Scholarly article on topic 'Distribution of Estrogens Along Licun River in Qingdao, China'

Distribution of Estrogens Along Licun River in Qingdao, China Academic research paper on "Chemical sciences"

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Abstract of research paper on Chemical sciences, author of scientific article — Xin Zhou, Ziru Lian, Jiangtao Wang, Liju Tan, Zhichao Zhao

Abstract Estrogens (estrone, estradiol and estriol) and synthetic compound (ethynyl estradiol) in the water and sediment of Licun River-Jiaozhou Bay area in Qingdao were monitored. Estrogens in waters were concentrated using modified C- 18 SPE cartridges, and estrogens in sediments were extracted by liquid-solid extraction. Silane derivatives of the extracted and concentrated estrogens were analyzed by GC-MS. The concentration of estrogens ranged from ND (below the detection limit) to 180ng/L in waters and ND to 10.8colong/kg (dry weight) in sediment. The concentrations of estrogen in river water were higher than those in seawater during the monitoring periods. The distribution of estrogen concentration along Licun river suggested that estrogens were different with distance from the respective effluent sites. The highest concentrations were detected at station 5 which directly receives huge quantities of pollutants from adjacent rivers containing large amounts of farming and industrial wastewater.

Academic research paper on topic "Distribution of Estrogens Along Licun River in Qingdao, China"

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Procedia Environmental Sciences 10 (2011) 1876 - 1880

2011 3rd International Conference on Environmental Science and Information Application Technology (ESIAT 2011)

Distribution of estrogens along Licun River in Qingdao,

Xin Zhou b *, Ziru Lian a, Jiangtao Wang a , Liju Tan a, Zhichao Zhao b

a Key Laboratory of Marine Chemistry Theory and Technology, Ministry of Education, Ocean University of China 266100,

b College of Chemical Engineering, Qingdao University of Science and Technology 266042, China zhouning1975@sina. cn

Abstract

Estrogens (estrone, estradiol and estriol) and synthetic compound (ethynyl estradiol) in the water and sediment of Licun River-Jiaozhou Bay area in Qingdao were monitored. Estrogens in waters were concentrated using modified C-18 SPE cartridges, and estrogens in sediments were extracted by liquid-solid extraction. Silane derivatives of the extracted and concentrated estrogens were analyzed by GC-MS. The concentration of estrogens ranged from ND (below the detection limit) to 180 ng/L in waters and ND to 10.8 ^g/kg (dry weight) in sediment. The concentrations of estrogen in river water were higher than those in seawater during the monitoring periods. The distribution of estrogen concentration along Licun river suggested that estrogens were different with distance from the respective effluent sites. The highest concentrations were detected at station 5 which directly receives huge quantities of pollutants from adjacent rivers containing large amounts of farming and industrial wastewater.

© 2011 Published by Elsevier Ltd. Selection and/or peer-review under responsibility of Conference ESIAT2011 Organization Committee.

Keywords: Estrogens; Licun River; water; sediment.

l.Introduction

Research has shown that environmental estrogens have potential risk to wildlife[1]. Recent years, a certain amount of natural and synthetic steroid hormones has emerged in natural environment because of their increasing use for human purposes and animal farming[2,3]. The levels of estrogens have been observed from being less than 0.1ng/L to 21ng/L in waters and up to 70ng/kg in soils [4]. When the concentration of natural estrogen, such as estradiol is 1 ng/L or the synthetic estrogen reaches 0.1 ^g/L in water, some wild male fish exhibit feminization [2,5].With the increasing of population and the development of farming, discharged estrogens increased steadily, which will seriously affects the water biology. Therefore, it is important to carried out investigation on estrogens in aquatic environment. In this

1878-0296 © 2011 Published by Elsevier Ltd. Selection and/or peer-review under responsibility of Conference ESIAT2011 Organization Committee. doi: 10.1016/j.proenv.2011.09.293

study, the estrogens, such as Estrone (E1), estradiol (E2), estriol (E3) and ethynyl estradiol (EE2) in water and sediment in Licun River-Jiaozhou Bay area of Qingdao were determined and the distribution of estrogens in this area was discussed.

