Black carbon-dominated PCDD/Fs sorption to soils at a former wood impregnation site.

The influence of black carbon (BC) on the sorption of 17 native polychlorinated-p-dibenzodioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) was studied in five soil samples from a sawmill site where wood used to be impregnated with chlorophenol preservatives. The presence of BC caused measured total organic carbon (TOC)-water distribution ratios (K(TOC)) to be a median factor of 51 (interquartile range 18-68, n=85) higher than modeled amorphous organic carbon (AOC)-water distribution ratios (K(AOC)). K(TOC) was a factor of 73+/-27 above K(AOC) for PCDFs (n=10) and a factor of 20+/-13 (n=7) for PCDDs. The reason for this difference is probably that attaining a planar configuration after sorption to BC is less thermodynamically favorable for PCDDs than for PCDFs. BC-water distribution ratios were calculated from K(TOC), K(AOC) and BC contents, and ranged from 10(9.9) (2,3,7,8-Tetra-CDD) to 10(11.5) l kg(-1) (Octa-CDF). More than 90% of the PCDD/Fs in the soil was calculated to be BC-sorbed. Dissolved organic carbon (DOC)-water distribution ratios were measured to be in the same order of magnitude as K(AOC). This study shows that strong sorption to BC should be included when assessing ecotoxicological risk or modeling transport to groundwater of PCDD/Fs in soil.

Net methylmercury production as a basis for improved risk assessment of mercury-contaminated sediments.

Sediments contaminated by various sources of mercury (Hg) were studied at 8 sites in Sweden covering wide ranges of climate, salinity, and sediment types. At all sites, biota (plankton, sediment living organisms, and fish) showed enhanced concentrations of Hg relative to corresponding organisms at nearby reference sites. The key process determining the risk at these sites is the net transformation of inorganic Hg to the highly toxic and bioavailable methylmercury (MeHg). Accordingly, Hg concentrations in Perca fluviatilis were more strongly correlated to MeHg (p < 0.05) than to inorganic Hg concentrations in the sediments. At all sites, except one, concentrations of inorganic Hg (2-55 microg g(-1)) in sediments were significantly, positively correlated to the concentration of MeHg (4-90 ng g(-1)). The MeHg/Hg ratio (which is assumed to reflect the net production of MeHg normalized to the Hg concentration) varied widely among sites. The highest MeHg/Hg ratios were encountered in loose-fiber sediments situated in southern freshwaters, and the lowest ratios were found in brackish-water sediments and firm, minerogenic sediments at the northernmost freshwater site. This pattern may be explained by an increased MeHg production by methylating bacteria with increasing temperature, availability of energy-rich organic matter (which is correlated with primary production), and availability of neutral Hg sulfides in the sediment pore waters. These factors therefore need to be considered when the risk associated with Hg-contaminated sediments is assessed.

Sequential extraction of sulfide-rich tailings remediated by the application of till cover, Kristineberg mine, northern Sweden.

A sequential extraction has been carried out on sulfide-rich mine tailings. The purpose was to investigate how elements released by oxidation are secondarily retained in the tailings and the possible consequences of the remediation. After investigating the solid tailings, seven samples were chosen for sequential extractions. Two samples were oxidised, situated just above the oxidation front; two samples from just below the former oxidation front with increased concentrations of several elements; two unoxidised samples were from an intermediate depth, and the deepest sample was from the tailings-peat boundary at the bottom of the impoundment. Five phases were extracted: adsorbed/exchangeable/carbonate; labile organics; amorphous Fe-oxyhydroxides/Mn-oxides; crystalline Fe-oxides; and organics/sulfides. The addition from dried porewater to the extracted fractions has been calculated and considered as minor. In the oxidised tailings, the sulfide fraction still dominates for elements such as Fe, S, Cd, Co, Cu, Hg and Zn, although the concentrations are low compared to the unoxidised tailings. Generally, the second most important fraction is the adsorbed/exchangeable/carbonate fraction. Below the oxidation front, the sulfide content of the tailings sharply increases. In the secondary enrichment zone, the total element concentrations increase compared with the deeper unoxidised samples, mainly due to secondary retention. For some elements, secondary retention is greater than the total amount extracted for the deeper unoxidised samples. In the secondary enrichment zone the adsorbed/exchangeable/carbonate fraction represents approximately 20 wt.% or more for Cd, Co, Mn, Ni and Zn. The amorphous iron oxyhydroxide or the crystalline iron oxide fractions are less important at this level, although for As, Ba and Cu the amorphous iron oxyhydroxide fraction represents up to 20 wt.%. At the lower border of the enrichment zone, the total concentration for most metals is lower, but the importance of the adsorbed/exchangeable/carbonate fraction is further enhanced for Cd, Cu, Ni and Zn. These elements have 35-60 wt.% of the total amount from this fraction. For As, Cd, Cu, Ni and Pb, the secondary fractions extracted (extractions A-D) represent between 60 and 80 wt.% of the total content. At greater depth in the impoundment the relative importance of the adsorbed/exchangeable/carbonate fraction decreases, whilst the importance of amorphous iron oxyhydroxide and crystalline iron oxide fractions increases. The adsorbed/exchangeable/carbonate fraction is the most easily remobilised fraction. A raised groundwater table previously situated below the enrichment zone may result in the release of secondarily retained metals.