Heavy metal contamination in the Tanat Valley,North Wales

The Tanat Valley area of North Powys, Wales, has a long history of metalliferous mining, the most active period of extraction being during the 18th century, while the largest mine, Llangynog, was in production until 1899. Ore minerals found in the area include galena (PbS), sphalerite (ZnS) and chalcopyrite (CuFeS2). Below the Llangynog mine the valley is heavily contaminated with elevated levels of Pb, Zn, Cu and Cd in soils and river sediments. On the valley floor subsoil metal levels frequently greatly exceed those of topsoils which probably reflects contamination of the floodplain during the peak period of mining. High levels of base metals in the stream sediments some 2 km downstream of the mine area are thought to be due to river erosion of the contaminated bank material. Contamination derived from the old mine tips results in extremely high levels of heavy metals in soils and stream sediments in the immediate vicinty of the old workings. Some metal contamination is also thought to derive from previously undetected mineralisation.     

Arsenic,antimony and bismuth in soil and pasture herbage in some old metalliferous mining areas in England

Soil and pasture herbage samples from some historical metalliferous mining and smelting areas in England were analysed for As, Sb and Bi by ICP-AES using a hydride generation method after ashing with Mg(NO₃)₂. The results showed that As, Sb and Bi concentrations in soils were elevated because of their associations with the Pb-Zn mineralisation in Derbyshire and Somerset, and Sn-Cu mineralisation in Cornwall. The distribution of As, Sb and Bi in soils reflected the chemical nature of different mine waste materials, and on a regional basis clearly reflected the geochemistry of the three mineral provinces. Historical smelting and calcination have caused intensive contamination in soils in the immediate vicinity of these activities. Antimony was highly elevated in soils at an old Pb smelter site in Derbyshire. Although the concentrations of As, Sb and Bi were generally low in the pasture herbage samples examined, the concentrations of As and Sb in herbage often reflected those of the corresponding soils. Soil pH had a large effect on the plant uptake of Bi from soils. The pasture herbage contaminated by soil can be an important exposure pathway of these elements to livestock grazing on contaminated land.     

Mercury contamination in agricultural soils from abandoned metal mines classified by geology and mineralization

This survey aimed to compare mercury concentrations in soils related to geology and mineralization types of mines. A total of 16,386 surface soils (0~15 cm in depth) were taken from agricultural lands near 343 abandoned mines (within 2 km from each mine) and analyzed for Hg by AAS with a hydride-generation device. To meaningfully compare mercury levels in soils with geology and mineralization types, three subclassification criteria were adapted: (1) five mineralization types, (2) four valuable ore mineral types, and (3) four parent rock types. The average concentration of Hg in all soils was 0.204 mg kg(-1) with a range of 0.002-24.07 mg kg(-1). Based on the mineralization types, average Hg concentrations (mg kg(-1)) in the soils decreased in the order of pegmatite (0.250) > hydrothermal vein (0.208) > hydrothermal replacement (0.166) > skarn (0.121) > sedimentary deposits (0.045). In terms of the valuable ore mineral types, the concentrations decreased in the order of Au-Ag-base metal mines ≈ base metal mines > Au-Ag mines > Sn-W-Mo-Fe-Mn mines. For parent rock types, similar concentrations were found in the soils derived from sedimentary rocks and metamorphic rocks followed by heterogeneous rocks with igneous and metamorphic processes. Furthermore, farmland soils contained relatively higher Hg levels than paddy soils. Therefore, it can be concluded that soils in Au, Ag, and base metal mines derived from a hydrothermal vein type of metamorphic rocks and pegmatite deposits contained relatively higher concentrations of mercury in the surface environment.     

江西兴国县农田土壤固碳潜力20a变化研究

通过GIS技术,采集38个农田土壤样品,研究了江西兴国县农田土壤有机碳变化量的空间分布特征.结果表明,20a来,兴国县农田土壤中土壤有机碳增加的面积为621.3km2,减少的面积为38.4km2,增幅主要在0~5g/kg和5~10g/kg;千枚岩、花岗岩、红砂岩、第四纪红粘土和紫色砂页岩发育的土壤中有机碳变化量分布的面积分别为361.7km2、144.7km2、76.5km2、48.7km2和18.0km2,海拔在300m以下、300~500m、500~800m和800m以上的土壤中有机碳变化量分布的面积分别为358.9km2、200.2km2、62.9km2、28.0km2.多元回归分析显示,20a来土壤有机碳变化量和初始含量呈负相关关系,土壤有机碳变化量和海拔、粘粒含量呈正相关关系.图1表2参15     

Some observations on heavy metal concentrations in soils of the Mendip region of north Somerset

Topsoiis in the Mendip Hills of north Somerset are strongly enriched in Pb, Zn and Cd. While much of this enrichment is the result of pollution stemming from previous base metal mining, analyses of soil profile samples reveals that, in several cases, there is considerable enrichment of heavy metals with depth. This, together with relatively high levels of base metals in samples of the limestone and sandstone bedrocks, suggests that some of the enrichment in soil of heavy metals is due to natural processes.     

