Stable chlorine intramolecular kinetic isotope effects from the abiotic dehydrochlorination of DDT

INTENTION, GOAL, SCOPE, BACKGROUND: Identifying different sources and following reaction pathways of chlorinated organic contaminants in the environment can be challenging, especially when only their concentrations are available. Compound-specific stable chlorine measurements of some contaminants have recently been shown to provide additional information and an increased understanding of their biogeochemistry. These studies, however, have been generally limited to volatile molecules. OBJECTIVE: Here, the stable chlorine isotope ratios of the semi-volatile pesticide, 1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane (DDT) were investigated. Specifically, the intramolecular stable chlorine isotopic compositions of DDT and the kinetic isotope effect (KIE) for the abiotic dehydrochlorination of DDT to 2,2-bis(p-chlorophenyl)-1,1-dichloroethene (DDE) were determined. METHODS: Selective chemical oxidation of DDT to dichlorobenzophenone (DCBP) and analysis of each compound was used to calculate the stable chlorine isotope ratios of the alkyl and aromatic chlorines in DDT. To determine the KIE for dehydrochlorination, DDT was reacted in a basic solution to yield DDE at 52 degrees C, 60 degrees C, and 72 degrees C for 3, 5, and 5 days, respectively. RESULTS AND DISCUSSION: Significant intramolecular stable chlorine isotopic differences were observed in one sample of DDT where the alkyl and aromatic delta 37Cl values were -5.76 +/- 0.45 and -2.21 +/- 0.24%@1000, respectively. Dehydrochlorination of DDT to DDE in basic solutions at 52, 60, and 70 degrees C resulted in a substantial intramolecular KIE where the alkyl chlorines of DDE shifted by approximately 3%@1000 relative to the alkyl chlorines in DDT. However, no temperature dependence was observed. The KIE, calculated by an iterative program, was 1.009. CONCLUSIONS: Intramolecular differences in the stable chlorine isotope ratios were observed in DDT and this is the first such finding. Dehydrochlorination of DDT yields a measurable and distinct intramolecular stable chlorine KIE. RECOMMENDATION AND OUTLOOK: The results of this study demonstrate the existence of significant intramolecular differences in chlorinated organic compounds. Many other chlorinated semi-volatile and volatile organic contaminants are synthesized from multiple sources of chlorine, and we recommend that similar studies be performed on many such molecules in order to attain a clear understanding of their intramolecular chlorine isotopic differences. The existence of a measurable KIE for the dehydrochlorination of DDT to DDE shows the potential strength of using isotopic measurements to investigate the biogeochemistry of these important compounds. For example, the isotopically depleted aqueous chloride produced by dehydrochlorination of DDT to DDE may be a useful tracer of these reactions in freshwater environments.     

绿化树种对大气金属污染物吸滞能力

研究测定了部分城市绿化树种对重金属大气铅、镉污染物的吸滞能力。结果表明：绿化树种对大气铅、镉污染物具有一定的吸收净化能力，并依污染气体和树种的不同具有明显差异；对铅吸收量高的树种有：桑树、黄金树、榆树、早树、梓树；吸镉量高的树种有：美青杨、桑树、早树、榆树、梓树、刺槐。     

Control division of agricultural non-point source pollution at medium-sized watershed scale in Southeast China

This paper presents the study carried out for controlling agricultural non-point source pollution (NSP) in a medium-sized watershed covering 1.47 × 10⁴ km² in Southeast China using quantitative analysis coupled with geographic information system (GIS), universal soil loss equation (USLE), soil conservation service-curve number (SCS-CN), nutrient loss equations, and annualized agricultural nonpoint source model (AnnAGNPS). Based on the quantitative results derived from GIS and environmental models, five control division units were generated for NSP control in Jiulong River watershed, namely, controlling unit for soil losses, controlling unit for livestock breeding and soil losses, controlling unit for excessive fertilizer use and livestock breeding, controlling unit for soil losses and fertilizer use, and controlling unit for excessive fertilizer use and soil losses. This study proved that integrating GIS with environmental models can be adopted to efficiently evaluate major sources and contributors of NSP, and identify the critical source areas of NSP, which enables adjusting measures to local conditions by further control division units developed through such study for control and management of water quality degradation induced by NSP in the Jiulong River watershed. __________ Translated from Research of Environmental Sciences, 2006, 19(4): 119–124 [译自: 环境科学研究]     

Particulate air pollution in Lanzhou China

Concentrations of total suspended particles (TSP) and PM(10) in Lanzhou China have been kept high for the past two decades. Data collected during the intensive observational period from October 1999 to April 2001 show high TSP and PM(10) concentrations. Starting from November, the PM(10) pollution intensifies, and reaches mid to high alert level of air pollution, continues until April next year, and is at low alert level in the summer. In the winter and spring, the TSP concentration is 2-10 times higher than the third-level criterion of air quality (severe pollution). Effects of intrinsic factors (sources of pollution) and remote preconditions (propagation of dust storms) for severe PM(10) and TSP pollution in Lanzhou are analyzed.     

Research progress of novel adsorption processes in water purification： A review

As an effective, efficient, and economic approach for water purification, adsorbents and adsorption processes have been widely studied and applied in different aspects for a long time. In the recent years, a lot of novel adsorption processes have been developed for enhancing the efficiency of removing the organic and inorganic contaminants from water. This article reviews some new adsorbents and advanced adsorption methods that specialize in their compositions, structures, functions, and characteristics used in water treatment. The review emphasizes adsorption/catalytic oxidation process, adsorption/catalytic reduction process, adsorption coupled with redox process, biomimetic sorbent and its sorption behaviors of POPs, and modified adsorbents and their water purification efficiency.     

