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1.
A pan-European monitoring campaign of the wastewater treatment plant (WWTP) effluents was conducted to obtain a concise picture on a broad range of pollutants including estrogenic compounds. Snapshot samples from 75 WWTP effluents were collected and analysed for concentrations of 150 polar organic and 20 inorganic compounds as well as estrogenicity using the MVLN reporter gene assay. The effect-based assessment determined estrogenicity in 27 of 75 samples tested with the concentrations ranging from 0.53 to 17.9 ng/L of 17-beta-estradiol equivalents (EEQ). Approximately one third of municipal WWTP effluents contained EEQ greater than 0.5 ng/L EEQ, which confirmed the importance of cities as the major contamination source. Beside municipal WWTPs, some treated industrial wastewaters also exhibited detectable EEQ, indicating the importance to investigate phytoestrogens released from plant processing factories. No steroid estrogens were detected in any of the samples by instrumental methods above their limits of quantification of 10 ng/L, and none of the other analysed classes of chemicals showed correlation with detected EEQs. The study demonstrates the need of effect-based monitoring to assess certain classes of contaminants such as estrogens, which are known to occur at low concentrations being of serious toxicological concern for aquatic biota.  相似文献   

2.
From 2010 to 2012, the Yangtze River and Hanjiang River (Wuhan section) were monitored for estrogenic activities during various water level periods. Using a recombinant yeast estrogen screen (YES) assay, 54 water samples were evaluated over the course of nine sampling campaigns. The mean 17β-estradiol equivalent (EEQ) value of raw water from the Yangtze River was 0–5.20 ng/L; and the EEQ level from the Hanjiang River was 0–3.22 ng/L. In Wuhan, drinking water treatment plants (DWTPs) using conventional treatments reduced estrogenic activities by more than 89 %. In general, water samples collected during the level period showed weaker estrogenic activities compared to those collected during the dry period. The samples collected in 2010 showed the strongest estrogenic activities of the 3-year period. The lack of correlations between estrogenic activities and selected common water quality parameters showed that estrogenic activity cannot be tied to common water quality parameters.  相似文献   

3.
17β-Estradiol (E2) and 17α-ethinyl estradiol (EE2), which are environmental estrogens, have been determined with LC-MS in freshwater. Their sensitive analysis needs derivatization and therefore is very hard to achieve in multiresidue screening. We analyzed samples from all the large and some small rivers (River Danube, Drava, Mur, Sava, Tisza, and Zala) of the Carpathian Basin and from Lake Balaton. Freshwater was extracted on solid phase and derivatized using dansyl chloride. Separation was performed on a Kinetex XB-C18 column. Detection was achieved with a benchtop orbitrap mass spectrometer using targeted MS analysis for quantification. Limits of quantification were 0.05 ng/L (MS1) and 0.1 ng/L (MS/MS) for E2, and 0.001 ng/L (MS1) and 0.2 ng/L (MS/MS) for EE2. River samples contained n.d.–5.2 ng/L E2 and n.d.–0.68 ng/L EE2. Average levels of E2 and EE2 were 0.61 and 0.084 ng/L, respectively, in rivers, water courses, and Lake Balaton together, but not counting city canal water. EE2 was less abundant, but it was still present in almost all of the samples. In beach water samples from Lake Balaton, we measured 0.076–0.233 E2 and n.d.–0.133 EE2. A relative high amount of EE2 was found in river Zala (0.68 ng/L) and in Hévíz-Páhoki canal (0.52 ng/L), which are both in the catchment area of Lake Balaton (Hungary).  相似文献   

