Occurrence, distribution, and sources of six phenolic endocrine disrupting chemicals in the 22 river estuaries around Dianchi Lake in China

The objectives of this study are to track the occurrence, distribution, and sources of phenolic endocrine disrupting compounds (EDCs) in the 22 rivers around Dianchi Lake in China, to estimate the input and output amounts of phenolic EDCs in the water system, and to provide more comprehensive fundamental data for risk assessment and contamination control of phenolic EDCs in aquatic environment. Six phenolic EDCs were systematically evaluated in water and surface sediment in the estuaries of those rivers. The water and sediment samples were preconcentrated by solid-phase extraction system and microwave-assisted extraction system, respectively. Phenolic EDCs were analyzed by GC-MS (Thermo Fisher Scientific, USA) after derivatization. Phenolic EDCs were found ubiquitously in the aquatic environment. The total concentrations ranged from 248 to 4,650 ng/L in water, and 113 to 3,576 ng/g dry weight in surface sediment. The residue amount of phenolic EDCs in Dianchi Lake was 258 kg/a. Concentrations of the phenolic EDCs in the Lake decreased with increase in distance to the estuaries of those rivers which run through urban and industrial areas. The rivers seriously contaminated by phenolic EDCs were Xin River, Yunliang River, Chuanfang River, Cailian River, Jinjia River, Zhengda River, and Daqing River which run through the old area of Kunming City. Satisfying correlations were observed between the concentrations of the target compounds in water and in surface sediment. NP1EO, NP2EO, and BPA were identified as the three predominant phenolic EDCs. There were significant correlations between phenolic EDCs and many basic water quality parameters. Urban and industrial areas are the major contributors for phenolic EDCs, especially in Kunming City. Compositional profiles of phenolic EDCs in surface sediment were similar to those in river water. The concentrations of phenolic EDCs in the rivers located in the northwest part of the valley were very high, and posed a potential risk to aquatic organisms and even human. The concentrations of NP2EO, NP1EO, and BPA were at moderate levels of other areas. The basic water quality parameters (TOC, TN, DO, and pH) play important roles on the distribution, fate, and behavior of phenolic EDCs in the valley.     

Parental phenols exposure and spontaneous abortion in Chinese population residing in the middle and lower reaches of the Yangtze River

Widespread use of phenols has led to ubiquitous exposure to phenols. In experimental animals, phenols increased resorptions, reduced live litter size and fetal body weights. However, there are limited epidemiological evidences of the relationships between exposure to phenols and pregnancy outcomes. We evaluated the associations between parental urinary levels of various phenols and spontaneous abortion in a Chinese population residing in the middle and lower reaches of the Yangtze River. A case-control study was conducted that included 70 case couples with medically unexplained spontaneous abortion and 180 control couples who did not have a history of spontaneous abortion and had at least one living child. Both parental urinary phenols were measured by ultra-high performance liquid chromatography-tandem mass spectrometry including bisphenol A (BPA), benzophenone-3 (BP-3), 2,3,4-trichlorophenol (2,3,4-TCP), pentachlorophenol (PCP), 4-n-octylphenol (4-n-OP) and 4-n-nonylphenol (4-n-NP). Compared with the low exposure group, there was an increased risk of spontaneous abortion with high paternal urinary PCP concentration [odds ratio (OR) = 2.09, 95% Confidence Interval (CI), 1.05–4.14], and maternal exposure to 4-n-OP and alkylphenol(s) also significantly increased the risk of spontaneous abortion (OR = 2.21, 95% CI, 1.02–4.80; OR = 2.81, 95% CI, 1.39–5.65, respectively). Our study firstly provides the evidence that paternal PCP exposure, maternal 4-n-OP and alkylphenol(s) exposure are associated with spontaneous abortion in humans.     

