Selenium contamination in the Colorado River Basin, western USA： Remediation by leaching and nanof＇dtration membranes

Selenium （Se） is an essential micronutrient to biota, but can become a potent toxicant at elevated concentrations. The natural sources and chemical properties of Se species make the boundary between deficiency and toxicity narrow for some biota, with both phenomena common around the globe. Large areas of farmland in the Colorado River Basin （CRB） generate salinized drainage water with Se concentrations much higher than 5 μg/L, the U.S. Environmental Protection Agency chronic water-quality criterion for the protection of aquatic life. We have carried out detailed field and laboratory studies to investigate Se geochemistry and remediation in two of these areas： the Middle Green River Basin, Utah and the Salton Sea Basin, California, located respectively in the Upper and Lower CRB. Results from these and other studies show that approximately 90% of the dissolved Se in the Colorado River and its tributaries originally is derived from the Upper Cretaceous Mancos Shale and equivalent pyritic marine units that outcrop in the Upper CRB. Selenium is mobilized commonly by biogeochemical oxidation of this pyritic shale and is concentrated mainly as selenate （SeO4^2-） in soils and agricultural drainage water of dry climates by evaporation. Minor （0%-5%） amounts of Se are present as the selenite species （HSeO3^-） and （SEO3^2-）, but these species and the more reduced species, elemental Se （SeO） and selenide （Se^2-）, have much lower solubility and/or have high sorptive affinity towards organic matter, clay minerals and iron oxyhydroxides. The concentration of dissolved Se （-2.5 μg/L） and salinity in the Lower Colorado River water are among the highest of the world major rivers. Because of low precipitation （7 cm/a） and extreme evapotranspiration （-1.8 m/a） rates in the Salton Sea Basin, California, Se values in irrigation water imported from the Colorado River increase to 〉300 μg/L in drainage wastewater. Removal of Se from contaminated wastewater by nanofiltration membranes was demonstrated in laboratory and pilot-scale field experiments.     

Associations and mobility of uranium in soils near a depleted uranium （DU） weapons testing site, SW Scotland

Natural uranium has three isotopes, ^238U, ^235U and ^234U, with natural abundances of 99.27 atom %, 0.72% and 0.0055%, respectively. Only ^235U is fissile and the production of nuclear fuel and nuclear weapons involves enrichment of uranium in ^235U. This process also results in separation of ^234U from ^238U, leaving depleted uranium （DU）, with typical ^234U/^238U and ^235U/^238U activity ratios of about 0.19 and 0.013, respectively, as a waste product. The high density, high melting and boiling points and chemical stability of uranium and the availability of DU in relatively pure form mean that DU has many uses, including armour-piercing munitions. Such munitions have been developed in the UK since the 1960s and testing has been carried out by the Ministry of Defence （MoD） at firing ranges such as Dundrennan, SW Scotland and Eskmeals, NW England. The firing of DU munitions can result in the dispersion of DU and its combustion products （oxides） as aerosols or as larger fragments, with the potential for human exposure either directly at the site of detonation or via post-depositional migration in the environment. The aim of this work was to investigate the potential environmental mobility of DU by characterizing the associations of U in soil porewaters with increasing distance from a firing site. To this end, several soil cores located down-wind of the firing site at Dundrennan, near Kirkcudbright, SW Scotland, were collected in May 2006. These were sectioned on-site into 1- or 2-cm depth intervals and porewaters were isolated by centfifugation （10 minutes; 8873 g） on return to the laboratory. Following filtration through 0.2-micron cellulose nitrate filters, the porewaters were analyzed by ICP-QMS （U concentration） and ICP-OES （Fe, Al, Ca, Mg, Mn concentrations）. Sub-samples were also subjected to centrifugal ultrafiltration （100, 30, and 3 kD） and to gel electrophoretic fractionation （agarose; 0.045 M Tris-borate; 20 mA, 30 minutes）. Results showed that U was present at up to 4 μg/L in the soil porewater and that the associations of U varied with sample location and soil depth.     

