生物表面活性剂及其在重金属污染生态修复中的应用

介绍了不同污染体系中重金属的存在形态,生物表面活性剂的种类、优点及生产方法。综述了几种典型的生物表面活性剂(鼠李糖脂、槐糖脂s、urfactin和皂角苷)及其在重金属污染生态修复中的应用。分析了生物表面活性剂去除重金属的作用机制,阐述了生物表面活性剂修复重金属污染的研究方向。     

Chromosome damage in individuals exposed to heavy metals†

Testing the mutagenic activity of environmental pollutants has become an important area of modern environmental science and prophylactic medicine. The most suitable method for short‐term mutagenicity testing on man, at present, are chromosome studies on somatic cells of exposed individuals. Mutation types analyzed by such studies are of high practical relevance as indicator system of genetic damage induced in man under in vivo conditions. A rather large series of such studies has been dedicated to the action of heavy metals on individuals contacted with these metals under therapeutic, ecological or occupational conditions or by intoxication. Lead, cadmium, chromium, nickel, mercury, zinc and other metals as well as their compounds have been under study. Analyses of that kind, of course, are hampered by difficulties with the distinct estimation of the actual load as well as unclear conditions of exposition, e.g. simultaneous exposition to different metals.

Results obtained till now arouse some suspicion of a direct or indirect mutagenic activity in man by certain chromium and platinum compounds, arsenic, mercury, and combinations of lead with other heavy metals (cadmium, zinc, arsenic, antimony, etc.). Life style, above all smoking habits, well may act comutagenic. In most cases, however, mutagenic activity of metals and metal compounds apparently is clearly superposed by their toxic activity. In specific cases, chromosome studies also may contribute to discover sources of ecological exposition and to monitor occupational load by heavy metals.     

Sulfur mediated heavy metal biogeochemical cycles in coastal wetlands: From sediments,rhizosphere to vegetation

• In sediments, the transformation of sulfides may lead to the release of heavy metals. • In the rhizosphere, sulfur regulates the uptake of heavy metals by plants. • In plants, sulfur mediates a series of heavy metal tolerance mechanisms. • Explore interactions between sulfur and heavy metals on different scales is needed. The interactions and mechanisms between sulfur and heavy metals are a growing focus of biogeochemical studies in coastal wetlands. These issues underline the fate of heavy metals bound in sediments or released into the system through sediments. Despite the fact that numerous published studies have suggested sulfur has a significant impact on the bioavailability of heavy metals accumulated in coastal wetlands, to date, no review article has systematically summarized those studies, particularly from the perspective of the three major components of wetland ecosystems (sediments, rhizosphere, and vegetation). The present review summarizes the studies published in the past four decades and highlights the major achievements in this field. Research and studies available thus far indicate that under anaerobic conditions, most of the potentially bioavailable heavy metals in coastal wetland sediments are fixed as precipitates, such as metal sulfides. However, fluctuations in physicochemical conditions may affect sulfur cycling, and hence, directly or indirectly lead to the conversion and migration of heavy metals. In the rhizosphere, root activities and microbes together affect the speciation and transformation of sulfur which in turn mediate the migration of heavy metals. As for plant tissues, tolerance to heavy metals is enhanced by sulfur-containing compounds via promoting a series of chelation and detoxification processes. Finally, to further understand the interactions between sulfur and heavy metals in coastal wetlands, some major future research directions are proposed.     

Co-pyrolysis of sludge and kaolin/zeolite in a rotary kiln: Analysis of stabilizing heavy metals

