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Detection, Occurrence and Fate of Pharmaceuticals and Steroid Hormones in Agricultural Environments Daniel D. Snow1, Shannon L. Bartelt–Hunt2, DelShawn L. Brown3, Jodi Sangster3, and David A. Cassada4

ABSTRACT: Thirty–six papers were published in 2009

INTRODUCTION: Nutrients, sediments, and pesticides are well known and extensively studied contaminants

describing new methods for analysis of veterinary

impacting water quality in agricultural environments. These

pharmaceuticals, natural and synthetic steroid hormones,

groups of contaminants typically occur at easily measured

and their occurrence in agricultural settings. New methods

concentrations in surface run–off in agricultural watersheds.

continue to be developed and applied toward understanding

Nutrients, especially nitrogen, and pesticides have also

the sources and environmental significance of these

been shown to impact ground water quality in areas

chemicals. Advances in sample preparation methods and

susceptible to

instrumentation provide detection limits into parts per

contamination.

Less

well-known

are

environmental impacts of newer classes of contaminants

trillion ranges. Analysis of water samples indicates that

such as pharmaceuticals, steroids, antibiotic–resistance

many of these compounds do occur in the environment.

genes and prion proteins. These “emerging” contaminants KEYWORDS:

pharmaceuticals,

steroid

hormones,

clearly have potential to enter the environment and cause

analytical methods, water and wastewater, agricultural

known or suspected adverse ecological or human health

environments

effects.

doi: 10.2175/106143010X12756668800618

often has occurred for quite some time, but methods for

Release of these contaminants to the environment

their detection at environmentally–relevant concentrations

____________________________________________________________________________________________ 1

Associate Professor and Laboratory Director, School of Natural Resources, 202 Water Science Laboratory, University of Nebraska–Lincoln, Lincoln, NE 68583–0844; Tel. 402–472–7539; Fax. 402–472–9599; email: [email protected]

have only recently become available. Evaluating the environmental fate and effects of

2

Assistant Professor, Department of Civil Engineering, 203B Peter Kiewit Institute, University of Nebraska–Lincoln, Omaha, NE 68182–0178, Tel. (402) 554–3868; Fax. (402) 554–3288; email: [email protected]

emerging contaminants includes research on compounds such as surfactants, antibiotics and other pharmaceuticals,

3

Graduate Research Assistant, Department of Civil Engineering, University of Nebraska–Lincoln Department of Civil Engineering, 203B Peter Kiewit Institute, University of Nebraska–Lincoln Omaha, NE 68182–0178, Tel. (402) 554–3868; Fax. (402) 554–3288;

steroid

hormones

compounds

and

(EDCs),

other fire

endocrine–disrupting

retardants,

sunscreens,

4

Chemist, School of Natural Resources, 202 Water Sciences Laboratory, University of Nebraska–Lincoln, Lincoln, NE 68583–0844; Tel. 402–472–7539; Fax. 402–472–9599; email: [email protected]

disinfection byproducts, new pesticides and pesticide metabolites, and naturally–occurring algal toxins. Detection

869 Water Environment Research, Volume 82, Number 10—Copyright © 2010 Water Environment Federation

of these contaminants in environmental matrices (water,

Pharmaceuticals and Antibiotics in Water.

wastewater, soils and sediments) is particularly challenging

Ding et al. (2009) describe a method for analysis of

because of the low detection limits required, the complex

macrolide antibiotics (erythromycin, roxithromycin, tylosin,

nature of the samples, and difficulty in separating these

and tilmicosin) using an on–line solid phase extraction

compounds from interferences. New extraction and

method

clean–up techniques, coupled with improvements in

spectrometry (LC/MS/MS). A commercial mixed phase

instrumental technologies provide the needed sensitivity

high–purity silica restricted access material (RAM) LC

and specificity for accurate measurement.

column coated with a thin film of silicone polymer was

with

liquid

chromatography–tandem

mass

The objective of this paper is to review the

used as a concentrator column with a 1 milliliter water

literature published in 2009 reporting detection, fate, and

sample. The unique packing material allows the direct

occurrence of emerging contaminants, with a particular

injection of biological samples without pretreatment and

focus on emerging contaminants in agricultural systems.

provides a measure of separation between the sample

Relevant contaminants are EDCs (particularly hormones

matrix and target compounds. Macrolide antibiotics were

and

other

extracted, interferences washed through with additional

pharmaceuticals associated with wastewater, antibiotic

water, and then compounds eluted in back–flush mode.

resistance genes in bacteria and prions. Studies on

Instrument detection limits ranged from 0.002 to 0.006

pesticides and flame retardants are not reviewed unless they

µg/L, and recoveries for fortified blanks ranged from 87 to

were evaluated in the same study.

