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1.
The objective of the study was to quantify the concentration and emission levels of sulfuric odorous compounds emitted from pig-feeding operations. Five types of pig-housing rooms were studied: gestation, farrowing, nursery, growing and fattening rooms. The concentration range of sulfuric odorous compounds in these pig-housing rooms were 30–200 ppb for hydrogen sulfide (H2S), 2.5–20 ppb for methyl mercaptan (CH3SH), 1.5–12 ppb for dimethyl sulfide (DMS; CH3SCH3) and 0.5–7 ppb for dimethyl disulfide (DMDS; CH3S2CH3), respectively. The emission rates of H2S, CH3SH, DMS and DMDS were estimated by multiplying the average concentration (mg m−3) measured near the air outlet by the mean ventilation rate (m3 h−1) and expressed either per area (mg m−2 h−1) or animal unit (AU; liveweight of the pig, 500 kg) (mg pig−1 h−1). As a result, the emission rates of H2S, CH3SH, DMS and DMDS in the pig-housing rooms were 14–64, 0.8–7.3, 0.4–3.4 and 0.2–1.9 mg m−2 h−1, respectively, based on pig's activity space and 310–723, 18–80, 9–39 and 5–22 mg AU−1 h−1, respectively, based on pig's liveweight, which indicates that their emission rates were similar, whether based upon the pig's activity space or liveweight. In conclusion, the concentrations and emission rates of H2S were highest in the fattening room followed by the growing, nursery, farrowing and gestation rooms whereas those of CH3SH, DMS and DMDS concentrations were largest in the growing room followed by the nursery, gestation and farrowing rooms.  相似文献   

2.
Abstract

The traditional technologies for odor removal of thiol usually create either secondary pollution for scrubbing, adsorption, and absorption processes, or sulfur (S) poisoning for catalytic incineration. This study applied a laboratory-scale radio-frequency plasma reactor to destructive percentage-grade concentrations of odorous dimethyl sulfide (CH3SCH3, or DMS). Odor was diminished effectively via reforming DMS into mainly carbon disulfide (CS2) or sulfur dioxide (SO2). The removal efficiencies of DMS elevated significantly with a lower feeding concentration of DMS or a higher applied rf power. A greater inlet oxygen (O2)/DMS molar ratio slightly improved the removal efficiency. In an O2-free environment, DMS was converted primarily to CS2, methane (CH4), acetylene (C2H2), ethylene (C2H4), and hydrogen (H2), with traces of hydrogen sulfide (H2S), methyl mercaptan (CH3SH), and dimethyl disulfide. In an O2-containing environment, the species detected were SO2, CS2, carbonyl sulfide, carbon dioxide (CO2), CH4, C2H4, C2H2, H2, formal-dehyde, and methanol. Differences in yield of products were functions of the amounts of added O2 and the applied power. This study provided useful information for gaining insight into the reaction pathways for the DMS dissociation and the formation of products in the plasmolysis and conversion processes.  相似文献   

3.
The photochemical oxidation and dispersion of reduced sulfur compounds (RSCs: H2S, CH3SH, DMS, CS2, and DMDS) emitted from anthropogenic (A) and natural (N) sources were evaluated based on a numerical modeling approach. The anthropogenic emission concentrations of RSCs were measured from several sampling sites at the Donghae landfill (D-LF) (i.e., source type A) in South Korea during a series of field campaigns (May through December 2004). The emissions of natural RSCs in a coastal study area near the D-LF (i.e., source type N) were estimated from sea surface DMS concentrations and transfer velocity during the same study period. These emission data were then used as input to the CALPUFF dispersion model, revised with 34 chemical reactions for RSCs. A significant fraction of sulfur dioxide (SO2) was produced photochemically during the summer (about 34% of total SO2 concentrations) followed by fall (21%), spring (15%), and winter (5%). Photochemical production of SO2 was dominated by H2S (about 55% of total contributions) and DMS (24%). The largest impact of RSCs from source type A on SO2 concentrations occurred around the D-LF during summer. The total SO2 concentrations produced from source type N around the D-LF during the summer (a mean SO2 concentration of 7.4 ppbv) were significantly higher than those (≤0.3 ppbv) during the other seasons. This may be because of the high RSC and SO2 emissions and their photochemistry along with the wind convergence.  相似文献   