The influence of acidic mine and spoil drainage on water quality in the mid-Wales area

The many abandoned base metal mines of the mid-Wales ore field are sources of extensive pollution. Some of the mineralised veins contain large amounts of pyrite and marcasite and oxidative weathering of these produces sulphuric acid resulting in very acidic mine drainage waters. In addition, the spoil tips associated with these mines can contain abundant iron sulphides. Drainage waters from these sources have pH values as low as 2.6 and are heavily contaminated with metals such as Al, Zn, Cd and Ni.Two of the main rivers of the area, the Rheidol and Ystwyth, intercept heavily contaminated acidic drainage which has a marked effect on water quality. The Rheidol contains over 100 g L^–1 Zn for 16 km downstream of the acid water influx. This level is over three times the recommended EEC limit for Zn in salmonoid waters of low hardness.     

Soil remediation using in situ immobilisation techniques

The main objective of this study was to investigate the efficiency of different substrates to reduce the extraction of heavy metals concentration in a heavily contaminated soil. Two contaminated soils by Cu and Zn were used to evaluate the effectiveness of eight substrates (calcium carbonate, bentonite, kaolinite, charcoal, manganese oxide, iron oxide, zeolite, phosphate) to reduce metal availability and to study the change of metals speciation in different forms using sequential extraction technique (single step). Sequential extraction technique (single step, 0.11 M acetic acid, HONH₃Cl, H₂O₂+NH₄OAc, Aqua regia) was applied on contaminated soils after and before treatment to evaluate metals speciation. Results indicate that the most effective treatments in decreasing available metal concentrations were calcium carbonate, zeolite and manganese or iron oxide. Metal sequential fractionations indicate that the exchangeable fraction of Cu and Zn in contaminated soils can be transformed into unavailable forms after chemical remediation.     

东莞市不同区域菜地土壤重金属污染状况研究

对东莞市及其不同区域菜地土壤重金属污染情况进行了调查和分析，参照国家土壤环境质量标准，运用单因子污染指数法和综合污染指数法对上述土壤质量进行了评价。结果表明，全市和各区土壤受到了不同程度的重金属污染，具体表现为：全市土壤Cd、Cu、Ni和Pb的超标率分别为4．9％，6．6％，3．3％和95．1％，均处于轻污染状态，以Pb污染最严重；土壤Cr未有超标，仅西北区域达到了警戒级水平。全市土壤重金属含量各样点间变异较大(Zn、Cr、Pb、Cd、Cu、Ni和有效Cu、Zn的变异系数分别为51．5％，54．1％，37．5％，48．8％，60．2％，57．3％和85．3％，64．7％)，但对各重金属元素而言却存在着不同程度的区域差异。     

Teil 1: PCDD/F in Böden,Vegetation und Kuhmilch

Soil samples were taken from residential gardens, grasslands and forests at 22 locations in Marsberg, North Rhine-Westphalia, and analyzed for PCDD/F. Sampling was concentrated on the vicinity of a former copper smelter where copper waste material (calledKieselrot) was deposited and emissions from former stacks contaminated a large land area. Maximum PCDD/F-concentrations were 407 ng TE GBA/kg dm in garden soil (0–30 cm depth), 98 ng TE BGA/kg dm in agricultural grassland (0–10 cm depth), 227 ng TE BGA/kg dm in wasteland, and up to 8073 ng TE BGA/kg dm in forest soils. PCDD/F-levels in soil decreased with increasing distance from the former sources providing a large historic emission problem, apart from the still existing kieselrot waste site. Ash residues from former flue gas duct showed up to 2,4 mg TE BGA/kg dm. PCDD/F-concentrations in vegetable samples from highly contaminated garden soils and grass from agricultural grassland were found to be relatively low in relation to soil values. PCDD/F-levels in salad showed a mean of 2,2 ng TE BGA/kg dm while grass concentrations were <6 ng TE BGA/kg dm. Thus, no correlation was found between soil and vegetation values with the exception for carrot roots where obviously a small transfer of PCDD/F between the two media took place. PCDD/F-content in grass taken over the vegetation period showed a tendency to increase toward the end of the growing season, which is probably related to changes in the dry matter yield over the season. No correlation was found in general between soil, grass and milk PCDD/F contents when all samples were taken from the same grassland. PCDD/F-concentrations in milk ranged between 0,6 and 1,1 pg TE BGA/g milkfat and were thus in the same range as consumer milk in the Federal Republic of Germany. PCDD/F in needles from conifers showed a clear relationship with respect to distance from the former waste site. The relatively high levels in conifer needles [36 ng TE BGA/kg dm] were obviously due to sporting activities (i.e. motocross racing where contaminated material was resuspended and deposited on surrounding trees).     

