In vitro agonistic and antagonistic endocrine disrupting effects of organic extracts from waste water of different treatment processes

Effluents from wastewater treatment plant （WWTP） have been reported to have a broad spectrum of endocrine disrupting compounds （EDCs）. The majority of studies have focused on the occurrence of estrogenic activity, while ignoring nuclear hormone receptors （NRs） pathways. In the present study, a battery of in vitro yeast bioassays and a cell bioassay, including antagonistic and agonistic effects on estrogen receptor （ER）, androgen receptor （AR）, progesterone receptor （PR）, estrogen- related receptor （ERR） and aryl hydrocarbon receptor （AHR）, were conducted to evaluate the removal efficien- cies of EDCs by different treatment processes of a WWTP located in Beijing. Estrogenic, anti-estrogenic, anti- androgenic, anti-progesteronic, anti-ERR and the activa- tion of AHR activities were detected in samples from all treatment processes and the receiving water. The concen- tration of estrogenic contaminants with estradiol （E2） equivalent concentrations ranged from 0.82 x 10-9 to 3.54 x 10 9g Ee_EQ.L-1. The concentration of anti-estrogenic contaminants with 4-hydroxytamoxifen （4-OHT） equiva- lent concentrations ranged from 1.24 × 10-6 to 2.36 x 10-6 g 4-OHT-EQ.L-1. The concentration of anti-androgenic contaminants ranged from 2.21 x 10-s to 3.52 × 10-6g flutamide-EQ. L-1. The concentration of anti-progesteronic contaminants ranged from 3.15 x 10^-5 to 2.71 x 10^-4g RU486-EQ. L-1. The concentration of anti-ERR contami- nants ranged from 7.09 x 10-5 to 6.50 x 104 g 4-OHT-EQ × L^-10. The concentration of AHR activators ranged from 1.7 × 10-10 to 3.4 × 10^-10g TCDD-EQ-L-1. These processes including secondary clarifier, coagulation, as well as coal and sand filtration could eliminated 67.2% of estrogenic contaminants, 47.0% of anti-estrogenic contaminants, 98.3% of anti-androgenic contaminants, 88.4% of anti- progesteronic contaminants, 65.4% of anti-ERR contami- nants and 46.9% of AHR activators. WWTP effluents contain multiple receptor disruptors may have very complex adverse effects on exposed organisms.     

A potentiometric cobalt-based phosphate sensor based on screen-printing technology

A potentiometric cobalt-based screen-pritning sensor was fabricated by electroplating cobalt on the surface of a screen-printing electrode as the sensitive layer for the determination of dihydrogenphosphate （H2PO4） in wastewater samples. The electrochemical performance of this sensor was fully examined to determine its detection calibration, detection limit, response time, selectivity, and interference with pH, various ions, and dissolved oxygen （DO）. The cobalt-based phosphate sensor showed a phosphate-selective potential response in the range of 10 5mol·L^-1 to 10^-1 mol^-1, yielding a detection limit of 3.16 × 10μmol·L^l and a slope of -37.51 mV·decade＇ in an acidic solution （pH 4.0） of H2PO4-. DO and pH were found to interfere with sensor responses to phosphate. Ultimately, the performance of the sensor was validated for detecting wastewater samples from the Xiaojiahe Waste- water Treatment Plant against the standard speetrophotometric methods for HzPO4 analysis. The discrepancy between the two methods was generally ＋5% （relative standard deviation）. Aside from its high selectivity, sensitivity, and stability, which are comparable with conventional bulk Co-wire sensors, the proposed phosphate sensor presents many other advantages, such as low price, compactness, ease of use, and the possibility of integration with other analytical devices, such as flow injectors.     

Preparation of hapten-specific monoclonal antibody for cadmium and its ELISA application to aqueous samples

High-affinity and specific monoclonal antibodies against cadmium-ethylene diamine tetraacetic acid (EDTA) complex have been produced using the hybridoma technique. A hapten was synthesized and characterized by Fourier Transform Infrared Spectroscopy (FT-IR) and UV-Vis. Competitive enzyme-linked immunosorbent assay (ELISA) for quantitative detection of cadmium in aqueous sample was developed. The monoclonal antibody with high level of binding affinity for Cd-IEDTA-BSA and high specificity for soluble Cd-EDTA complex showed less than 0.99% cross-reactivity with other 11 metals. The limit of detection was 0.10 μg·L^-1, and the effective linear range was 10^-1–10³ μg·L^-1. The intra- and inter-assay coefficient variations were 1.5%–6.3% and 3.2%–7.4%, respectively. The spike recovery in different water samples were between 98.5% and 110.3%. The detection limit of this assay was well below the allowable concentration of cadmium (3 μg·L^-1), and the working range was wider than that of other methods which showed the range of 2.19–86.38 and 0–10³ μg·L^-1. The competitive ELISA established in this paper was sensitive and accurate in the screening of cadmium in aqueous samples. The results will lay a solid foundation for construction of an immunoassay kit for cadmium.     