4.
In this study, the concentrations of reduced sulfur compounds (RSC: H2S, CH3SH, DMS, and DMDS) were continuously measured from an odor monitoring station over a 4-month period (August–November 2005) using an on-line GC system. The hourly measurement data of RSC, collected along with some major aromatic VOCs (benzene, toluene, xylene, etc.), approached the sum of 1500; the mean for all hourly H2S was computed to be 295 ppt, while those of the others were seen at 7 (DMS), 1 (CH3SH), and 0.4 ppt (DMDS). When these RSC data were compared across two seasons and on a 24 h scale basis, the values for either the summer or nighttime periods were generally high relative to their counterparts in the fall and daytime. Analysis of these RSC data generally suggests that most RSCs occur at some ppt concentration ranges and that their values frequently fall below detection limits (DL) values (except for H2S). If the total number of effective data sets (i.e., above DL values) are compared to each other, the results tend to differ significantly between H2S and the others: the proportion of effective number was as high as 75% for H2S, while the others were very low (6% of DMS and even less than that for the others). The distributions of RSC were hence clearly distinguished from those of VOCs in that the determination of the latter was scarcely limited by the instrumental detectability. According to the present study, the H2S data exhibit strong potential as the malodor tracers, while those of the other RSCs are unlikely due to the limited detectability. The overall results of this study hence suggest that several factors which include the selection of target compounds, the location of the monitoring points, and the scale (or number) of total monitoring points should be considered simultaneously to effectively track down the odor occurrence patterns in areas near strong source processes.  相似文献   

5.
Dimethyl sulfide (DMS) and atmospheric aerosols were sampled simultaneously over the Atlantic Ocean in the vicinity of Bermuda using the NOAA King Air research aircraft. Total and fine (50% cutoff at 2 μm diameter) aerosol fractions were sampled using two independent systems. The average nonsea-salt (nss)SO42− concentrations were 1.9 and 1.0 μg m−3 (as SO42−) for the total and the fine fractions in the boundary layer (BL) and 0.53 and 0.27 μg m−3 in the free troposphere (FT). Non-sea-salt SO42− in the two aerosol fractions were highly correlated (r = 0.90), however a smaller percentage (55%) was found in the fine aerosol near Bermuda relative to that (90%) near the North American continent. The BL SO42− concentrations measured in this study were higher than those measured by others at remote marine locations despite the fact that the 7-day air mass back trajectories indicated little or no continental contact at altitudes of 700 mb and below; the trajectories were over subtropical oceanic areas that are expected to be rich in DMS. DMS concentrations were higher near the ocean surface and decreased with increasing altitude within the BL; the average DMS concentration was 0.13 μg m−3. Trace levels of DMS were also measured in the FT (0.01 μg m−3). Computer simultation of the oxidation and removal of DMS in the marine atmosphere suggests that <50% of the SO42− observed could be related to the natural S cycle.  相似文献   

6.
Reduced sulfur compounds (RSCs) such as carbonyl sulfide (OCS), dimethyl sulfide (DMS) and carbon disulfide (CS2) impact radiative forcing, ozone depletion, and acid rain. Although Asia is a large source of these compounds, until now a long-term study of their emission patterns has not been carried out. Here we analyze 16 months of RSC data measured at a polluted rural/coastal site in the greater Pearl River Delta (PRD) of southern China. A total of 188 canister air samples were collected from August 2001 to December 2002. The OCS and CS2 mixing ratios within these samples were higher in autumn/winter and lower in summer due to the influence of Asian monsoon circulations. Comparatively low DMS values observed in this coastal region suggest a relatively low biological productivity during summer months. The springtime OCS levels in the study region (574 ± 40 pptv) were 25% higher than those on other East Asia coasts such Japan, whereas the springtime CS2 and DMS mixing ratios in the PRD (47 ± 38 pptv and 22 ± 5 pptv, respectively) were 3–30 times lower than elevated values that have been measured elsewhere in East Asia (Japan and Korea) at this time of year. Poor correlations were found among the three RSCs in the whole group of 188 samples, suggesting their complex and variable sources in the region. By means of backward Lagrangian particle release simulations, air samples originating from the inner PRD, urban Hong Kong and South China Sea were identified. The mean mixing ratio of OCS in the inner PRD was significantly higher than that in Hong Kong urban air and South China Sea marine air (p < 0.001), whereas no statistical differences were found for DMS and CS2 among the three regions (p > 0.05). Using a linear regression method based on correlations with the urban tracer CO, the estimated OCS emission in inner PRD (49.6 ± 4.7 Gg yr?1) was much higher than that in Hong Kong (0.32 ± 0.05 Gg yr?1), whereas the estimated CS2 and DMS emissions in the study region accounted for a very few percentage of the total CS2 and DMS emission in China. These findings lay the foundation for better understanding sulfur chemistry in the greater PRD region of southern China.  相似文献   

