Heavy metal pollution in China: Origin,pattern and control

GOAL, SCOPE AND BACKGROUND: Heavy metal is among one of the pollutants, which cause severe threats to humans and the environment in China. The aim of the present review is to make information on the source of heavy metal pollution, distribution of heavy metals in the environment, and measures of pollution control accessible internationally, which are mostly published in Chinese. METHODS: Information from scientific journals, university journals and governmental releases are compiled focusing mainly on Cd, Cu, Pb and Zn. Partly Al, As, Cr, Fe, Hg, Mn and Ni a included also in part as well. RESULTS AND DISCUSSION: In soil, the average contents of Cd, Cu, Pb and Zn are 0.097, 22.6, 26.0 and 74.2 mg/kg, respectively. In the water of the Yangtze River Basin, the concentrations of Cd, Cu, Pb and Zn are 0.080, 7.91, 15.7 and 18.7 microg/L, respectively. In reference to human activities, the heavy metal pollution comes from three sources: industrial emission, wastewater and solid waste. The environment such as soil, water and air were polluted by heavy metals in some cases. The contents of Cd, Cu, Pb and Zn even reach 3.16, 99.3, 84.1 and 147 mg/kg, respectively, in the soils of a wastewater irrigation zone. These contaminants pollute drinking water and food, and threaten human health. Some diseases resulting from pollution of geological and environmental origin, were observed with long-term and non-reversible effects. CONCLUSIONS: In China, the geological background level of heavy metal is low, but with the activity of humans, soil, water, air, and plants are polluted by heavy metals in some cases and even affect human health through the food chain. RECOMMENDATIONS AND OUTLOOK: To remediate and improve environmental quality is a long strategy for the polluted area to keep humans and animals healthy. Phytoremediation would be an effective technique to remediate the heavy metal pollutions.     

Quantifying chlorinated ethene degradation during reductive dechlorination at Kelly AFB using stable carbon isotopes

Stable isotope analysis of chlorinated ethene contaminants was carried out during a bioaugmentation pilot test at Kelly Air Force Base (AFB) in San Antonio Texas. In this pilot test, cis-1,2-dichloroethene (cDCE) was the primary volatile organic compound. A mixed microbial enrichment culture, KB-1, shown in laboratory experiments to reduce chlorinated ethenes to non-toxic ethene, was added to the pilot test area. Following bioaugmentation with KB-1, perchloroethene (PCE), trichloroethene (TCE) and cDCE concentrations declined, while vinyl chloride (VC) concentrations increased and subsequently decreased as ethene became the dominant transformation product. Shifts in carbon isotopic values up to 2.7 per thousand, 6.4 per thousand, 10.9 per thousand and 10.6 per thousand were observed for PCE, TCE, cDCE and VC, respectively, after bioaugmentation, consistent with the effects of biodegradation. While a rising trend of VC concentrations and the first appearance of ethene were indicative of biodegradation by 72 days post-bioaugmentation, the most compelling evidence of biodegradation was the substantial carbon isotope enrichment (2.0 per thousand to 5.0 per thousand) in ?13C(cDCE). Fractionation factors obtained in previous laboratory studies were used with isotope field measurements to estimate first-order cDCE degradation rate constants of 0.12 h(-1) and 0.17 h(-1) at 115 days post-bioaugmentation. These isotope-derived rate constants were clearly lower than, but within a factor of 2-4 of the previously published rate constant calculated in a parallel study at Kelly AFB using chlorinated ethene concentrations. Stable carbon isotopes can provide not only a sensitive means for early identification of the effects of biodegradation, but an additional means to quantify the rates of biodegradation in the field.     

Analysis of anaerobic BTX biodegradation in a subarctic aquifer using isotopes and benzylsuccinates

In situ biodegradation of benzene, toluene, and xylenes in a petroleum hydrocarbon contaminated aquifer near Fairbanks, Alaska was assessed using carbon and hydrogen compound specific isotope analysis (CSIA) of benzene and toluene and analysis of signature metabolites for toluene (benzylsuccinate) and xylenes (methylbenzylsuccinates). Carbon and hydrogen isotope ratios of benzene were between -25.9 per thousand and -26.8 per thousand for delta13C and -119 per thousand and -136 per thousand for delta2H, suggesting that biodegradation of benzene is unlikely at this site. However, biodegradation of both xylenes and toluene were documented in this subarctic aquifer. Biodegradation of xylenes was indicated by the presence of methylbenzylsuccinates with concentrations of 17-50 microg/L in three wells. Anaerobic toluene biodegradation was also indicated by benzylsuccinate concentrations of 10-49 microg/L in the three wells with the highest toluene concentrations (1500-5000 microg/L toluene). Since benzylsuccinate typically accounts for a very small fraction of the toluene present in groundwater (generally <1 mol%), the signature metabolite approach works best at higher toluene concentrations when it is not constrained by detection limits. In wells with lower toluene concentrations (410-640 microg/L), carbon and hydrogen isotopic values were enriched by up to approximately 2 per thousand for delta13C and approximately 70 per thousand for delta2H. This evidence of isotopic fractionation verifies the effects of biodegradation in these low concentration wells where metabolites may already be below detection limits. The combined use of signature metabolite and CSIA data is particularly valuable given the challenge of verifying biodegradation in subarctic environments where degradation rates are typically much slower than in temperate environments.     