2.Instruments and Methods

Materials and instruments

N-methyl-N-trimethylsilyl-triflouoroacetamide (MSTFA) and estradiol (E2, HPLC>97%) were supplied by Aldrich (Milwaukee, WI, USA). HPLC-grade Pentacosane, estril (E3, HPLC>97%), estrone (E1, HPLC>97%) and ethynyl estradiol (EE2, HPLC>97%) were obtained from Fluka (Zwijndrecht, the Netherlands). HPLC-grade Eicosane (C-20) was obtained from the Shanghai First Reagent Factory. Squalane (C-30) was from Britain by the Shanghai Chemical Reagents Purchasing and Supply Station. Supelco LC-18 SPE cartridge (50mm*5mm I.D.) containing 100 mg of LC-C18 packing were from Supelco. C-18 solid sorbent (40-70 ^m) was obtained from Japan. Individual stock solutions, diluted standards and mixtures of the estrogens were prepared in methanol. Other solutions of the compounds were prepared in trichloromethane.

A Thermo Finnigan TRACE gas chromatograph - mass spectrometer was used to determining the concentrations of estrogens. Sampling

Locations of water samples were shown as Fig.1. There are 6 sampling station from the upriver of the Licun river to Jiaozhou Bay. Sediment samples were collected from station 2, 5 and 6.The samples were collected in April, 2007. The water samples were taken with 5L plastic barrels and sediment samples were collected using a trowel preserved with plastic bags. All samples were processed immediately after being sampled.

Fig.1 Ssampling sites in Licun River -Jiaozhou Bay area

Extraction of estrogens

2 to 4 liter water samples were centrifuged at speed of 2000 r/min to remove large suspended substances. Then the samples were filtered through 0.45 ^m polar cellulose filter membrane and pass through a SPE cartridge that had been sequentially pre-washed with 10 mL of methanol, 10 mL of de-ionized water, 150 ^L of C-20 and 50 ^L of C-25 using an auto filter system with the flow rate 1~2 mL/min. After that, the cartridge was dried with a nitrogen stream for 20 min and was eluted with solvent mixture consisting of 0.5 mL methanol, 3 mL n-hexane and 3 mL dichloromethane. The solvent extracts eluted was evaporated by a low flow of nitrogen gas after 20 ^L C-30 were added as internal standard [6]. The remainder was then transferred to a vial by dichloromethane for future use.

Freeze-dried sediment (5.0g) was grinded and sieved through 20 mesh sieve. 20mL extraction solvent which consists of methanol, ethyl acetate, n-hexane and dichloromethane (v:v = 3:4:7:3) were added into the soil in the conical flask. The flask was sealed and extracted by supersonic for 20 min. The

supernatant was transferred to a small beaker while the residue was washed twice with 10mL of extraction solvent mentioned above. The solvents of extracts were removed by N2 at 40 °C. Then the residue was dissolved in 1mL of dichloromethane and 300mg of silica was added to the solution. The dichloromethane was vaporized at room temperature and the silica containing extracts was transferred to a small column of polythene. The column was connected to a C18 cartridge pre-conditioned using method mentioned above. 100mL of polar cellulose membrane filtered water passed through the silica column and C18 cartridge at a speed of 1-2mL/min [7]. Extracts on the C18 cartridge was eluted and condensed by the way mentioned above.

1. Analysis of estrogens

Extracts of water and sediment samples were derivatized with MSTFA and detected by GC-MS. The following oven program was used: 2 min at 80°C, first ramp at 10°C/min to 250°C (held for 15 min), second ramp at 1°C/min to 260°C (held for 20 min). The GC-MS interface and the ion trap temperature were set at 250 and 270°C respectively. Mass spectra were obtained in the m/z interval from 25 to 550 using electron impact ionization (70 eV). Retention times and m/z ratios were used for the identification of target compounds. The concentrations of estrogens in the samples were quantified using internal standard correlation curves.

