Sodium borohydride reduction of individual polybrominated diphenyl ethers

Many chemicals in use today lack appropriate documentation on their environmental properties, fate, and effects. To counteract this lack of documentation it is vital to thoroughly investigate a compound’s fate in the environment before it comes into use. The present study is describing a novel method for assessing the reduction potential of polybrominated diphenyl ethers (PBDEs), as a part of a project aimed to create an experimental model for determination of chemical persistence. The reductive transformation of 15 PBDE congeners using sodium borohydride was determined. Pseudo-first-order reaction rate constants of the transformations were determined by monitoring the disappearance of the investigated congeners. The reductions lead primarily to formation of lower brominated PBDEs. Each PBDE congener was tested in a total of ten replicates which showed a relative standard deviation of 31% or less. The decaBDE, BDE-209 was approximately 3 times as prone to reductive transformation as BDE-207. The three nonaBDEs, BDE-206, BDE-207, and BDE-208, showed similar reductive potential. The reactivity of the tested octaBDEs was quite variable, from 5% to 24% of the reactivity of BDE-209 for BDE-196 and BDE-198, respectively. The heptaBDEs studied were in the range of the less reactive octaBDEs, except for BDE-181 which was as high as 13% of the reactivity of BDE-209. The results presented give a method for measuring the propensity of PBDEs, and possibly similar compounds, to undergo reductions. They indicate a potential route to a vital piece of information in the assessment of environmental persistence of chemicals.     

Are methylmercury concentrations in the wetlands of Kejimkujik National Park, Nova Scotia, Canada, dependent on geology?

In the relatively pristine ecosystem in Kejimkujik Park, Nova Scotia, methylmercury (MeHg) concentrations in loons, Gavia immer, are among the highest recorded anywhere in the world. This study investigated the influence of bedrock lithology on MeHg concentrations in wetlands. Twenty-five different wetland field sites were sampled over four different bedrock lithologies; Kejimkujik monzogranite, black sulfidic slate, gray slate, and greywacke. Soil samples were analyzed for ethylmercury (EtHg), MeHg, total Hg, acid-volatile sulfides (AVS), organic matter, and water content as well as the biological parameters, mercury methyltransferase (HgMT) activity, sulfate reduction rates, fatty acid methyl ester (FAME) composition, and acidity. Methylmercury concentrations in the wetlands were highly dependent (P < 0.08) on lithology with no significant difference between bogs, fens, and swamps. Methylmercury concentrations in wetland soils developed on Kejimkujik monzogranite averaged 900 ng kg(-1) compared with only 300 ng kg(-1) in wetland soils developed on black sulfidic slate. Fatty acid methyl ester composition was also lithologically dependent (P < 0.001) with biomarkers for Desulfobulbus spp. discriminating between sites containing high and low MeHg concentrations. Levels of MeHg in wetlands were predicted mainly (41% of the sum of squares) by HgMT activity that differed (P < 0.009) between wetlands, with activity in bogs almost three times that present in swamps. Wetland MeHg concentrations are highly dependent on the lithology on which they have developed for largely biological reasons.     

Increasing self-awareness among older drivers: The role of self-screening

Introduction

Self-screening by older drivers has shown considerable promise for increasing self-awareness about functional abilities associated with safe driving. The purpose of this study was to improve upon existing self-screening instruments by focusing entirely on “health concerns” that affect driving - that is, the symptoms that people experience due to medical conditions and the medications used to treat them - rather than the medical conditions or medications themselves.

Method

A computer-based, easy-to-use self-screening instrument for older drivers was developed to provide individualized feedback intended to increase self-awareness about declines in driving-related abilities, as well as suggestions for behavioral changes or safety tips to maintain safe driving, further evaluation from a physician/health professional, and vehicle modifications to help compensate for driving-related declines.

Results

This paper describes the development of the self-screening instrument and summarizes findings relative to increasing self-awareness among older drivers. This research represents an important first step in improving self-awareness among older drivers through self-screening.     

Creating sense of community: The role of public space

A strong sense of community has been associated with improved wellbeing, increased feelings of safety and security, participation in community affairs and civic responsibility. Although interest in how the broader built environment influences sense of community is gaining momentum, there is a dearth of empirical research examining the association between sense of community and the quality of public space. This study investigates the relationship between four public spaces – Public Open Space (POS), community centres, schools and shops – and sense of community in residents of new housing developments in the Perth metropolitan area, Western Australia. Data was obtained from a cross-sectional survey (n = 911), a POS audit, and Geographical Information Systems, and analysed using linear regression. The perceived quality of neighbourhood POS and shops was significantly and positively associated with sense of community. This relationship appears to be unaffected by how frequently people use these spaces. High quality public spaces may be important settings for enhancing sense of community within residents of new housing developments.     