4.
5.
The estrogenic activity (by E-screen bioassay), the concentrations of PCBs, PCDDs/PCDFs (and their resulting toxicity equivalents, TEQ) and several endocrine disrupting chemicals (EDCs: e.g., bisphenol A, nonylphenol, Butyl benzylpthalate (BBP), di-n-butylphthalate (DBP), 17alpha-ethynyl-estradiol or 4-octylphenol) have been analyzed from leachates of each step (before treatment, after biodegradation/sedimentation and after charcoal treatment) of a controlled landfill leachate treatment plant. The comparison of the effluent of the examined landfill leachate treatment plant with water from a nearby river in this study indicated no additional dioxin-like (e.g., TEQ: 0.027 compared to 1.01 pg TEQ/l; PCBs: 1.2 compared to 3.9 ng/l) or estrogenic impact (2.8 compared to 3.5 ng estradiol equivalents EE/l; analyzed by E-screen bioassay) from the leachate treatment plant into the surrounding water environment. The impact of dioxin-like compounds from uncleaned leachates into the final cleaned effluents could be sufficiently reduced by the leachate treatment plant for PCDDs (75%), PCDFs (62%), dioxin-like PCBs (97%), and the sum of TEQ (78%). The leachate treatment plant also achieved a reduction of the estrogenic activity as determined by E-screen (from 4.8 to 2.8 ng EE/l = 42%), by GC/MS for bisphenol A (>96% and nonylphenol (>98%) or by ELISA for estradiol (>80%). Additionally, for the validation of the E-screen, five known endocrine disrupting chemicals (EDCs: bisphenol A, BBP, DBP, 17 alpha-ethynyl-estradiol, 4-octylphenol) were analyzed. The EC50 values and estradiol equivalents factors (EEFs) for the five EDCs determined in this study were comparable to previously published data. The combined biological and chemical trace analysis data have provided valuable information on the relative contribution of natural, synthetic, and non-steroidal anthropogenic chemicals to the estrogenic and dioxin-like activity in leachates from a wastewater treatment plant, and water from a nearby river.  相似文献   

6.

Background, aim and scope

Groundwaters and source waters are exposed to environmental pollution due to agricultural and industrial activities that can enhance the leaching of organic contaminants. Pesticides are among the most widely studied compounds in groundwater, but little information is available on the presence of phthalates, alkylphenols and bisphenol A. These compounds are used in pesticide formulations and represent an emerging family of contaminants due to their widespread environmental presence and endocrine-disrupting properties. Knowledge on the occurrence of contaminants in source waters intended for bottling is important for sanitary and regulatory purposes. So the aim of the present study was to evaluate the presence of phthalates, alkylphenols, triazines, chloroacetamides and bisphenol A throughout 131 Spanish water sources intended for bottling. Waters studied were spring waters and boreholes which have a protection diameter to minimize environmental contamination.

Materials and methods

Waters were solid-phase extracted (SPE) and analysed by gas chromatography coupled to mass spectrometry (GC-MS). Quality control analysis comprising recovery studies, blank analysis and limits of detection were performed.

Results and discussion

Using SPE and GC-MS, the 21 target compounds were satisfactorily recovered (77?C124?%) and limits of quantification were between 0.0004 and 0.029???g/L for pesticides, while for alkylphenols, bisphenol A and phthalates the limits of quantification were from 0.0018???g/L for octylphenol to 0.970???g/L for bis(2-ethylhexyl) phthalate. Among the 21 compounds analysed, only 9 were detected at levels between 0.002 and 1.115???g/L. Compounds identified were triazine herbicides, alkylphenols, bisphenol A and two phthalates. Spring waters or shallow boreholes were the sites more vulnerable to contaminants. Eighty-five percent of the samples did not contain any of the target compounds.

Conclusions

Target compounds were detected in a very low concentration and only in very few samples. This indicates the good quality of source waters intended for bottling and the effectiveness of the protection measures adopted in Spain. None of the samples analysed exceeded the maximum legislated levels for drinking water both in Spain and in the European Union.  相似文献   

7.
The levels of organochlorine pesticides (OCPs) in the water, suspended solids, and sediments from Lake Chaohu during the high water level period were measured by a solid-phase extraction gas chromatograph–electron capture detector. The spatial distributions of the three phases and the water/suspended solids and sediment/water partition coefficients were analyzed. The results showed the following: (1) The mean contents of OCPs in the water, suspended solids, and sediments were 132.4?±?432.1 ng/L, 188.1?±?286.7 ng/g dry weight (dw), and 13.7?±?9.8 ng/g dw, respectively. The dominant OCP components were isodrin (85.1 %) for the water, DDTs (64.4 %) for the suspended solids, and both isodrin (48.5 %) and DDTs (31.8 %) for the sediments. (2) β-HCH was the primary isomer of HCHs in the water and sediments, and the proportions were 61.7 and 41.3 %; γ-HCH was the primary isomer in the suspended solids, accounting for 49.3 %; p,p′-DDT was the dominant content of DDTs in the water and suspended solids, whereas p,p′-DDD was the main metabolite of DDTs in the sediments. (3) The concentrations of contaminants in the water from the western lake were greater than those from the eastern lake, but the concentrations in the suspended solids from the western lake were less than those from the eastern lake. (4) There was no significant correlation between the water–suspended solids partition coefficient K d and the n-octanol–water partition coefficient K ow, and between the sediment–water organic-C weighted sorption coefficients K oc and K ow.  相似文献   