Ozone kinetics of dimethyl sulfide in the presence of water vapor

The outdoor smog chamber was used to thorough investigate the rate constants of gas-phase reaction between dimethyl sulfide （DMS） and ozone （O3） under conditions of relative humidity 55.0%-67.8% at （296±2）K for the first time. The rate constants were measured, at a total pressure of 1 atm, to be （10.4±0.2） × 10^-19 cm^3·molecule^-1·s^-1 at relative humidity of 67.5%±0.3% at 298K, （10.1±0.1） × 10^-19cm^3·molecule^-1·s^-1 at relative humidity of 66.5%±0.5% at 296K, （7.75±0.39） × 10^-19cm^3·molecule^-1·s^-1 at relative humidity of 64.8%± 0.1% at 294K and （3.42±0.21） × 10^-19cm^3·molecu- le^-1·s^-1at relative humidity of 55.8%±0.8% at 295K. Base on these results, it is possible to see the reaction of O3/ DMS in the presence of water vapor as an important sink for DMS in the earth atmosphere.     

Gold modified microelectrode for direct tetracycline detection

The residues of tetracycline antibiotics in water have attracted many concerns due to their harmful impact to human health. This paper reports an electrochemical sensor for the determination of tetracycline (TC) by the microelectrode, which was fabricated by electrodeposited gold colloids on tungsten tip. Cyclic voltammerty was used to study the electrochemical behavior of TC on the microelectrode. Well anodic wave was obtained at about 1.5 V in acidic solutions. Electrochemical determination of tetracycline was investigated using microelectrode by cyclic voltammetry. Under optimized conditions, the calibration curves for TC were obtained. The oxidation peak currents were linearly related to TC concentrations in the range of 1–10 mg·L^-1 and 10–100 mg·L^-1, respectively. The detection limit was 0.09 mg·L^-1 (S/N = 3).     

球磨零价镁/石墨(ZVMg/C)降解水中三氯乙烯

利用机械球磨法制备了零价镁/石墨(ZVMg/C)材料,并将其用于水溶液中三氯乙烯(TCE)的降解.研究通过SEM、BET和XRD等分析手段解析了ZVMg/C的表面形态结构和成分组成;采用正交实验方法优化了ZVMg/C的制备参数,比较了石墨含量对材料性能的影响;并考察了ZVMg/C投加量、溶液初始pH和地下水中常见阴(C...     

Modified pretreatment method for total microbial DNA extraction from contaminated river sediment

Extraction of high-quality microbial DNA from contaminated environmental samples is an essential step in microbial ecological study. Based on previously published methods for soil and sediment samples, a modified pretreatment method was developed for extracting microbial DNA from heavily contaminated river sediment samples via selection of optimal pretreatment parameters (i.e., reagent solution, reaction duration, and temperature). The pretreatment procedure involves washing the river sediment sample for three times with a solution containing 0.1 mol·L^-1 ethylene diamine tetraacetic acid (EDTA), 0.1 mol·L^-1 Tris (pH 8.0), 1.5 mol·L^-1 NaCl, 0.1 mol·L^-1 NaH₂PO₄, and Na₂HPO₄ at 65°C with 180 r·min^-1 for 15 min to remove humic materials and heavy metals prior to the employment of standard DNA extraction procedures. We compared the results of standard procedure DNA extraction following pretreatment, without pretreatment, and with using a commercial PowerSoil^TM DNA Isolation Kit. The results indicated that the pretreatment significantly improved the DNA quality based on DNA yield, DNA fragment length, and determination of prokaryotic diversity. Prokaryotic diversity exhibited in the DNA with the pretreatment was also considerably higher than that extracted with the PowerSoil^TM DNA Isolation Kit only. The pretreatment method worked well even with a small amount of sediment sample (0.25 g or even lower). The method provides a novel, simple, cost-effective tool for DNA extraction for microbial community analysis in environmental monitoring and remediation processes.     

