Elsevier

Chemosphere

Volume 61, Issue 11, December 2005, Pages 1594-1606
Chemosphere

Screening 31 endocrine-disrupting pesticides in water and surface sediment samples from Beijing Guanting reservoir

https://doi.org/10.1016/j.chemosphere.2005.04.091Get rights and content

Abstract

For screening 31 potential or suspected endocrine-disrupting pesticides in water and surface sediments, a multiresidue analysis method based on gas chromatography with electron capture detection (GC/ECD) was developed. Solid phase extraction (SPE) technology with Oasis® HLB cartridge was also applied in sample extraction. The relevant mean recoveries were 70–103% and 71–103% for water and sediment, respectively. Relative standard deviations (RSD) are 2.0–7.0%, 4.0–8.0% for water and sediment, respectively. Thirty one pesticides (α-HCH, β-HCH, γ-HCH, δ-HCH, hexachlorobenzene (HCB), aldrin, heptachlor, endosulfan I & II, p,p′-DDD, o,p′-DDT, p,p′-DDT, p,p′-DDE, endrin aldehyde, endosulfan sulphate, methoxychlor, hepachlor epoxide, α-chlordane, γ-chlordane, dieldrin, endrin, dicofol, acetochlor, alachlor, metolachlor, chlorpyriphos, nitrofen, trifluralin, cypermethrin, fenvalerate, deltamethrin) in water and surface sediment samples from Beijing Guanting reservoir were analyzed. Concentrations of pesticides ranged from 7.59 to 36.0 ng g−1 on a dry wt. basis for sediment samples, from 279.3 to 2740 ng l−1 for pore waters and from 48.8 to 890 ng l−1 for water samples, respectively, with a mean concentration of 10.7 ng g−1 in sediment, 735 ng l−1 in pore water and 295 ng l−1 in water, respectively. The data obtained provides information on the levels and sources of endocrine-disrupting pesticides in Guanting reservoir. These results underscore the need to improved environmental protection measures in order to reduce the exposure of the population and aquatic biota to these endocrine-disrupting compounds.

Introduction

Endocrine disruptors are ubiquitous environmental contaminants found in a variety of products, such as pesticides, wood preservatives, paints and plastics as well as occurring naturally in some plants. It is hypothesized that they can cause adverse effects by interfering in some way with the body’s hormones or chemical messengers and may induce a broad spectrum of biochemical and toxic responses at low environmentally relevant dose (Colborn et al., 1996). Their potential health effects include reproductive disorders, cancer and impaired development (Hileman, 1994, Colborn and Smolen, 1996, Turusov et al., 2002, Zhou et al., 2004). Studies have suggested that some pesticides have been identified as potential or suspected endocrine disruptors. However, pesticide application safety was used to be internationally assessed by Maximum Residue Levels (MRL) based on the Acceptable Daily Intake (ADI) with a considerable safety margin. Safety assessments of pesticides do not take into account of possible endocrine disrupting properties of pesticides. Many MRLs may well be too high to exclude hormone disruption as a possible effect of being exposed to residues in food and drinking water. Studies have suggested that, unfortunately, there are no desirable methods to screen and test endocrine disruptors at present (Zhou et al., 2004). Pesticides not only can be concentrated in the environment through biogeochemical processes, but also often scavenged from the water through sorption onto suspended material and get deposited to become a part of the bottom substrate. The sediment component of aquatic ecosystems can be sunk for pesticides. Consequently, bottom sediments often become reservoirs of pesticides in the environment (Khan, 1977, Chau and Afgan, 1982). Therefore, the investigation of distribution of endocrine disrupting pesticides in water and sediment can provide a valuable record of contamination in aquatic environments (Doong et al., 2002).

Different pesticides pose varying degrees and types of risk to water quality. Some surveys of pesticide contamination in water have reported in coastal and estuarine sediments collected from Asian countries such as Vietnam, Turkey, Korea and China (Hong et al., 1999, Khim et al., 1999, Nhan et al., 1999, Doong et al., 2002, Bakan and Ariman, 2004, Zhang et al., 2004) indicating the presence of significant source of pesticides in these regions. China is the world’s second largest producer of pesticides, and a pesticide production of 260 000 tonnes was recorded in 1994 (Zhang et al., 2002a). Several studies have reported, despite the ban and restriction on the usage of some organochlorine pesticides (OCPs) since 1983 in China, the presence of elevated levels of OCPs, such as DDTs and HCHs, in seawater and coastal sediments (e.g. Zhou et al., 2001) and some river/estuarine systems (Hong et al., 1995, Chen et al., 1996, Wu et al., 1999, Zhou et al., 2000). Furthermore, DDT concentrations in marine mussels collected from China were still high, one to two orders of greater than those of other Asian countries (Nakata et al., 2002, Monirith et al., 2003, Li et al., 2001). These results suggest significant pollution sources of pesticides are present in China. However, most studies examined pesticides (such as OCPs) levels in waters, sediments from the marine environment (Qiu et al., 2004, Nakata et al., 2005), and up to now, in China, very little field monitoring data is available for the presence of environmental endocrine disrupting pesticide residues in freshwater. An understanding of the impacts of endocrine disrupting pesticides on China’s environment is therefore very limited.

