Bisphenol A and Bisphenol S release in milk under household conditions from baby bottles marketed in Italy

A simple and sensitive validated analytical method based on liquid chromatography coupled to tandem fluorescence (FD) and ultraviolet (UV) spectrophotometry was applied to monitor the presence of bisphenol A and bisphenol S in plastic baby bottles marketed in Italy. The limits of detection (LOD) were 3.75 ng mL^?1 and 80.00 ng mL^?1, and those of quantification (LOQ) were 12.51 ng mL^?1 and 260.00 ng mL^?1 for BPA (FD detection) and for BPS (UV detection), respectively. BPA was found in only four samples, two samples undergone to microwave heating and two samples undergone to bottle warmer heating either at 40°C or at 80°C. Although the quantities of leached BPA were well below the reference dose for daily intake established by the European Food Safety Authority (EFSA) (4.0 µg kg^?1 bw/day), the release of BPA and BPS from these plastic materials should be carefully considered by the government authorities to increase people's awareness on this issue and to protect the most vulnerable population group.     

Overcoming the toxicity effects of municipal wastewater sludge and biosolid extracts in the Yeast Estrogen Screen (YES) assay

For nearly two decades, the Yeast Estrogen Screen (YES) has been used as a valuable tool for determining the total estrogenic potency of various environmental samples, including influent and effluent streams at municipal wastewater plants. However, applying the YES assay to wastewater sludges and stabilized biosolids has been problematic. This is due to co-extracted compounds from the solids either proving toxic to the yeast or masking the presence of estrogenic substances. The present research describes the development and validation of sample preparation steps that mitigate the toxicity effects of municipal wastewater sludge and biosolid samples in the YES assay, while allowing for reliable dose-dependent expression of estrogenic activity. A copper work-up for sulfur removal and chromatographic cleanup with silica and alumina were required in addition to solid-phase extraction to adequately remove interfering compounds. Sample stabilization methods such as autoclaving, lyophilization and formaldehyde treatment were found to be detrimental to the assay. Hence, heat-drying is recommended to prevent cytotoxicity and the degradation of estrogenic substances.     

不同水体中环境类雌激素污染状况调查与分析

对80个不同水体样品进行了环境雌激素检测,共有42个样品为阳性(阳性率52.5%),阳性样品主要来自于医疗废水、市政排污口、污水处理厂及与工业污染源废水,水源水中未检出。42个阳性样品检测值均超过EPA标准规定的壬基酚4 d平均浓度限值(6.6μg/L),其中12个样品检测值超过了该标准中规定的壬基酚小时平均浓度限值(28μg/L)。     

Consumer safety evaluation after monitoring of endocrine disruptor pesticide residues: a case study of Thessaly,Central Greece

Abstract

A large number of pesticides used in agricultural practice has been characterized or suspected to be Endocrine Disruptors, with dietary intake to be the major route of consumer’s exposure. In the present study the safety to consumer after the consumption of pome fruits and fruiting vegetables originated from the area of Thessaly, Central Greece was assessed. Objective samplings of 110 samples were conducted in local retail markets in an effort to quantify potential residues of targeted pesticides, previously characterized as endocrine disruptors. For the determination of residues, a QuEChERs-based multiresidue method coupled with liquid and gas chromatographic systems was applied and fully validated in accordance with the European Unions’s requirements in apples and tomatoes in three fortification levels. Acceptable results were obtained for all the validation parameters studied and the limit of quantification of 0.01?mg/kg and limit of detection of 0.0033?mg/kg were achieved. Based on the determined results, the most frequently determined pesticide was chlorpyrifos with a maximum concentration of 0.32?mg/kg in tomato samples. Cypermethrin and dimethoate were also determined in tomatoes and aubergines. The EFSA PRIMo rev.3.1 model was applied for all positive samples and acute risk for consumers was confirmed only in the case of determination of chlorpyrifos in tomatoes.     

