Real-world emissions of carbonyl compounds from in-use heavy-duty diesel trucks and diesel Back-Up Generators (BUGs)

Emissions of carbonyl compounds such as formaldehyde, acetaldehyde, and acrolein are of interest to the scientific and regulatory communities due to their suspected or likely impacts on human health. The present work investigates emissions of carbonyl compounds from nine Class 8 heavy-duty diesel (HDD) tractors and also from nine diesel-powered backup generators (BUGs); the former were chosen because of their ubiquity as an emission source, and the latter because of their proximity to centers of human activity. The HDD tractors were operated on the ARB 4-Mode heavy heavy-duty diesel truck (HHDDT) driving cycle, while the BUGs were operated on the ISO 8178 Type D2 5-mode steady-state cycle and sampled using a mobile emissions laboratory (UCR MEL) equipped with a full-scale dilution tunnel. Samples were analyzed using the SAE930142 (Auto/Oil) method for 11 aldehydes, from formaldehyde to hexanaldehyde, and 2 ketones (acetone and methyl ethyl ketone). Although absolute carbonyl emissions varied widely by BUG, the relative contributions of the different carbonyls were similar (e.g., median: 56% for formaldehyde). A slight increasing trend with engine load was observed for relative formaldehyde contribution, but not for acetaldehyde contribution, for the BUGs. On-road per-mile carbonyl emission factors were a strong function of operating mode of the ARB HHDDT cycle, and found to decrease in the order Creep>Transient>Cruise. This order is qualitatively similar to emission factors for PAHs and n-alkanes determined for the same set of Class 8 diesel tractors in an earlier work. In general, relative carbonyl contributions for the HDD tractors were similar to those for BUGs (e.g., median: 54% for formaldehyde). These results indicate that while engine operating mode and application appear to exert a strong influence on the total absolute mass emission rate of the carbonyls measured, they do not appear to exert as strong an influence on the relative mass emission rates of individual carbonyls.     

An on-line analysis of 7 odorous volatile organic compounds in the ambient air surrounding a large industrial complex

The concentrations of seven odorous volatile organic compounds (VOCs) including styrene (S), toluene (T), xylene (X), methyl ethyl ketone (MEK), isobutyl alcohol (i-BuAl), methyl isobutyl ketone (MIBK), and butyl acetate (BuAc) were measured continuously at hourly intervals from an on-line odor monitoring station in Ansan city, Korea (August 2005 to December 2007). Their concentration data (ppb) exhibited a narrow range of mean values despite large variabilities: 1.33 ± 8.81, 16.1 ± 96.6, 3.32 ± 11.5, 7.45 ± 10.3, 20.4 ± 2.38, 1.31 ± 1.16, and 2.43 ± 3.02, respectively. However, unlike aromatics, the distribution of other VOCs was characterized by infrequent occurrences, e.g., as large as 97.5% of i-BuAl data below detection limit. Comparison of temporal patterns indicates that aromatic VOCs are the highest in summer, while others tend to peak during fall (or summer). If the relative compositions of these VOCs were compared in terms of odor intensity, their contribution in the study area is unlikely significant as the malodor components. Evaluation of the data suggests that the distribution of the target VOCs should be affected more sensitively by local traffic activities rather than industrial processes in the surrounding area. Nonetheless, the potent roles of these volatile components should not be underestimated with respect to human health.     

Measurement of Organic Acids,Aldehydes, and Ketones in Residential Environments and Their Relation to Ozone

