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1.
Formaldehyde and acetaldehyde are two most abundant carbonyls in ambient air. Biogenic emission has been proposed as a significant source other than anthropogenic emissions and atmospheric secondary formation. Here at a forest site in South China, the carbon isotopic compositions of formaldehyde and acetaldehyde emitted from leaves of three tree species (Litsea rotundifolia, Canarium album and Castanea henryi) were measured in comparison with the bulk carbon isotopic compositions of tree leaves. δ13C data of the emitted aldehydes (from ?31‰ to ?46‰) were quite different for tree species, which were all more depleted in 13C than the tree-leaf bulk δ13C values (from ?27‰ to ?32‰). Formaldehyde in ambient air at the forest site had δ13C values different from those of leaf-emitted formaldehyde, indicating other sources for ambient formaldehyde apart from direct emission from leaves, most probably the photooxidation of biogenic hydrocarbon like isoprene and monoterpene. The δ13C differences of acetaldehyde between ambient data and those of tree leaves emission were less than 1‰, implying direct biogenic emission as the dominant source.  相似文献   

2.
《Chemosphere》2013,90(11):1407-1413
This study presents carbon (δ13C) and hydrogen (δD) isotope values of volatile organic compounds (VOCs) in various emission sources using thermal desorption–gas chromatography–isotope ratio mass spectrometry (TD–GC–irMS). The investigated VOCs ranged from C6 to C10. Samples were taken from (i) car exhaust emissions as well as from plant combustion experiments of (ii) various C3 and (iii) various C4 plants. We found significant differences in δ values of analysed VOCs between these sources, e.g. δ13C of benzene ranged between (i) −21.7 ± 0.2‰, (ii) −27.6 ± 1.6‰ and (iii) −16.3 ± 2.2‰, respectively and δD of benzene ranged between (i) −73 ± 13‰, (ii) −111 ± 10‰ and (iii) −70 ± 24‰, respectively. Results of VOCs present in investigated emission sources were compared to values from the literature (aluminium refinery emission). All source groups could be clearly distinguished using the dual approach of δ13C and δD analysis. The results of this study indicate that the correlation of compound specific carbon and hydrogen isotope analysis provides the potential for future research to trace the fate and to determine the origin of VOCs in the atmosphere using thermal desorption compound specific isotope analysis.  相似文献   

3.
The sources and distribution of carbon in ambient suspended particles (PM2.5 and PM10) of Mexico City Metropolitan Area (MCMA) air were traced using stable carbon isotopes (13C/12C). Tested potential sources included rural and agricultural soils, gasoline and diesel, liquefied-petroleum gas, volcanic ash, and street dust. The complete combustion of LP gas, diesel and gasoline yielded the lightest δ13C values (?27 to ?29‰ vs. PDB), while street dust (PM10) represented the isotopically heaviest endmember (?17‰). The δ13C values of rural soils from four geographically separated sites were similar (?20.7 ± 1.5‰). δ13C values of particles and soot from diesel and gasoline vehicle emissions and agricultural soils varied between ?23 and ?26‰. Ambient PM samples collected in November of 2000, and March and December of 2001 at three representative receptor sites of industrial, commercial and residential activities had a δ13C value centered around ?25.1‰ in both fractions, resulting from common carbon sources. The predominant carbon sources to MCMA atmospheric particles were hydrocarbon combustion (diesel and/or gasoline) and particles of geological origin. The significantly depleted δ13C values from the industrial site reflect the input of diesel combustion by mobile and point source emissions. Based on stable carbon isotope mass balance, the carbon contribution of geological sources at the commercial and residential sites was approximately 73% for the PM10 fraction and 54% for PM2.5. Although not measured in this study, biomass-burning emissions from nearby forests are an important carbon source characterized by isotopically lighter values (?29‰), and can become a significant contributor (67%) of particulate carbon to MCMA air under the prevalence of southwesterly winds. Alternative sources of these 13C-depleted particles, such as cooking fires and municipal waste incineration, need to be assessed. Results show that stable carbon isotope measurements are useful for distinguishing between some carbon sources in suspended particles to MCMA air, and that wind direction has an impact on the distribution of carbon sources in this basin.  相似文献   

