selected presentation from the instaar monday noon seminar...
Post on 20-Mar-2020
1 Views
Preview:
TRANSCRIPT
Selected Presentation from the INSTAAR Monday Noon Seminar Series.
Institute of Arctic and Alpine Research, University of Colorado at Boulder.http://instaar.colorado.edu
http://instaar.colorado.edu/other/seminar_mon_presentations
This seminar presentation has been posted to the internet to foster communication with the science community and thepublic.
Most of the INSTAAR presentations were originally given in PowerPoint format; they were converted to Adobe PDF forposting. You may need to install the free Adobe Acrobat Reader to view these files.
These presentations are "works in progress". They are not peer reviewed. They should not be referenced for any kind ofpublication. Contact the author for proper references and additional information before any use, even for unpublishedworks such as your own presentations.
LICENSING AGREEMENT.Free use of these presentations is limited to a nonprofit educational or private non-commercial context and requires thatyou contact the author, give credit to the author, and display the copyright notice. All rights to reproduce thesepresentations are retained by the copyright owner. Images remain the property of the copyright holder. By accessingthese presentations, you are consenting to our licensing agreement.
16 Sep. 2002 Larry Barber, USGS, Email: lbbarber@usgs.gov“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 BarberU. S. Geological Survey
National Research Program
Boulder, CO
Chemical Transformations in
Water Reclamation and ReuseNature and Fate of Organic Matter in Natural Waters
bulk characterization
trace analysis
Environmental
Analytical Chemistry
sorption
biological transformation
volatilization
Process Level
Research
ground water
surface water
wetlands
Integrated
Hydrologic Systems
Natural - Anthropogenic
Compounds (water,
sediment, atmosphere)
Interdisciplinary Interorganizational
1.E+00
1.E+01
1.E+02
1.E+03
1.E+04
1.E+05
1.E+06
1.E+07
1.E+08
1.E+09
1.E-061.E-051.E-041.E-031.E-021.E-011.E+001.E+011.E+021.E+03
Decreasing Concentration
Incr
easi
ng N
um
ber
of
Com
pou
nd
sConcentration and Composition
Everything is
EverywhereHierarchical Analytical Approach
selectivity vs sensitivity
ppm
ppb
ppt
1970s
1980s
1990s
Dissolved Organic Carbon Cycle
NOM
Biogeochemistry
Contaminant
Biogeochemistry
Thurman, 1985
Barber and others, 1995
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
WWTP, Atlanta
• WWTP
• Domestic Disposal
Systems
• Industrial Discharges
(Medical)
Wastewater Pathways
• Animal Feeding Operationsß Waste lagoons
ß Land application
• Aquaculture
Wastewater Pathways
Hog Facility, near South Fork Iowa River
ManureProduction
Human 1.5Cow 30Hog 4Sheep 1.5Chicken 0.14(kg wet weight/capita)
• Intended Reuse
- Direct
- Indirect
• Unintended
Water Reuse
Consumer Products
• Cleaning
• Pharmaceutical
• Agricultural
Consumer Product Cycle
EDTA Use = 1
g/person/day
Water Use = 100
L/person/day
Population = 100,000
Daily Output = 100 kg/day = 10 mg/L
Wastewater Treatment Plant
Removal Rate = 90%
Concentration = 1 mg/L
Stream Dilution Factor = 90%
Concentration = 0.1 mg/L
In Stream Removal and Transport
Drinking Water
Intake
The Human Endocrine System
After Colborn et al., 1996
– System of glands
that produce
chemical
messengers
(hormones) and
corresponding
receptors.
• Sexual
Development
• Cancers
• Fertility
EXPOSURE TO POTENTIAL ENVIRONMENTAL AGENTS
Exogenous sex hormone disrupters (xenoestrogens)
PRIMARY MOLECULAR AND BIOCHEMICAL RESPONSES
Changes blood hormone levels, effects on neuro-endocrine system
SECONDARY BEHAVIOURAL AND MORPHOLOGICAL EFFECTS
Changes in sexual characteristics affecting mating
INDIVIDUAL REPRODUCTIVE EFFECTS
Impaired reproductive success of individual animals
POPULATION EFFECTS
Reproductive output falls below critical level required to maintain population's surviva
ECOSYSTEM EFFECTS
Ecosystem change
Effects of Endocrine Disrupting ChemicalsAfter Campbell and Hutchinson, 1998
Feminization of Wild Fish in the UKJobling 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, PROTIENSSTEROIDS THYROID
HORMONES
OTHER
MOLECULESCHOLESTEROL
1,25-DIHYDROXYCHOLECALCIFEROL
(Vitamin D)
CORTICOSTEROIDS
Glucocorticoids
Cortisol
Corticosterone
Mineralocorticoids
Aldosterone
STRESS:
carbohydrate
metabolism and
ionic regulation
PROGESTOGENS
Progesterone
PregnenoloneMaintains pregnancy
or endometrium, inhibits
gonadotropin release
Regulates
calcium absorption
by intestine.
