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16 Sep. 2002 Larry Barber, USGS, Email: [email protected]
“Sex, Drugs, and Water : Emerging contaminants in the Boulder Creek Watershed".
Seminar given at INSTAAR, University of Colorado. Copyright 2002 Larry Barber. All Rights Reserved.
Barber presentation (1.1 Mb PDF).
SEX
DRUGS
WATER
Larry B Barber
U. S. Geological Survey
National Research Program
Boulder, CO
Chemical Transformations in
Water Reclamation and Reuse
Nature and Fate of Organic Matter in Natural Waters
Interdisciplinary
Natural - Anthropogenic
Compounds (water,
sediment, atmosphere)
Interorganizational
Environmental
Analytical Chemistry
Process Level
Research
Integrated
Hydrologic Systems
bulk characterization
trace analysis
sorption
biological transformation
volatilization
ground water
surface water
wetlands
Concentration and Composition
Everything is
Everywhere
Hierarchical Analytical Approach
selectivity vs sensitivity
Increasing Number of Compounds
1.E+09
1990s
ppt
1.E+08
1.E+07
1.E+06
1980s
ppb
1.E+05
1.E+04
1.E+03
1970s
ppm
1.E+02
1.E+01
1.E+00
1.E+03 1.E+02 1.E+01 1.E+00 1.E-01 1.E-02 1.E-03 1.E-04 1.E-05 1.E-06
Decreasing Concentration
Dissolved Organic Carbon Cycle
NOM
Biogeochemistry
Barber and others, 1995
Thurman, 1985
Contaminant
Biogeochemistry
Why Sewage Effluents?
• National (Global) significance issue because
all communities produce wastewater
• Domestic and municipal effluents are
complex mixtures of natural and synthetic
organic chemicals
• Major source of endocrine disrupting
compounds (EDC)
• Treatment regimes affect the suite of
chemicals present
Wastewater Pathways
• WWTP
• Domestic Disposal
Systems
• Industrial Discharges
(Medical)
WWTP, Atlanta
Wastewater Pathways
• Animal Feeding Operations
ß Waste lagoons
ß Land application
• Aquaculture
Manure
Production
Human 1.5
Cow
30
Hog
4
Sheep
1.5
Chicken 0.14
(kg wet weight/capita)
Hog Facility, near South Fork Iowa River
Water Reuse
• Intended Reuse
- Direct
- Indirect
• Unintended
Consumer Products
• Cleaning
• Pharmaceutical
• Agricultural
Consumer Product Cycle
Drinking Water
Intake
Water Use = 100
L/person/day
In Stream Removal and Transport
EDTA Use = 1
g/person/day
Population = 100,000
Daily Output = 100 kg/day = 10 mg/L
Stream Dilution Factor = 90%
Concentration = 0.1 mg/L
Wastewater Treatment Plant
Removal Rate = 90%
Concentration = 1 mg/L
The Human Endocrine System
– System of glands
that produce
chemical
messengers
(hormones) and
corresponding
receptors.
• Sexual
Development
• Cancers
• Fertility
After Colborn et al., 1996
Effects of Endocrine Disrupting Chemicals
After Campbell and Hutchinson, 1998
ECOSYSTEM EFFECTS
Ecosystem change
POPULATION EFFECTS
Reproductive output falls below critical level required to maintain population's surviva
INDIVIDUAL REPRODUCTIVE EFFECTS
Impaired reproductive success of individual animals
SECONDARY BEHAVIOURAL AND MORPHOLOGICAL EFFECTS
Changes in sexual characteristics affecting mating
PRIMARY MOLECULAR AND BIOCHEMICAL RESPONSES
Changes blood hormone levels, effects on neuro-endocrine system
EXPOSURE TO POTENTIAL ENVIRONMENTAL AGENTS
Exogenous sex hormone disrupters (xenoestrogens)
Feminization of Wild Fish in the UK
Jobling and others, ES&T, 1998
Other Suspected Effects
• Damage to the Immune, Neurological,
and Developmental Systems
– Other types of endocrine disruption have
been observed in wildlife. Similar effects are
suspected to occur with exposed humans.
– The classic work that brought chemical
pollution in wildlife to our attention is Rachel
Carson’s Silent Spring, written in 1962.
