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1.
《Marine pollution bulletin》2012,64(5-12):556-563
The endocrine-disrupting chemicals (EDCs) was investigated in 28 riverine sediments from the Pearl River system, China and analyzed by an ultrasonication extraction and GC–MS method. The concentrations of 4-tert-octylphenol (OP), 4-nonylphenol (NP), and bisphenol A (BPA) in the sediments were in the ranges of <2.0–210, 107–16198 and <1.7–430 ng/g dw, respectively. The steroid estrogens estrone (E1) and 17β-estradiol (E2) in the sediments ranged from <1.3 to 10.9 ng/g dw and from <0.9 to 2.6 ng/g dw, respectively. The spatial distribution of these chemicals was related to the discharge of domestic and industrial wastewater along the rivers. The positive correlation between EDCs and total organic carbon indicates that sedimentary organic carbon is an important factor in controlling the distributions of EDCs. Compared with other previous studies, the ZR and DR rivers from the PRD were heavily contaminated by APs and BPA.  相似文献   

2.
The endocrine-disrupting chemicals (EDCs) was investigated in 28 riverine sediments from the Pearl River system, China and analyzed by an ultrasonication extraction and GC-MS method. The concentrations of 4-tert-octylphenol (OP), 4-nonylphenol (NP), and bisphenol A (BPA) in the sediments were in the ranges of <2.0-210, 107-16198 and <1.7-430 ng/g dw, respectively. The steroid estrogens estrone (E1) and 17β-estradiol (E2) in the sediments ranged from <1.3 to 10.9 ng/gdw and from <0.9 to 2.6 ng/gdw, respectively. The spatial distribution of these chemicals was related to the discharge of domestic and industrial wastewater along the rivers. The positive correlation between EDCs and total organic carbon indicates that sedimentary organic carbon is an important factor in controlling the distributions of EDCs. Compared with other previous studies, the ZR and DR rivers from the PRD were heavily contaminated by APs and BPA.  相似文献   

3.
Natural estrogens from humans increasingly attract attention because of their strong endocrine disrupting potency. The discharge of sewage water is considered as the most important source of these endocrine disrupting chemicals (EDCs) in the environment. Therefore, a GC‐MS method was developed for the simultaneous analysis of six natural free estrogens and their sulfate conjugates in municipal wastewater, in which natural free estrogens and sulfate conjugates were successfully separated from an Oasis HLB solid phase extraction (SPE) cartridge with two different eluents, and the sulfate conjugates were then transformed to their corresponding free estrogens by acid solvolysis. Before the analysis with GC‐MS, samples were derivatized by N,O‐bis (trimethylsilyl) trifluoroacetamide (BSTFA) plus 1% trimethylchlorosilane (TMCS) at 80°C for 40 min. Satisfactory recoveries ranging from 64 to 112.3% were obtained by spiking ultra‐purified water, raw, and treated municipal wastewater with the six estrogens at 50, 100, and 50 ng/L, respectively. The method was successfully applied to wastewater samples from one WWTP, which suggested that E1 was the dominant natural estrogens in effluent and E3‐3S was one of the conjugates possibly occurring in the effluent.  相似文献   

4.
Dispersive liquid–liquid microextraction based on solidification of floating organic droplet (DLLME‐SFO) technique was successfully applied for simultaneous assay of eight polychlorinated biphenyls, two organochlorine, and four pyrethroid pesticides multi‐residue in aqueous samples by using GC‐electron capture detection. The effects of various parameters such as kind of extractant and dispersant and volume of them, extraction time, effect of salt addition, and pH were optimized. As a result, 5.0 µL 1‐dodecanol was chosen as extraction solvent, 600 µL methanol were used as dispersive solvent without salt addition, pH was adjusted to 7. Under the optimized conditions, the limits of detection (LOD) were ranged from 1.4 to 8.3 ng L?1. Satisfactory linear range was observed from 5.0 to 2000 ng L?1 with correlation coefficient better than 0.9909. Good precisions were also acquired with RSD better than 13.6% for all target analytes. The enrichment factors of the method were ranged from 786 to 1427. The method can be successfully applied to simultaneous separation and determination of three class residues in real water samples and good recoveries were obtained ranging from 76 to 130, 73 to 129, and 78 to 130% for tap water, lake water, and industrial waste water, respectively.  相似文献   

