某石油污染含水层降解能力地球化学评估

含水层降解能力是石油类污染场地监控自然衰减需获取的重要参数.通过测定某石油污染场地地下水电子供体（苯系物、化学耗氧量）和电子受体/产物（DO、NO₃^-、Mn²⁺、Fe²⁺、SO₄^2-和HCO₃^-）等地球化学指标,分析了电子供受体分布规律,确定了电子受体背景值,采用传统地球化学评估法,计算了所有单井降解能力;在此基础上,引入累积概率曲线法,更科学的评估了场地含水层降解能力,结合地下水更新能力,估算了污染物降解速率;同时,划分了含水层降解能力强弱区.结果显示：该场地单井降解能力为36.49~70.05mg/L,其累积概率拟合曲线符合F（x）=0.008e^0.07x指数模型,以此评估含水层降解能力为57.83mg/L.以径流量132m³/d估算地下水更新能力,估算污染物降解速率为2790kg/a;强降解能力区位于下游源区,面积约为5100m²,占场地总面积的5.3%;地下水中硫酸盐、硝酸盐消耗严重,强化硫酸盐还原和反硝化作用可能是该场地管理修复的一个有效方法.     

不同组织碳、氮元素含量和同位素分馏特征研究—以抚仙湖草鱼、鱇浪白鱼为例

结合抚仙湖浮游植物、水生植物等样品,对野生植食性草鱼(Ctenopharyngodon idellus)31个组织和野生肉食性鱇浪白鱼(Anabarilius grahami)17个组织样品碳、氮元素含量和稳定同位素比值(δ13C、δ15N)进行了对比分析.结果显示,鱼类不同组织的碳稳定同位素分馏效应显著,草鱼不同组织...     

Removal natural organic matter in typical south-China source water during enhanced coagulation of a with IPF-PACl

Systematic investigation on enhancing removal of natural organic matter （NOM） using inorganic polymer flocculant （IPF）, polyaluminum chloride（PACI） and polyacrylamide（PAM） was performed in a typical south-China source water. Enhanced coagulation and applying polymer flocculant-aid were compared through jar tests and pilot tests. Raw water and settled water were characterized and fractionated by resin adsorption. The results show that DOC composes major part of TOC. The DOC distribution keeps relatively stable all around the year with typical high amounts of the hydrophilic matter around 50%. The distribution between HoB, HoA and HoN varies and undergoes fluctuation with the year round. During the summer season, the HoN becomes gradually the major part in hydrophobic parts. PACI with the species being tailor-made shows little pH effect during coagulation. The enhanced coagulation dosage for PACI could be 4.5 mg/L for the typical source water. The highest TOC removal achieved 31%. To be economically, 3 mg/L dose is the optimum dosage. Although hydrophilic fractions of NOM of both treatment strategies are removed about 30%, NOM causing UV254 absorbance were well removed（about 90%）. Hydrophobic bases and acids fractions are much more removed under enhanced conditions. The hydrophilic fraction could be better removed using PAM, the polymer coagulant aid.     

Assessment of aerobic biodegradation of lower-chlorinated benzenes in contaminated groundwater using field-derived microcosms and compound-specific carbon isotope fractionation