An Investigation Into the Mechanism by Which Synthetic Zeolites Reduce Labile Metal Concentrations in Soils

The addition of synthetic zeolites and similar materials to metal contaminated soils has been shown to reduce soil phytotoxicity and to improve the quality of plant growth on such amended soils. To gain an understanding of the mechanism by which the phytotoxicity of contaminated soils is reduced when treated with synthetic zeolites, sequential extraction procedures and soil solution techniques have been used to identify changes associated with metal speciation in amended soils. Sequential extraction data and changes in soil solution composition are presented for three different contaminated soils, amended with three synthetic zeolites (P, 4A and Y) at concentrations of 0.5%, 1% and 5% w/w, or lime at 1%. The soils were collected from the site of a metal refinery, an old lead zinc mine spoil tip and from a field which had been treated with sewage sludge. After incubation of the zeolite treated soils for between one and three months, results showed a reduction in the metal content of the ammonium acetate fraction between 42% and 70%, depending on soil, zeolite and rate of addition, compared with the unamended soils. In addition, soil solution experiments indicated that synthetic zeolite amendments were more efficient at reducing metal content than comparable lime treatment. The mechanism by which synthetic zeolites reduce metal bioavailability in contaminated soils is discussed and compared to other amendments.     

模拟酸雨对红壤铝形态的影响

用动态淋洗试验，研究了不同pH的模拟酸雨对红壤中铝形态和性质的影响．结果表明，酸雨淋洗引起红壤中盐基离子的淋失和土壤铝的溶出．随着酸雨溶液pH的降低，盐基淋矢量和铝溶出量增加．酸雨淋洗影响土壤铝形态的转化，使红壤中交换态铝上升，吸附态羟基铝有所下降．这说明在酸雨长期作用下，羟基铝溶解，并转化为交换态铝和引起铝的溶出，使铝进入环境，危害生态系统．     

Mercury pollution in a mining area of Guizhou,China: Fluxes over contaminated surfaces and concentrations in air,biological and geological samples

A dynamic flux chamber has been used to estimate fluxes of mercury over different types of surfaces in an abandoned open‐cut mine of Tongren prefecture, Guizhou province, China during spring and summer of 1996. The highest fluxes were obtained over cinnabar slag and contaminated soils, whereas the emissions above cinnabar ore were substantially lower. These fluxes was scaled up to estimate the contribution of mercury emissions to air from mercury wastes, compared to anthropogenic activities in the province of Guizhou, China. Atmospheric mercury concentrations measured were enhanced in the mining area (<1.3 μg m^‐3) compared to regional background sites (1.8–5.1 ng m^‐3). The spreading of mercury was estimated by using biological and geological samples. Moss bags have been employed to estimate long‐time dry‐ and wet‐deposition to this area.     

模拟酸雨下自然红壤与污染红壤中Cd,Cu,Zn的释放特征

通过对2个自然红壤和2个污染红壤的模拟酸雨土柱淋溶试验,研究了酸雨作用下红壤中重金属Cd,Cu,Zn的释放特征与影响因素,比较了自然红壤与污染红壤重金属释放特征的差异,结果表明,自然红壤中Cd,Cu,Zn的释放量均随酸雨淋溶量增加而线性增加,累积释放量有Zn＞Cu＞Cd的规律,并且随酸雨酸度增加而增加,3种重金属释放量之间存在显著的线性关系,在污染红壤中,Cd的释放随着酸雨淋溶量的增加呈现对数型增长,Cu的释放模式仍为直线型增长,而Zn的释放在弱酸性酸雨作用下为直线型增长,在强酸性酸雨作用下则为对数型增长,3种重金属释放鼍之间存在非线性关系,污染红壤中重金属释放量顺序为Cd＞Zn＞＞Cu,大约26%-76%的外源Cd和11%-68%的外源Zn被酸雨淋溶释放,但99%以上的外源Cu被土壤吸附,同时,3种重金属累积释放量均与淋出液中H+离子累积量呈现显著的对数关系;Cd和Zn与TOC累积释放量之间呈现显著的对数关系,Cu与TOC呈现显著的乘幂关系,在酸雨作用下,自然红壤由于重金属释放最很小,出现重金属污染的可能性较小;但污染红壤中大量Cd和zn的释放可能导致土壤,水体系统发生重金属污染.     

