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1.
Based on the molecular distribution of bound fatty acid (BFA) compound classes in core sediments of Lake Dianchi combined with the compound-specific δ13C values of the straight-chain BFAs, origin and vertical changes of organic matters in the sediments were investigated. The results indicated a significant change of BFA sources over the past 700 years. Contrast to the low concentrations of the terrestrial BFAs, the abundance of BFAs derived from the plankton/bacteria in the top sections (1944–recent) was more than 80 %. The increasing proportions of the branched and unsaturated BFAs in total fatty acids were closely correlated with the heavy eutrophication and the frequent algal blooms in the decades. Furthermore, the positive shift of δ 13C of C16 and C18 (~2?‰) in the upper section might be an indicator of the excess phytoplankton productivity. However, it was found that the plankton/bacteria-derived BFAs were more easily degraded during the early diagenetic process. The special compound carbon isotopic compositions of the long straight-chain BFAs (C24 and C26) in the sediments showed a depletion of heavier δ 13C values (ca. ?30?‰) in the midsections (1559–1787), reflecting a relatively growing contribution of C3 plants to C4 plants or that C4 plant growth was inhibited in cold and arid climates during the period.  相似文献   

2.
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   

3.
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   

4.
Carbonyls emitted from essential oils can affect the air quality when they are used in indoors, especially under poor ventilation conditions. Lavender, lemon, rose, rosemary, and tea tree oils were selected as typical and popular essential oils to investigate in terms of composition, thermal characteristics and fifteen carbonyl constituents. Based on thermogravimetric (TG) analysis, the activation energy was 7.6–8.3 kcal mol?1, the reaction order was in the range of 0.6–0.7 and the frequency factor was 360–2838 min?1. Formaldehyde, acetaldehyde, acetone, and propionaldehyde were the dominant carbonyl compounds, and their concentrations were 0.034–0.170 ppm. The emission factors of carbonyl compounds were 2.10–3.70 mg g?1, and acetone, propionaldehyde, acetaldehyde, and formaldehyde accounted for a high portion of the emission factor of carbonyl compounds in essential oil exhaust. Some unhealthy carbonyl species such as formaldehyde and valeraldehyde, were measured at low-temperature during the vaporization of essential oils, indicating a potential effect on indoor air quality and human health.  相似文献   

5.
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   

6.
《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   

7.
Eucalypts are among the highest emitters of biogenic volatile organic compounds, yet there is relatively little data available from field studies of this genus. Emissions of isoprene, monoterpenes and the short-chained carbonyls formaldehyde, acetaldehyde and acetone were determined from four species (Eucalyptus camaldulensis, Eucalyptus globulus, Eucalyptus grandis, and Eucalytpus viminalis) in Australia. A smaller comparative study was conducted on E. camaldulensis in south-eastern Australia. Carbonyl emissions, reported here for the first time from eucalypts, were generally comparable with rates reported for other species, with diurnal emissions peaking at about 4, 75 and 34 nmol m?2 min?1 for acetone, formaldehyde and acetaldehyde respectively. There was wide variation in diurnal isoprene and monoterpene emissions between species, but under standard conditions, isoprene emissions were much lower than previous reports. Conversely, standard emission rates of monoterpenes were as much as six times greater than previous reports for some species. Emission of each carbonyl was correlated with its ambient concentration across different species, but more weakly related to temperature. Acetaldehyde emission in particular was significantly correlated with transpiration, but not with sap flow or with ethanol concentrations in xylem sap, suggesting fermentation within the leaf and stomatal conductance are primary controlling processes. Differences in acetaldehyde exchange velocities between sites, in addition to transpiration differences, suggest stomata may indeed exert long term emission regulation, in contrast to compounds for which no biological sink exists.  相似文献   

