Multimedia fate and human intake modeling: spatial versus nonspatial insights for chemical emissions in Western Europe

Multimedia fate and multipathway human exposure models are widely adopted in assessments of toxicological risks of chemical emissions at the regional scale. This paper addresses the question of how much spatial detail is necessary in such models when estimating the intake by the entire population in large, heterogeneous regions such as Europe. The paper presents a spatially resolved multimedia fate and multipathway exposure model for Western Europe, available as IMPACT 2002. This model accounts for relationships between the location of food production and drinking water extraction as well as where population cohorts live relative to where chemical emissions occur. The model facilitates estimation of environmental concentration distributions, related levels of contaminants in foods, and the fraction of a chemical release that will be taken in by the entire human population (the intake fraction) at the regional scale. To evaluate the necessary spatial resolution, the paper compares estimates of environmental concentrations and the intake fraction from the spatially resolved model with the results of a consistent clone without spatial resolution. An evaluation for disperse emissions of PeCDF (2,3,4,7,8-pentachlorodibenzofuran, CAS# 5120731-4) suggests reasonable agreement with monitoring data for most impact pathways with both versions of the model, but that the generic vegetation models for estimating contaminant concentrations in agricultural produce require improvement. A broader comparison for a range of organic chemicals demonstrates that the nonspatial models are likely to be appropriate in general for assessing dispersed sources of emissions. However, it is necessary to include generic compartments in such nonspatial models to account separately for emissions that enter lakes with long residence times versus rivers that feed directly into seas. For assessing an emission source in a specific location, using models that are not spatially resolved can result in underestimation, or overestimation, of the population's intake by at least 3 orders of magnitude for some chemicals.     

Night-time atmospheric fate of acrolein and crotonaldehyde

The absolute rate coefficients for the gas-phase reaction of the NO3 radical with acrolein and crotonaldehyde have been measured overthe temperature range 249-330 K, using a discharge flow system and monitoring the NO3 radical by laser induced fluorescence (LIF). The obtained rate coefficients at 298 K for NO3 reactions with acrolein and crotonaldehyde were (3.30 +/- 0.39) x 10(-15) cm3 molecule(-1) s(-1) for acrolein and (1.35 +/- 0.04) x 10(-14) cm3 molecule(-1) s(-1) for crotonaldehyde, and the proposed Arrhenius expressions are k(T) = (1.72 +/- 0.5) x 10(-13) exp[(-1190 +/- 43)/T] and k(T) = (5.02 +/- 0.7) x 10(-13) exp[(-1076 +/- 47)/T], respectively, in units of cm3 molecule(-1) s(-1). In addition, the products and mechanisms were investigated using an environmental chamber/FTIR absorption system. Formaldehyde, CO, and acryloylperoxy nitrate were identified as the main products for the acrolein reaction with molar yields of 31.6 +/- 2.0, 20.9 +/- 1.9, and 47 +/- 3, respectively. In the crotonaldehyde reaction the main products detected were crotonylperoxy nitrate and CO with yields of 93.6 +/- 4.3 and 8.3 +/- 1.1, respectively. On the basis of the rate constant measured, the activation energy calculated, and the identified products, abstraction of the aldehydic H seems to be the main degradation pathway at room temperature for the reaction of acrolein with NO3. For crotonaldehyde, the mechanism is unclear on the basis of the experimental results. The atmospheric implications of the reactions in question are also discussed.     

European emissions of halogenated greenhouse gases inferred from atmospheric measurements

