土壤中有效态重金属的化学试剂提取法研究进展

土壤重金属污染是国内外关注的热点问题，针对采用全量重金属评价土壤污染存在的问题，本文综述了近年来土壤有效态重金属的化学提取方法研究进展，比较分析了各种单一提取法和影响土壤重金属提取率的因素。在此基础上，评价了各类提取方法的特点及其在应用上的优势和局限，指出了筛选通用提取剂的原则和依据。结合实验初步提出以去离子水作为通用提取剂的可行性及尚需研究解决的问题。     

鞍山市郊蔬菜基地土壤重金属污染状况调查

通过对鞍山市郊蔬菜基地土壤中重金属含量的分析表明,所采集的菜地土壤中Cd的超标率为44．4％,Cu、Pb、Cr、As、Hg无超标现象。大田菜菜地土壤中As、Hg、Pb含量比大棚菜菜地略高,Hg、Pb、Cu、Cr、Cd含量超背景值。     

大冶龙角山地区土壤中重金属污染现状与评价

为了研究大冶龙角山地区尾砂坝内尾砂排放对下游耕地土壤中重金属含量的影响,本文对尾矿坝及河流两岸的耕地进行布点采样,通过等离子体发射光谱仪（ICP—OES）测定土壤中A5、Cd、Cr、Cu、Pb、Zn6种重金属的含量,并用污染指数法进行分析评价。旨在调查研究的基础上,使人们认识当地重金属污染的严重性,加大环境保护力度。     

Leaching Characteristics of Arsenic and Heavy Metals in Urban Roadside Soils Using a Simple Bioavailability Extraction Test

Regular ingestion of soils could pose a potential health threat due to long-term toxic element exposure. In order to estimate the human bioavailability quotients for As and heavy metals, 12 urban roadside soil samples were collected and analyzed for As, Pb, Cu, Zn, Ni, Co, and Cr using Simple Bioavailability Extraction Test (SBET). The quantities of As, Pb, Cu, Zn, Ni, Co, and Cr leached from soils within the simulated human stomach for 1 h indicated, on average, 27.3, 71.7, 40.4, 59.3, 17.7, 27.2 and 5.6% bioavailability, respectively. Significant positive correlations were observed between the amounts leached using SBET and the total amounts dissolved with HNO₃-HCl-HF acid mixtures. Stepwise multiple regression analysis indicated that the amounts leached with SBET for As, Pb, Zn, Ni, and Co were not related to any of the physic-chemical parameters measured (i.e., soil texture, pH, total organic matter). These results may be valuable for providing input data for risk assessment at sites subject to anthropogenic soil contamination.     

Leaching Characteristics of Heavy Metals and As from Two Urban Roadside Soils

The leaching tests, including the Toxicity Characteristic Leaching Procedure (TCLP), EDTA extraction and BCR sequential extractions before and after EDTA treatments, were performed on two specific soils to elucidate heavy metal-associated mineral fractions and general leachability. The TCLP illustrated the low leachability of heavy metals in soils from two sites. EDTA is a strong chelator and therefore had higher extraction efficiency compared to that of TCLP. The lower extraction percentages by EDTA for As and Sb were found compared to the other heavy metals derived from anthropogenic sources. Sequential extractions showed that the importance of acid-extractable, organically-bound and Fe–Mn oxide fractions was identified for anthropogenic heavy metals with the exception of As and Ni while the importance of residual fraction was identified for endogenous metals. Changes in sequential fractions of heavy metals after leaching with EDTA are very complex and it is difficult to generalize on which fraction was more mobile than the others. These combined results are helpful in elucidating the association of heavy metals to soil fractions and the mobility characteristics of heavy metals under certain environmental conditions.     

Metal Fractionation Studies in Surfacial and Core Sediments in the Achankovil River Basin in India