8.
A novel analytical-scale concept to improve reliability of detection and analysis of natural and processed wastewater samples from a purification plant was developed. A sequential sample clean-up system of polymer-based octadecyl and silane-based quaternary amine sorbents were used for concentrating human based steroid hormones and their metabolites and detecting them by UV absorption with capillary electrophoresis (CE). The water samples were collected from influent and effluent processes of the water purification plant in Helsinki, Finland.The CE methods were partial-filling micellar electrokinetic chromatography and capillary zone electrophoresis. The analysis times and method concentration levels were optimized with eight steroids at the range of 0.5–10 mg/L. Since in CE the detectable quantities were higher than the existing amounts in the process waters, the real samples needed matrix removal combined with steroid enrichment. After 20,000-fold concentration testosterone-glucoside, androstenedione, progesterone, and estradiol-glucoside could be determined in the process water samples. The amounts of individual steroids in influent and effluent waters were 0–429 and 0–207 ng/L, respectively. Correspondently, their total amounts were 735 and 212 ng/L with excellent in day and inter-day repeatability. The RSD values were less than 1, 9.7, and 19% in repeated analyses, calculated from 60 analyses during 24 h, and from 130 analyses during 15 months, respectively. The steroid removal in purification process was 65% on average. The solid particles separated in three steps during the water clean-up concept contained 9.8–45 ng/g steroids in combined dry precipitates.  相似文献   

9.
10.
An efficient pretreatment and analytical method was developed to investigate the occurrence and fate of four free estrogens (estrone (E1), 17β-estradiol (17β-E2), estriol (E3), and 17α-ethinylestradiol (EE2)), four conjugated estrogens (estrone-3-sulfate sodium salt (E1-3S), 17β-estradiol-3-sulfate sodium salt (E2-3S), estrone-3-glucuronide sodium salt (E1-3G), and 17β-estradiol-3-glucuronide sodium salt (E2-3G)), and bisphenol A (BPA) in three livestock farms raising beef cattle, cows, sheep, swine, and chickens in Qi County, which is located in North China. The results demonstrated that one cow and one beef cattle excreted 956.25–1,270.41 and 244.38–319.99 μg/day of total (free and conjugated) estrogen, respectively, primarily through feces (greater than 91 %), while swine excreted 260.09–289.99 μg/day of estrogens, primarily through urine (98–99 %). The total estrogen excreted in sheep and broiler chicken feces was calculated to be 21.64–28.67 and 4.62–5.40 μg/day, respectively. It was determined that conjugated estrogens contributed to 21.1–21.9 % of the total estrogen excreted in cow feces and more than 98 % of the total estrogen excreted in swine urine. After composting, the concentration of total estrogen decreased by 18.7–59.6 %; however, increased levels of BPA were measured. In treated compost samples, estrogens were detected at concentrations up to 74.0 ng/g, which indicates a potential risk of estrogens entering the surrounding environment.  相似文献   

11.
The removal of estrogenic chemicals during wastewater reclamation has been a great concern. Current advanced treatment processes are inefficient for the removal of estrogenic chemicals from secondary effluents of municipal wastewater treatment plants (WWTPs) due to the coexistence of other pollutants with less environmental significance which are also removed simultaneously. The search for highly selective and low-cost removal methods is warranted. Therefore, surface-molecular-imprinted polymer-modified TiO2 nanotube (S-MIP-TiO2 NT) photocatalysts were fabricated, characterized, and tested for the removal of estrogenic pollutants from wastewater in this study for the first time. Scanning electron microscopy and Fourier-transform infrared spectroscopy studies showed that the TiO2 NTs (with an average diameter of 60 nm) were successfully imprinted with functional groups (i.e., carboxyl). The adsorption selectivity and photocatalytic activity of the S-MIP-TiO2 NTs towards template compound (17β-estradiol, E2) were improved, compared with neat TiO2 NTs. Interestingly, S-MIP-TiO2 NTs exhibited higher adsorption intensity and photocatalytic selectivity at low concentrations (from 10 ng/L to 100 μg/L, as normal estrogenic chemical concentrations in secondary effluents) of E2 than that at high concentrations (from 10 to 1,000 mg/L). It was also found that some representative estrogenic chemicals and estrogenic activity could be selectively and rapidly removed from secondary effluents of municipal wastewater treatment plants using S-MIP-TiO2 NTs as photocatalysts. In addition, S-MIP-TiO2 NT photocatalysts exhibited excellent regeneration characteristics. Photocatalytic treatment using S-MIP-TiO2 NTs could be a promising approach for the effective removal of estrogenic chemicals from secondary effluents of municipal WWTPs.  相似文献   