高效液相色谱-串联质谱法同时检测水体中26种药物及个人护理品

通过优化固相萃取条件和高效液相色谱-串联质谱参数,建立了可以同时检测地表水和地下水中26种典型药物及个人护理品(pharmaceuticals and personal care products,PPCPs),包括磺胺类、大环内酯类、喹诺酮类、酰胺醇类、精神类、消炎止痛类以及个人护理品的检测方法.通过将水样pH值调节...     

基于氮掺杂碳量子点的制备及其对Hg2+的响应

以乙二胺和抗坏血酸为原料,通过一步水热法制备了水溶性的氮掺杂碳量子点(N-CQDs).研究了N-CQDs的形貌特征、光学性能和应用分析.表征结果说明,N-CQDs形态为均匀分散的球形,有明显的晶格条纹,抗光漂白性能良好,表面富有含氧官能团,具有良好的水溶性.此外发现N-CQDs还具有优良的荧光性能和荧光稳定性,量子产率可以高达12.29%.分析得出,Hg²⁺对N-CQDs在1.0—120μmol·L^-1范围内有一定的猝灭效应,可作为Hg²⁺的荧光探针,检出限达230 nmol·L^-1.     

Occurrence of estrogenic endocrine disrupting chemicals concern in sewage plant effluent

The purpose of this study was to give a worldwide overview of the concentrations of typical estrogenic endocrine disrupting chemicals （EDCs） in the effluent of sewage plants and then compare the concentra- tion distribution of the estrogenic EDCs in ten countries based on the survey data of the estrogenic EDCs research. The concentrations of three main categories （totally eight kinds） of estrogenic EDCs including steroidal estrogens （estrone （El）, estradiol （E2）, estriol （E3） and 17a- ethynylestradiol （EE2））, phenolic compounds （nonylphe- nol （NP） and bisphenol A （BPA）） and phthalate esters （dibutyl phthalate （DBP） and dibutyl phthalate （2- ethylhexyl） phthalate （DEHP）） in the effluents of sewage plants reported in major international journals over the past decade were collected. The statistics showed that the concentration distributions of eight kinds of EDCs were in the range of ng·L^-1 to μg·L^-1. The concentrations of steroidal estrogens mainly ranged within 50.00 ng. L-1, and the median concentrations of El, E2, E3 and EE2 were 11.00, 3.68, 4.90 and 1.00 ng·L^-1, respectively. Phenolic compounds and phthalate esters were found at pg. L-1 level （some individual values were at the high level of 40.00 μg·L^-1）. The median concentrations of BPA, NP, DBP and DEHP were 0.06, 0.55, 0.07 and 0.88 μg·L^-1, respectively. The concentrations of phenolic compounds and phthalate esters in the effluents were higher than that of steroids estrogens. The analysis of the concentration in various ten countries showed that steroids estrogens, phenolic compounds and phthalate esters in sewage plant effluents were detected with high concentration in Canada, Spain and China, respectively.     

固相萃取-液相色谱法测定食品废水中8种色素残留

建立了食品工业废水中8种合成色素残留的固相萃取-液相色谱测定方法.水样经固相萃取柱富集,氮吹浓缩定容后直接进样.采用C18色谱柱分离,以甲醇-乙酸铵(0.01mol·L^-1)溶液为流动相,进行梯度洗脱,最后利用二极管阵列检测器(DAD)进行可变波长分析,外标法定量.结果表明,8种合成色素在1.0—50mg·L^-1的浓度范围内线性良好,相关系数均大于0.999,定量限为1.6—2.4μg·L^-1.以实际废水样品为加标对象,分别考察了低、中、高三个浓度水平的加标回收率和精密度,平均加标回收率在82.3%—95.9%之间,精密度均小于5.45%.该方法准确可靠,灵敏度高,可用于食品工业废水中痕量色素残留的测定.     

通过式固相萃取/超高效液相色谱-串联质谱法测定蔬菜中18种农药残留

建立了超高效液相色谱-串联质谱(UPLC-MS;MS)快速测定蔬菜中18种农药残留的方法.样品经乙腈提取后,经Oasis PRiME HLB固相萃取柱净化,采用ACQUITY UPLC HSS T3 C18(50 mm×2.1 mm,1.8μm)色谱柱进行分离,以0.1%甲酸水溶液和乙腈作为流动相进行梯度洗脱.采用电喷雾电离源、正离子模式下以多反应监测(MRM)进行定性和定量分析.结果表明,18种农药在0.5—50μg·L^-1范围内线性关系良好(r2>0.995),方法最低检出限为0.4—1.5μg·kg^-1,最低定量限为1.4—5.0μg·kg^-1.在韭菜、芹菜、番茄、白菜基质中,5、10、50μg·kg^-1添加水平下的加标回收率为60.2%—126.9%,相对标准偏差(RSD)为0.4%—21.6%(n=3).     

