ '.j.yCv.vIjT
Contaminant movement,,.
J|k
CHEMISTRY FDR ENVIRONMENTAL PROFESSIONALS- APPLIED
PAGE17
-------
Contaminant Fate and Transport in Groundwater
CONTAMINANT FATE
AND TRANSPORT
IN
GROUNDWATER
Fate and Transport in Groundwater
Objectives
•	Define hydrogeologic terms: Aquifer
(unconfined or confined), hydraulic
gradient, hydraulic conductivity, porosity,
and permeability
•	Define oxidation/reduction components:
Electron donor, electron acceptor,
metabolic by-products, and energy
Fate and Transport in Groundwater
	Objectives	
•	Describe how groundwater chemical
parameters such as Eh, pH, chemical
concentration, and specific
conductance/total dissolved solids change
in response to hydrocarbon contamination
•	Define geochemical parameters: Alkalinity,
hardness, and complexation
•	Define contaminant retardation
CHEMISTRY FOR ENVIRONMENTAL PROFESSIONALS-APPLIED
PAGE 1
-------
Contaminant Fate and Transport in Groundwater
<3-
Votalilcarton
Percolation
i vadose zone ^s#5sp Diffuson	Oisiersion i_!>5
' vVAv!
Detraaalron '
iiEvAd sorption
	 $ft:SA
;i_yRetaraation
~ &lffL5.0-i	
hoioc hemic af:
reactions
a. •
o ~~ •
Microbial
-vv-?. tran sf orrn
• • xf-1- • —
y^. - -x>^°5urf ace A'ater
Dispersior L4> >,,* TT:-*
l/V/?af /'s an Aquifer?
•	Matric potential: adhesive and cohesive
forces are satisfied
•	Free water now available to move
through aquifer
What is an Aquifer?
Unconfined Aquifer
\4~4hh HlkJljv,ii
^ eX'l
\J a kU
1.1
0
CHEMISTRY FOR ENVIRONMENTAL PROFESSION ALB APPLIED
-------
Contaminant Fate and Transport in Groundwater
Physical and Chemical Properties
of Aquifers
• Geologic material
-	Heterogeneity
-	Porosity and permeability
-	Mineralogy
fj
Physical and Chemical Properties
	of Aquifers
•	Hydrogeologic parameters
-	Hydraulic gradient
-	Hydraulic conductivity (K)
-	Groundwater flow direction and velocity
-	Matric potential
•	Background chemistry of groundwater
-APPLIED
PAGE 3
What is an Aquifer?
Confined Aquifer
-------
Contaminant Fate and Transport in Groundwater
Contaminants Considered
•	Metal ions
•	LNAPLs
•	DNAPLs
•	Landfill/sewage-leachate
Oxidation-Reduction Reactions
Electron donor + electron acceptor
(Metabolic) by-products + energy
Oxidation-Reduction Reactions
Electron donors:
•	Petroleum hydrocarbons (LNAPLs)
•	Landfill leachate and natural organic
carbon
Electron acceptors:
« 02) N03- Mn+4, Fe+3, S04"2, C02
PAGE 4
, " CHEMiSTRY FOR ENVIRONMENTAL PROFESSiONALS^ APPLIED
-------
Contaminant Fate and Transport in Groundwater
Oxidation-Reduction Reactions
Metabolic by-products:
•	C02l N2, Mn+2, Fe+2, H2S, CH4
•	Energy for microbes, e.g., e~ ATP
Parameters to Evaluate
Chemical Changes
•
Eh/pH-related reactions
•
Dissolved gases
•
Alkalinity/pH buffer
•
Specific conductance/ total dissolved

solids
•
Hardness
•
Complexation
r o
Chemical Parameter Changes from
LNAPL Contamination
CHEMSTRYFOR ENVIRONMENTAL PROFESSIONALS—APPLIED
PAGES
-------
Contaminant Fateand Transportin Groundwater

(J,
*&if\

n
Eh-pH
+ 1 0-
+0.8-
+0.6
+0.4 -
+0.2-
Eh 00
(volts) _0 2
-04
-0 6-|
-0.8
-1 0
i	SV ty-
V
*¦«*	vQr/a.
. -.
. *'
*> $/,
'•a
V

->.	"Vj.	"7a.
h.
Js*,


C*C ??a,
¦X
¦P6.
oxidizing
neutral
reducing
l	1	1—i—i—r
0 2 4 6 B 10 12 14
	pH (S.U.)
Eh-pH
Diagram for
Lead (Pb.)
Eh
(volts)

r®y;
Pb \
\
pH
(su)
Contaminated Groundwater Chemistry
Dissolved Hydrocarbon
•- ••¦--T.fr
Aquitard
GVV
BTEX concentration
m Medium Q Lew