98% at a wide range of environmentally relevant

anabolic

steroids),

antibiotics

and

Reviews. Kümmerer provided a 2 part review of

concentrations.

the literature on the occurrence of antimicrobials in the

Garcia–Ac et al. (2009) describe development

aquatic environment. The first review, Kümmerer (2009a),

and validation of an on–line solid phase extraction

briefly covers present state of knowledge concerning the

LC/MS/MS method using a styrene divinyl benzene

sources, occurrence, fate and effects of antibiotics from

(Strata–XTM, Phenomenex, Torrence, CA) concentrator

both municipal and agricultural sources in the environment.

column for drinking and surface water monitoring. A wide

The second review, Kümmerer (2009b), covers the

range

implications of the occurrence of antibiotics in aquatic

of

human

and

veterinary

pharmaceuticals

(clarithromycin,

sulfamethoxazole,

trimethoprim,

systems for the development of antibiotic resistance genes

carbamazepine,

cyclophosphamide,

methotrexate),

in bacteria. Together these papers provide a good general

herbicides (atrazine, cyanzine, simazine) and metabolites

overview of the literature on this topic.

were included in the method. Analyte recoveries were

Analytical Methods for Emerging Contaminants

compared for several reverse phase concentrator columns, as well as a graphite packed column, and the SDVB


packing provided the best overall performance for larger

assessed

(10mL) sample volumes based on breakthrough volume

consequence of extended crop irrigation with wastewater

estimation. Compound recoveries ranged between 60 to

containing these contaminants at measured levels. The

109%, while detection limits ranged from 0.0006 to 0.006

modeling results suggest that pharmaceuticals and metals

µg/L. Samples of tap water, as well as river water samples

pose the greatest environmental risk to indigenous

were analyzed demonstrating the utility of the method for

organisms ( Muñoz et al. 2009).

raw and treated drinking water supplies near Montreal,

using

several

toxicological

models

as

a

Pailler et al. (2009) measure concentrations of

Canada.

hormones (estrone, 17β–estradiol, 17α–ethynylestradiol), Li et al. (2009) used an off line SPE method, with

analgesics

(ibuprofen,

diclofenac)

and

antibiotics

ultrahigh pressure liquid chromatography (UPLC) tandem

(sulfathiazole,

mass spectrometry for determination of several classes of

sulfadimethoxine,

antimicrobials in raw and treated wastewater. Recoveries

chlortetracycline) in storm water run–off in a small 35 km2

for seven classes of antibiotics ranged from 60% to 110%

watershed in Luxembourg. Samples were collected using

with method detection limits ranging from 0.0003 to 0.060

storm water samplers during 29 run–off events between

µg/L for treated waste water. The use of UPLC provided

October 2006 and May 2008. Water samples were

very short analysis times (60%, and detection limits were in the range 0.0002 to

quinolones, and 2 sulfonamide compounds, in water was

0.030 µg/L. Nineteen compounds were detected in raw and

described by Tamtam et al. (2009). Filtered 100 milliliter

treated wastewater from four main slaughterhouses in

samples were extracted off–line using polymeric (Oasis

Beijing,

HLBTM, Waters Corporation, Milford, MA) cartridges, and

China.

tetracyclines

and

Sulfanamides, macrolide

fluoroquinolones,

antibiotics

were

most

a wash step (methanol:water) incorporated to minimize

frequently detected, with the highest level near 3 µg/L in

matrix

raw wastewater and 1µg/L in treated wastewater. Several

chromatography (UPLC) was used for separation with

compounds were detected in river water receiving effluent

electrospray ionization tandem mass spectrometry in

with a highest level of up to 0.2 µg/L (Shao et al. 2009).

positive ion detection mode. An external calibration curve

interferences.