Seasonal variations in hepatic Cd and Cu concentrations and in the sub-cellular distribution of these metals in juvenile yellow perch (Perca flavescens)

Temporal fluctuations in metal (Cd and Cu) concentrations were monitored over four months (May to August) in the liver of juvenile yellow perch (Perca flavescens) sampled from four lakes situated along a metal concentration gradient in northwestern Quebec: Lake Opasatica (reference lake, low metal concentrations), Lake Vaudray (moderate metal concentrations) and lakes Osisko and Dufault (high metal levels). The objectives of this study were to determine if hepatic metal concentrations and metal-handling strategies at the sub-cellular level varied seasonally. Our results showed that Cd and Cu concentrations varied most, in both absolute and relative values, in fish with the highest hepatic metal concentrations, whereas fish sampled from the reference lake did not show any significant variation. To examine the sub-cellular partitioning of these two metals, we used a differential centrifugation technique that allowed the separation of cellular debris, metal detoxified fractions (heat-stable proteins such as metallothionein) and metal sensitive fractions (heat-denaturable proteins (HDP) and organelles). Whereas Cd concentrations in organelle and HDP fractions were maintained at low concentrations in perch from Lakes Opasatica and Vaudray, concentrations in these sensitive fractions were higher and more variable in perch from Lakes Dufault and Osisko, suggesting that there may be some liver dysfunction in these two fish populations. Similarly, Cu concentrations in these sensitive fractions were higher and more variable in perch from the two most Cu-contaminated lakes (Dufault and Osisko) than in perch from the other two lakes, suggesting a breakdown of homeostatic control over this metal. These results suggest not only that metal concentrations vary seasonally, but also that concentrations vary most in fish from contaminated sites. Furthermore, at the sub-cellular level, homeostatic control of metal concentrations in metal-sensitive fractions is difficult to maintain in perch with high hepatic metal concentrations.     

A technique for estimating one-dimensional diffusion coefficients in low-permeability sedimentary rock using X-ray radiography: comparison with through-diffusion measurements

The measurement of diffusive properties of low-permeability rocks is of interest to the nuclear power industry, which is considering the option of deep geologic repositories for management of radioactive waste. We present a simple, non-destructive, constant source in-diffusion method for estimating one-dimensional pore diffusion coefficients (D(p)) in geologic materials based on X-ray radiography. Changes in X-ray absorption coefficient (Deltamicro) are used to quantify changes in relative concentration (C/C(0)) of an X-ray attenuating iodide tracer as the tracer solution diffuses through the rock pores. Estimated values of D(p) are then obtained by fitting an analytical solution to the measured concentration profiles over time. Measurements on samples before and after saturation with iodide can also be used to determine iodide-accessible porosity (phi(I)). To evaluate the radiography method, results were compared with traditional steady-state through-diffusion measurements on two rock types: shale and limestone. Values of D(p) of (4.8+/-2.5)x10(-11) m(2).s(-1) (mean+/-standard deviation) were measured for samples of Queenston Formation shale and (2.6+/-1.0)x10(-11) m(2).s(-1) for samples of Cobourg Formation limestone using the radiography method. The range of results for each rock type agree well with D(p) values of (4.6+/-2.0)x10(-11) m(2).s(-1) for shale and (3.5+/-1.8)x10(-11) m(2).s(-1) for limestone, calculated from through-diffusion experiments on adjacent rock samples. Low porosity (0.01 to 0.03) and heterogeneous distribution of porosity in the Cobourg Formation may be responsible for the slightly poorer agreement between radiography and through-diffusion results for limestones. Mean values of phi(I) for shales (0.060) and limestones (0.028) were close to mean porosity measurements made on bulk samples by the independent water loss technique (0.062 and 0.020 for shales and limestones, respectively). Radiography measurements offer the advantage of time-saving for diffusion experiments because the experiment does not require steady-state conditions and also allows for visualization of the small-scale heterogeneities in diffusive properties within rocks at the mm to cm scale.     