-------
Contaminant Fate and Transport in Groundwater
Contaminated Groundwater Chemistry
Oxidation of Hydrocarbons, e.g., Benzene
1
Larvflll


*
-1

"" "







u


« r •

Gw
"l
J
V
y
V

I.
\ /" " '
L-


Chemical oxygen demand
RS5 H»qh S3 Me dun Cj !_«*•
Oxygen concentration
KB Hqh EZ3 Med-jn CZj Low
Oxidation-Reduction Reactions in
Contaminated Groundwater
® Benzene oxidation - manganese reduction:
C6H6 + 50, + Mn(OH)4
Benzene
6C02 + 6H+ + 8e~ + Mn+2 + 2H20
Oxidation-Reduction Reactions in
Contaminated Groundwater
• Benzsne oxidation - iron reduction:
C6H6 + 502 + Fe(OH)3 -*
Benzene
6C02 + 7H+ + 9e~ + Fe+2 + H20
CHEM1STRYFDR ENVIRONMENTAL PROFESSIONALS—APPLIED
PAGE7
-------
Contaminant Fate and Transport in Groundwater
Contaminated Groundwater Chemistry
Oxidation of Hydrocarbons, e.g., Benzene
Sulfate Reduction/Sulfide Oxidation
Oxidation-Reduction Reactions in
Contaminated Groundwater
• Benzene oxidation - sulfate reduction:
C6H6 + 502 + SO,"2
6C02 + H+ + 2e~ + HS~ + 2H20
Contaminated Groundwater Chemistry
Oxidation of Hydrocarbons, e.g., Benzene
Iron and Manganese Reduction
Fe" concentration
52	Me
-------
Contaminant Fate and Transport in Groundwater
Oxidation-Reduction Reactions in
Contaminated Groundwater
• Benzene oxidation - denitrification:
2N03" + 2H+ + C6H6 + 502
6C02 + N2 + 4H20
Contaminated Groundwater Chemistry
Oxidation of Hydrocarbons, e.g., Benzene
Nitrification of Ammonia

t
3
§2
m t
I
m
t


; T OiV ^
• +
¦ i
; +

I
*
c 3
D g
I
n
c

rT:
'Djmp' l
Aqjrtw 4
GW



Ammonium concentration
K8J Hah C3 O to-



Nitrate concentration
tS High E3 Median CU Low












Contaminated Groundwater Chemistry
pH Changes
Example:
® Benzene oxidation - iron reduction:
C6H6 + 502 + Fe(OH)3 -4
Benzene
6C02 + 7H++ 9e" + Fe+2 + H20
CHEMISTRY FOR ENVIRONMENTAL PROFESSIONALS-APPLIED	PAGES
-------
Contaminant Fateand Transport in Groundwater
Alkalinity
HCO3-1 + CO3-2 + OH-+ CaC03
•	Provides buffer for pH changes
« H,0 + C02 = H2C03
•	H2C03 = HCO3- + H+
•	HCO3- = H+ + CO3-2
Contaminated Groundwater Chemistry
Oxidating Hydrocarbons, e.g., Benzene
Dissolved Gases
Contaminated Groundwater Chemistry
pH Changes

4
£
% 3
J*
m t
I
«
%
*
Landfll
I **"" r'	
..
| S:*v-v.v;
A^jtard
X.

A.
i
s
a
§ 8
m 2
I
«
c
A'
Lan<*ll



pH
gg L»» CZ3
~ *9h


COj(g) concentration







PAGE *ID
CHEMISTRYFORENVIRONMENTALPRDFESSIONALS-APPLIED
-------
Contaminant Fate andTransport in Groundwater
Alkalinity
GW
Total Alkalinity as HC03
ggB High OT Medium |w3 Low
Dissolved Ions
Cations
Anions
Ca+2 .
HCO3-
Mg+2
co3-2
Na+
OH"
K+
cr
Fe+2
S04"2
H+
NOf
1
Specific Conductance (SC)
vs. Total Dissolved Solids (TPS)
• High SC measurements
® High TDS
CHEMISTRY FDR ENVIRONMENTAL PRDFESSIDNAUS-APPLIEjD