– The classic work that brought effects of
endocrine disruptors in wildlife to our
attention is Theo Colborn et al.’s Our
Stolen Future, written in 1996.
WHAT ARE HORMONES?
Chemical regulators, secreted by
glands to the blood that effect a change at a target site.
TYPES OF CHEMICAL REGULATORS
AMINO ACIDS, AMINES,
PEPTIDES, PROTIENS
THYROID
HORMONES
STEROIDS
OTHER
MOLECULES
CHOLESTEROL
CORTICOSTEROIDS
Glucocorticoids
STRESS:
Cortisol
carbohydrate
Corticosterone
metabolism and
ionic regulation Mineralocorticoids
Aldosterone
PROGESTOGENS
Progesterone
Maintains pregnancy
or endometrium, inhibits Pregnenolone
gonadotropin release
ESTROGENS
17b-Estradiol
Supports and
stimulates female Estrone
E: stimulates endometrial proliferation,
reproduction.
Estriol positive and negative feedback on estrous
cycle.
G: converted from androgens, stimulates
hypothalamus and sexual behavior.
ANDROGENS
Testosterone
Stimulates
Androstenedione
development of
male characteristics. 11-Ketotestosterone
Androsterone
1,25-DIHYDROXYCHOLECALCIFEROL
(Vitamin D)
Regulates
calcium absorption
by intestine.
E: from adrenal cortex and ovaries, precursors for estrogen
synthesis, stimulates sexual behavior.
G: from testis, stimulates spermatogenesis, sex glands, and
secondary sex characteristics.
OCCURRENCE OF “VERTEBRATE GONADAL-TYPE” STEROIDS
PLANTSF? & j?
FUNGI F & > j?
PORIFERA (sponges)
CTENOPHORA
CNIDERIA (jellyfish, coral) F
PLATYHELMINTHES &
ROTIFERA
PROTISTA &
NEMOTODA
NEMERTEA
MOLLUSCA F & >
ANNELIDA
ARTHROPODA F & >? j
MONERA &
BRYOZOA
CHEPHALOCHORDATA
BRACHIPODA
UROCHORDATA
PHORONIDA
AGNATHA F & >
ECHINODERMATA F & >
CHONDRICHTHYES F & >
CHORDATA F & >
OSTEICHTHYES F & >
AMPHIBIA F & >
F: in vivo biosynthesis of “vertebrate gonadal-type” steroids
REPRILIA F & >
&: biotransformation of “vertebrate gonadal-type” steroids
AVES F & >
>: where evidence suggests the gonadal steroids function as hormones
MAMMALIA F & >
j: “vertebrate gonadal-type” steroids used for non-reproductive purposes, such as defense
Steroid Nomenclature Simple Compound to Complex Mixtures
1
2
A
3
4
19
11
9
10
5
B
6
12
C
8
18
13
17
D
14
7
Cyclopentenophenanthrene
Steroid skeleton
16
15
Major Endogenous Sex
Hormones
OH
CH3 H
OH
CH3 H
H
H
H
H
H
HO
H
HO
17-a-Estradiol
17- b-Estradiol
H3C OH
O
CH3
H
H
H
HO
HO
Estriol
Estrone
OH
CH3
CH3
H
H
H
O
Testosterone
OH
Conjugated Forms
17-b-Estradiol
OH
CH3
-
OSO3
CH3 H
H
H
H
-
H
H
O3SO
-
Estradiol-3-sulfate
H
O3SO
Estradiol-3,17- disulfate
OH
CH3 H
-
OSO3
CH3 H
H
H
Livestock
Hormones
H
H
HO
Estradiol-17-sulfate
HO
HO
HO
H
O
OH
CH3
CH3
O
CH3
HO
Zeranol
CH3
17-Methyltestosterone
OCCH3
CH3
H3C
HO
O
Estradiol-3-glucuronide
H
O
O
H
CH3
H
H
OH
H
-
CO2
O
OH
C
O
OCCH3
O
CH3
O
F
O
Trenbolone Acetate
Flurogestone Acetate
CH3
H3C
C
CH3
O
OCCH3
