Removal of estrone and 17β-estradiol from water by adsorption
Introduction
Recently there has been increasing evidence of some chemicals having endocrine-modulating characteristics, which are defined as endocrine disrupting chemicals (EDCs). EDCs are the focus of current environmental concern, as they can cause adverse health effects in an intact organism, or its progeny, subsequent to endocrine function. Adverse effects already being observed include hormone-dependent cancers, reproductive tract disorders, and reduction in reproductive fitness. Numerous studies on the effects of EDCs on a range of wildlife species have been reported, including intersex in wild roach and vitellogenin induction in rainbow trout caused by estrone and 17β-estradiol (Rodger-Gray et al., 2001), intersex in lobster in Nova Scotia and abnormal sex ratios in harpacticoid copepods near sewage discharge in the Firth of Forth (Matthiessen and Gibbs, 1998), and sex reversal in male turtle hatchings caused by PCBs (Lye et al., 1997).
Most EDCs are man-made organic chemicals being introduced to the environment by anthropogenic activities, including industrial chemicals (e.g. surfactants), crop protection products (e.g. pesticides), antifouling compounds, pharmaceuticals and personal care products. In addition, EDCs can be naturally occurring in the environment. For example, the natural female hormones estrone and 17β-estradiol are both excreted by women, and are therefore ubiquitous in the aquatic environment receiving sewage inputs. These two compounds are among the most potent of all EDCs being implicated in causing adverse effects in fish adjacent to sewage outfalls. Such steroids are sufficiently stable to survive sewage treatment processes and are reactivated during those processes through deconjugation.
As a result of the importance of EDCs such as estrone and 17β-estradiol, their occurrence and environmental behaviour has been widely studied. In comparison to traditional contaminants such as pesticides, the concentrations of the most potent EDCs (e.g. steroidal hormones) are low, generally within ng/l range. In a study of several sewage treatment works (STW) in the UK, STW effluents contained estrone at a concentration of 1–80 ng/l, 17β-estradiol at a concentration of 1–50 ng/l, and 17α-ethynylestradiol at a concentration of 0–7.0 ng/l (Desbrow et al., 1998). Effluents from three Dutch STW also contained estrone, 17β-estradiol and 17α-ethynylestradiol at concentrations of <0.4–47, 0.6–12 and 0.2–7.5 ng/l, respectively (Belfroid et al., 1999). In 16 German municipal STW effluents, estrogens were measured at concentrations up to 80 ng/l of estrone, 3 ng/l of 17β-estradiol, and 15 ng/l of 17α-ethynylestradiol, and in 10 Canadian STW effluents corresponding values of 48 ng/l of estrone, 64 ng/l of 17β-estradiol, and 42 ng/l of 17α-ethynylestradiol were reported (Ternes et al., 1999). In Sweden, a minor STW discharged 5.8 ng/l of estrone, 1.1 ng/l of 17β-estradiol, and 4.5 ng/l of 17α-ethynylestradiol (Larsson et al., 1999). This effluent also contained 840 ng/l of 4-nonylphenol and 490 ng/l of bisphenol A. In addition, EDCs have been detected in drinking water supplies. Kuch and Ballschmiter (2001) detected some of these compounds in drinking water in pg/l range. Bisphenol A was found in concentrations ranging from 300 pg/l to 2 ng/l, 4-nonylphenol from 2 to 15 ng/l, 4-tert-octylphenol from 150 pg/l to 5 ng/l, and steroids from 100 pg/l to 2 ng/l. All these results would suggest that the current sewage treatment processes have limited capacity in removing certain EDCs.
Considering the potential impacts of EDCs, it is highly important to remove them from wastewater before discharge. The current data suggest that wastewater treatment processes (e.g. activated sludge) have variable performance in removing EDCs. It is therefore essential to install additional treatment processes after secondary treatment step. The aim of this project was therefore to study the feasibility of removing EDCs from aqueous solutions by adsorption. Various adsorbents were chosen in this study, including GAC, carbonaceous adsorbent prepared from industrial waste, chitin, chitosan and ion-exchange resin. The objectives were therefore to study the kinetics and equilibria of EDCs removal from water by adsorption, and to evaluate the effects of various parameters on adsorption performance.
