Carbon isotope signature of dissolved inorganic carbon (DIC) in precipitation and atmospheric CO2

This paper describes results of chemical and isotopic analysis of inorganic carbon species in the atmosphere and precipitation for the calendar year 2008 in Wroc?aw (SW Poland). Atmospheric air samples (collected weekly) and rainwater samples (collected after rain episodes) were analysed for CO₂ and dissolved inorganic carbon (DIC) concentrations and for δ¹³C composition. The values obtained varied in the ranges: atmospheric CO₂: 337-448 ppm; δ¹³C_CO2 from −14.4 to −8.4‰; DIC in precipitation: 0.6-5.5 mg dm⁻³; δ¹³C_DIC from −22.2 to +0.2‰. No statistical correlation was observed between the concentration and δ¹³C value of atmospheric CO₂ and DIC in precipitation. These observations contradict the commonly held assumption that atmospheric CO₂ controls the DIC in precipitation. We infer that DIC is generated in ambient air temperatures, but from other sources than the measured atmospheric CO₂. The calculated isotopic composition of a hypothetical CO₂ source for DIC forming ranges from −31.4 to −11.0‰, showing significant seasonal variations accordingly to changing anthropogenic impact and atmospheric mixing processes.     

The stable carbon isotope composition of atmospheric PAHs

A method for compound-specific stable carbon isotope analysis of atmospheric polycyclic aromatic hydrocarbons (PAHs) in carbonaceous aerosols is described. Atmospheric aerosol samples containing PAHs (C-10 to C-20) were collected on filters using a high-volume sampling technique, solvent extracted, taken through a cleanup procedure, separated by gas chromatography, oxidized to CO₂ on-line, and introduced into an isotope ratio mass spectrometer for analysis. The method can be used to determine the isotope composition of a few nanograms of PAHs. This technique was used to analyse and compare the isotope composition of atmospheric PAHs from standards, as well as two samples from urban and rural locations. Isotopic variability in atmospheric PAHs is greater than measurement uncertainties which makes this a potentially useful technique for source identification when used together with concentration measurements.     

Response of stable carbon isotope in epilithic mosses to atmospheric nitrogen deposition

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 δ¹³C_moss 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 δ¹³C_moss 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.     

A new look at atmospheric carbon dioxide

Carbon dioxide is increasing in the atmosphere and is of considerable concern in global climate change because of its greenhouse gas warming potential. The rate of increase has accelerated since measurements began at Mauna Loa Observatory in 1958 where carbon dioxide increased from less than 1 part per million per year (ppm yr^?1) prior to 1970 to more than 2 ppm yr^?1 in recent years. Here we show that the anthropogenic component (atmospheric value reduced by the pre-industrial value of 280 ppm) of atmospheric carbon dioxide has been increasing exponentially with a doubling time of about 30 years since the beginning of the industrial revolution (～1800). Even during the 1970s, when fossil fuel emissions dropped sharply in response to the “oil crisis” of 1973, the anthropogenic atmospheric carbon dioxide level continued increasing exponentially at Mauna Loa Observatory. Since the growth rate (time derivative) of an exponential has the same characteristic lifetime as the function itself, the carbon dioxide growth rate is also doubling at the same rate. This explains the observation that the linear growth rate of carbon dioxide has more than doubled in the past 40 years. The accelerating growth rate is simply the outcome of exponential growth in carbon dioxide with a nearly constant doubling time of about 30 years (about 2%/yr) and appears to have tracked human population since the pre-industrial era.     

Stable hydrogen,carbon and chlorine isotope measurements of selected chlorinated organic solvents

Stable hydrogen isotopes of two chlorinated solvents, trichloroethylene (TCE) and 1,1,1-trichloroethane (TCA), provided by five different manufacturers, were determined and compared to their carbon and chlorine isotopic signatures. The isotope ratio for delta2H of different TCEs ranged between +466.9 per thousand and +681.9 per thousand, for delta13C between -31.57 per thousand and -27.37 per thousand, and for delta37Cl between -3.19 per thousand and +3.90 per thousand. In the case of the TCAs, the isotope ratio for delta2H ranged between -23.1 per thousand and +15.1 per thousand, for delta13C between -27.39 per thousand and -25.84 per thousand, and for delta37Cl between -3.54 per thousand and +1.39 per thousand. As well, a column experiment was carried out to dechlorinate tetrachloroethylene (PCE) to TCE using iron. The dechlorination products have completely different hydrogen isotope ratios than the manufactured TCEs. Compared to the positive values of delta2H in manufactured TCEs (between +466.9 per thousand and +681.9 per thousand), the dechlorinated products had a very depleted delta2H (less than -300 per thousand). This finding has strong implications for distinguishing dechlorination products (PCE to TCE) from manufactured TCE. In addition, the results of this study show the potential of combining 2H/1H analyses with 13C/12C and 37Cl/35Cl for isotopic fingerprinting applications in organic contaminant hydrogeology.     