European emissions of nine representative halocarbons (CFC-11, CFC-12, Halon 1211, HCFC-141b, HCFC-142b, HCFC-22, HFC-125, HFC-134a, HFC-152a) are derived for the year 2009 by combining long-term observations in Switzerland, Italy, and Ireland with campaign measurements from Hungary. For the first time, halocarbon emissions over Eastern Europe are assessed by top-down methods, and these results are compared to Western European emissions. The employed inversion method builds on least-squares optimization linking atmospheric observations with calculations from the Lagrangian particle dispersion model FLEXPART. The aggregated halocarbon emissions over the study area are estimated at 125 (106-150) Tg of CO(2) equiv/y, of which the hydrofluorocarbons (HFCs) make up the most important fraction with 41% (31-52%). We find that chlorofluorocarbon (CFC) emissions from banks are still significant and account for 35% (27-43%) of total halocarbon emissions in Europe. The regional differences in per capita emissions are only small for the HFCs, while emissions of CFCs and hydrochlorofluorocarbons (HCFCs) tend to be higher in Western Europe compared to Eastern Europe. In total, the inferred per capita emissions are similar to estimates for China, but 3.5 (2.3-4.5) times lower than for the United States. Our study demonstrates the large benefits of adding a strategically well placed measurement site to the existing European observation network of halocarbons, as it extends the coverage of the inversion domain toward Eastern Europe and helps to better constrain the emissions over Central Europe.     

Estimation of the production, consumption, and atmospheric emissions of pentabrominated diphenyl ether in Europe between 1970 and 2000

A European consumption and atmospheric emissions inventory for pentabrominated diphenyl ethers (PeBDEs) is derived for the period 1970-2000. This time frame has seen a rise in the widespread usage of PeBDE, followed by more recent restrictions/bans. It is estimated that a total of 3000-5000 t of PeBDEs was produced in Europe during this period, with a further 9000-10,000 t imported in finished articles. The main uses for PeBDE are to flame retard consumer products as well as in packaging and solid elastomers. Their major stocks are predicted to be in polyurethane (flexible) foams with up to 30% in cars; more than 10% in furniture foam; and the rest in textiles, building material, packaging, and solid applications. Release of PeBDEs from treated products into environmental media are estimated with a focus on atmospheric inputs via volatilization from their use in cars, upholstered furniture, textiles, television sets, personal computers, and other recycled material. Different emission factors are used to derive different emission scenarios. A peak in atmospheric emissions of between 22 and 31 t of BDE-47 is estimated to have occurred around 1997, with a decline of approximately 20% in 2000. Comparisons with long-term environmental monitoring data revealed that the time trends of human blood and milk concentrations follow similar patterns to the generated emissions, while sediment core levels increase more slowly, probably because they respond to a mix of atmospheric and catchment inputs. The emissions data derived here can be used in a spatially and temporally resolved form as input data for multi-media environmental fate modeling.     

Response of atmospheric particulate matter to changes in precursor emissions: a comparison of three air quality models

Three mathematical models of air quality (CMAQ, CMAQ-MADRID, and REMSAD) are applied to simulate the response of atmospheric fine particulate matter (PM2.5) concentrations to reductions in the emissions of gaseous precursors for a 10 day period of the July 1999 Southern Oxidants Study (SOS) in Nashville. The models are shown to predict similar directions of the changes in PM2.5 mass and component (sulfate, nitrate, ammonium, and organic compounds) concentrations in response to changes in emissions of sulfur dioxide (SO2), nitrogen oxides (NO(x)), and volatile organic compounds (VOC), except for the effect of SO2 reduction on nitrate and the effect of VOC reduction on PM2.5 mass. Furthermore, in many cases where the directional changes are consistent, the magnitude of the changes are significantly different among models. Examples are the effects of SO2 and NO(x) reductions on nitrate and PM2.5 mass and the effects of VOC reduction on organic compounds, sulfate and nitrate. The spatial resolution significantly influences the results in some cases. Operational model performance for a PM2.5 component appears to provide some useful indication on the reliability of the relative response factors (RRFs) for a change in emissions of a direct precursor, as well as for a change in emissions of a compound that affects this component in an indirect manner, such as via oxidant formation. However, these results need to be confirmed for other conditions and caution is still needed when applying air quality models for the design of emission control strategies. It is advisable to use more than one air quality model (or more than one configuration of a single air quality model) to span the full range of plausible scientific representations of atmospheric processes when investigating future air quality scenarios.     

