Laura E McAllister’s research while affiliated with Lancaster University and other places

The ability of carbonaceous geosorbents (CGs) such as black carbon (BC) to extensively sorb many common environmental contaminants suggests that they potentially possesses qualities useful to the sequestration of harmful xenobiotics within contaminated land. Presently, however, there is limited understanding of the implications for the bioaccessibility, mobility and environmental risk of organic contaminants while sorbed to BC in soil and sediment, in addition to the inherent toxicity of BC itself to terrestrial flora and fauna. We review both the processes involved in and factors influencing BC sorption characteristics, and ultimately consider the impacts BC will have for bioavailability/bioaccessibility, toxicity and risk assessment/remediation of contaminated land. We conclude that while the application of BC is promising, additional work on both their toxicity effects and long-term stability is required before their full potential as a remediation agent can be safely exploited.

The observed strong sorption of polycyclic aromatic hydrocarbons (PAHs) to black carbon (BC) presents potential implications for PAH bioaccessibility in soils. The effects of BC on the desorption kinetics and mineralisation of phenanthrene in four soils was investigated after 1, 25, 50 and 100d soil-PAH contact time, using sequential hydroxypropyl-β-cyclodextrin (HPCD) extractions in soils amended with 0, 0.1, 1 and 5% (dry wt. soil) activated charcoal (AC, a form of BC). The Rrapidly (%Frap) and slowly (%Fslow) desorbing phenanthrene fractions and their rate constants were determined using a first-order two-compartment (biphasic) desorption model. A minimum 7.8-fold decrease in %Frap occurred when AC was increased from 0-5%, with a corresponding increase in %Fslow. Desorption rate constants followed the progression krap(% h-1) > kslow(% h-1) and were in the order of 10-1 to 10-2 and 10-3 to 10-4, respectively. Linear regressions between %Frap and the fractions degraded by a phenanthrene inoculum (% Fmin) indicated that slopes did not approximate 1 at concentrations greater than 0% AC; %Fmin often exceeded %Frap, indicating a fraction of sorbed phenanthrene (%Fslow) remained microbially accessible. Therefore, sorption-HPCD-desorption kinetics alone may not be an adequate basis for the prediction of the bioaccessibility of PAHs to microorganisms and/or bioremediation potential in AC amended soils.

The desorption of polycyclic aromatic hydrocarbons (PAHs) often exhibits a biphasic profile similar to that observed for biodegradation whereby an initial rapid phase of degradation or desorption is followed by a phase of much slower transformation or release. Most investigations to-date have utilised a polymeric sorbent, such as Tenax, to characterise desorption, which is methodologically unsuitable for the analysis of soil. In this study, desorption kinetics of (14)C-phenanthrene were measured by consecutive extraction using aqueous solutions of hydroxypropyl-beta-cyclodextrin (HPCD). The data indicate that the fraction extracted after 24 h generally approximated the linearly sorbed, rapidly desorbing fraction (F(rap)), calculated using a three-compartment model. A good linear correlation between phenanthrene mineralised and F(rap) was observed (r(2) = 0.89; gradient = 0.85; intercept = 8.20). Hence HPCD extraction (24 h) and first-order three-compartment modelling appear to provide an operationally straightforward tool for estimating mass-transfer limited biodegradation in soil.

The development of phenanthrene catabolism in four soils amended with varying concentrations of activated charcoal (AC) (0%, 0.1%, 1% and 5%), a type of black carbon, was investigated. Mineralisation of (14)C-phenanthrene was monitored after 1, 25, 50 and 100 d soil-PAH contact time; lag phases, rates and extents of mineralisation of the (14)C-phenanthrene to (14)CO(2) were determined. At concentrations >0.1% AC rates and extents of mineralisation were reduced by more than 99%. This revealed that the presence of >0.1% AC in soils may substantially diminish the rate at which the catabolic activity of indigenous soil microflora develops in contaminated soil. Soil C, which had the highest organic carbon (OC) content, consistently exhibited the highest extents of degradation. It is suggested that, in accordance with other researchers, OC may have blocked available phenanthrene sorption sites. This enhanced phenanthrene availability ultimately facilitated a greater level of catabolic activity within this soil. Such results reflect the complex nature of interactions between soil, biota and contaminants and their influence on the degradation of contaminants in the environment.

The quantification of organic contaminant bioaccessibility in soils and sediments is essential for the risk assessment and remediation of contaminated land. Within this framework, practitioners require standardised protocols. Cyclodextrins are a group of macrocyclic compounds that can form inclusion complexes with organic xenobiotics. This occurrence can be exploited to measure the labile/rapidly desorbable compound fraction, which correlates with microbial degradation. We present a rapid and easily reproducible HPCD shake extraction technique that has been experimentally demonstrated to directly predict microbial availability and degradation in soil. This method can provide practitioners with both an indication of bioremediation end-points and may be valuable in the risk assessment of contaminated land.