重金属污染土壤的电动原位修复技术研究

电动力学修复技术作为一种新型的修复技术,由于其处理土壤污染的高效性,近几年来受到了越来越多的关注。综述了电动力学修复技术原理及近几年来其在重金属修复中的最新研究进展,阐述了电动力学修复技术相对于其它修复技术的优势,并指出了电动修复技术中需要克服的技术障碍,探讨了其大规模商业应用的可行性。电动技术能够强化土壤物质的传质过程,能够高效、快速定向迁移土壤中重金属离子达到去除的目的;同时电动技术可以与其它修复技术结合发展出系列组合修复技术,具有广泛的应用前景。从单一电动到复合电动是今后电动力学技术发展的重要方向。目前对污染物质复合电动力学效应下的迁移机理及模型、不同土壤性质(组分、酸碱性等)对于污染物质去除效率及其调控措施的研究仍需进一步深入。     

Bioaccessible lead in soils, slag, and mine wastes from an abandoned mining district in Brazil

We determined the amount of bioaccessible lead in samples of contaminated soils and in mining and refining wastes collected in the surroundings of a former smelter in a rural area in south-eastern Brazil. Previous studies showed that some resident children and adults had blood Pb levels above recommended limits, but the contamination route was not established. The incidental ingestion of contaminated soils and dusts is considered to be a major route of lead uptake by humans. Bioavailability of heavy metals like Pb depends on solubility during digestion. We used in vitro tests that simulate human gastrointestinal (GI) media to measure the amount of soluble Pb under such conditions. Pb in soil and solid waste samples ranged from 0.03 to 4.1% and 1.2 to 15%, respectively. On average, 70% of the lead content was soluble in three different simulated gastric solutions (pH 1.5 and 1.7). For the same samples, lead solubility decreased to 2–22% when the pH was raised to pH 7 to approximate conditions found in the small intestine. These results indicate that if soils and dusts of the area are ingested, most of the lead will dissolve in the stomach, and part of it will remain soluble in the duodenum, i.e., would be potentially available for absorption. These findings may explain the high blood Pb levels previously reported.     

Mapping Soil Lead and Remediation Needs in Contaminated Soils

For the past two decades, the Taiwan Environmental Protection Administration has made a systematic investigation of As, Cd, Cr, Cu, Pb, Hg, Ni and Zn in agricultural soils to identify soil pollution from industrial production. The EPA has cooperated with local governmental agencies to establish a soil quality monitoring system that would upgrade the land recovery ability and prohibit polluted lands from being cultivated or turned over to other uses. Based on an island-wide soil survey, more than 1,000 hectares of arable soils in Taiwan were found to be considerably contaminated by heavy metals. One of the heavy metal contaminated sites, located near a ceramic product manufacturing factory in Nantou County, was identified as lead contaminated. According to the Nantou Environmental Protection Bureau, the lead content in contaminated sites showed a great variation of several mg Pbkg^–1 soil to several thousands mg Pbkg^–1 soil. Therefore, it is appropriate to estimate the lead spatial distribution through geostatistics such as Kriging. The soil lead concentration contour maps obtained by Kriging can help us to identify the pollution patterns and delineate the range of contaminated sites. The purpose of this study is to determine the Pb concentrations at each location by performing detailed soil sampling on those Pb contaminated sites and estimating the lead spatial distributions by Kriging. A total of 70 soils were sampled from different locations at two experiment sites. Lead contents were determined with 0.1M HCl extractable lead content of the soils. The results obtained by investigating the lead contents in each 15cm segment down to a 60cm depth, revealed that lead contents were greater in arable land near the ceramic products manufacturing factory, and lead concentrations decreased with depth. In addition, Pb concentrations in heavily contaminated soils showed heavy concentrations of Pb in specific locations. Results from Pb content spatial distributions indicated that the Kriging model is a useful tool and can provide decision-makers with critical information for delineating hazardous areas in heavy metal contaminated sites.     

