Temporal variability in dynamic and colloidal metal fractions determined by high resolution in situ measurements in a UK estuary

In recent environmental legislation, such as the Water Framework Directive in the European Union (WFD, 2000/60/EC), the importance of metal speciation and biological availability is acknowledged, although analytical challenges remain. In this study, the Voltammetric In situ Profiler (VIP) was used for high temporal resolution in situ metal speciation measurements in estuarine waters. This instrument simultaneously determines Cd, Cu and Pb species within a size range (ca. <4 nm) that is highly relevant for uptake by organisms. The colloidal metal fraction can be quantified through a combination of VIP measurements and analyses of total dissolved metal concentrations.VIP systems were deployed over tidal cycles in a seasonal study of metal speciation in the Fal Estuary, southwest England. Total dissolved concentrations were 4.97-315 nM Cu, 0.13-8.53 nM Cd and 0.35-5.75 nM Pb. High proportions of Pb (77 ± 17%) and Cu (60 ± 25%) were present as colloids, which constituted a less important fraction for Cd (37 ± 30%). The study elucidated variations in the potentially toxic metal fraction related to river flow, complexation by organic ligands and exchanges between dissolved and colloidal phases and the sediment. Based on published toxicity data, the bioavailable Cu concentrations (1.7-190 nM) in this estuary are likely to severely compromise the ecosystem structure and functioning with respect to species diversity and recruitment of juveniles. The study illustrates the importance of in situ speciation studies at high resolution in pursuit of a better understanding of metal (bio)geochemistry in dynamic coastal systems.     

Transcriptional profiles induced by the Aryl Hydrocarbon Receptor agonists 2,3,7,8-tetrachlorodibenzo-p-dioxin, 2,3,7,8-tetrachlorodibenzofuran and 2,3,4,7,8-pentachlorodibenzofuran in primary rat hepatocytes

Toxicogenomics was used to examine mRNA expression profiles obtained from primary rat hepatocytes treated for 24 h with 0.01 or 1.0 nM 2,3,7,8-tetrachlorodibenzo-p-dioxin (2,3,7,8-TCDD), 0.02 or 2.0 nM 2,3,4,7,8-pentachlorodibenzofuran (2,3,4,7,8-PeCDF) and 0.1 or 10 nM 2,3,7,8-tetrachlorodibenzofuran (2,3,7,8-TCDF). The concentrations of 2,3,4,7,8-PeCDF and 2,3,7,8-TCDF were chosen to be equivalent to 2,3,7,8-TCDD’s concentration based on the toxic equivalency factor/toxic equivalent (TEF/TEQ) method for estimating biological potency. 2,3,7,8-TCDD at 1.0 nM altered the expression of 533 genes; 2,3,4,7,8-PeCDF at 2.0 nM altered 182 genes, and 2,3,7,8-TCDF at 10 nM altered 154 genes. Of these, 57 genes were affected by all three congeners. Agglomerative hierarchical clustering revealed distinct congener-dependent gene subclusters. Principal components analyses of the microarray data revealed that these congeners cluster independently of one another. Data presented here demonstrate that equivalent TEQ concentrations of 2,3,7,8-TCDD, 2,3,4,7,8-PeCDF and 2,3,7,8-TCDF, while altering the expression of a small battery of genes in common, also produce substantial congener specific alterations in gene expression.     

Preparation and X-ray structural characterization of further stereoisomers of 1,2,5,6,9,10-hexabromocyclododecane

Technical 1,2,5,6,9,10-hexabromocyclododecane (HBCD) consists largely of three diastereomers (α-, β-, and γ-HBCD) produced by the trans addition of bromine to cis,trans,trans-cyclododeca-1,5,9-triene (CDT). However, another seven diastereomers are theoretically possible and may be produced by trans addition of bromine across the double bonds of the other three isomers of 1,5,9-CDT. There are indications that small amounts of the minor HBCD isomers may be present in commercial HBCD mixtures or in products containing this brominated flame retardant (BFR). Such minor components may indeed derive from traces of other 1,5,9-CDTs in the cis, trans, trans starting material, however their formation may also be possible through isomerizations during the processing of this BFR or by bioisomerization subsequent to its release into the environment. Two of the seven additional diastereomers (δ- and ε-HBCD) were synthesized previously from trans,trans,trans-CDT. We now report the preparation of the remaining five diastereomers, ζ-, η-, and θ-HBCD from cis,cis,trans-CDT and ι- and κ-HBCD from cis,cis,cis-CDT, and their characterization by ¹H NMR spectroscopy and X-ray crystallography. The availability of these further diastereomers of HBCD should aid in determining if the minor isomers are present in commercial samples of this BFR, in products containing HBCDs, or in environmental samples. We have also carried out an X-ray crystal structure determination on ε-HBCD, so that crystal structures are now available for all 10 HBCD diastereomers.     

