Biodegradation potential of MTBE in a fractured chalk aquifer under aerobic conditions in long-term uncontaminated and contaminated aquifer microcosms

The potential for aerobic biodegradation of MTBE in a fractured chalk aquifer is assessed in microcosm experiments over 450 days, under in situ conditions for a groundwater temperature of 10 °C, MTBE concentration between 0.1 and 1.0 mg/L and dissolved O₂ concentration between 2 and 10 mg/L. Following a lag period of up to 120 days, MTBE was biodegraded in uncontaminated aquifer microcosms at concentrations up to 1.2 mg/L, demonstrating that the aquifer has an intrinsic potential to biodegrade MTBE aerobically. The MTBE biodegradation rate increased three-fold from a mean of 6.6 ± 1.6 μg/L/day in uncontaminated aquifer microcosms for subsequent additions of MTBE, suggesting an increasing biodegradation capability, due to microbial cell growth and increased biomass after repeated exposure to MTBE. In contaminated aquifer microcosms which also contained TAME, MTBE biodegradation occurred after a shorter lag of 15 or 33 days and MTBE biodegradation rates were higher (max. 27.5 μg/L/day), probably resulting from an acclimated microbial population due to previous exposure to MTBE in situ. The initial MTBE concentration did not affect the lag period but the biodegradation rate increased with the initial MTBE concentration, indicating that there was no inhibition of MTBE biodegradation related to MTBE concentration up to 1.2 mg/L. No minimum substrate concentration for MTBE biodegradation was observed, indicating that in the presence of dissolved O₂ (and absence of inhibitory factors) MTBE biodegradation would occur in the aquifer at MTBE concentrations (ca. 0.1 mg/L) found at the front of the ether oxygenate plume. MTBE biodegradation occurred with concomitant O₂ consumption but no other electron acceptor utilisation, indicating biodegradation by aerobic processes only. However, O₂ consumption was less than the stoichiometric requirement for complete MTBE mineralization, suggesting that only partial biodegradation of MTBE to intermediate organic metabolites occurred. The availability of dissolved O₂ did not affect MTBE biodegradation significantly, with similar MTBE biodegradation behaviour and rates down to ca. 0.7 mg/L dissolved O₂ concentration. The results indicate that aerobic MTBE biodegradation could be significant in the plume fringe, during mixing of the contaminant plume and uncontaminated groundwater and that, relative to the plume migration, aerobic biodegradation is important for MTBE attenuation. Moreover, should the groundwater dissolved O₂ concentration fall to zero such that MTBE biodegradation was inhibited, an engineered approach to enhance in situ bioremediation could supply O₂ at relatively low levels (e.g. 2–3 mg/L) to effectively stimulate MTBE biodegradation, which has significant practical advantages. The study shows that aerobic MTBE biodegradation can occur at environmentally significant rates in this aquifer, and that long-term microcosm experiments (100s days) may be necessary to correctly interpret contaminant biodegradation potential in aquifers to support site management decisions.     

Laboratory stabilization/solidification of tank sludges: GAAT, OHF, and combined tank sets

Highly radioactive, mixed-waste sludges that have been collected at Oak Ridge over several decades are being combined for treatment and disposal. Stabilization of the sludges in the different tank sets was tested prior to the proposed combination and treatment. This paper, which follows a previous article on the Melton Valley Storage Tank/Bethel Valley Evaporator Storage Tank set, documents the testing of the Gunite and Associated Tank and Old Hydrofracture Facility tank sets, as well as the combined sludges of all the Oak Ridge National Laboratory tank sets; the third paper on this subject will discuss efforts to maximize the sludge loading. The grout formulations were tested in the laboratory with surrogates. A wet-sludge loading of 60wt% resulted in strong wasteforms with no free water and gave a volume increase of about 30-40vol%. The Resource Conservation and Recovery Act metals included in the surrogate testing were silver, cadmium, chromium, lead, selenium, thallium, zinc, and mercury. The grout formulations stabilized these metals within the Universal Treatment Standards limits. In addition, a grout leachability index of about 10.0-12.0 was measured for both (85)Sr and (137)Cs, meeting the recommended requirement of >6.0.     