优势菌种活细胞对天然水体中Pb^2＋和Cd^2＋的吸附

通过对天然水环境———伊通河中优势菌种活细胞吸附Pb2 、Cd2 的研究发现 :pH对Pb2 、Cd2 吸附的影响是不同的 ,对Pb2 的吸附量在 pH =5 .0～ 7.0时变化不大 ,对Cd2 的吸附量在 pH =6 .0～ 8.0时变化不大 ;温度对活细胞吸附Pb2 、Cd2 影响明显不同 ;活细胞对Pb2 、Cd2 的吸附量随着细菌密度的增加而增大 ,随着渗透压的增大而降低 .图 5表 1参 8     

根际土壤中Cd、Pb形态转化及其植物效应

采用根袋盆栽试验和连续形态分析方法研究根际土壤中Cd、Pb形态转化及其植物效应。结果表明，(1)在低Cd质量分数(≤1mg／kg)污染条件下，根际土壤中cd主要以残渣态存在；在较高cd质量分数(≥5mg／kg)污染条件下，cd主要以交换态和碳酸盐结合态存在，即根际土壤中Cd由残渣态向交换态和碳酸盐结合态转化，Cd活性增强。(2)Pb在根际土壤中主要以有机结合态和铁锰氧化物结合态存在，交换态质量分数很低，并随Pb污染水平的提高，其主要存在形态未改变。(3)土壤中Cd、Pb总质量分数及各形态质量分数(残渣态除外)与小麦根、茎叶中Cd、Pb质量分数呈正相关性，而与鲜质量呈负相关性；当w(Cd)添加量≥5mg／kg时，小麦鲜质量明显下降；当w(Pb)≥500mg／kg时，小麦鲜质量下降。     

Characterisation of Acid Mine Drainage Using a Combination of Hydrometric, Chemical and Isotopic Analyses, Mary Murphy Mine, Colorado

The legacy of mining continues to affect stream water quality throughout the western United States. Traditional remediation, involving treatment of acid mine drainage from portals, is not feasible for the thousands of abandoned mines in the West as it is difficult and expensive. Thus, the development of new methods to address acid mine drainage is critical. The purpose of this study was two fold; to identify and test new tools to identify sources of metal pollution within a mine and to identify low-cost treatment alternatives through the use of these tools. Research was conducted at the Mary Murphy Mine in Colorado, a multiple-level underground mine which produced gold, silver, copper, lead and zinc from 1870 to 1951. Source waters and flowpaths within the mine were characterised using analysis of hydrogen and oxygen isotopes of water (water isotopes) in combination with solute analysis and hydrometric techniques. Hydrometric measurements showed that while discharge from a central level portal increased by a factor of 10 during snowmelt runoff (from 0.7 to 7.2 Ls^–1), Zn concentrations increased by a factor of 9 (from 3,100 to 28320gL^–1). Water isotopes were used as conservative tracers to represent of baseflow and snowmelt inputs in a hydrologic mixing model analysis. The results showed that less than 7% of peak discharge was from snowmelt. Within the mine, approximately 71% of the high-flow Zn loading was caused by a single internal stream characterised by extremely high Zn concentrations (270600gL^–1) and low pH (3.4). Somewhat surprisingly, hydrologic mixing models using water isotopes showed that new water contributed up to 79% of flow in this high-Zn source during the melt season. Diversion of this high-Zn source within the mine resulted in a decrease in Zn concentrations at the portal by 91% to 2,510gL^–1, which is lower than the base-flow Zn concentration. The results suggest that in some mines remediation efforts can be concentrated on specific areas within the mine itself. Using the characterisation techniques demonstrated in this study, problem areas can be identified and contaminated flows diverted or isolated. The results also suggest that it may be possible to dewater contamination areas, greatly reducing costs of remediation.     