• Adding kaolin/zeolite promotes the formation of stable heavy metals. • The potential ecological risk index of co-pyrolysis biochar is extremely low. • Increasing the pyrolysis temperature reduces the leaching toxicity of heavy metals. • The toxicity of biochar reduces with the increasing content of stable heavy metals. Pyrolysis is a promising technique used for treating of sewage sludge. However, the application of pyrolysis products is limited due to the presence of heavy metals. In this study, sewage sludge mixed with kaolin/zeolite was pyrolyzed in a rotary kiln, aiming to improve the immobilization of heavy metals in pyrolytic carbon. The total concentrations, speciation distributions, leaching toxicities, and potential ecological risk indices of heavy metals in pyrolysis biochar were explored to examine the effects of kaolin/zeolite and pyrolytic temperature on immobilizing heavy metals. Further, mineral composition and surface morphology of biochar were characterized by X-ray diffraction and scanning electron microscopy to reveal the potential mechanism of immobilizing heavy metals. Increasing pyrolysis temperature facilitated the stabilization of heavy metals in pyrolysis biochar. The proportions of stable heavy metals in biochar obtained at 650℃ were 54.50% (Cu), 29.73% (Zn), 79.29% (Cd), 68.17% (Pb) and 86.70% (Cr). Compared to sewage sludge, the potential contamination risk index of pyrolysis biochar obtained at 650℃ was reduced to 17.01, indicating a low ecological risk. The addition of 7% kaolin/zeolite further reduced the risk index of co-pyrolysis biochar prepared at 650℃ to 10.86/15.28. The characterization of biochar revealed that increase in the pyrolysis temperature and incorporation of additives are conducive to the formation of stable heavy metal-inorganics. This study demonstrates that the formation of stable mineral compounds containing heavy metals is the key to stabilizing heavy metals in pyrolysis biochar.     

矿区周围土壤中重金属危害性评估研究

分别用总量法和连续萃取法对广东大宝山矿周围土壤、植物和沉积物中重金属的总量和化学形态进行了详细分析。结果发现，矿山废水流入的横石河沉积物中Pb、Zn、Cu和Cd的质量分数分别为1841．02、2326．28、1522．61和10.33mg／kg；经此河水灌溉的稻田中重金属(Cu、Cd、Pb和Zn)的质量分数也远远超出了土壤环境二级标准值，其中Cu、Cd超标倍数分别为14．01和4．17倍。结果还表明，生长在矿区周围的植物也受到不同程度重金属的污染且不同植物吸收和积累重金属的能力相差很大。用Tessier连续法对土壤中重金属进行萃取发现，虽然重金属主要存在于残余态中，但在Fe-Mn氧化态、有机结合态中的质量分数也很高．说明这些土壤确实受到了有毒有害重金属元素的严重污染。     

Adsorption von Blei und Cadmium an Tonen

Clay minerals as major components of soils can adsorb heavy metals. The release of toxic heavy metals such as lead and cadmium into soil presents a serious problem. To evaluate the behaviour of these elements in the environment, it is necessary to develop methods which allow precise analysis of heavy metals. This article compares and optimizes AAS methods for lead and cadmium.     

Zn,Cu和Ni污染土壤中重金属的化学固定

利用化学固定剂处理被污泥中Zn,Cu和Ni污染的土壤,研究不同化学药剂对重金属离子的固定技术.结果表明,石灰、硫化物和硅酸盐对Zn都有较好的稳定效果,硫化物对Cu的稳定效果较好,硅酸盐和石灰对Ni的稳定效果较好;对于被Zn,Cu和Ni污染的土壤,混合药剂对重金属污染物的固定效果最佳.研究表明通过调解系统的pH和生成稳定化合物形态使土壤中Zn,Cu和Ni得以固定.通过硫化物 石灰化学固定处理,固定前后Zn,Cu和Ni的不稳定形态含量分别减少了69%,56%和59%.     

利用藻红外测试技术研究多种重金属溶液对滇池铜绿微囊藻的毒性作用

为考察多种重金属同时存在的混合溶液对藻类的生物毒性,选择Cr(Ⅲ)、Pb(Ⅱ)、Hg(Ⅱ)、Cd(Ⅱ)、Mn(Ⅱ)5种重金属,以按照国家饮用水卫生标准限值浓度配制的单一重金属溶液和多种重金属混合溶液为受试样品,并利用本实验室开发的藻红外测试技术,评价了低浓度下单一重金属溶液和多种重金属共存溶液对藻的生物毒性。实验结果显示:按照饮用水标准限值配制的5种单一重金属溶液均未观察到对藻有生物毒性,但在多种重金属共存的27个不同组合的混合溶液中,有73.1%的样品表现出明显的生物毒性;藻响应出现率与混合溶液中重金属的总浓度呈正相关关系(r=0.8942)。当多种重金属以二元至五元混合时,藻响应出现率分别为50%、80%、100%、100%,表明随着重金属组分的增加,混合溶液的毒性作用越来越显著。当不同混合溶液的重金属总浓度大于0.11 mg·L-1时,平均累积藻响应占比显著上升到93%,表明重金属混合溶液中藻的毒性与总浓度之间存在剂量响应关系。采用平均藻响应出现率分析,结果显示混合溶液中不同重金属的相对影响顺序为:Cr(Ⅲ)87.5%>Pb(Ⅱ)和Hg(Ⅱ)58.3%>Cd(Ⅱ)和Mn(Ⅱ)54.3%,表明Cr(Ⅲ)表现出的藻毒性远高出其他重金属。现行的水质标准通常采用单一指标和限值,本研究结果表明采用单一指标不能有效规避多种污染物共存体系的环境风险。     

