Theoretical versus observed gas-particle partitioning of carbonyl emissions from motor vehicles

A state-of-the-science thermodynamic model describing gas-particle absorption processes was used to predict the gas-particle partitioning of mixtures of approximately 60 carbonyl compounds emitted from low-emission gasoline-powered vehicles, three-way catalyst gasoline-powered vehicles, heavy-duty diesel vehicles under the idle-creep condition (HDDV idle), and heavy-duty diesel vehicles under the five-mode test (HDDV 5-mode). Exhaust was diluted by a factor of 120-580 with a residence time of approximately 43 sec. The predicted equilibrium absorption partitioning coefficients differed from the measured partitioning coefficients by several orders of magnitude. Time scales to reach equilibrium in the dilution sampling system were close to the actual residence time during the HDDV 5-mode test and much longer than the actual residence time during the other vehicle tests. It appears that insufficient residence time in the sampling system cannot uniformly explain the failure of the absorption mechanism to explain the measured partitioning. Other gas-particle partitioning mechanisms (e.g., heterogeneous reactions, capillary adsorption) beyond the simple absorption theory are needed to explain the discrepancy between calculated carbonyl partitioning coefficients and observed partitioning. Both of these alternative partitioning mechanisms imply great challenges for the measurement and modeling of semi-volatile primary organic aerosol (POA) species from motor vehicles. Furthermore, as emitted particle concentrations from newer vehicles approach atmospheric background levels, dilution sampling systems must fundamentally change their approach so that they use realistic particle concentrations in the dilution air to approximately represent real-world conditions. Samples collected with particle-free dilution air yielding total particulate matter concentrations below typical ambient concentrations will not provide a realistic picture of partitioning for semi-volatile compounds.     

The influence of sampling protocol on nonmethane hydrocarbon mixing ratios

The effect of sampling protocol on ambient air hydrocarbon mixing ratios was examined on eight sampling days in Los Angeles during 2007 and 2008. Four protocols, which were based on previously published multi-city urban hydrocarbon studies in the United States, were compared and differences were quantified. Whole air canister samples were collected and analyzed for nonmethane hydrocarbons (NMHCs). Differing sampling protocols resulted in large differences in mixing ratios, up to an order of magnitude, for certain NMHCs on the same sampling day. However, the magnitude of the variability between NMHC levels obtained by the four protocols was not consistent throughout the eight sampling days. It was found that sampling time, followed by sampling location, had the greatest influence on the magnitude of the mixing ratio. Ratios between hydrocarbons, often used in urban studies to gain information on emission sources, also varied depending on the protocol used. Comparison of absolute NMHC mixing ratios collected in urban environments using differing sampling protocols should be made with care.     

Spatial variability of carbonaceous aerosols and associated source tracers in two cites in the Midwestern United States

Semi-continuous and 24-h averaged measurements of fine carbonaceous aerosols were made concurrently at three sites within each of two U.S. Midwestern Cities; Detroit, Michigan and Cleveland, Ohio; during two, one-month intensive campaigns conducted in July of 2007 and January & February of 2008. A comparison of 24-h measurements revealed substantial intra-urban variability in carbonaceous aerosols consistent with the influence of local sources, and excesses in both PM_2.5 organic carbon (OC) and elemental carbon (EC) were identified at individual sites within each city. High time-resolved black carbon (BC) measurements indicated that elemental carbon concentrations were higher at sites adjacent to freeways and busy surface streets, and temporal patterns suggested that excess EC at sites adjacent to freeways was dominated by mobile source emissions while excesses in EC away from traffic corridors was dominated by point/area source emissions. The site-to-site variability in OC concentrations was approximately 7% within the neighborhood scale (0.5–4 km) and between 4 and 27% at the urban scale (4–100 km). In contrast, measurements of organic source tracers, in conjunction with a Chemical Mass Balance (CMB) source-apportionment model, indicated that the spatial variation in the contribution of both mobile and stationary sources to PM_2.5 OC often exceeded the variation in OC mass concentration by a factor of 3 or more. Markers for mobile sources, biomass smoke, natural gas, and coal combustion differed by as much as 60% within the neighborhood scale and by greater than 200% within the urban scale. The observations made during this study suggest that the urban excess of carbonaceous aerosols is much more complex than has been previously reported and that a more rigorous, source-oriented approach should be taken in order to assess the risk associated with exposure to carbonaceous aerosols within the industrialized environments of the Midwestern United States.     