PAGE11
-------
Contain inant Fate and Transport in Groundwater

Total Dissolved Solids
f
Leaking LIST
I

0)

c ca
o a>
''
> c
Is
me
a>
g
n
ca
^Free-phase LNAPL liquid
GVV
a-
^5


Total dissolved solids

High i&&] Medium Low
Hardness
Calcium and magnesium salts cf
• Sulfate

noncarbonate or
« Chloride
permanent hardness
• Nitrate

• Carbonate
carbonate or
• Bicarbonate
temporary hardness
Hardness
Type
mg/L expressed as CaC03
Soft
0-60
Moderately hard
61-120
Hard
120-180
Very hard
/
>180
PAGE 12
CHEMISTRY FOR ENVIRONMENTAL PROFESSIONALS- APPLIED
-------
Contaminant Fate and Transport in Groundwater
"Classic" Inorganic Solubility vs. pH
pH (s u.)
Complexation/Colloids
•
Can change actual inorganic solubility
•
Eh-pH dependent
•
Humic and fulvic acid complexes
•
Oxyhydroxide colloids, e.g., FeO • OH
•
Other ionic colloids
Fe Colloid [Fe02(0H)"']
I I
0	o
1	I
"HO— Fe —O—Fe — OFT
I I
0	o
1	I
HO— Fe —O—Fe —OH"
I	I
o	o
PAGE 13
-------
Contaminant Fate and Transport in Groundwater
What about DNAPL Compounds?
Bedrock

Transformation of Chlorinated
Solvents i.e., PCE
DNAPL
Source
LNAPL
Source
"Background
chemistry"
Oxic
Anoxic
Oxygen begins to
increase
4,%LhoUM.
I#***7 //
^3,

PAGE 14
CHEMISTRY FOR ENVIRONMENTAL PROFESSIONALS - APPLI ED
-------
Contaminant Fate arid Transport in Groundwater
Oxidation-Reduction Reactions
•	Reductive dechlorination of DNAPLs by
microbial degradation:
PCE, TCE, TCA
•	LNAPL electron donors
•	DNAPL by-products:
TCE, DCE and VC
Contaminated Groundwater
•	Benzene oxidation - PCE reduction:
C2CI4 + C6H6 + 502 + 2H20
PCE
6C02 + C2HCI3 + CI" + 9H+ + 8e-
•	Iron reduction - vinyl chloride oxidation:
Fe(OH)3 + C2H3CI + 202
vc
2C02 + e" + cr + 3H20 + Fe+i

a

CHEMISTRYFOR ENVIRONMENTAL PROFESSIONALS-APPLIED
-------
Contaminant Fate and Transport in Groundwater
Retardation (Rd)

•	Rd = 1+ -
•	Adsorption %Kd
Adsorption Coefficients
• K K
1 xom' 1 xoc
K
ow
*	fom' foe
•	Kh
Benzene Distribution
U)
a



Krt =
A
c,„
^oc x ^oc
Cw (mmol/l)
CHEMISTRY FOR ENVIRONMENTALPROFESSIONALS-APPLIED
-------
The Rea/World
%>;v •,
C'0>Ssi^£- '&)
. , £ 		
FIGURE ly^'Sllc^c-rToo'Map	:V?
Case Study
CHEMISTRY FDR ENVIRONMENTAL PROFESSIONALS- APPLIED
PAGE17
-------
Section 11
-------
Data Usability

Anirjn Irr-Jt vn -vmi -jntl
ac=t tree -In ~J^CC
fHrrcirs" *e '-•ve in
«;¦» Jlr-^u jtai .ty
H » ine •een-rsor.iv J \rr. jay
tcnr«i-me ¦urrrti m rWa.1
iwrajn tv nm rioxjrrl
s«—lI 1 ! ( 1 -I ill
DATA
USABILITY
for Environmental
Data Generation