Removal of sulfamethoxazole and sulfapyridine by carbon nanotubes in fixed-bed columns

Sulfamethoxazole (SMX) and sulfapyridine (SPY), two representative sulfonamide antibiotics, have gained increasing attention because of the ecological risks these substances pose to plants, animals, and humans. This work systematically investigated the removal of SMX and SPY by carbon nanotubes (CNTs) in fixed-bed columns under a broad range of conditions including: CNT incorporation method, solution pH, bed depth, adsorbent dosage, adsorbate initial concentration, and flow rate. Fixed-bed experiments showed that pH is a key factor that affects the adsorption capacity of antibiotics to CNTs. The Bed Depth Service Time model describes well the relationship between service time and bed depth and can be used to design appropriate column parameters. During fixed-bed regeneration, small amounts of SMX (3%) and SPY (9%) were irreversibly bonded to the CNT/sand porous media, thus reducing the column capacity for subsequent reuse from 67.9 to 50.4 mg g^?1 for SMX and from 91.9 to 72.9 mg g^?1 for SPY. The reduced column capacity resulted from the decrease in available adsorption sites and resulting repulsion (i.e., blocking) of incoming antibiotics from those previously adsorbed. Findings from this study demonstrate that fixed-bed columns packed with CNTs can be efficiently used and regenerated to remove antibiotics from water.     

Effect of chlorination and ultraviolet disinfection on tetA-mediated tetracycline resistance of Escherichia coli

Antibiotic-resistant bacteria are an emerging threat to public health during drinking water consumption and reclaimed water reuse. Several studies have shown that the proportions of antibiotic-resistant bacteria in waters may increase when exposed to low doses of UV light or chlorine. In this study, inactivation of tetracycline-resistant Escherichia coli and antibiotic-sensitive E. coli by UV disinfection and chlorination was compared to determine the tolerance of tetracycline-resistant E. coli to UV light and chlorine, and tetracycline resistance of a tetracycline-resistant E. coli population was studied under different doses of the disinfectants. Our results showed that relative to antibiotic-sensitive E. coli, tetracycline-resistant E. coli had the same tolerance to UV light and a potentially higher tolerance to chlorination. The mortality frequency distributions of tetracycline-resistant E. coli exposed to tetracycline were shifted by both chlorination and UV disinfection. When compared to the hemi-inhibitory concentrations (IC₅₀) of tetracycline-resistant E. coli with no exposure to UV or chlorination, the IC₅₀ of tetracycline-resistant E. coli treated with tetracycline was 40% lower when inactivation by UV light or chlorination reached 3-log but was 1.18 times greater when inactivation by chlorination reached 4.3-log. Chlorination applied to drinking water or reclaimed water treatment may increase the risk of selection for highly tetracycline-resistant E. coli.     

基于核心企业视角的虚拟生态工业园构建分析

虚拟生态工业园(VEIP)是一种基于循环经济的新型的大循环生态工业组织形式,是对实体生态工业园的补充和扩展.而核心企业作为VEIP的组建者,是整个园区日常运营的信息指挥中枢,对VEIP的成功运营至关重要.分析了核心企业的内涵和应具备的特质,然后从核心企业的视角出发,给出了核心企业构建VEIP的一般流程,并阐述了核心企业在VEIP构建过程中的主要职能.     

基于BP人工神经网络的城市PM2.5浓度空间预测

针对PM2.5日均质量浓度,采用BP人工神经网络模型,预测研究区空气中PM2.5浓度的空间变异,通过与普通克里格(Ordinary Kriging)插值方法对比验证BP人工神经网络预测模型的精度.结果表明:BP人工神经网络预测模型下研究区检验样本点位置的PM2.5仿真浓度与观测浓度之间的均方差、平均绝对误差、平均相对偏差和相关系数分别为0.296 μg2/m6、0.412 μg/m3、1.650％和0.851;而与此同时,普通克里格插值方法下的对应结果分别为1.041 μg2/m6、0.689 μg/m3、11.910％、0.638.研究成果在肯定BP人工神经网络预测模型可用于揭示PM2.5浓度空间变异特征的同时,也证实了其相对于普通克里格插值方法在固定空间点位准确预测PM2.5浓度方面的优势.     