Seasonal monoterpene and sesquiterpene emissions from Pinus taeda and Pinus virginiana

Seasonal volatile organic compound emission data from loblolly pine (Pinus taeda) and Virginia pine (Pinus virginiana) were collected using branch enclosure techniques in Central North Carolina, USA. P. taeda monoterpene emission rates were at least ten times higher than oxygenated monoterpene and sesquiterpene emissions in all seasons. α-pinene and β-pinene were the most abundant emissions, while β-caryophyllene had the highest sesquiterpene emission rate from this species. β-phellandrene was the dominant compound emitted from P. virginiana, followed by the sesquiterpene β-caryophyllene. Sesquiterpene emissions from P. virginiana have not been reported in the literature previously. Summer sesquiterpene emissions from P. virginiana were nearly as high as monoterpene emissions, but were 4–12 times lower than monoterpene emissions in the other seasons. Oxygenated monoterpenes and 2-methyl-3-buten-2-ol were emitted at higher rates from P. taeda than from P. virginiana. Temperature response of the pinenes from P. taeda is similar to previously reported values used in emission models, while that for other compounds falls at the lower end of the previously reported range. Temperature response of all compounds from P. virginiana is in reasonable agreement with previously reported values from other pine species. There is evidence of light dependence of sesquiterpene emission after accounting for temperature response from both species. This effect is somewhat stronger in P. taeda. Bud break, needle expansion, and needle fall (and therefore wind events) seemed to increase monoterpene emission during non-summer seasons. In some instances springtime monoterpene emissions were higher than summertime emissions despite cooler temperatures. Emissions of individual compounds within monoterpene, oxygenated monoterpene, and sesquiterpene classes were highly correlated with each other. Compounds from different classes were much less correlated within each species. This is due to a varying temporal emission patterns for each BVOC class and suggests different production, storage, and emission controls for each. Analysis of enclosure blanks and diurnal patterns indicates that, despite precautions, disturbance due to the enclosure technique may still impact monoterpene emission rate estimates. This did not appear to affect sesquiterpene emissions.     

Potentials and impacts of short-rotation coppice plantation with aspen in Eastern Germany under conditions of climate change

Woody biomass generated in short-rotation coppice (SRC) plantations with aspen (Populus tremula L.) has good properties for bioenergy crop production: annual yields are high, labour input per year is low, and it is ecologically valuable because of the multi-year rotation periods. Eastern Germany has a special advantage in producing bioenergy crops: the former “agricultural cooperatives” built up quite large farms with, compared to Western Germany, comparatively large fields. Therefore, a modelling study of the potential and the impacts of aspen SRC plantations in the five eastern federal states of Germany under the recent climate and future climate projections was conducted. The ecophysiological forest growth model 4C was used to simulate the growth of aspen SRC plantations and their impacts on carbon in soils, and groundwater recharge, on selected suitable areas currently under crops but with marginal site conditions for cropping. A clear signal to enhanced growth condition over the whole area can be seen in the simulation of the mean annual woody biomass yield under conditions of climate change, which increased from 7.47 t DW ha⁻¹ a⁻¹ under the recent climate to 9.26 t DW ha⁻¹ a⁻¹ at the end of the considered future period 2034–2055 under climate change. The mean soil carbon sequestration rate was 0.81 t C ha⁻¹ a⁻¹ under the recent climate and could rise up to 0.93 t C ha⁻¹ a⁻¹ under the assumption of climate change. On the other hand, the mean annual percolation rate, used as an indicator of impacts on the regional water budget, will diminish under future climatic conditions. The results suggest that aspen SRC plantations are a suitable contribution to regional CO₂ mitigation and carbon sequestration under possible change of climate, but that negative impacts on the regional water budget are possible.     