Data Usability Objectives
Objectives:.
•	Define detection limits, Sample
Quantitation Limit (SQL), Method
Detection Limit (MDL), and Instrument
Detection Limit (IDL).
•	Define data qualifiers, "u", "j", and "r".
•	Define data quality indicators, precision,
accuracy, etc
® Chemists
-	Develop analytical methods
-	Perform analyses
-	"Lords" of analytical chemistry
® Sampling specialists
-	Develop sampling methods
-	Write and implement sampling plans
-	"Lords" of sampling world
\AM
-------
Data; Usability:
Decision-makers
Project Managers, RPMs, etc.
• Decision-makers
-	Primary data users
-	Not necessarily chemists or sampling
experts
-	Must be able to interpret information
-generated by data producers
-	Must be assured that data is adequate
for its intended use, i.e., decision to be
made
Data Gathering System
What we have here is a failure to communicate
® Decision-makers
-	Must specify objectives for data collection
activities
-	Make decision based on what's produced
•	Data producers
-	Interpret data users' stated objectives
-	Prepare and execute sampling plan
-	Present data
•	Communication is essential to ensure data
are appropriate for its intended use
Environmental Data Quality
What are the Issues to be Discussed?
®	General requirements
«	Measurement limits
®	Data qualifiers
®	Data quality indicators
•	Technical and legal defensibility
PAGE .2
CHEMISTRY FOR ENVIRONMENTAL PROFESSIONALS - APPLIED
R12/02
-------
Date Usability
Environmental Data Quality
What are the General Requirements?
•	Measurement sensitivity requirements
-	Parts per million (ppm) or parts per
billion (ppb)
•	Data type
-	Analyte-specific
-	Laboratory vs. field
-	"Broad" spectrum preferred (at least one
per medium)
•	Media
-	Air, water, soil, biota, waste, etc.

Measurement Limits

Types
•
Instrument detection limit (IDL)
•
Method detection limit (MDL)
•
Sample quantitation limit (SQL)
•
Others
Instrument Detection Limit
® Describes instrument sensitivity under
ideal conditions
•	Operational definition: 3 * SD of seven
replicate analyses at lowest concentration
that is statistically different from blank
•	Neither method-specific nor sample-
specific
•	Least useful measurement for assessing
data quality
CHEMISTRY FOR ENVIRONMENTAL PROFESSIONALS^ APPLIED
PAGE 3
-------
Instrument Detection Limit
Analyte
I
o
CO
X
CO
¦MWM


IDL
\ <- Instrument noise
	Method Detection Limit
•	Minimum analyte concentration that can be
reliably identified by a specific analytical
method
•	Operational definition: 3 x SD of seven
replicate spike samples run according to
the complete method
•	Accounts for sample size, reagents,
preparation, etc.
•	Not sample-specific; determined under
ideal conditions
Method Detection Limit
Analyte
1
	MDL
3 * SD
-------
Data Usability
Sample Quantitation Limit
•	Operational definition: MDL adjusted to
reflect sample-specific action, e.g., extra
dilution, sample size adjustment
•	Most useful measurement limit
•	-SQL-may-vary from sample to sample
Sample Quantitation Limit
Sample X
40 100 XO 340 Xt> »0 400 450 WO
Concentration imgfrn')
Sample X
Diluted sample X (0, = 10)
Cone read	Actual
SQL by analyst	sample cone
25 7500	">
250 400	4000'
*(IR) K (D,) = Actual concentration in
original sample
400 * 10= 4000
Measurement Limits
	Others	
•	Contract-required quantitation limit (CRQL)
-	Performance standard for EPA's Contract
Lab Program (CLP)
-	Applies to organic analyses (CRDL
applies to inorganic analyses)
•	Practical quantitation limit (PQL)
-	Lowest limit reliably achievable under
routine laboratory conditions
CHEMISTRY FOR ENVIRDNMENtALPROFESSjDNALSr-: APPLIED
PAGES
-------
Data Usability

Qualified Data
Common Data Qualifiers
! Qualifier .
i
Analyses Explanations
u
!
The chemical was analyzed, but was not
detected. The associated numerical value is i
the sample quantitation limit
: J
The chemical is present. The associated
numerical value is of less certain quantitation ;
! R
The data are unusable (chemical may or
may not be present). Resampling and
reanalysis are necessary for verification
Qualified Data
•	Chemists' "codes" to identify data
inadequacies
•	Indicative of QC problems with a sample
or set of samples
•	Data may be qualified by:
-	Laboratory - "good"
-	Independent third party - "better"

Applying Data Qualifiers to
Quantitation Limits
i
r Certain detection
Certain qjantitatian
			 SQL
a
09
m
c
o
Sample


" Certain detection ianaiyst's judgement)
" Uncertair cjjanttatioo
c
•I)
£
o
U
Sample 1 :


¦* Uncertair detection
" Uncertair quanb'aion
Sample 1 = "u - not detected
Sample 2 = "j - uncertain quantitation
Sample 3 = no qualifier


