Temperature-dependent rate coefficients for the reactions of Cl atoms with methyl methacrylate,methyl acrylate and butyl methacrylate at atmospheric pressure

Rate coefficients for the gas-phase reactions of Cl atoms with a series of unsaturated esters CH₂C(CH₃)C(O)OCH₃ (MMA), CH₂CHC(O)OCH₃ (MAC) and CH₂C(CH₃)C(O)O(CH₂)₃CH₃ (BMA) have been measured as a function of temperature by the relative technique in an environmental chamber with in situ FTIR detection of reactants. The rate coefficients obtained at 298 K in one atmosphere of nitrogen or synthetic air using propene, isobutene and 1,3-butadiene as reference hydrocarbons were (in units of 10^?10 cm³ molecule^?1 s^?1) as follows: k_(Cl+MMA) = 2.82 ± 0.93, k_(Cl+MAC) = 2.04 ± 0.54 and k_(Cl+BMA) = 3.60 ± 0.87. The kinetic data obtained over the temperature range 287–313 K were used to derive the following Arrhenius expressions (in units of cm³ molecule^?1 s^?1): k_(Cl+MMA) = (13.9 ± 7.8) × 10^?15 exp[(2904 ± 420)/T], k_(Cl+MAC) = (0.4 ± 0.2) × 10^?15 exp[(3884 ± 879)/T], k_(Cl+BMA) = (0.98 ± 0.42) × 10^?15 exp[(3779 ± 850)/T]. All the rate coefficients display a slight negative temperature dependence which points to the importance of the reversibility of the addition mechanism for these reactions. This work constitutes the first kinetic and temperature dependence study of the reactions cited above.An analysis of the available rates of addition of Cl atoms and OH radicals to the double bond of alkenes and unsaturated and oxygenated volatile organic compounds (VOCs) at 298 K has shown that they can be related by the expression: log k_OH = 1.09 log k_Cl ? 0.10. In addition, a correlation between the reactivity of unsaturated VOCs toward OH radicals and Cl atoms and the HOMO of the unsaturated VOC is presented. Tropospheric implications of the results are also discussed.     

Distribution and ratios of Cs and K in control and K-treated coconut trees at Bikini Island where nuclear test fallout occurred: effects and implications

Coconut trees growing on atolls of the Bikini Islands are on the margin of K deficiency because the concentration of exchangeable K in coral soil is very low, ranging from only 20 to 80 mg kg⁻¹. When provided with additional K, coconut trees absorb large quantities of K and this uptake of K significantly alters the patterns of distribution of ¹³⁷Cs within the plant. Following a single K fertilization event, mean total K in trunks of K-treated trees is 5.6 times greater than in trunks of control trees. In contrast, ¹³⁷Cs concentration in trunks of K-treated and control trees is statistically the same while ¹³⁷Cs is significantly lower in edible fruits of K-treated trees. Within one year after fertilization (one rainy season), K concentration in soil is back to naturally low concentrations. However, the tissue concentrations of K in treated trees stays very high internally in the trees for years while ¹³⁷Cs concentration in treated trees remains very low in all tree compartments except for the trunk. Potassium fertilization did not change soil Cs availability.     

Rural southeast Texas air quality measurements during the 2006 Texas Air Quality Study

The authors conducted air quality measurements of the criteria pollutants carbon monoxide, nitrogen oxides, and ozone together with meteorological measurements at a park site southeast of College Station, TX, during the 2006 Texas Air Quality Study II (TexAQS). Ozone, a primary focus of the measurements, was above 80 ppb during 3 days and above 75 ppb during additional 8 days in summer 2006, suggestive of possible violations of the ozone National Ambient Air Quality Standard (NAAQS) in this area. In concordance with other air quality measurements during the TexAQS II, elevated ozone mixing ratios coincided with northerly flows during days after cold front passages. Ozone background during these days was as high as 80 ppb, whereas southerly air flows generally provided for an ozone background lower than 40 ppb. Back trajectory analysis shows that local ozone mixing ratios can also be strongly affected by the Houston urban pollution plume, leading to late afternoon ozone increases of as high as 50 ppb above background under favorable transport conditions. The trajectory analysis also shows that ozone background increases steadily the longer a southern air mass resides over Texas after entering from the Gulf of Mexico. In light of these and other TexAQS findings, it appears that ozone air quality is affected throughout east Texas by both long-range and regional ozone transport, and that improvements therefore will require at least a regionally oriented instead of the current locally oriented ozone precursor reduction policies.     