羟基磷灰石对沉积物中重金属释放特性的影响

以羟基磷灰石掺杂前后模拟重金属污染沉积物为研究对象,利用混匀释放实验及化学连续萃取法分析沉积物中重金属的释放特征及形态分布特性,考察了羟基磷灰石对重会属污染沉积物中Cu、zn、Pb、Cd稳定性的影响.结果表明不同来源模拟污染沉积物中松花江沉积物中的重金属最易重新释放,而伊通河沉积物中的重金属释放量最小;同时伊通河沉积物中残渣态重金属的比例较其它沉积物高很多,而可交换态和碳酸盐结合态的重金属比例较其它沉积物低很多,说明同时进入沉积物中的重金属,伊通河沉积物中的重金属相对稳定一些.羟基磷灰石的掺杂不同程度降低了沉积物中重金属的释放能力,促使沉积物中的重金属由较不稳定结合态向较稳定结合态转化,减小了沉积物中重金属的生物可利用性,增强了重金属的稳定性.     

万家寨引黄工程水源地水质调查分析

利用气相色谱法分别在黄河沙汾河水库水中检出296和241个色谱峰；利用色质联用技术分别在黄河水和汾河水库水中检出74个和95个质谱峰，并定性56种和78种化合物。采用化学物质的潜在危害指数法，筛选出10种毒性较大的化合物，用气相以谱外标法给予了准确定量。结果表明，邻苯二甲酸酯类、苯系物和多环芳烃是黄河水和汾河水库水中主要的有机污染物，其浓度大小的排列顺序为：邻苯二甲酸酯类＞苯系物＞多环芳烃。     

长三角和珠三角农业土壤对Pb、Cu、Cd的吸附解吸特性

研究了长江三角州和珠江三角州10种代表性农业土壤对重金属Pb、Cu和Cd的吸附与解吸特性。结果表明:大多数土壤对重金属有较强吸附能力,土壤性质对重金属吸附与解吸行为有很大影响。其中,pH值是影响土壤对重金属吸附与解吸的最重要因素,土壤重金属吸附量随pH值增加而增加。土壤pH值和有机质或粘粒含量较高的土壤(如乌栅土、青紫泥田、黄斑田),其对重金属吸附能力高于pH值和有机质或粘粒含量较低的土壤(如黄筋泥、粉泥田)。重金属解吸量随重金属吸附量和土壤重金属饱和度增加呈指数增加趋势;土壤对重金属的吸附能力从强至弱依次为Pb、Cu、Cd;当3种重金属共存时,重金属之间竞争能力强弱顺序与吸附能力顺序相同。重金属之间竞争作用随土壤酸度和重金属污染程度的增加而增强。     

城市地表颗粒物重金属分布特征及其影响因素分析

城市地表颗粒物作为重金属的重要载体,严重危害城市人群和水体,已成为城市环境的重要研究对象。阐述了对地表颗粒物重金属的空间、粒径、赋存形态等分布特征及其影响因素进行系统分析的意义。通过对国内不同城市不同功能区的重金属（主要为：Zn、Cu、Cd、Pb）数据进行对比分析,各功能区重金属污染情况为：Cu、Pb：工业区〉商业区〉交通区〉居民区〉休闲区;Zn：工业区〉交通区〉商业区〉居民区〉休闲区;Cd：交通区〉工业区〉商业区〉居民区〉休闲区,同时各功能区中Zn、Pb含量波动性较大。整体上国内工业区、交通区和商业区地表颗粒物重金属污染严重。与我国的土壤重金属背景值相比,4种金属中Cd污染程度最为严重。探讨了与国外部分城市地表颗粒重金属污染特征之间的差异,指出国内城市重金属含量均值整体上低于欧美发达城市,而国内一线城市重金属含量明显偏高。系统分析了颗粒物重金属的粒级效应,赋存形态以及生物有效性。综述了城市交通活动（主要为交通流量、车辆行驶速度、变速频率、车辆类型、道路特征等）、降雨冲刷事件、雨前干燥期、大气风力作用、和其他因素对地表颗粒物重金属分布特征的影响。某种程度上,道路车辆的行驶速度和变速对颗粒物重金属累积的影响作用大于交通流量。不同降雨事件和雨前干燥期对重金属分布特征影响的研究结论不一,但地表颗粒对大气PM2.5重金属贡献较大。今后应在以下方面进一步加强对城市地表颗粒物重金属的研究：建立颗粒物粒径划分标准;加强重金属在降雨冲刷过程变化规律的分析;探讨地表颗粒物与大气颗粒物重金属转换关系;还应开展中小型城市,城乡结合部（城中村）地表颗粒物重金属污染特性研究。     