5.
A solid‐phase extraction (SPE)‐gas chromatography (GC)‐mass spectrometry (MS) analytical method was developed for the simultaneous analysis of natural free estrogens and their conjugates in wastewater samples. Natural free estrogens and their conjugates in wastewater were successfully separated by the oasis hydrophilic‐lipophilic balance solid phase extraction (Oasis HLB SPE) method, and the conjugates were initially enzyme hydrolyzed by β‐glucuronidase or arylsulfatase from Helix pomatia prior to derivatization. N‐methyl‐N‐(tert‐butyldimethylsilyl)trifluoroacetamide (MTBSTFA) plus 1% tert‐butyldimetheylchlorosilane (TBDMCS) was chosen as the derivatization reagent, and the most appropriate conditions of derivatization were determined to be at 95°C for 90 min. The recovery ratios of nine target chemicals were determined by spiking them in 1 L of ultra‐purified water or the influent of a wastewater treatment plant (WWTP). The recovery ratios of six out of nine for the analytes ranged from 73.3–114.9% with relative standard deviations (RSD) from 1.6–19.9%. The established method was successfully applied to environmental wastewater samples which were collected from one municipal wastewater treatment plant (WWTP) in Osaka, Japan, for the determination of natural free estrogens and their conjugates. In the influent sample, E1, E2, E1‐3S, E3‐3S, and E1‐3G were detected at concentrations of 16.6, 9.6, 8.2, 21.9, and 3.2 ng L–1, respectively. However, only E1 was detected at a high concentration of 44 ng L–1 in the effluent sample, suggesting that it is the dominant natural free estrogen in the effluent.  相似文献   

6.
The ultrasound‐assisted emulsification–microextraction (USAEME) method was combined with graphite furnace atomic absorption spectrometry (GFAAS) for the determination of trace Pb using dithizone (H2DZ) as chelating reagent. Some effective parameters influenced the detection and microextraction, such as ashing temperature and atomization temperature, pH, extraction solvent, sample volume, extraction time, and extraction temperature were selected and optimized. After extraction, the calibration curves for Pb was in the concentration range of 0.1–10 ng mL?1, and the linear equation was y = 0.097 x + 0.023 (R = 0.99). Under the optimized conditions, the detection limit of the method was 20 pg mL?1 with an enrichment factor of 70 and the relative standards deviation (RSD) for seven determinations of 1 ng mL?1 Pb was 11%. The proposed method was successfully applied to determine trace Pb in Yueya Lake water, pond water, and spiked samples. Furthermore, a certified reference material of Environment Water (GBW08607) was analyzed and the determined value was in good agreement with the certified value, which showed the accuracy, recovery, and applicability of the reported method.  相似文献   

7.
Phthalates are considered priority pollutants because of their potential adverse effects on ecosystems and human health. The objectives of this study were to determine the occurrence of five phthalates (DMP, DEP, DBP, BBP, and DEHP) in sewage sludge and to determine the seasonal variability of these contaminants at three (Bahçe?ehir, Pa?aköy, and Tuzla) full‐scale municipal and domestic wastewater treatment plants (WWTP) in Istanbul, Turkey. Mass balance was also calculated for DEHP at Tuzla WWTP sludge treatment units. DMP, DEP, DBP, BBP, and DEHP concentrations in sewage sludge ranged from 1.4 to 2.7 mg/kg dry weight (dw), 1.1 to 2.8, 0.6 to 4.6, 2.8 to 6.2, 18 to 490 mg/kg dw, respectively. Phthalate concentrations from the Bahçe?ehir and Pa?aköy WWTPs met the limit (100 mg/kg dw) of Turkey national sludge regulation and the Europe Union draft of sludge directive for land application, whereas phthalate concentrations from Tuzla WWTP exceeded the maximum permissible concentration. Phthalate concentrations did not show seasonal variations for Bahçe?ehir and Pa?aköy WWTPs, which receive mainly household wastewater while some fluctuations were observed DEP, DBP, and DEHP at Tuzla WWTP which has a lot of industrial wastewater contribution. The mass balance showed that approximately 17% of DEHP in the primary and secondary sludge was removed by anaerobic digestion, while 43% returned back to the beginning of the WWTP and 40% remained in the dewatered sludge. This study suggests that phthalates in sludge from WWTPs with industrial wastewater contribution may limit the use of sludge for land application.  相似文献   

