Elvira Vassilieva

Potential release of selected trace elements (As, Cd, Cu, Mn, Pb and Zn) from sediments in Cam River-mouth (Vietnam) under influence of pH and oxidation.

Since contaminated river-bed sediments in the Cam River-mouth (Vietnam) are regularly dredged and disposed on land, an understanding of the influence of time, pH and oxidation on the leaching behavior of heavy metals (Cd, Cu, Mn, Pb and Zn) and arsenic is necessary for the management of these dredged materials. A 96 h pH(stat)-leaching test to examine the leaching behavior of elements at pre-set pH values (2, 4, 6, 8 (natural), 9 and 11) and a BCR 3-step extraction to clarify the element fractionation, were performed on a freshly-collected wet suboxic sediment and a dry oxidized sediment. All heavy metals and arsenic display a V-shaped pH-dependent leaching pattern with important releases at pHs 2 and 11. At the investigated pH values, the release of As, Mn, Pb and Zn from the oxidized sediment is slower and lower if compared with the suboxic sediment while the opposite trend is found for Cd and Cu at pHs 2-8. The transfer from the acid-soluble (exchangeable and carbonate-bound) fraction to the reducible (Fe and Mn hydr/oxide-bound) fraction is consistent with the lower leachability of As, Mn and Zn at pHs 2-8 and Pb at pHs 4-8 after oxidation, while the transfer from the oxidizable (organic matter and sulfide-bound) fraction to the reducible fraction relates to the higher leachability of Cd and Cu at pHs 2-8. The lower leachability of all elements at alkaline pHs 9-11 is due to lower leached concentration of organic matter from the oxidized sediment. Sulfides only play a minor role in controlling the leachability of heavy metals and arsenic.

Assessment on Pollution by Heavy Metals and Arsenic Based on Surficial and Core Sediments in the Cam River Mouth, Haiphong Province, Vietnam

The Cam River mouth (Haiphong Province) is one of the main river mouths of the Red River System, which is one of the most important water resources in Northern Vietnam. Over the past 50 years, the strong socio-economic development in the area has caused a considerable contamination with heavy metals (Co, Cr, Cu, Mn, Ni, Pb, and Zn) and arsenic. In this study, the vertical and horizontal distributions of heavy metals and arsenic in sediments from the Cam River mouth were investigated. In addition, the history, origin, and degree of contamination were assessed. Normalized (with respect to Al) heavy metal and arsenic concentrations in sediment cores and absolute dates obtained from the 137Cs analysis were used to reconstruct the pollution history of the river mouth. As, Cu, Mn, Pb, and Zn concentrations increase rapidly by approximately two times or more from 1954 to 1975, and then remain nearly unchanged from 1975 until 2008, whereas Co, Cr, and Ni concentrations slightly increase from 1954 until 2008. In addition, background values for heavy metals and arsenic have also been determined with regard to the period before 1954. In the study area, Co, Cr, Cu, Ni, Mn, and Zn are evaluated as minorly enriched, whereas As and Pb are classified as moderately enriched. Generally, the anthropogenic activities in the Haiphong harbor and industrial zone locally contribute to the contamination by heavy metals and arsenic in the Cam River mouth.

Speciation and Mobility of Selected Trace Metals (As, Cu, Mn, Pb and Zn) in Sediment with Depth in Cam River-Mouth, Haiphong, Vietnam

The speciation and mobility of some selected trace metals (As, Cu, Mn, Pb and Zn) in sediments with depth was investigated in the Cam River-mouth (Vietnam) by collecting sediment cores and analysing porewater and sediment composition, complemented with single (ammonium-EDTA) and sequential (BCR 3-step) extractions and mineralogical analysis (XRD). All trace metals show overall decreasing trends with depth in porewater as a result of anthropogenic input in upper sediment layers. High porewater concentrations of As, Mn and Pb in oxic and suboxic sediment layers may result in groundwater pollution. Sediment-bound Pb and Mn dominate in the reducible and the acid-soluble fraction, respectively, while Cu and Zn distribute rather evenly between four extracted fractions. The porewater metal speciation, as predicted by a geochemical model Visual MINTEQ version 3.0, indicates that the toxicity of Cu, Mn, Pb and Zn (presented by the proportions of free metal ions) decreases with depth, while the toxicity of As increases when As(III) becomes more abundant. The dissolved concentrations of trace metals are not only controlled by the precipitation/dissolution of discrete hydroxide/oxide, carbonate and phosphate minerals, but also by sorption processes on major sorbents (i.e. As on goethite, and Mn and Zn on calcite and dolomite). Sulphide minerals do not show any control even in the anoxic zone most likely because of the low concentration of sulphur.

Insights into solid phase characteristics and release of heavy metals and arsenic from industrial sludge via combined chemical, mineralogical, and microanalysis

This study investigates the solid phase characteristics and release of heavy metals (i.e., Cd, Co, Cu, Cr, Mo, Ni, Pb, and Zn) and arsenic (As) from sludge samples derived from industrial wastewater treatment plants. The emphasis is determining the influence of acidification on element mobilization based on a multidisciplinary approach that combines cascade and pHstat leaching tests with solid phase characterization through X-ray diffraction (XRD), field emission gun electron probe micro analysis (FEG-EPMA), and thermodynamic modeling (Visual MinteQ 3.0). Solid phase characterization and thermodynamic modeling results allow prediction of Ni and Zn leachabilities. FEG-EPMA is useful for direct solid phase characterization because it provides information on additional phases including specific element associations that cannot be detected by XRD analysis. Cascade and pHstat leaching test results indicate that disposal of improperly treated sludges at landfills may lead to extreme environmental risks due to high leachable concentrations of Zn, Ni, Cu, Cr, and Pb. However, high leachabilities under acid conditions of Ni and Zn as observed from pHstat leaching test results may provide a potential opportunity for acid extraction recovery of Ni and Zn from such sludges.