Influence of transport and trends in atmospheric CO2 at Lampedusa

The study of the CO₂ 15-year records at Lampedusa (35° 31′N, 12° 37′E) is presented in this work. Short- and long-term CO₂ variability has been investigated. No significant diurnal variations are observable thus remarking the background character and representativeness of the observation site. The CO₂ long-term trend shows a mean linear growth rate (GR) of 1.9 ppm yr^?1. The periodic behaviour of the time series has been analysed and the mean seasonal cycle amplitude has been found to be 8.72 ppm. The seasonal cycle amplitude shows a marked interannual variability. The lowest value of the seasonal cycle amplitude has been detected in 2003, in concomitance with the strong anomalous heat wave recorded in Europe. CO₂ GR behaviour has been related to global processes such as El Niño Southern Oscillation (ENSO) and global temperature (T_g). The influence of ENSO event on GR is remarkable only during 1998. CO₂ GR curve shows peaks in the periods 1995, 2001 and 2005 (1.9, 3.7, 3.2 ppm yr^?1 respectively) that are characterized by high T_g values and by intense biomass burning events. The anomalous decrease in the GR during the warm 2003 has been attributed to changes in the atmospheric circulation regime. Evaluation of the influence of transport on CO₂ variability has been carried out using backward air-mass trajectory analysis and highlights the effect of the regional distribution of sources and sinks. The industrial activities and forests located in the Eastern European and Russian sector strongly affect the CO₂ mixing ratio. The CO₂ content of air-masses originating from this region is influenced in summertime by the high efficiency of the vegetation sink while in the winter period prevails the effect of industrial emissions.     

CO2 deficit in temperate forest soils receiving high atmospheric N-deposition

Evidence is provided for an internal CO2 sink in forest soils, that may have a potential impact on the global CO2-budget. Lowered CO2 fraction in the soil atmosphere, and thus lowered CO2 release to the aboveground atmosphere, is indicated in high N-deposition areas. Also at forest edges, especially of spruce forest, where additional N-deposition has occurred, the soil CO2 is lowered, and the gradient increases into the closed forest. Over the last three decades the capacity of the forest soil to maintain the internal sink process has been limited to a cumulative supply of approximately 1000 and 1500 kg N ha(-1). Beyond this limit the internal soil CO2 sink becomes an additional CO2 source, together with nitrogen leaching. This stage of "nitrogen saturation" is still uncommon in closed forests in southern Scandinavia, however, it occurs in exposed forest edges which receive high atmospheric N-deposition. The soil CO2 gradient, which originally increases from the edge towards the closed forest, becomes reversed.     

A fast response atmospheric CO2 sensor for eddy correlation flux measurements

The direct measurement of carbon dioxide fluxes in the atmospheric boundary layer is of considerable importance in studies of ocean-atmosphere exchange and in productivity of crops and forests. A promising technique for measuring CO₂ fluxes, the eddy correlation method, requires a sensitive fast response sensor. We describe the sensor requirements and present a design which has proved successful in a preliminary CO₂ flux measurement. The sensor responds to gas concentration fluctuations up to a frequency of 10 Hz with an rms noise corresponding to CO₂ concentration fluctuations of about 0.3 ppm.     

CO2高温活化活性炭材料对苯酚的吸附行为研究

以CO2为活化气体,在高温条件下对国产椰壳活性炭进行活化。研究了活化前后的活性炭在不同温度和pH等条件下对水溶液中苯酚的吸附行为。结果表明,活性炭经活化后,微孔体积和中孔体积增加,吸附容量明显提高;苯酚在活性炭上的吸附符合Freundlich吸附等温方程和准二级反应动力学方程;在一定范围内降低温度有利于吸附的进行;在pH为2～8时,吸附效果较好;在pH9时,吸附效率明显降低。     

Elevated atmospheric CO2 concentration and temperature across an urban–rural transect

The heat island effect and the high use of fossil fuels in large city centers are well documented, but by how much fossil fuel consumption is elevating atmospheric CO₂ concentrations and whether elevations in both atmospheric CO₂ and air temperature from rural to urban areas are consistently different from year to year are less well known. Our aim was to record atmospheric CO₂ concentrations, air temperature and other environmental variables in an urban area and compare it to suburban and rural sites to see if urban sites are experiencing climates expected globally in the future with climate change. A transect was established from Baltimore city center (Urban site), to the outer suburbs of Baltimore (suburban site) and out to an organic farm (rural site). At each site a weather station was set-up to monitor environmental variables for 5 years. Atmospheric CO₂ was consistently and significantly increased on average by 66 ppm from the rural to the urban site over the 5 years of the study. Air temperature was also consistently and significantly higher at the urban site (14.8 °C) compared to the suburban (13.6 °C) and rural (12.7 °C) sites. Relative humidity was not different between sites whereas the vapor pressure deficit (VPD) was significantly higher at the urban site compared to the suburban and rural sites. An increase in nitrogen deposition at the rural site of 0.6% and 1.0% compared to the suburban and urban sites was small enough not to affect soil nitrogen content. Dense urban areas with large populations and high vehicular traffic have significantly different microclimates compared to outlying suburban and rural areas. The increases in atmospheric CO₂ and air temperature are similar to changes predicted in the short term with global climate change, therefore providing an environment suitable for studying future effects of climate change on terrestrial ecosystems.     

