pH influence on sorption characteristics of heavy metal in the vadose zone

Sorption is an important process in the modelling and prediction of the movement of heavy metals in unsaturated clay barriers. This experimental study investigates the effect of pH changes in the acidic range on the sorption characteristics of heavy metals such as: lead, copper and zinc in an unsaturated soil. A series of one-dimensional coupled solute and moisture leaching column tests, using different heavy metal solutions, were conducted on an unsaturated illitic soil at varying pH values. Variations of volumetric water content (VWC) with distance were measured for different time durations, and concentrations of heavy metals in the liquid and solid phases were analysed. Partitioning coefficient profiles of contaminants along the soil column were determined for each individual layer in the soil.

Results from column leaching tests showed that the sorption characteristics of heavy metals are controlled by many factors which should be taken into consideration, i.e. the VWC, time of wetting, soil pH, and the influent heavy metal concentrations. Simplification of K_d as a constant and of the VWC as a linear function cannot be considered a good assumption and may lead to an improper evaluation of the sorption phenomena and also to serious errors in predicting contaminant transport through unsaturated soils.     

Humic Ion-Binding Model VI: An Improved Description of the Interactions of Protons and Metal Ions with Humic Substances

Humic Ion-Binding Model VI, a discrete site/electrostatic model of the interactions of protons and metals with fulvic and humic acids, is applied to 19 sets of published data for proton binding, and 110 sets for metal binding. Proton binding is described with a site density, two median intrinsic equilibrium constants, two parameters defining the spread of equilibrium constants around the medians, and an electrostatic constant. Intrinsic equilibrium constants for metal binding are defined by two median constants, log K_MA and log K_MB, which refer to carboxyl and weaker-acid sites respectively, together with a parameter, LK₁, defining the spreads of values around the medians. A further parameter, LK₂, takes account of small numbers of strong binding sites. By considering results from many data sets, a universal average value of LK₁ is obtained, and a correlation established between log K_MB and log K_MA. In addition, a relation between LK₂ and the equilibrium constant for metal-NH₃ complexation is tentatively suggested. As a result, metal-binding data can be fitted by the adjustment of a single parameter, log K_MA. Values of log K_MA are derived for 22 metal species. Model VI accounts for competition and ionic strength effects, and for proton-metal exchange.     

Size Fractionation (Dissolved, Colloidal and Particulate) of Trace Metals in the Thur River, Switzerland

The distribution of some trace metals (Cu, Zn, Ni, Co,Fe, Mn) and of DOC over a particulate (> 1 m),a colloidal (size < 0.45 m and molecular weight > 10 kD) and an ultrafiltered fraction (< 10 kD)was determined at several sites on the Thur River,Switzerland, at various times of the year. Thecomplexation of Cu by strong ligands in theultrafiltrate and in the conventional filtrate (<0.45 m) was compared using a ligand-exchange/CSV method.The <0.45 m concentrations of Cu (from anaverage of 7 nM to 24 nM), Zn (<5–23 nM), Ni (5–13 nM),Co (1.5–3 nM) and Mn (7–92 nM)increased downstream. The major part of Cu, Zn, Niand Co usually occurred in the ultrafiltratefraction at all sites, whereas Fe and Mn were mostlyin the particulate fraction, under conditions of lowsuspended matter content (< 10 mg L^-1) in theriver. The percentage of metal in the colloidalfraction, with respect to the 0.45-m filtrate,decreased in the order: Cu (median 11%) > Zn Ni(median 5–6%) > Mn Co (median < 5%). DOCalso consisted mostly of molecules in the < 10 kDrange.Cu was strongly complexed by natural organic ligandsin all filtrate and ultrafiltrate samples. A largepart of the strong Cu binding ligands consisted ofcompounds in the < 10 kD range, but colloidalligands with similar properties also occurred. Cu wasdistributed among the dissolved and the colloidalligands, roughly in proportion to organic carbon.The colloidal fraction (as defined here) did notincrease in its proportional amount downstream and wasonly of limited significance in transporting traceelements in the Thur River under low discharge conditions.     

胶州湾沉积物对海洋生物重金属富集的影响分析

本文对胶州湾沉积物和海洋生物重金属含量进行了统计分析。首先用地球化学法对海洋生物重金属富集特征进行了分析,然后用Spearman’s相关系数法分析了沉积物重金属含量和海洋生物重金属含量的相关性。分析结果表明鱼类对重金属的富集能力最差,而贝类和藻类较强;沉积物重金属均能促进或抑制海洋生物对重金属的富集,而对贝类的抑制作用最强。此结果可以为海洋生物的选择性养殖和种植提供依据。     

Bioavailability and toxicity of aluminium in a model planktonic food chain (Chlamydomonas-Daphnia) at neutral pH

Dissolved aluminium (Al) is generally at low concentrations in neutral freshwater due to its insolubility. However, a fall in pH resulting from acid deposition and mining alters the mobility of Al and so entry to adjacent neutral waters. The present study examines the environmental behaviour, cell-associated surface adsorption/absorption and toxicity of Al at neutral pH to the alga Chlamydomonas gigantea in the presence and absence of the key Al-binding ligand silica. We then examined transfer of Al from C. gigantea to the planktonic crustacean Daphnia pulex. Finally, the effect of Al on the elemental composition (and hence nutritional value) of the two organisms was compared to unexposed controls. C. gigantea increased the amount of Al in the algal culture medium. Binding of Al to extracellular glycoprotein is probably the reason why only one-third of the biosorbed Al was absorbed (accumulated) by C. gigantea. Aluminium concentrations between 50 and 500 μg l⁻¹ reduced growth of C. gigantea at 16 days exposure to the metal. Silica reduced biosorption, accumulation and toxicity of Al by C. gigantea. The concentration of Al in D. pulex fed Al-contaminated C. gigantea for 16 days did not differ from those fed alga grown in the absence of added Al. C. gigantea contaminated with Al contained less sulphur, magnesium, potassium and sodium although only sulphur fell in D. pulex subsequently fed the contaminated alga. Chloride, calcium, iron and silicon were significantly higher in D. pulex.     

