The behaviour of residual contaminants at a former station site,Antarctica

In 1994, New Zealand's only mainland Antarctic base, Vanda Station, was removed from the shores of Lake Vanda, in the McMurdo Dry Valleys region of southern Victoria Land, Antarctica. Residual chemical contamination of the station site has been identified, in the form of discrete fuel spills, locally elevated Pb, Zn, Ag and Cd concentrations in soil and elevated Cu, Ni, Co and phosphate concentrations in suprapermafrost fluids in a gully formerly used for domestic washing water disposal. Pathways for contaminant transfer to Lake Vanda, potential environmental impacts and specific remediation/monitoring options are considered. While some contaminants (particularly Zn) could be selectively leached from flooded soil, during a period of rising lake level, the small area of contaminated soils exposed and low level of contamination suggests that this would not adversely affect either shallow lake water quality or the growth of cyanobacteria. Phosphate-enhanced growth of the latte may, however, be a visible consequence of the minor contamination occurring at this site.     

Analysis of colloid and tracer breakthrough curves

We consider the dispersion and elution of colloids and dissolved nonsorbing tracers within saturated heterogeneous porous media. Since flow path geometry in natural systems is often ill-characterized macroscopic (mean) flow rates and dispersion tensors are utilized in order to account for the sub-model scale microscopic fluctuations in media structure (and the consequent hydrodynamic profile). Even for tracer migration and dispersal this issue is far from settled.Here we consider how colloid and tracer migration phenomena can be treated consistently. Theoretical calculations for model flow geometries yield two quantitative predictions for the transport of free (not yet captured) colloids with reference to a non-sorbing dissolved tracer within the same medium: the average migration velocity of the free colloids is higher than that of the tracer; and that the ratio of the equivalent hydrodynamic dispersion rates of colloids and tracer is dependent only upon properties of the colloids and the porous medium, it is independent of pathlengths and fluid flux, once length scales are large enough.The first of these is well known, since even in simple flow paths free colloids must stay more centre stream. The second, if validated suggests how solute and colloid dispersion may be dealt with consistently in macroscopic migration models. This is crucial since dispersion is usually ill-characterized and unaddressed by the experimental literature. In this paper we present evidence based upon an existing Drigg field injection test for the validity of these predictions.We show that starting from experimental data the fitted dispersion rates of both colloids and non-sorbing tracers increase with the measured elution rates (obeying slightly different rules for tracers and colloids); and that the ratio of colloid and nonsorbing tracer elution rates, and the ratio of colloid and nonsorbing tracer dispersion rates may be dependent upon properties of the colloids and the medium (not the flow regime).It is important to realize that even for unretarded species, an earlier peak in the breakthrough curve does not necessarily correspond to a faster mean elution rate, or vice versa. But rather that a colloid may elute faster but disperse less than an equivalent tracer. Hence its peak may be retarded compared to that of the tracer, even assuming no retardation. Hence one must consider a combination of mean elution rate and mean dispersion rate, and not rely on “peak times” to corroborate chromatographic effects. The importance of this lies in the fact that these processes are not independent and yet upscale differently. Thus realistic estimates of effective colloid dispersion rates should be upscaled in a way consistent with that adopted for tracers within the same system.     

New passive samplers for chlorinated semivolatile organic pollutants in ambient air