Abstract

Ozone and several polar volatile organic compounds (VOCs) including organic acids and carbonyls (aldehydes and ketones) were measured over an approximately 24 hour period in four residences during the winter of 1993 and in nine residences during the summer of 1993. All residences were in the greater Boston, Massachusetts area. The relation of the polar VOCs to the ozone concentration was examined. Indoor carbonyl concentrations were similar between the summer and winter, with the total mean winter concentration being 31.7 ppb and the total mean summer concentration being 36.6 ppb. However, the average air exchange rate was 0.9 hr^?1 during the winter and 2.6 hr^?1 during the summer. Therefore, the estimated carbonyl emission rates were significantly higher during the summer. Indoor organic acid concentrations were about twice as high during the summer as during the winter. For formic acid, the indoor winter mean was 9.8 ppb, and the summer indoor mean was 17.8 ppb. For acetic acid, the indoor winter mean was 15.5 ppb, and the summer indoor mean was 28.7 ppb. The concentrations of the polar VOCs were found to be significantly correlated with one another. Also, the emission rates of the polar VOCs were found to be correlated with both the environmental variables such as temperature and relative humidity and the ozone removal rate; however, it was difficult to apportion the relative effects of the environmental variables and the ozone removal.     

Carbonyl emissions from commercial cooking sources in Hong Kong

Cooking fumes are an important carbonyl emission source, especially in a highly urbanized city, such as Hong Kong. Cooking exhaust from 15 commercial kitchens of a variety of cooking styles was sampled and analyzed for a suite of 13 carbonyl compounds. Carbonyl compositions were varied among the different cooking styles. Formaldehyde was generally the most abundant carbonyl, and its contribution to the total carbonyl amount on a molar basis ranged from 12 to 60%. Acrolein was also found to be an abundant carbonyl in the cooking exhaust. The highest contribution by acrolein to the total carbonyls was found to be 30% in the exhaust of a western-style steak restaurant. Long-chain saturated carbonyls, that is, heptanal, octanal, and nonanal, accounted for a significant fraction (> 40%) of the total carbonyls in kitchens that always used heated cooking oils. Two dicarbonyls, glyoxal and methylglyoxal, had a various presence in the cooking emissions, ranging from negligible to 10%. The presence of benzaldehyde and tolualdehyde was mostly negligible in the sampled kitchen exhaust. Annual emission rates of both individual carbonyls and total carbonyls were estimated for various types of commercial kitchens. Local-style fast-food shops contributed the highest total carbonyl emissions per year mainly because of the large number of this kind of restaurant in Hong Kong. The citywide annual emission rates of the three most toxic carbonyls, formaldehyde, acetaldehyde, and acrolein, were estimated assuming that the limited number of sampled restaurants were representative of the average restaurants. Such estimates of carbonyl emission rates were comparable to the estimated carbonyl emissions from vehicular sources, suggesting the importance of commercial cooking as a source for carbonyls in Hong Kong.     

Carbonyl Emissions from Commercial Cooking Sources in Hong Kong

Abstract

Cooking fumes are an important carbonyl emission source, especially in a highly urbanized city, such as Hong Kong. Cooking exhaust from 15 commercial kitchens of a variety of cooking styles was sampled and analyzed for a suite of 13 carbonyl compounds. Carbonyl compositions were varied among the different cooking styles. Formal dehyde was generally the most abundant carbonyl, and its contribution to the total carbonyl amount on a molar basis ranged from 12 to 60%. Acrolein was also found to be an abundant carbonyl in the cooking exhaust. The highest contribution by acrolein to the total carbonyls was found to be 30% in the exhaust of a western-style steak restaurant. Long-chain saturated carbonyls, that is, heptanal, octanal, and nonanal, accounted for a signifi-cant fraction (>40%) of the total carbonyls in kitchens that always used heated cooking oils. Two dicarbonyls, glyoxal and methylglyoxal, had a various presence in the cooking emissions, ranging from negligible to 10%. The presence of benzaldehyde and tolualdehyde was mostly negligible in the sampled kitchen exhaust. Annual emission rates of both individual carbonyls and total carbon-yls were estimated for various types of commercial kitchens. Local-style fast-food shops contributed the highest total carbonyl emissions per year mainly because of the large number of this kind of restaurant in Hong Kong. The citywide annual emission rates of the three most toxic carbonyls, formaldehyde, acetaldehyde, and acrolein, were estimated assuming that the limited number of sampled restaurants were representative of the average restaurants. Such estimates of carbonyl emission rates were comparable to the estimated carbonyl emissions from vehicular sources, suggesting the importance of commercial cooking as a source for carbonyls in Hong Kong.     