Ultrahigh

pressure

liquid

Tagiri–Endo et al. (2009) describe a method for

was used over a concentration range corresponding to

analysis of veterinary antimicrobials in swine wastewater

0.005 to 2.5 µg/L in the extracted sample. Several SPE

using on–line SPE with LC tandem MS detection. The

cartridge phases were compared, and the best overall

on–line extraction system used an autosampler and a 6–port

recovery (70±20%) using the Oasis HLB cartridge. Method

switching valve outfitted with a 20 mm×2.1 mm i.d.

detection limits ranged between 0.0002 and 0.006 µg/L.

polymeric (Oasis HLB; Waters Corporation, Milford, MA)

The authors included some experiments to evaluate the

concentrator column. Samples (900 µL) of wastewater

effect of dissolved organic matter on recovery and matrix

were mixed with analyte for quantification by standard

interference. Trace levels of sulfamethoxazole, up to 0.020

addition prior to filtration and loading a 100 µL sample

µg/L, and 2 fluoroquinolones were detected in samples of

aliquot the concentrator column. LC separation and

river water collected in the Seine River basin (Tamtam et al.

electrospray

2009).

ionization

tandem

mass

spectrometry

(LC/MS/MS) allowed determination of 5 veterinary

Tong et al. (2009) describe development of a

antibiotics (florfenicol, lincomycin, oxytetracycline, tylosin,

method for analysis of four classes of widely used


antibiotics

in

pig

farms,

including

sulfonamides,

(Strata–X, Phenomenex, Torrence, CA).

Three labeled

fluoroquinolones, tetracyclines and chloramphenicol in a

compounds were used as surrogates to monitor extraction

variety of aqueous matrices. Sample size was varied from

efficiency with recoveries varying between 56 and 144%.

50 (waste water) to 500 (groundwater) milliliters depending

Samples of runoff water were collected from agricultural

on the source, and off line extraction conducted using a 60

fields before and after application of municipal biosolids,

mg polymeric SPE cartridge (Oasis HLBTM, Waters

as well as surface water samples draining the watershed.

Corporation, Milford, MA). Cartridges were washed with

Several human and veterinary pharmaceuticals, including

mixture of methanol and water to minimize matrix

caffeine, carbamazepine and several antibiotics, were

interferences, and analytes eluted with a mixture of

detected in the study (Wu et al. 2009).

methanol and methyl terbutyl ether (MTBE). High pressure reverse

phase

liquid

chromatography

coupled

Analysis of Steroid Hormones in Water. Chang

with

et al. (2009) describe a method for analysis of steroid

electrospray ionization tandem mass spectrometry was used

hormones and corticosteroids in river water. Although not

for detection of antimicrobial compounds in both positive

in an agricultural setting the results are compelling and the

and negative ion detection modes. Two multiple reaction

methods could be adapted to study these compounds in

monitoring (MRM) transitions were used for analyte

agricultural settings.

detection and confirmation, and an external calibration

formaldehyde and filtered (glass fiber) prior to off line

curve used for quantification.

Detection limits were

extraction with a polymeric Oasis HLBTM SPE cartridge.

estimated from variability in instrument response for a low

Cartridges were eluted with ethyl acetate followed by a

level fortified blank and matrix samples, averaging between

mixture of ethyl acetate and acetonitrile prior to analysis by

0.001 and 0.005 µg/L for ground and surface water and up

UPLC and electrospray ionization LC/MS/MS. Florisil

to 0.100 µg/L for waste water. Several tetracyclines,

clean up was used for extracts analyzed for estrogens. Five

fluoroquinolones and sulfonamide antimicrobials were

estrogens, 9 androgens, 9 progestogens, 6 glucocorticoids,

detected in ground and surface water samples collected

and a mineralocorticoid were analyzed by the method.

from swine facilities in China (Tong et al. 2009).