12.
To collect a complete dataset regarding the occurrence of organic substances in groundwater, this study presents the examination of 66 organic contaminants in the groundwater of overseas departments, including pesticides, pharmaceutical compounds, hormones and some industrial substances. The selective and sensitive analytical methods are described. These techniques begin with solid-phase extraction (SPE) followed by analysis using liquid chromatography–tandem mass spectrometry (LC-MS/MS) and gas chromatography–mass spectrometry (GC-ToF-MS). The paper summarises the analytical results from 40 sampling points collected during two campaigns in Guadeloupe, Martinique, Reunion, Mayotte and Guiana, representing 80 samples. Of the 66 target substances, 36 were determined at least once. Among the most frequently detected are bisphenol A (frequency, 96 %; max., 7,400 ng/L), caffeine (frequency, 91 %; max., 1,240 ng/L), pentachlorophenol (frequency, 55 %; max., 418 ng/L), and carbamazepine (frequency, 56 %; max., 22 ng/L). The results do not put in evidence that the origin of the sample or climatic characteristics of these regions influence the dilution and release of micropollutants.  相似文献   

13.
Simple and effective extraction methods based on matrix solid-phase dispersion (MSPD), dispersive liquid–liquid microextraction (DLLME), and solid-phase extraction (SPE) coupled with high-performance liquid chromatography with diode array detector (HPLC-DAD) were developed to determine triketone herbicides—sulcotrione (SUL), mesotrione (MES), tembotrione (TEMB), and their degradation products—in plant tissues and water samples. The extraction procedures were employed to enable quantification of the accumulation of selected triketone herbicides and their degradation products in a model aquatic plant, Egeria densa. To obtain comprehensive information about the triketones' influence on an aquatic plant, changes in chlorophyll concentration in plants exposed to these triketones were monitored. The average recovery ranged from 58 to 115 % (coefficients of variation 7–12 %) for plant tissues and from 52 to 96 % (coefficients of variation 8–20 %) for water samples. The limit of detection (LOD) for the MSPD–HPLC-DAD procedure was in the range of 0.06–0.23 μg/g, whereas for DLLME–HPLC-DAD and SPE–HPLC-DAD, LOD was in the range of 0.06–0.26 μg/mL. Symptoms of the phytotoxicity of sulcotrione, mesotrione, tembotrione, and their degradation products (decrease of chlorophyll concentration in plant sprouts) were observed for E. densa cultivated in water with herbicide concentrations of 100 μg/L. Moreover, the tembotrione degradation product exhibited a high level of accumulation and low metabolism in plant tissues in comparison to the other triketones and their degradation products.  相似文献   

14.
Water is fundamental to the existence of life since it is essential to a series of activities, such as agriculture, power generation, and public and industrial supplies. The residual water generated by these activities is released into the environment, reaches the water systems, and becomes a potential risk to nontarget organisms. This paper reports the development and validation of a quantitative method, based on solid-phase extraction and liquid chromatography tandem mass spectrometry, for the simultaneous analysis of 18 pharmaceuticals and personal care products (PPCPs) and 33 pesticides in surface and drinking waters. The accuracy of the method was determined by calculating the recoveries, which ranged from 70 to 120 % for most pesticides and PPCPs, whereas limits of quantification ranged from 0.8 to 40 ng/L. After the validation step, the method was applied to drinking and surface waters. Pesticides and PPCPs were found in concentrations lower than 135.5 ng/L. The evaluation of different water sources with regard to contamination by pesticides and PPCPs has been quite poor in southern Brazil.  相似文献   