PAGE6 ; "
CHEMISTRY FOR ENVIRONMENTAL PROFESSIONALS—APPLIED
-------
Data Usability
Applying Data Qualifiers
Student Exercise
7.
6 |
I
5
;i
i
2,
1 '
oi.
Sample 3
" Certain oetecticn
" Certain quentitatian
SQL
Ce-ttin awecticn (analyst s judgement)
Uncertain cjjanitaoon
ft; •' Uncertain detection
v> «» Uncertain quantitation
Sample 1 = 	
Sample 2 =	:	
Sample 3 =	
Data Quality Indicators
PARCC Parameters
•	Tools for describing, specifying, defining
data quality
-	Precision
-	Accuracy
-	Representativeness
-	Comparability
-	Completeness
•	Specify in Quality Assurance Project Plan
(QAPP) and/or Sampling and Analysis
Plan (SAP)

V, ¦
V
Precision
/
Measurement of the degree of agreement
among individual measurements
Usually evaluated using duplicate samples
Evaluateyelative percent difference (RPD)
^ I s, - S, I
rpd= iVsj/f *100
50%
si/

CHEMISTRY FOR ENVIRONMENTAL PROFESSIONALS—APPLIED
-------
Data Usability
Precision
~
Sample 1:
i

Duplicati
Sample 1 .






RPD =
£
TCE Analysis
100 i.g/L
1100 - 130|
(TOO" + 130)/2
£
TCE Analysis
130 -g/L
X 100
30
115
100 = 26%
=o&M tfrd
Accuracy
•	Closeness of a measurement to the true
value
•	Usually evaluated using spiked samples
•	Results reported as "bias," a component
of accuracy
•	Use of field spikes is not recommended
for soils
-/iceMuMvf'
Precision and Accuracy
Low Precision + Low Bias
Low Accuracy
High Precision + High Bias
Low Accuracy
Low Precision + High Bias ¦
Low Accuracy
High Precision + Low Bias ;
High Accuracy
tfD & qo
Jdi
-JtiOd

PAGE 8	CHEMISTRY FOR ENVIRONMENTAL PROFESSIONALS-APPLIED
-------
Data Usability

Measurement Error
What Factors Affect
Precision and Accuracy?

• Random errors
-	Uncertainties inherent in every physical
measurement
-	As likely to be positive as negative
(unbiased)

-	Limit precision of measurement
-	Detectable via multiple measurement,
e.g., duplicates

Measurement Error
Random Error
100
AA
A A A
A

True
Value


Systematic Error
100


A I A A
A
True
Value
A = Sample Value
Measurement Error
What Factors Affect
Precision and Accuracy?
• Systematic errors
-	Defect in method, sampling technique
or design, instrument malfunction, or
analyst error
-	Results in "biased" data, i.e., the error
tends to be mostly high or mostly low
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CHEMISTRY FDR ENVIRONMENTAL PROFESSIONALS- APPLIED
PAGES
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Data Usability
Evaluating Bias - Example
Sample f
Analysis
£
20 ppb Pb
Is this the true value?
Sample 1
10 ppb Pb
fSpjkedl^
Analysis
XI
25 ppb Pb
Expected value :
30 ppb Pb
Evaluating Bias - Example
% Recovery = (spiked result) - (unspiked result)^ 0Q
amount spiked
25 ppb — 20 ppb
% Recovery = — i q ppfe *100 = 50%

Representativeness
@ Data must be representative of exposure
or assessment area
•	Representative samples depend on study
objective
-	Average exposure vs. maximum, upper
percentile, etc.
-	Surface soil interval
-	Temporal and/or spatial variability
•	Non-representative samples introduce bias
into data
page10

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Technical and Legal Defensibility
» Standard Operating Procedures (SOPs)
® Standard analytical methods
9 Quality Assurance / Quality Control
(QA/QC) samples
Completeness
•	Acceptable data must be available for
"decision-critical" samples
•	Data may be incomplete for a number of
reasons:
-	Sample loss - broken bottle or couldn't
collect sample
-	Analytical loss - mercury analysis
qualified "r," rejected
Comparability
•	Qualitative evaluation - can different data
sets be combined?
•	Consider differences in:
-	Sampling design
-	Analytical methods
-- -Sample preparation
-	Laboratories
-	Media variability
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Data Usability
Standard Operating Procedures
•	SOPs - detailed standard and
accepted procedures, protocols, and
methods for specific tasks
•	Developed by recognized authority
(EPA, ASTM, state water department)
Standard Analytical Methods
•	Analytical methods ¦
-	EPA
-	USGS
-	OSHA
-	ASTM
•	Recognized by courts
•	Increase comparability
QA/QC Samples
• Field samples
-	Field blanks
-	Trip blanks
-	Rinsate blanks
-	Duplicates

PAGE12

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Data Usability
QA/QC Samples
9 Laboratory samples
-	Reagent blanks/method blank
-	Matrix spike/matrix spike duplicate
-	Duplicates
-	Performance evaluation (PE) samples
The Real World

- i
,. .V-T3"ssr •. - ¦— -'.-1
•••w. C c. - ...
7 
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Data Usability
PAGE 14
The Real World
Case Study
Given Ohio EFA site assessment data:
« What was the sample matrix1or~*
DRM001? —l'U
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Summary

Considerations for Data Usability

• Is the precision (random variability) known?