The Fractionation of Fe, Zn, Cu, Pb, Mn and Cd in the sediments of the Achankovil River, Western Ghats, India using a sequential extraction method was carried out to understand the metal availability in the basin for biotic and abiotic activities. Spatial distribution of heavy metals has been studied. Sediment grain size has significant control over the heavy metal distribution. The fluctuations in their concentration partly depend upon the lithology of the river basin and partly the anthropogenic activities. The sediments are dominated by sand and are moderately to strongly positively skewed and are very leptokurtotic in nature. The quartzite and feldspars are abundant minerals along with significant amount of mica with low clay content. The core sediments show increasing trend of heavy metal concentration with depth due to the recent addition of anthropogenic sources and post-diagenic activities. Significant amount of Cd (18%) was found in carbonate fraction, which may pose environmental problems due to its toxic nature. Small concentrations of metals, except Cd and Cu, are in exchangeable fraction, which indicate low bio-availability. Enrichment Factor (EF) for individual metals shows the contribution from terrregious and in part from anthropogenic sources. Selective Sequential Extraction (SSE) study shows the variation in specific metal distribution pattern, their distribution in different phases and their bio-availability. Maximum amount of the metals were bound to the non-residual fractions (mainly Fe-oxides). Overall, bio-availability of these micronutrients from sediments seems to be very less. Non-residual phase is the most important phase for majority of heavy metals studied. Among the non-residual fraction, maximum amount of the heavy metals bound to Fe-oxides. The study high lights the need for in-depth study of heavy metals distribution and fractionation in the smaller river basins to get precise information on the behavior and transport of heavy metals in the fluvial environment and their contribution to the world ocean.     

Heavy Metals Fractionation in Ganga River Sediments, India

The Ganga River is the largest river in India which, originates in the Himalayas and along with the Brahmaputra River, another Himalayan river, transports enormous amounts of sediments from the Indian sub-continent to the Bay of Bengal. Because of the important role of river sediments in the biogeochemical cycling of elements, the Ganga river sediments, collected from its origin to the down stretches, were studied in the present context, to assess the heavy metals associated with different chemical fractions of sediments. The fractionation of metals were studied in the sediments using SM&T protocol for the extraction of heavy metals and geo-accumulation index (GAI) (Muller, Schwermetalle in den sedimenten des rheins – Veranderungen seit. Umschau, 79, 778–783, 1979) and Metal Enrichment Factor (MEF) in different fractions were calculated. As with many river systems, residual fractions constitute more than 60% of total metals, except Zn, Cu and Cr. However, the reducible and organic and sulfide components also act as major sinks for metals in the down stretches of the river, which is supported by the high GAI and MEF values. The GAI values range between 4 and 5 and MEF exceed more than 20 for almost all the locations in the downstream locations indicating to the addition of metals through urban and industrial effluents, as compared to the low metals concentrations with less GAI and MEF in the pristine river sediments from the rivers in Himalayas.     

Ecotoxicological Assessment of the Impact of Residual Heavy Metals on Soil Nematodes in the Guadiamar River Basin (Southern Spain)

On 25 April 1998, as a consequence of the breaking of a dam containing the tailings of a pyrite mine, a land strip of approximately 43 km in length was covered with a layer of black sludge, containing high levels of heavy metals, along the Guadiamar River Basin (southern Spain). In this investigation we carried out an ecotoxicological assessment (field and laboratory studies) of the impact of residual heavy metals (Cu, Pb, Zn, Ni) on soil nematodes in the impacted riparian zone, two years after the huge mine spillage. Concentrations of residual heavy metals were significantly (P<0.05) higher at the impacted sampling sectors (S-2, S-3, S-4, S-5) than at the unpolluted (reference) sampling sector (S-1). Nickel however exhibited the lowest increases at the impacted sectors. As a consequence, correlation coefficients between concentrations of heavy metals and values of ecological indices were not significant for Ni. In contrast, copper, lead and zinc exhibited significant (P<0.05) negative correlation coefficients with ecological indices, particularly with diversity indices (including the~number of taxa). In addition, the toxicity of Cu and Pb to nematode test species (Aphelenchus avenae and Cephalobus persegnis) during short-term toxicity bioassays was much higher than the toxicity of Zn and Ni. We conclude that residual heavy metals were still influencing adversely the community of soil nematodes in the impacted riparian zone of the Guadiamar River Basin. Cu, Pb and, to a lesser extent, Zn would be major responsible for the observed impact.     

