Hydrochemical and isotopic effects associated with petroleum fuel biodegradation pathways in a chalk aquifer

Hydrochemical data, compound specific carbon isotope analysis and isotopic enrichment trends in dissolved hydrocarbons and residual electron acceptors have been used to deduce BTEX and MTBE degradation pathways in a fractured chalk aquifer. BTEX compounds are mineralised sequentially within specific redox environments, with changes in electron acceptor utilisation being defined by the exhaustion of specific BTEX components. A zone of oxygen and nitrate exhaustion extends approximately 100 m downstream from the plume source, with residual sulphate, toluene, ethylbenzene and xylene. Within this zone complete removal of the TEX components occurs by bacterial sulphate reduction, with sulphur and oxygen isotopic enrichment of residual sulphate (epsilon(s) = -14.4 per thousand to -16.0 per thousand). Towards the plume margins and at greater distance along the plume flow path nitrate concentrations increase with delta15N values of up to +40 per thousand indicating extensive denitrification. Benzene and MTBE persist into the denitrification zone, with carbon isotope enrichment of benzene indicating biodegradation along the flow path. A Rayleigh kinetic isotope enrichment model for 13C-enrichment of residual benzene gives an apparent epsilon value of -0.66 per thousand. MTBE shows no significant isotopic enrichment (delta13C = -29.3 per thousand to -30.7 per thousand) and is isotopically similar to a refinery sample (delta13C = -30.1 per thousand). No significant isotopic variation in dissolved MTBE implies that either the magnitude of any biodegradation-induced isotopic fractionation is small, or that relatively little degradation has taken place in the presence of BTEX hydrocarbons. It is possible, however, that MTBE degradation occurs under aerobic conditions in the absence of BTEX since no groundwater samples were taken with co-existing MTBE and oxygen. Low benzene delta13C values are correlated with high sulphate delta34S, indicating that little benzene degradation has occurred in the sulphate reduction zone. Benzene degradation may be associated with denitrification since increased benzene delta13C is associated with increased delta15N in residual nitrate. Re-supply of electron acceptors by diffusion from the matrix into fractures and dispersive mixing is an important constraint on degradation rates and natural attenuation capacity in this dual-porosity aquifer.     

From food to pest: Conversion factors determine switches between ecosystem services and disservices

Ecosystem research focuses on goods and services, thereby ascribing beneficial values to the ecosystems. Depending on the context, however, outputs from ecosystems can be both positive and negative. We examined how provisioning services of wild animals and plants can switch between being services and disservices. We studied agricultural communities in Laos to illustrate when and why these switches take place. Government restrictions on land use combined with economic and cultural changes have created perceptions of rodents and plants as problem species in some communities. In other communities that are maintaining shifting cultivation practices, the very same taxa were perceived as beneficial. We propose conversion factors that in a given context can determine where an individual taxon is located along a spectrum from ecosystem service to disservice, when, and for whom. We argue that the omission of disservices in ecosystem service accounts may lead governments to direct investments at inappropriate targets.

     

Ozone alters carbon allocation in loblolly pine: assessment with carbon-11 labeling

Loblolly pine (Pinus taeda L.) seedlings were exposed to 0.120 micromol mol(-1) (ppm) ozone for 7 h per day, 5 days per week for 12 weeks. No visible damage resulted from this regime. A short-lived radioisotope of carbon ((11)C) was used to characterize changes in plant physiology caused by ozone, the first time this technique has been used for ozone exposure studies. In comparison to plants kept in charcoal-filtered air, pines exposed to ozone exhibited reductions in photosynthesis (16%), speed of phloem transport (11%), phloem photosynthate concentration (40%) and total carbon transport toward roots (45%). Photosynthate not transported to the roots appeared to accumulate in the stems. Primary branches of pines exposed to ozone were some 50-60% heavier than those of control pines. Ozone was thus shown to have a significant short-term impact on phloem transport processes that results in a shift in allocation of photosynthate favoring stems.     

Simplified contaminant source depletion models as analogs of multiphase simulators

Four simplified dense non-aqueous phase liquid (DNAPL) source depletion models recently introduced in the literature are evaluated for the prediction of long-term effects of source depletion under natural gradient flow. These models are simple in form (a power function equation is an example) but are shown here to serve as mathematical analogs to complex multiphase flow and transport simulators. The spill and subsequent dissolution of DNAPLs was simulated in domains having different hydrologic characteristics (variance of the log conductivity field=0.2, 1 and 3) using the multiphase flow and transport simulator UTCHEM. The dissolution profiles were fitted using four analytical models: the equilibrium streamtube model (ESM), the advection dispersion model (ADM), the power law model (PLM) and the Damkohler number model (DaM). All four models, though very different in their conceptualization, include two basic parameters that describe the mean DNAPL mass and the joint variability in the velocity and DNAPL distributions. The variability parameter was observed to be strongly correlated with the variance of the log conductivity field in the ESM and ADM but weakly correlated in the PLM and DaM. The DaM also includes a third parameter that describes the effect of rate-limited dissolution, but here this parameter was held constant as the numerical simulations were found to be insensitive to local-scale mass transfer. All four models were able to emulate the characteristics of the dissolution profiles generated from the complex numerical simulator, but the one-parameter PLM fits were the poorest, especially for the low heterogeneity case.     