碳同位素在溢油鉴定中的应用研究

通过分析中国代表性原油、氯仿沥青A组分碳同位素和正构烷烃单体碳同位素组成,探讨其在溢油鉴定中的应用.结果表明,原油的碳同位素组成具有母质继承效应,不同来源的原油及其氯仿沥青A组分的碳同位素类型曲线形状不同,可以利用这种规律进行溢油鉴定.碳同位素的抗风化性是其用于油指纹鉴别的最大优点.正构烷烃单体碳同位素分析使得有机质碳同位素研究进入分子级水平,因其特征性和稳定性正日益成为重要且有效的油类污染物的环境示踪剂.     

A new approach for the fractionation of water-soluble organic carbon in atmospheric aerosols and cloud drops

A novel approach is described for the fractionation of water-soluble organic carbon (WSOC) in atmospheric aerosols and cloud drops. The method is based on the preliminary adsorption of the sample, acidified at pH 2, on a polymeric styrene-divinylbenzene resin (XAD-2) and subsequent elution with a series of solvents, which leads to the fractionation of the sample into three classes of compounds. The method was set up using synthetic mixtures of organic compounds and then applied to selected samples of atmospheric aerosols and cloud drops. All samples and collected fractions were analysed using size exclusion chromatography (SEC). This method proved particularly useful both in providing information on the organic content of the samples and for the characterisation of the macromolecular compounds (MMCs) in the samples. Synthetic samples were prepared using humic, fulvic and tannic acid to simulate naturally occurring MMCs. In the first fraction, eluted with HCl, only the most soluble organic compounds (oxalic acid, formic acid and acetic acid) were collected. In the second fraction, eluted with methanol, the major part of the organic material was collected together with the more hydrophilic constituents of the humic substances. In the third fraction, it was possible to separately recover the more hydrophobic component of the humic substances. A large number of atmospheric samples (fog, aerosol, cloud) were then analysed using SEC. Most of these samples evidenced a noteworthy chromatogram at 254 nm. Moreover, the chromatographic area evidenced a clear linear correlation with the total organic carbon (TOC) values. The fractionation method on XAD-2 was finally applied to selected atmospheric samples, yielding three classes of organic compounds. In each sample, a non-negligible amount of compounds with dimensional and chemical properties similar to humic substances were collected in the third fraction. The carbon content in this latter fraction was estimated both by TOC and by means of the correlation between TOC and SEC area.     

Stable isotope dynamics of nitrogen sewage effluent uptake in a semi-arid wetland

Our objectives were to determine (1) how much N is transferred into the food web via plants from a wetland receiving not only inputs of treated sewage effluent, but also containing contaminants such as polychlorinated biphenyls (PCBs), (2) how birds, as consumers, utilize exogenous N and uptake PCBs in relation to the food web of the wetlands, (3) the feasibility of using isotopic analysis in estimating trophic levels in a semi-arid system. Our results demonstrate that there is very high spatial variability in the N isotopic composition of primary producers. Birds had lower variability in delta15N, despite feeding at multiple trophic levels. In very high spatial variability in delta15N of primary producers, it is difficult to use N isotope techniques to define trophic levels relevant to the bioaccumulation of organic pollutants, but it is possible to track the flow of exogenous N through the food web.     

Plant responses to atmospheric CO2 enrichment with emphasis on roots and the rhizosphere