Detection limits generally ranged below 0.001 µg/L for

Samples were preserved with

The occurrence of selected pharmaceutical

most compounds in both river water and sewage treatment

compounds in water and solid samples collected an

plant effluent. Steroid hormones in samples of river water

agricultural watershed was described by Wu et al. (2009)

near Bejing, China were composed primarily of androgens,

with analysis SPE with LC/MS/MS. Solid samples were

with lesser levels of glucocorticoids, progestogens, and

extracted with accelerated solvent extraction prior to clean

estrogens.

up with SPE. Water samples (250 milliliter) were extracted

Huang et al. (2009) describe a relatively simple

using styrene divinyl benzene polymeric cartridges

method for analysis of steroid hormones in wastewater


using stir bar sorptive extraction (SBSE) combined with

β–estradiol in the water. Concentrations of estriol were

HPLC with diode array detection. The stir bar extraction

found to be lower in sediments than estrone, β–estradiol,

method used poly(vinylpyridine–ethylene dimethacrylate)

17α–ethynylestradiol and 17–valerate.

Diethylstilbesterol

monolithic material (SBSEM) which was also compared to was found in lower concentrations than the other five commercially available polydimethylsiloxane (PDMS) stir estrogens in both the sediments and surface waters of all bar. Seven synthetic and natural steroid hormones were rivers sampled.

In addition, there was some correlation

extracted from water fortified at 50 µg/L and extraction found between the organic carbon content of the sediments conditions optimized. Target compounds were eluted from and sorption of the estrogens tested. the sorbent using acetonitrile and detection limits were Lavado

et

al.

(2009)

consistently

found

estimated in the range of 0.1 to 0.5 µg/L. estrogenic activity in six of the sixteen agriculturally impacted sites sampled in the Central Valley of California, Fate and Transport of Steroid Hormones U.S.A.. The highest estradiol equivalents (EEQs) measured Agricultural practices contribute significantly to through both in vitro and in vivo bioassays occurred in the hormone loading to the environment.

These hormones are Sacramento River Delta and Napa River. While the study

often present in livestock waste, and reach the environment did not identify the occurrence of specific compounds, through runoff from feedlots and application of manure as a research indicates fractionation of samples may be used to nutrient source. Understanding the occurrence and fate of separate estrogenic compounds from antagonistic ones hormones in the environment is important in order to which reduce estrogenic bioactivity. reduce the impacts of these contaminants on wildlife and Steroids associated with wastes from trenbolone humans. acetate:estradiol (TBA:E) implanted steers have been found Hormone Occurrence.

Lei et al. (2009) to contain biologically active hormones. Sellin et al.

determined the concentrations of six estrogens in surface (2009a) exposed fathead minnows (Pimephales promelas) water and sediment from 38 sites located on three rivers in to urine and fecal slurry from implanted and unimplanted the Tianjin area of northern China. The locations were steers for 7 days. There was no significant difference chosen to represent effluents from chemical factories, between fish exposed to the two urine treatments regardless drainage outlets, bridges, high roads, river confluence of the exposure concentration. Both treatment groups had reaches, tributaries, and river entrances. Concentrations of lower relative expression of the egg yolk precursor, all six estrogens were above method detection limits. vitellogenin (Vtg), than fish that were not exposed to urine. Estrone was detected at all sampling sites and at a higher Fish exposed to fecal slurry from TBA:E implanted steers concentration than β–estradiol. Higher concentrations of at a fecal concentration of 1600 mg/L showed significantly estriol were found than those of 17α–ethynylestradiol and

more relative Vtg expression than all other treatment


groups. This data suggests the endocrine disrupting activity

directly related to the precipitation and drainage conditions

of urine is not dependent on the implant history of steers.

of the sample areas. The average mass of 17β–estradiol

The fecal slurry from TBA:E implanted steers had subtle

recovered was three times greater than the mass of

feminizing and demasculinizing effects. These biological

17β–estradiol applied for each treatment. This suggests an

findings were confirmed by chemical analysis of the urine

additional source of 17β–estradiol was present beyond the

and manure. Comparable quantities of 4–androstenedione, surface applied manure even though the fields had not had 17β–estradiol, and estrone were found in urine samples manure applied for three years prior to this study. from both the implanted and unimplanted steers.

The

17β–estradiol

detections

were

fairly

constant

and

same compounds were detected in the manure from TBA:E significantly related to the depth of the water table. implanted steers. Only testosterone was detected in manure 17β–estradiol was found to be mobile and persistent within samples from unimplanted animals. the scope of this study.