Biodegradation of lower chlorinated benzenes (tri-, di- and monochlorobenzene) was assessed at a coastal aquifer contaminated with multiple chlorinated aromatic hydrocarbons. Field-derived microcosms, established with groundwater from the source zone and amended with a mixture of lower chlorinated benzenes, evidenced biodegradation of monochlorobenzene (MCB) and 1,4-dichlorobenzene (1,4-DCB) in aerobic microcosms, whereas the addition of lactate in anaerobic microcosms did not enhance anaerobic reductive dechlorination. Aerobic microcosms established with groundwater from the plume consumed several doses of MCB and concomitantly degraded the three isomers of dichlorobenzene with no observable inhibitory effect. In the light of these results, we assessed the applicability of compound stable isotope analysis to monitor a potential aerobic remediation treatment of MCB and 1,4-DCB in this site. The carbon isotopic fractionation factors (ε) obtained from field-derived microcosms were -0.7‰ ± 0.1 ‰ and -1.0‰ ± 0.2 ‰ for MCB and 1,4-DCB, respectively. For 1,4-DCB, the carbon isotope fractionation during aerobic biodegradation was reported for the first time. The weak carbon isotope fractionation values for the aerobic pathway would only allow tracing of in situ degradation in aquifer parts with high extent of biodegradation. However, based on the carbon isotope effects measured in this and previous studies, relatively high carbon isotope shifts (i.e., ∆δ¹³C > 4.0 ‰) of MCB or 1,4-DCB in contaminated groundwater would suggest that their biodegradation is controlled by anaerobic reductive dechlorination.     

鼠李糖脂对林丹-重金属复合污染土壤的同步淋洗效果研究

选取典型有机氯农药林丹及典型重金属Pb、Cd为目标污染物,以模拟污染土壤为对象,考察了鼠李糖脂对林丹/重金属的增溶/配合作用及其影响因素,同时分析了淋洗前后土壤重金属的形态变化,并深入研究了鼠李糖脂对林丹-重金属复合污染土壤的淋洗效果.结果表明,林丹溶解度随鼠李糖脂浓度及离子强度的提高显著增大,但随pH(5.0~10.0)的提高而逐渐降低.鼠李糖脂对Pb的配合能力大于Cd,两种重金属的配合浓度随鼠李糖脂浓度的增加而增加;pH提高对Pb的配合有抑制作用,而对Cd有所促进.鼠李糖脂在土壤上的吸附符合线性等温吸附.当鼠李糖脂浓度高于5000 mg·L-1时,其对3种污染物的淋洗开始有显著效果;当鼠李糖脂浓度为40000 mg·L-1时,其对林丹、Pb及Cd的去除率分别达到76.9%、18.0%和100%,且pH为7.0时淋洗效果最好.同时,鼠李糖脂对不同形态Pb和Cd的去除能力有差异,其中,对可交换态重金属的去除最为有效.     

Antibiotics along an alpine river and in the receiving lake with a catchment dominated by grazing husbandry

The livestock breeding industries face overuse of antibiotics, which has been intensively studied in recent years. However, the occurrence and fate of antibiotics as well as their potential threats to the aquatic environments in alpine and arid regions remain unclear. This study investigated the relationship of the occurrence and concentrations of antibiotics between the Kaidu River and Bosten Lake in a typical alpine basin in China. Hot spots with antibiotic pollution source were explored. The antibiotic concentrations in river water and suspended sediment (SPS) were 2.20-99.4 ng/L and 1.03-176 ng/g. The dominant antibiotics were tetracyclines, sulphacetamide, and ofloxacin in river water and sulfonamides, clarithromycin, roxithromycin, and ofloxacin in SPS. The apparent differences in pollution sources and landscapes in different reaches led to the obvious spatial patterns of antibiotics in the Kaidu River. Higher partition coefficient of antibiotic between SPS and water phases for sulfonamides than tetracyclines was because that tetracyclines strongly responded to clay contents while sulfonamides significantly responded to organic carbon contents in SPS. There were significant differences in detected antibiotic categories between the river and the lake. Fluoroquinolones (especially ciprofloxacin and enrofloxacin) were detected in the lake while sulphacetamide was only detected in the river. Therefore, the surrounding husbandry and aquaculture around the Bosten Lake was an important antibiotic pollution source in addition to inputs from the Kaidu River. This research suggested that alpine lakes could be an important sink of antibiotics in alpine dry regions, and thus impose greater threats to the aquatic ecosystem.     