4.
Iron isotope compositions of various Fe pools in aquifer sediments were measured at a known As-contaminated site in the Datong Basin, China. The δ56Fe values of HCl-extracted poor-crystalline Fe(III) range widely from ?0.41‰ to 0.36‰. We interpret the low Fe(II)/FeExtractable ratios (<50%) and the negative correlation between Fe(II)/FeExtractable and δ56Fe values in HCl-extracted poor-crystalline Fe to be best explained by redox cycling of Fe induced by microbial Fe(III) reduction. However, the high Fe(II)/FeExtractable ratios (?70%) and positive correlation between Fe(II)/FeExtractable and δ56Fe values for HCl-extracted poor-crystalline Fe indicates production of sulfides (FeSs). The δ56Fe values of crystalline Fe(III) extracted by reductant appears to be comparatively small varying from ?0.01‰ to 0.24‰, which is consistent with the δ56Fe values for ferric oxides/hydroxides having undergone microbial Fe(III) reduction. The Fe isotope composition of various Fe pools shows the transformation between crystalline Fe(III) and poor-crystalline crystalline Fe(III) and the secondary Fe(II) phases has already occurred or is occurring in aquifer sediments. More importantly, there is a significant difference in the As concentrations in crystalline Fe(III) oxides/hydroxides and HCl-extracted Fe phases. The concentrations of As range from 1.6 to 29.9 mg kg?1 and from 0.6 to 3.0 mg kg?1, for crystalline Fe(III) and HCl-extracted Fe phases respectively. Accordingly, the transformation of Fe minerals induced by microbial Fe(III) reduction can contribute to the mobilization of As. This study is the first to examine the Fe isotope compositions in high As aquifer sediments; the results show that the Fe isotope would be an important tool in demonstrating the enrichment of As in groundwater.  相似文献   

5.
This paper describes results of applying the palynological and carbon isotopic analysis of the organic fraction of Total Suspended Particles (TSP) to discriminate distinct pollution sources and assess the anthropogenic impact for the investigated areas. The samples of atmospheric particles were collected in Czerniawa and Cieplice (two health resorts in Lower Silesia, SW Poland) twice a year in summer and winter season (from July 2006 to February 2008). The palynological spectra represent in the vast majority local plant communities without a noticeable contribution of long-transported plant particles. Palynological analysis revealed also differences in the specificity of the two sampling areas, i.e. the higher contribution of identified organic material in Czerniawa stands for more natural character of this site, but is also responsible for the higher allergic pressure when compared to Cieplice. The carbon isotopic composition of TSP varied seasonally (δ13C value from ?27.09‰ in summer to ?25.47‰ in winter). The increased δ13C value in winter (heating period) is most probably caused by uncontrolled contribution of coal soot. On the basis of isotopic mass balance the calculated contribution of anthropogenic organic particles in the atmosphere reached in winter season 72% in Czerniawa and 79% in Cieplice.  相似文献   

6.
Mosses have been recognized as a useful tool for biomonitoring atmospheric deposition and assessing regional environment. This study was carried on whether the same moss growing in areas with identical regional atmospheric deposition while under different growing environments would have the same indicating signals.Similar variations in mean δ13C and δ15N signatures were found between mosses collected from five habitats, with an increasing sequence from mosses under canopies to epilithic mosses, indicating that habitats were potentially regulating δ13C and δ15N values of mosses. Dryer habitats (lower water availability) and input of more aerosol N were the main reasons for higher δ13C and δ15N values of mosses at open sites (especially for epilithic species), while more negative values of mosses under canopies were attributed to their wetter habitats and less uptake of aerosol N. Additionally, δ15N values not δ13C varied linearly with canopy thickness from −7.84‰ (1 m) to −4.71±0.7‰ (4 m), suggesting δ15N was more sensitive for indicating canopy retention.Consequently, isotopic data of mosses under different environments could not be compared for atmospheric deposition research with each other even collected at the same site. Moss δ13C and δ15N were affected not only by regional atmospheric N sources but also by their growing environments. δ15N of epilithic Haplocladium microphyllum at open sites can be taken as confident bio-indicator of atmospheric N deposition, which would deepen the application of stable nitrogen isotope of bryophytes in atmosphere–plant system study.  相似文献   

