Modeling transport and deposition of contaminants to ecosystems of concern: a case study for the Laurentian Great Lakes

Transfer efficiency (TE) is introduced as a model output that can be used to characterize the relative ability of chemicals to be transported in the environment and deposited to specific target ecosystems. We illustrate this concept by applying the Berkeley-Trent North American contaminant fate model (BETR North America) to identify organic chemicals with properties that result in efficient atmospheric transport and deposition to the Laurentian Great Lakes. By systematically applying the model to hypothetical organic chemicals that span a wide range of environmental partitioning properties, we identify combinations of properties that favor efficient transport and deposition to the Lakes. Five classes of chemicals are identified based on dominant transport and deposition pathways, and specific examples of chemicals in each class are identified and discussed. The role of vegetation in scavenging chemicals from the atmosphere is assessed, and found to have a negligible influence on transfer efficiency to the Great Lakes. Results indicate chemicals with octanol-water (K(ow)) and air-water (K(aw)) partition coefficients in the range of 10(5)-10(7) and 10(-4)-10(-1) combine efficient transport and deposition to the Great Lakes with potential for biaccumulation in the aquatic food web once they are deposited. A method of estimating the time scale for atmospheric transport and deposition process is suggested, and the effects of degrading reactions in the atmosphere and meteorological conditions on transport efficiency of different classes of chemicals are discussed. In total, this approach provides a method of identifying chemicals that are subject to long-range transport and deposition to specific target ecosystems as a result of their partitioning and persistence characteristics. Supported by an appropriate contaminant fate model, the approach can be applied to any target ecosystem of concern.     

Comparison of measurement methods for the characterization of the black carbon emissions from a T63 turboshaft engine burning conventional and Fischer-Tropsch fuels

Emission measurements of black carbon (BC) mass were conducted on a T63 turboshaft engine, operated at idle and cruise power with conventional and alternative fuels, using an Artium LII-300 laser-induced incandescence analyzer (LII) and AVL model 483 micro soot sensor (MSS) photoacoustic instrument using the manufacturer’s calibration for both instruments. These measurements were compared with elemental carbon (EC) determined by manual and semicontinuous thermal-optical transmission analyses according to National Institute for Occupational Safety and Health (NIOSH) method 5040 as the reference method. The results indicate that both the LII and MSS instruments show good linear correlation with EC for the two fuels and two engine power conditions evaluated. The LII measurements were observed to be biased high (27–49%) and the MSS measurements were biased low (24–35%) relative to EC. The agreement between the instruments and the reference method was substantially improved by applying a calibration of the instruments against a common BC aerosol source. Test data also suggest that the two instruments show some sensitivity to particle size (or properties related to size), specifically for particles with a geometric mean diameter (GMD) <30 nm. This sensitivity is problematic, since new engines or certain combustion conditions in current engines will produce smaller particles compared with the T63 model tested in this study. Further assessments of instrument performance for particles within this size range are therefore warranted.

Implications: Accurate black carbon emission measurements are needed to certify new and in-production commercial aircraft engines. Both the Artium LII-300 and AVL 483 micro soot sensor are currently approved by the International Civil Aviation Organization for this purpose. This study compares the two instruments against elemental carbon (EC) using NIOSH method 5040 as the reference using a T63 turboshaft engine. The results indicate that both instruments correlate reasonably well with EC, and the correlation substantially improved when applying a calibration against a common aerosol source. Sensitivity to particle size may be an issue for both instruments.     

(<Emphasis Type="Italic">Z</Emphasis>)-9-Pentacosene − contact sex pheromone of the locust borer, <Emphasis Type="Italic">Megacyllene robiniae</Emphasis>

Summary. Male locust borers, Megacyllene robiniae (Förster), responded to females only after contacting them with their antennae, indicating that mate recognition was mediated by a contact sex pheromone. GC-MS analyses of whole-body extracts of males and females determined that the profiles of compounds in the extracts were qualitatively similar, but differed considerably in the ratios of compounds between sexes. Biological activities of reconstructed blends of the most abundant straight-chain (nC₂₃, nC₂₄, nC₂₅, nC₂₆), methyl-branched (3me-C₂₃, 3me-C₂₅), and unsaturated (Z9:C₂₃, Z9:C₂₅, Z9:C₂₇ compounds in extracts from females were assessed in arena bioassays, assessing four distinct steps in the mating behavior sequence of males (orientation, arrestment, body alignment, mounting and attempting to couple the genitalia). Males were unresponsive to freeze-killed, solventwashed females treated with blends of straight-chain and methyl-branched alkanes, but responded strongly to females treated with the blend of alkenes. Further trials determined that the complete sequence of mating behaviors, up to and including coupling the genitalia, was elicited by Z9:C₂₅ alone. Z9:C₂₅ comprised 16.4 ± 1.3% of the total hydrocarbons in whole-body hexane extracts of females and was co-dominant with two other hydrocarbons that were not active. In contrast, in solid phase microextraction (SPME) wipe samples from several areas of the cuticle, Z9:C₂₅ appeared as the single dominant peak, comprising 34.6 – 37.8% of the sampled hydrocarbons. Our data indicate that Z9:C₂₅ is a contact sex pheromone of M. robiniae, being the most abundant hydrocarbon on the surface of the cuticular wax layer of females where it is readily accessible to the antennae of males.     