The effect of variability in industrial emissions on ozone formation in Houston, Texas

Ambient observations have indicated that high concentrations of ozone observed in the Houston/Galveston area are associated with plumes of highly reactive hydrocarbons, mixed with NO_x, from industrial facilities. Ambient observations and industrial process data, such as mass flow rates for industrial flares, indicate that the VOCs associated with these industrial emissions can have significant temporal variability. To characterize the effect of this variability in emissions on ozone formation in Houston, data were collected on the temporal variability of industrial emissions or emission surrogates (e.g., mass flow rates to flares). The observed emissions variability was then used to construct regionwide emission inventories with variable industrial emissions, and the impacts of the variability on ozone formation were examined for two types of meteorological conditions, both of which lead to high ozone concentrations in Houston. The air quality simulations indicate that variability in industrial emissions has the potential to cause increases and decreases of 10–52 ppb (13–316%), or more, in ozone concentration. The largest of these differences are restricted to regions of 10–20 km², but the variability also has the potential to increase regionwide maxima in ozone concentrations by up to 12 ppb.     

Seasonal characteristics of ambient volatile organic compounds in Seoul,Korea

The measurements of C₂–C₉ volatile organic compounds (VOC) were carried out at a site in Seoul, the capital of Korea from August 1998 to July 1999. Air samples were collected for 24 h in 6 l SUMMA canisters every 6 days. The canister samples were quantitatively analyzed by a GC/FID and GC/MS. The species with the highest mean concentration among the 70 identified was propane (7.8 ppb), followed by toluene (6.4 ppb) and ethylene (5.9 ppb). The high concentration of propane was mainly attributed to the emissions by liquefied petroleum gas (LPG) usage for cooking and heating, and butane fuel for transportation. The general trend of the seasonal variation shows higher concentrations in winter and lower ones in summer. This behavior was mainly caused by the variations of temperature, and resultant VOC source strengths, coupled with the variations of the mixing depth. According to the analysis of concentration ratios, the seasonal contributions of the major emission sources to the VOC concentrations were influenced by ambient temperature. Further, it was identified that the contributions by the use of solvents, natural gas, LPG, and butane fuel were closely related to the variations of consumption pattern according to seasons. Through the analysis of the concentration correlations between less reactive compound and highly reactive ones for summer and winter months, it was found that photochemical reactivity affects relative concentration of reactive compound.     

Sensitivity analysis of source regions to PM2.5 concentration at Fukue Island,Japan

The authors analyze the sensitivities of source regions in East Asia to PM_2.5 (particulate matter with an aerodynamic diameter of ≤2.5 µm) concentration at Fukue Island located in the western part of Japan by using a regional chemical transport model with emission sensitivity simulations for the year 2010. The temporal variations in PM_2.5 concentration are generally reproduced, but the absolute concentration is underestimated by the model. Chemical composition of PM_2.5 in the model is compared with filter sampling data in spring; simulated sulfate, ammonium, and elemental carbon are consistent with observations, but mass concentration of particulate organic matters is underestimated. The relative contribution from each source region shows the seasonal variation, especially in summer. The contribution from central north China (105°E–124°E, 34°N–42°N) accounts for 50–60% of PM_2.5 at Fukue Island except in summer; it significantly decreases in summer (18%). Central south China (105°E–123°E, 26°N–34°N) has the relative contribution of 15–30%. The contribution from the Korean Peninsula is estimated at about 10% except in summer. The domestic contribution accounts for about 7% in spring and autumn and increases to 19% in summer. We also estimate the relative contribution to daily average concentration in high PM_2.5 days (>35 μg m^?3). Central north China has a significant contribution of 60–70% except in summer. The relative contribution from central south China is estimated at 46% in summer and about 30% in the other seasons. The contributions from central north and south China on high PM_2.5 days are generally larger than those of their seasonal mean contributions. The domestic contribution is smaller than the seasonal mean value in every season; it is less than 10% even in summer. These model results suggest that foreign anthropogenic sources have a substantial impact on attainment of the atmospheric environmental standard of Japan at Fukue Island.