A different study by Sellin et al. (2009b) detailed

Urine was found to affect the leaching and

the occurrence and bioactivity of agrichemicals found in

persistence of estrogen in the soils. Lucas and Jones (2009)

two Nebraska watersheds. Fathead minnows were deployed

used leaching columns containing three soils to investigate

with polar organic chemical integrative samplers (POCIS)

the influence of the aqueous matrix on the sorption and

for 7 days. Several pesticides were detected in the POCIS.

desorption of estrone and 17β–estradiol. Hormones were

Traces of estriol, the only steroid hormone detected of the The

applied in either a water or sheep urine matrix. Hormone

Platte River was impacted by heavier agricultural use with

sorption was similar for all soil types regardless of the

feedlots and row crops, while the Dismal River was

aqueous matrix used for application. It was found hormone

reflective of lower agricultural land use. It was suggested

leaching was influenced by both soil type and aqueous

the lack of steroid hormone detection may be due to the

matrix in which it was applied. Sheep urine increased the

short sampling time used with POCIS samplers.

total amount of estrogen available for leaching and the rate

14 measured, were detected in both watersheds.

Hormone Transport. Thompson et al. (2009)

of leaching observed. In addition, urine reduced the

evaluated the persistence and transport pathways of

mineralization of hormones which may be due to inhibited microbial function in the soil.

17β–estradiol from manure sources in agricultural soils

Hormone Fate. Scherr et al. (2009a) conducted

using capillary wick lysimeters and a fluorobenzoic acid

batch–equilibrium studies for estrone and estrone–3–sulfate

(FBA) tracer. Lysimeters were placed at a depth of

sorption to three agriculture soils from the Waikato region

approximately 0.61 meters. Recoveries of the tracer were

in New Zealand. Calcium chloride (CaCl2) and an artificial

low giving little indication as to lysimeter efficiencies.

urine (AU) solution were used to determine the influence of

FBA detections were variable throughout the study and


mediator solutions on compound sorption to soils common

plants from three stream systems: Fourmile Creek near

to dairy farms. Environmentally relevant doses of estrone

Ankeny, Iowa; Boulder Creek near Boulder, Colorado;

and estrone–3–sulfate were determined by estimating

South Platte River near Denver, Colorado. Replicate bed

average excretion rates per cow per day. Sorption isotherms

sediment microcosms and sterilized controls were prepared

were modeled using the Freundlich sorption model and

under aerobic conditions. Little difference in hormone

normalized by organic carbon content to allow comparison

mineralization was seen in Fourmile Creek between the

between different sorbents. It was found the sorption

three collection sites due to low contribution of effluent to

capacity for estrone–3–sulfate was approximately one order

stream flow. In general, sediments collected upstream

of magnitude lower than that for estrone in the soils used.

exhibited substantial aerobic mineralization of hormones.

Sorption of estrone in the artificial urine solution was

Testosterone was more biodegradable than estrone or

significantly less than that of the calcium chloride solution.

17β–estradiol. Mineralization of the “A” ring of estrone

It was thought the glycine and urea in the AU solution

and testosterone decreased immediately downstream of an

compete for sorption sites thus lowering the magnitude of

outfall while 17β–estradiol increased.

hormone sorption.

Estrone–3–sulfate was observed to be

The different

response between 17β–estradiol and estrone is interesting

less hydrophobic and did not exhibit competitive effects considering their structural similarity. This suggests with the AU solution components. Estrone formed as a microbial

communities

exhibit

specificity

towards

metabolite during the equilibrium of estrone–3–sulfate. compounds and 17β–estradiol mineralization did not This effect was magnified in the calcium chloride solution involve initial conversion to estrone.

where estrone formation equal to 4.6 – 6.7% of the initial

was no correlation between biological oxygen demand

mass of estrone–3–sulfate was observed depending on the

(BOD) and mineralization of estrone and testosterone.

soil tested. Based on the results of this project, Sorption of

Overall, the potential for microbial mineralization is

estrone and estrone–3–sulfate cannot be related solely to

substantial in the sediment phase and may be an important

the organic content of the soils. Normalizing partition

mechanism

coefficients to the organic carbon content of soils may not

the

hormones was explored by Bradley et al. (2009). Stream were

used

attenuation

of

endocrine

disrupting

In another study Scherr et al. (2009b) assessed

The importance of microbial degradation of

microorganisms

for

compounds.

be useful in the case of the compounds tested.

sediment

In addition, there

to

degradation

and

metabolite

formation

of

17β–estradiol–3–sulfate in three New Zealand pasture

access

soils: Hamilton clay loam, Matawhero silt loam, and

mineralization of steroid hormones, 17β–estradiol, estrone,

Gibsons

and testosterone. Sediment was collected upstream,

fine

sandy

loam.

