Research and application of method of oxygen isotope of inorganic phosphate in Beijing agricultural soils

Phosphorus (P) in agricultural ecosystems is an essential and limited element for plants and microorganisms. However, environmental problems caused by P accumulation as well as by P loss have become more and more serious. Oxygen isotopes of phosphate can trace the sources, migration, and transformation of P in agricultural soils. In order to use the isotopes of phosphate oxygen, appropriate extraction and purification methods for inorganic phosphate from soils are necessary. Here, we combined two different methods to analyze the oxygen isotopic composition of inorganic phosphate (δ¹⁸O_P) from chemical fertilizers and different fractions (Milli-Q water, 0.5 mol L^?1 NaHCO₃ (pH = 8.5), 0.1 mol L^?1 NaOH and 1 mol L^?1 HCl) of agricultural soils from the Beijing area. The δ¹⁸O_P results of the water extracts and NaHCO₃ extracts in most samples were close to the calculated equilibrium value. These phenomena can be explained by rapid P cycling in soils and the influence of chemical fertilizers. The δ¹⁸O_P value of the water extracts and NaHCO₃ extracts in some soil samples below the equilibrium value may be caused by the hydrolysis of organic P fractions mediated by extracellular enzymes. The δ¹⁸O_P values of the NaOH extracts were above the calculated equilibrium value reflecting the balance state between microbial uptake of phosphate and the release of intracellular phosphate back to the soil. The HCl extracts with the lowest δ¹⁸O_P values and highest phosphate concentrations indicated that the HCl fraction was affected by microbial activity. Hence, these δ¹⁸O_p values likely reflected the oxygen isotopic values of the parent materials. The results suggested that phosphate oxygen isotope analyses could be an effective tool in order to trace phosphate sources, transformation processes, and its utilization by microorganisms in agricultural soils.     

Compound-specific isotopic and congener-specific analyses of polychlorinated biphenyl in the heat medium and rice oil of the Yusho incident

Compound-specific isotope analysis (CSIA) can be used to examine the source and transformation processes of organic pollutants in the environment. We performed a carbon stable isotope analysis of polychlorinated biphenyl (PCB) congeners in the PCB heat-transfer medium (heat medium) and the original Kanechlor-400 (KC-400, a commercial brand of PCBs) involved in the Yusho incident. The main purpose is to investigate whether isotope fractionation occurred in the rice oil deodorization process that caused the incident. The carbon isotope ratios (δ¹³C values) of the targeted PCB congeners ranged from ? 29.39 to ? 27.00‰ in the heat medium and from ? 28.77 to ? 27.05‰ in the original KC-400. No significant differences were found in the δ¹³C values, suggesting carbon isotope fractionation did not occur for the targeted PCB congeners in the heat medium when deodorization of rice oil occurred at temperatures above 200 °C. Furthermore, we also conducted a congener-specific analysis of 64 PCB congeners found in the heat medium and rice oil contaminated by it. The total PCB congener concentrations were 503 mg/g in the heat medium and 81 μg/g in the rice oil. The concentrations of the highly chlorinated congeners were significantly lower in the heat medium than in the original KC-400, and the compositional ratios of the lowly chlorinated congeners were relatively lower in the rice oil than in the heat medium. These results suggest that the PCB congener patterns gradually changed from that of the original KC-400 in the deodorization process and subsequent contamination into the rice oil. Thus, a combination of CSIA and congener-specific analysis is a new approach for investigating the changing PCB congener profiles in samples from the Yusho incident.     

Atmospheric pathways of chlorinated pesticides and natural bromoanisoles in the northern Baltic Sea and its catchment

Long-range atmospheric transport is a major pathway for delivering persistent organic pollutants to the oceans. Atmospheric deposition and volatilization of chlorinated pesticides and algae-produced bromoanisoles (BAs) were estimated for Bothnian Bay, northern Baltic Sea, based on air and water concentrations measured in 2011–2012. Pesticide fluxes were estimated using monthly air and water temperatures and assuming 4 months ice cover when no exchange occurs. Fluxes were predicted to increase by about 50 % under a 2069–2099 prediction scenario of higher temperatures and no ice. Total atmospheric loadings to Bothnian Bay and its catchment were derived from air–sea gas exchange and “bulk” (precipitation + dry particle) deposition, resulting in net gains of 53 and 46 kg year^?1 for endosulfans and hexachlorocyclohexanes, respectively, and net loss of 10 kg year^?1 for chlordanes. Volatilization of BAs releases bromine to the atmosphere and may limit their residence time in Bothnian Bay. This initial study provides baseline information for future investigations of climate change on biogeochemical cycles in the northern Baltic Sea and its catchment.     