7.
Seawater, atmospheric dimethylsulfide (DMS) and aerosol compounds, potentially linked with DMS oxidation, such as methanesulfonic acid (MSA) and non-sea-salt sulfate (nss-SO42?) were determined in the North Yellow Sea, China during July–August, 2006. The concentrations of seawater and atmospheric DMS ranged from 2.01 to 11.79 nmol l?1 and from 1.68 to 8.26 nmol m?3, with average values of 6.20 nmol l?1 and 5.01 nmol m?3, respectively. Owing to the appreciable concentration gradient, DMS accumulated in the surface water was transferred into the atmosphere, leading to a net sea-to-air flux of 6.87 μmol m?2 d?1 during summer. In the surface seawater, high DMS values corresponded well with the concurrent increases in chlorophyll a levels and a significant correlation was observed between integrated DMS and chlorophyll a concentrations. In addition, the concentrations of MSA and nss-SO42? measured in the aerosol samples ranged from 0.012 to 0.079 μg m?3 and from 3.82 to 11.72 μg m?3, with average values of 0.039 and 7.40 μg m?3, respectively. Based on the observed MSA, nss-SO42? and their ratio, the relative biogenic sulfur contribution was estimated to range from 1.2% to 11.5%, implying the major contribution of anthropogenic source to sulfur budget in the study area.  相似文献   

8.
An analytical method for measuring atmospheric methyl halides was established based on canister sampling and capillary GC/MS. Stability tests for air samples collected in two kinds of canisters (electro-chemical buffing and fused-silica lined) with smooth inner surfaces, showed that both provided stable storage for CH3Cl, CH3Br, and CH3I. The method was applied to the measurement of methyl halides at a remote island (Okinawa, Japan) in August 1996, where nocturnal ozone depletion had been observed in summer. We found that atmospheric CH3Cl increased during stable nights and was negatively correlated with surface ozone concentration. The highest CH3Cl concentration amounted to as high as 1400 pptv and indicated that CH3Cl emitted from the surrounding coastal areas had accumulated in the boundary layer under a stable atmosphere at that time. A positive correlation was observed between CH3Br and CH3I, suggesting a common source in the area.  相似文献   

9.
A global time series of atmospheric methylchloride (CH3Cl) concentrations is reported showing the variability with latitude and season. Springtime concentrations of CH3Cl at 45°N latitude are 7.5%±3.5% higher than during other seasons. Lowest concentrations were generally observed during fall. CH3Cl was found to be more abundant by about 6% (±5% NH, ±3% SH) in the tropical regions of both hemispheres. No significant difference in the burdens of CH3Cl was observed between the two hemispheres. Based on these data the ratio of the average hydroxyl radical (HO) concentration over the southern hemisphere to that over the northern hemisphere was estimated to be 1.3 or less.  相似文献   

10.
The traditional technologies for odor removal of thiol usually create either secondary pollution for scrubbing, adsorption, and absorption processes, or sulfur (S) poisoning for catalytic incineration. This study applied a laboratory-scale radio-frequency plasma reactor to destructive percentage-grade concentrations of odorous dimethyl sulfide (CH3SCH3, or DMS). Odor was diminished effectively via reforming DMS into mainly carbon disulfide (CS2) or sulfur dioxide (SO2). The removal efficiencies of DMS elevated significantly with a lower feeding concentration of DMS or a higher applied rf power. A greater inlet oxygen (O2)/DMS molar ratio slightly improved the removal efficiency. In an O2-free environment, DMS was converted primarily to CS2, methane (CH4), acetylene (C2H2), ethylene (C2H4), and hydrogen (H2), with traces of hydrogen sulfide (H2S), methyl mercaptan (CH3SH), and dimethyl disulfide. In an O2-containing environment, the species detected were SO2, CS2, carbonyl sulfide, carbon dioxide (CO2), CH4, C2H4, C2H2, H2, formaldehyde, and methanol. Differences in yield of products were functions of the amounts of added O2 and the applied power. This study provided useful information for gaining insight into the reaction pathways for the DMS dissociation and the formation of products in the plasmolysis and conversion processes.  相似文献   