Inconsistent temporal changes in the megabenthos of the English Channel

A survey was undertaken of the benthic communities found at ten stations that were sampled by Norman Holme in the 1950s. These stations were selected because Holme recorded the presence of large bivalve species (Glycymeris glycymeris and Paphia rhomboides). Fauna with large body-size are known to be most susceptible to disturbance by human activity, so the presence or absence of these organisms might indicate whether such disturbance has increased at these sites since the 1950s. As expected, differences were detected in the community composition between sites that were located in deeper or shallower water. These differences were consistent for the communities sampled in the present study and for those sampled by Holme. The brittlestar Ophiothrix fragilis was highly abundant at only one site. Nevertheless, long-lived bivalve species still occurred at most of the sites sampled in 1998. G. glycymeris was absent from two sites sampled in 1998 and P. rhomboides was absent from only one site in 1998. Holme suggested that his reported decline in the abundance of O. fragilis might be attributed to the increase in bottom fishing in the English Channel. However, the continued presence of long-lived bivalves at most sites would suggest that other factors could be responsible. A comparison of bivalve and echinoderm species that occurred in the 1950s and in 1998 indicated the occurrence of relatively large temporal changes, as might be expected over a period of more than 40 years. However, this occurred at eight of the ten sites. At two sites, the spatial variation was quantitatively similar to the temporal variation. This suggests that areas of the sea bed exist that have a similar community composition to those found prior to the general increase in bottom-fishing disturbance.     

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.     

Effects of Clear-Cut Harvesting on Boreal Ground-Beetle Assemblages (Coleoptera: Carabidae) in Western Canada

We compared pitfall catches from four types of mature lodgepole pine—white spruce forest with those from five age classes of young forest regenerating subsequent to clear-cutting. Ground beetles were most abundant in the youngest sites (1–2 years since cutting) and in the mature stands on moist soil. Species richness was higher in regenerating sites than in mature forest. Cluster analysis grouped the ground-beetle fauna according to forest age and forest type, suggesting that there is a general pattern of recovery after logging. Responses of common species to forest cutting fell into three groups: (1) forest generalists (2 species) were not dramatically affected, (2) species of open habitat (27 species) appeared and/or increased in abundance, and (3) mature forest species (10 species) disappeared or decreased in abundance. Populations of many mature forest species appear to recover following logging, but several specialists did not recolonize even the oldest regenerating stands. Furthermore, fragmentation and creation of large areas of relatively homogeneous young forest stages through logging may have detrimental long-term effects even on the more abundant forest generalists. We must better understand subtle variations in habitat in order to maintain invertebrate diversity while harvesting the boreal forest.     

The mating system of two hybridizing species of water striders (Gerridae)

Summary We studied oviposition, feeding and mating behavior of the water striders Limnoporus dissortis and L. notabilis in sympatric and allopatric populations occurring on semi-permanent ponds in Alberta and British Columbia, Canada. Here we describe the mating system of the species and consider the evolution and maintenance of reproductive strategies employed by both sexes. Females of both species oviposited along edges of floating vegetation, either with a guarding, postcopulatory male in attendance, or alone and independent of copulation. Some females ovipositing alone were discovered by males, and when pressed for copulation, either (1) abandoned oviposition or (2) copulated and then resumed oviposition. Females that oviposited with a guarding male laid more eggs than those that completed oviposition alone. Most breeding females accepted prey offered experimentally, while a large proportion of males rejected prey but responded to model gerrids with aggressive displays and mating behavior. Males displayed three mating tactics: (1) territorial-signaling (TS), (2) patrol-signaling (PS), and (3) silent patrolling (SP). All territorial males produced surface waves from oviposition sites before attempting to mate. Some patrolling males signaled, while approaching potential mates as an aid in sex discrimination, but others did not signal and mounted both males and females. When presented with dead gerrid models, males of L. notabilis discriminated between sexes while those of L. dissortis mounted both male and female conspecifics. Collectively, males employing TS tactics fertilized more eggs than patrolling males and TS males of L. notabilis fertilized relatively more eggs than those of L. dissortis. Individual males switched frequently between territorial and patrolling behavior both under natural conditions and in field exclosures. TS males gave more signals per encounter than PS males suggesting that signaling varies with male dominance. Choice of tactic did not depend upon hunger level and was not associated with significant differences in body length in single-species populations. However, in a mixed population, the smaller males of L. dissortis were rarely territorial and signaled infrequently.     

Adult flight in a water strider exposed to habitat drydown in the larval stages

Aquarius paludum inhabits a wide variety of water surfaces, ranging from temporary to permanent ponds and lakes throughout the Palearctic. Thus, some larvae of A. paludum will be exposed to habitats that dry out. We assess here the influence of drying on water strider growth and development. When exposed to drying-out in the larval stage, the growth period was prolonged. Drying-out during one of the first three instars was associated with longer maintenance of flight muscles without histolysis and reduced the number of eggs laid by long-winged (LW) adults that shifted to a "flyer" strategy. Alternatively, adults exposed to dry habitats during whole larval period expressed shorter preoviposition periods and shifted to a "non-flying, reproducer" strategy. These contrasting responses to drying can be understood as flexible physiological functions depending on the drying history to which larvae are exposed. This flexibility may be a significant factor in allowing A. paludum to occupy such a wide range of habitats in Eurasia.     

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.     

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.