Implications: The contribution from several source regions in East Asia to PM_2.5 concentration at Fukue Island, a remote island located in the western part of Japan and close to the Asian continent, is estimated using a three-dimensional chemical transport model. The model results suggest that PM_2.5 that is attributed to foreign anthropogenic sources have a larger contribution than that of domestic pollution and have a substantial impact on attainment of the atmospheric environmental standard of Japan at Fukue Island.     

Emission of non-methane volatile organic compounds (VOCs) from boreal peatland microcosms—effects of ozone exposure

Non-methane volatile organic compounds (VOCs) emitted from boreal peatland microcosms were semiquantitatively determined using gas chromatography–mass spectrometry techniques in a growth chamber experiment. Furthermore, effects of vegetation composition and different ozone concentrations on these emissions were estimated by multivariate data analyses. The study concentrated on the less-studied VOCs, and isoprene was not analyzed. The analyses suggest that a sedge Eriophorum vaginatum is associated with emissions of the four most-emitted VOC groups (cyclic, aromatic, carbonyl and aliphatic hydrocarbon compounds) and also with VOCs emitted in smaller amounts (terpenoids and N-containing compounds). A woody dwarf shrub Andromeda polifolia was strongly associated with emissions of aromatic, carbonyl and terpenoid compounds. Results suggest that exposure to an ozone concentration of 150 ppb leads to an increased emission of most VOC groups. Emission of aromatic compounds seems to increase linearly with increasing ozone concentration. These observations indicate that peatlands may be a source of a vast range of volatile compounds to the atmosphere. For more accurate assessment of the impact of elevated tropospheric ozone on the terpenoid and non-terpenoid VOC emissions from peatlands, well-replicated open-air ozone-exposure experiments should be conducted.     

Hydrocarbon emissions from industrial release events in the Houston-Galveston area and their impact on ozone formation

Ambient measurements have shown that ozone formation in the Houston-Galveston area of Texas is frequently much more rapid than in other urban areas. One of the contributing factors is believed to be short-term episodic or “event” emissions from industrial facilities, particularly releases that contain significant mass fractions of highly reactive volatile organic compounds (HRVOCs). In this work, time series analyses are used to compare average annual flow rates for air pollutant emissions with those released during reported emission events. The results indicate that the magnitude and frequency of HRVOC event emissions are an important element in accurately reflecting ozone precursor emission patterns in the Houston-Galveston area, particularly in Harris, Brazoria, Galveston, and Chambers counties. More than 50% of the reported episodic (event) emissions of HRVOCs are ethene and approximately a third are propene; the remainders are isomers of butene and 1,3-butadiene. Most events last less than 24 h. The mass released in an event can vary from a few hundred to more than 100,000 lb, and the dominant type of industrial source is chemical manufacturers (SIC 2869). Daily emissions from a single facility can vary from annual average emissions by multiple orders of magnitude at a frequency of several times a year. Because there are so many facilities in the Houston-Galveston area, HRVOC emission variability of this magnitude can be expected daily, at some time and some location in the Houston-Galveston area. If the emission variability occurs at times and locations where atmospheric conditions are conducive to ozone formation, both ambient data and photochemical modeling indicate that industrial emission events can lead to elevated concentrations of ozone. Specifically, peak, area-wide ozone concentration can be increased by as much as 100 ppb for large HRVOC emission events.     