Rapid

degradation

of

17β–estradiol–3–sulfate without a lag phase was observed

downstream and far downstream of wastewater treatment


in all soils. Values for DT50 and DT90 increased with

17β–estradiol and estrone was higher than that of

decreasing temperature. The primary metabolite in all soils

17α–ethynylestradiol for all soils tested. Conversion of

was estrone–3–sulfate. The maximum percentage formed

17β–estradiol was rapid and patterns were similar in all

varied for each soil (55–100%) and was temperature soils. This indicates the conversion of 17β–estradiol is dependent. 17β–estradiol was identified as a second microbially mediated. The mineralization of 17β–estradiol primary metabolite with its formation dependent on both was more than twice that of 17α–ethynylestradiol. This

temperature and soil type. 17β–estradiol dissipated faster

suggests

with increasing temperature. Estrone was identified as a

17α–ethynylestradiol

mineralization

is

not

third metabolite accounting for 7–30% of the parent

microbially dependent but may be due to some other factor.

compound depending on the soil type. Estrone showed

There was no correlation found between soil properties

temperature

(texture,

dependence with

respect

to

the peak

SOC,

and

pH)

and


mineralization.

concentrations found. The organic carbon content of the

The same study evaluated the effects of nitrogen,

soil was proportional to first order rate constants for the reactions. In addition, increased formation of estrone

glucose,

saw

occurred with degradation of both estrone–3–sulfate and

biodegradation of the hormones. Results varied for the

17β–estradiol.

different

soils

dust,

streptomycin,

tested.

In

and

general,

catechol on

17β–estradiol

The same study evaluated the role arylsulfatases

mineralization was reduced with the addition of each

(AryS) play in the degradation of 17β–estradiol–3–sulfate.

compound while 17α–ethynylestradiol mineralization either

Degradation of 17β–estradiol–3–sulfate was slower in soils

remained the same or increased. This suggests different

where AryS activity was inhibited. Formation and

microbially

persistence of metabolites estrone–3–sulfate and estrone

estrogenic compounds.

communities

exhibit

specificity

towards

was more pronounced. The maximum percent conversion

A different study by Stumpe and Marschner

was higher in soils where the AryS activity was not

(2009a) evaluated the effects of dissolved organic carbon

inhibited.

of

from cattle manure and sewage sludge on the sorption and

biological

mineralization of 17β–estradiol and 17α–ethynylestradiol

This

indicates

17β–estradiol–3–sulfate was

conversion

mediated

by

in agricultural soils. KD values were higher for sorption of

activity.

sewage sludge dissolve organic carbon than cattle manure

Stumpe and Marschner (2009b) characterized 17β–estradiol,

estrone,

and

to soils. In general, sorption of estrogenic compounds to


waste derived organic matter was lower than that with

mineralization in 17 natural soils from grassland, field, orchard, and forested

indigenous sources in the soil matrix. Decreased estrogen

sites. The mineralization of

sorption in the presence of added dissolved organic carbon


was observed in two of the three soils tested. 17β–estradiol

each of the sediment samples based on the estrogenic

was mineralized faster than 17α–ethynylestradiol in all

hormones

soils tested. The addition of waste organic matter reduced

17α–ethynylestradiol were considered the most important

estrogen mineralization. It is thought the bonding of

contributors (up to 98%) of total EEQ. Results indicate that

estrogenic compounds to dissolved organic compounds

EEQ may underestimate the results seen in the fish when a

may either mask the molecular structure from or be too big

limited number of compounds are considered. Next, soil

for uptake by enzymes present in the soil. This may explain

particles were separated into 3 ranges: >50µm, 1–50µm,

the persistence and transport of estrogenic compounds

and 450nm–1µm. Each of the sediment fractions were

through agricultural soils.

spiked with 17β–estradiol. Unspiked samples showed no

found.