Possibility of degradation of phenylarsonic acid in the presence of ferrihydrite

Although inorganic species are predominant in natural systems, but there are many kinds of organoarsenic species such as methylated and phenylated arsenic compounds. Phenylarsonic acid （PA） is a degradation product of organoarsenics used for chemical warfare agents, which has been detected in well water at the disposal site of the agents in Japan. There are few reports studying behavior of PA in soil. In this study, PA was adsorbed onto ferrihydrite and its chemical forms were determined using high performance liquid chromatography connected to inductivity-coupled plasma mass spectrometry （HPLC-ICP-MS）. 100 mg/kg of PA was mixed with 0.03 g of 2-line ferrihydrite. For each suspension, pH was adjusted by HNO3 or NaOH. Each sample was incubated for more than 19 hours and the final pH was measured. After filtration, the chemical form of arsenic in the filtrate was measured using HPLC-ICP-MS. In addition, ferrihydrite separated by filtration was dissolved by 3 ml of 0.5 M HCI and the arsenic species in the solution was detected by HPLC-ICP-MS （column： Tosoh TSKgel SuperlC-AP, eluent： 0.01 M HNO3）. It was verified that PA is not degraded by heating in 0.5 M HCl solution. At pH 3.1, any arsenic compounds were not detected from the solution, because almost all arsenic species were adsorbed onto ferrihydrite at lower pH. At pH= 12, however, 7%-10% of inorganic arsenic was detected in the solution. In solid phase, there are some problems to determine the precise ratio of inorganic and organic species. When the solution includes Fe ion at 0.01 M level, the retention time of arsenic species drifted compared to those in standard solution, which makes it difficult to determine precisely the arsenic species adsorbed on ferrihydrite. Therefore, more study is needed to determine the ratio of inorganic and organic species in the system.     

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.     

Permeable Reactive Barrier for the treatment of contaminated surface water in Katedan industrial development area, Hyderabad, India

Permeable Reactive Barrier （PRB） is an emplacement of inert material （s） in the subsurface, designed to intercept a contaminated plume, provides a preferential flow path through the reactive media, and transforms the contaminant into environmentally acceptable forms to attain concentration remediation goals at the discharge of the barrier. The phenomena, which help in remediation within PRB, are adsorption/sorption, precipitation, oxidation/reduction and biodegradation. Various materials like zero-valent iron, zero-valent bi-metals, natural zeolites, organic carbon, fly ash, zeolites, limestone, activated alumina, apatites, etc. have been tried by many researchers to remove organic and inorganic contaminants. In USA, Canada, and many European countries commercial full-scale and pilot scale PRBs are successfully working. The design and installation of full scale PRBs needs laboratory treatability and dynamic flow column experiments？ The concept of PRB is being applied to treat contaminated surface water in the Katedan industrial area, Hyderabad, India. National Geophysical Research Institute （NGRI）, Hyderabad, India, conducted systematic studies in collaboration with Norwegian Geotechnical Institute （NGI）, Norway, to develop PRB technique to decontaminate the surface water pollution due to industrial effluent. A site assessment study in the Katedan Industrial Area, were carried out and water, soil and sediment from the lakes of the area were found to be polluted with high concentrations of heavy metals like As, Pb, Cr, Cd, Ni, etc. Adsorption studies at NGRI with synthetic samples and in-situ industrial effluent using different reactive media for removing contaminants like arsenic, chromium, cadmium, copper, nickel, lead and zinc have been carried out and yielded satisfactory results. The performance of zero-valent iron and limestone is encouraging in removing As,     

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.     

Synergistic effect of combining sulfate reducing bacteria and zerovalent iron permeable reactive barriers on the treatment of groundwater rich in uranium, sulfate and heavy metals

Uranium processing and mining activities that generate many contaminants, such as high concentrations of U （VI）, sulfate and heavy metals （Zn, Cu, Ni, etc）, may pose a serious threat to the groundwater resources. In recent years, considerable research has been conducted respectively on two kinds of permeable reactive barriers （PRB）, including zerovalent iron （ZVI） and sulfate reducing bacteria （SRB）, for in-situ removal of these pollutants from groundwater. However, little investigation has been carried out on the potential benefits of bioaugmenting ZVI barriers to enhance the elimination of the pollutants by combining ZVI with SRB systems. The main goal of this study was to conduct batch and column experiments to determine whether the combination of SRB and ZVI can function synergistically and accelerate the rate of pollutant removal. The results of anaerobic batch experiments demonstrated that although the integrated ZVI/PRB system itself has no ability to reduce and remove sulfate directly, SRB can utilize hydrogen gas produced during the slow process of ZVI corrosion as an electron donor to raise biomass yields significantly and accelerate reductive sulfate removal. In particular, ferrous cations produced as the byproduct of ZVI corrosion process reacted with hydrogen sulfide from sulfate reduction and formed iron-bearing sulfide precipitates, which can stimulate the growth of SRB and promote sulfate removal activity by eliminating the biotoxicity of hydrogen sulfide. It was also shown that secondary mineral products （pyrite/ferrous sulfide） formed as a consequence of microbial sulfate reduction and ZVI corrosion process can enhance the microbial precipitation of soluble U （VI） as insoluble uraninite（uranium dioxide）.