7.
The aerosol samples were collected from a high elevation mountain site, Nainital, in India (1958 m asl) during September 2006 to June 2007 and were analyzed for water-soluble inorganic species, total carbon, nitrogen, and their isotopic composition (δ13C and δ15N, respectively). The chemical and isotopic composition of aerosols revealed significant anthropogenic influence over this remote free-troposphere site. The amount of total carbon and nitrogen and their isotopic composition suggest a considerable contribution of biomass burning to the aerosols during winter. On the other hand, fossil fuel combustion sources are found to be dominant during summer. The carbon aerosol in winter is characterized by greater isotope ratios (av. ?24.0?‰), mostly originated from biomass burning of C4 plants. On the contrary, the aerosols in summer showed smaller δ13C values (?26.0?‰), indicating that they are originated from vascular plants (mostly of C3 plants). The secondary ions (i.e., SO4 2?, NH4 +, and NO3 ?) were abundant due to the atmospheric reactions during long-range transport in both seasons. The water-soluble organic and inorganic compositions revealed that they are aged in winter but comparatively fresh in summer. This study validates that the pollutants generated from far distant sources could reach high altitudes over the Himalayan region under favorable meteorological conditions.  相似文献   

8.
This study presents carbon (δ13C) and hydrogen (δD) isotope values of volatile organic compounds (VOCs) in various emission sources using thermal desorption-gas chromatography-isotope ratio mass spectrometry (TD-GC-irMS). The investigated VOCs ranged from C6 to C10. Samples were taken from (i) car exhaust emissions as well as from plant combustion experiments of (ii) various C3 and (iii) various C4 plants. We found significant differences in δ values of analysed VOCs between these sources, e.g. δ13C of benzene ranged between (i) −21.7 ± 0.2‰, (ii) −27.6 ± 1.6‰ and (iii) −16.3 ± 2.2‰, respectively and δD of benzene ranged between (i) −73 ± 13‰, (ii) −111 ± 10‰ and (iii) −70 ± 24‰, respectively. Results of VOCs present in investigated emission sources were compared to values from the literature (aluminium refinery emission). All source groups could be clearly distinguished using the dual approach of δ13C and δD analysis. The results of this study indicate that the correlation of compound specific carbon and hydrogen isotope analysis provides the potential for future research to trace the fate and to determine the origin of VOCs in the atmosphere using thermal desorption compound specific isotope analysis.  相似文献   

9.
Concentrations and profiles of 2,3,7,8-substituted polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans (PCDD/Fs) and dioxin-like polychlorinated biphenyls (dl-PCBs) were investigated in sediment and plants collected from a salt marsh in the Tejo estuary, Portugal. The highest PCDD/F and dl-PCB concentrations were detected in uncolonized sediments, averaging 325.25?±?57.55 pg g?1 dry weight (dw) and 8,146.33?±?2,142.14 pg g?1 dw, respectively. The plants Sarcocornia perennis and Halimione portulacoides growing in PCDD/F and dl-PCB contaminated sediments accumulated contaminants in roots, stems, and leaves. It was observed that PCDD/F and dl-PCB concentrations in roots were significantly lower in comparison with stems and leaves. In general, concentration of ΣPCDD/Fs and Σdl-PCBs in H. portulacoides tissues were found to be twofold higher than those in S. perennis, indicating a difference in the accumulation capability of both species. Furthermore, congener profiles changed between sediments and plant tissues, reflecting a selective accumulation of low chlorinated PCDD/Fs and non-ortho dl-PCBs in plants.  相似文献   

10.
Abstract

Products of a power plant flue gas desulfurization scrubber are discharged into a pond as sludge consisting of calcite (initial δ13C 3.2–3.8‰), gypsum (initial δ34S 7.6–8.6‰), and aqueous solution. Reducing conditions exist below a boundary that appears to move vertically as a function of changes in pond water level. Under reducing conditions, bacteria partially reduce aqueous sulfate to low-δ34S sulfide, consuming organic carbon and generating low-δ13C bicarbonate. Under oxidizing conditions, sulfide is converted to sulfate, leading to calcite dissolution, gypsum precipitation, and isotopic re-equilibration of remaining calcite with dissolved bicarbonate near the pond surface. The gypsum has δ34S near 6‰, and calcite has δ13C as low as -1.7‰; the changes from initial values correspond to predictions based on isotopic balance and reaction stoichiometry. The pond largely contains the products of bacterial reduction. After the pond is abandoned, these products may adversely affect attempts to revegetate the site. Future bacterial reduction may be best controlled by dewatering and limiting the supply of organic matter in percolating surface water.  相似文献   