Outdoor and indoor cadmium distributions near an abandoned smelting works and their relations to human exposure

The relationship of measured or modelled Cd concentrations in soil, house dust and available to plants with human urinary Cd concentrations were assessed in a population living around a Cd/Pb/Zn smelter in the UK. Modelled air concentrations explained 35% of soil Cd variation indicating the smelter contributed to soil Cd loads. Multi-variate analysis confirmed a significant role of biological and life-style factors in determining urinary Cd levels. Significant correlations of urinary Cd with soil, house dust and modelled plant available Cd concentrations were not, however, found. Potential reasons for the absence of clear relationships include limited environmental contact in urban populations; the role of undefined factors in determining exposure; and the limited spatial scope of the survey which did not sample from the full pollution gradient. Further, the absence of any significant relationship indicates that environmental measures provide limited advantage over atmospheric model outputs for first stage human exposure assessment.     

Characterization of spatial impact of particles emitted from a cement material production facility on outdoor particle deposition in the surrounding community

The objective of this study was to estimate the contribution of a facility that processes steel production slag into raw material for cement production to local outdoor particle deposition in Camden, NJ. A dry deposition sampler that can house four 37-mm quartz fiber filters was developed and used for the collection of atmospheric particle deposits. Two rounds of particle collection (3-4 weeks each) were conducted in 8-11 locations 200-800 m downwind of the facility. Background samples were concurrently collected in a remote area located -2 km upwind from the facility. In addition, duplicate surface wipe samples were collected side-by-side from each of the 13 locations within the same sampling area during the first deposition sampling period. One composite source material sample was also collected from a pile stored in the facility. Both the bulk of the source material and the < 38 microm fraction subsample were analyzed to obtain the elemental source profile. The particle deposition flux in the study area was higher (24-83 mg/m2 x day) than at the background sites (13-17 mg/m2day). The concentration of Ca, a major element in the cement source production material, was found to exponentially decrease with increasing downwind distance from the facility (P < 0.05). The ratio of Ca/Al, an indicator of Ca enrichment due to anthropogenic sources in a given sample, showed a similar trend. These observations suggest a significant contribution of the facility to the local particle deposition. The contribution of the facility to outdoor deposited particle mass was further estimated by three independent models using the measurements obtained from this study. The estimated contributions to particle deposition in the study area were 1.8-7.4% from the regression analysis of the Ca concentration in particle deposition samples against the distance from the facility, 0-11% from the U.S. Environmental Protection Agency (EPA) Chemical Mass Balance (CMB) source-receptor model, and 7.6-13% from the EPA Industrial Source Complex Short Term (ISCST3) dispersion model using the particle-size-adjusted permit-based emissions estimates.     

Environmental analysis of groundwater in Mecosta County, Michigan

Groundwater withdrawal has major economic, social, and environmental implications. In Michigan, recent legislative activity has begun to address the issue of groundwater sustainability. However, more hydrologic data are needed to help inform policy and legislation. A study was conducted in Mecosta County, Michigan to: (1) determine if a relationship could be established between land use/land cover and groundwater quality; and (2) develop a conceptual model for the shallow groundwater system of the study region. In general, groundwater quality was good, with below detection levels of E. coli, low total bacterial counts, and relatively low nutrient concentrations. No statistically significant associations were found between the bacterial numbers and either land use or the physical/chemical attributes measured, which may be because the scale of our spatial analysis was too coarse to detect patterns. Finer-scale, localized processes may have a greater influence on microorganism growth and abundance than coarser-scale, regional processes in this area. Our groundwater analysis suggested that shallow groundwater flow paths are generally consistent with regional surface water flow networks, and that shallow groundwater levels in most of the region have fluctuated within 1–2 m over the past 30 years, with no obvious increasing or decreasing trend.     

Methyl bromide as a building disinfectant: interaction with indoor materials and resulting byproduct formation

Several buildings were contaminated with Bacillus anthracis in the fall of 2001. These events required consideration of how to disinfect large indoor spaces for continued worker occupation. The interactions of gaseous disinfectants with indoor materials may inhibit the disinfection process, cause persistence of the disinfectant, and lead to possible byproduct formation and persistence. Methyl bromide (CH3Br) is a candidate for disinfection/deactivation of biological agents in buildings. In this study, 24 indoor materials were exposed to CH3Br for 16 hr at concentrations ranging from 100 to 2500 ppm in 48-L electropolished stainless steel chambers. CH3Br concentrations were measured during and after disinfection. Its interactions with materials were observed to be small, with nearly complete and rapid desorption. Between 3% and 8% of CH3Br adsorbed to four materials (office partition, ceiling tile, particle-board, and gypsum wallboard with satin paint), and the degree of adsorption decreased with increasing relative humidity. The percentage of adsorption to all other materials was <2%. This result suggests that when designing disinfection events with CH3Br, loss to indoor materials can be neglected in terms of disinfectant dose calculations. Possible reaction products were identified and/or quantified before and after exposure to CH3Br. Several monomethylated and dimethylated aliphatic compounds were observed in chamber air at low concentrations after the exposures of six materials to CH3Br. Concentration increases also occurred for chemicals that were observed to naturally off-gas from materials before exposure to CH3Br, suggesting that CH3Br may play a role in enhancing the natural off-gassing of chemicals, for example, by competitive displacement of compounds that already existed in the materials. The results described in this paper should facilitate the design of building disinfection systems involving CH3Br.     