17β–estradiol,

estrone,

and

Neale et al. (2009) evaluated the influence of pH

significant difference from the negative control. All spiked

on partitioning of estradiol, estrone, progesterone, and

particle sizes tested showed increased bioactivity compared

testosterone

matter.

to the negative control. Particles less than 1µm showed

Environmentally relevant concentrations of humic acid,

significantly higher bioactivity than larger particles spiked

alginic acid, and tannic acid were used in this study. Tannic

with 17β–estradiol.

in

the

presence

of

organic

acid had the strongest interaction with the hormones tested

Studies have shown cattle implanted with growth

and partitioning was influenced significantly by pH.

hormone, trenbolone acetate (TBA), excrete androgenic

Estrone and progesterone sorption rates were significantly

hormones. It is important to determine if these hormones

greater than testosterone and estradiol in the presence of

may leach into aquatic systems. Khan et al. (2009)

humic and tannic acids. Alginic acid showed the highest

evaluated

sorption

properties

of

17α–trenbolone,

partitioning with estradiol. In general, sorption of hormones 17β–trenbolone, and trendione in five agricultural soils to organic matter was the strongest at acidic pH with using batch equilibrium experiments. It was found that

partitioning decreasing significantly in alkaline solutions.

sorption for all hormones, TBA metabolites, were

Duong et al. (2009) evaluated the effect of

proportional to the organic carbon content of the soil. particle size on the bioavailability of 17β–estradiol from Trendione sorbed the most followed by 17β–trenbolone sediments. In addition, the presence and bioactivity of which

4–nonylphenol, 4–tert–octylphenol, bisphenol A, estrone,

consistently

17α–trenbolone

17α–ethynylestradiol, and genistein was assessed in

in

sorbed all

soils

twice

as

tested.

This

much

as

indicates

17α–trenbolone has higher mobility and is more likely to

sediments collected from the Yeongsan River and its tributaries. Hepatic vitellogenin (Vtg) concentrations were

leach from agricultural soils than the other compounds

measured in Japanese medaka after 7 day sediment

tested.

exposures. Estradiol equivalent (EEQ) were calculated for


Occurrence

and

fate

of

veterinary

and adsorption coefficients.

The half lives of the

pharmaceuticals. Wu et al. (2009) performed a study in an

compounds ranged from 0.8 to 20.4 d for bisphenol A and

agricultural area of the Lake Erie basin.

diclofenac, respectively.

The occurrence

and fate of 18 pharmaceuticals were investigated for

Tong et al. (2009) evaluated the occurrence of 13

occurrence and fate in aqueous and soil locations. Surface

antibiotics

waters in Lake Erie basin do not receive wastewater

tetracyclines, and chloramphenicols.

effluent, but are susceptible to agricultural and septic tank

collected at two pig farm waste streams (P1 & P2) during

runoff.

In addition, runoff from fields with biosolids

the summer and winter in Hubei, China. Eight distinct

application can contribute to pharmaceutical loading in

samples were collected from the sites, which include

Lake Erie.

Caffeine was detected most frequently

groundwater summer, groundwater winter, lake water

detected, and the highest concentration detected was 4.3

summer, lake water winter, P1 summer, P1 winter, P2

µg/L.

Veterinary pharmaceuticals including erythromycin,

summer, and P2 winter. Fluoroquinolone and tetracycline

lincomycin, sulfamethazine, and sulfamethoxazole were

concentrations were considerably higher in the winter

detected at frequencies ranging from 6 to 24 percent.

months, which may be attributed to decreased microbial

These compounds had maximum detected concentrations of

activity.

0.438, 0.005, 0.010, and 0.112 µg/L, respectively.

concentration (0.012 µg/L) was ciprofloxacin.

No

including

sulfonamides,

fluoroquinolones, Grab samples were

In winter, the compound observed at the highest The

pharmaceutical compounds were present above method

compound measured at the highest concentration in

detection limits (MDL) in sediment samples, which the

summer lake water was tetracycline at a concentration of

authors attributed to the polar, hydrophilic nature of the

0.012 µg/L.

compounds.

samples were not as high as in the lake water samples and were in the range of 0.002 to 0.009 µg/L. Large quantities

Xu et al. (2009) published a study on agricultural

soils

for

of antibiotics were present in P1 and P2 wastewater

The degradation and adsorption

effluents. Sulfamerazine, exceeding 10 µg/L in one case,

properties of clofibric acid, ibuprofen, naproxen, triclosan,

was detected at the highest concentrations in the

diclofenac, and bisphenol A were measured.