硝酸钙投加频次对污泥生物调理效果的影响

在接种了反硝化菌的剩余污泥中投加硝酸钙药剂,利用反硝化菌消耗NO3-进行反硝化作用去除污泥中易生物降解的有机物,利用Ca2＋的中和、架桥作用,改善污泥的脱水性能.固定NO;总投加浓度为100 mg?g-1 TS,在6d的时间内,按1次、2次、3次、6次的投加频次向污泥中投加硝酸钙.结果表明,1次投加对污泥脱水性能的提升...     

Upgrade of three municipal wastewater treatment lagoons using a high surface area media

Lagoon-based municipal wastewater treatment plants (WWTPs) are facing difficulties meeting the needs of rapid population growth as well as the more stringent requirements of discharge permits. Three municipal WWTPs were modified using a high surface area media with upgraded fine-bubble aeration systems. Performance data collected showed very promising results in terms of five-day biochemical oxygen demand (BOD₅), ammonia (NH₃) and total suspended solids (TSS) removal. Two-year average ammonia effluents were 4.1 mg·L^-1 for Columbia WWTP, 4 mg·L^-1 for Larchmont WWTP and 2.1 mg·L^-1 for Laurelville WWTP, respectively. Two- year average BOD₅ effluents were 6.8, 4.9 and 2.7 mg·L^-1, and TSS effluents were 15.0, 9.6 and 7.5 mg·L^-1. The systems also showed low fecal coliform (FC) levels in their effluents.     

Using crosslinked polyvinyl alcohol polymer membrane as a separator in the microbial fuel cell

Separator between anode and cathode is an essential part of the microbial fuel cell （MFC） and its property could significantly influence the system perfor- mance. In this study we used polyvinyl alcohol （PVA） polymer membrane crosslinked with sulfosuccinic acid （SSA） as a new separator for the MFC. The highest power density of 7594-4 mW-m-2 was obtained when MFC using the PVA membrane crosslinked with 15% of SSA due to its desirable proton conductivity （5.16 x 10-2 S.cml）. The power density significantly increased to 11064- 30 mW.m-2 with a separator-electrode-assembly config- uration, which was comparable with glass fiber （11704- 46 mW.m-2）. The coulombic efficiencies of the MFCs with crosslinked PVA membranes ranged from 36.3% to 45.7% at a fix external resistance of lO00f2. The crosslinked PVA membrane could be a promising alter- native to separator materials for constructing practical MFC system.     

Effect of illumination on the hydrogen-production capability of anaerobic activated sludge

To investigate the influence of illumination on the fermentative hydrogen production system, the hydrogen production efficiencies of two kinds of anaerobic activated sludge (floc and granule) from an anaerobic baffled reactor were detected under visible light, dark and light-dark, respectively. The 10 mL floc sludge or granular sludge was respectively inoculated to 100 mL diluted molasses (chemical oxygen demand of 8000 mg·L^-1) in a 250 mL serum bottle, and cultured for 24 h at 37°C under different illumination conditions. The results showed that the floc was more sensitive to illumination than the granule. A hydrogen yield of 19.8 mL was obtained in the dark with a specific hydrogen production rate of 3.52 mol·kg^-1MLVSS·d^-1 (floc), which was the highest among the three illumination conditions. Under dark condition, the hydrogen yield of floc sludge reached the highest with the specific hydrogen production rate of 3.52 mol·kg^-1MLVSS·d^-1, and under light-dark, light, the specific hydrogen production rate was 3.11 and 2.21 mol·kg^-1MLVSS·d^-1, respectively. The results demonstrated that the illumination may affect the dehydrogenase activity of sludge as well as the activity of hydrogen-producing acetogens and then impact hydrogen production capacity.     

电感耦合等离子体质谱法分析锰结核中的多种元素含量

本文使用岛津ICPMS-2030电感耦合等离子体质谱仪,采用微波消解法对锰结核样品进行前处理,测定了锰结核样品中32种元素含量.实验结果表明,各元素在1.0-100μg·L-1范围内线性关系良好,相关系数均大于0.9998,检出限低,各元素检出限都在0.00004-0.73 μg·g-1之间.该方法操作简便、快速,测试...     