2. Results and Discussions

Evaluation of quantitative analysis method

The linearity of the method was tested with derivatized standard mixtures between estrogen concentrations from 1 to 1000 ng/L. The linear regression equations are obtained and the correlation coefficients were about 0.99 for the four compounds[6]. The detect limits were 0.9 ng/L. Recoveries of the estrogen in water samples from different stations at the Licun River-Jiaozhou Bay area were between 70 to 110%. The results confirmed that the developed method can be used to determine estrogen concentration in water and sediments in this area. Concentrations of estrogen in water

As shown in Table 1, estrogens were found in every water sample. The amount ranged from 18 to 180 ng/L for E1, ND to 134ng/L for E2 and 4 to 94 ng/L for E3. The estrogen contents in this area were higher than those (1.6 to 30.8 ng/L) from Tai Lake in China [8] but lower than those (260-300ng/L) in seawater near the sewage discharge points in Shenzhen[9]. Estrogen concentrations in influent of wastewater treatment plants (WWTPs) was 62 ng/L in Spain [7], 0.5-120 ng/L in Italy[10], ND -43 ng/L in California[11] and ND-76 ng/L in England[2]. The concentrations of estrogens in the study area are same or somewhat higher than those reported. This means that the water in the Licun -Jiaozhou Bay area has been polluted by estrogens.

From upriver to the station 5, the concentration of estrogen continued increasing and reached a peak value. Then the concentration decreased until to seawater.The polluted water was concentrated at station 5, which made the concentrations of estrogens in the water the highest. It was also found that estrogen contents vary over time at the same station which means that the quality of river water changes and the components of the water were affected by the discharge of wastewater or sewage.

Xin Zhou et al. /Procedia Environmental Sciences 10 (2011) 1876 - 1880 Table 1. Levels of estrogens in water in Licun River-Jiaozhou Bay area

_Concentrationa(ng/L)_

Sampling Locations

E1 E2 EE2 E3

1 14 11 7 4

2 18 13 8 4

3 20 30 15 21

4 28 ND 21 83

5 180 134 24 94

6 21 21 10 50

Levels of Estrogens in Sediment

Concentrations of estrogens in sediment in Licun River- Jiaozhou Bay area were monitored and E1 and E3 were founded in all samples (Table 2). E1 levels ranged from 3.0 to 10.8^g/kg dry weight (dw) and E3 from 1.0 to 7.6^g/kg (dw). Concentration of E1 and E3 in this area were similar to those sediment of Nan river in Chengdu( ND~28.6^g/kg)[12]and those in Germany (0.05~22.8 ^g/kg)[13]. Only a small amount of E2 was detected and the concentration was low in this area. This may be caused by the degradation of E2 because of the frequent contact of surface sediment with air[14,15]. In addition, the levels of E1 in sediment were higher than that of E3 because of the stronger adsorption of E1 than E3 on sediment [16] and lower removal rates for E1 [17]. EE2 was only found in several samples which related to the use of contraceptive pills. The estrogens in sediment might be gradually released into aquatic environment and have potential risk to aquatic lives' health for long periods [4].

Moreover, estrogens were also found in sludge samples from Licun River Wastewater Treatment Plant. The concentrations of estrogens were between 1.2~5.9^g/kg dry weight which were lower than that of sludge in Germany (2~49^g/kg dw).

Table 2 Levels of estrogens in sediment in Licun River (/kg dry weight)

location E1 E2 EE2 E3

2 7.2 ND 1.4 5.5

5 10.8 ND ND 7.6

6 3.0 ND ND 1.0

Licun WWTP 5.9 1.2 5.1 1.4

Summary

Estrone, estradiol, ethynyl estradiol, and estril in environmental water were determined in the Licun River - Jiaozhou Bay area in April, 2007. The determination recovery rate was 71-113%. The results showed that the concentration of estrogens (mainly natural estrogens) ranged from ND to 180 ng/L in water and from nd~10.8^g/kg dry weight in sediments in the Licun River-Jiaozhou Bay area. The distribution of estrogens along this area is due to sewage drainage. The more sewage is discharged into the river, the higher the estrogen levels were in the water. The persistence of estrogens in water and sediment shows that these sewage discharges may resulted pollution for the local aquatic environment.

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