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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