8.
Occurrence of selected estrogens in mangrove sediments   总被引:1,自引:0,他引:1  
This paper presents results related to the occurrence and distribution of estrogens along the Brazilian coast. Three mangrove areas were chosen to evaluate the presence of estrogens in surface sediments of mangrove forests. The presence of estrogens was observed in all studied sites. 17-α-Ethinylestradiol (EE2), a synthetic estrogen, was the most common and has been found in higher concentration (0.45-129.78 ng/g) compared to 17-β-estradiol (E1) and estrone (E2) (both being natural estrogens). The concentrations of E1 and E2 ranged from 0.02 to 49.27 ng/g and 0.03 to 39.77 ng/g, respectively. Theoretically, under anaerobic conditions EE2 can be reduced to E1 even in environments such as sediments of mangrove forests, which are essentially anaerobic. Even if the concentrations of estrogens seem to be insignificant in some samples, the effects remain uncertain.  相似文献   

9.
An optimized analysis method based on headspace liquid phase microextraction (HS‐LPME) and gas chromatography coupled with mass spectrometry was proposed for the determination of trihalomethanes (THMs) in drinking water. The response surface method (RSM) was used to optimize the extraction of THMs for analysis by HS‐LPME. The temperature, extraction time and NaCl concentration were found to be important extraction parameters. The coefficient of determination (R2) for the model was 94.97%. A high probability value (P < 0.0001) for the regression indicated that the model had a high level of significance. The optimum conditions were seen to be: temperature 42.0°C, NaCl concentration 0.30 g/mL, and extraction time 28 min. The response variable was the summation of the THMs chromatography peak areas and the reproducibility of this was investigated in five replicate experiments under the optimized conditions. The relative standard deviations (RSD%) of the THMs ranged from 8.0–11.6%. The limits of detection (LODs), based on a signal‐to‐noise ratio (S/N) of three ranged from 0.42–0.78 μg/L, and were lower than the maximum limits for THMs in drinking water established by the WHO.  相似文献   

10.
A reliable and sensitive analytical method for the determination of estrone (E1), 17β-estradiol (E2), and the synthetic hormone 17α-ethinylestradiol (EE2) has been established. Samples are concentrated using automated solid-phase extraction and analysis is performed by liquid chromatography with detection by tandem mass spectrometry. Recoveries of all analytes were between 93% and 107%, and limits of quantification (LOQs) between 0.1 and 0.4 ng/L for purified sewage, and surface, ground, and drinking water, and between 1 and 2 ng/L in case of raw sewage. For the investigation of estrogen release into the environment and its behavior during sewage and surface water treatment, and during ground water recharge, samples from municipal waste water treatment plants (WWTPs), a surface water treatment plant, a bank filtration site, and a ground water enrichment (GWE) pond were analyzed. El was found in the raw waste water with an average concentration of 157 ng/L, whereas E2 and EE2 were found with mean concentrations of only 18 and 9 ng/L, respectively. Sewage treatment by municipal WWTPs affected a removal of EE2 (76%), El (92%), and E2 (94%). In the investigated surface water of Berlin, only E1 could be detected at concentrations around or below 1 ng/L. E2 and EE2 were not present in the Berlin surface water above the LOQ of 0.2 ng/L, respectively. Surface water treatment also leads to a significant removal of E1 (> 80%). In the ground water samples from the GWE site near Lake Tegel, only a few samples contained detectable concentrations of E1. These samples were collected from a shallow monitoring well located very close to the bank of the pond. Even a short distance between the bank and observation wells led to concentrations of El below the LOQ showing the potential of ground water recharge systems for the retention of estrogenic steroids depending on the environmental setting.  相似文献   