Sensitivity of potential natural vegetation in China to projected changes in temperature,precipitation and atmospheric CO2

A sensitivity study was performed to investigate the responses of potential natural vegetation distribution in China to the separate and combined effects of temperature, precipitation and [CO₂], using the process-based equilibrium terrestrial biosphere model BIOME4. The model shows a generally good agreement with a map of the potential natural vegetation distribution based on a numerical comparison using the ΔV statistic (ΔV = 0.25). Mean temperature of each month was increased uniformly by 0–5 K, in 0.5- or 1-K intervals. Mean precipitation of each month was increased and decreased uniformly by 0–30%, in 10% intervals. The analyses were run at fixed CO₂ concentrations of 360 and 720 ppm. Temperature increases shifted most forest boundaries northward and westward, expanded the distribution of xeric biomes, and confined the tundra to progressively higher elevations. Precipitation increases led to a greater area occupied by mesic biomes at the expense of xeric biomes. Most vegetation types in the temperate regions, and on the Tibetan Plateau, expanded westward into the dry continental interior with increasing precipitation. Precipitation decreases had opposite effects. The modelled effect of CO₂ doubling was to partially compensate for the negative effect of drought on the mesic biomes and to increase potential ecosystem carbon storage by about 40%. Warming tended to counteract this effect, by reducing soil carbon storage. Forest biomes showed substantial resilience to climate change, especially when the effects of increasing [CO₂] were taken into account. Savannas, dry woodland and tundra biomes proved sensitive to temperature increases. The transition region of grassland and forest, and the Tibetan plateau, was the most vulnerable region.     

Flood management: prediction of microbial contamination in large-scale floods in urban environments

With a changing climate and increased urbanisation, the occurrence and the impact of flooding is expected to increase significantly. Floods can bring pathogens into homes and cause lingering damp and microbial growth in buildings, with the level of growth and persistence dependent on the volume and chemical and biological content of the flood water, the properties of the contaminating microbes, and the surrounding environmental conditions, including the restoration time and methods, the heat and moisture transport properties of the envelope design, and the ability of the construction material to sustain the microbial growth. The public health risk will depend on the interaction of these complex processes and the vulnerability and susceptibility of occupants in the affected areas. After the 2007 floods in the UK, the Pitt review noted that there is lack of relevant scientific evidence and consistency with regard to the management and treatment of flooded homes, which not only put the local population at risk but also caused unnecessary delays in the restoration effort. Understanding the drying behaviour of flooded buildings in the UK building stock under different scenarios, and the ability of microbial contaminants to grow, persist, and produce toxins within these buildings can help inform recovery efforts. To contribute to future flood management, this paper proposes the use of building simulations and biological models to predict the risk of microbial contamination in typical UK buildings. We review the state of the art with regard to biological contamination following flooding, relevant building simulation, simulation-linked microbial modelling, and current practical considerations in flood remediation. Using the city of London as an example, a methodology is proposed that uses GIS as a platform to integrate drying models and microbial risk models with the local building stock and flood models. The integrated tool will help local governments, health authorities, insurance companies and residents to better understand, prepare for and manage a large-scale flood in urban environments.     

To duckweeds (Landoltia punctata), nanoparticulate copper oxide is more inhibitory than the soluble copper in the bulk solution

CuO nanoparticles (CuO-NP) were synthesized in a hydrogen diffusion flame. Particle size and morphology were characterized using scanning mobility particle sizing, Brunauer-Emmett-Teller analysis, dynamic light scattering, and transmission electron microscopy. The solubility of CuO-NP varied with both pH and presence of other ions. CuO-NP and comparable doses of soluble Cu were applied to duckweeds, Landoltia punctata. Growth was inhibited 50% by either 0.6 mg L⁻¹ soluble copper or by 1.0 mg L⁻¹ CuO-NP that released only 0.16 mg L⁻¹ soluble Cu into growth medium. A significant decrease of chlorophyll was observed in plants stressed by 1.0 mg L⁻¹ CuO-NP, but not in the comparable 0.2 mg L⁻¹ soluble Cu treatment. The Cu content of fronds exposed to CuO-NP is four times higher than in fronds exposed to an equivalent dose of soluble copper, and this is enough to explain the inhibitory effects on growth and chlorophyll content.     