深圳河典型内分泌干扰物分布和季节变化规律研究

2011年6月至2012年5月在深圳河沿程采集水样,采用固相萃取一氮吹一衍生化的预处理方法和气相色谱/质谱联用法,对壬基酚(NP)、辛基酚(OP)、双酚A(BPA)、雌酮(E1)、雌二醇(E2)、17α-雌二醇(17α-E2)、雌三醇(E3)、雌炔醇(EE2)等8种内分泌干扰物(EDCs)在深圳河的浓度分布和时空变化规律进行了研究.同时通过主成分分析考察了EDCs与常规水质污染物的关系.结果表明,NP、BPA、E1、E3、EE2在深圳河各河段均有检出,而OP、17α-E2、E2的检出率均低于20％,EDCs主要来源是NP和BPA;深圳河旱季和雨季EDCs的浓度变化大,其中NP浓度表现出旱季高雨季低的规律,旱季浓度是雨季的1.74～5.63倍,但BPA和3种甾醇类雌激素的浓度呈现出了雨季高旱季低的相反变化规律,这应该与污水处理厂雨季污水溢流有关；通过主成分分析发现,BPA与DO存在明显的负相关关系,生物作用可能在BPA去除和甾醇类雌激素转化中起到了重要作用,具体机制还有待进一步研究.     

Exposure assessment of French women and their newborn to brominated flame retardants: determination of tri- to deca- polybromodiphenylethers (PBDE) in maternal adipose tissue, serum, breast milk and cord serum

In the frame of a French monitoring program, tri- to deca- polybromodiphenylethers (PBDE) have been measured in maternal and cord serum, adipose tissue, and breast milk samples, collected from 93 volunteer women during caesarean deliveries. The seven major tri- to heptaBDE (BDE-28, 47, 99, 100, 153, 154, and 183) were detected in adipose tissue and breast milk with cumulated median values of 2.59 and 2.51 ng g⁻¹ l w. Nine highly brominated octa- to decaBDE (BDE-196, 197, 201, 202, 203, 206, 207, 208 and 209) was performed in the same samples, with cumulated median values of 2.73 and 3.39 ng g⁻¹ l w in adipose tissue and breast milk, respectively. At this opposite, median levels of octa- to decaBDE in maternal and cord serum appeared significantly higher than the levels of tri- to heptaBDE in the same matrices, i.e. 8.85 and 12.34 versus 0.98 and 0.69 ng g⁻¹ l w, respectively.     

Assessment of estrogen disrupting potency in animal foodstuffs of China by combined biological and chemical analyses

Food has been documented as one of major routes for human exposure to environmental estrogens（EEs）, but information on the occurrence of EEs in animal foodstuffs is still scarce.This study analyzed estrogenic activity in 16 types of animal foodstuffs（n = 142） collected from four cities（Wuhan, Guangzhou, Wenzhou and Yantai） of China by combined yeast estrogen screen（YES） bioassay and chemical analysis. By bioassay, all samples＇ extracts were found to induce estrogenic activities and the bioassay-derived 17β-estradiol equivalent（EEQbio） ranged from 8.29 to 118.32 ng/g. In addition, the samples were analyzed by liquid chromatography coupled to tandem mass spectrometry for further chemical analysis. 17β-Estradiol was found in all samples in this survey at levels of 0.44 to 15.04 ng/g.All samples had 33.1% detection rate of 17α-ethinylestradiol（EE2）, and the maximum concentration was 2.80 ng/g. Bisphenol A and 4-nonylphenols were detected in 83.8% and83.1% of samples, with concentrations up to 12.56 ng/g and 35.76 ng/g, respectively.However, the concentrations of estrone, diethylstilbestrol and 4-t-octylphenol were found to be below the limit of detection. A comparison of EEQbiomeasured from the YES assay and EEQchemcalculated from chemical analysis showed good correlation（R2= 0.84）. Based on the results, the YES assay can be used as a rapid pre-screening method for monitoring the levels of estrogenic activity in large numbers of animal foodstuffs, and chemical analysis used in combination can be used for the identification of specific EEs.     