Case study I: application of the divalent cation bridging theory to improve biofloc properties and industrial activated sludge system performance-direct addition of divalent cations.

The objectives of this study were to examine the application of the divalent cation bridging theory (DCBT) to improve settling, dewatering, and effluent quality in pilot-scale reactors and a full-scale system treating an industrial wastewater. This was accomplished by lowering the monovalent-to-divalent (M/D) cation ratio by direct divalent cation addition. Research has shown that the M/D ratio is a potential indicator for settling and dewatering problems at wastewater treatment plants, and M/D ratios above 2 have been associated with poor settling, dewatering, and effluent quality. The M/D ratio of the wastewater in this study ranged from 6 to 20. The cations studied were calcium and magnesium. Results showed that the addition of calcium improved floc properties compared to control reactors with no calcium addition. The reductions in sludge volume index, effluent chemical oxygen demand (COD), and effluent total suspended solids (TSS) were approximately 35, 34, and 55%, respectively, when the M/D ratio was decreased to approximately 2:1. In addition, the cake solids from a belt filter press simulator increased by 72% and the optimum polymer dose required for conditioning was reduced by 70% in the reactor fed the highest calcium concentration when compared to control reactors with no calcium addition. The addition of calcium also decreased the negative effect of high filamentous organism numbers. In general, the addition of magnesium (Mg2+) had similar effects on effluent quality and dewatering properties, although some differences were measured. A full-scale test using calcium addition was performed. Measurements of effluent quality and floc properties were performed before, during, and after the calcium (Ca2+) addition period. The average M/D ratio during these periods was 6.2, 4.6, and 14.0, respectively. The addition of Ca2+ decreased the effluent five-day biochemical oxygen demand, effluent TSS, and effluent COD. The increased Ca2+ concentration also improved dewatering measured by a decrease in specific resistance to filtration and capillary suction time. Overall, the addition of divalent cations to the pilot- and full-scale activated sludge systems improved floc properties and the data fit well with the DCBT.     

Emissions of organic compounds and trace metals in fine particulate matter from motor vehicles: a tunnel study in Houston, Texas

Fine particulate matter (PM) samples collected in a highway tunnel in Houston, TX, were analyzed to quantify the concentrations of 14 n-alkanes, 12 polycyclic aromatic hydrocarbons, and nine petroleum biomarkers, as well as 21 metals, with the ultimate aim of identifying appropriate tracers for diesel engines. First, an exploratory multivariate dimensionality reduction technique called principal component analysis (PCA) was employed to identify all potential candidates for tracers. Next, emission indices were calculated to interpret PCA results physically. Emission indices of n-heneicosane, n-docosane, n-tricosane, n-tetracosane, n-pentacosane, fluoranthene, and pyrene were correlated highly and increased strongly with percentage carbon present in the tunnel emanating from diesel vehicles. This suggests that these organic compounds are useful molecular markers to separate emissions from diesel and gasoline engines. Additionally, the results are the first quantification of the metal composition of PM with aerodynamic diameters smaller than 2.5 microm (PM2.5) emissions from mobile sources in Houston. PCA of trace metal concentrations followed by emission index calculations revealed that barium in fine airborne particles can be linked quantitatively to diesel engine emissions, demonstrating its role as an elemental tracer for heavy-duty trucks.     

Coordination geometry of Zn~(2+) on hexagonal turbostratic birnessites with different Mn average oxidation states and its stability under acid dissolution

Hexagonal turbostratic birnessite,with the characteristics of high contents of vacancies,varying amounts of structural and adsorbed Mn~(3+),and small particle size,undergoes strong adsorption reactions with trace metal(TM)contaminants.While the interactions of TM,i.e.,Zn~(2+),with birnessite are well understood,the effect of birnessite structural characteristics on the coordination and stability of Zn~(2+)on the mineral surfaces under proton attack is as yet unclear.In the present study,the effects of a series of synthesized hexagonal turbostratic birnessites with different Mn average oxide states(AOSs)on the coordination geometry of adsorbed Zn~(2+)and its stability under acidic conditions were investigated.With decreasing Mn AOS,birnessite exhibits smaller particle sizes and thus larger specific surface area,higher amounts of layer Mn~(3+)and thus longer distances for the first Mn\O and Mn\Mn shells,but a low quantity of available vacancies and thus low adsorption capacity for Zn~(2+).Zn K-edge EXAFS spectroscopy demonstrates that birnessite with low Mn AOS has smaller adsorption capacity but more tetrahedral Zn(~(IV)Zn)complexes on vacancies than octahedral(~(VI)Zn)complexes,and Zn~(2+)is more unstable under acidic conditions than that adsorbed on birnessite with high Mn AOS.High Zn~(2+)loading favors the formation of~(VI)Zn complexes over~(IV)Zn complexes,and the release of Zn~(2+)is faster than at low loading.These results will deepen our understanding of the interaction mechanisms of various TMs with natural birnessites,and the stability and thus the potential toxicity of heavy metal pollutants sequestered by engineered nano-sized metal oxide materials.     