Two new types of passive samplers were designed and tested on semivolatile organic compounds. The first type (a spiral-rod sampler) consists of a low-density polyethylene membrane acting as a permeation film and a silicone elastomer as the receiving material; the second (a stir-bar sampler) has the same membrane material but a polydimethylsiloxane-coated stir bar acting as the collector phase and installed radially symmetrically in the sampler. The advantages of the new samplers are their simple design, low costs, and their easy processing via thermodesorption coupled with capillary gas chromatography and mass selective detection. In both samplers, the uptake of selected analytes was integrative over exposure periods of up to 384 h. The sampling rates calculated from a laboratory calibration study using the chlorinated semivolatiles hexachlorobenzene, hexachlorocyclohexane isomers and polychlorinated biphenyls ranged from 88.1 ml h-1 for delta-hexachlorocyclohexane to 3443 ml h-1 for 2,2',5,5'-tetrachlorobiphenyl. A field trial at a hazardous waste dump near Bitterfeld, Germany, for up to 21 days combined with periodical determinations of air concentrations using low-volume sampling indicated that the new samplers can in principle be used in the field, although the sampling rates derived from the field results differed considerably from the laboratory findings. Nevertheless the preliminary results suggest that the new sampler types are promising for the long-term air monitoring of semivolatiles.     

Toxicity of the mosquito control pesticide Scourge to adult and larval grass shrimp (Palaemonetes pugio)

This study investigated the toxicity of various concentrations of technical resmethrin and Scourge on adult and larval Palaemonetes pugio, a common grass shrimp species. Two types of tests were conducted for each of the resmethrin formulations using adult and larval grass shrimp life stages, a 96-h static renewal aqueous test without sediment, and a 24-h static nonrenewal aqueous test with sediment. For resmethrin, the 96-h aqueous LC50 value for adult shrimp was 0.53 microg/L (95% confidence interval (CI): 0.46-0.60 microg/L), and for larval shrimp was 0.35 microg/L (95% CI: 0.28-0.42 microg/L). In the presence of sediment, technical resmethrin produced a 24-h LC50 value for adult shrimp of 5.44 microg/L (95% CI: 4.52-6.55 microg/L), and for larval shrimp of 2.15 microg/L (95% CI: 1.35-3.43 microg/L). For Scourge, the 96-h aqueous LC50 for adult shrimp was 2.08 microg/L (95% CI: 1.70-2.54 microg/L), and for larval shrimp was 0.36 microg/L (95% CI: 0.24-0.55 microg/L). The 24-h sediment test yielded an LC50 value of 16.12 microg/L (95% CI: 14.79-17.57 microg/L) for adult shrimp, and 14.16 microg/L (95% CI: 12.21-16.43 microg/L) for larvae. Adjusted LC50 values to reflect the 18% resmethrin concentration in Scourge are 0.37 microg/L (adult), 0.07 microg/L (larvae) for the 96-h aqueous test, and 2.90 microg/L (adult), 2.6 microg/L (larvae) for the 24-h sediment test. Larval grass shrimp were more sensitive to technical resmethrin and Scourge than the adult life stage. The results also demonstrate that synergized resmethrin is more toxic to P. pugio than the nonsynergized form, and that the presence of sediment decreases the toxicity of both resmethrin and Scourge.     

Biodegradation of trace gases in simulated landfill soil cover systems

The attenuation of methane and seven volatile organic compounds (VOCs) was investigated in a dynamic methane and oxygen counter gradient system simulating a landfill soil cover. The VOCs investigated were: Tetrachloromethane (TeCM), trichloromethane (TCM), dichloromethane (DCM), trichloroethylene (TCE), vinyl chloride (VC), benzene, and toluene. Soil was sampled at Skellingsted landfill, Denmark. The soil columns showed a high capacity for methane oxidation, with oxidation rates up to 184 g/m2/d corresponding to a 77% reduction of inlet methane. Maximal methane oxidation occurred at 15-20 cm depth, in the upper part of the column where there were overlapping gradients of methane and oxygen. All the chlorinated hydrocarbons were degraded in the active soil columns with removal efficiencies higher than 57%. Soil gas concentration profiles indicated that the removal of the fully chlorinated compound TeCM was because of anaerobic degradation, whereas the degradation of lower chlorinated compounds like VC and DCM was located in the upper oxic part of the column. Benzene and toluene were also removed in the active column. This study demonstrates the complexity of landfill soil cover systems and shows that both anaerobic and aerobic bacteria may play an important role in reducing the emission of trace components into the atmosphere.     