Estimating the contribution of precursor compounds in consumer exposure to PFOS and PFOA

The exposure of humans to perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) was quantified with emphasis on assessing the relative importance of metabolic transformation of precursor compounds. A Scenario-Based Risk Assessment (SceBRA) approach was used to model the exposure to these compounds from a variety of different pathways, the uptake into the human body and resulting daily doses. To capture the physiological and behavioral differences of age and gender, the exposure and resulting doses for seven consumer groups were calculated. The estimated chronic doses of a general population of an industrialized country range from 3.9 to 520 ng/(kg day) and 0.3 to 140 ng/(kg day) for PFOS and PFOA, respectively. The relative importance of precursor-based doses of PFOS and PFOA was estimated to be 2-5% and 2-8% in an intermediate scenario and 60-80% and 28-55% in a high-exposure scenario. This indicates that sub groups of the population may receive a substantial part of the PFOS and PFOA doses from precursor compounds, even though they are of low importance for the general population. Similar to a preceding study, uptake of perfluorinated acids from contaminated food and drinking water was identified as the most important pathway of exposure for the general population. The biotransformation yields of telomer-based precursors and to a lesser extent perfluorooctanesulfonylfluoride-based precursors were identified as influential parameters in the uncertainty analysis. Fast food consumption and fraction of food packaging paper treated with PFCs were influential parameters for determining the doses of PFOA.     

Distribution and partitioning of depleted uranium (DU) in soils at weapons test ranges - investigations combining the BCR extraction scheme and isotopic analysis

Depleted uranium (DU) has become a soil contaminant of considerable concern in many combat zones and weapons-testing sites around the world, including locations in Europe, the Middle East and the USA, arising from its dispersion via the application of DU-bearing munitions. Once DU is released into the environment its mobility and bioavailability will, like that of other contaminants, largely depend on the type of associations it forms in soil and on the nature of the soil components to which it binds. In this study we used the BCR sequential extraction scheme to determine the partitioning of DU amongst soil fractions of texturally varying soils from locations affected by weapons-testing activities. Isotopic analyses (MC-ICP-MS and alpha-spectrometry) were performed to verify the presence of DU in whole soils and soil fractions and to determine any preferential partitioning of the contaminant. Results identified soil organic matter as being consistently the most important component in terms of DU retention, accounting for 30-100% of DU observed in the soils examined. However, at greater distances from known contamination points, DU was also found to be largely associated with the exchangeable fraction, suggesting that DU can be mobilised and transported by surface and near-surface water and does remain in an exchangeable (and thus potentially bioavailable) form in soils.     

Model and input uncertainty in multi-media fate modeling: benzo[a]pyrene concentrations in Europe

This paper evaluates the contribution of (i) uncertainty in substance properties, (ii) lack of spatial variability, (iii) intermodel differences and (iv) neglecting sorption to black carbon (BC) to the uncertainty of Benzo[a]pyrene (BaP) concentrations in European air, soil and fresh water predicted by the multi-media fate model Simplebox. Uncertainty in substance properties was quantified using probabilistic modeling. The influence of spatial variability was quantified by estimating variation in predicted concentrations with three spatially explicit fate models (Impact 2002, EVn BETR and BETR Global). Intermodel differences were quantified by comparing concentration estimates of Simplebox, Impact 2002, EVn BETR and the European part of BETR Global. Finally, predictions of a BC-inclusive version of Simplebox were compared with predictions of a BC-exclusive version. For air concentrations of BaP, the lack of spatial variability in emissions was most influential. For freshwater concentrations of BaP, intermodel differences and lack of spatial variability in dimensions of fresh water bodies were the dominant sources of uncertainty. For soil, all sources of uncertainty were of comparable magnitude. Our results indicate that uncertainty in Simplebox can be as large as three orders of magnitude for BaP concentrations in the environment and would be substantially underestimated by focusing on one source of uncertainty only.