O
H2C
H3C
OH
H
O
CH3
Megestrol Acetate
Desogestrel
C
CH
17-b-Estradiol
Influent
Influent GFF
Effluent
8
7
Concentration, ng/L
6
5
4
3
2
1
0
Location
Left Bank
Right Bank
Endocrine-Disrupting Chemicals
Herbicides
2,4-D
Alachlor
Atrazine
Trifluralin
Industrial Chemicals
Insecticides
Cadmium
Dioxin
Lead
Mercury
PCB’s
Pentachlorophenol
Nonylphenols
Phthalates
Styrenes
Bisphenol A
b-HCH
Chlordane
Dieldrin
DDT / DDE
Endosulfan
Heptachlor
Lindane
Methoxychlor
Mirex
Oxychlordane
Parathion
Pyrethroids
Toxaphene
Transnonachlor
Biodegradation of Alkylphenol Surfactants
H19C9
O (CH2 CH2 O)n H
n = 0-20
Aerobic
H19C9
Anaerobic
O
O (CH2 CH2 O)n CH2COH
+
H19C9
O (CH2 CH2 O)n H
+
n = 0-1
H19C9
n = 1-2
H19C9
O (CH2 CH2 O)n H
n = 1-2
OH
Anaerobic
Treatment
H19C9
OH
Effluent
Sludge
Endocrine Effects of Alkylphenols
Routledge and Sumpter, 1996
algae metabolism, trout testicle growth, salmon metabolic
enzymes, carp sexual differentiation, trout OSI (growth), daphnia
testosterone metabolism
Downstream Removal of Alkylphenol
Compounds
100
90
Concentration (ug/L)
80
70
60
30 km
50
100 km
40
30
20
10
0
Stickney
Des Plaines River
Illinois River
DTBB
BHA
NP
NP1EO
NP2EO
bisphenol A
NP1EC
NP2EC
NP3EC
NP4EC
U.S. RANKING OF PRESCRIPTION DRUGS
Ranking
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
1998
Trade Name
Premarin
Synthroid
Trimox
Hydrocodone
Prozac
Prilosec
Zithromax
Lipitor
Norvasc
Claritin
Lanoxin
Zoloft
Albuterol Aerosol
Paxil
Amoxicillin
Common Name
Trade Name
Conjugated Estrogens Trimox
Levothyroxine
Premarin
Amoxicillin
Synthroid
Hydrocodone
Hydrocodone
Fluoxetine
Prozac
Omeprazole
Lanoxin
Azithromycin
Prilosec
Atorvastatin
Vasotec
Amlodipine
Zithromax
Loratadine
Norvasc
Digoxin
Zoloft
Sertraline
Claritin
Albuterol
Coumadin
Paroxetine
Augmentin
Amoxicillin
Zocor
1997
Common Name
Amoxicillin
Conjugated Estrogens
Levothyroxine
Hydrocodone
Fluoxetine
Digoxin
Omeprazole
Enalapril
Azithromycin
Amlodipine
Sertraline
Loratadine
Warfarin
Amoxicillin/Clavulanate
Simvastatin
Pharmaceutical Hormones
Contraception
58 million women practice contraception
10 million use oral contraceptives
Dose ~35 ug, 21 days on/ 7 days off
Annual Use = 88 kg/yr
OH
CH3
C
CH
H
H
H
HO
Hormone Replacement Therapy
40 million post-menopausal
13 million use hormone replacement drugs
Dose is ~625 ug, 25 days on/ 5 days off
Annual Use = 1688 kg/yr
Expected Introduction Concentration
EIC = (kg/yr prescribed)/(L/yr entering POTW)
= (88 kg/yr)/(4x1013 L/yr)
= ~2 ng/L 17-a-ethynylestradiol
= ~100 ng/L 17-b-estradiol
17-a-Ethynylestradiol
H3C
HO
Equilin
O
Kolpin, Furlong, Meyer, Thurman, Zaugg, Barber,
and Buxton, 2002, Pharmaceuticals, hormones, and
other organic wastewater contaminants in U.S.
Streams, 1999-2000: A national Reconnaissance:
ES&T, v. 36, p. 1202.