11.
A simple and selective solid phase extraction procedure for the trace analysis of iron(III) in water samples has been developed. Sodium dodecyl sulfate coated alumina, modified with polyphenolic compounds (extracted from black tea) was used for the extraction and preconcentration of iron(III) from water samples before determination by flame atomic absorption spectrometry. Due to the complexation reaction between iron(III) and polyphenol compounds, iron(III) was quantitatively extracted on the proposed sorbent and then eluted by 2.0 mL of HCl (1.0 mol/L). The effects of extraction parameters, such as pH and volume of sample solution, amount of polyphenolic compounds, type of eluting agent and the effect of interfering ions on the extraction of iron(III), were investigated. It was found that the proposed method had a good linear range (15.0–100.0 μg/L) and a low detection limit (10.0 μg/L). The procedure was successfully applied for iron determination in drinking water samples.  相似文献   

12.
The fate of the steroid hormones 17 β‐estradiol, estrone, estriol, 16 α‐hydroxyestrone, and β‐estradiol 17‐acetate, the hormone‐conjugates β‐estradiol 3‐sulfate and estrone 3‐sulfate, and the oral contraceptives 17 α‐ethinylestradiol and mestranol were studied during wastewater treatment as wastewater treatment plants are the major source contamination of urban surface waters with steroid hormones. The elimination efficiencies of three different concepts of WWTPs, i. e., activated sludge versus trickling filter, were compared over four weeks at different weather conditions. While larger WWTPs operating on activated sludge eliminated hormones more constantly than smaller WWTPs, heavy rainfall events led to a collapse of the elimination efficiency. By using trickling filter techniques for the treatment of wastewater an elimination of the steroid hormones could not be observed. Additionally, mass flows on a per person basis are compared. In the three experiments, which ran continuously for four weeks each, it turned out that the concentrations of ethinylestradiol and mestranol were below 6 ng/L in all samples. The inflow concentrations were 70 to 82 ng/L (estrone), 17 to 44 ng/L (estradiol), 61 to 130 ng/L (hydroxyestrone), 189 to 255 ng/L (estriol), 10 to 17 ng/L (estrone‐3‐sulfate) and about 28 ng/L (estradiol‐3‐ sulfate). While in the activated sludge treatment plants the elimination of estrone was 90 and 50%, respectively, estrone was formed from precursors in the trickling filter plant. A similar situation occurred for 17β‐estradiol, estrone 3‐sulfate, and estradiol 3‐sulfate. Hydroxyestrone was eliminated with similar efficiencies in all wastewater treatment plants (64 to 82%), as well as estriol (34 to 69%). Accordingly, the emissions of the wastewater treatment plants differed largely and were not attributed to the size of the respective plant, only.  相似文献   

13.
Surface sediment and biota were collected from 12 sampling sites – seven along the Pearl River Delta and five along the Hong Kong coastline. Perfluorinated compound (PFC) concentrations were detected using a high-performance-liquid-chromatogram–tandem-mass-spectrometry system. Analytical results indicated that the total PFC concentrations were in the range of 0.15–3.11 ng/g dry weight in sediments, while the total PFC concentrations in oyster and mussel samples were between 0.46–1.96 and 0.66–3.43 ng/g wet weight, respectively. The major types of PFCs detected in the sediment samples were perfluorooctanesulfonic acid (PFOS) and perfluorobutanoic acid (PFBA), with concentrations ranging from low limits of quantification to 0.86 ± 0.12 ng/g dry weight and 1.50 ± 0.26 ng/g dry weight, respectively. In bivalve samples, PFOS was the dominant contaminant with concentrations ranging from 0.25 ± 0.09 to 0.83 ± 0.12 ng/g wet weight in oysters and 0.41 ± 0.14 to 1.47 ± 0.25 ng/g wet weight in mussels. An increase in PFC concentration was found to be correlated with increased human population density in the study areas.  相似文献   

14.
In this work, a new separation–preconcentration method was developed for the determination of trace amounts of Cu(II), Ni(II), and Fe(III) by flame atomic absorption spectrometry (FAAS). Analytes were complexed by using zincon (2‐[2‐[alpha(2‐hydroxy‐5‐sulfophenylazo) benzylidene] hydrazino] benzoic acid sodium salt). The analyte ions were quantitatively adsorbed on a Diaion HP‐20 resin at pH 5. The retained metal ions on the resin were eluted by acetone. The analytical parameters such as pH of the sample, eluent type and volume, sample volume, and flow rates of the solution and the eluent were investigated. The influences of concomitant ions on the recoveries of the analytes were also examined. The instrumental detection limits for the analytes after application of the presented solid‐phase extraction procedure were in the range of 0.72–1.41 µg/L. The validation of the presented procedure was checked by analyzing certified reference material of SRM1515 Apple Leaves. The procedure was performed by analyzing some spice samples.  相似文献   