8.
《Chemosphere》2009,74(11):1793-1798
A study on tropospheric aerosols involving Fe particles with an industrial origin is tackled here. Aerosols were collected at the largest exhausts of a major European steel metallurgy plant and around its near urban environment. A combination of bulk and individual particle analysis performed by SEM–EDX provides the chemical composition of Fe-bearing aerosols emitted within the factory process (hematite, magnetite and agglomerates of these oxides with sylvite (KCl), calcite (CaCO3) and graphite carbon). Fe isotopic compositions of those emissions fall within the range (0.08‰ < δ56Fe < +0.80‰) of enriched ores processed by the manufacturer (−0.16‰ < δ56Fe < +1.19‰). No significant evolution of Fe fractionation during steelworks processes is observed. At the industrial source, Fe is mainly present as oxide particles, to some extent in 3–4 μm aggregates. In the close urban area, 5 km away from the steel plant, individual particle analysis of collected aerosols presents, in addition to the industrial particle type, aluminosilicates and related natural particles (gypsum, quartz, calcite and reacted sea salt). The Fe isotopic composition (δ56Fe = 0.14 ± 0.11‰) measured in the close urban environment of the steel metallurgy plant appears coherent with an external mixing of industrial and continental Fe-containing tropospheric aerosols, as evidenced by individual particle chemical analysis. Our isotopic data provide a first estimation of an anthropogenic source term as part of the study of photochemically promoted dissolution processes and related Fe fractionations in tropospheric aerosols.  相似文献   

9.
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   

10.
The concentrations of C1–C8 carbonyl compounds were measured at two urban sites in Hong Kong from October 1997 to September 2000. The daily total carbonyl concentrations were found to range from 2.4 to 37 μg m−3. Formaldehyde was the most abundant species, which comprised from 36 to 43% of the total detected carbonyls, followed by acetaldehyde (18–21%) and acetone (8–20%). The highest 24-hour average concentrations measured were 10 and 7.7 μg m−3 for formaldehyde and acetaldehyde, respectively. Seasonal and temporal variations in the concentrations of formaldehyde and acetaldehyde were not obvious, but lowest concentrations often occurred from June to August. The mean formaldehyde/acetaldehyde molar ratios at the two sites in summer (2.8±1.1 and 2.5±1.2) were significantly higher (p⩽0.01) than those in winter periods (1.9±0.6 and 2.0±0.6). The phenomena were explained by influences of both photochemical reactions and local meteorological conditions. Better correlations between formaldehyde and acetaldehyde, and between NOx and each of the two major carbonyls were obtained in winter periods indicating direct vehicular emissions were the principal sources. The ambient formaldehyde and acetaldehyde concentrations in the urban atmosphere of Hong Kong were within the normal ranges reported in the literature for other urban sites world-wide.  相似文献   

11.
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   

12.
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   

13.
Recent experiments have shown that dry and fresh leaves, other plant matter, as well as several structural plant components, emit methane upon irradiation with UV light. Here we present the source isotope signatures of the methane emitted from a range of dry natural plant leaves and structural compounds. UV-induced methane from organic matter is strongly depleted in both 13C and D compared to the bulk biomass. The isotopic content of plant methoxyl groups, which have been identified as important precursors of aerobic methane formation in plants, falls roughly halfway between the bulk and CH4 isotopic composition. C3 and C4/CAM plants show the well-established isotope difference in bulk 13C content. Our results show that they also emit CH4 with different δ13C value. Furthermore, δ13C of methoxyl groups in the plant material, and ester methoxyl groups only, show a similar difference between C3 and C4/CAM plants. The correlation between the δ13C of emitted CH4 and methoxyl groups implies that methoxyl groups are not the only source substrate of CH4.Interestingly, δD values of the emitted CH4 are also found to be different for C3 and C4 plants, although there is no significant difference in the bulk material. Bulk δD analyses may be compromised by a large reservoir of exchangeable hydrogen, but no significant δD difference is found either for the methoxyl groups, which do not contain exchangeable hydrogen. The δD difference in CH4 between C3 and C4 plants indicates that at least two different reservoirs are involved in CH4 emission. One of them is the OCH3 group, the other one must be significantly depleted, and contribute more to the emissions of C3 plants compared to C4 plants. In qualitative agreement with this hypothesis, CH4 emission rates are higher for C3 plants than for C4 plants.  相似文献   

