paper's from Kieron's PhD studies, 2001-2005

Laboratory based studies on the fate of organic contaminants in soil typically requires the test compound(s) to be spiked into the test medium. Consequently, such studies are inherently dependent on the homogeneity of the contaminant within the spiked soil. Three blending methods were compared for the addition of a phenanthrene-transformer oil mixture into field-wet soil. Spiking homogeneity, reproducibility and artefacts were assessed based on dichloromethane and hydroxypropyl-beta-cyclodextrin chemical extractability, and bacterial mineralization. Spiking using a stainless-steel spoon, consistently produced good spike homogeneity as determined by sample oxidation, chemical extraction and mineralization, and was consistently more reliable than either the Waring blender or modified bench drill. Overall, neither transformer oil-concentration nor blending method influenced chemical extractability or mineralization of the PAH following 1 day equilibration. In general, spiking procedures require validation prior to use, as homogeneity cannot be assured.

Contamination of soil by polycyclic aromatic hydrocarbons is frequently associated with non-aqueous-phase liquids. Measurement of the catabolic potential of a soil or determination of the biodegradable fraction of a contaminant can be done using a slurried soil respirometric system. This work assessed the impact of increasing the concentration of transformer oil and soil:water ratio on the microbial catabolism of [14C]phenanthrene to 14CO2 by a phenanthrene-degrading inoculum. Slurrying (1:1, 1:2, 1:3 and 1:5 soil:water ratios) consistently resulted in statistically higher rates and extents of mineralisation than the non-slurried system (2:1 soil:water ratio; P<0.01). The maximum extents of mineralisation observed occurred in the 1:2–1:5 soil:water ratio microcosms irrespective of transformer oil concentration. Transformer oil concentrations investigated displayed no statistically significant effect on total mineralisation (P>0.05). Soil slurries 1:2 or greater, but less than 1:5 (soil:water), are recommended for bioassay determinations of total contaminant bioavailability due to greater overall mineralisation and improved reproducibility.

Organic matter is considered to be the single most importantfactor limiting availability and mobility of persistent organic pollutants (POPs) in soil. This study aimed to characterize the distribution of 14C-PCB (congeners 28 and 52) and 14C-PAH (fluoranthene and benzo[a]pyrene) residues in an Orthic Luvisol soil obtained from two lysimeter studies initiated in 1990 at the Agrosphere Institute (Forschungszentrum Jülich GmbH, Germany). The lysimeter soils contained a low-density OM fraction, isolated during soil washing, which contained a significant fraction (3-12%) of the total 14C-activity. Soils were also fractionated according to three particle sizes: >20, 20-2, and <2 microm. Relative affinity values of 14C-activity for the different particle sizes varied in the order 20-2 microm > (<2 microm) approximately (>20 microm) for the PCBs. Relative affinity values of 14C-activity for the different particle sizes varied in the order 20-2 microm > (<2 microm) > (>20 microm) for the PAHs. The distribution of 14C-PCB or 14C-PAH residues in the organic and inorganic matrixes of the particle-size fractions was determined using methyl isobutyl ketone (MIBK). 14C-PCB and 14C-PAH-associated activities were primarily located in the humin fraction of the 20-2 and <2 microm particle-size fractions of the soil. A small fraction was associated with the fulvic and humic acid fractions; these were quantitatively more important for the PAHs than the PCBs. There appeared to be a high degree of association of 14C-activity with the mineral fraction following MIBK separation of the humic fractions, ranging between 8 and 52% for 14C-PCBs and 57-80% for 14C-PAHs. The mineral (inorganic) component of the soils apparently played a significant (previously unreported) role in the sequestration of both PCBs 28 and 52 and the PAHs fluoranthene and benzo[a]pyrene.