Section snippets
EDC standards and analysis
The experiments were carried out using 14C-radiolabelled standards of estrone (E1) and 17β-estradiol (E2) (NEN Life Science Products, Belgium) with a specific activity of 2.1 and 2.0 GBq/mmol, respectively, both having a purity greater than 97%. The stock solutions of the two compounds were prepared at concentrations of 17.8 μg/l for E1 and 24.8 μg/l for E2, respectively. While not in use, the stock solutions were kept at −15 °C to minimise evaporation and degradation.
To accurately measure the
Adsorption of E1 and E2 onto GAC
The results from the kinetics for the adsorption of E1 onto the GAC are shown in Fig. 1a, where the data points on the graph represent the mean concentration with standard deviation of the measurement from duplicate samples. The concentration of E1 adsorbed by the GAC (Q, μg/g) increased with time whilst the concentration in water (C, μg/l) decreased with time. The adsorption of E1 reached its equilibration in the first 25 h, beyond which the concentrations in both phases did not change
Conclusions
E1 and E2 are the natural female hormones excreted by women and are, therefore, ubiquitous in aquatic environment receiving sewage inputs. The removal of these compounds is of importance due to their high potency in causing estrogenic effects in fish. The adsorption capacities of several adsorbents were studied in detail and found to be in the following order: carbonaceous adsorbent >granular activated carbon >ion-exchange resin >chitin >chitosan, suggesting the potential for reusing solid
Acknowledgements
The project benefited from financial support from the Leverhulme Trust (F/00230/H). The authors wish to thank Dr. Bhatnagar, Indian Institute of Technology for the provision of the carbonaceous adsorbent used in this study.
References (29)
- et al.
Analysis and occurrence of estrogenic hormones and their glucuronides in surface water and waste water in the Netherlands
Sci. Total Environ.
(1999) - et al.
Sediment–water interaction of nature oestrogens under estuarine conditions
Mar. Chem.
(2002) - et al.
Adsorption isotherms of 17β-estradiol on granular activated carbon
Chemosphere
(2001) - et al.
Utilization of industrial waste products as adsorbents for the removal of dyes
J. Hazard. Mat.
(2003) - et al.
Removal of pesticide from surface water by combined physicochemical process
Chemosphere
(1995) - et al.
Interaction between polychlorinated biphenyls and marine humic substance. Determination of association coefficients
Chemosphere
(1989) - et al.
Ethinylestradiol—an undesired fish contraceptive?
Aquat. Toxicol.
(1999) - et al.
Abnormalities in the reproductive health of flounder Platichthys flesus exposed to effluent from a sewage treatment works
Mar. Pollut. Bull.
(1997) - et al.
Removal of chlorophenols from groundwater by chitosan sorption
Water Res.
(2004) - et al.
Kinetics and equilibria of the interactions between diethylhexyl phthalate and sediment particles in simulated estuarine systems
Mar. Chem.
(2000)
Partition of synthetic pyrethroid insecticides between dissolved and particulate phases
Water Res.
Fluoranthene and pyrene on suspended particulate matter and surface sediments from the Humber estuary
Mar. Pollut. Bull.
The partition of fluoranthene and pyrene between particulate and dissolved phases in the Humber estuary: a study of controlling factors
Sci. Total Environ.
Determination of alkylphenols and alkylphenol mono and diethoxylates in environmental samples by HPLC
Anal. Chem.
Cited by (181)
17β-estradiol (E2) removal in anode-electrodialysis (anode-ED) during nutrient recovery from pig manure digestate
2024, Journal of Hazardous MaterialsSustainable technologies for adsorptive removal of estrogens from water: A comprehensive review for current advances
2023, Journal of Environmental Chemical EngineeringSand and sand-GAC filtration technologies in removing PPCPs: A review
2022, Science of the Total EnvironmentRobust strategies to eliminate endocrine disruptive estrogens in water resources
2022, Environmental PollutionCitation Excerpt :It is widely used for adsorbents due to its efficiency and economical ease in availability (Babel and Kurniawan, 2003; Rivera-Utrilla et al., 2011). In this direction, activated carbon granulate shows high adsorption capacity, and the kinetically controlled process can be affected by environmental conditions (Zhang and Zhou, 2005). The pore size of activated carbon can also affect adsorption capacity, i.e., an increase in pore size reduces the adsorption of estrogens due to their high hydrophobic nature (Fukuhara et al., 2006).
Functional nanomaterials based opto-electrochemical sensors for the detection of gonadal steroid hormones
2022, TrAC - Trends in Analytical Chemistry