Efficiency of lipopeptide biosurfactants in removal of petroleum hydrocarbons and heavy metals from contaminated soil

This study describes the potential application of lipopeptide biosurfactants in removal of petroleum hydrocarbons and heavy metals from the soil samples collected from industrial dumping site. High concentrations of heavy metals (like iron, lead, nickel, cadmium, copper, cobalt and zinc) and petroleum hydrocarbons were present in the contaminated soil samples. Lipopeptide biosurfactant, consisting of surfactin and fengycin was obtained from Bacillus subtilis A21. Soil washing with biosurfactant solution removed significant amount of petroleum hydrocarbon (64.5 %) and metals namely cadmium (44.2 %), cobalt (35.4 %), lead (40.3 %), nickel (32.2 %), copper (26.2 %) and zinc (32.07 %). Parameters like surfactant concentration, temperature, agitation condition and pH of the washing solution influenced the pollutant removing ability of biosurfactant mixture. Biosurfactant exhibited substantial hydrocarbon solubility above its critical micelle concentration. During washing, 50 % of biosurfactant was sorbed to the soil particles decreasing effective concentration during washing process. Biosurfactant washed soil exhibited 100 % mustard seed germination contradictory to water washed soil where no germination was observed. The results indicate that the soil washing with mixture of lipopeptide biosurfactants at concentrations above its critical micelle concentration can be an efficient and environment friendly approach for removing pollutants (petroleum hydrocarbon and heavy metals) from contaminated soil.     

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.     

A contemporary assessment of polybrominated diphenyl ethers (PBDE) in the ambient air and soil of Azerbaijan

PBDEs were measured in air and soil across Azerbaijan to establish contemporary concentrations at 13 urban and rural sites. Polyurethane foam passive air samplers (PUF-PAS) were deployed for a period of a month with surface soil samples collected at the same sites. Unlike organochlorine pesticides previously surveyed by our group, PBDE concentrations in both contemporary air and soil were low in comparison to recent European and Asian studies. For example, mean ∑₉PBDE concentrations in air and soil were 7.13 ± 1.66 pg m^?3 and 168 ± 57 pg g^?1, respectively. The fully brominated BDE-209 was the most abundant congener observed in soil (174.8 ± 58.5 pg g^?1), comprising ~ 96% of ∑₁₀PBDE. However, the PAS-derived air concentrations for highly brominated congeners must be viewed with caution as there is uncertainty over the uptake rates of particle-bound chemicals using these devices. Some of the highest concentrations in air were observed at sites with the highest wind speeds and at several remote locations in the north of the country and this requires further research. Levels of BDE-47 and 99 (the two most abundant congeners in the widely used penta-formulation) were lower than levels reported elsewhere suggesting limited use/import of the penta-BDE formulation in Azerbaijan.     

Multimedia fate of petroleum hydrocarbons in the soil: Oil matrix of constructed biopiles

A dynamic multimedia fugacity model was used to evaluate the partitioning and fate of petroleum hydrocarbon fractions and aromatic indicator compounds within the soil: oil matrix of three biopiles. Each biopile was characterised by four compartments: air, water, soil solids and non-aqueous phase liquid (NAPL). Equilibrium partitioning in biopile A and B suggested that most fractions resided in the NAPL, with the exception of the aromatic fraction with an equivalent carbon number from 5 to 7 (EC₅₋₇). In Biopile C, which had the highest soil organic carbon content (13%), the soil solids were the most important compartment for both light aliphatic fractions (EC₅₋₆ and EC₆₋₈) and aromatic fractions, excluding the EC₁₆₋₂₁ and EC₂₁₋₃₅. Our starting hypothesis was that hydrocarbons do not degrade within the NAPL. This was supported by the agreement between predicted and measured hydrocarbon concentrations in Biopile B when the degradation rate constant in NAPL was set to zero. In all scenarios, biodegradation in soil was predicted as the dominant removal process for all fractions, except for the aliphatic EC₅₋₆ which was predominantly lost via volatilization. The absence of an explicit NAPL phase in the model yielded a similar prediction of total petroleum hydrocarbon (TPH) behaviour; however the predicted concentrations in the air and water phases were significantly increased with consequent changes in potential mobility. Further comparisons between predictions and measured data, particularly concentrations in the soil mobile phases, are required to ascertain the true value of including an explicit NAPL in models of this kind.     