ANDROGENS
Testosterone
Androstenedione
11-Ketotestosterone
Androsterone
Stimulates
development of
male characteristics.
ESTROGENS
17b-Estradiol
Estrone
Estriol
Supports and
stimulates female
reproduction.E: stimulates endometrial proliferation,
positive and negative feedback on estrous
cycle.
G: converted from androgens, stimulates
hypothalamus and sexual behavior.
E: from adrenal cortex and ovaries, precursors for estrogen
synthesis, stimulates sexual behavior.
G: from testis, stimulates spermatogenesis, sex glands, and
secondary sex characteristics.
MONERA &
PROTISTA &
FUNGI F & > j?
PLANTSF? & j?
PORIFERA (sponges)
CTENOPHORA
CNIDERIA (jellyfish, coral) F
PLATYHELMINTHES &
ROTIFERA
NEMOTODA
NEMERTEA
MOLLUSCA F & >
ANNELIDA
ARTHROPODA F & >? j
BRYOZOA
BRACHIPODA
PHORONIDA
ECHINODERMATA F & >
CHORDATA F & >
CHEPHALOCHORDATA
UROCHORDATA
AGNATHA F & >
CHONDRICHTHYES F & >
OSTEICHTHYES F & >
AMPHIBIA F & >
REPRILIA F & >
AVES F & >
MAMMALIA F & >
OCCURRENCE OF “VERTEBRATE GONADAL-TYPE” STEROIDS
F: in vivo biosynthesis of “vertebrate gonadal-type” steroids
&: biotransformation of “vertebrate gonadal-type” steroids
>: where evidence suggests the gonadal steroids function as hormones
j: “vertebrate gonadal-type” steroids used for non-reproductive purposes, such as defense
1
2
3
45
6
7
8
9
1014 15
16
1718
1911
12
13
A B
C D
Steroid skeleton
Steroid Nomenclature -
Simple Compound to Complex Mixtures
Cyclopentenophenanthrene
HO
CH3
H H
H
OHH
17-a-Estradiol
HO
CH3
H H
H
OHH
17- b-Estradiol
O
OHCH3
H H
HCH3
Testosterone
HO
H3COH
OH
Estriol
HO
OCH3
H H
H
Estrone
Major Endogenous Sex
Hormones
-O3SO
CH3
H H
H
OH
H
-O3SO
CH3
H H
H
OSO3-
H
HO
CH3
H H
H
OSO3-
H
O
HOH
H
HH
CH3
O
CO2-
HO
HO
HO
Estradiol-3-sulfate Estradiol-3,17- disulfate
Estradiol-17-sulfateEstradiol-3-glucuronide
Conjugated Forms
17-b-Estradiol
OH
HO
O
OH
CH3
O
O
OHCH3
H H
HCH3
CH3
O
OCCH3CH3
O
H3C
CH3
O
C
OCCH3
CH3
O
O
F
HO
H3C
CH3
O
CH3
C
OCCH3
CH3
O
O
Zeranol 17-Methyltestosterone
Trenbolone AcetateFlurogestone Acetate
OH
H
H2C
H3C
C CH
DesogestrelMegestrol Acetate
Livestock
Hormones
0
1
2
3
4
5
6
7
8C
on
cen
trati
on
, n
g/L
Location
Influent Influent GFF Effluent Left Bank Right Bank
17-b-Estradiol
Endocrine-Disrupting Chemicals
Herbicides
2,4-DAlachlorAtrazineTrifluralin
Industrial Chemicals
Cadmium
Dioxin
Lead
Mercury
PCB’s
Pentachlorophenol
Nonylphenols
Phthalates
Styrenes
Bisphenol A
Insecticides
b-HCHChlordaneDieldrinDDT / DDEEndosulfanHeptachlorLindaneMethoxychlorMirexOxychlordaneParathionPyrethroidsToxapheneTransnonachlor
H19C9
OH
+
H19C9
O (CH2 CH2 O)n H
n = 0-20
H19C9
O (CH2 CH2 O)n CH2COH
O
n = 0-1
H19C9
O (CH2 CH2 O)n H
n = 1-2+
H19C9
OH
H19C9
O (CH2 CH2 O)n H
n = 1-2
Aerobic Anaerobic
Anaerobic
Treatment
Effluent Sludge
Biodegradation of Alkylphenol Surfactants
algae metabolism, trout testicle growth, salmon metabolic
enzymes, carp sexual differentiation, trout OSI (growth), daphnia
testosterone metabolism
Routledge and Sumpter, 1996
Endocrine Effects of Alkylphenols
0
10
20
30
40
50
60
70
80
90
100
Co
ncen
trati
on
(u
g/L
)
Illinois RiverDes Plaines RiverStickney
Downstream Removal of Alkylphenol
Compounds
DTBB BHA NP NP1EO NP2EO
bisphenol A NP1EC NP2EC NP3EC NP4EC
30 km
100 km
U.S. RANKING OF PRESCRIPTION DRUGS