- Will it affect the usability of the data?

• Is the magnitude and direction of bias

known?

- Will it affect the usability of the data?
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CHEMISTRYFDR ENVIRONMENTAL PROFESSIONALS-APPLIED
PAGE 15
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Sample Collection
Information and
Parameters
DRM001
M9/I
volatile Orqanics


acetone
<
50
benzene
<
5
bromodichloromethane
<
5
bromoform
<
5
bromomethane
<
10
2-butanone(MEK)
- <
100
carbon disulfide
<
5
carbon tetrachloride
<
5
chlorobenzene
<
5
chlorodibromomethane
<
5
chloroethane
<
10
2-chloroethylvinylelher
<
. 10
chloroform
<
5
chloromethane
<
10
1,1-dichloroethane
<
5
1.2-dichloroethane
<
5
1,1-dichloroethene

11
trans-1,2-dichloroethene
<
14
1,2-dichloropropane
<
5
cis-1 ;3-dichloropropene
<
5
trans-1,3-dichloropropene
<
5
ethylbenzene
<
5
2-hexanone
<
50
methylene chloride

2 J
,4-methyl-2-pentanone
<
50
styrene
<
5
1.1.2.2-tetra chloroethane
<
5
tetrachloroethene
<
5
toluene
<
5
1.1,1-trichloroethane

70
1.1,2-trichloroethane
<
5
tnchloroethene


trichlorofluoromethane
<
5
vinyl acetate
<
50
vinyl chloride
<
10
xylenes (total)
<
5
J - Less than limit of quantitation but greater than zero
Real World Case Study
RESULTS OF CHEMICAL ANALYSIS OF
OEPA-COLLECTED SAMPLES
DRM002
M9/I
Sample Number
DRM003
ng/kg
S001
Mg/kg
S002
pg'/kg
S003
ng/kg

32 J
< 5,000,000

16
< 500,000
<
5
< 500,000
<
5
< 500,000
<
10
< 1,000,000
<
100
< 1,000,000
<
5
< 500.000
<
5
1,400,000
<
5
-< 500,000
<
5
< 500,000
<
10
< 1,000,000
<
10
< 1,000,000
<
5
< 500,000
<
10
< 1,000,000
<
5
< 500,000
<
5
< 500,000
<
5
< 500,000
<
5
< 500.000
<
5
< 500.000
<
5
< ¦ 500.000
<
5
< 500,000
<
5
2,700,000
<
50
< 5,000,000

20
< 500,000
<
-50
< 5,000,000
<.
5
< 500.000
<
5
< 500,000
<
5
< 500,000

3 J
3,300,000
<
5
< 500,000-
<
5
< 500,000

51
< 500,000
<
5
< 500,000
<
50
< 5,000,000
<
10
< 1,000,000
<
5
17,000,000
5,000
500
500
500
1,000
10,000
500
500
500
500
1,000
1,000
200
1,000
500
500
500
500
500
500
500
2,900
5,000
200
5,000
500
500
500
5,800
500
500
1,100
200
5,000
1,000
36,000
44 J
< 10.000
<
5
<
1.000
<
5
<
1,000
4
5
<
1,000
<
10
<
2,000
<100
< 20,000

16
<
1.000
<
2 J
<
1,000
<
5
<
1,000
<
5
<
1,000
<
10
<
2,000
<
10
<
2,000
<
5

1,600
<
10
<
2,000
<
5
<
1.000
<
5
<
1.000
<
5
<
1.000
<
5
<
1.000
<
5
<
1.000
<
5
<
1.000
<
5
<
1.000

4 J


<
50 .
<10,000
32
<
1,000
<
50
< 10,000
<
5
<
1,000
<
5
<
1,000
<
5
33
<
1.000
<
5
<
1,000
<
5
<
1,000
<
5
<
1,000