Reconstructing historical trends of polycyclic aromatic hydrocarbon deposition in a remote area of Spain using herbarium moss material

Herbarium mosses from 1879–1881, 1973–1975 and 2006–2007 were used to investigate the historical changes of atmospheric deposition of polycyclic aromatic hydrocarbons (PAHs) at a remote site in Northern Spain. Natural abundance of nitrogen and carbon isotopes was also measured in order to assess the evolution of emissions from anthropogenic sources. Nitrogen and PAH concentrations as well as δ¹³C and δ¹⁵N ratios were significantly higher in 19th century samples compared to present century samples. Moreover, PAH distribution varied over the centuries, with the trend towards enrichment in light PAHs. The carbon, nitrogen and PAH concentrations measured in the mosses tally with the historical evolution of anthropogenic emissions in the area, mainly influenced by changes in economic activities, domestic heating and road traffic density. Mosses provided by herbaria seem to offer the possibility of studying long-term temporal evolution of atmospheric PAH deposition.     

Engineered in situ bioremediation of a petroleum hydrocarbon-contaminated aquifer: assessment of mineralization based on alkalinity, inorganic carbon and stable carbon isotope balances

A concept is proposed to assess in situ petroleum hydrocarbon mineralization by combining data on oxidant consumption, production of reduced species, CH₄, alkalinity and dissolved inorganic carbon (DIC) with measurements of stable isotope ratios. The concept was applied to a diesel fuel contaminated aquifer in Menziken, Switzerland, which was treated by engineered in situ bioremediation. In the contaminated aquifer, added oxidants (O₂ and NO₃⁻) were consumed, elevated concentrations of Fe(II), Mn(II), CH₄, alkalinity and DIC were detected and the DIC was generally depleted in ¹³C compared to the background. The DIC production was larger than expected based on the consumption of dissolved oxidants and the production of reduced species. Stable carbon isotope balances revealed that the DIC production in the aquifer originated mainly from microbial petroleum hydrocarbon mineralization, and that geochemical reactions such as carbonate dissolution produced little DIC. This suggests that petroleum hydrocarbon mineralization can be underestimated if it is determined based on concentrations of dissolved oxidants and reduced species.     

Soil concentrations and source apportionment of polybrominated diphenyl ethers (PBDEs) and trace elements around a heavily industrialized area in Kocaeli,Turkey

Air pollutants are transported by dry deposition, wet deposition, and gas exchange accumulated in soil. Therefore, soil is an important environmental medium reflecting the level and the spatial distribution of air pollutants such as polybrominated diphenyl ethers (PBDEs) and heavy metals. Soil concentrations of seven PBDE congeners and 21 trace elements were determined in a heavily industrialized region (Dilovasi) in Kocaeli, Turkey. At all sites, Σ₇PBDE concentrations ranged from 0.70 to 203 with a mean value of 26.3 μg kg^?1 (dry weight). The congener profiles and mass inventories of PBDEs and their interactions with soil organic matter (SOM) were also investigated. BDE-209 was the dominant congener at all sites, followed by BDE-99 and/or -47. The estimated inventory of PBDEs for the Dilovasi district was 310 kg. However, there are several additional industrial regions in Kocaeli city. Considering the total land area, the potential inventory would be much larger for this city. The relationship between the PBDE concentrations in soil and SOM content indicated that factors other than soil properties have a greater influence on soil concentrations. Crustal enrichment factors (EFs) were determined; correlation analysis and factor analysis (FA) were also applied to generated data set to identify and apportion the sources polluting the soil. Sn, Mn, Ca, As, Zn, Pb, and Cd had significantly high average EF values, indicating that their soil concentrations were mainly influenced by anthropogenic activities. In FA, six factors were extracted with a cumulative variance of 84.4 % and industrial activities and traffic were found to be the main factors affecting the soil profile.     

Nitrate dynamics in an alpine forest site (Mühleggerköpfl) O and N stable isotope analysis in natural water samples

Stable isotope analysis of¹⁵N/¹⁴N and¹⁸O/¹⁶O - nitrate was used to investigate the nitrate dynamics and potential groundwater pollution in an Alpine forest stand in Tyrol/Austria. The dynamics of δ¹⁵−N_nitrate values were followed in a forest ecosystem. The stable isotopic values of the throughfall are comparable with other studies. The completely decoupled dynamics of the δ¹⁵−N_nitrate of the precipitation and the surface water was observed. High variations in δ¹⁵-N - nitrate values in rainfall indicate that nitrate of different sources is deposited at that site. A significant correlation between the δ¹⁵N_nitrate values of the surface water and soil water was obtained, while no significant correlation between the δ¹⁵N_nitrate values of any precipitation sample with the surface water could be found. This suggests that the main source of nitrate in soil water originates from microbiological activity such as nitrification reactions and less from nitrate input by deposition. The results of δ¹⁸O_nitrate measurements strongly supported the microbiological origin of nitrate in the surface and soil water. In an additional lysimeter experiment,¹⁵N - labelled nitrate was applied to study nitrate transport in soil. After 130 days and the collection of 300 L leachate, a total of 52% of the applied nitrate was detected in seepage water.