139 streams in 30 states
•
•
62 Intense AFO activities
52 Intense Urbanization
•
•
17 Mixed Land Use
8 Minimally developed
•
22 Antibiotics
•
14 Prescription Drugs
•
5 Nonprescription Drugs
•
15 Hormones and Steroids
•
39 Household and Industrial
30 Most Frequently Detected
Compounds
Commonly Detected Drugs
Antibiotics
trimethoprim
erythromycin-H2O
lincomycin
sulfamethoxazole
tylosin
Detection %
27
22
19
19
13
Pharmaceutical
acetaminophen
dehydronifedipine
diltiazem
codeine
cimetidine
ibuprofen
Detection %
24
14
13
11
10
10
Hormone
estriol
17-a-ethynyl estradiol
cis-androsterone
19-norethisterone
17-b-estradiol
mestranol
Detection %
21
16
14
13
11
11
Colorado Front Range
Urban Gradient Sampling Sites
St. Vra
in
reek
C
r
e
ould
B
h
t
Nor
eek
r
C
lder
u
o
eB
l
d
d
Mi
River
k
ree
C
er
d
l
u
Bo
URBAN
m S/cm)
SPECIFIC CONDUCTANCE
(
RURAL
CRYSTALLINE BEDROCK
SANDSTONES AND SHALES
1200
BC High-Flow
BC Low-Flow
Inflows High-Flow
Inflows Low-Flow
1000
800
600
Dry Creek
Coal Creek
St. Vrain
Boulder Wastewater
Nederland Wastewater
400
Fourmile Creek
200
0
URBAN / AGRIC.
Eben Fine
0
10000
20000
30000
40000
50000
60000
DISTANCE FROM MBC-ELDORA (m)
70000
Low Flow – EDTA and NPEC
NTA
EDTA
NPEC
600000
CONCENTRATION IN NANOGRAMS PER LITER
500000
400000
300000
200000
100000
0
MBC-ELD
BC-CAN
BC-30
BC-aSTP
BC-75
BC-aCC
SITE
BC-aSV
NED-EFF
BLD-EFF
CC
Low Flow Wastewater Compounds
1,4-DCB
1,2-DCB
MP
TBP
TPP
BHT
TOP
OP1E0
OP3EO
AND
A-E2
50
45
CONCENTRATION (NG/L)
40
35
30
25
20
15
10
5
0
MBC-ELD
BC-CAN
BC-30
BC-aSTP
BC-75
BC-aCC
SITE
BC-aSV
NED-EFF
BLD-EFF
CC
B-E
Low Flow Pharmaceutical Compounds
COT
CIM
ACET
1,7-DMX
COD
CAF
TMP
SULFA
DILT
IBU
600
CONCENTRATION IN NANOGRAMS PER LITER
500
400
300
200
100
0
MBC-ELD
BC-CAN
BC-30
BC-aWWTP
SITE
BC-75
BC-aCC
BC-aSV
CC
DPHA
Pharmaceuticals in Boulder Creek
Compound
Use
Acetaminophen
Analgesic
Caffeine
Stimulant
Cimetidine
Antacid
Codeine
Cough suppressant
Cotinine
Nicotine metabolite
Diltiazem
Antiangial
Dimethylxanthine
Caffeine metabolite
Diphenhydramine
Antihistamine
Ibuprofen
Analgesic
Ranitidine
Antacid
Sulfamethoxazole
Antibiotic
Trimethoprim
Antibiotic
- 9 of 20 compounds
detected at high flow
- 11 of 28 compounds
detected at low flow
- Concentrations were
less than 1 ppb
- Compounds only
present in and below
WWTP effluents
- Always occur as
mixtures
- Presence indicative of
other related but not
detected compounds of
concern
Inorganic Indicators
AgCaCuHoMoRbSnTmAlCdDyKNaReSrUAsCeErLaNdSTbVBClEu
REE-ENVIRONMENTAL SIGNATURES
-4
Positive gadolinium anomaly associated with medical waste
10
WATER/NASC
Boulder Wastewater
Treatment Plant Effluent
10-5
Boulder Cr.
above WWTP
10-6
Boulder Cr.
below WWTP
Nederland Wastewater
Treatment Plant Effluent
-7
10
La Ce Pr Nd
Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
With Water
Without Water