11.
We investigated the distribution of phytoplankton species and the associated dimethyl sulfur species, dimethylsulfoniopropionate (DMSP) and dimethylsulfide (DMS) on a cruise into the spring bloom region of the northern North Atlantic (near 47 degrees N, 19 degrees W). The cruise was timed to characterize the relationship between plankton dynamics and sulfur species production during the spring plankton bloom period. At the same time, we measured the DMS concentrations in the atmospheric boundary layer and determined the abundance and composition of the atmospheric aerosol.The water column studies showed that the interplay of wind-driven mixing and stratification due to solar heating controlled the evolution of the plankton population, and consequently the abundance of particulate and dissolved DMSP and DMS. The sea-to-air transfer of DMS was modulated by strong variations in wind speed, and was found to be consistent with currently available transfer parameterizations. The atmospheric concentration of DMS was strongly dependent on the sea surface emission, the depth of the atmospheric boundary layer and the rate of photooxidation as inferred from UV irradiance. Sea-salt and anthropogenic sulfate were the most abundant components of the atmospheric aerosol. On two days, a strong dust episode was observed bringing mineral dust aerosol from the Sahara desert to our northerly study region. The background concentrations of marine biogenic sulfate aerosol were low, near 30-60 ppt. These values were consistent with the rate of sulfate production estimated from the abundance of DMS in the marine boundary layer.  相似文献   

12.
The use of alcohol fuel has received much attention since 1980s. In Brazil, ethanol-fueled vehicles have been currently used on a large scale. This paper reports the atmospheric methanol, ethanol and isopropanol concentrations which were measured from May to December 1997, in Osaka, Japan, where alcohol fuel was not used, and from 3 to 9 February 1998, in Sao Paulo, Brazil, where ethanol fuel was used. The alcohols were determined by the alkyl nitrite formation reaction using gas chromatography (GC-ECD) analysis. The concentration of atmospheric alcohols, especially ethanol, measured in Sao Paulo were significantly higher than those in Osaka. In Osaka, the average concentrations of atmospheric methanol, ethanol, and isopropanol were 5.8±3.8, 8.2±4.6, and 7.2±5.9 ppbv, respectively. The average ambient levels of methanol, ethanol, and isopropanol measured in Sao Paulo were 34.1±9.2, 176.3.±38.1, and 44.2±13.7 ppbv, respectively. The ambient levels of aldehydes, which were expected to be high due to the use of alcohol fuel, were also measured at these sampling sites. The atmospheric formaldehyde average concentration measured in Osaka was 1.9±0.9 ppbv, and the average acetaldehyde concentration was 1.5±0.8 ppbv. The atmospheric formaldehyde and acetaldehyde average concentrations measured in Sao Paulo were 5.0±2.8 and 5.4±2.8 ppbv, respectively. The C2H5OH/CH3OH and CH3CHO/HCHO were compared between the two measurement sites and elsewhere in the world, which have already been reported in the literature. Due to the use of ethanol-fueled vehicles, these ratios, especially C2H5OH/CH3OH, are much higher in Brazil than these measured elsewhere in the world.  相似文献   

13.
An automatic process gas chromatograph has been developed for use on the recovery furnace stack of a Kraft pulp mill. The instrument analyzes for widely varying concentrations of H2S, SO2, CH3SH and higher order sulfur compounds. It is insensitive to the fixed gases and water vapor, and performs its analysis in approximately ten minutes. The instrument features a microcoulometric detector giving it sensitivity to H2S as low as 0.1 ppm, and SO2 and CH3SH as low as 0.5 ppm. The major limit to even higher sensitivity at this stage of development lies with two problems: the background noise level in the detector and the sulfur compound absorption in the Porapak Q chromatograph column. At the reported sensitivity, a 40-ml gas sample was used. The instrument also contains a data analysis system supplementary to the usual strip chart recorder. This system is made up of a digital voltmeter, a digital translator, and a teletype and hence allows the transfer of the output data to a digital computer for processing. The processed data are usually presented in the form of ppm quantities of the component gases in the stack gas. The instrument has worked successfully on small furnace effluent for periods of 25 hr but has not been tried on recovery furnace stacks. It has also run on prepared samples for periods of up to seven days with no maintenance or attendance necessary.  相似文献   

