Evaluating mobilization and transport of arsenic in sediments and groundwaters of Aquia aquifer, Maryland, USA

Groundwater and sediment samples were collected along a flow path in the Aquia aquifer (Paleocene), Maryland in order to examine and study the factors influencing "evolution" of arsenic (As) in these groundwaters. The Aquia crops out near Washington, DC, where it is unconfined, and extends approximately 90 km down dip to the south and east towards and beneath the Chesapeake Bay. The studied flow path was chosen owing to (i) the number of accessible wells, (ii) differences in total dissolved As concentrations in groundwaters from some of the sampled wells, which reach values >/=667 nmol kg(-1) or >/=50 ppb, and (iii) the distinct difference in total dissolved As concentrations in Aquia groundwaters between the northern and southern portions of the study area. In groundwater samples, in situ separation of inorganic As species [As(III) and As(V)] were performed by using anion exchange chromatography. Subsequently, As concentrations were determined by inductively coupled plasma mass spectrometry. In situ measurements of Fe concentrations and speciation, dissolved S(-II) concentrations, pH, alkalinity, and oxidation-reduction potential (Eh) were determined to establish the oxidation-reduction conditions and solution chemistry along the flow path. Concentrations of As in 12 analyzed groundwater samples range from approximately 0.75 to 1 072 nmol kg(-1), and As(III) concentrations ranging from 0.24 to 980 nmol kg(-1) appears to be the dominant form of As in solution. 50% of the studied wells yielded groundwaters with concentrations that exceed the US EPA's Maximum Contaminant Level for As in drinking water of 133 nmol kg(-1) or 10 ppb. In order to examine the solid phase speciation of As within the aquifer sediments, we collected a number of Aquia sediment samples from a drill core that was archived at the Maryland Geological Survey. These sediment samples were evaluated using a previously established sequential extractions procedure. Solid phase As concentrations range between 973 and 2,012 nmol kg(-1). Additionally, petrographic, X-Ray diffraction and diffuse reflectance spectroscopy analyses of the Aquia sediments reveal presence of glauconite, and smectite along with goethite and hematite within the samples. Here, we present the possible mechanisms responsible for the elevated As concentrations in the studied groundwaters of the Aquia aquifer.     

Effect of natural organic matter on thallium and silver speciation

Natural organic matter (NOM) is known to play an important role in the transport and binding of trace metal elements in aquatic and soil systems. Thallium is a pollutant for which the extent of the role played by NOM is poorly known. Consequently, this study investigates thallium(I) and its complexation to a purified humic substance as proxy for NOM. Experiments were performed with the Donnan Membrane Technique to separate, for the first time, the free Tl⁺ ion from its complexed form in the bulk solution. Various pH and concentrations were investigated at constant ionic strength and constant NOM proxy concentrations in solution. Experimental results were described with NICA-Donnan model. Thallium complexation was compared to silver complexation using literature data and using the same NICA-Donnan formalism. Parameters for these two cations (Tl⁺ and Ag⁺) are reported in this article, for the first time. Results display low thallium complexation to the NOM proxy while silver competes with divalent cations for the NOM binding sites. Calculated speciation for dissolved thallium highlights the dominance of free thallium (Tl⁺) in solution whereas Tl-NOM complexes contribute roughly 15% to total Tl(I) species in river and lake type waters. Similar results are obtained for soil solutions, Tl-bound to NOM < 30% of total, from UK soils with different land use and geochemistry.     

Trace metal speciation and fluxes within a major French wastewater treatment plant: impact of the successive treatments stages

Seven metals (Cd, Co, Cr, Cu, Fe, Ni and Pb) were monitored at the Seine-Aval wastewater treatment plant during 6 sampling campaigns in April 2004. Particulate and dissolved metals have been measured in 24 h composite samples at each treatment stage (primary settling, secondary activated sludge and tertiary flocculation by FeCl₃). In addition, the diffusive gradient in thin film technique (DGT) was used to determine the dissolved inert and labile metal fraction. Although all treatment stages were able to decrease particulate metals concentrations in wastewater, most dissolved metals concentrations were mainly affected during primary settling. This unexpected result was attributed to tertiary sludge filtrate recirculation. Metals added via the FeCl₃ reagent at the tertiary treatment were shown to lower the overall Cr removal from wastewater and to enrich Ni in effluents. The plant operating conditions (recirculation and reagent addition) appear therefore as important as treatment processes for the metals removal. Total metal fluxes were highly decreased by the whole treatment plant for Cd, Cr, Cu and Pb and to a lesser extend for Co and Ni. However, the labile metal fluxes were poorly decreased for Cu (18%), not significantly decreased for Ni and increased for Fe. The labile fraction of Cd, Co and Cr was not detectable at any stage of the plant. Discharged labile fluxes, at least for Ni, were potentially significant compared to the labile metal fluxes in the river measured downstream the plant. Treated urban wastewater discharges should be carefully considered as a possible source of bioavailable trace metals.     

Effects of substrate types on the transformation of heavy metal speciation and bioavailability in an anaerobic digestion system

Chemical speciation can fundamentally affect the potential toxicity and bioavailability of heavy metals. The transformation of heavy metal speciation and change of bioavailability were investigated in an anaerobic digestion (AD) system using four different substrates (pig manure (PM), cattle manure (CAM), chicken manure (CHM) and rice straw (RS)). The results obtained indicated that the total contents of heavy metals in PM, CHM and CAM were higher than in RS and decreased in the order Zn > Cu > Ni > Pb > As > Cd in all substrates. Moreover, the speciation with the largest proportion for each heavy metal was the same both in the different substrates and the biogas residues. Among them, Zn, Ni, Cd and As were mainly in the reducible fraction (F2), while Cu was mainly in the oxidizable fraction (F3) and Pb occurred predominantly in the residual fraction (F4). Our results further indicated that the AD process had a greater effect on the speciation of heavy metals in CHM and PM, but less on CAM and RS. The rates of change in bioavailability followed the order PM > CHM > CAM > RS. Changes in organic matter, humic acid or local metal ion environment as a result of AD were inferred as likely mechanisms leading to the transformation of heavy metal speciation. These results enhanced our understanding of the behavior of heavy metals in AD and provided a new perspective for the treatment and disposal of the substrates.