上海、乌鲁木齐与昌吉三市城市土壤重金属富集特征比较研究

选择上海、乌鲁木齐、昌吉3个城市,通过对其城市土壤重金属含量水平、分布特征及活性的比较研究,发现城市土壤中Cr、Cu、Pb、Zn含量均远高于背景值,但Mn、Fe含量与背景值差别不大;上海市Cr、Pb、Zn含量最高,而昌吉市Cu含量最高,城市规模的大小并不能直接反映土壤重金属含量的高低,工业污染物排放量、交通量、城市规模大小、城市发展历史、工业区位置及变迁、土壤背景值等因素均会影响土壤重金属含量水平。除Mn、Fe无明显的功能区分布差异外,各城市重金属功能区分布规律并不相同,城市污染来源的不同可能是主要原因。重金属活性并未与其含量分布规律完全一致,上海土壤重金属活性大于乌鲁木齐、昌吉,上海土壤pH值小于乌鲁木齐、昌吉可能是主要影响因素,但也存在上海土壤中个别重金属活性小于乌鲁木齐、昌吉的现象,污染物来源存在差异等可能是主要原因。也可能较强,反之亦然。     

奎屯市北郊蔬菜污灌区土壤重金属污染调查

通过对奎屯市北郊污灌区菜地土壤中重金属含量的分析表明,所调查的污灌菜地土壤中铅、锌、镉、砷和汞均未超标,部分地块铜超标,说明多年来因工业废水的浇灌,已造成铜对局部区域土壤的污染。     

乌鲁木齐市米东污灌区农田土壤重金属污染评价

对米东污灌区农田土壤重金属含量进行监测分析,利用不同的评价方法和标准对土壤重金属的环境质量进行评价。结果表明：米东污灌区农田土壤重金属含量分别为Cd（0.12±0.06）mg/kg,Cu（40.43±5.30）mg/kg,Zn（78.38±11.04）mg/kg,Pb（11.66±11.79）mg/kg,Ni（20.24±8.05）mg/kg,Cr（75.81±8.05）mg/kg。以国家土壤环境质量标准（二级）为标准评价,各元素的污染指数排序为Cu〉Ni〉Cr〉Zn〉Cd〉Pb,综合污染指数为0.337,污染程度为安全。以食用农产品产地土壤环境质量要求为标准评价,各元素的污染指数排序为Cu〉Ni〉Cr〉Zn〉Cd〉Pb,综合污染指数为0.343,污染程度为安全。表明米东污灌区农田土壤重金属含量尚能达到食用农产品产地土壤环境质量要求。Pb、Cu、Zn的平均含量超过乌鲁木齐市土壤背景值,这说明污灌区土壤重金属Pb、Cu、Zn近年来已有所累积,存在一定的污染风险。     

Heavy Metals and Chlorinated Hydrocarbon Concentrations in the Red Fox in Relation to Some Biological Paramaters

Heavy metals and organochlorine contamination were analyzed in tissues of red foxes (Vulpes vulpes) from the Province of Siena (central Italy). Mercury (Hg), cadmium (Cd) and lead (Pb) concentrations were assessed in liver tissues and the data were analyzed for differences in relation to sex and age. Overall Hg, Cd and Pb mean values were 0.16, 0.62 and 0.64 g g^_1 d.w., respectively. HCB, DDT and PCB concentrations were assayed in fatty tissues and muscle. The highest levels of those pollutants were found in muscle (0.47, 1.16 and 20.2 g g^_1 lipid basis of HCB, DDTs and PCBs respectively), rather than in fat (0.23, 0.49 and 7.2 g g^_1 l.b. of HCB, DDTs and PCBs respectively). Pollutant accumulation was analyzed in relation to sex, age and sexual maturity of females.     

Environmental Monitoring of Heavy Metals in Bulgarian Black Sea Green Algae

Fe, Mn, Cu, Pb and Cd concentration distribution in six green macroalgae species from the Bulgarian Black Sea coast were determined. The measurement of these metals was carried out during six seasons from 1996 to 2002 using atomic absorption spectrometry (AAS). Samples were collected from eight different sites–Shabla, Kaliakra, Tuzlata, Ravda, Ahtopol and Sinemoretz. The obtained heavy metal (HM) data (mean values g/g) for all algae are: 650 ± 100 for Fe, 184 ± 15 for Mn, 5.6 ± 0.5 for Cu, 3.3 ± 0.3 for Pb and 1.1 ± 0.2 for Cd. The obtained HM contents indicate that different species demonstrate various degree of metal accumulation and the obtained higher values in the northern sector of the studied zone can be attributed to the discharge influence of the big rivers, entering the Black Sea–Danube, Dnyepr, Dnester and local pollutant emissions. All data show that there is no serious contamination in green macroalgae with heavy and toxic metals along the whole Bulgarian Black Sea coast.     