Degradation

wastewater effluent samples in both summer and winter.

and adsorption were assessed as function of 4 agricultural

Ciprofloxacin had the highest treatment system elimination

soil types.

Handford loamy sand (HLS), Arlington sandy

rate of approximately 96%, while doxycycline had the

loam (ASL), Imperial silty clay (ISC), and Palouse silt

lowest of 65%. Sulfathiazole and chlortetracycline were

loam (PSL) were the soils tested in experimental portion of

barely detected in the wastewater effluents.

study.

attributed to adequate treatment removal via biodegradation,

irrigation purposes.

receiving

wastewater

effluent

Concentrations detected in groundwater

First order exponential decay and Freundlich

isotherm models were used to estimate degradation rates

This may be

sorption, and photolysis processes.


Chang, H.; Wan, Y.; Hu, J. (2009) Determination and Source

Kuchta and Cessna (2009) identified lincomycin

Apportionment of Five Classes of Steroid Hormones in

in snowmelt runoff water after land application of liquid swine manure.

Urban Rivers. Environ. Sci. Tech., 43 (20), 7691–7698.

Sampling sites included closed basins,

Ding, J.; Ren, N.; Chen, L.; Ding, L. (2009) On–line coupling of

ephemeral wetlands, and dugouts in Saskatchewan, Canada. solid–phase extraction to liquid

The amount of liquid manure applied to closed basin chromatography–tandem mass spectrometry for the

section of field 1 and field 2 was 88,000 and 110,000 L/ha, respectively.

determination of macrolide antibiotics in environmental

Lincomycin was present in all runoff

water. Anal. Chim. Acta, 634 (2), 215–221.

samples acquired from each site location at a mean

Duong, C. N.; Schlenk, D.; Chang, N. I.; Kim, S. D. (2009) The

concentration of 0.27 μg/L and 0.39 ug/L for field 1 and field 2, respectively.

effect of particle size on the bioavailability of estrogenic chemicals from sediments. Chemosphere, 76

Manure was not applied to wetlands,

(3), 395–401.

so as expected the mean concentration was lower at Edwards, M.; Topp, E.; Metcalfe, C. D.; Li, H.; Gottschall, N.;

approximately 0.16 μg/L.

Lincomycin had a mean

Bolton, P.; Curnoe, W.; Payne, M.; Beck, A.; Kleywegt,

concentration in the dugout portion of fields 1 and 2 of 0.12

S.; Lapen, D. R. (2009) Pharmaceutical and personal

µg/L and 0.21 μg/L, respectively.

care products in tile drainage following surface

Water present in the

spreading and injection of dewatered municipal

dugouts may have contributed to decreased antibiotic

biosolids to an agricultural field. Sci. Total Environ.,

concentrations through dilution. 407 (14), 4220–4230.

Edwards

et

al.

(2009)

investigated Garcia–Ac, A.; Segura, P. A.; Viglino, L.; Fürtös, A.; Gagnon, C.;

pharmaceutical occurrence in liquid municipal biosolids

Prévost, M.; Sauvé, S. (2009) On–line solid–phase

(LMB) and dewatered municipal solids (DWB) land

extraction of large–volume injections coupled to liquid

applied to agricultural fields.

chromatography–tandem mass spectrometry for the

Solid phase extraction was

used for analyzing aqueous samples, while pressurized

quantitation and confirmation of 14 selected trace

liquid

organic contaminants in drinking and surface water. J.

extraction

was

used

for

biosolids.

Chromatogr. A, 1216 (48), 8518–8527.

Sulfamethoxazole, the only sulfonamide antimicrobial

Huang, X.; Lin, J.; Yuan, D.; Hu, R. (2009) Determination of

evaluated, was detected at concentrations below the limits steroid sex hormones in wastewater by stir bar sorptive

of quantification (LOQ). extraction based on poly(vinylpyridine–ethylene dimethacrylate) monolithic material and liquid

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