石墨炉原子吸收直接测定大气颗粒物中的铅和锰

以少量HNO_3-HF-HClO_4消解粉尘滤膜,石墨炉原子吸收法测定铅和锰,进行了最佳条件选择,采用本法测定粉尘中的铅和锰,其回收率分别为87％～98％和94％～105％,用标准加入法检验结果吻合,方法变异系数分别为铅4.1％,锰3.7％。     

深圳再生水补水河流溶解N2O空间分布和产生机制

为了探究在再生水回补城市河流的条件下河流N₂O的微生物产生过程及其空间变化特征,以深圳市西乡河为研究对象,分析了河水中c（溶解性N₂O）、c（NH₄+-N）、c（NO₃--N）、δ15Nbulk-N₂O、δ18O-N₂O、同位素异位体位嗜值（site preference,SP）及其他环境因子,并基于端元混合模型和同位素分馏模型定量计算硝化和反硝化作用对河水中N₂O贡献百分比.结果表明:①随着流速降低,西乡河河水从上游的好氧环境逐渐发育成中下游的厌氧环境.②再生水进入西乡河后河水c（溶解性N₂O）从1.36 μmol/L沿程降至0.19 μmol/L;相关性分析表明,影响c（溶解性N₂O）的主要因素为ρ（DO）（R2=0.800,P < 0.01）和c（CH₄）（R2=-0.736,P < 0.01）.③硝化和反硝化作用对河水中N₂O贡献率分别为14.36%~80.53%和19.47%~85.64%;N₂O的来源在好氧河段中以硝化作用为主,在厌氧河段则以反硝化作用为主;N₂O还原成N₂的比例与ρ（DO）具有显著负相关关系（R2=-0.782,P < 0.01）.研究显示,再生水回补城市河流引入了较高质量浓度的N₂O和NO₃--N,而河道的厌氧环境促进河水中N₂O还原成N₂,下游河流成为N₂O的汇.      

纳米金增强SPR铅离子检测器构建

为满足采用简便方法检测痕量铅离子（Pb²⁺）的需求,构建了新型的超灵敏、高特异性表面等离子体共振（SPR）生物传感器,用于水中Pb²⁺检测.以硫醇化GR-5脱氧核酶（DNAzyme）为Pb²⁺特异性识别探针,并自组装到芯片金膜表面,底物官能化的纳米金（S-AuNPs）用于信号增强,并与DNAzyme杂交形成传感薄膜.AuNPs不仅增加了质量变化,其局部表面等离子体共振（LSPR）与芯片表面传播SPR的耦合作用也可产生信号放大的效果.在Pb²⁺离子存在下,DNAzyme催化底物裂解,导致AuNPs的去除并引起SPR信号显著变化.通过X射线光电子能谱和扫描电镜对芯片表面的表征分析验证了传感薄膜构建过程和检测原理.Pb²⁺检测实验结果表明,1 μmol/L DNAzyme修饰的传感器检测效果最好,检测限为80pmol/L,并在100nmol/L范围内与Pb²⁺浓度的对数呈线性关系（R²=0.992）.该传感器对10倍浓度的其他金属离子无明显响应,说明其具有良好的Pb²⁺特异性;检测自来水和地下水中Pb²⁺的结果与ICP-MS方法有良好的一致性.研究建立的Pb²⁺检测方法具有高灵敏度和特异性,且操作简便,具有现场检测的应用前景.     

三峡水库蓄水期支流水体营养盐来源估算

通过对蓄水前后三峡水库库首支流香溪河沉积物-上覆水中的氢氧同位素和氮磷营养盐的测定,分析了蓄水前后沉积物-上覆水氢氧同位素和氮磷营养盐的分布特征,并利用二元线性混合模型计算了长江干流（CJ River）和古夫源头（GFYT）的贡献率.结果表明,整个蓄水期沉积物以源的形式向上覆水体释放NH₄⁺-N、DTP、PO₄^3--P,以汇的形式吸收上覆水体中的NO₃^--N.利用营养盐贡献率公式进一步分析得到,蓄水前沉积物-上覆水中氮营养盐主要来源于CJ干流,其中以DTN和NO₃^--N最为显著,蓄水后GFYT的贡献率明显上升,其中3号和4号采样点最为明显,其中DTP在蓄水前后几乎均以GFYT为主要来源,PO₄^3--P在蓄水前则以CJ干流为主要来源,蓄水后以GFYT为主要来源.说明尽管蓄水期库湾水体在较大程度上受干流倒灌影响的支配,但对于沉积物-上覆水而言受GFYT的影响更为显著.