16
<
1,000
<
50
<10,000
<
10
<
2,000
24
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Data Quality Objectives
THE DATA QUALITY
OBJECTIVES
PROCESS
For Environmental
Data Generation
Quality
What is Quality?
•	Peculiar and essential y
character, i.e., essence -g
fa
® Quality can be "good" or f- jf!
"bad" VI
•	Customers prefer "good"
quality and good value 1
UALITY
;ed Cars
t[\\ »
Mr'
i

CHEMISTRY FOR ENVIRONMENTAL PROFESSIONALS- APPLIED	PAGE1
Data Quality Objectives Process
Objectives
Describe components of a quality
management system
Identify DQO process steps
Define false positive and false neg
decision errors
ative
I
-ff/L
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Data Quality Objectives
Quality
	What is "Good" Quality?
•	Good quality is not an accident
•	It is the result of:
-	Planning
-	Assessment
-	Investment
-	Communication
•	Organizations employ management
systems to ensure goals are attained
Quality
What is "Good" Quality?
«
Doing things right the first
time
Adherence to standards
Meeting expectations
precisely or within tolerable
limits
Appropriate for the
intended use
QUALITY
Environmental
. - Data
Quality
What is Quality?
•	Peculiar and essential
character, i.e., essence
•	Quality can be "good" or ff
"bad"
•	A wise customer knows his
needs and "checks under
the hood" before buying
QUALITY
Environmental
Data

CHEMISTRY FOR ENVIRONMENTAL PROFESSIONALS^APPLIED
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Data Quality Objectives
Quality
Quality Management System (QMS)
•	A management system for ensuring that
quality goals are attained
•	EPA's plan for ensuring data quality
-	EPA Directive 5360.1
-	Policies and program requirements
-	Management authority: ORD Quality
Assurance Division
jtj j ^
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if
CHEMISTRY FDR ENVIRONMENTAL PROFESSIONALS- APPLIED
PAGE 3
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Quality Management System
Quality Control p-r-p
r;
.....cz
J^/ctsPL
UU/M
OuHtf Control
QC: Technical activities that measure
performance relative to standards for
verification that those standards are met
-	Calibrating instruments
-	Duplicate samples, etc.
Is a quality-assurance project plan
(qaprTqaV QC?
Quality Assurance Project Plan (QAPP)
•	QAPP must address:
-	Project management and responsibilities
-	Measurement methods and procedures
-	Assessment/oversight activities
-	Data validation and usability criteria
•	Problem: How does the decision-maker
formulate and then communicate data
needs?
Data Quality Objectives
(DQO) Process
•	Structured tool for project planning
•	Provides communication between the data
collector and the data user
•	Ensures data will be appropriate to support
decision-making
•	Provides basis for developing QAPP
and/or sampling and analysis plan (SAP)
PAGE 4
CHEMISTRY FORENVlRDNMENTALPROFESSiONAL^^AP^[#ff
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Data Quality Objectives

Scope of the DQO Process

Who uses the DQO process?
•	Applicable to all types of environmental sites
•	U.S. EPA-developed guidance
-	Guidance for the Data Quality Objectives
Process (EPA/600/R-96/055)
-	Data Quality Objectives Process for Superfund
(E PA/540/R-93/071)

• Applicable to various levels of investigation
- Initial investigation through cleanup
confirmation

Seven Steps of the DQO Process
1.	State the problem
2.	Identify the decision
3.	Identify inputs to the decision/-
4.	Define study boundaries	£
5.	Develop a decision rule
6.	Specify limits on decision errors
7.	Optimize the design
-------

res
Step 1: State the Problem
What is the environmental and regulatory context?
•	What are the known or suspected
contaminants, sources, pathwaysTand
receptors?
•	What is the appropriate regulatory —	
authority?
•	What are the limits on budget, equipment,
and time?




kv
^' *%)(.
O&dL*L
r
Step 2: Identify the Decision
When you know the problem, what do you need to decide?
•	Determine whether the lagoon is
releasing contaminants to the aquifer
•	Determine whether nearby DW wells
are contaminated above health-based
standards or action levels

Wfyurf "SM4

Step 3: Identify Inputs to the Decision
What information is needed to support the decision?
Is there a release from the lagoon?
GW samples from monitoring wells
Monitoring well depths and construction
Background GW samples 		
Source samples from lagoon	Wd
GW flow direction
Historical information

}cd3^
>	CHEMISTRY FDR ENVIRONMENTAL PROFESSIONALS—APPLIED,
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Data Quality Objectives

Step 3
What information is needed to support the decision?