Distribution of steroid- and dioxin-like activities between sediments, POCIS and SPMD in a French river subject to mixed pressures

The contamination of aquatic systems by endocrine disrupting chemicals (EDCs) is now a widely established fact. Nevertheless, there is still a scarcity of knowledge concerning the source, transport, fate and bioavailability of such active compounds. In the present study we assessed the distribution of estrogenic, (anti-)androgenic, pregnane X receptor-like (PXR) and dioxin-like activities between sediment and water compartments using a polar organic compound integrative sampler (POCIS) and a semi-permeable membrane device (SPMD) passive sampler in a river where sediment has been previously described as highly and multi-contaminated. We first confirmed the contamination pattern of this river sediment between 2004, 2009 and 2010 samples, suggesting that this river is subject to a constant high contamination level. However, we showed a different distribution pattern of these activities between compartments: estrogenic activity was mainly detected in POCIS extracts and to a lesser extent in sediment and SPMD extracts; anti-androgenic activities were mainly detected in SPMD and sediment extracts while no activity was detected in POCIS extracts; PXR-like activity was detected in all three investigated compartments, with POCIS > SPMD > sediment; dioxin-like activity was mainly found in the sediment and the SPMD extracts. Overall, partitioning of the biological activities was in accordance with physicochemical properties (e.g., log K _ow) of typical known active chemicals in each bioassay. Furthermore, in order to establish whether the chemicals involved in these activities were similar between the compartments, we fractionated sediment, POCIS and SPMD extracts using a multi-step fractionation procedure. This highlighted differences in the nature of active chemicals between compartments. Altogether, our results support the need to consider different compartments in order to enhance exposure assessment.     

Change in Pulmonary Function in Children Associated with Air Pollution Episodes

Pulmonary function of approximately 200 school children in Steubenville, OH was measured before and immediately following air pollution alerts in the fall of 1978 and 1979. TSP concentrations exceeded the National Primary Ambient Air Quality 24 h standards in 1978. SO₂ exceeded the standard in 1979. The children were then reexamined in three weekly visits following each alert. Estimated mean Forced Vital Capacity (FVC) was approximately 2% lower following each alert, although the lowest means were observed one to two weeks after the episodes. Forced Expired Volume in 0.75 sec (FEV_0.75) did not change during the 1978 study, but was 4% lower immediately following the 1979 alert. The children were measured again in five weekly examinations in the spring and fall of 1980. Air pollution levels did not exceed the standards on either occasion. In the spring of 1980, estimated mean FVC and FEV_0.75 showed a decline similar to that observed following the alerts in 1978 and 1979. In the fall of 1980, there were no significant differences in the estimated mean FVC or FEV_0.75 between the examinations. A total of 335 children were tested in the four studies, including 194 who participated in more than one study. The evidence for each child from all the studies was combined in a regression analysis of pulmonary function on TSP and SO₂ average concentrations in the previous 24 h. The distribution of the individual regression coefficients was centered significantly below zero, implying a decrease in pulmonary function with increasing TSP and SO₂ concentrations. The magnitude of the median change was less than 1% of the mean FVC and FEV_0.75 over the range of TSP and SO₂ concentrations observed.     

Sensitivity of Portuguese forest fires to climatic, human, and landscape variables: subnational differences between fire drivers in extreme fire years and decadal averages

Within the changing fire regimes of Portugal, the relative importance of humans and climatic variability for regional fire statistics remains poorly understood. This work investigates the statistical relationship between temporal dynamics of fire events in Portugal and a set of socioeconomic, landscape, and climatic variables for the time periods of 1980–1990, 1991–2000, and extreme fires years. For 10 of 15 districts, it was possible to observe moderate shifts in the significance of fire drivers for the first two decadal periods. For others, pronounced changes of the significance of fire drivers were found across time. Results point toward a dynamic (perhaps highly non-linear) behavior of socioeconomic and landscape fire drivers, especially during the occurrence of extreme fire years of 2003 and 2005. At country level, population density alone explained 42% of the inter-annual and inter-district deviance in number of fires. At the same temporal and spatial scale, the explanatory power of temperature anomalies proved to explain 43% of area burnt. We highlight the necessity of including a broad set of socioeconomic and landscape fire drivers in order to account for potential significance shifts. In addition, although climate does trigger broad favorable fire conditions across Portugal mainland, socioeconomic and landscape factors proved to determine much of the complex fire patterns at a subnational scale.