Isotopic modelling of the significance of bacterial sulphate reduction for phenol attenuation in a contaminated aquifer

A Triassic sandstone aquifer polluted with a mixture of phenolic hydrocarbons has been investigated by means of high-resolution groundwater sampling. Samples taken at depth intervals of 1 m have revealed the presence of a diving pollutant plume with a sharply defined upper margin. Concentrations of pollutant phenols exceed 4 g/l in the plume core, rendering it sterile but towards the diluted upper margin evidence for bacterial sulphate reduction (BSR) has been obtained. Groundwaters have been analysed for both delta34S-SO4 and delta18O-SO4. Two reservoirs have been identified with distinct sulphate oxygen isotope ratios. Groundwater sulphate (delta18O-SO4 = 3-5/1000) outside the plume shows a simple linear mixing trend with an isotopically uniform pollutant sulphate reservoir (delta18O-SO4 = 10-12/1000) across the plume margin. The sulphur isotope ratios do not always obey a simple mixing relation, however, at one multilevel borehole, enrichment in 34SO4 at the plume margin is inversely correlated with sulphate concentration. This and the presence of 34S-depleted dissolved sulphide indicate that enrichment in 34SO4 is the result of bacterial sulphate reduction. Delta34S analysis of trace hydrogen sulphide within the plume yielded an isotope enrichment factor (epsilon) of -9.4/1000 for present-day bacterial sulphate reduction. This value agrees with a long-term estimate (-9.9/1000) obtained from a Rayleigh model of the sulphate reduction process. The model was also used to obtain an estimate of the pre-reduction sulphate concentration profile with depth. The difference between this and the present-day profiles then gave a mass balance for sulphate consumption. The organic carbon mineralisation that would account for this sulphate loss is shown to represent only 0.1/1000 of the phenol concentration in this region of the plume. Hence, the contribution of bacterial sulphate reduction to biodegradation has thus far been small. The highest total phenolic concentration (TPC) at which there is sulphur isotope evidence of bacterial sulphate reduction is 2000 mg/l. We suggest that above this concentration, the bactericidal properties of phenol render sulphate-reducing bacteria inactive. Dissolved sulphate trapped in the concentrated plume core will only be utilised by sulphate reducers when toxic phenols in the plume are diluted by dispersion during migration.     

Farm, land, and soil nitrogen budgets for agriculture in Europe calculated with CAPRI

We calculated farm, land, and soil N-budgets for countries in Europe and the EU27 as a whole using the agro-economic model CAPRI. For EU27, N-surplus is 55 kg N ha⁻¹ yr⁻¹ in a soil budget and 65 kg N₂O–N ha⁻¹ yr⁻¹ and 67 kg N ha⁻¹ yr⁻¹ in land and farm budgets, respectively. NUE is 31% for the farm budget, 60% for the land budget and 63% for the soil budget. NS values are mainly related to the excretion (farm budget) and application (soil and land budget) of manure per hectare of total agricultural land. On the other hand, NUE is best explained by the specialization of the agricultural system toward animal production (farm NUE) or the share of imported feedstuff (soil NUE). Total N input, intensive farming, and the specialization to animal production are found to be the main drivers for a high NS and low NUE.     

The distribution of octachlorostyrene (OCS) in environmental samples from Europe

Although octachlorostyrene (OCS) was never used as a commercial product, it may be produced during incineration and combustion processes involving chlorinated compounds. Its environmental spreading was evaluated through the analysis of several representative samples. OCS could not be measured in soil samples collected from urban and rural areas or sediments, but was present (up to 5.41 ng/g dry weight) in industrial soil collected near chemically polluted areas. For aquatic biota samples, the OCS concentrations in freshwater mussels ranged from <0.01 ng/g wet weight (ww) to 0.18 ng/g ww (mean 0.06 ng/g ww) and similar levels could be measured in 11 freshwater fish species from Belgium and Romania. A higher OCS contamination level was found in shrimps (mean 0.08 ng/g ww) compared to marine fish (mean 0.02 ng/g ww for bib and 0.01 ng/g ww for sole and whiting, respectively). OCS could also be measured in 19 harbour porpoise (Phocoena phocoena) liver samples with a mean value of 1.90 ng/g ww. According to these data, it could be computed that the biomagnification factor for OCS was one order of magnitude lower than that of HCB in the fish-porpoise food chain. The mean OCS concentrations in blue tits (Parus caeruleus) eggs and great tits (Parus major) adipose tissue were 1.24 ng/g ww and 3.24 ng/g ww, respectively. OCS could be measured in different tissues of hedgehog (Erinaceus europaeus), with the highest concentrations found in adipose tissue (mean 0.34 ng/g ww) and liver (mean 0.39 ng/g ww). In contrast, only low concentrations of OCS could be measured in human adipose tissue (up to 0.38 ng/g ww) and liver (up to 0.05 ng/g ww), while it could not be detected in human brain or lung. The relationship between the concentrations of OCS and HCB was also discussed for each species.     