臭氧-BAF组合工艺对石化行业废水深度处理的中试研究

采用臭氧-曝气生物滤池（BAF）组合工艺对中石化九江分公司二级生化出水进行深度处理中试实验。探讨了臭氧投加量、进水水质冲击负荷等因素对该组合工艺出水COD、NH₄⁺-N的影响。中试结果表明,在该水质条件下,臭氧最佳投加量为20~25 mg/L;组合工艺处理后出水COD低于40 mg/L,NH₄⁺-N低于5 mg/L,达到中水回用设计标准;该组合工艺能够经受一定冲击负荷。     

碱式硫酸铝溶液中SO42-的测定

建立了以铬黑T为指示剂,乙二胺四乙酸二钠反滴定过量BaCl₂的碱式硫酸铝溶液中SO₄^2-的测定方法。实验确定的操作条件为：待测试样稀释后ρ（SO_4^2-）为0.025 ~0.100 g/L,BaCl₂过量率为25%~100%,并且在加入BaCl₂前将试样煮沸,三乙醇胺加入量为0.10 L/L。该法回收率在98.90%~100.72%,相对标准偏差小于1%。测定方法准确,可靠,且操作简便、快速。     

Determination of o-phthalic acid in snow and its photochemical degradation by capillary gas chromatography coupled with flame ionization and mass spectrometric detection

Phthalic acid and its photochemical degradation has been determined in snow and rainwater samples collected during winters (2003-2010) in the Southeast of Massachusetts using capillary gas chromatography (GC) with flame ionization and mass spectrometric detection. Water samples were dried using a rotary evaporator and derivatized with a 14% BF₃/methanol reagent before GC analysis. The developed method proved simple and accurate. Phthalic acid was found in snow samples collected in a concentration range of 7.22-76.5 nM. The photodegradation of phthalate was carried out under 300 nm UV light. The direct photodecomposition of the acid is slow (5% h⁻¹). However, the addition of dissolved Fe(III) species at 2.0 μM accelerated the light-induced degradation of phthalic acid by 3.5 times in the atmospheric water samples. Photodegradation rates of phthalic acid increases with decreasing pH value of water samples in the range of pH 2.8-4.5.     

Chlorination of chlortoluron: kinetics, pathways and chloroform formation

Chlortoluron chlorination is studied in the pH range of 3-10 at 25 ± 1 °C. The chlorination kinetics can be well described by a second-order kinetics model, first-order in chlorine and first-order in chlortoluron. The apparent rate constants were determined and found to be minimum at pH 6, maximum at pH 3 and medium at alkaline conditions. The rate constant of each predominant elementary reactions (i.e., the acid-catalyzed reaction of chlortoluron with HOCl, the reaction of chlortoluron with HOCl and the reaction of chlortoluron with OCl⁻) was calculated as 3.12 (± 0.10) × 10⁷ M⁻² h⁻¹, 3.11 (±0.39) × 10² M⁻¹ h⁻¹ and 3.06 (±0.47) × 10³ M⁻¹ h⁻¹, respectively. The main chlortoluron chlorination by-products were identified by gas chromatography-mass spectrometry (GC-MS) with purge-and-trap pretreatment, ultra-performance liquid chromatography-electrospray ionization-MS and GC-electron capture detector. Six volatile disinfection by-products were identified including chloroform (CF), dichloroacetonitrile, 1,1-dichloropropanone, 1,1,1-trichloropropanone, dichloronitromethane and trichloronitromethane. Degradation pathways of chlortoluron chlorination were then proposed. High concentrations of CF were generated during chlortoluron chlorination, with maximum CF yield at circumneutral pH range in solution.