青岛市饮用水源地重金属污染物健康风险初步评价

对青岛市某饮用水源地饮用水的钼、铍、硼、锑、钡、钒、钛、铊、砷、镉、铅、汞、镍、铜、锌共15种重金属元素进行了分析,并应用美国环保局推荐的健康风险评价模型对其所引起的健康风险作了初步评价。结果表明,通过饮水途径所致健康风险中,由致癌物砷所致的健康风险为8.15E-6 a-1,低于国际辐射防护委员会ICRP推荐的最大可接受风险水平5.0×10-5a-1;由非致癌物所致的健康风险中砷最大,铜和硼次之,二者的风险水平为10-9a-1和10-10a-1,均低于ICRP推荐的最大可接受风险水平。     

Assessment of the Heavy Metal Pollution Effects on the Soil Respiration in the Baix Llobregat (Catalonia, NE Spain)

A main goal of investigations is to determine could a soilrespiration be an indicator of the soil pollution. In this case a measured levelof the soil oxygen consumption depends of its pollution. It alsomeans that the pollution reduces biological processes in edaphon.Investigated soil samples were taken from polluted andnon-polluted places in the Baix Llobregat near Barcelona (Catalonia, NE Spain). Soil samples were taken from the top ofsoil (0–5 cm) without a litter. Soil analysis were done, determining percentage shares of coarsefragments, coarse sand, fine sand, coarse silt, fine silt, clay,CaCO₃, organic matter as well as water pH and conductivityCE (1:5 [mS cm^-1]). Also were determined (in mg kg^-1)quantities of heavy metals, as Fe, Al, Mn, Zn, Cr, Ni, V, Cu, Cd, Pb.The soil respiration was investigated in temperatures15 and 30 °C and with controlled humidity.The respiration in 30 °C is number of times greater thenin 15 °C both for polluted and non-polluted soils.Particularly high coefficients of correlation between the soilrespiration and soil pollution in polluted soils were obtainedfor Pb: r = 0.75 in 15 °C and r = 0.98 in30 °C; for Ba: 0.90 and 0.57; for V: 0.99 and 0.81. In non-polluted soils highest correlation coefficients are for Pb: r = 0.70 in 15 °C; Fe: 0.60 and 0.72; Al: 0.68 and0.64; Mn: 0.51 and 0.66; Ba: 0.63 and 0.61; Cr: 0.94 and0.70; Ni: 0.64 and 0.65; Cu: 0.69 and 0.48; as well as V: 0.62in 15 °C; and Cd: 0.69 in 15 °C.This way the soil respiration could be a good indicator of the soil pollution.     

Potential Use of the Plant Antioxidant Network For Environmental Exposure Assessment of Heavy Metals in Soils

In recent years, awareness has risen that the total soil content of pollutants by itself does not suffice to fully assess the potential ecotoxicological risks involved. Chemical analysis will require to be complemented with biological assays in a multidisciplinary approach towards site specific ecological risk assessment (SS-ERA). This paper evaluates the potential use of the plants' antioxidant response to metal-induced oxidative stress to provide a sensitive biological assay in SS-ERA. To this end, plants of Phaseolus vulgaris were grown for two weeks on 15 soils varying in contamination level. Morphological parameters and enzymatic plant responses were measured upon harvest. Foliar concentrations of the (heavy) metals Al, Cu, Cd, Cr, Fe, Mn, Ni, Pb, Zn were also determined. Metal mobility in the soil was further assessed by determining soil solution and NH₄OAc extractable levels. In general more significant correlations were observed between plant responses and foliar metal concentrations or exchangeable/soluble levels than between plant responses and the total soil content. The study demonstrates the potential use of the plants' antioxidant defence mechanisms to assess substrate phytotoxicity for application in SS-ERA protocols. However, the system, based on calculation of a soil Phytotoxicity Index (PI), will require adaptation and fine-tuning to meet the specific needs for this type of environmental monitoring. Large variation was observed in phytotoxicity classification based on the various test parameters. The thresholds for classification of the various morphological and enzymatic response parameters may require adaptation according to parameter stress sensitivity in order to decrease the observed variation. The use of partial PI's (leaves and roots separately) may in addition increase the sensitivity of the system since some metals show specific effects in one of both organs only. Loss of biological functionality of enzymes, as was observed for ICDH in one of the more strongly contaminated soils, may also be recognized as an additional stress symptom when assigning phytotoxicity classification, whereas the current system only considers increasing enzymatic capacities. Other easily distinguishable parameters, which could be added to the current indexation are: failure to germinate and the incapacity to develop roots in the toxic substrate.Additional research will be required to determine the possible application range of soil properties for this biological assay and to further improve its performance in SS-ERA.     