Adsorption property of direct fast black onto acid-thermal modified sepiolite and optimization of adsorption conditions using Box-Behnken response surface methodology

The adsorption of direct fast black onto acid-thermal modified sepiolite was investigated. Batch adsorption experiments were performed to evaluate the influences of experimental parameters such as initial dye concentration, initial solution pH and adsorbent dosage on the adsorption process. The three-factor and three-level Box-Behnken response surface methodology (RSM) was utilized for modeling and optimization of the adsorption conditions for direct fast black onto the acid-thermal modified sepiolite. The raw sepiolite was converted to acid-thermal modified sepiolite, and changes in the fourier transform infrared spectrum (FTIR) adsorption bands of the sample were noted at 3435 cm^-1 and 1427 cm^-1. The zeolitic water disappeared and the purity of sepiolite was improved by acid-thermal modification. The decolorization rate of direct fast black adsorbed increased from 68.2% to 98.9% on acid-thermal modified sepiolite as the initial solution pH decreased from 10 to 2. When the adsorbent dosage reached to 2.5 g·L^-1, 2.0 g·L^-1, 1.5 g·L^-1 and 1.0 g·L^-1, the decolorization rate was 90.3%, 86.7%, 61.0% and 29.8%, respectively. When initial dye concentration increased from 25 to 200 mg·L^-1, the decolorization rate decreased from 91.9% to 60.0%. The RSM results showed that the interaction between adsorbent dosage and pH to be a significant factor. The optimum conditions were as follows: the adsorbent dosage 1.99 g·L^-1, pH 4.22, and reaction time 5.2 h. Under these conditions, the decolorization rate was 95.1%. The three dimensional fluorescence spectra of direct fast black before and after treatment showed that the direct fast black was almost all adsorbed by the acid-thermal modified sepiolite.     

Validation of polymer-based nano-iron oxide in further phosphorus removal from bioeffluent: laboratory and scaledup study

The efficient removal of phosphorous from water is an important but challenging task. In this study, we validated the applicability of a new commercially available nanocomposite adsorbent, i.e., a polymer-based hydrated ferric oxide nanocomposite (HFO-201), for the further removal of phosphorous from the bioeffluent discharged from a municipal wastewater treatment plant, and the operating parameters such as the flow rate, temperature and composition of the regenerants were optimized. Laboratory-scale results indicate that phosphorous in real bioeffluent can be effectively removed from 0.92 mg·L^-1 to<0.5 mg·L^-1 (or even<0.1 mg·L^-1 as desired) by the new adsorbent at a flow rate of 50 bed volume (BV) per hour and treatable volume of 3500–4000 BV per run. Phosphorous removal is independent of the ambient temperature in the range of 15°C–40°C. Moreover, the exhausted HFO-201 can be regenerated by a 2% NaOH+ 5% NaCl binary solution for repeated use without significant capacity loss. A scaled-up study further indicated that even though the initial total phosphorus (TP) was as high as 2 mg·L^-1, it could be reduced to<0.5 mg·L^-1, with a working capacity of 4.4–4.8 g·L^-1 HFO-201. In general, HFO-201 adsorption is a choice method for the efficient removal of phosphate from biotreated waste effluent.     

Kinetics of oxidation of dimethyl trisulfide by potassium permanganate in drinking water

Metabolites of algae such as geosmin, 2-methylisoborneol etc. are reported to induce pungent odors into drinking water and attract additional scientific attention. Recently, in China, taste and odor outbreaks in drinking water supply have become increasingly common. In source water affected by eutrophication, dimethyl trisulfide, speculated to be produced by decayed algae, was found to be the source of taste and odor issues and can be removed effectively by usual oxidation agents. In this experimental study, batch scale tests were carried out focusing on the removal of dimethyl trisulfide. Reaction kinetics of dimethyl trisulfide oxidized by potassium permanganate in water had been studied; influence factors such as pH, organic substrate, other existed taste, and odor contaminant in equivalent concentration were also discussed. Results showed that dimethyl trisulfide can be removed by potassium permanganate efficiently; the ratio can reach more than 70% with oxidant dosage of 4 mg·L^-1 and contact time prolonged to 120 min. The dimethyl trisulfide decomposition followed a second-order kinetics pattern with a rate constant k = 0.00213 L·(min·mg)^-1. Typically, the degradation rate of dimethyl trisulfide was increased with the increasing KMnO₄ dosage, but dramatically dropped with the increasing levels of humic acid (1.8–4.5 mg·L^-1) and other odor-causing compounds (e.g. β-cyclocitral, 0–1886.0 μg·L^-1). Solution pH (5.2–9.0) and initial dimethyl trisulfide concentration did not significantly affected the degradation. This study demonstrates that KMnO₄ oxidation is an effective option to remove dimethyl trisulfide from water.