典型生活污水处理工艺对雌激素效应的去除

针对水环境中内分泌干扰物低浓度、高风险的特点,采用酵母菌法和酶联免疫法对3个污水处理工艺流程中污水的雌激素活性和雌二醇(E2)水平进行评价.结果表明,污水厂进水的雌二醇当量(EEQ)和E2的水平分别为4.35~7.58 ng·L~(-1)和36.95~83.43 ng·L~(-1).雌激素活性和E2的去除主要发生在生物处理阶段,如氧化沟、A~2/O和A~2/O+MBR工艺,且经以上工艺处理之后,雌激素活性和E2分别降低71.10%~75.54%和75.88%~80.72%.污泥对雌激素效应具有一定的去除作用,通过吸附作用污泥的EEQ和E2的含量分别为1.84~2.43 ng·g~(-1)和8.45~12.84 ng·g~(-1).但污水厂出水仍具有较高的雌激素活性,其EEQ为1.06~2.19 ng·L~(-1),对受纳水体的水生生物具有潜在的危害.酶联免疫法与酵母菌法具有很好的一致性,并为水环境雌激素的快速筛选和评价提供了一个新方法.     

Mass fluxes and spatial trends of xenobiotics in the waters of the city of Halle, Germany

The behaviour and the effects of xenobiotics including pharmaceuticals and fragrances in the environment are widely unknown. In order to improve our knowledge, field investigations and modelling approaches for the entire area of the city of Halle/Saale, Germany, were performed. The distribution of the concentration values and mass fluxes are exemplified using indicators such as Bisphenol A, t-Nonylphenol, Carbamacepine, Galaxolide, Tonalide, Gadolinium and isotopes. Concentrations at a magnitude of ng/L to microg/L were found ubiquitously in the ground and surface waters. Using the concentration values, the impact of the city concerning the indicators was not always evident. Only the assessment of the mass fluxes shows significant urban impacts along the city passage. The calculation of the mass fluxes shows increasing values for all investigated xenobiotics during the city passage; only Bisphenol A stagnates. A balance model of water and indicator mass fluxes was built up for the entire city area.     

Endocrine disrupting activities in sewage effluent and river water determined by chemical analysis and in vitro assay in the context of granular activated carbon upgrade

As part of endocrine disruption in catchments (EDCAT) programme, this work aims to assess the temporal and spatial variations of endocrine disrupting chemicals (EDCs) in River Ray, before and after the commissioning of a full-scale granular activated carbon (GAC) plant at a sewage treatment works (STW). Through spot and passive sampling from effluent and river sites, estrogenic and anti-androgenic activities were determined by chemical analysis and in vitro bio-assay. A correlation was found between chemical analyses of the most potent estrogens (estrone (E1), 17β-estradiol (E2), 17α-ethinylestradiol (EE2)) and yeast estrogen screen (YES) measurement, both showing clearly a reduction in estrogenic activity after the commissioning of the GAC plant at the STW. During the study period, the annual average concentrations of E1, E2 and EE2 had decreased from 3.5 ng L⁻¹, 3.1 ng L⁻¹ and 0.5 ng L⁻¹ to below their limit of detection (LOD), respectively, with a concentration reduction of at least 91%, 81% and 60%. Annual mean estrogenic activity measured by YES of spot samples varied from 1.9 ng L⁻¹ to 0.4 ng L⁻¹ E2 equivalent between 2006 and 2008 representing a 79% reduction. Similarly, anti-androgenic activity measured by yeast anti-androgen screen (anti-YAS) of spot samples was reduced from 148.8 to 22.4 μg flutamide L⁻¹, or by 85%. YES and anti-YAS values were related to each other, suggesting co-existence of both types of activities from chemical mixtures in environmental samples. The findings confirm the effectiveness of a full-scale GAC in removing both estrogenic and anti-androgenic activities from sewage effluent.