14.
The spatial and temporal behavior of atmospheric methane (CH4) in the Nagoya metropolitan area was investigated in relation to the regional meteorological and topographical characteristics. It was found that the daily maximum CH4 concentrations in the central city area were observed when the northeast wind blew from the foothill of the northeastern mountainous area down into the central city areas, under stable atmospheric conditions. The large and active landfills are the major anthropogenic CH4 sources and are located at the hill sites in the northeast. Therefore, it was considered that the air mass with the high concentration of CH4 flowed from the landfill sites into the urban area, and exerted substantial influences on the spatial and temporal variations of atmospheric CH4 concentrations in the central city area.  相似文献   

15.
ABSTRACT

The possibility of using electronic noses (ENs) to measure odor intensity was investigated in this study. Two commercially available ENs, an Aromascan A32S with conducting polymer sensors and an Alpha M.O.S. Fox 3000 with metal oxide sensors, as well as an experimental EN made of Taguchi-type tin oxide sensors, were used in the experiments. Odor intensity measurement by sensory analysis and EN sensor response were obtained for samples of odorous compounds (n-butanol, CH3COCH3, and C2H5SH) and for binary mixtures of odorous compounds (n-butanol and CH3COCH3). Linear regression analysis and artificial neural networks (ANN) were used to establish a relationship between odor intensity and EN sensor responses.

The results suggest that large differences in sensor response to samples of equivalent odor intensity exist and that sensitivity to odorous compounds varies according to the type of sensors. A linear relationship between odor intensity and averaged sensor response was found to be appropriate for the EN based on conducting polymer sensors with a correlation coefficient (r) of 0.94 between calculated and measured odor intensity. However, the linear regression approach was shown to be inadequate for both ENs, which included metal oxide-type sensors. Very strong correlation (r = 0.99) between measured odor intensity and calculated odor intensity using the ANN developed were obtained for both commercial ENs. A weaker correlation (r = 0.84) was found for the experimental instrument, suggesting an insufficient number of sensors and/or not enough diversity in sensor responses. The results demonstrated the ability of ENs to measure odor intensity associated with simple mixtures of odorous compounds and suggest that ANN are appropriate to model the relationship between odor intensity measurement and EN sensor response.  相似文献   

16.
Volatile organic sulfur compounds in a stratified lake   总被引:3,自引:0,他引:3  
Hu H  Mylon SE  Benoit G 《Chemosphere》2007,67(5):911-919
Three volatile organic sulfur compounds (VOSCs), dimethyl sulfide (DMS), carbon disulfide (CS(2)), and dimethyl disulfide (DMDS), were detected in the stratified water column of a lake (Linsley Pond) in Connecticut. The compounds DMS and DMDS appeared in both the oxic and the anoxic portions of the water column, CS(2) was primarily found in anoxic hypolimnion. Algal metabolism and/or bacterial degradation of sulfur-containing amino acids or other organic materials are potential sources of VOSCs in the oxic lake water. Reactions of hydrogen sulfide with organic compounds and microbial degradation of organic matter may be responsible for the production of VOSCs in the anoxic lake water. The vertical distribution patterns of these three VOSCs varied from month to month in the summer, but the daily profiles obtained in one 5-day period in the summer displayed consistency. No clear diurnal pattern for any of the three VOSCs was observed. Based on observation that these VOSCs were not present in surface and near surface waters of Linsley Pond, freshwater inputs of reduced sulfur compounds to the atmosphere may be insignificant.  相似文献   

17.
Measurements have been made of sulfur and nitrogen compounds in precipitation since 1980 and in air since 1981 in Ontario. This paper presents results of the atmospheric deposition measurement program to the end of 1985. As is to be expected from the distribution of emission sources, annual concentrations of SO42− andNO3 in precipitation, and of SO2,SO42− andNO3 in air are higher in southern Ontario than in northern Ontario. The corresponding distribution pattern for deposition is similar to that of concentration. A wet SO42− deposition rate of 20 kg ha1− y1−, a value considered critical for the acidification of sensitive water bodies, is exceeded in all of central and southern Ontario. On a province-wide basis, sulfur wet deposition is about four times higher than sulfur dry deposition. For nitrogen, wet and dry deposition are more comparable, though the former is still higher. The S- and N-species display different seasonal trends in concentration and deposition reflecting a dependence on meteorological factors, and on the associated chemical transformation rates. On the other hand, year to year variations are small.  相似文献   