15.
Distribution of Natural and Synthetic Estrogenic Steroid Hormones in Water Samples from Southern and Middle Germany Natural and synthetic hormones can reach surface waters via domestic sewage effluents. For drinking water production, bank filtration of river waters is a common procedure and hormone contaminations can potentially reach groundwater levels and drinking water sources. In order to analyse steroid hormones in the different aquatic compartments (raw sewage and effluent, surface water, groundwater, raw and drinking water) of South and Middle Germany, a sensitive analytical method was developed and employed to detect the natural steroid hormones estradiol (E2) and estrone and the synthetic estrogen ethinylestradiol (EE2). Samples which were taken in two subsequent series were subjected to clean‐up and enrichment procedure and subsequently analysed by HPLC‐MS. The limit of quantitation for the method was determined to be 0.05 to 0.5 ng/L, depending on the matrix. By treating the samples with glucuronidases/arylsulfatases, conjugates were amenable to analysis and the sum of conjugates and unconjugated steroids was calculated. In raw sewage, the median of the concentrations of the unconjugated steroids was 7 ng/L for EE2, 1.5 ng/L for E2, and 5.5 ng/L for estrone. After cleavage of conjugates, the medians of total steroids were 9.5 ng/L (EE2), 3 ng/L (E2), and 13 ng/l (estrone). Conjugates therefore contributed up to 50 % of the total steroid concentration in raw sewage. In treated effluents, the concentrations of steroids were much lower than in the raw sewage. The medians of free steroids were determined to be 0.3 ng/L for EE2, 0.2 ng/L for E2, and 2.5 ng/L for estrone. Overall the medians in the effluent were thus less than 10% of those in the influent. Conjugates still contributed significantly (40% and more) to the steroid concentrations (medians: EE2: 0.5 ng/L, E2: 0.8 ng/L, and estrone: 8 ng/L).  相似文献   

16.
A miniaturized ultrasonic extraction procedure was developed for the determination of polycyclic aromatic hydrocarbons (PAHs) in soil by gas chromatography‐mass spectrometry. After determination of the most suitable extraction solvent with 5 min sonication time, several other parameters (sample amount, solvent volume and number of extraction times) were optimized using a 23 factorial experimental design. Recoveries of PAHs from spiked soil samples were over 90% for three different fortification levels between 50 and 300 μg/kg, and relative standard deviations of the recoveries were in the range of < 1–15%. The limits of detection ranged from 0.002 to 1.87 μg/kg. The performance of the developed procedure was also compared with other traditional Soxhlet, shake flask and large scale ultrasonic extraction procedures on real soil samples, and extraction methods showed comparable efficiencies. The proposed procedure required small volumes of solvent and sample. It was practicable, rapid and easy to use for analysis of PAHs in soils.  相似文献   

17.
Perfluorinated compounds (PFCs) have emerged as significant global environmental pollutants with persistent, bioaccumulative and toxic properties. The aim of this study was to determine the occurrence of PFCs in water (wastewater, submarine emissaries and port-waters), sediment and transplanted mussels in estuarine areas of high urban and industrial impact from Northern Spain. Five PFCs of industrial use were studied: perfluorooctanesulfonate, perfluorohexanesulfonate, perfluorobutanesulfonate, perfluorooctanoate acid and perfluorononanoate acid. After selective extraction, samples were analyzed by Ultra Performance Liquid Chromatography coupled to tandem mass spectrometry. ΣPFCs ranged from 0.06 to 10.9 ng/L in water, with higher levels in wastewater treatment plants effluents and port waters than in submarine emissaries. Little accumulation was observed in sediments and mussels with ΣPFCs ranging from 0.01-0.13 ng/g dw and 0.01-0.06 ng/g ww, respectively. Most ubiquitous compounds were PFOS and PFOA. Mass fluxes of PFCs to the Cantabrian Sea are estimated and the impact to the coastal ecosystem is discussed.  相似文献   