Levels and temporal trends (1983-2003) of persistent organic pollutants (POPs) and mercury (Hg) in seabird eggs from Northern Norway

The main objective of this study was to investigate possible temporal trends of persistent organic pollutants (POPs) and mercury in eggs of herring gulls (Larus argentatus), black-legged kittiwakes (Rissa tridactyla), common guillemots (Uria aalge) and Atlantic puffins (Fratercula arctica) in Northern Norway. Eggs were collected in 1983, 1993 and 2003. Egg concentrations of POPs (PCB congeners IUPAC numbers: CB-28, 74, 66, 101, 99, 110, 149, 118, 153, 105, 141, 138, 187, 128, 156, 157, 180, 170, 194, 206, HCB, alpha-HCH, beta-HCH, gamma-HCH, oxychlordane, trans-chlordane, cis-chlordane, trans-nonachlor, cis-nonachlor, p,p'-DDE, o,p'-DDD, p,p'-DDD, o,p'-DDT and p,p'-DDT) and mercury were quantified. Generally, POP levels decreased between 1983 and 2003 in all species. No significant temporal trend in mercury levels was found between 1983 and 2003.     

Estimation and simulation for geospatial porosity and permeability data

Reservoir simulation of \(\hbox {CO}_2\) sequestration, energy recovery, and environmental contamination scenarios must be accompanied by uncertainty quantification. Typically this is done by stochastically modeling porosity and permeability fields, simulating realizations based on the model, and then numerically simulating flow and transport. The challenge is to generate simulated porosity and permeability fields with characteristics as similar as possible to those known of the reservoir under study. In this paper we focus on the first two steps above in analyzing a large 3-dimensional array of geospatial porosity data and using the results to produce simulated data with characteristics mimicking those of the original porosity observations. The spatial covariance is empirically approximated from horizontal cross sections of the data via a kernel principle component analysis yielding dimension reduction. Simulations in three dimensions are produced by linking consecutive parallel cross sections via conditioning on a small subarray of the data. The conditional simulations effectively reproduce observed channeling, an important large scale feature of interest in the sub-surface relevant to transport of contaminates. The original porosity data is non-Gaussian and requires additional analysis and transformation to generate both porosity and permeability fields.     

Proximate and ultimate explanations of mammalian sex allocation in a marsupial model

Offspring sex ratios in mammals vary in potentially adaptive yet unpredictable ways. An integrative approach that simultaneously examines proximate and ultimate explanations of mammalian sex ratios would greatly advance the field. We examined the importance of maternal glucose and stress hormones for offspring sex (male or female) as mechanisms associated with the Trivers–Willard and the local resource competition hypotheses of sex allocation. We tested this framework in a marsupial mammal, the tammar wallaby (Macropus eugenii). Mothers that were better able to maintain body condition over the driest part of the year, a presumptive proxy for local resource availability, were more likely to produce daughters (the philopatric sex), consistent with local resource competition. Maternal glucose was correlated with offspring sex, but in the opposite direction than we predicted—higher maternal glucose was associated with female pouch young. These patterns, however, were not consistent across the 2 years of our study. Maternal stress hormone metabolites measured from fecal samples did not predict glucose or offspring sex. A causative glucose mechanism may underlie an adaptive strategy for mothers with high local resources (high glucose) to produce philopatric daughters that will benefit from inheriting resource access. Examining species-specific relationships between glucose and offspring sex across mammals could provide crucial insight into the disparate ecological and selective pressures faced by mammals with respect to offspring sex ratio.     

The secondary adjustment of clutch size in red-winged blackbirds (Agelaius phoeniceus)

More than a half century ago, the British ornithologist David Lack suggested that parent birds may use brood reduction to track uncertain food, a process facilitated by the asynchronous hatching of their young. Lack sketched the logic of asymmetric sibling rivalry: the phenotypic handicap imposed upon last-hatched marginal offspring renders their growth and survival conditional upon uncertain ecological conditions while buffering first-hatched core offspring from the inimical effects of overcrowding during periods of stringency. Though subjected to numerous indirect tests in short-term studies, the central prediction of Lack's hypothesis - that parents use marginal offspring to track unpredictable brood-rearing conditions and thus achieve a secondary adjustment of clutch size - has never been tested directly. Here we present the results of a 7-year study of marsh-nesting red-winged blackbirds (Agelaius phoeniceus) showing that (1) brood size tracks interannual variability in growth and survival of nestlings, (2) the growth and mortality of marginal but not core offspring is contingent upon stochastic environmental conditions (mean air temperature) during brood rearing, (3) the mortality of marginal but not core offspring is strongly affected by developmental uncertainty in the form of both experimental and natural alterations of brood size, (4) the phenotypic handicap of hatching asynchrony buffers core offspring from poor growth conditions, but (5) its effects upon marginal nestlings are reversible when growth conditions are favourable and especially when brood size is reduced either experimentally or via hatching failure. The presence of marginal offspring ensures that blackbird parents are not left with a too small brood when brood-rearing conditions are favourable. Parents create two castes of progeny: marginal offspring that are strongly affected by both ecological and developmental stochasticity, and core offspring that are not.