11.
One strategy to combat nitrate (NO3-N) contamination in rivers is to understand its sources. NO3-N sources in the East Tiaoxi River of the Yangtze Delta Region were investigated by applying a 15N–18O dual isotope approach. Water samples were collected from the main channel and from the tributaries. Results show that high total N and NO3-N are present in both the main channel and the major tributaries, and NO3-N was one of the most important N forms in water. Analysis of isotopic compositions (δ 18O, δD) of water suggests that the river water mainly originated from three tributaries during the sampling period. There was a wide range of δ 15N-NO3 (?1.4 to 12.4 ‰) and a narrow range of δ 18O-NO3 (3.7 to 9.0 ‰) in the main channel waters. The δ 15N and δ 18O-NO3 values in the upper, middle, and lower channels along the river were shifted as 8.2, 3.5, and 9.5 ‰, and 9.0, 4.2, and 6.0 ‰, respectively. In the tributary South Tiao, the δ 15N and δ 18O-NO3 values were as high as 9.5 and 7.0 ‰, while in the tributaries Mid Tiao and North Tiao, NO3-N in most of the samples had relatively low δ 15N and δ 18O-NO3 values from 2.3 to 7.5 ‰ and 4.7 to 7.0 ‰, separately. Our results also suggest that the dual isotope approach can help us develop the best management practice for relieving NO3-N pollution in the rivers at the tributary scale.  相似文献   

12.
Many authors have pointed out the need for simpler assessment and management procedures for avoiding overexploitation in small-scale fisheries. Nevertheless, models for providing scientific advice for sustainable small-scale fisheries management have not yet been published. Here we present one model; the case of the Barefoot Fisheries Advisors (BFAs) in the Galician co-managed Territorial Users Rights for Fishing. Based on informal interviews, gray literature and our personal experience by being involved in this process, we have analyzed the historical development and evolution of roles of this novel and stimulating actor in small-scale fisheries management. The Galician BFA model allows the provision of good quality and organized fisheries data to facilitate and support decision-making processes. The BFAs also build robust social capital by acting as knowledge collectors and translators between fishers, managers, and scientists. The BFAs have become key actors in the small-scale fisheries management of Galicia and a case for learning lessons.  相似文献   

13.
In the present study, controlled laboratory column experiments were conducted to understand the biogeochemical changes during the microbial sulfate reduction. Sulfur and oxygen isotopes of sulfate were followed during sulfate reduction in zero valent iron incubated flow through columns at a constant temperature of 20 ± 1 °C for 90 d. Sulfur isotope signatures show considerable variation during biological sulfate reduction in our columns in comparison to abiotic columns where no changes were observed. The magnitude of the enrichment in δ34S values ranged from 9.4‰ to 10.3‰ compared to initial value of 2.3‰, having total fractionation δS between biotic and abiotic columns as much as 6.1‰. Sulfur isotope fractionation was directly proportional to the sulfate reduction rates in the columns. Oxygen isotopes in this experiment seem less sensitive to microbial activities and more likely to be influenced by isotopic exchange with ambient water. A linear relationship is observed between δ34S and δ18O in biotic conditions and we also highlight a good relationship between δ34S and sulfate reduction rate in biotic columns.  相似文献   