18.
The rigin and fate of six phthalate esters (dimethyl phthalate (DMP), diethyl phthalate (DEP), di‐n‐butyl phthalate (DnBP), butyl benzyl phthalate (BBP), di (2‐ethylhexyl) phthalate (DEHP) and di‐n‐octyl phthalate (DnOP)), were investigated during 2005 and 2006 in the densely populated Seine river estuary. Four compounds, DMP, DEP, DnBP and DEHP were detected at all the stations with DEHP (160–314 ng L?1), followed by DEP (71–181 ng L?1) and next DnBP (67–319 ng L?1), except at la Bouille, where DnBP was the second most important compound. BBP and DnOP concentrations remained low and were not found at all the stations. Considering all six phthalates, Caudebec‐en‐Caux (beginning of the salinity gradient) was the least polluted station (464 ng L?1), whereas Honfleur (771 ng L?1) and La Bouille (716 ng L?1) displayed the highest contamination levels, probably related to important industrial plants. From Caudebec‐en‐Caux to Honfleur (maximum turbidity), variation of DEHP concentration was related to that of suspended matter. In addition, the salinity rise in that area might have facilitated DEHP sorption upon particles. A significant correlation between flow magnitude and DEHP concentration was found (P < 0·01, n = 12), supporting the influence of the hydrological cycle upon contamination. Runoff contribution (56·9 kg d?1) to river contamination was confirmed by the annual evolution of phthalate concentrations in the Seine river at Poses. Concentrations of DEHP in the tributaries were in the same range as those of the Seine River (100–350 ng L?1), except for two in densely populated and industrialized areas: Robec (800 ng L?1) and Cailly (970 ng L?1). The treatment plant discharge fluxes were in the same range as those of tributaries (30·4–250 g d?1). During high flow periods, the influence of tributaries and of treatment plants seemed to play a minor part in the contamination level of the Seine river estuary. Copyright © 2009 John Wiley & Sons, Ltd.  相似文献   

19.
Trace organic (chlorinated pesticides, PCBs, PAHs and dioxins/furans) and trace metal concentrations were measured in surficial sediment and biological tissues (i.e., worms, crustaceans, bivalve molluscs, and fish livers) collected from the Russian Arctic. Total DDT, chlordane, PCB and PAH concentrations ranged from ND to 1.2, ND to <0.1, ND to 1.5 and <20-810 ng g(-1), respectively, in a suite of 40 surficial sediment samples from the Kara Sea and the adjacent Ob and Yenisey Rivers. High sedimentary concentrations of contaminants were found in the lower part of the Yenisey River below the salt wedge. Total dioxins/furans were analysed in a subset of 20 sediment samples and ranged from 1.4 to 410 pg g(-1). The highest trace organic contaminant concentrations were found in organisms, particularly fish livers. Concentrations as high as 89 ng g(-1) chlordane; 1010 ng g(-1) total DDTs; 460 ng g(-1) total PCBs; and 1110 ng g(-1) total PAH, were detected. A subset of 11 tissue samples was analysed for dioxins and furans with total concentrations ranging from 12 to 61 pg g(-1). Concentrations of many trace organic and metal contaminants in the Kara Sea appear to originate from riverine sources and atmospheric transport from more temperate areas. Most organic contaminant concentrations in sediments were low; however, contaminants are being concentrated in organisms and may pose a health hazard for inhabitants of coastal villages.  相似文献   

20.
We have studied the distribution and value of phenolic endocrine disrupting chemicals (EDCs) in surface sediment samples taken from Anzali Wetland, Iran. These samples were collected from 22 stations during the time span of June-May 2010. In each of the sampling stations, we detected 4-nonylphenol (4-NP), octylphenol (OP), and bisphenol A (BPA) with maximal concentrations of 29, 4.3, and 7 μg g(-1) dry weight (dw), respectively. High levels of alkylphenols (APs) and BPA were also found near urban areas. Furthermore there were no significant differences between those stations in terms of the detected levels. One of the important factors in controlling the fate of these compounds in the aquatic environment appeared to be Total Organic Carbon (TOC). Hierarchical cluster analysis showed differences in the biomarker characteristics of EDCs and TOC between the stations. Our findings indicate that EDCs are ubiquitous in sediments from northeast Wetlands of Iran, contaminating the aquatic habitats in this area.  相似文献   

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