2
534
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estrogens in river water and effluents using solid-phase extraction
and gas chromatography—Negative chemical ionization mass
spectrometry of the pentafluorobenzoyl derivatives. J Chroma-
togr A 923:195–204.
samples are shown in Table 5. The River Thames showed
higher surface area and chlorophyll than the other rivers in
spring that may be related to a higher algal population. The
relatively poor algal production in the urban/industrial reaches
of the Yorkshire rivers has been noted previously [34].
Many factors could influence the suspended sediment qual-
ity, such as intensity of rainfall, change in land use, and inputs
from STWs and industrial sources [35]. The hydrophobicity
of the organic matter [36], as measured by the C:N ratio has
been suggested to be particularly important in this respect. A
higher C:N ratio is associated with greater hydrophobicity of
the organic carbon in the sediment and, therefore, with a larger
capacity to bind hydrophobic molecules, but it is not possible
to confirm that based on our spring 2000 samples only. No
clear correlations could be found between the Kd values of the
suspended sediments and the river and sample parameters mea-
sured (Table 5). As noted previously with the bed sediments,
3. Harries JE, Sheahan DA, Jobling S, Matthiessen P, Neall M,
Sumpter JP, Taylor T, Zaman N. 1997. Estrogenic activity in five
United Kingdom rivers detected by measurement of vitellogenesis
in caged male trout. Environ Toxicol Chem 16:534–542.
4
. Desbrow C, Routledge EJ, Brighty GC, Sumpter JP, Waldock M.
1
998. Identification of estrogenic chemicals in STW effluent. 1.
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. Aherne GW, Briggs R. 1989. The relevance of the presence of
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. Montagnani DB, Puddefoot J, Davie TJA, Vinson GP. 1996. En-
vironmentally persistent estrogen-like substances in UK river sys-
tems. Journal of the Chartered Institution of Water and Envi-
ronmental Management 10:399–406.
. Purdom CE, Hardiman PA, Bye VJ, Eno NC, Tyler CR, Sumpter
JP. 1994. Estrogenic effects of effluents from sewage treatment
works. Chem Ecol 8:275–285.
5
6
7
generally higher Kd values were obtained with EE than with
2
E ; however, this was less clear for suspended sediments, with
8. Stumpf M, Ternes TA, Haberer K, Baumann W. 1996. Nachweis
2
¨
von nat u¨ rlichen und synthetischen Ostrogenen in Kl a¨ ranlagen und
Fließgew a¨ ssern. Vom Wasser 87:251–261.
some samples showing even lower Kd values for EE than for
2
E . Overall, suspended sediments would, in most cases, re-
2
9
. R o¨ mbke J, Knacker T, Stahlschmidt-Allner P. 1996. Umwelt-
probleme durch Arzneimittel. UBA Texte 60/96. Literaturstudie.
Umweltbundesamt, Berlin, Germany.
move less than 1% from the water column (Table 5).
CONCLUSIONS
1
0. Ternes TA, Stumpf M, M u¨ ller J, Haberer K, Wilken RD, Servos
M. 1999. Behavior and occurrence of estrogens in municipal sew-
age treatment plants—I. Investigations in Germany, Canada and
Brazil. Sci Total Environ 225:81–90.
11. Baronti C, Curini R, d’Ascenzo G, Di Corcia A, Gentili A, Sam-
peri R. 2000. Monitoring natural and synthetic estrogens at ac-
tivated sludge sewage treatment plants and in a receiving river
water. Environ Sci Technol 34:5059–5066.