15.
Bisphenol A (BPA) and nonylphenols (NP) are of major concern to public health due to their high potential for human exposure and to their demonstrated toxicity (endocrine disruptor effect). A limited number of studies have shown that BPA and NP are present in drinking water. The chlorinated derivatives that may be formed during the chlorination step in drinking water treatment plants (DWTP) exhibit a higher level of estrogenic activity than their parent compounds. The aim of this study was to investigate BPA, 353NP, and their chlorinated derivative concentrations using an accurate and reproducible method of quantification. This method was applied to both surface and treated water samples from eight French DWTPs producing from surface water. Solid-phase extraction followed by liquid chromatography?Ctandem mass spectrometry was developed in order to quantify target compounds from water samples. The limits of detection ranged from 0.3 to 2.3?ng/L for BPA and chlorinated BPA and from 1.4 to 63.0?ng/L for 353NP and chlorinated 353NP. BPA and 353NP were found in most analyzed water samples, at a level ranging from 2.0 to 29.7?ng/L and from 0 to 124.9?ng/L, respectively. In most of DWTPs a decrease of BPA and 353NP was observed between surface water and treated water (36.6 to 78.9?% and 2.2 to 100.0?% for BPA and 353NP, respectively). Neither chlorinated BPA nor chlorinated 353NP was detected. Even though BPA and 353NP have been largely removed in the DWTPs studied, they have not been completely eliminated, and drinking water may consequently remain a source of human exposure.  相似文献   

16.
Phenoxyacetic and benzoic acid herbicides are widely used agricultural, commercial, and domestic pesticides. As a result of high water solubility, mobility, and persistence, 2,4-dichlorophenoxyacetic acid (2,4-D), methylchlorophenoxypropionic acid (mecoprop), and 3,6-dichloro-2-methoxybenzoic acid (dicamba) have been detected in surface and waste waters across Canada. As current municipal wastewater treatment plants do not specifically address chronic, trace levels of contaminants like pesticides, an urgent need exists for an efficient, environmentally friendly means of breaking down these toxic herbicides. A commercially available herbicide mix, WeedEx, containing 2,4-D, mecoprop, and dicamba, was subjected to treatment using membrane bioreactor (MBR) technology. The three herbicides, in simulated wastewater with a chemical oxygen demand of 745 mg/L, were introduced to the MBR at concentrations ranging from 300 μg/L to 3.5 mg/L. Herbicides and biodegradation products were extracted from MBR effluent using solid-phase extraction followed by detection using high-performance liquid chromatography coupled with mass spectrometry. 2,4-D was reduced by more than 99.0 % within 12 days. Mecoprop and dicamba were more persistent and reduced by 69.0 and 75.4 %, respectively, after 112 days of treatment. Half-lives of 2,4-D, mecoprop and dicamba during the treatment were determined to be 1.9, 10.5, and 28.3 days, respectively. Important water quality parameters of the effluent such as dissolved oxygen, pH, ammonia, chemical oxygen demand, etc. were measured daily. MBR was demonstrated to be an environmentally friendly, compact, and efficient method for the treatment of toxic phenoxyacetic and benzoic acid herbicides.  相似文献   

17.
The levels of polycyclic aromatic hydrocarbons (PAHs) in the water and the sediment samples collected near the Mopanshan Reservoir—the most important drinking water resource of Harbin City in Northeast China—were examined. A total of 16 PAHs were concurrently identified and quantified in the three water bodies tested (Lalin River, Mangniu River, and Mopanshan Reservoir) and in the Mopanshan drinking water treatment plant during the high- and low water periods. The total PAH concentrations in the water and sediment samples ranged from 122.7 to 639.8 ng/L and from 89.1 to 749.0 ng/g dry weight, respectively. Similar spatial and temporal trends were also found for both samples. The lowest Σ16PAH concentration of the Mopanshan Reservoir was obtained during the high water period; by contrast, the Lalin River had the highest concentration during the low water period. The PAH profiles resembling the three water bodies, with high percentages of low-molecular weight PAHs and dominated by two- to three-ring PAHs (78.4 to 89.0 %). Two of the molecular indices used reflected the possible PAH sources, indicating the main input from coal combustion, especially during the low water period. The conventional drinking water treatment operations resulted in a 20.7 to 67.0 % decrease in the different-ringed PAHs in the Mopanshan-treated drinking water. These findings indicate that human activities negatively affect the drinking water resource. Without the obvious removal of the PAHs in the waterworks, drinking water poses certain potential health risks to people.  相似文献   