Variations in stable hydrogen and oxygen isotopes in atmospheric water vapor in the marine boundary layer across a wide latitude range

The newly-developed cavity ring-down laser absorption spectroscopy analyzer with special calibration protocols has enabled the direct measurement of atmospheric vapor isotopes at high spatial and temporal resolution. This paper presents real-time hydrogen and oxygen stable isotope data for atmospheric water vapor above the sea surface, over a wide range of latitudes spanning from 38°N to 69°S. Our results showed relatively higher values of 8180 and 82H in the subtropical regions than those in the tropical and high latitude regions, and also a notable decreasing trend in the Antarctic coastal region. By combining the hydrogen and oxygen isotope data with meteoric water line and backward trajectory model analysis, we explored the kinetic fractionation caused by subsiding air masses and related saturated vapor pressure in the subtropics, and the evaporation-driven kinetic fractionation in the Antarctic region. Simultaneous observations of meteorological and marine variables were used to interpret the isotopic composition characteristics and influential factors, indicating that d-excess is negatively correlated with humidity across a wide range of latitudes and weather conditions worldwide. Coincident with previous studies, d-excess is also positively correlated with sea surface temperature and air temperature （Tair）, with greater sensitivity to Tair. Thus, atmospheric vapor isotopes measured with high accuracy and good spatial- temporal resolution could act as informative tracers for exploring the water cycle at different regional scales. Such monitoring efforts should be undertaken over a longer time period and in different regions of the world.     

含氯有机污染物中氯同位素测定方法及应用进展

本文综述了四种稳定氯同位素的测定方法。重点比较了当前使用最为广泛的两种测定方法,基于CH3Cl+离子的正电离气体质谱法(PEIMS)和基于Cs2Cl+离子的正热电离质谱法(PTIMS)。论述了稳定氯同位素体系(37Cl/35Cl)在含氯有机污染物来源、迁移及转换过程中的应用研究。     

表面活性剂增强修复地下水中PCE的砂箱实验及模拟

在石英砂充填的二维砂箱中开展表面活性剂（Tween 80）冲洗四氯乙烯（PCE）的修复实验,基于图像分析技术监测不同污染源区结构条件下NAPL相的去除过程.由于实验条件限制,实验中缺乏溶解相浓度数据.为此进一步基于UTCHEM数值模拟方法来理解NAPL相和溶解态之间的质量传输过程,并探讨表面活性剂浓度、注入速率等因素对修复效率的影响.综合砂箱实验和数值模拟结果表明：介质均质和非均质条件下会形成不同类型DNAPL污染源区结构,表现为离散状PCE与池状PCE体积比（GTP）差异.由于离散状污染物与表面活性剂的接触面积更大,更易被优先去除;初始GTP值越高,污染物的修复速率和修复效率也越高.增大表面活性剂浓度或提高表面活性剂的注入速率,虽然能提高DNAPL的修复速率,但会明显降低表面活性剂的修复效率,实验过程中修复效率降幅可达93%.线性驱动溶解模型可以有效地模拟表面活性剂修复DNAPLs过程,基于数值模拟方法选择合适的表面活性剂配比可有效的节省实际污染场址修复经费和时间成本.     

湖北黄石市天然水铬污染及其同位素特征

元素Cr(Ⅵ)作为水体中重要的污染物质,其同位素组成对水体环境变化具有较强的敏感性.笔者以黄石振华有限公司周围污染水体为分析实例,通过研究发现:在靠近铬渣堆附近的水中,受到的污染较为严重,随着距离的增大,污染程度减小;同时δ63Cr具有较好的指示意义,δ63Cr值基本上随着Cr(Ⅵ)浓度的增大而呈现逐渐减小的趋势.     