18.
Possibilities for monitoring emissions of reduced sulfur compounds in pulp and paper mills were investigated using ion mobility spectrometry (IMS) and a self-organizing map (SOM) algorithm. The reduced sulfur compounds measured were hydrogen sulfide (H2S), dimethyl sulfide (DMS), and methyl mercaptan (MM). Attention was paid to momentary concentrations because there is no monitoring device able to measure peak concentrations of reduced sulfur compounds under field conditions. These methods were evaluated by measuring the reduced sulfur compounds first in the laboratory and then at a process monitoring site at a pulp factory. The aim was to find out whether it would be possible to use the laboratory measurements to recognize the same reduced sulfur compounds at the monitoring site. Data collection was followed by analysis using the SOM algorithm and Sammon's mapping. The results showed that the IMS spectra of reduced sulfur compounds and their mixtures can be distinguished from each other by computationally intelligent methods and that the spectra from the process monitoring site corresponded with the laboratory measurements to a certain extent.  相似文献   

19.
Results of a laboratory study indicate that the rate of solution of atmospheric sulfur dioxide in distilled water, over the range of atmospheric concentrations of 0.81?8.73 mg SO2/M3, is a function of the concentration of SO2 in the atmosphere, with saturation being reached more rapidly at the higher concentrations. This would indicate that rain water, with constantly renewed surfaces, can be very effective in the removal of atmospheric SO2. The pH of the exposed water samples reached values of 4.0 or less, comparable to values observed in fog and cloud water near large industrial areas. Overall solubility of sulfur dioxide in distilled water did not follow the law of partial pressure. At the atmospheric concentrations used it was found that over 98.5% of the sulfite in solution was in the form of the bisulfite ion with, the remainder present as unionized sulfurous acid. Computations using the concentration of unionized sulfurous acid in the solution showed that the solubility of this portion of dissolved sulfite did follow the law of partial pressure.  相似文献   

20.
Chemically active climate compounds are either primary compounds like methane (CH4), removed by oxidation in the atmosphere, or secondary compounds like ozone (O3), sulfate and organic aerosols, both formed and removed in the atmosphere. Man-induced climate–chemistry interaction is a two-way process: Emissions of pollutants change the atmospheric composition contributing to climate change through the aforementioned climate components, and climate change, through changes in temperature, dynamics, the hydrological cycle, atmospheric stability, and biosphere-atmosphere interactions, affects the atmospheric composition and oxidation processes in the troposphere. Here we present progress in our understanding of processes of importance for climate–chemistry interactions, and their contributions to changes in atmospheric composition and climate forcing. A key factor is the oxidation potential involving compounds like O3 and the hydroxyl radical (OH). Reported studies represent both current and future changes. Reported results include new estimates of radiative forcing based on extensive model studies of chemically active climate compounds like O3, and of particles inducing both direct and indirect effects. Through EU projects like ACCENT, QUANTIFY, and the AeroCom project, extensive studies on regional and sector-wise differences in the impact on atmospheric distribution are performed. Studies have shown that land-based emissions have a different effect on climate than ship and aircraft emissions, and different measures are needed to reduce the climate impact. Several areas where climate change can affect the tropospheric oxidation process and the chemical composition are identified. This can take place through enhanced stratospheric–tropospheric exchange of ozone, more frequent periods with stable conditions favoring pollution build up over industrial areas, enhanced temperature induced biogenic emissions, methane releases from permafrost thawing, and enhanced concentration through reduced biospheric uptake. During the last 5–10 years, new observational data have been made available and used for model validation and the study of atmospheric processes. Although there are significant uncertainties in the modeling of composition changes, access to new observational data has improved modeling capability. Emission scenarios for the coming decades have a large uncertainty range, in particular with respect to regional trends, leading to a significant uncertainty range in estimated regional composition changes and climate impact.  相似文献   

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