14.
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   

15.
CO concentration and its isotopic composition (13C, 14C, 17O and 18O) are used to characterize air pollution events observed at Schauinland, Germany, in August 2000. After determination of the background signal, we could identify and characterize five pollution events. Particularly, 14CO and δ18O variations help to determine the nature of the pollution source (fossil fuel or biomass combustion) and its origin (local or regional/continental). By using a box model, further information about the age of the polluted air mass is derived. We particularly establish that one polluted air mass was about 10 days old and that this event was due to long-range transport of products emitted from forest fires in Canada.  相似文献   

16.
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   

17.
Epilithic mosses are characterized by insulation from substratum N and hence meet their N demand only by deposited N. This study investigated tissue C, total Chl and δ13C of epilithic mosses along 2 transects across Guiyang urban (SW China), aiming at testing their responses to N deposition. Tissue C and total Chl decreased from the urban to rural, but δ13Cmoss became less negative. With measurements of atmospheric CO2 and δ13CO2, elevated N deposition was inferred as a primary factor for changes in moss C and isotopic signatures. Correlations between total Chl, tissue C and N signals indicated a nutritional effect on C fixation of epilithic mosses, but the response of δ13Cmoss to N deposition could not be clearly differentiated from effects of other factors. Collective evidences suggest that C signals of epilithic mosses are useful proxies for N deposition but further works on physiological mechanisms are still needed.  相似文献   

18.
The effect of ozone on leaf gas diffusion was investigated by analyzing the stable oxygen isotopic signatures (δ18O) in leaves of Holcus lanatus L., Plantago lanceolata L., Ranunculus friesianus (Jord.), and Trifolium pratense L. grown in temperate, semi-natural grassland. Dried material from plants exposed to ambient or elevated ozone levels in a long-term free-air experiment was sampled in 2002 and 2003. A general increase in δ18O in elevated ozone indicated increased limitation to gas diffusion, which was strongest during the driest and warmest period in 2003. In three out of four species, the increase in δ18O paralleled an increase in δ13C measured earlier in the same samples, meaning that the dominant effect of ozone was on gas diffusion and not on CO2 fixation. Only in R. friesianus, ozone affected both processes simultaneously. It is concluded that elevated ozone not only affects productivity, but also the water status of important component species of grassland communities.  相似文献   

19.
The importance that nitrogen (N) deposition has in driving the carbon (C) sequestration of forests has recently been investigated using both experimental and modeling approaches. Whether increased N deposition has positive or negative effects on such ecosystems depends on the status of the N and the duration of the deposition. By combining δ13C, δ18O, δ15N and dendrochronological approaches, we analyzed the impact of two different sources of NOx emissions on two tree species, namely: a broadleaved species (Quercus cerris) that was located close to an oil refinery in Southern Italy, and a coniferous species (Picea abies) located close to a freeway in Switzerland. Variations in the ci/ca ratio and the distinction between stomatal and photosynthetic responses to NOx emissions in trees were assessed using a conceptual model, which combines δ13C and δ18O. δ15N in leaves, needles and tree rings was found to be a bioindicator of N input from anthropogenic emissions, especially at the oil refinery site. We observed that N fertilization had a stimulatory effect on tree growth near the oil refinery, while the opposite effect was found for trees at the freeway site. Changes in the ci/ca ratio were mostly related to variations in δ13C at the freeway site and, thus, were driven by photosynthesis. At the oil refinery site they were mainly related to stomatal conductance, as assessed using δ18O. This study demonstrates that a single method approach does not always provide a complete picture of which physiological traits are more affected by N emissions. The triple isotope approach combined with dendrochronological analyses proved to be a very promising tool for monitoring the ecophysiological responses of trees to long-term N deposition.  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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