Degradation rates of aged petroleum hydrocarbons are likely to be mass transfer dependent in the field

Evidence for on site biodegradation may be difficult to provide at heterogeneous sites without additional experiments in controlled laboratory conditions. In this study, microbial activities measured as CO₂ and CH₄ production were compared in situ, in intact soil cores and in bottle microcosms containing sieved soils. In addition, biodegradation rates were determined by measuring the decrease in petroleum hydrocarbon concentrations at 7°C in aerobic and anaerobic conditions. Elevated concentrations of CO₂ and CH₄ in the soil gas phase indicated that both the aerobic and anaerobic microbial activity potentials were high at the contaminated site. Aerobic and anaerobic microbial degradation rates in laboratory experiments of petroleum hydrocarbons were highest in soils from the most contaminated point and degradation in the aerobic and anaerobic microcosms was linear throughout the incubation, indicating mass-transfer-dependent degradation. Different results for microbial activity measurements were obtained in laboratory studies depending on pretreatment and size of the sample, even when the environmental conditions were mimicked. These differences may be related to differences in the gas exchange rates as well as in changes in the bioavailability of the contaminant in different analyses. When predicting by modeling the behavior of an aged contaminant it is relevant to adapt the models in use to correspond to conditions relevant at the contaminated sites. The variables used in the models should be based on data from the site and on experiments performed using the original aged contaminant without any additions.     

贵州万山汞矿地区耐汞野生植物研究

在贵州万山地区废弃汞矿堆和矿山附近,受长期高剂量汞暴露的影响经过的自然选择,该地区出现了一些能耐受汞毒性的生态型植物。对汞耐受及汞富集植物的筛选对于汞污染土壤的植物修复具有一定的现实意义。通过对万山梅子溪地区汞污染土壤及汞耐受植物采样调查发现,该区域采样土壤中汞的含量均在50 mg·kg-1以上,达到重度汞污染水平。对该地区野生植物的采样分析发现,蔷薇科植物悬钩子不仅数量较多,单株植物生物量较大,表现出很强的耐汞毒性的能力,而且植株内可以很大程度地富集汞,在其植株中汞的含量可达20 mg·kg-1左右,属于汞富集植物,另外发现野蒿对汞也具有较强的富集能力,其植株中汞的含量可达10 mg·kg-1以上。该类型植物的发现将为植物的汞耐受以及汞富集机理研究提供新的素材,为汞污染土壤的植物修复技术提供新的植物类型,也为进一步开发汞污染土壤处理技术提供了一种可能。     

Aluminium in tea plantations: mobility in soils and plants, and the influence of nitrogen fertilization

The levels of extractable aluminum (Al) in soils of tea plantations, Al concentrations in tea leaves and the impact of nitrogen fertilization on these two parameters were investigated. In addition, the properties of soils from tea plantations were compared to those from soils of adjacent non-tea fields to evaluate the effect of land use conversion (from non-tea soils to tea soils). Exchangeable Al (extracted in 1 mol l⁻¹ KCl) ranged from 0.03 to 7.32 cmol_c kg⁻¹ in 94 tea fields and decreased rapidly with increasing soil pH. In comparison with non-tea soils, tea soils had a significantly lower pH and exchangeable Mg²⁺ concentration but higher organic matter contents and exchangeable K⁺ concentration. Contents of extractable Al were not different (P > 0.05) between these two soils. The concentrations of Al in mature tea leaves correlated significantly with exchangeable Al in soil samples taken at a depth of 20–40 cm and with exchangeable Al saturations in soil sampled at␣depths of 0–20 and 20–40 cm. In the pot experiment, nitrogen fertilization significantly increased extractable Al levels but decreased soil pH and the levels of exchangeable base cations. Nevertheless, the levels of Al in mature leaves and young shoots were significantly reduced by the application of large amounts of N fertilizer.     

云南会泽废弃铅锌矿区植物丛枝菌根和深色有隔内生真菌研究

用碱解离、酸性品红染色法对云南省会泽县者海镇废弃铅锌矿区的17科21种植物的丛枝菌根状况进行了调查,结果发现,15种植物形成典型的丛枝菌根,占所调查植物的71%;2种植物不确定是否形成丛枝菌根,占所调查植物的10%;4种植物没有形成丛枝菌根,占所调查植物的19%.用湿筛沉淀法从这些植物根际土壤中共分离鉴定出了4属20种丛枝菌根真菌(AMF),即无梗囊霉属(Acaulospora)4种,球囊霉属(Glomus)14种,巨孢囊霉属(Gigaspo-ra)1种,盾巨孢囊霉属(Scutellospora)1种;其中,球囊霉属分离频率为77%,是样地的优势属.在AMF中,疣突球囊霉(G.verruculosum)分离频率最高,在20种植物的根际土中都有发现;此外,聚生球囊霉(G.fasciculatum)的相对多度最大,为56%,具有最强的产孢能力.同时,在13种植物的根中发现了深色有隔内生真菌(DSE),占调查植物的62%,其中,10种植物同时被DSE和AMF感染.本调查研究表明,AMF和DSE能普遍存在于Pb、Zn重金属污染土壤中.