Heavy Metals in the Eggs and Muscle of Horseshoe Crabs (Limulus Polyphemus) from Delaware Bay

Lead, mercury, cadmium, chromium and manganese concentrations were measured in the eggs of horseshoe crabs (Limulus polyphemus) from 1993, 1994 and 1995; and from chelicera muscle in 1995 from Delaware Bay. Metal concentrations in the eggs represent levels derived from females. In eggs, mercury levels were below 100 ppb or were non-dectable; cadmium levels were generally low in 1993 and 1995 but were relatively higher in 1994; lead levels in eggs decreased from 558 ppb in 1993 to 87 ppm in 1995; selenium increased from 1993 to 1995; chromium decreased from 1993 to 1995; and manganese generally decreased. Leg muscles had significantly lower levels of all metals than eggs, except for mercury.     

Estimation of Heavy Metals in Different Berberis Species and Its Market Samples

Popularity of herbal drugs is increasing all over the world because of lesser side effects as compared to synthetic drugs. Besides, it costs less and easily available to poor people particularly in developing countries. But quality assurance of herbal drugs is very necessary prior to its use. Because in today's polluted environment, even herbal drugs are not safe. Berberis spp. is very important medicinal plant, having various medicinal properties. It is also included in Indian and British pharmacopoeias. Its demand is quite high in herbal drug market. So, to check the quality of market samples of this drug, ten different samples were procured from different drug markets of India for heavy metal estimation. Besides, genuine samples of four species of Berberis viz. B. aristata, B. chitria, B. lycium, B. asiatica were also collected from natural habitats to compare heavy metal concentration in both market and genuine samples. It was found that market samples were much more contaminated than genuine samples. Lead (Pb) concentration is far beyond from WHO permissible limit (10 ppm) for herbal drugs, reaching to maximum 49.75 ppm in Amritsar market sample. Likewise, concentration of all other metals like Cd, Cr and Ni were also very high in market samples as compared to genuine samples.     

Assessment of Atmospheric Deposition of Heavy Metals and Other Elements in Belgrade Using the Moss Biomonitoring Technique and Neutron Activation Analysis

This study aimed at assessing atmospheric deposition of heavy metals and other elements using the moss genera Brachythecium sp. (B. rutabulum and B. salebrosum) and Eurhynchium sp. (E. hians and E. striatum) collected in autumn 2004 in the urban area of Belgrade. The concentrations of 36 elements (Na, Mg, Al, Cl, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Zn, As, Se, Br, Rb, Sr, Mo, Sb, I, Cs, Ba, La, Ce, Sm, Tb, Dy, Hf, Ta, W, Hg, Th, U) were determined in moss and local topsoil samples by instrumental neutron activation analysis. The concentration of elements in moss positively correlated to those obtained for topsoil. High enrichment factors for As, Zn, Mo, Br, Sb, Se, Hg and Cl, calculated to continental crust composition, gave an evidence for anthropogenic impact on urban area, mainly due to intensive vehicular traffic and fossil fuel combustion. The concentration of elements in moss, characteristic for fossil fuel combustion, obtained in this study were substantially lower than in the previous investigation (2000) conducted in the area of Belgrade. The level of concentrations for V, Cr, Ni, and As in moss from this study correlated to those measured for neighboring countries, and were several times higher than the base-level data from low polluted areas. The level of accumulated elements in both investigated moss genera were similar and all studied species could be combined for biomonitoring purposes in urban areas.     

Plant Uptake/Bioavailability of Heavy Metals from the Contaminated Soil after Treatment with Humus Soil and Hydroxyapatite

Cellulose nitrate membrane filter was used for the preconcentration-separation of Cu, Co, Cd, Pb and Cr ions. The analyte ions were collected on the membrane filter by the aid of carmine. Then membrane filter was dissolved by using nitric acid. The levels of the analytes in the final solutions were determined by flame atomic absorption spectrometry (FAAS). The analytical parameters including pH, amounts of carmine, sample volumes etc. have been optimized. No influences have been observed from the matrix ions. The detection limits for analytes were in the range of 0.08 μg/l-0.93 μg/l. The validation of the procedure was checked by the analysis of standard reference sediment (GBW 07309). The present method has been successfully applied for the FAAS determinations of analyte ions in real samples including black tea and magnesium salts.