Assessment of a regulatory model's performance relative to large spatial heterogeneity in observed ozone in Houston, Texas

In Houston, some of the highest measured 8-hr ozone (O3) peaks are characterized by sudden increases in observed concentrations of at least 40 ppb in 1 hr or 60 ppb in 2 hr. Measurements show that these large hourly changes appear at only a few monitors and span a narrow geographic area, suggesting a spatially heterogeneous field of O3 concentrations. This study assessed whether a regulatory air quality model (AQM) can simulate this observed behavior. The AQM did not reproduce the magnitude or location of some of the highest observed hourly O3 changes, and it also failed to capture the limited spatial extent. On days with measured large hourly changes in O3 concentrations, the AQM predicted high O3 over large regions of Houston, resulting in overpredictions at several monitors. This analysis shows that the model can make high O3, but on these days the predicted spatial field suggests that the model had a different cause. Some observed large hourly changes in O3 concentrations have been linked to random releases of industrial volatile organic compounds (VOCs). In the AQM emission inventory, there are several emission events when an industrial point source increases VOC emissions in excess of 10,000 mol/hr. One instance increased predicted downwind O3 concentrations up to 25 ppb. These results show that the modeling system is responsive to a large VOC release, but the timing and location of the release, and meteorological conditions, are critical requirements. Attainment of the O3 standard requires the use of observational data and AQM predictions. If the large observed hourly changes are indicative of a separate cause of high O3, then the model may not include that cause, which might result in regulators enacting control strategies that could be ineffective.     

Primary sources of selected POPs: regional and global scale emission inventories

During the last decade, a number of studies have been devoted to the sources and emissions of Persistent Organic Pollutants (POPs) at regional and global scales. While significant improvements in knowledge have been achieved for some pesticides, the quantitative understanding of the emission processes and emission patterns for "non-pesticide" POPs are still considered limited. The key issues remaining for the non-pesticide POPs are in part determined by their general source classification. For industrial chemicals, such as the polychlorinated biphenyls (PCBs), there is considerable uncertainty with respect to the relative importance of atmospheric emissions from various source categories. For PCBs, temperature is discussed as a potential key factor influencing atmospheric emission levels and patterns. When it comes to the unintentional by-products of combustion and industrial processes (PCDD/Fs), there is still a large uncertainty with respect to the relative contribution of emissions from unregulated sources such as backyard barrel burning that requires further consideration and characterisation. For hexachlorobenzene (HCB), the relative importance of primary and secondary atmospheric emissions in controlling current atmospheric concentrations remains one of the key uncertainties. While these and other issues may remain unresolved, knowledge concerning the emissions of POPs is a prerequisite for any attempt to understand and predict the distribution and fate of these chemicals on a regional and global scale as well as to efficiently minimise future environmental burdens.     

Future year ozone source attribution modeling study using CMAQ-ISAM

ABSTRACT

To achieve the current United States National Ambient Air Quality Standards (NAAQS) attainment level for ozone or particulate matter, current photochemical air quality models include tools to determine source apportionment and/or source sensitivity. Previous studies by the authors have used the Ozone and Particulate Matter Source Apportionment Technology and Higher-order Decoupled Direct Method probing tools in CAMx to investigate these source-receptor relationships for ozone. The recently available source apportionment for CMAQ, referred to as the Integrated Source Apportionment Method (ISAM), was used in this study to conduct future year (2030) source attribution modeling. The CMAQ-ISAM ozone source attribution results for selected cities across the U.S. showed boundary conditions were the dominant contributor to the future year highest July maximum daily 8-hour average (MDA8) ozone concentrations. Point sources were generally larger contributors in the eastern U.S. than in the western U.S. The contributions of on-road mobile emissions were around 5 ppb at most of the cities selected for analysis. Off-road mobile source contributions were around 20 ppb or nearly 30%. Since boundary conditions play an important role in future year ozone levels, it is important to characterize future year boundary conditions accurately. The current implementation of ISAM in CMAQ 5.0.2 requires significant computing resources for ozone source attribution, making it difficult to conduct long-term simulations for large domains. The computing requirements for PM source attribution are even more onerous. CMAQ 5.2 was released after this study was completed, and does not include ISAM. If an efficient version of ISAM becomes available, it could be used in long-term ozone and PM2.5 studies. Implications: Ozone source attribution results provide useful information on important emission source contribution categories and provide some initial guidance on future emission reduction strategies. This study explains a new source apportionment technique, CMAQ-ISAM, and compares it to CAMx OSAT. The techniques have similar results: ozone’s highest source contributor is boundary conditions, followed by point sources, then off-road mobile sources. The current version of ISAM in CMAQ 5.0.2 requires significant computing resources for ozone source attribution, while the computing requirements for PM source attribution are even more onerous. CMAQ 5.2 was released after this study was completed, and does not include ISAM.     