Risk assessment of heavy metal contaminated soil in the vicinity of a lead/zinc mine

Heavy metal contamination of soils through anthropogenic activities is a widespread and serious problem confronting scientists and regulators throughout the world. In this study we investigated the distribution, chemical species and availability of lead, zinc, cadmium and copper in nine surface（0 to 20 cm） soils from near an abandoned lead/zinc mine tailings located in Shaoxing, Zhejiang, China. Total heavy metal contents ranged from 5271 to 16369 mg/kg for Pb, 387 to 1221 mg/kg for Zn, 3.0 to 9.3 mg/kg for Cd and 65 to 206 mg/kg for Cu. In general, all heavy metals exceeded China National Standards for Soil Environmental Quality of Heavy Metals by a factor of 3-65 times. Comparison of the heavy metal concentrations（Pb, Zn, Cd and Cu） with clay content revealed a strongly significant relationship while significant relationship（ P 〈 0.001 ） was also obtained between Cd ＋ Zn and Pb ＋ Cu. Solid phase speciation of the soils using Tessier procedure showed that the heavy metals were distributed in the order： residual 〉〉 organically complexed-Fe-Mn oxides occluded 〉 carbonate bound 〉 exchangeable 〉 water soluble. In the organic matter fraction, the ratio of Pb（29.1% ） to its total concentration in the soils was higher than those of Zn（4.70% ）, Cd（3.16% ） and Cu（9.50% ）. The percentages of the water soluble and the exchangeable fractions of Pb（1.80% ） and Cd（2.74% ） were markedly greater than those of Zn（0.10% ） and Cu（0.15% ）, suggesting that Pb and Cd are relatively more mobile and hence more toxic in the contaminated soils. Strongly significant relationships between H20-Pb, H20-Zn and H20-Cu, strong positive correlations between H20-Pb, H20-Zn, H20-Cu and organic matter in soil were found. The content of H20-Pb, H20-Zn, H20-Cu was negatively correlated with pH values. The similar negative relationships between pH values and exchangeable heavy metals were also recorded. It is suggested that increasing soil pH or liming the soil could decrease bioavailability of heavy metals in the soil.     

基于文献计量的重金属污染土壤修复材料研究热点和前沿分析

基于Web of Science（WoS）核心合集数据库和中国知网（CNKI）,采用文献计量学方法和可视化分析软件揭示国内外重金属污染土壤修复材料研究领域近20年来的发展脉络、研究热点及发展方向。结果显示,相较于2001—2004年,2013—2016年和2017—2020年重金属污染土壤修复材料研究领域发文量显著增加,增长率分别为1 302%和2 201%。我国在该领域研究起步较晚,但发展迅速。关键词热点分析显示,当前污染修复研究侧重于农田土壤修复治理,重金属镉、铅及钝化材料应用。关键词聚类分析显示,钝化材料筛选和应用是当前热点主题,其中钝化材料修复机理和效果评估是该主题的重点和难点。当前农田土壤重金属污染修复材料研究正处于快速发展时期,钝化材料的功能化改性及其在农田应用中的研究有望取得较好的修复成效,绿色无污染和安全可持续的修复材料研发和应用是当下及未来的研究热点。

     

Groundwater contamination and natural attenuation capacity at a petroleum spilled facility in Korea

As a remedial option, the natural attenuation capacity of a petroleum contaminated groundwater at a military facility was examined. Hydrogeological conditions, such as high water level, permeable uppermost layer and frequent heavy rainfall, were favorable to natural attenuation at this site. The changes in the concentrations of electron acceptors and donors, as well as the relevant hydrochemical conditions, indicated the occurrence of aerobic respiration, denitrification, iron reduction, manganese reduction and sulfate reduction. The calculated BTEX expressed biodegradation capacity ranged between 20.52 and 33.67 mg/L, which appeared effective for the reduction of the contaminants levels. The contribution of each electron accepting process to the total biodegradation was in the order: denitrification > iron reduction > sulfate reduction > aerobic respiration > manganese reduction. The BTEX and benzene point attenuation rates were 0.0058-0.0064 and 0.0005-0.0032 day^-1, respectively, and the remediation time was 0.7-1.2 and 2.5-30 years, respectively. The BTEX and benzene bulk attenuation rates were 8.69 × 10^-4 and 1.05 × 10^-3 day^-1, respectively, and the remediation times for BTEX and benzene were 7.2 and 17.5 years, respectively. However, most of the natural attenuation occurring in this site can be attributed to dilution and dispersion. Consequently, the biodegradation and natural attenuation capacities were good enough to lower the contaminants levels, but their rates appeared to be insufficient to reach the remediation goal within a reasonable time frame. Therefore, some active remedial measures would be required.     