Empirical records provide incontestable evidence of global changes: foremost among these changes is the rising concentration of CO(2) in the earth's atmosphere. Plant growth is nearly always stimulated by elevation of CO(2). Photosynthesis increases, more plant biomass accumulates per unit of water consumed, and economic yield is enhanced. The profitable use of supplemental CO(2) over years of greenhouse practice points to the value of CO(2) for plant production. Plant responses to CO(2) are known to interact with other environmental factors, e.g. light, temperature, soil water, and humidity. Important stresses including drought, temperature, salinity, and air pollution have been shown to be ameliorated when CO(2) levels are elevated. In the agricultural context, the growing season has been shortened for some crops with the application of more CO(2); less water use has generally, but not always, been observed and is under further study; experimental studies have shown that economic yield for most crops increases by about 33% for a doubling of ambient CO(2) concentration. However, there are some reports of negligible or negative effects. Plant species respond differently to CO(2) enrichment, therefore, clearly competitive shifts within natural communities could occur. Though of less importance in managed agro-ecosystems, competition between crops and weeds could also be altered. Tissue composition can vary as CO(2) increases (e.g. higher C: N ratios) leading to changes in herbivory, but tests of crop products (consumed by man) from elevated CO(2) experiments have generally not revealed significant differences in their quality. However, any CO(2)-induced change in plant chemical or structural make-up could lead to alterations in the plant's interaction with any number of environmental factors-physicochemical or biological. Host-pathogen relationships, defense against physical stressors, and the capacity to overcome resource shortages could be impacted by rises in CO(2). Root biomass is known to increase but, with few exceptions, detailed studies of root growth and function are lacking. Potential enhancement of root growth could translate into greater rhizodeposition, which, in turn, could lead to shifts in the rhizosphere itself. Some of the direct effects of CO(2) on vegetation have been reasonably well-studied, but for others work has been inadequate. Among these neglected areas are plant roots and the rhizosphere. Therefore, experiments on root and rhizosphere response in plants grown in CO(2)-enriched atmospheres will be reviewed and, where possible, collectively integrated. To this will be added data which have recently been collected by us. Having looked at the available data base, we will offer a series of hypotheses which we consider as priority targets for future research.     

A passive sampling method for radiocarbon analysis of atmospheric CO2 using molecular sieve

Radiocarbon (¹⁴C) analysis of atmospheric CO₂ can provide information on CO₂ sources and is potentially valuable for validating inventories of fossil fuel-derived CO₂ emissions to the atmosphere. We tested zeolite molecular sieve cartridges, in both field and laboratory experiments, for passively collecting atmospheric CO₂. Cartridges were exposed to the free atmosphere in two configurations which controlled CO₂ trapping rate, allowing collection of sufficient CO₂ in between 1.5 and 10 months at current levels. ¹⁴C results for passive samples were within measurement uncertainty of samples collected using a pump-based system, showing that the method collected samples with ¹⁴C contents representative of the atmosphere. δ¹³C analysis confirmed that the cartridges collected representative CO₂ samples, however, fractionation during passive trapping means that δ¹³C values need to be adjusted by an amount which we have quantified. Trapping rate was proportional to atmospheric CO₂ concentration, and was not affected by exposure time unless this exceeded a threshold. Passive sampling using molecular sieve cartridges provides an easy and reliable method to collect atmospheric CO₂ for ¹⁴C analysis.     

Light absorption by water-soluble organic carbon in atmospheric fine particles in the central Tibetan Plateau

Environmental Science and Pollution Research - Brown carbon (BrC) has recently received much attention because of its light absorption features. The chemical compositions, optical properties, and...     

Stable isotope fractionation analysis as a tool to monitor biodegradation in contaminated acquifers

The assessment of biodegradation in contaminated aquifers has become an issue of increasing importance in the recent years. To some extent, this can be related to the acceptance of intrinsic bioremediation or monitored natural attenuation as a means to manage contaminated sites. Among the few existing methods to detect biodegradation in the subsurface, stable isotope fractionation analysis (SIFA) is one of the most promising approaches which is pronounced by the drastically increasing number of applications. This review covers the recent laboratory and field studies assessing biodegradation of contaminants via stable isotope analysis. Stable isotope enrichment factors have been found that vary from no fractionation for dioxygenase reactions converting aromatic hydrocarbons over moderate fractionation by monooxygenase reactions (epsilon=-3 per thousand) and some anaerobic studies on microbial degradation of aromatic hydrocarbons (epsilon=-1.7 per thousand) to larger fractionations by anaerobic dehalogenation reactions of chlorinated solvents (epsilon=between -5 per thousand and -30 per thousand). The different isotope enrichment factors can be related to the respective biochemical reactions. Based on that knowledge, we discuss under what circumstances SIFA can be used for a qualitative or even a quantitative assessment of biodegradation in the environment. In a steadily increasing number of cases, it was possible to explain biodegradation processes in the field based on isotope enrichment factors obtained from laboratory experiments with pure cultures and measured isotope values from the field. The review will focus on the aerobic and anaerobic degradation of aromatic hydrocarbons and chlorinated solvents as the major contaminants of groundwater. Advances in the instrumental development for stable isotope analysis are only mentioned if it is important for the understanding of the application.     

Alteration in biochemical constituents and nutrients partitioning of Asparagus racemosus in response to elevated atmospheric CO2 concentration

Environmental Science and Pollution Research - Understanding the response of medicinal plants to elevated CO2 concentrations is crucial to evaluate the climate change impacts on medicinal...