Modeling and direct sensitivity analysis of biogenic emissions impacts on regional ozone formation in the Mexico-U.S. border area

A spatially and temporally resolved biogenic hydrocarbon and nitrogen oxides (NOx) emissions inventory has been developed for a region along the Mexico-U.S. border area. Average daily biogenic non-methane organic gases (NMOG) emissions for the 1700 x 1000 km2 domain were estimated at 23,800 metric tons/day (62% from Mexico and 38% from the United States), and biogenic NOx was estimated at 1230 metric tons/day (54% from Mexico and 46% from the United States) for the July 18-20, 1993, ozone episode. The biogenic NMOG represented 74% of the total NMOG emissions, and biogenic NOx was 14% of the total NOx. The CIT photochemical airshed model was used to assess how biogenic emissions impact air quality. Predicted ground-level ozone increased by 5-10 ppb in most rural areas, 10-20 ppb near urban centers, and 20-30 ppb immediately downwind of the urban centers compared to simulations in which only anthropogenic emissions were used. A sensitivity analysis of predicted ozone concentration to emissions was performed using the decoupled direct method for three dimensional air quality models (DDM-3D). The highest positive sensitivity of ground-level ozone concentration to biogenic volatile organic compound (VOC) emissions (i.e., increasing biogenic VOC emissions results in increasing ozone concentrations) was predicted to be in locations with high NOx levels, (i.e., the urban areas). One urban center--Houston--was predicted to have a slight negative sensitivity to biogenic NO emissions (i.e., increasing biogenic NO emissions results in decreasing local ozone concentrations). The highest sensitivities of ozone concentrations to on-road mobile source VOC emissions, all positive, were mainly in the urban areas. The highest sensitivities of ozone concentrations to on-road mobile source NOx emissions were predicted in both urban (either positive or negative sensitivities) and rural (positive sensitivities) locations.     

Expected ozone benefits of reducing nitrogen oxide (NOx) emissions from coal-fired electricity generating units in the eastern United States

On hot summer days in the eastern United States, electricity demand rises, mainly because of increased use of air conditioning. Power plants must provide this additional energy, emitting additional pollutants when meteorological conditions are primed for poor air quality. To evaluate the impact of summertime NO_x emissions from coal-fired electricity generating units (EGUs) on surface ozone formation, we performed a series of sensitivity modeling forecast scenarios utilizing EPA 2018 version 6.0 emissions (2011 base year) and CMAQ v5.0.2. Coal-fired EGU NO_x emissions were adjusted to match the lowest NO_x rates observed during the ozone seasons (April 1–October 31) of 2005–2012 (Scenario A), where ozone decreased by 3–4 ppb in affected areas. When compared to the highest emissions rates during the same time period (Scenario B), ozone increased ～4–7 ppb. NO_x emission rates adjusted to match the observed rates from 2011 (Scenario C) increased ozone by ～4–5 ppb. Finally in Scenario D, the impact of additional NO_x reductions was determined by assuming installation of selective catalytic reduction (SCR) controls on all units lacking postcombustion controls; this decreased ozone by an additional 2–4 ppb relative to Scenario A. Following the announcement of a stricter 8-hour ozone standard, this analysis outlines a strategy that would help bring coastal areas in the mid-Atlantic region closer to attainment, and would also provide profound benefits for upwind states where most of the regional EGU NO_x originates, even if additional capital investments are not made (Scenario A).