Effect of gasoline formulation on the formation of photosmog: a box model study

Based on exhaust gas analyses from the combustion of five different types of gasoline in a passenger car operated on a chassis dynamometer, box model simulations of the irradiation of exhaust/NOx/air mixtures using an established chemical mechanism for a standardized photosmog scenario were performed. The fuel matrix used covered wide fractional ranges for paraffinic, olefinic, and aromatic hydrocarbons. Two fuels also contained methyl tertiary butyl ether (MTBE). The different O3 profiles calculated for each run were compared and interpreted. The O3 levels obtained were strongly influenced by the exhaust gas concentrations of aromatic and olefinic hydrocarbons. The higher exhaust content of these compounds caused higher O3 production in the smog system investigated. The conclusion of the present study is that the composition of gasoline cannot be taken directly for the estimation of the emissions' O3 creation potential from its combustion. Variation of the dilution in the different calculations showed evidence for an additional influence of transport effects. Accordingly, further detailed exhaust gas analyses followed by more complex modeling studies are necessary for a proper characterization of the relationship between fuel blend and gasoline combustion products.     

Application of a pathogenicity marker found in Escherichia coli for the assessment of irrigation water quality.

A polymerase chain reaction (PCR)-based method was developed to differentiate between pathogenic and nonpathogenic Escherichia coli (E. coli). A pathogenicity marker, linked to the deletion of the ygfB gene, was identified in 80% of the clinical E. coli isolates tested. This marker, combined with the malic acid dehydrogenase gene, formed the duplex PCR that was subsequently used to screen E. coli isolates recovered from two secondary wastewater treatment plants (STPs) and a river site. All waters samples are used to irrigate dairy farm pasture in the West Gippsland region of Victoria, Australia. Results from three consecutive months of sampling (December 2001 and January and February 2002) indicated that Longwarry STP showed 8, 8, and 0% pathogenic E. coli; Pakenham STP showed 0, 12.5, and 33%; and the Bunyip river site showed 20, 12, and 25% respectively.     

Sub-canopy deposition of ozone in a stand of cutleaf coneflower

Although there has been a great deal of research on ozone, interest in exposure of native, herbaceous species is relatively recent and it is still not clear what role the pollutant has in their ecological fitness. The ozone exposure of a plant is usually expressed in terms of the concentration above the canopy or as a time-weighted index. However, to understand the physiological effects of ozone it is necessary to quantify the ozone flux to individual leaves as they develop, which requires knowing the deposition velocity and concentration of the pollutant as a function of height throughout the plant canopy. We used a high-order closure model of sub-canopy turbulence to estimate ozone profiles in stands of cutleaf coneflower (Rudbeckia laciniata L.) located in the Great Smoky Mountains National Park, USA. The model was run for periods coinciding with a short field study, during which we measured vertical concentration profiles of ozone along with measurements of atmospheric turbulence and other meteorological and plant variables. Predictions of ozone profiles by the model are compared with observations throughout the canopy.     

The internal barriers of rotation for the 209 polychlorinated biphenyls

The internal barrier of rotation (Erot) was calculated for all 209 polychlorinated biphenyls (PCBs) by using a semi-empirical method, viz. the Austin Model 1 (AMI) Hamiltonian. The difference in total energy between a forced planar state and an optimised twisted structure was defined as Erot. The Erot values were in the range of 8.33 to 483 kj/mol, and were significantly influenced by the number of chlorine atoms inortho position. An additional structural characteristic of the PCBs influencing Erot ofortho substituted congeners was substitution by chlorine atoms in vicinalmeta positions, which is assumed to prevent outward bending ofortho substituents. This so-called buttressing effect contributed with 4 to 31 kj/mol per added chlorine atom. In conclusion, the internal barrier of rotation, calculated for all 209 PCBs, provides an important structure dependent physico-chemical parameter for multivariate modelling of future quantitative structure-activity and structure-property relationships (QSARs/QSPRs).