14.
This study investigated the extent of arsenic (As) contamination in five common species of freshwater fish (northern snakehead [Channa argus], mandrarin fish [Siniperca chuatsi], largemouth bass [Lepomis macrochirous], bighead carp [Aristichthys nobilis] and grass carp [Ctenopharyngodon idellus]) and their associated fish pond sediments collected from 18 freshwater fish ponds around the Pearl River Delta (PRD). The total As concentrations detected in fish muscle and sediment in freshwater ponds around the PRD were 0.05–3.01 mg?kg?1 wet weight (w. wt) and 8.41–22.76 mg?kg?1 dry weight (d. wt), respectively. In addition, the As content was positively correlated (p?<?0.05) to total organic carbon (TOC) contents in sediments. Biota sediment accumulation factor (BSAF) showed that omnivorous fish and zooplankton accumulated higher concentrations of heavy metals from the sediment than carnivorous fish. In addition, feeding habits of fish also influence As accumulation in different fish species. In this study, two typical food chains of the aquaculture ponds were selected for investigation: (1) omnivorous food chain (zooplankton, grass carp and bighead carp) and (2) predatory food chain (zooplankton, mud carp and mandarin fish). Significant linear relationships were obtained between log As and δ 15N. The slope of the regression (?0.066 and ?0.078) of the log transformed As concentrations and δ 15N values, as biomagnifications power, indicated there was no magnification or diminution of As from lower trophic levels (zooplankton) to fish in the aquaculture ponds. Consumption of largemouth bass, northern snakehead and bighead carp might impose health risks of Hong Kong residents consuming these fish to the local population, due to the fact that its cancer risk (CR) value exceeded the upper limit of the acceptable risk levels (10?4) stipulated by the USEPA.  相似文献   

15.
Elemental (S and N) and isotopic (δ34S and δ15N) contents in the moss Haplocladium microphyllum at urban, rural and forested sites in acid rain area of South China have been analyzed for comparisons to show whether they are different and can be effectively used to identify S and N sources of atmospheric deposition. Average moss S content at rural sites (0.29 ± 0.06%) was found to be in between those at urban (0.35 ± 0.05%) and forested (0.25 ± 0.04%) sites, which are significantly different. Average N contents of urban (2.60 ± 0.56%) and rural mosses (2.84 ± 0.77%) are not significantly different, while both are significantly different to that of forested mosses at most areas, indicating that the atmosphere over rural sites has been polluted by N as seriously as that over urban sites. Nitrogen supply, relative to S supply, was in excess of the requirement for protein synthesis, especially at rural and forested sites. Moss stable isotope signatures have been proven to be effective tools for deciphering atmospheric S and N sources at these sites. Through moss δ34S signatures, we found that atmospheric S at urban and forested sites was mainly from local coal combustion and domestic biomass burning, respectively, whereas northerly air masses contributed more S to forested sites. The relatively negative moss δ15N values (?7.5 ± 3.0, ?3.4 ± 2.1 and ?0.8 ± 2.1‰) demonstrated that the main form in the N deposition was NHx in these sites. More negative δ15N signatures in urban mosses (?7.5 ± 3.0‰) indicated the contribution of NH3 released from untreated city sewage and wastes, while relatively less negative δ15N for rural and forested mosses (3.4 ± 2.1 and ?0.8 ± 2.1‰) was largely derived from agricultural NH3.  相似文献   

16.
Stable carbon isotope ratio (δ13C) data can provide important information regarding the sources and the processing of atmospheric organic carbon species. Formic, acetic and oxalic acid were collected from Zurich city in August–September 2002 and March 2003 in the gas and aerosol phase, and the corresponding δ13C analysis was performed using a wet oxidation method followed by isotope ratio mass spectrometry. In August, the δ13C values of gas phase formic acid showed a significant correlation with ozone (coefficient of determination (r2) = 0.63) due to the kinetic isotope effect (KIE). This indicates the presence of secondary sources (i.e. production of organic acids in the atmosphere) in addition to direct emission. In March, both gaseous formic and acetic acid exhibited similar δ13C values and did not show any correlation with ozone, indicating a predominantly primary origin. Even though oxalic acid is mainly produced by secondary processes, the δ13C value of particulate oxalic acid was not depleted and did not show any correlation with ozone, which may be due to the enrichment of 13C during the gas - aerosol partitioning.The concentrations and δ13C values of the different aerosol fractions (water soluble organic carbon, water insoluble organic carbon, carbonate and black carbon) collected during the same period were also determined. Water soluble organic carbon (WSOC) contributed about 60% to the total carbon and was enriched in 13C compared to other fractions indicating a possible effect of gas - aerosol partitioning on δ13C of carbonaceous aerosols. The carbonate fraction in general was very low (3% of the total carbon).  相似文献   