• Have residential wells been affected and
at what level?
-	DW well samples
-	Background samples
-	Residential well depths and construction

- Identify appropriate health-based action
levels

Step 4: Define Study Boundaries
What are the study's spatial and temporal boundaries?
•	Spatial - Limited to aquifer(s) in actual
or potential contact with the lagoon
•	Temporal - Potential health effects
dictate that residential well study be
done quickly. Confirmation of release
from the lagoon should take into	^ \
account seasonal GW flow variability. J S/i>'
		
htd-

Step 5: Develop a Decision Rule
"If..., then" statement
If mean contaminant concentration in
monitoring wells is greater than background,
then GW contamination exists and further
investigation is needed to determine what/if
remedial response is necessary
If maximum contaminant concentration in DW
wells is above action levels, then an immediate
response is required (carbon adsorption,
bottled water, etc.) to protect residential
population
CHEMISTRY FOR ENVIRONMENTAL PROFESSIONALS—APPLIED
PAGE?
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Data Quality Objectives
Step 6: Specify Limits on Decision Errors
What amount of error is tolerable?
•	Consider consequences of making an
incorrect decision
•	Must communicate with decision-maker
•	Select analytical methods and QA/QC
procedures that will provide appropriate
data for the decision
Decision Errors
thought I was wrong once, but I was mistaken...
•	False positive —. "7^/ flJU \ jAAdh
-	A contaminant is not actually present above
decision point but is mistakenly identified as
such
-	Example: laboratory contamination of sample
with phthalates
•	False negative fuffiji ^
-	A contaminant exceeds the decision level but is
not correctly quantified
-	Example: error in extraction procedure produces
extract with too little contaminant
False Positive Decision Errors
Consequences
•	Example: A release to the aquifer is
identified when in reality there has been
no release
•	Consequences:
-	Expend resources on unnecessary
remediation or further study
-	No adverse consequences to human
health
CHEMISTRYFDR ENVIRONMENTAL PROFESSIONALS-rAPPLIED
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Data Quality Objectives
False Negative Decision Errors
Consequences
•	Example: A release to the aquifer whicn
exceeds health-based action levels is rot
identified
•	Consequences:
-	No further resources are expended fa-
investigation or cleanup
-	Potential exists for adverse human health
effects
-	In this example, the false negative decision
error carries the more severe consequences
fa

Specify Limits on Decision Errors
0 -
95-
9 -
6 -
5 -
4 -
3 -
Acceptable false
negative error -stes
Gray region. Urge
decision error rates.
Default to more
conservative decsion.
Acceptable faise
positive error ra:es
I II I II II II II I I I I I
40 50 60 70 SO 90 100 110 120 130 140 150 160 : 70 *.HJ 190 200
True Value (ppm)	^
¥ QK.
- qQc&m Up
6%
Ct&M clU

Step 7: Optimize the Design
•	Develop resource-effective sampling and
analysis design that satisfies ail DGOs
•	Document operational details (QA/QC,
sampling locations, chain-of-custody, etc.)

alVtafw - 90
CHEMISTRY FOR ENVIRONMENTAL PROFESSIONALS- APPLIED
PAGE 9
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Data Quality Objectives
Case Study
• Situation June 1996: Source removal
completed
-	14,000 drums excavated and disposed
-	10,000 yd3 impacted soil treated and
disposed
-	What additional threats might remain?
-	Use DQO process (steps 2-4 only)
I
Case Study - DQO Steps
Step 1: State the problem:
-	Authority: Superfund
-	Resources: $30-300K (10-100 samples);
6 mo. timeframe
-	Team members: Group of 3-5 students
Step 2: Identify decision(s): include rationale
The Real World
Case Study
PAGE 1D	¦, CHEMISTRY FOR ENVIRONMENTAL PROFESSIONALS-APPLIED
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Data Quality Objectives
Case Study - DQO Steps
Step 3: Identify inputs: (sediment pathway
only)
Step 4: Define study boundaries:
(sediment pathway only); locations, depth
interval, sampling strategy, etc. •
Summary
•	Quality management systems
-	Planning, management, and auditing (QA)
-	Measurement and assessment (QC)
•	DQO process
-	Seven-step process	\
-	Requires knowledge about chemistry,
fate, and analytical methods
•	Decision errors	Dtyc
-	False positive/false negative
-	Must specify acceptable limits
CHEMISTRY FOR ENVIRONMENTAL PROFESSIONALS- APPLIED
PAGE 11
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