Implications: With the 8-hr maximum ozone National Ambient Air Quality Standard (NAAQS) decreasing from 75 to 70 ppb, modeling results indicate that use of postcombustion controls on coal-fired power plants in 2018 could help keep regions in attainment. By operating already existing nitrogen oxide (NO_x) removal devices to their full potential, ozone could be significantly curtailed, achieving ozone reductions by up to 5 ppb in areas around the source of emission and immediately downwind. Ozone improvements are also significant (1–2 ppb) for areas affected by cross-state transport, especially Mid-Atlantic coast regions that had struggled to meet the 75 ppb standard.     

Status of PCDD/F-emission control in Germany on the basis of the current legislation and strategies for further action

The protection of environment from polychlorinated dibenzodioxin and -furan (PCDD/F) impacts, caused by a heterogeneous spectrum of thermal stationary sources and several others in chemical industry, bases on a comprehensive legislation in Germany. The results of this emission reduction strategy are presented by emission inventories for stationary, mainly industrial sources comparing in this paper data for emissions between 1994 and 2001. These results show that the implementation of best available techniques (BAT) at industrial sources for PCDD/F-reduction has been nearly fully exhausted at nearly all relevant sources and extensive overall emission reductions were achieved by the end of the 1990s. Further reductions for PCDD/F are needed for specific sources in metallurgical industries, especially sinter plants, and for domestic furnaces only. For coplanar PCBs (co-PCBs) almost no emission data are available from German sources; a few data from measurements of co-PCB have been published from two waste incineration plants. These measurements show that the emission limit value of 0.1 ng TEQ/m3 is not exceeded by co-PCBs in the waste gas in addition to the background PCDD/F concentration. As a consequence from the new appraisals for toxicity equivalences (TEQ) and tolerable daily intakes (TDI) of the World Health Organisation the Federal Environmental Agency in Germany discusses a level of 1 pg WHO TEQ/(kg(bw) d) as an acceptable limit value for adult's burden, taking into account, that this value is too much for children in the pre- and post-natal age and further action for PCDD/F- and co-PCB reduction is needed for the last sensitive group. As a summary can be reported that PCDD/F and co-PCB intakes into the nutrition chain could not have their origin from stationary industrial sources mainly. More attention should be given to more diffuse source such as residential combustion and others, which are more directly connected to the nutrition chain, like green food drying. Important effects could be expected by restrictions of PCDD/F impacts by regulations for control of feed, feed components and compounds feed for pigs and cattle.     

Review of concentrations and chemistry of trichloroacetate in the environment

This paper reviews the concentrations of trichloroacetate (TCA) in the atmosphere-plant-soil system. Data originate mainly from Europe. The median TCA concentration in rainwater and canopy drip decreased until 1995. From then the median TCA concentration in rainwater remains rather constant while for canopy drip later data are not available. The same seems to hold for concentrations in air although a very limited data set is available. The median concentrations in coniferous needles and groundwater are constant for the period observed. The median TCA concentrations in soil decreased until 1992 and then remained constant.The TCA formation from chlorinated solvents in the atmosphere may explain a substantial percentage of the TCA amount in the atmosphere. The TCA concentrations in rainwater and canopy drip indicate that there will be other sources contributing to 10-50%. Waste incineration, biomass burning and natural formation in the marine boundary layer are potential candidate sources of TCA, but nothing can be said as yet on their TCA emission rates. Anthropogenic emissions of chlorine could also be a source.TCA can be formed from chlorinated solvents by biota. However, for coniferous trees the uptake of TCA from soil may be the predominant route. Biotic and abiotic reactions can cause to formation of TCA in soil, but also formation of TCA from chlorinated solvents by biota that excrete TCA, may contribute. Mass balance calculations of the bioactive soil top layer show that the production rate of TCA in certain soil types could be substantial. The mass balance calculations could not distinguish between natural and anthropogenic sources in soil.     

