基于形态学分析铅锌矿不同功能区土壤重金属元素的分布特征及污染评价

为掌握尤溪铅锌矿区土壤重金属元素分布特征和污染现状,通过采集尤溪铅锌矿不同功能区0~20cm表层土壤样品,测定土壤中Pb、Zn、Cd、Cu、Cr 5种重金属元素的总量及其化学形态,分析不同功能区土壤重金属污染及分布特征,同时采用次生相与原生相比值法(RSP)进行污染评价。结果表明,尤溪铅锌矿不同功能区土壤中Pb、Zn、Cd含量均超过国家土壤环境质量三级标准,废弃冶炼区土壤Cd、Cu、Pb、Zn含量均最高,分别为标准值的14.78、1.13、3.73、1.34倍,采矿区Cr含量最高,但未超过标准限值。重金属形态结果表明,相比其他元素,Cd弱酸提取态所占比例最高,Cu可交换态比例最高,Pb、Zn、Cr以残渣态为主。RSP法评价表明,不同重金属的污染程度表现为:Cu(1.15)Cd(0.80)Pb(0.59)Zn(0.57)Cr(0.54);不同功能区土壤重金属污染表现为:尾矿库区冶炼区废弃冶炼区采矿区。SPEF法评价表明,尤溪铅锌矿区受人为污染明显,采矿区和尾矿库区Zn污染最为严重,冶炼区和废弃冶炼区Pb污染最为严重,功能区污染顺序为:尾矿库区冶炼区废弃冶炼区采矿区。     

Physico-chemical Speciation of Lead in South San Francisco Bay

The speciation of lead at a site in the South San Francisco Bay was determined using a combination of physical size fractionation and electrochemical analyses. The ‘ total dissolvable ’ Pb was 8·1 nM from analysis of an acidified unfiltered sample. The ‘ dissolved ’ Pb was equal to 0·20 nM (41 ng l⁻¹), only 2·5% of the ‘ total dissolvable ’ Pb. The difference yielded the ‘ particulate ’ Pb equal to 7·9 nM (1·6 μg l⁻¹). Results from crossflow ultrafiltration indicated that almost all (0·19 nM) of the dissolved Pb was ‘ in solution ’ [<10K nominal molecular weight (MW)] and that colloidal Pb (10K MW to 0·2 μm)accounted for onlyc. 1% of the dissolved Pb at this station. This small concentration (0·01 nM) of colloidal Pb may be attributed to the low amount of organic carbon associated with colloid size fraction as determined by dissolved organic carbon analyses.The chemical speciation of lead was determined in the dissolved sample and ultrafiltered sub-sample. Differential pulse anodic stripping voltammetry (DPASV) on a thin mercury film (TMF) rotating glassy carbon disk electrode (RGCDE) was used to distinguish the kinetically labile inorganic species (Pb′) from the Pb-chelated by organic ligands (PbL_i). Lead titration results were similar for both samples revealing that Pb′, PbL_iand excess unbound ligands were present primarily in the ultrafiltrate, rather than in the colloidal phase. The titration data can be interpreted as dissolved Pb being influenced by two classes of Pb-binding ligands. In the dissolved sample, the concentration of the stronger class of ligands was [L₁]=0·89±0·35 nM, with a conditional stability constant ofK^cond_L1,Pb′=3±1×10¹⁰M⁻¹. The weaker class was [L₂]=12·8±1·9 nM, withK^cond_L1,Pb′=4±1×10⁸ M⁻¹. The presence of these ligands, in excess of the dissolved Pb, resulted in [Pb′]=7±2 pM and [Pb²⁺]=0·3 pM (62 pg l⁻¹). While less than 2·4% of the ambient Pb was ‘ in solution ’, it existed chiefly in the form of organic complexes with [PbL₁]=0·15 nM and [PbL₂]=0·03 nM. More significantly, there were large concentrations of unchelated Pb-binding ligands, (L_i′), available to buffer the free Pb²⁺concentration in the event of perturbations in dissolved Pb.     

Arsenic Speciation in Lichens and in Coarse and Fine Airborne Particulate Matter by HPLC–UV–HG–AFS

A three-step sequential extraction procedure with Milli-Q, CaCl₂ and H₃PO₄ was applied for extraction of arsenic species in lichen transplants and airborne particulate matter (fine and coarse fractions). The samples used in this work were collected in 1994–1995 near coal-fired power plants. Both transplant lichens and airborne particulate matter were submitted to the same environment simultaneously. Arsenic species identification and quantification was performed by HPLC–UV–HG–AFS. Inorganic forms of arsenic (arsenite and arsenate) were present in significant amounts in most of the samples. Only in lichens also organic forms of arsenic (monomethyl arsonic acid and dimethyl arsinic acid) were identified which may indicate biotransformation of inorganic arsenic.     