What are heavy metals? Long-standing controversy over the scientific use of the term ‘heavy metals’ – proposal of a comprehensive definition

The term ‘heavy metals’ is commonly used in the environmental literature to refer to metals and metalloids associated with environmental pollution, toxicity and adverse effects on biota. The term has been diversely defined, mostly in terms of density, relative atomic mass and atomic number. This diversity of definitions has raised questions about the nomenclature of these elements. The inclusion of the metalloid As and the nonmetal Se with heavy metals is also an important issue. Some people have called the term as meaningless, imprecise and poorly defined and have suggested abandoning the use of the term. The term itself may not be problematic but the careless and inconsistent use of terminology has led to a confusion about the meaning of the term. The use of the term may be continued but it should be defined in a more comprehensive and scientific way. Here, a more comprehensive definition of the term ‘heavy metals’ is suggested as ‘naturally occurring metals having atomic number (Z) greater than 20 and an elemental density greater than 5 g cm^?3.’ A screening of the Periodic Table according to this definition yields 51 elements to be called ‘heavy metals.’ As and Se are excluded from heavy metals.     

Heavy metals fraction and ecological risk evaluation in municipal solid waste gasification slag non-burnt bricks

The heavy metals in non-burnt bricks made from municipal solid waste (MSW) gasification slags with a modified European Bureau Community of Reference procedure were studied. Heavy metals were present in the form of oxidizable and residual fractions, which were stable and not easy to dissolve. The preparation process of non-burnt bricks displayed prominent solidification effect for some heavy metals in the gasification slag. The solidified rate for metals, such as As, Cd, Cr, Ni, and Zn reached 89.82%, 79.57%, 73.64%, 66.73%, and 88.05%, respectively. Moreover, the leaching concentrations of eight heavy metals were all below 8 mg/kg. On the basis of these observations, the risk of exposure to heavy metals in non-burnt bricks was evaluated using the solidification formula and the leaching concentration of heavy metals combined with the assessments of the Hakanson potential ecological risk and pollution ratio of secondary phase and primary phase. Results showed that the preparation of MSW gasification slag non-burnt bricks was not harmful to the environment, but attention is warranted for possible migration of heavy metal cadmium (Cd) in the long term, which may result in an impact on the ecological environment.     

The uptake and translocation of selected elements by cole (Brassica) grown using oasis soils in pot experiments

Pot experiments were conducted on cole (Brassica) grown in soils jointly treated with traces of two heavy metals cadmium (Cd) and zinc (Zn). As the concentration of heavy metals in the soil increased, the uptake of these metals by the plants rose. However, the ratio of heavy metal concentration in soil to uptake by plants increased at a slower rate. Bioavailability of heavy metals considered between the roots and soil using non-linear regressions was shown to be statistically significant. Similarly, the bioavailability of these two heavy metals between leaves and roots using a linear regression was also statistically significant. The bioconcentration factors (BCFs) for Cd and Zn were 0.282 and 4.289, respectively. Significant variation of BCF with the heavy metal bioavailability in soil was noted from non-linear models. The transfer factors (TFs) were 4.49 for Cd and 1.39 for Zn. The Zn concentration in leaves under all treatments did not exceed threshold set standards, but Cd levels exceeded these standards when the concentration of Cd in the soil was more than 1.92 mg kg^?1 dry weight (dw). Data indicate that cole (Brassica) is not a suitable crop for oasis soils because of plant contamination with heavy metals, especially Cd.     