The study focuses on developing a method based on a pesticide multi-residue analysis to screen endocrine disrupting pesticides in water and sediment. Some pesticides identified as potential or suspected endocrine disruptors such as α-HCH, β-HCH, γ-HCH, δ-HCH, hexachlorobenzene (HCB), aldrin, heptachlor, endosulfan, p,p′-DDD, o,p′-DDT, endrin aldehyde, endosulfan sulphate, p,p′-DDT, p,p′-DDE, methoxychlor, hepachlor epoxide, chlordane, dieldrin, endrin, dicofol, acetochlor, alachlor, metolachlor, chlorpyriphos, nitrofen, trifluralin (HEPO), cypermethrin, fenverate, deltamethrin were simultaneously determined. These pesticides were selected to be screened because they have been identified as potential pollutants in food or drinking water and also been listed as endocrine disrupting chemicals by EU or by the European Commission or US EPA (Kelce et al., 1995, US EPA, 1998, Ren and Jiang, 2001) or by the Federal Environment Agency in Germany (ENDS, 1999), and because they either are widely used in the studied area for agricultural and public purposes or are present as persistent residues of previous uses. The data would be useful to local government to renew Guanting reservoir, a Beijing municipal water supply source.

Section snippets

Study area and sampling locations

Guanting reservoir located in the northwest of Beijing is one of two main water resources for agriculture, industry and living uses of Beijing. Since Guanting reservoir has suffered from extensive pollution over the last decades (particularly in 1980s) due to runoff from non-point sources, direct dumping of waste into rivers and pollutants carried by rivers (Wang et al., 2000, Zhang et al., 2002b), Guanting reservoir has not supplied with living water for Beijing city since 1997. Particularly,

Physicochemical characteristics of sediment and water samples

Table 2 provides the basic physicochemical parameters of sediment samples collected from the Guanting reservoir. The depth of the water column above the sediment layer was between 8.5 and 1.2 m. The water content of sediments ranged from 36.1% to 71.5%. The organic matter (denoted by loss on ignition, LOI%) of sediments ranged from 3.98% to 8.49%. The maximum organic matter of the sediment samples was observed at the sampling site 7 that is located in front of a dam. Sediments with high organic

Summary

A method based on a pesticide multi-residue analysis to screen potential or suspected endocrine-disrupting pesticides in water and sediment was developed. The analyzed samples showed the presence of 31 pesticides in water and sediments from Beijing Guanting reservoir. The concentrations of pesticides in water are generally lower than the Chinese standards (in the grade 1–3 surface water) for surface water. However, values in a few sites are considerately high considering to being used as a

Acknowledgements

This study was financially supported by Ministry of Sciences and Technology, China (2003CB415005). The authors wish to thank Mr. Zhe Cao from Agilent Technologies, Beijing Environment Laboratory for helping with mass spectrometric confirmations. The authors also to thank to Dr. Xue-tong Wang and Dr. Yang-Zhao Sun for the help of sampling site.

References (58)

  • H. Nakata et al.

    Concentrations and composition of organochlorine contaminants in sediments, soils, crustaceans, fishes, and birds collected from Lake Tai, Hangzhou Bay, and Shanghai city region, China

    Environ. Pollut.

    (2005)
  • D.D. Nhan et al.

    Organochlorine pesticides and PCBs along the coast of north Vietnam

    Sci. Total Environ.

    (1999)
  • J.M.F. Nogueira et al.

    Multiresidue screening of neutral pesticides in water samples by high performance liquid chromatography-electrospray mass spectrometry

    Anal. Chim. Acta

    (2004)
  • B.J. Richardson et al.

    Chlorinated hydrocarbon contaminants in Hong Kong surficial sediments

    Chemosphere

    (1999)
  • A. Sarkar et al.

    Pesticide residues in sediments from the west coast of India

    Mar. Pollut. Bull.

    (1991)
  • S. Tanabe et al.

    Global contamination by persistent organochlorines and their ecotoxicological impact on marine mammals

    Sci. Total Environ.

    (1994)
  • Y. Wu et al.

    Persistent organochlorine residues in sediments from Chinese river/estarine systems

    Environ. Pollut.

    (1999)
  • Z.L. Zhang et al.

    Fate and assessment of persistent organic pollutants in water and sediment from Minjiang River Estuary, Southeast China

    Chemosphere

    (2003)
  • Z. Zhang et al.

    Occurrence of PAHs, PCBs and organochlorine pesticides in the Tonghui River of Beijing, China

    Environ. Pollut.

    (2004)
  • J.L. Zhou et al.

    Polychlorinated biphenyl congeners and organochlorine insecticides in the water column and sediments of Daya Bay, China

    Environ. Pollut.

    (2001)
  • Bakan, G., Kaya, S., Ozkoc, H.B., Kurt, P., 1999. Certain organic pollutant levels in surface sediment of the mid Black...
  • L.E. Castillo et al.

    Pesticide residues in the aquatic environment of banana plantation areas in the North Atlantic Zone of Costa Rica

    Environ. Toxicol. Chem.

    (2000)
  • A.S.Y. Chau et al.
    (1982)
  • W.Q. Chen et al.

    Concentrations and distributions of HCHs, DDTs and PCBs in surface sediments of sea area between Xiamen and Jinmen

    Journal of University (Natural Science) (in Chinese)

    (1996)
  • T. Colborn et al.

    Our Stolen Future: are We Threatening Our Fertility, Intelligence, and Surival? Scientific Detective Story

    (1996)
  • T. Colborn et al.

    Epidemiological analysis of persistent organochlorine contaminations in cetaceans

    Rev. Environ. Contam. Toxicol.

    (1996)
  • D. Crain et al.

    Reptilesas models of contaminant-induced endocrine disruption

    Animal Reprod. Sci.

    (1998)
  • H.M. Dutta et al.

    Histopathological changes induced by malathion in the liver of a freshwater catfish, Heteropneustis fossilis

    Bull. Environ. Contam. Toxicol.

    (1993)
  • ENDS, 1999, Industry glimpses new challenges as endocrine science advances. ENDS Report 290, pp....
  • Cited by (153)

    View all citing articles on Scopus
    View full text