FeSO4对铬污染土的稳定特性及风险评价试验研究

采用硫酸亚铁（FeSO4）对铬污染土进行稳定化处理。选用浸出试验、Cr(VI)残留值试验和形态提取试验,研究了粒径和有机质对铬污染土稳定特性的影响规律。试验结果表明,粒径和有机质对铬污染土稳定特性有较大影响。粒径的减小可显著降低稳定土中Cr(VI)和总Cr的浸出浓度及稳定土中Cr(VI)的含量;当污染土粒径小于2 mm时,Fe(II)/Cr(VI)摩尔比为3,稳定土中Cr(VI)和总Cr的浸出浓度分别为4.68、8.9 mg/L,均低于我国《危险废弃物鉴别标准 浸出毒性鉴别》（GB/T5085.3－2007）的限值。有机质添加量的增加可明显降低稳定土中Cr(VI)和总Cr的浸出浓度及Cr(VI)的含量。当Fe(II)/Cr(VI)摩尔比为3时,有机质的添加量为5%,稳定土中Cr(VI)的含量为28.3 mg/kg,低于我国《土壤环境质量标准》（GB15618－2008）中工业和商业用地限值（30 mg/kg）;当有机质的添加量为10%时,稳定土中Cr(VI)的含量为4.8 mg/kg,低于居住用地限值（5 mg/kg）。形态提取试验结果表明：粒径的减小可降低弱酸提取态的铬含量,增加可还原态的铬含量,而对可氧化态和残渣态的铬含量影响不大;有机质可促使弱酸提取态、可还原态的铬转化为可氧化态的铬,而残渣态的铬变化不大。稳定土中铬从活性态向较稳定态转化,是铬稳定土稳定特性和环境风险变化的根本原因。     

湖北恩施地区土壤-植物系统中Se元素的 地球化学特征

在对恩施地区典型农业活动区——芭蕉、长平和鱼塘坝三地土壤中Se元素含量进行调查的基础上,通过与富Se土壤质量标准进行对比,发现除长平地区外,其余两地分别属于富Se和高Se地区,并通过土壤理化性质、形态分析和土壤中所生长的植物进行比较,初步研究了Se在土壤-植物体系中迁移转化的规律。结果表明：整体来看,鱼塘坝地区属于超富Se地区,植物中Se的含量也最高,长平地区属于非富Se地区,芭蕉地区则属于中等富Se地区;植物对Se的吸收受一定的土壤理化性质的影响,不同类型的植物对Se的吸收富集相差较大;形态分析研究表明,鱼塘坝地区土壤中生物可利用的Se含量较高,而芭蕉地区土壤中残渣态Se的比例较高,表现为Se的生物可利用性低于鱼塘坝地区。     

Relations between free copper and salinity, dissolved and particulate organic carbon in the Oosterschelde and Westerschelde, Netherlands

In a previous investigation, relatively simple relations were found to estimate free Cu, and hence a good approximation of bio-available Cu, at two sites in estuarine waters of the Dutch Oosterschelde and Westerschelde. In the present study, these relations are validated for the remainder of the two sea arms. In the Westerschelde the relation between the concentration of a dissolved organic ligand (K=10¹³), DOC (dissolved organic carbon) and salinity is valid in a range of salinities at least from 10 up to 25 to 30. This ligand group is primarily riverine and partly estuarine. It is, as far as we know, the strongest ligand for Cu, and its concentration dominantly affects the free Cu ion concentrations, which are around 50 fM. At high salinities, dilution and mineralisation diminish the riverine member of the ligand group too much and the relation with salinity and DOC is no longer valid. In the Oosterschelde the relations between POC (particulate organic carbon) and particulate Cu and between POC and the ratio of particulate and dissolved Cu are valid for the western, central and eastern compartments. Since equilibrium was assumed to exist between dissolved and particulate Cu, free Cu can be calculated from POC and particulate Cu concentrations. Due to the large adsorption capacity of POC, the Oosterschelde is with respect to Cu a very well-buffered system with [Cu²⁺] of 20 fM.     