青岛城市公园灰尘重金属的形态分布及健康风险评价

对青岛市南、市北、四方和李沧四区的公园灰尘样品的重金属全量和形态分布进行分析,并对公园灰尘重金属的污染状况进行了健康风险评价。结果表明：青岛城市公园土壤和灰尘均在不同程度上受到Cu、Zn、Pb、cd的污染,李沧区4种重金属含量均在四区最高。市南区公园灰尘中的Cu、Pb、cd的含量最低,市北区的Zn含量最低;Cu主要以有...     

Pollution distribution of heavy metals in surface soil at an informal electronic-waste recycling site

We studied distribution of heavy metals [lead (Pb), copper (Cu) and zinc (Zn)] in surface soil at an electronic-waste (e-waste) recycling workshop near Metro Manila in the Philippines to evaluate the pollution size (spot size, small area or the entire workshop), as well as to assess heavy metal transport into the surrounding soil environment. On-site length-of-stride-scale (~70 cm) measurements were performed at each surface soil point using field-portable X-ray fluorescence (FP-XRF). The surface soil at the e-waste recycling workshop was polluted with Cu, Zn and Pb, which were distributed discretely in surface soil. The site was divided into five areas based on the distance from an entrance gate (y-axis) of the e-waste recycling workshop. The three heavy metals showed similar concentration gradients in the y-axis direction. Zn, Pb and Cu concentrations were estimated to decrease to half of their maximum concentrations at ~3, 7 and 7 m from the pollution spot, respectively, inside the informal e-waste recycling workshop. Distance from an entrance may play an important role in heavy metal transport at the soil surface. Using on-site FP-XRF, we evaluated the metal ratio to characterise pollution features of the solid surface. Variability analysis of heavy metals revealed vanishing surficial autocorrelation over metre ranges. Also, the possibility of concentration prediction at unmeasured points using geostatistical kriging was evaluated, and heavy metals had a relative “small” pollution scales and remained inside the original workshop compared with toxic organohalogen compounds. Thus, exposure to heavy metals may directly influence the health of e-waste workers at the original site rather than the surrounding habitat and environmental media.     

Zur Problematik der Anwendung von Hintergrundwerten beim Vollzug des Bodenschutzrechts

The knowledge about background levels of heavy metals in soils is essential for the use of the precautionary values for heavy metals as provided by the German Soil-Protection-Act. In the northeast of Bavaria the 90th percentiles in the back-ground levels of heavy metals in the soil exceed the precautionary values in many cases. Background levels were determined separately for soils of different parent materials of rocks, soil horizons and land use (agricultural or forest soils), with the parent material of rock having the strongest influence on the content of heavy metals in different soils. Precautionary values are highly exceeded by chrome and nickel in basic and ultrabasic rocks. High variability of heavy metal contents was found even in soils of the same parent material (C-horizons), which is due to the natural geochemical variability of rocks and the mixing of different parent materials during the Pleistocene. For an effective use of the German Soil-Protection-Order, areas must be defined where the probability is high that the 90th percentiles of the background levels of heavy metals exceed the precautionary values. It has to be determined, how the risk of mobilisation of heavy metals can be estimated within these areas and what has to be done if heavy metal contents in soils exceed not only the precautionary values but also the background levels.     

日本虎斑猛水蚤的重金属急性毒性及其作为标准测试生物的潜在意义

以静态实验法研究重金属Cu、Cd、Pb和Zn单独以及两两联合对日本虎斑猛水蚤(Tigriopus japonicus)的急性毒性效应,并分析其是否适宜作为我国海水重金属毒性测试的标准生物.结果显示,单独作用下,cu、Cd、Pb和Zn对受试生物的24 hLC50分别为0.26、0.14、0.40和0.65 mg·L-1,...     

衡阳市菜园使用的商品有机肥和有机废弃物中重金属含量状况调查

对衡阳市菜园使用的12个有机肥样品中的Zn、Cu、Cr、Pb、Cd、Ni、Hg和As的指标进行检测,样品中重金属总As、总Hg、总Pb、总Cd、总Cr等的含量按照中国NY525—2012有机肥料重金属限量指标,总Ni、总Cu、总Zn重金属参照德国腐熟堆肥中重金属限量标准进行分析,结果表明,除牛粪、菜籽饼肥外,有9个样品均发现有超限量值的重金属成分,超标样品数占总样品数的75%,超标的重金属成分以Cu和Zn较为普遍,分别占样品总数的75%和41.7%.而在超标程度方面,有两个样品的中的Cu和两个样品中的Cr均为严重超标.这些肥料使用不当,对菜园土和蔬菜品质产生不良影响,应给予关注.