Controls on Leaching of N Species in Upland Moorland Catchments

Spatial and temporal changes in mobility of N species have been studied for three UK upland river networks, the Etherow in the South Pennines, the Nether Beck in the Lake District and the Dee in NE Scotland. The catchments are subject to N deposition at 35.1, 22.0 and 10.8–15.6 kg N ha^–1 yr^–1, respectively. TheNH ₄ ⁺ leaching appears to be predominantly regulated by flowpath in more polluted upland catchments. It is greatest where water draining acidified peaty soils contributes more to total discharge. Soluble organic matter may provide the dominant counter anion. In the Etherowand Dee catchments, which are dominated by acid mineral and organic soils, at high discharge NO ₃ ^– also appears to be associated with greater input of water from acidified soils. In contrast, for the Nether Beck, higher NO ₃ ^– concentrations are associated with tributaries draining soils contributingwater with higher alkalinity, suggesting nitrification is important. For the Etherow and Dee, dissolved organic N (DON) appears to originate predominantly from acidified, peaty soils. Spiking experiments with peat soil from the Etherow catchment confirmed the limited capacity of these soils to utilize inorganic N inputs, favouring equilibration with NH ₄ ⁺ inputs and leaching losses of inorganic N throughout the year.     

Promiscuity in mice is associated with increased vaginal bacterial diversity

Differences in the number of sexual partners (i.e., mating system) have the potential to exert a strong influence on the bacterial communities present in reproductive structures like the vagina. Because this structure serves as a conduit for gametes, bacteria present there may have a pronounced, direct effect on host reproductive success. As a first step towards the identification of the relationship between sexual behavior and potentially pathogenic bacterial communities inhabiting vital reproductive structures, as well as their potential effects on fitness, I sought to quantify differences in bacterial diversity in a promiscuous and monogamous mammal species. To accomplish this, I used two sympatric species of Peromyscus rodents—Peromyscus californicus and Peromyscus maniculatus that differ with regard to the number of sexual partners per individual to test the hypothesis that bacterial diversity should be greater in the promiscuous P. maniculatus relative to the monogamous P. californicus. As predicted, phylogenetically controlled and operational taxonomic unit-based indices of bacterial diversity indicated that diversity is greater in the promiscuous species. These results provide important new insights into the effects of mating system on bacterial diversity in free-living vertebrates, and may suggest a potential cost of promiscuity.     

Body-pillar vision obstructions and lane-change crashes

INTRODUCTION: This exploratory study investigated the relationship between vision obstructions from body pillars and lane-change crashes. METHODS: The vision obstructions were quantified by measuring, from the driver's perspective, the horizontal angular sizes and locations of the driver-side A-, B-, and C-pillars. The sample consisted of 21 vehicle models, including 13 passenger cars, 6 SUVs, 1 minivan, and 1 pickup truck. To control for driver differences, going-straight crashes were used for comparison, with the dependent variable being the ratio of lane-change crashes to going-straight crashes. The analysis used North Carolina crash data. RESULTS: The results of a multiple regression indicate that the relative frequency of lane-change crashes tended to increase with both wider A-pillars and with A-pillars located farther away from straight ahead. IMPACT ON INDUSTRY: The finding supports the hypothesis that visibility obstructions due to A-pillars have safety implications.     

Preservation of ancient DNA in thermally damaged archaeological bone

Evolutionary biologists are increasingly relying on ancient DNA from archaeological animal bones to study processes such as domestication and population dispersals. As many animal bones found on archaeological sites are likely to have been cooked, the potential for DNA preservation must be carefully considered to maximise the chance of amplification success. Here, we assess the preservation of mitochondrial DNA in a medieval cattle bone assemblage from Coppergate, York, UK. These bones have variable degrees of thermal alterations to bone collagen fibrils, indicative of cooking. Our results show that DNA preservation is not reliant on the presence of intact collagen fibrils. In fact, a greater number of template molecules could be extracted from bones with damaged collagen. We conclude that moderate heating of bone may enhance the retention of DNA fragments. Our results also indicate that ancient DNA preservation is highly variable, even within a relatively recent assemblage from contexts conducive to organic preservation, and that diagenetic parameters based on protein diagenesis are not always useful for predicting ancient DNA survival.