Ranking
Trade Name Common Name Trade Name Common Name
1 Premarin Conjugated Estrogens Trimox Amoxicillin
2 Synthroid Levothyroxine Premarin Conjugated Estrogens
3 Trimox Amoxicillin Synthroid Levothyroxine
4 Hydrocodone Hydrocodone Hydrocodone Hydrocodone
5 Prozac Fluoxetine Prozac Fluoxetine
6 Prilosec Omeprazole Lanoxin Digoxin
7 Zithromax Azithromycin Prilosec Omeprazole
8 Lipitor Atorvastatin Vasotec Enalapril
9 Norvasc Amlodipine Zithromax Azithromycin
10 Claritin Loratadine Norvasc Amlodipine
11 Lanoxin Digoxin Zoloft Sertraline
12 Zoloft Sertraline Claritin Loratadine
13 Albuterol Aerosol Albuterol Coumadin Warfarin
14 Paxil Paroxetine Augmentin Amoxicillin/Clavulanate
15 Amoxicillin Amoxicillin Zocor Simvastatin
1998 1997
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 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
H3C
HO
O
Equilin
17-a-Ethynylestradiol
HO
CHC
OH
H
HH
CH3
Pharmaceutical Hormones
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
Antibiotics Detection %
trimethoprim 27
erythromycin-H2O 22
lincomycin 19
sulfamethoxazole 19
tylosin 13
Commonly Detected Drugs
Hormone Detection %
estriol 21
17-a-ethynyl estradiol 16
cis-androsterone 14
19-norethisterone 13
17-b-estradiol 11
mestranol 11
Pharmaceutical Detection %
acetaminophen 24
dehydronifedipine 14
diltiazem 13
codeine 11
cimetidine 10
ibuprofen 10
Colorado Front Range
Boulder Cre
ek
St. Vrain River
Middle Boulder Creek
North Boulder Creek
Urban Gradient Sampling Sites
0 10000 20000 30000 40000 50000 60000 700000
200
400
600
800
1000
1200
Eben Fine
URBAN / AGRIC.URBAN
SANDSTONES AND SHALES
RURAL
CRYSTALLINE BEDROCK
St. Vrain
Dry Creek
Coal Creek
Boulder Wastewater
Nederland Wastewater
Fourmile Creek
BC High-Flow
BC Low-Flow
Inflows High-Flow
Inflows Low-Flow
SP
EC
IFIC
CO
ND
UC
TA
NC
E (
mS
/cm
)
DISTANCE FROM MBC-ELDORA (m)
0
100000
200000
300000
400000
500000
600000
MBC-ELD BC-CAN BC-30 BC-aSTP BC-75 BC-aCC BC-aSV NED-EFF BLD-EFF CC
SITE
CO
NC
EN
TR
AT
ION
IN
NA
NO
GR
AM
S P
ER
LIT
ER
NTA EDTA NPEC
Low Flow – EDTA and NPEC
0
5
10
15
20
25
30
35
40
45
50
MBC-ELD BC-CAN BC-30 BC-aSTP BC-75 BC-aCC BC-aSV NED-EFF BLD-EFF CC
SITE
CO
NC
EN
TR
AT
ION
(N
G/L
)
1,4-DCB 1,2-DCB MP TBP TPP BHT TOP OP1E0 OP3EO AND A-E2 B-E
Low Flow Wastewater Compounds
0
100
200
300
400
500
600
MBC-ELD BC-CAN BC-30 BC-aWWTP BC-75 BC-aCC BC-aSV CC
SITE
CO
NC
EN
TR
AT
ION
IN
NA
NO
GR
AM
S P
ER
LIT
ER
COT CIM ACET 1,7-DMX COD CAF TMP SULFA DILT IBU DPHA
Low Flow Pharmaceutical Compounds
Pharmaceuticals in Boulder Creek
AntibioticTrimethoprim
AntibioticSulfamethoxazole
AntacidRanitidine
AnalgesicIbuprofen
AntihistamineDiphenhydramine
Caffeine metaboliteDimethylxanthine
AntiangialDiltiazem
Nicotine metaboliteCotinine
Cough suppressantCodeine
AntacidCimetidine
StimulantCaffeine
AnalgesicAcetaminophen
UseCompound - 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
10-7
10-6
10-5
10-4
Positive gadolinium anomaly associated with medical waste REE-ENVIRONMENTAL SIGNATURES
Nederland Wastewater
Treatment Plant Effluent
Boulder Wastewater
Treatment Plant Effluent
Boulder Cr.
below WWTP
Boulder Cr.
above WWTP
La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
WA
TE
R/N
AS
C
With Water
Without Water
top related