浅析有色金属浮选尾矿排放工艺与选矿生产用水重复利用率的关系

随着有色金属采选建设项目的增加,选矿生产的耗水量日渐为公众及管理部门所关注,在整个生产过程中,除精矿粉中会带走精矿重量约10%的水分外,绝大部分排放水是尾矿矿浆经输送至尾矿库澄清后排出的。因此从环境保护及提高水的利用率角度考虑,选矿废水应回用,而尾矿的排放方式又对生产用水回用率有着很大的影响。     

Distribution of trace metals in the Odra River system: Water–suspended matter–sediments

Extensive investigations of trace metals concentrations in water, suspended particulate matter (SPM) and bottom sediments of the whole Odra River system were carried out over the years 1997–2000. The vertical distribution of selected metals and their mobility were also studied in the sediment cores from upper and middle river sections. Significant levels of metal contamination were found. Median concentrations (Cd, Pb, Cu, Zn and As) in the SPM and sediments were (mg kg⁻¹) 7.1 and 8.9 Cd, 128 and 146 Pb, 81 and 119 Cu, 1198 and 1204 Zn, 48 and 54 As, respectively. The highest metal pollution of the Odra River solids was found with cadmium, zinc, lead and arsenic, showing high similarity in their frequency distributions in both SPM and sediments. Cd, Zn and As appear to be of particular concern because of the high levels, that appear to be bioavailable, and their high mobility. The exchangeable and carbonate chemical forms of Cd and Zn reached up to 50% of their total amount. Besides the determination of total metal concentration, the metal chemical forms in river solids were investigated. The results of very wide studies of the Odra River system through 4 years suggest that metal pollution decreased, especially for Zn, Pb and Cu. Among all metals studied in the Odra River sediments, substantial reductions of Cd contamination were observed neither in the period after ’97 flood, nor if compared with the earlier results obtained before ’97. No essential differences of the metal contents were observed among the samples for the same river compartment, from the same locality, taken within the five sampling campaigns. The pattern of spatial and vertical metal distributions in the river solids indicates that a variety of sources might be responsible for the contamination; very intensive, historical and current mining and smelting activities probably are the most important ones.     

Geochemical modeling,fate distribution,and risk exposure of potentially toxic metals in the surface sediment of the Shyok suture zone,northern Pakistan

The objective of the current study was to assess the contamination of potentially toxic metals (PTMs) in weathered surface sediment, along stream tributaries, and surrounding area of the river Chitral, Shyok suture zone district Chitral, Pakistan. To understand the geochemical features of 113 sediment, samples were collected from the Mirkhani and Drosh area. Then, different statistical tools including the geo-accumulation index (Igeo), cluster analysis (CA), principal component analysis (PCA), and ecological risk assessment (ERA) were used to unravel the origin, intensity, and exposure level of PTMs to control risk and restore the ecosystem within the study area. The results for the PTMs namely nickle (Ni), chromium (Cr), copper (Cu), cadmium (Cd), lead (Pb), zinc (Zn), and cobalt (Co) in Mirkhani and Drosh were in the following ranges: 10–150, 15–210, 15–250, 0.08–1.00, 10–70, 76–240 and 14–51; and 13–240, 17–210, 15–150, 0.08–0.60, 7–140, 47–150 and 13–36 mg/kg, respectively. In consequence, the potential ecological risk caused by Pb, Ni, Cu, Co, Cr, and Zn is reflected by the percentages of samples with an ecological risk index (ERI) greater than one which were 100%, 91%, 100%, 100%, 92%, and 100%, respectively. However, the overall mean decreasing order of ecological risk of PTMs in the district Chitral was Pb > Ni > Cu > Co > Cr > Zn > Cd. Moreover, the PCA yielded 78% variability which indicated that mineral prospects play an important role in the contamination of sediment. Furthermore, the mineral phases of Pb and Zn suggested supersaturation, while that for Cd revealed unsaturation. The results of Igeo, ERI, and CA indicated contamination of PTMs in the study area. The ERI value of Pb, Ni, Cu, Co, Cr, and Zn was higher than 1 suggesting an ecological risk in the study area. Moreover, the current study showed the dominance of geogenic contamination with major contributions from ultramafic rock and known mineral prospects. Therefore, contaminated sediment of the Shyok suture zone is extremely detrimental to the aquatic ecosystem of the study area.     

A summer and winter apportionment of particulate matter at urban and rural areas in northern France

The apportionment of atmospheric aerosols undertaken in Northern France during two sampling campaigns allowed to determine the influence of the atmospheric contribution of a heavy industrialized urban center on the particulate matter composition at a nearby rural site. The concentrations of major components and trace elements sampled by bulk filtration have been determined on June–July 2000 and January–February 2001, and the comparison of these two campaigns shows very well the importance of wind directions. The sources of 10 trace elements (Al, Ba, Cu, Fe, K, Mn, Pb, Sr, Ti and Zn) and 7 major components (Cl⁻, NO₃⁻, SO₄²⁻, NH₄⁺, Na, Mg and Ca) are better identified by studying their elemental contribution at each sampling site according to wind sectors. This kind of study shows that the concentrations recorded at the urban sampling site are always higher than those observed at the rural site as well during the summer campaign (about + 35%) as during the winter campaign (+ 90%), because of the predominance of the W–NW wind sector, corresponding to the influence of the urban and industrialized areas.