Synthesis and application of lignin-based copolymer LSAA on controlling non-point source pollution resulted from surface runoff

In this article,alkali lignin separated from paper pulp waste was grafted into a novel copolymer LSAA (a copolymer of lignin,starch, acrylamide,and acrylic acid).Its practical application effect and environmental safety were studied.The results of field simulation experiment indicated that the application of LSAA significantly affected the output of the runoff and pollutants.The runoff quantity was decreased by 16.67%-47.00%and the loads of total suspended solids (TSS),chemical oxygen demand (COD),total ...     

黄河兰州段水环境污染状况和成因分析

较详细的描述了兰州水污染现状,从工业废水和生活污水排放及黄河入河排放口排放历史和趋势进行了分析和预测,对近几年的兰州市区段污染物的主要成分、污染物来源、污染物的总量和污染物浓度,不同时期兰州市区段水质与不同断面水污染状况做了分析与对比。找出黄河兰州段水污染的主要污染物与污染源,并对造成黄河兰州段污染的原因做了归纳总结,指出黄河兰州段水污染问题需要通过合理利用水资源,控制污染物的随意排放,调整产业结构等手段来解决。     

微塑料的老化特性、机制及其对污染物吸附影响的研究进展

针对微塑料的老化特性、机制及其对污染物吸附的研究进展进行了归纳总结：（1）微塑料在环境中经长期老化,其表面变得粗糙不平,部分呈现薄片状脱落,造成比表面积增加,同时在光照、氧气等老化因子作用下,形成羟基、羧基等含氧官能团;此外由于微塑料长期受到老化作用,其聚合物中的长链发生断裂,引起结晶度的变化.（2）微塑料老化过程主要涉及多方面：物理层面上,受到外界剪切力和拉伸力的作用引起聚合物内部的分子链断链,破坏其稳定结构;化学层面上,光氧化降解是其主要的老化机理;生物层面上,通过定殖生物在微塑料表面形成的生物膜引起其物理、化学特性（粗糙度、表面电荷、表面自由能）的变化.（3）微塑料老化后对污染物的吸附能力增强,吸附主要通过范德华力、静电作用、络合作用、疏水作用、氢键等作用方式吸附重金属和有机污染物.未来应加强微塑料在真实自然环境中老化特征及同多种污染物的交互作用的研究,以模型量化表示其内在联系,为科学合理地认识微塑料的环境行为及生态风险评估提供理论依据.     

Historical trends of PCBs and PBDEs as reconstructed in a lake sediment from southern Tibetan Plateau

High-altitude lake sediment can be used as a natural archive to reconstruct the history of pollutants. In this work, the temporal distribution of polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) were determined using a high-resolution gas chromatography coupled with high-resolution mass spectrometer (HRGC/HRMS) in an alpine lake sediment core collected from the southern Tibetan Plateau (TP) to examine whether the expected decreasing trends due to the implementation of the international Conventions could be observed. The concentrations of PCBs and PBDEs in the sediment core were in the range of 11.8–142 pg/g dw and ND-457 pg/g dw, and their fluxes were in the range of 2.51–31.7 ng/(m²·yr) and ND-43.2 ng/(m²·yr), respectively. The prevalence of low-chlorinated (tri-CB) PCBs and low-brominated (tri- to tetra-) PBDEs in most sections of the sediment profiles was observed, suggesting that the light molecular weight PCBs and PBDEs have most likely reached lake sediments by long-range atmospheric transport from distant sources. Despite the restrictions on their applications, the sediment records for the concentrations and fluxes showed no corresponding decreasing trend with restrictions for PCBs, which suggested that these POPs (e.g., PCBs) were still emitted to the environment owing to the influence of primary or secondary emissions. To our knowledge, this is the first report on input history of atmospheric PCBs and PBDEs recorded in TP Lake sediment.     

2010—2018年西安市大气污染物变化特征分析

日益严重的大气污染问题不仅对西安市的城市形象,还对人们的身体健康造成危害。对西安市13个国控环境空气质量自动监测站6类污染物的数据进行时空变化特征分析,对各污染物的相关性进行分析,并探讨大气污染原因,结果表明：2010—2018年SO₂浓度显著降低,PM₁₀和NO₂年均浓度总体并未呈现下降趋势,2013—2018年PM_2.5浓度变化趋势与PM₁₀浓度变化趋势相同,二者污染情况均较严重,CO浓度呈减小趋势,2013—2016年O₃的污染状况有恶化趋势;第二、三产业增加值的大幅上升所反映的工业、旅游业、交通运输、餐饮业的大规模发展,对西安空气质量有较大影响;SO₂的工业减排对大气SO₂浓度水平下降效果明显,但NO_x和烟（粉）尘排放量的下降却没有反映在大气NO₂和颗粒物浓度下降上。说明大气NO₂来源除了工业来源外,还有其他重要来源（如：机动车排放、天然气燃烧产物）,同时也反映了大气颗粒物来源的复杂,单纯依靠降低烟（粉）尘排放量无法有效降低颗粒物浓度。高增速的机动车保有量和能源消费结构均对西安市大气污染问题有重要影响。