淮河流域平原区第四系含水层划分及特征分析

以中国地质调查局资助的《淮河流域环境地质调查》项目为依托,对收集到的区域基础地质和水文地质资料进行了二次开发。并根据近三年来淮河流域环境地质调查项目新取得的水文地质钻孔资料、水化学及同位素样品分析结果,科学地对淮河流域平原区第四系含水层进行了划分和印证,结合项目阶段研究成果,对淮河流域平原区第四系含水层特征进行了初步分析和总结。     

Dissipation of S-metolachlor and butachlor in agricultural soils and responses of bacterial communities: Insights from compound-specific isotope and biomolecular analyses

The soil dissipation of the widely used herbicides S-metolachlor(SM) and butachlor(BUT)was evaluated in laboratory microcosms at two environmentally relevant doses(15 and 150 μg/g) and for two agricultural soils(crop and paddy).Over 80% of SM and BUT were dissipated within 60 and 30 days,respectively,except in experiments with crop soil at 150 μg/g.Based on compound-specific isotope analysis(CSIA) and observed dissipation,biodegradation was the main process responsible for the observed decrease of SM and BUT in the paddy soil.For SM,biodegradation dominated over other dissipation processes,with changes of carbon isotope ratios(Δδ~(13)C) of up to 6.5‰ after 60 days,and concomitant production of ethane sulfonic acid(ESA) and oxanilic acid(OXA) transformation products.In crop soil experiments,biodegradation of SM occurred to a lesser extent than in paddy soil,and sorption was the main driver of apparent BUT dissipation.Sequencing of the 16 S rRNA gene showed that soil type and duration of herbicide exposure were the main determinants of bacterial community variation.In contrast,herbicide identity and spiking dose had no significant effect.In paddy soil experiments,a high(4:1,V/V) ESA to OXA ratio for SM was observed,and phylotypes assigned to anaerobic Clostridiales and sulfur reducers such as Desulfuromonadales and Syntrophobacterales were dominant for both herbicides.Crop soil microcosms,in contrast,were associated with a reverse,low(1:3,V/V)ratio of ESA to OXA for SM,and Alphaproteobacteria,Actinobacteria,and Bacillales dominated regardless of the herbicide.Our results emphasize the variability in the extent and modes of SM and BUT dissipation in agricultural soils,and in associated changes in bacterial communities.     

Mercury transformation processes in nature: Critical knowledge gaps and perspectives for moving forward

The transformation of mercury (Hg) in the environment plays a vital role in the cycling of Hg and its risk to the ecosystem and human health. Of particular importance are Hg oxidation/reduction and methylation/demethylation processes driven or mediated by the dynamics of light, microorganisms, and organic carbon, among others. Advances in understanding those Hg transformation processes determine our capacity of projecting and mitigating Hg risk. Here, we provide a critical analysis of major knowledge gaps in our understanding of Hg transformation in nature, with perspectives on approaches moving forward. Our analysis focuses on Hg transformation processes in the environment, as well as emerging methodology in exploring these processes. Future avenues for improving the understanding of Hg transformation processes to protect ecosystem and human health are also explored.     