Influence of mobile air-conditioning on vehicle emissions and fuel consumption: a model approach for modern gasoline cars used in Europe

The influence of air-conditioning activity on the emissions and fuel consumption of passenger cars is an important issue, since fleet penetration and use of these systems have reached a high level. Apart from the MOBILE6 study in the United States, little data is available on the impact of air-conditioning devices (A/Cs). Since weather conditions and A/C technologies both differ from those in the U. S., a test series was designed for the European setting. A fleet of six modern gasoline passenger cars was tested in different weather conditions. Separate test series were carried out for the initial cooldown and for the stationary situation of keeping the interior of the vehicle cool. As assumed, CO2 emissions and fuel consumption rise with the thermal load. This also causes a notable rise in CO and hydrocarbons (HCs). Moreover, A/Cs do not stop automatically at low ambient temperatures; if necessary, they produce dry air to demist the windscreen. A model is proposed that shows a constant load for lower temperatures and a linear trend for higher temperatures. The initial cooldown tests highlight significant differences among cars but show that A/C operation for the initial cooling of an overheated passenger compartment does not result in any extra emissions for the fleet as a whole.     

Development and application of a mobile laboratory for measuring emissions from diesel engines. 1. Regulated gaseous emissions

Information about in-use emissions from diesel engines remains a critical issue for inventory development and policy design. Toward that end, we have developed and verified the first mobile laboratory that measures on-road or real-world emissions from engines at the quality level specified in the U.S. Congress Code of Federal Regulations. This unique mobile laboratory provides information on integrated and modal regulated gaseous emission rates and integrated emission rates for speciated volatile and semivolatile organic compounds and particulate matter during real-world operation. Total emissions are captured and collected from the HDD vehicle that is pulling the mobile laboratory. While primarily intended to accumulate data from HDD vehicles, it may also be used to measure emission rates from stationary diesel sources such as back-up generators. This paper describes the development of the mobile laboratory, its measurement capabilities, and the verification process and provides the first data on total capture gaseous on-road emission measurements following the California Air Resources Board (ARB) 4-mode driving cycle, the hot urban dynamometer driving schedule (UDDS), the modified 5-mode cycle, and a 53.2-mi highway chase experiment. NOx mass emission rates (g mi(-1)) for the ARB 4-mode driving cycle, the hot UDDS driving cycle, and the chase experimentwerefoundto exceed current emission factor estimates for the engine type tested by approximately 50%. It was determined that congested traffic flow as well as "off-Federal Test Procedure cycle" emissions can lead to significant increases in per mile NOx emission rates for HDD vehicles.     

Temporal changes in U.S. benzene emissions inferred from atmospheric measurements

The 1990 Clean Air Act Amendments required the United States Environmental Protection Agency (U.S. EPA) to enact stricter regulations aimed at reducing benzene emissions. In an effort to determine whether these new regulations have been successful in reducing atmospheric benzene concentrations, we have evaluated benzene-to-acetylene ratios from data sets spanning nearlythree decades, collected during several field studies and from the U.S. EPA's Photochemical Assessment Monitoring Station (PAMS) network. The field-study data indicate a decrease in benzene relative to acetylene of approximately 40% from 1994 to 2002. This corresponds to a decrease in benzene alone of approximately 56% over the same period. In contrast, the PAMS data exhibit high interannual variability with no discernible trend. This discrepancy is attributed to measurement problems in the PAMS data sets.     

红曲色素及其在欧洲的应用前景

本文阐述了红曲色素在食品加工中的应用和功能,同时也分析了在欧洲广泛应用的可能性.     

Assessment of air emissions from industrial kiln drying of Pinus radiata wood

D. Don) at 100 °C dry bulb and 70 °C wet bulb, were assessed by measuring the concentration of chemical components in the kiln atmosphere at regular time intervals and determining air-flows and temperature differentials across the stack. The volatile organic compounds (VOC) were trapped on activated carbon and analyzed by GC-MS. The aldehydes were trapped in 2,4-dinitrophenol-hydrazine solution and the aldehyde derivatives analysed by HPLC. Polar compounds were trapped in water and then alcohols were analysed by GC and organic acids by ion exchange chromatography. The two major VOC found were α-pinene and β-pinene, which made up 90% of the total discharge (405 g/m³ wood). Most of the VOC fraction was released during the early stages of drying. The release of potentially hazardous components (formaldehyde, acetaldehyde, furfural) was found to be relatively low (1.1, 8.7, and 0.1 g/m³ wood, respectively) provided the kiln emissions are well dispersed, these levels of release are unlikely to cause adverse environmental effects.     