This study has demonstrated the potential for E and EE2
2
to sorb to sediments in a range of English rivers. Sorption of
E has not been measured in the present study, but given its
1
similar characteristics, E is expected to bind to sediments to
1
a similar extent as E . Regression analysis indicated that sorp-
2
tion to bed sediments was most closely associated with particle
size. Although the Kd values for suspended sediments tended
to be higher than those for bed sediments, they are not likely,
given the ambient concentrations of suspended sediments, to
be important in reducing the water concentration. From the
environmental point of view, the removal of a proportion of
the steroid estrogens from the water phase and onto sediments,
where they are consumed by the resident microorganisms,
could be considered a benefit. We know that E and E have
1
2. Belfroid AC, Van der Horst A, Vethaak AD, Sch a¨ fer AJ, Rijs
GBJ, Wegener J, Cofino WP. 1999. Analysis and occurrence of
estrogenic hormones and their glucuronides in surface water and
waste water in The Netherlands. Sci Total Environ 225:101–108.
3. Johnson AC, Belfroid A, Di Corcia A. 2000. Estimating steroid
estrogen inputs to activated sludge treatment works and obser-
vations on their removal from the effluent. Sci Total Environ 256:
1
1
63–173.
14. Larsson DGJ, Adolfsson-Erici M, Parkkonen J, Pettersson M,
Olsson P-E, F o¨ rlin L. 1999. Ethinylestradiol—An undesired fish
contraceptive? Aquat Toxicol 45:91–97.
2
1
a short half-life under aerobic conditions in river water [25].
1
5. Tabak HH, Bloomhuff RN, Bunch RL. 1981. Steroid hormones
as water pollutants. II. Studies on the persistence and stability of
natural urinary and synthetic ovulation-inhibiting hormones in
It has been found that E is particularly susceptible to bio-
2
degradation under both aerobic and anaerobic conditions in
bed sediment and, so, would be unlikely to accumulate. A
untreated and treated wastewaters.
519.
Dev Ind Microbiol 22:497–
short-duration microcosm experiment suggested that E might
1
1
6. Snyder SA, Keith TL, Verbrugge DA, Snyder EM, Gross TS,
Kannan K, Giesy JP. 1999. Analytical methods for detection of
selected estrogenic compounds in aqueous mixtures. Environ Sci
Technol 33:2814–2820.
persist in anaerobic sediments [25]. Whether EE , which is
2
more resistant to biodegradation, may be preserved, at least
to a limited extent, and remain bioavailable has still to be
established. The potential for E and EE to bind and persist
1
2
17. Lee HB, Peart TE. 1998. Determination of 17-estradiol and its
in natural bed sediments should receive further attention.
metabolites in sewage effluent by solid-phase extraction and gas
chromatography mass spectrometry. J AOAC Int 81:1209–1216.
8. Shore LS, Gurevich M, Shemesh M. 1993. Estrogen as an en-
vironmental pollutant. Bull Environ Contam Toxicol 51:361–366.
19. Metcalfe CD, Metcalfe TL, Kiparissis Y, Koenig BG, Khan C,
Hughes RJ, Croley TR, March RE, Potter T. 2001. Estrogenic
potency of chemicals detected in sewage treatment plant effluents
as determined by in vivo assays with Japanese medaka (Oryzias
latipes). Environ Toxicol Chem 20:297–308.
1
Acknowledgement—This work was jointly funded by the United King-
dom Department for the Environment, Food and Rural Affairs and
the Environment Agency (England and Wales). This research forms
part of the Agency’s Endocrine Disruptor research program, managed
by the Agency’s National Centre for Ecotoxicology and Hazardous
Substances. M. J u¨ rgens was funded by the European Union research
program COMPREHEND. The authors would like to thank Paul Wass,
Craig White, Margaret Neal, Lal Bhardwaj, and Luisa Patrolecco for
additional assistance.
2
0. Lai KM, Johnson KL, Scrimshaw MD, Lester JN. 2000. Binding
of waterborne steroid estrogens to solid phases in river and es-
tuarine systems. Environ Sci Technol 34:3890–3894.
2
1. Robson AJ, Neal C. 1997. A summary of regional water quality
for Eastern UK rivers. Sci Total Environ 194/195:15–37.
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