Estimating the hydraulic properties of the fracture network in a sandstone aquifer

The potential hydraulic behaviour of the fracture network in a major Triassic sandstone aquifer in the UK has been evaluated. The properties of the fracture network were determined using results from detailed scan line surveys at 10 sites, television and geophysical borehole logging, and packer testing. Six sets of discontinuities common to all sites were identified and statistically characterised (dip, strike, orientation, density, size, and estimated transmissivity). A discrete fracture network model was then used stochastically to investigate the properties of the network. In general, the network is poorly connected: it is estimated that 9% of the discontinuities intersecting boreholes are transmissive. The hydraulic behaviour of the network is generally dominated by one sub-horizontal bedding plane fracture set, although when present, a relatively infrequent north-south striking, sub-vertical set modifies the bulk flow properties significantly. Ignoring this latter set, the network's minimum representative volume is about 35 x 35 x 35 m. The upscaled permeability is anisotropic, being typically 23 times greater in the horizontal than in the vertical. Tortuosity in the north-south direction is around 1.6.     

Enhancement of reproductive success through mate choice in a social rock-wallaby, Petrogale assimilis (Macropodidae) as revealed by microsatellite markers

The reason why a female who is socially paired to one particular male seeks extra-pair copulations (EPCs) with others has important implications in life history models and to the study of behaviour. The Allied rock-wallaby, Petrogale assimilis, lives in spatially isolated colonies in tropical north Queensland, Australia. Extensive observations of a colony at Black Rock showed that intense behavioural bonding occurs between pairs of adult males and females; about two-thirds of males paired with one female, the remainder paired with two females simultaneously. Single-locus microsatellite profiling determined the paternity of 63 offspring from 21 females for which long-term behavioural data were available. One-third of the young were fathered by males which were not paired socially with the mother. The mating system was heterogeneous: (1) all offspring of 11 females were fathered by the mother's partner, (2) all young of 5 females were fathered by extra-pair males, and (3) only some of the young of 5 females were fathered by their regular consort. Analysis of individual longitudinal demographic records showed that females whose young were always fathered by their consort had higher reproductive success than those whose young were always fathered as a result of (EPCs). However, females with some offspring fathered by their regular consort and others via EPCs had the highest probability of raising young to independence. These females were significantly more likely to have an offspring fathered as a result of an EPC if their previous young had failed to survive to pouch emergence. These results are consistent with the hypothesis that females choose mates for their genetic quality. Comparison of the males with which these females sought EPCs and the regular consorts suggested that arm length rather than body weight or testes size was used as the index of genetic quality. Results from a second colony of rock-wallabies in which the reproductive rate was accelerated were also consistent with the genetic-quality hypothesis. These results imply that by choosing better-quality fathers irrespective of social pairing, females are able to maximise their overall lifetime reproductive success, and presumably, those of their offspring. Received: 8 June 1997 / Accepted after revision: 28 February 1998     

Distribution of foraging habitats of male loggerhead turtles (Caretta caretta) as revealed by stable isotopes and satellite telemetry

Most studies on the foraging ecology of loggerhead turtles (Caretta caretta) have focused on adult females and juveniles. Little is known about the foraging patterns of adult male loggerheads. We analyzed tissues for carbon and nitrogen stable isotopes (δ¹³C and δ¹⁵N) from 29 adult male loggerheads tracked with satellite transmitters from one breeding area in Florida, USA, to evaluate their foraging habitats in the Northwest Atlantic (NWA). Our study revealed large variations in δ¹³C and δ¹⁵N and a correlation between both δ¹³C and δ¹⁵N and the latitude to which the loggerheads traveled after the mating season, thus reflecting a geographic pattern in the isotopic signatures. Variation in δ¹³C and δ¹⁵N can be explained by differences in food web baseline isotopic signatures rather than differences in loggerhead trophic levels. Stable isotope analysis may help elucidate residency and migration patterns and identify foraging sea turtle subpopulations in the NWA due to the isotopically distinct habitats used by these highly migratory organisms.