Effective pollutant emission heights for atmospheric transport modelling based on real-world information

Emission data needed as input for the operation of atmospheric models should not only be spatially and temporally resolved. Another important feature is the effective emission height which significantly influences modelled concentration values. Unfortunately this information, which is especially relevant for large point sources, is usually not available and simple assumptions are often used in atmospheric models. As a contribution to improve knowledge on emission heights this paper provides typical default values for the driving parameters stack height and flue gas temperature, velocity and flow rate for different industrial sources. The results were derived from an analysis of the probably most comprehensive database of real-world stack information existing in Europe based on German industrial data. A bottom-up calculation of effective emission heights applying equations used for Gaussian dispersion models shows significant differences depending on source and air pollutant and compared to approaches currently used for atmospheric transport modelling.     

Measurements of personal exposure to nitrogen dioxide in four Mexican cities in 1996

Nitrogen dioxide is a ubiquitous pollutant in urban areas. Indoor NO2 concentrations are influenced by penetration of outdoor concentrations and by indoor sources. The objectives of this study were to evaluate personal exposure to NO2, taking into account human time-activity patterns in four Mexican cities. Passive filter badges were used for indoor, outdoor, and personal NO2 measurements over 48 hr and indoor workplace measurements over 16 hr. Volunteers completed a questionnaire on exposure factors and a time-activity diary during the sample period. An unpaired t test, an analysis of variance (ANOVA), and a linear regression were performed to compare differences among cities and mean personal NO2 concentrations involving housing characteristics, as well as to determine which variables predicted the personal NO2 concentration. Sampling periods were in April, May, and June 1996 in Mexico City, Guadalajara, Cuernavaca, and Monterrey. All 122 volunteers in the study were working adults, with a mean age of 34 (SD +/- 7.38); 64% were female, and the majority worked in public offices and universities. The highest NO2 concentrations were found in Mexico City (36 ppb for outdoor, 57 ppb for indoor, and 39 ppb for personal concentration) and the lowest in Monterrey (19 ppb for outdoor, 24 ppb for indoor, and 24 ppb for personal concentration). Significant differences in NO2 concentrations were found among the cities in different microenvironments. During the sampling period, volunteers spent 85% of their time indoors. The highest personal NO2 concentration was found when volunteers kept their windows closed (p = 0.03). In the regression model adjusted by city and gender, the best predictors of personal NO2 concentration were outdoor levels and time spent outdoors (R2 = 0.68). These findings suggest that outdoor NO2 concentrations were an important influence on the personal exposure to NO2, due to the specific characteristics and personal behavior of the people in these Mexican cities.     

Tetrachloroethylene emissions and exposure in dry cleaning

Tetrachloroethylene (PCE) emissions and the exposure of workers in six commercial and three industrial dry-cleaning establishments that use dry-to-dry machines were determined. The personal samples and area samples [8-hr time-weighted average (TWA) and short-term exposure] were collected with charcoal tubes and passive monitors. The temporal variation of PCE concentration in the workplace air was monitored using a Fourier transform infrared analyzer (FTIR). The PCE emission rates were determined by multiplying the average PCE concentration in the room and the total airflow rate in the room. The PCE emissions were related to the cleaning rate in units of kg/hr. The operators' mean TWA exposure in commercial shops and industrial establishments was 28 (4.1 ppm) and 32 mg/m3 (4.6 ppm), and the pressers' exposure was 3.4 (0.5 ppm) and 7.7 mg/m3 (1.1 ppm), respectively. The customer service personnel had the lowest TWA exposure with a mean value of 0.8 mg/m3 (0.1 ppm). The highest peak concentration (2300 mg/m3; 334 ppm) was observed during cleaning of the lint and button trap, during which operation respirators were used. The PCE emission rates ranged from 4 to 118 g/hr corresponding to emission factors (mass of solvent evaporated per mass of cleaned cloths) of 0.3-3.6 g/kg. The workers' exposure to PCE was below the occupational limit values in the United States [according to the American Conference of Governmental Industrial Hygienists (ACGIH)] and in Finland. The outdoor PCE emissions were clearly below the limit values given in the European Union volatile organic compound (VOC) directive requirements.