Succession,palaeoecology, evolution,and speciation of Pennsylvanian non‐marine bivalves,Northern Appalachian Basin,USA

Seventeen horizons of non‐marine bivalves are described within the Appalachian succession from the base of the Pottsville Group of Westphalian A‐B age to the Uniontown coal of Stephanian C age at the top of the Carboniferous System. A new highly variable fauna of Anthraconaia from the roof shales of the Upper Freeport coal near Kempton, west Maryland, dates from late Westphalian D or very early Cantabrian time, on the evidence of non‐marine shells and megafloras. Below this horizon, the Appalachian sequence reveals zones of Anthraconauta phillipsii and Anthraconauta tenuis in the same order as in Britain, whereas faunas of Anthraconaia of these zones are less common and differ from those of Britain. In all horizons above the Upper Freeport coal all non‐marine bivalve faunas consist of stages in the sequences of two natural species, the groups of Anthraconaia prolifera and Anthraconaia puella‐saravana. The first shows evidence of having lived in well‐oxygenated, probably shallow, fresh water conditions of relatively wide extent. The second group lived preferentially in a plant‐rich environment of relatively stagnant fresh water. Both groups are found in horizons associated with coal seams and may be seen together in the same habitats, but diagrams of variation (pictographs) suggest that there was no interbreeding between the two groups in either the Northern Appalachians or in southern Germany where the species split was first recognized. In the northern Spanish coalfields of Guardo‐Valderrueda and Central Asturia, facies evidence suggests how an initial split may have taken place in the same morphological directions and into the same palaeoenvironments as the later split into two species. Appalachian deposition was generally slow and intermittent with frequent palaeosols. There is also evidence of erosion and of small palaeontological breaks in the sequence, especially near the eastern edge of the Northern Appalachian Basin in western Maryland. The amount of accumulated sediment was less than one‐tenth of that of western Europe when basin centre deposition is compared. We found no evidence of a major palaeontological break representing Westphalian D strata overlain by Stephanian C strata. We figure non‐marine bivalve faunas of Stephanian B age in association with the Pittsburgh and the Little Pittsburgh coals. Two new species of non‐marine bivalves are described: Anthraconaia anthraconautiformis sp. nov. and Anthraconaia extrema sp. nov. Copyright © 2003 John Wiley & Sons, Ltd.     

美国罗德河流域地下水中铝形成动力学

In the Rhode River estuarine/watershed area, increased acidity of precipitation from atmospheric acidic deposition has deleterious effects on the freshwater ecosystems. One of the characteristics of an acidic watershed is the mobilization of aluminum from soils to aquatic environment. Increased concentrations of aluminum in surface waters are toxic to living organisms. Detection of long-term changes of acidity and elevated Al concentrations in surface and soil waters is a central issue. In this present paper, the dynamics ofAl speciation in the shallow ground waters from Rhode River watershed 110 (la) were investigated. This research provides a unique, regional analysis of important controls on the transport of Al speciation through the rural watershed of the Chesapeake Bay.     

珠江河口及近海水体中铜的水平和形态分布

对夏季(2002-07)和冬季(2003-01)航次中珠江河口及近海水域样品中金属铜的总含量以及总溶解态、颗粒态、游离态铜含量进行对比分析。结果发现,夏季铜的总浓度水平分布并非完全体现陆源性规律,而是随河口向外海递增。而在冬季,总铜浓度的空间变化呈现和夏季完全相反的趋势,即随河口向外海逐渐降低。说明研究水域中金属铜可能具有其他来源,同时在很大程度上受到夏季沿岸上升流的影响。但是,游离态铜的分布在冬季和夏季却呈现相同的趋势,即自河口向外海逐渐降低。说明铜的形态分布在更大程度上取决于水体的理化性质。     

与高岭石固相平衡的酸性天然地表水中铝形态分布的计算机模拟

基于热力学平衡计算,用计算机模拟研究了与高岭石固相平衡的酸性天然地表水中铝的形态分布,讨论了影响铝莆态分布的各种因素,同三水铝石固相平衡相比,与高岭石固相平衡的酸性天然地表水中,铝的形态分布与溶解硅酸的浓度密度相关,聚合态铝浓度较低,总溶解铝浓度明湿减小约２个数量级,模型被用于实际水样的分析,所得结果与实验值符合较好,最后用Ｍｏｎｔｅ Ｃａｒｌｏ模拟考察了由于平衡常数的选择而带来的不确定性。