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1.
Products of a power plant flue gas desulfurization scrubber are discharged into a pond as sludge consisting of calcite (initial delta13C 3.2-3.8 per thousand), gypsum (initial delta34S 7.6-8.6 per thousand), 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-delta34S sulfide, consuming organic carbon and generating low-delta13C 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 delta34S near 6 per thousand, and calcite has delta13C as low as -1.7 per thousand; 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   

2.
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   

3.
Hydrogen (δ2H), carbon (δ13C), oxygen (δ18O) and nitrogen (δ15N) isotopes of tree rings growing in field conditions can be indicative of past pollution effects. The characteristic δ13C trend is a positive shift generally explained by invoking closure of stomata, but experimental studies suggest that increased rates of carboxylation could also generate such trends. In many cases the δ18O and δ2H values decrease in trees exposed to pollution and exhibit inverse coinciding long-term trends with δ13C values. However, some trees exposed to diffuse pollution and experimental conditions can show an increase or no δ18O change even if δ13C values increase. These diverse responses depend on how stress conditions modify physiological functions such as stomatal conductance, carboxylation, respiration, and perhaps water assimilation by the root system. Recent studies suggest that δ15N changes in trees can be caused by soil acidification and accumulation of anthropogenic emissions with isotopic signals deviating from natural N.  相似文献   

4.
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   

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.
Stable sulfur isotope ratios and major ions in bulk snowpack samples were monitored at a network of 52 high-elevation sites along and near the Continental Divide from 1993 to 1999. This information was collected to better define atmospheric deposition to remote areas of the Rocky Mountains and to help identify the major source regions of sulfate in winter deposition. Average annual δ34S values at individual sites ranged from +4.0 to +8.2‰ and standard deviations ranged from 0.4 to 1.6‰. The chemical composition of all samples was extremely dilute and slightly acidic; average sulfate concentrations ranged from 2.4 to 12.2 μeq l−1 and pH ranged from 4.82 to 5.70. The range of δ34S values measured in this study indicated that snowpack sulfur in the Rocky Mountains is primarily derived from anthropogenic sources. A nearly linear relation between δ34S and latitude was observed for sites in New Mexico, Colorado, and southern Wyoming, which indicates that snowpack sulfate in the southern part of the network was derived from two isotopically distinct source regions. Because the major point sources of SO2 in the region are coal-fired powerplants, this pattern may reflect variations in the isotopic composition of coals burned by the plants. The geographic pattern in δ34S for sites farther to the north in Wyoming and Montana was much less distinct, perhaps reflecting the paucity of major point sources of SO2 in the northern part of the network.  相似文献   

7.
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   

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.
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   

10.
Stable isotopes of carbon (δ13C) and nitrogen (δ15N) are used frequently in ecotoxicological investigations of birds to relate contaminant levels to trophic position (δ15N) or foraging location (δ13C) and many researchers using avian feathers in such investigations use δ13C or δ15N as a predictor of contaminant concentrations. Contaminants, especially mercury, however, are integrated into feathers over different time periods than are stable isotopes, resulting in spurious relationships that have no biological meaning. I show the fundamental principles behind the conclusion that relating δ13C or δ15N to contaminant concentrations in feathers is not appropriate in light of the number of recent studies that have employed this approach, and make recommendations for those wishing to investigate the relationship between contaminants and stable isotope ratios.  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.
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   

13.
Utilizing the analytical capability to measure S isotope ratios of small quantities of S in biological material without any chemical pretreatment, the variation of δ34S within a lichen thallus was investigated using old and young segments of fruticose lichen thalli (Alectoria sarmentosa) from an oil refinery area in Come-By-Chance and two coastal areas, Newfoundland, Canada. Old segments of lichen samples from the oil refinery area showed significantly higher δ34S values (1.0-2.5‰) than their corresponding young segments. Lichen samples from two coastal areas showed no noticeable differences in δ34S values between old and young segments. These results demonstrate that lichen thalli record temporal changes in the isotopic composition of atmospheric S and hence constitute a historical archive of atmospheric S pollution.  相似文献   

14.
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   

15.
《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   

16.
The present paper examines the use of zinc isotopes as tracers of atmospheric sources and focuses on the potential fractionation of Zn isotopes through anthropogenic processes. In order to do so, Zn isotopic ratios are measured in enriched ores and airborne particles associated with pyrometallurgical activities of one of the major Pb–Zn refineries in France. Supporting the isotopic investigation, this paper also compares morphological and chemical characteristics of Zn particles collected on dry deposition plates (“environmental samples”) placed within a 5 km radius of the smelter, with those of Zn particles collected inside the plant (“process samples”), i.e. dust collected from the main exhaust system of the plant. To ensure a constant isotopic “supply”, the refinery processed a specific set of ores during the sampling campaigns, as agreed with the executive staff of the plant. Enriched ores and dust produced by the successive Zn extraction steps show strong isotope fractionation (from ?0.66 to +0.22‰) mainly related to evaporation processes within the blast furnaces. Dust from the main chimney displays a δ66Zn value of ?0.67‰. Application of the Rayleigh equation to evaluate the fractionation factor associated with the Zn vapor produced after a free evaporation gives a range of αore/vapor from 1.0004 to 1.0008. The dry deposits, collected on plates downwind of the refinery, display δ66Zn variations of up to +0.7‰. However, it is to be noted that between 190 and 1250 m from the main chimney of the refinery, the dry deposits show a high level of large (>10 μm) Zn, S, Fe and O bearing aggregates characterized by positive δ66Zn values (+0.02 to +0.19‰). These airborne particles probably derive from the re-suspension of slag heaps and local emissions from the working-units. In contrast, from 1720 to 4560 m, the dry deposits are comprised of small (PM10) particles, including spherical Zn-bearing aggregates, showing negative δ66Zn values (?0.52 to ?0.02‰). Our results suggest that the source of the distal dry fallouts is the main chimney plume, whose light Zn isotopic signature they preserve. Based on Zn isotopic analysis in combination with morphological and chemical characteristics of airborne particles, the present study suggests the traceability of smelter dusts by Zn isotopes.  相似文献   

17.
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   

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.
Boron (B) concentrations and isotopic compositions were measured in the precipitations of Guiyang, China for one year. Most precipitation samples have boron concentrations of from 2.1 to 4.8 ng ml?1, and δ11B values of from +2.0‰ to +30.0‰. Boron concentrations and δ11B values of heavy rain samples are generally higher than those of light rain and snow samples. Anthropogenic inputs provided most of the SO42? and NO3?, which were predominant ions in the precipitation. The major cation Ca2+ in the precipitation was mainly originated from local dust.The total boron in precipitation from Guiyang is explained by the mixing model of three boron sources. Assuming a δ11B value of +45‰ for the seawater component, contributions of marine source, organic matter and biomass combustion, and coal combustion were estimated to be 32%, 49%, and 19%, respectively to the total boron in Guiyang precipitations. The coal combustion and biomass (and/or organic matter) combustion showed different contributions of boron to the rainwaters in different seasons, the former in cold season while the latter in summer season had a more marked influence on the chemical and isotopic composition of the rainwater. The largest contribution of seawater-originated boron was observed for the heavy rain samples, which was up to 68%. This study indicates that the atmospheric environment of Guiyang city was strongly influenced by human activities, and boron isotopic composition is of great sensitivity to anthropogenic sources and can be a powerful technique to trace various sources of atmospheric emissions and even their origins.  相似文献   

20.
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   

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