18.
The first study aimed to investigate the polychlorinated biphenyl (PCB) concentration level, spatial distribution pattern, and ecological risk assessment of water and sediment samples from two tributaries (Nullah Aik and Palkhu) of the River Chenab, Punjab Province, Pakistan. A total of 32 PCB congeners were analyzed, and PCB concentration in sediment and water samples ranged between 0.80 and 60 ng/g and 0.20 and 28 ng/L, respectively, where tetra-CBs and tri-CBs dominated over other studied PCB homologs. Dioxin toxicity equivalency (TEQ) was calculated and PCB-126 and PCB-169 showed the higher TEQ values compared with the WHO guidelines, and sediment samples were more toxic than the water samples. The results of the present study should be considered seriously by government authorities to take a proper action against unchecked discharge of contaminants in ecological integrities; otherwise, there may be drastic results in the near future.  相似文献   

19.
Five estrogenic hormones (unconjugated?+?conjugated fractions) and 10 beta blockers were analyzed in three wastewater treatment plant (WWTP) effluents and receiving river waters in the area of Lyon, France. In the different samples, only two estrogens were quantified: estrone and estriol. Some beta blockers, such as atenolol, acebutolol, and sotalol, were almost always quantified, but others, e.g., betaxolol, nadolol, and oxprenolol were rarely quantified. Concentrations measured in river waters were in the nanogram per liter range for estrogens and between 0.3 and 210 ng/L for beta blockers depending on the substance and the distance from the WWTP outfall. The impact of the WWTP on the receiving rivers was studied and showed a clear increase in concentrations near the WWTP outfall. For estrogens, the persistence in surface waters was not evaluated given the low concentrations levels (around 1 ng/L). For beta blockers, concentrations measured downstream of the WWTP outfall were up to 16 times higher than those measured upstream. Also, the persistence of metoprolol, nadolol, and propranolol was noted even 2 km downstream of the WWTP outfall. The comparison of beta blocker fingerprints in the samples collected in effluent and in the river also showed the impact of WWTP outfall on surface waters. Finally, a tentative environmental risk evaluation was performed on 15 sites by calculating the ratio of receiving water concentrations to predicted non-effect concentrations (PNEC). For estrogens, a total PNEC of 5 ng/L was considered and these substances were not linked to any potential environmental risk (only one site showed an environmental risk ratio above 1). Unfortunately, few PNECs are available and risk evaluation was only possible for 4 of the 10 beta blockers studied: acebutolol, atenolol, metoprolol, and propranolol. Only propranolol presented a ratio near or above 1, showing a possible environmental risk for 4 receiving waters out of 15.  相似文献   

20.
Background, aim, and scope  Food consumption is an important route of human exposure to endocrine-disrupting chemicals. So far, this has been demonstrated by exposure modeling or analytical identification of single substances in foodstuff (e.g., phthalates) and human body fluids (e.g., urine and blood). Since the research in this field is focused on few chemicals (and thus missing mixture effects), the overall contamination of edibles with xenohormones is largely unknown. The aim of this study was to assess the integrated estrogenic burden of bottled mineral water as model foodstuff and to characterize the potential sources of the estrogenic contamination. Materials, methods, and results  In the present study, we analyzed commercially available mineral water in an in vitro system with the human estrogen receptor alpha and detected estrogenic contamination in 60% of all samples with a maximum activity equivalent to 75.2 ng/l of the natural sex hormone 17β-estradiol. Furthermore, breeding of the molluskan model Potamopyrgus antipodarum in water bottles made of glass and plastic [polyethylene terephthalate (PET)] resulted in an increased reproductive output of snails cultured in PET bottles. This provides first evidence that substances leaching from plastic food packaging materials act as functional estrogens in vivo. Discussion and conclusions  Our results demonstrate a widespread contamination of mineral water with xenoestrogens that partly originates from compounds leaching from the plastic packaging material. These substances possess potent estrogenic activity in vivo in a molluskan sentinel. Overall, the results indicate that a broader range of foodstuff may be contaminated with endocrine disruptors when packed in plastics.  相似文献   

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