Geochemistry of soils derived from black shale, central Hunan, China

The black shale formed under anoxic conditions usually contains high concentrations of many metals. Weathering of such black shale might cause the emission of many metals. Moreover, soils derived from black shale （SBS） are believed to be affected by black shale weathering. In recent years, many studies such as Lee et al. （2002）, Woo et al. （2002）, Fang et al. （2002）, Pasava et al. （2003）, and Peng et al. （2004） have approached the heavy metal contaminations of SBS, but systematical geochemical study is rare. Presently, the SBS and its corresponding black shales （CBS） were both sampled from central Hunan （China）, and analyzed for a large number of elements, using an Elan6000 ICP-MS/AES machine at Guangzhou Institute of Geochemistry, CAS. In this paper, some preliminary results are reported. The analytical results show that the SBS in central Hunan contains very high concentrations of heavy metals such as Co, Cu, Hg, Mo, Pb, Zn, U, Th, Sb, T1, Cd, Cr, Sc, V, Sn, As, Se, and Ni.     

A novel strategy using biodegradable EDDS for the chemically enhanced phytoextraction of soils contaminated with heavy metals

For the sake of cost and potential environmental risk, it is necessary to minimize the amount of chelates used in chemically-enhanced phytoextraction. In the present study, a biodegradable chelating agent, EDDS was added in a hot solution at 90℃ to the soil in which garland chrysanthemum （Chrysanthemum coronarium L.） and beans （Phaseolus vulgaris L., white bean） were growing. The application of hot chelate solutions was much more efficient than the application of normal chelate solutions （25℃） in improving the uptake of heavy metals by plants. When 1 mmol kg1 of EDDS as a hot solution was applied to soil, the concentrations ofCu, Zn and Cd and the total phytoextraction by the shoots of the two plant species exceeded or approximated those in the shoots of plants treated with 5 mmol kg^-1 of normal EDTA solution. The concentrations of metals in the shoots of beans were significantly correlated with the relative electrolyte leakage rate of root cells, indicating that the root damage resulting from the hot solution might play an important role in the process of chelate-enhanced metal uptake. The soil leaching study demonstrated that decreasing the dosage of chelate resulted in decreased concentrations of soluble metals in soils. On the 28th day following the application of chelate, the concentrations of soluble metals in the EDDS treated soil were not significantly different from the concentrations in the control soil to which chelates had not been applied.     

Heavy metal contamination in the sediment of the Second Songhua River

The Second Songhua River was subjected to a large amount of untreated effluent from petrochemical industries in Jilin City in the 1960s to the 1970s. The objectives of this study were to investigate the mercury and other heavy metal contamination in the sediment of the river. The river bottom sediment was sampled from the river segment between Jilin City to Haerbin City in 2005. Total concentrations of Hg, Cd, Cu, Cr, Pb, Zn, Ni, As, Sc, and major cations （A1, Fe, Mg, Ca, K, Na） in the sediment were measured by atomic fluorescence spectrometer, ICP-MS, and ICP-OES, respectively, following digestion with various acids. We found the concentrations of most elements in the uncontaminated sediment were significantly correlated to those of Sc.     

High resolution profiles of trace metals in pore waters of marine and riverine sediments assessed by DET and DGT

In polluted aquatic systems, toxic metals are often accumulated in bottom sediments. They are, however, not necessarily stored definitively because diagenetic processs can modify redox, pH and even the amount of complexing ligands, releasing the trace metals back into the pore waters and the water column. Especially the labile metal fraction in the pore waters is important since this is the bioavailable fraction determining the bio-toxicity of the sediments. The goal of our study was therefore to assess, with novel sampling techniques, this bioavailable metal fraction in the pore waters as well as the flux towards the overlying water column. High-resolution profiles of trace metals in pore waters of marine and riverine sediments were assessed by DET （diffusive equilibrium in thin films） and DGT （diffusive gradients in thin films） gel techniques. The DET technique uses a diffusive gel layer that equilibrates with the aquatic system and with this technique the concentrations of total dissolved trace metals are obtained directly. The DGT technique uses an acrylamide diffusive gel backed by a resin gel （Chelex） which binds trace metals. With the DGT technique only labile species of selected metals can be captured. According to the redox potential measurements, the marine sediments were suboxic （200 mV to -220 mV versus Ag/AgCl electrode）, while the riverine sediments were completely anoxic （-160 mV to -220 mV versus Ag/AgCl electrode）. This redox potential was apparently controlling the trace metals species in the pore waters： for example a strong correlation between Mn and Co was found in the riverine sediments （for DET and DGT sampling）, while in the marine sediments trace metals presented various behaviors.     

Attenuation of aqueous metal transport at two natural acid rock drainage occurrences in the Yukon Territory, Canada

Naturally acidic drainage associated with pyritic black shale has been observed in many locations in the Yukon Territory. While not necessarily linked to known mineral deposits, most of these natural acid rock drainage occurrences show elevated dissolved concentrations of trace elements, especially zinc, nickel, copper, cadmium and arsenic. Based on field observations, microbial investigation, chemical analyses and geochemical modeling, the fate and transport of potentially deleterious elements at two natural acid drainage occurrences with slightly different settings are examined. The Macintosh Creek is a small, acidic stream （pH 2.98-3.40）, 2 km long, located in the Macmillan Pass area of east-central Yukon amidst known sedimentary exhalative massive sulfide mineralization but remains undisturbed by exploration activities. Its trace metal content is apparently derived from groundwater discharges, which gave as much as 5.0, 2.5, 0.7, 0.13 and 0.03 mg/L ofZn, Ni, Cu and As, respectively. Interaction and sorption reactions with algal mats, biofilms and iron oxyhydroxides appear to be the dominant mechanisms attenuating aqueous contaminant transport along the stream. Cryogenic precipitation further consolidates the ferricrete formation and reduces the mobility of the sorbed metals. The tributaries of the Engineering Creek along the Dempster Highway in northern Yukon drain through a series of dolomite, phyllite, argillite, limestone, black shale, sandstone and conglomerate with no known concentration of mineralization. In this area, the water chemistry fully reflects the local geology with acidic streams invariably associated with black shale occurrences. Groundwater seeps in the headwaters area of the km-180 Creek completely enclosed in black shale gave pH 3.0 and as much as 148, 39, 2.9 and 9.1 mg/L of Zn, Ni, Cu and As, respectively. Sorption with iron oxyhydroxide and organic matter appear to dominate the attenuation of contaminant transport along the stream. However, once entered into carbonate-dominated terrains, secondary carbonate minerals exercise additional geochemical control on the local water chemistry as a result of neutralization.     

Influence of humic acid on bioavailability of heavy metals in sediments

The mimetic ocean environment and chemical method were used to research the bioavailability effect of humic acid on five heavy metals in sediment, including Cd, Cu, Zn, Pb and Ni. The sediment was separated into four containers with artificial seawater, and each of them had different concentrations of humic acid. The values of concentrations covered the whole range found in natural sediment （0.1%-10%）. According to the 48 hours LC50 of clam and distribution coefficient, metals were added in artificial seawater, and their speciation was determined at first and then after two days＇ incubation. It was found the bioavailability of heavy metals was reduced in the presence of humic acid. The obvious negative effect on Zn was observed, but the influence on Cd was not remarkable. In addition, the contents of Pb and Ni increased obviously in organic phase, and they are correlative with the concentrations of humic acid.