Distribution of polychlorinated biphenyls (PCBs) and organochlorine pesticides in soils from the East Antarctic coast

Concentrations of hexachlorobenzene (HCB), alpha-, beta- and gamma-hexachlorocyclohexane (HCH) isomers, 6 o,p'-and p,p'-isomers of DDT and 28 PCB congeners have been measured in eleven soil samples and one lichen collected on the Eastern coast of Antarctica from 5 Russian stations. For samples with low concentrations of PCBs (range 0.20-0.41 ng g(-1) dry weight) and pesticides (0.86-4.69 ng g(-1) and 0.11-1.22 ng g(-1) dry weight for HCHs and DDTs, respectively), atmospheric long-range transport from Africa, South America or Australia was suggested as the sole source of contamination. The profile of PCB congeners was dominated by the more volatile tri-, tetra- and penta-PCBs congeners, thus supporting long-range transport hypothesis. Four samples contained moderate levels of PCBs (range 1.98-6.94 ng g(-1) dry weight) and variable concentrations of pesticides (gamma-HCH, p,p'-DDT and o,p'-DDT being the main contaminants). For samples with high concentrations of PCBs (range 90.26-157.45 ng g(-1)) and high concentrations of pesticides, the presence of high molecular weight PCB congeners such as: 153, 180, 187, 170 etc, strongly suggest a local source (biotic) of PCBs rather than atmospheric transport. It is likely that on a local scale, biotic focussing of pollutants, due to bird activities (nesting and excrement) can cause high contamination levels and become more significant than contaminant input via abiotic pathways.     

Female mimicry and resource defense polygyny by males of a tropical rove beetle,Leistotrophus versicolor (Coleoptera : Staphylinidae)

Summary Adults of the staphylinid beetle Leistotrophus versicolor Grav. aggregate at vertebrate dung and carrion where males and females forage for adult Diptera. Some males aggressively exclude others from dung and carrion. Winners in male combat gain access to many females, which are often receptive at these foraging sites. The mating system can be categorized as resource defense polygyny. Males vary greatly in size, are larger than females on average, and have allometrically enlarged mandibles that they use in fighting. Large males consistently defeat smaller ones. Some males employ female mimicry in order to avoid aggression, remaining at dung where they forage and even obtain copulations while being courted by rival males. Female mimicry is most often practiced by males that are smaller than their rivals or by males that are unable to use their jaws aggressively because they are feeding or courting females when encountered by an opponent. Female mimicry is a conditional tactic of mature males; some individuals behave like females toward larger males but attack smaller rivals. Offprint requests to: J. Alcock     

Distribution of organochlorine pesticides, polychlorinated biphenyls and alpha-HCH enantiomers in pork tissues

The distribution of HCH isomers, DDT analogues and selected PCB congeners in pork organs collected from the same individuals raised in Romanian farms was investigated. Organochlorine pesticides (HCHs and DDTs) were the principal contaminants in all samples, while PCB concentrations were low, in accordance with previously reported concentrations from Romanian animal farms. The most part of the pollutant load in the body is retained in the adipose tissue, with HCHs ranging between 16 and 27.7 ng/g lipid and with higher concentrations of DDTs ranging between 65.9 and 334.5 ng/g lipid. The highest PCB levels (up to 32 ng/g lipid) were measured in lung and liver. The lipid-normalized concentrations in the brain were lower than in all other tissues due to the presence of the blood-brain barrier or due to a lower proportion of the neutral lipids such as triglycerides. The highest concentrations of DDTs were measured in muscle and fat, with p,p'-DDE being the principal contributor and with a variable contribution of p,p'-DDD and p,p'-DDT. In liver, p,p'-DDD has a higher contribution to the sum DDTs, while in all analyzed livers, the concentration of p,p'-DDT was very low. beta-HCH was the most persistent HCH isomer in all tissues, accounting for 40-97% of sum HCHs. For all animals, the highest concentrations of beta-HCH and HCHs were found in liver, while the lowest HCH concentrations were measured in brain and spinal marrow. Additionally, the distribution of alpha-HCH enantiomers in the tissues was discussed. In all samples (except 2 brain samples), (+) alpha-HCH was depleted and (-) alpha-HCH was enantioenriched. Enantiomeric ratios in brain were the highest measured values between all organs. For all studied animals, ERs increased in the order fat < muscle < liver < brain.