Occurrence and rates of terminal electron-accepting processes and recharge processes in petroleum hydrocarbon-contaminated subsurface.

The occurrence and rates of terminal electron acceptor processes, and recharge processes in the unsaturated zone of a boreal site contaminated with petroleum hydrocarbons in the range C(10) to C(40) were examined. Soil microcosms were used to determine the rates of denitrification, iron (Fe) reduction, sulfate (SO(4)) reduction, and methanogenesis in two vertical soil profiles contaminated with oil, and in a noncontaminated reference sample. Furthermore, the abundances of the 16S rRNA genes belonging to Geobacteracaea in the samples were determined by real-time quantitative polymerase chain reaction (PCR). Analyses of ground water chemistry and soil gas composition were also performed together with continuous in situ monitoring of soil water and ground water chemistry. Several lines of evidence were obtained to demonstrate that both Fe reduction and methanogenesis played significant roles in the vertical profiles: Fe reduction rates up to 3.7 nmol h(-1) g(-1) were recorded and they correlated with the abundances of the Geobacteracaea 16S rRNA genes (range: 2.3 x 10(5) to 4.9 x 10(7) copies g(-1)). In the ground water, ferrous iron (Fe(2+)) concentration up to 55 mg L(-1) was measured. Methane production rates up to 2.5 nmol h(-1) g(-1) were obtained together with methane content up to 15% (vol/vol) in the soil gas. The continuous monitoring of soil water and ground water chemistry, microcosm experiments, and soil gas monitoring together demonstrated that the high microbial activity in the unsaturated zone resulted in rapid removal of oxygen from the infiltrating recharge thus leaving the anaerobic microbial processes dominant below 1.5 m depth both in the unsaturated and the saturated zones of the subsurface.

Extractability of metals and ecotoxicity of soils from two old wood impregnation sites in Finland.

Four metal-contaminated soil samples were classified using physical methods, extracted by selective extraction procedures and analyzed for chemical concentrations. De-ionized water, 0.01 mol/l barium chloride, 1 mol/l ammonium acetate and concentrated nitric acid were used as extraction solutions. Ecotoxicity of water extracts and soil samples was analyzed in order to describe the bioavailability of the contaminants. Samples from old wood impregnation plants contained high amounts of As, Cu, Cr and Zn, which originated from chromated copper arsenate, ammoniacal copper-zinc arsenate, and ammoniacal copper quaternary compound. Total As concentrations of the heavily contaminated samples varied from 752 to 4340 mg/kg, Cu concentrations from 339 to 2330 mg/kg, Cr concentrations from 367 to 2,140 mg/kg and Zn concentrations from 79 to 966 mg/kg. The extractabilities of metals differed according to soil type, extractant and element. Cu and Zn were proposed to cause the highest toxicity in the water extracts of the soils. Ecotoxicity tests displayed rather high differences in sensitivity both for water extracts and for solid soil samples. Reproduction of Enchytraeus sp. was the most sensitive and seed germination of Lactuca sativa the least sensitive and the other tests were in decreasing order of sensitivity: Folsomia candida>reverse electron transport>MetPLATE>Toxichromotest>Allium cepa root growth>Lemna sp. growth. As a conclusion, polluted soils rich in sand retain heavy metals with less firm bindings, particularly in the case of Cu and Zn, than soils rich in clay, indicating that chemical methods for measuring the bioavailability of metals need to be optimized taking into account the soil type, acidity, redox state and the individual contaminants.