17.
This study evaluated the toxicity of herbicide atrazine, along with its bioaccumulation and biodegradation in the green microalga Chlamydomonas mexicana. At low concentration (10 μg L?1), atrazine had no profound effect on the microalga, while higher concentrations (25, 50, and 100 μg L?1) imposed toxicity, leading to inhibition of cell growth and chlorophyll a accumulation by 22 %, 33 %, and 36 %, and 13 %, 24 %, and 27 %, respectively. Atrazine 96-h EC50 for C. mexicana was estimated to be 33 μg L?1. Microalga showed a capability to accumulate atrazine in the cell and to biodegrade the cell-accumulated atrazine resulting in 14–36 % atrazine degradation at 10–100 μg L?1. Increasing atrazine concentration decreased the total fatty acids (from 102 to 75 mg g?1) and increased the unsaturated fatty acid content in the microalga. Carbohydrate content increased gradually with the increase in atrazine concentration up to 15 %. This study shows that C. mexicana has the capability to degrade atrazine and can be employed for the remediation of atrazine-contaminated streams.  相似文献   

18.

Introduction

The Zha Long Wetland, the first water bird conservation area in China, lies on the northern bank of the Song Nen Plain with an area of 2,100 km2. In many areas of the Zha Long Wetland, water pollution has led to a decrease in the wetland??s ecological function, vegetation degradation, a decrease in the number of bird species, and the depletion of fish resources.

Materials and methods

The sediments used in this study were collected from the surface sediment of seven sites and from different depths in three types of marshes in the Zha Long Wetland in northeast China in late October 2006. The levels and distribution patterns of 17 organochlorine pesticides (OCPs; ??-HCH, ??-HCH, ??-HCH, ??-HCH, p,p??-DDE, p,p??-DDD, p,p??-DDT, endosulfan I, endosulfan II, endosulfan sulfate, heptachlor, heptachlor epoxide, aldrin, dieldrin, endrin, endrin aldehyde, and methoxychlor) in surface sediments as well as hexachlorocyclohexane (HCH) and 1,1,1-trichloro-2,2-bis(4-chlorophenyl)ethane (DDT) in vertical sediments were investigated.

Results and discussion

The concentrations of HCHs, DDTs, endosulfans, heptachlors, aldrin, and methoxychlor in surface sediments ranged from 10.44 to 41.97 ng/g, nd (undetectable levels) to 211.88 ng/g, nd to 69.89 ng/g, nd to 28.10 ng/g, 9.81 to 623.83 ng/g, and from nd to 3.99 ng/g, respectively. The highest levels of OCPs were detected in Tangtugangzi at a total concentration of 727.72 ng/g, where the dominant compound was endrin at a concentration of 483.04 ng/g. In the vertical sediments, the HCHs and DDTs were in the ranges of nd?C136.00 and nd?C214.06 ng/g, respectively.

Conclusions

Different distributions of HCHs, DDTs, and other OCPs indicated that they originated from different contamination sources. Composition analyses in surface sediments indicated recent OCP usage or discharge at some sample sites in the Zha Long Wetland.  相似文献   

19.
Trace elements (22) and stable isotope ratios (δ15N and δ13C) were analyzed in marine organisms from shallow (SW) and deep-water (DW) of the East China Sea to understand biomagnification and prey source of trace elements. In the benthic marine organisms from DW, δ15N values were negatively correlated with Ba, Cu, Ag, Mo, Sr, As, and Co concentrations. This may be due to the specific accumulation in lower trophic animals and/or the biodilution through the food web in DW. Relationships between δ15N and concentrations of Co, Cr, Bi, and Tl in fish and Ag, Bi, V, Hg, and Tl in crustaceans showed positive correlations, suggesting that trophic position was affecting the concentrations of those elements in phyla, with higher trophic animals retaining higher concentrations than the lower trophic animals. Positive correlations between δ13C and Rb were observed in marine organisms. Therefore, Rb may be a possible substitute of δ13C as tracer of prey source in the East China Sea although further investigation is required.  相似文献   

20.
Annual growth rings sampled from three free-standing trees (Platanus hybrida sp.), grew in the metropolitan area of Palermo (Italy) and covering a 118 years time span (1880–1998), have been studied for their 13C/12C carbon isotope ratios. It has been found that the 13C/12C tree ring record, during the study time interval, decreased of −3.6‰, from −26.4‰ in 1880 to −30‰ in 1998. Such a progressive depletion has been attributed to the addition of anthropogenic 13C depleted carbon dioxide to the local atmosphere. The observed 13C/12C decrease has been used to infer some possible pathways of atmospheric CO2 change in the study urban area.  相似文献   

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