Infectivity studies of both ash and air emissions from simulated incineration of scrapie-contaminated tissues

We investigated the effectiveness of 15 min exposures to 600 and 1000 degrees C in continuous flow normal and starved-air incineration-like conditions to inactivate samples of pooled brain macerates from hamsters infected with the 263K strain of hamster-adapted scrapie with an infectivity titer in excess of 10(9) mean lethal doses (LD50) per g. Bioassays of the ash, outflow tubing residues, and vented emissions from heating 1 g of tissue samples yielded a total of two transmissions among 21 inoculated animals from the ash of a single specimen burned in normal air at 600 degrees C. No other ash, residue, or emission from samples heated at either 600 or 1000 degrees C, under either normal or starved-air conditions, transmitted disease. We conclude that at temperatures approaching 1000 degrees C under the air conditions and combustion times used in these experiments, contaminated tissues can be completely inactivated, with no release of infectivity into the environment from emissions. The extent to which this result can be realized in actual incinerators and other combustion devices will depend on equipment design and operating conditions during the heating process.     

Anthropogenic atmospheric emissions of antimony and its spatial distribution characteristics in China

An integrated inventory of atmospheric antimony (Sb) emissions from anthropogenic activities in China is compiled for the years 2005-2009. Emissions are estimated for all major anthropogenic sources for the first time. We estimate that the national emissions of antimony are 818 metric tons (t) in 2009, with the largest contribution from coal combustion at 61.8% of the total, while 26.7% of Sb is emitted from nonferrous metals smelting. Emissions are heaviest in Guizhou province, mainly due to small-scale combustion of high-Sb coal without emission control devices, and in Hunan province, where extensive smelting occurs. Furthermore, Sb emissions from 2188 large point sources and area sources are distributed within latitude/longitude-based grids with a resolution of 30 min × 30 min where Sb emissions are largely concentrated in highly populated and industrialized southwestern China, the east central region, and coastal areas. The uncertainties in our bottom-up inventory are quantified as -11% to 40% by Monte Carlo simulation. We recommend continuous field testing of coal combustors and smelters in China to improve the accuracy of these estimates.     

Characterization of atmospheric ammonia emissions from a commercial chicken house on the Delmarva Peninsula

A three-dimensional sampling grid using passive collectors was used to characterize the downwind gas-phase ammonia plumes originating from a commercial chicken house on the Delmarva Peninsula in the Chesapeake Bay watershed. Inverse Gaussian plume modeling was used to determine the source strength of the chicken house and the corresponding chicken emission factors. A total of seven field deployments were performed during two different flocks with a sampling duration ranging from 6 to 12.6 h. The deployments occurred during weeks 3, 4, and 5 of the 6-week chicken grow-out period in the months of May-July 2002. The ammonia emission factors ranged from 0.27 to 2.17 g of NH3-N bird(-1) day(-1) with a mean of 1.18 g of NH3-N bird(-1) day(-1). Weighted emissions factors that accounted for the nonlinear increase in ammonia emissions over the 6-week grow-out period were also calculated and ranged from 0.14 to 1.65 g of NH3-N bird(-1) day(-1) with a mean of 0.74 g of NH3-N bird(-1) day(-1). These weighted emission values would correspond to an annual release of approximately 18 x 10(6) kg of NH3-N to the atmosphere from broiler production on the Delmarva Peninsula. This assumes that the emission factors in this study are representative for the entire year with varying meteorological conditions and are representative of all chicken husbandry practices. The Delmarva Peninsula could represent a significant source of nutrient nitrogen to the Chesapeake Bay and Delaware Bay watersheds through atmospheric deposition when considering the size of this annual release rate, the relative short atmospheric lifetime of ammonia due to deposition, and the proximity of the Delmarva Peninsula to the Chesapeake and Delaware Bays.