地球物理方法在地下水有机污染DNAPLs的调查与监测中的应用

地下水有机污染特别是重非水相液体(densenon-aqueousphaseliquids,缩写为DNAPLs)污染是当前国际上地下水污染控制的热点问题,而对DNAPLs的调查与监测也一直是近年来环境地球物理研究的热点。文章简述了DNAPLs的运移、分布规律和DNAPLs与周围土壤及岩石存在的物理性质差异,综述了地球物理方法在DNAPLs的调查与监测应用中的有效性,探讨了地球物理方法直接探测DNAPLs的可行性,并提出了展望。     

BTEX在乙醇汽油和传统汽油污染地下水中的衰减行为对比

地下燃油储藏罐泄漏造成苯、甲苯、乙苯和二甲苯（BTEX）影响生态环境和公众健康的问题一直备受关注,随着乙醇汽油的推广使用,乙醇对BTEX修复策略的影响成为需要重视的新问题.为揭示乙醇汽油污染地下水中BTEX的衰减行为,本文通过室内两个独立砂槽投注实验和近3年的监测,对比了乙醇汽油和传统汽油中BTEX自然衰减和基于硫酸盐-硝酸盐补充的增强生物修复行为.结果表明,传统汽油BTEX自然衰减较快,乙醇汽油BTEX自然衰减较慢,一级衰减速率常数分别为0.0055~0.0329 d^-1和0.0045~0.0124 d^-1;苯衰减最快,其次为甲苯.补充硫酸盐和硝酸盐能促进生物修复,单独补充硫酸盐时其利用率为89.7%~92.9%,同时补充硝酸盐时硫酸盐利用被抑制,硝酸盐利用率为79.9%~87.2%.水位波动会促进BTEX溶解和迁移,增大质量通量.乙醇汽油不仅能消耗更多电子受体,使得BTEX衰减被抑制,而且可能会扩大水位波动引起的增溶效应.     

ORC-GAC-Fe0 system for the remediation of trichloroethylene and monochlorobenzene contaminated aquifer: 1. Adsorption and degradation

Activities at a former Chemistry Triangle in Bitterfeld, Germany, resulted in contamination of groundwater with a mixture of tdchloroethylene(TCE) and monochlorobenzene(MCB). The objective of this study was to develop a barrier system,which includes an ORC(oxygen release compounds) and GAC(granular activated carbon) layer for adsorption of MCB and bioregeneration of GAC, a Fe^0 layer for chemical reductive dechlorination of TCE and other chlorinated hydrocarbon in situ. A laboratory-scale column experiment was conducted to evaluate the feasibility of this proposed system. This experiment was performed using a series of continuous flow Teflon columns including an ORC column, a GAC column, and a Fe^0 column. Simulated MCB and TCE contaminated groundwater was pumped upflow into this system at a flow rate of 1.1 ml/min. Results showed that 17%-50% of TCE and 28%-50% of MCB were dissipated in ORC column. Chloride ion, however, was not released, which suggest the dechlorination do not happen in ORC column. In GAC column, the adsorption of contaminants on activated carbon and their induced degradation by adapted microorganisms attached to the carbon surface were observed. Due to competitive exchange processes, TCE can be desorbed by MCB in GAC column and further degraded in iron column. The completely dechlorination rate of TCE was 0.16-0.18 cm^-1, 1-4 magnitudes more than the formation rate of three dichloroethene isomers. Cis-DCE is the main chlorinated product, which can be cumulated in the system, not only depending on the formation rate and its decaying rate, but also the initial concentration of TCE.     

土壤中多环芳烃的稳定碳同位素特征及其对污染源示踪意义

分析了天津市不同功能区土壤中多环芳烃的稳定碳同位素组成特征、土壤中菲、甲基菲、荧葸和芘的δ^13C值范围分别为-29．5‰～-23．2‰、-39．8‰～-23．4‰、-27．2％～-23．6‰和-28．1‰～-22．6‰,不同功能区稳定碳同位素组成的差异反映了PAHs来源的差异．稳定碳同位素组成特征表明,在研究区内,化石燃料燃烧产物的干-湿沉降是土壤PAHs的最主要来源之一,其它可能的来源有污水携带的油污、农作物茎杆及薪柴不完全燃烧产物等．就具体地点而言,土壤PAHs以二元混合输入为主,据此,运用稳定碳同位素组成的二元复合数值模型对不同来源PAHs的相对贡献率进行了估算