     

Influence of ciprofloxacin on the microbial catabolic diversity in soil

In this study, the effect of ciprofloxacin (CIP) on the catabolic diversity of soil microbial communities was evaluated. Soil samples were spiked with ciprofloxacin (0, 1, 5 and 50 mg?kg^?1) and were incubated for 1, 3, 9, 22 and 40 days. Untreated controls received only water. The functional diversity of the microbial community studied was characterized using a catabolic response profile (CRP). Six substrate groups were tested: carbohydrates, amino acids, carboxylic acids, aromatic chemicals, alcohols and polymers. After 40 days, the CIP concentrations in the soil samples ranged from 25% to 58% of the initial concentrations. Soil respiratory responses to the individual substrates D-glucose, lactose, D-mannose, L-glutamic, Na-citrate, malic acid and inosine were inhibited at the high CIP concentrations (5 and 50 mg·kg^?1) in the soils and were increased at the lowest CIP concentration (1 mg·kg^?1). Soil respiration was inhibited at all of the CIP concentrations after the addition of D-galactose and glycerol. The CIP concentration and incubation time explained 45.3% of the variance of the catabolic responses. The CRP analysis clearly discriminated among the different CIP concentrations. The results suggest that CIP strongly affects the catabolic diversities of soil microbial communities and that its effect is more significant than that of incubation time.     

Relationships between stable isotopes and metal contaminants in feathers are spurious and biologically uninformative

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.     

Atmospheric deposition of organochlorine pesticides by precipitation in a coastal area

Wet deposition fluxes of organochlorine pesticides (OCPs) were determined for rain samples collected in a coastal area of Turkey. Seventeen precipitation samples were collected over a 1-year period from 2008 to 2009. Rainwater was accumulated at the beginning of rain events using real time monitoring. Atmospheric concentrations were also measured in parallel with deposition samples. Both atmospheric concentrations and deposition fluxes were determined as particle and gas phases. The particle phase and dissolved phase deposition fluxes were 794.26?±?756.70 ngm^?2 day^?1 and 800.77?±?672.63 ngm^?2 day^?1, respectively. The washout ratios for OCP compounds were calculated separately for the particle and dissolved phases using the atmospheric concentrations and rain concentrations. The minimum washout ratio for the particle phase was 2339.47 for Endrin aldehyde, whereas the maximum washout ratio was 497593.34 for Methoxychlor. The maximum washout ratio for the dissolved phase was 247523.89 for Endosulfan beta, whereas the minimum washout ratio was 10169.69 for p,p′-DDT. The dry deposition velocities ranged from 0.01 to 1.67 cms^?1. The partitioning of wet deposition between the particle and dissolved phases was 50 % in terms of total OCP deposition.     

Tree-ring stable isotopes and historical perspectives on pollution - An overview

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.     

Use of CALPUFF for exposure assessment in a near-field,complex terrain setting

CALPUFF is an atmospheric source-receptor model recommended by the U.S. Environmental Protection Agency for use on a case-by-case basis in complex terrain and wind conditions. The ability of the model to provide useful information for exposure assessments in areas with those topographical and meteorological conditions has received little attention. This is an important knowledge gap for use of CALPUFF outside of regulatory applications, such as exposure analyses conducted in support of risk assessments and health studies. We compared deposition of cadmium (Cd), lead (Pb), and zinc (Zn) calculated with CALPUFF as a result of emissions from a zinc smelter with corresponding concentrations of the metals measured in attic dust and soil samples obtained from the surrounding area. On a point-by-point analysis, predictions from CALPUFF explained 11% (lead) to 53% (zinc) of the variability in concentrations measured in attic dust. Levels of heavy metals in soil interpolated to 100 residential addresses from the distribution of concentrations measured in soil samples also agreed well with deposition predicted with CALPUFF: R² of 0.46, 0.76, and 079 for Pb, Cd, and Zn, respectively. Community-average concentrations of Cd, Pb, and Zn measured in soil were significantly (p < 0.0001) and strongly correlated (R² ranged from 0.77 to 0.98) with predicted deposition rates. These findings demonstrate that CALPUFF can provide reasonably accurate predictions of the patterns of long-term air pollutant deposition in the near-field associated with emissions from a discrete source in complex terrain. Because deposition estimates are calculated as a linear function of air concentrations, CALPUFF is expected to be reliable model for prediction of long-term average, near-field ambient air concentrations in complex terrain as well.     

Influence of soil and hydrocarbon properties on the solvent extraction of high-concentration weathered petroleum from contaminated soils

Petroleum ether was used to extract petroleum hydrocarbons from soils collected from six oil fields with different history of exploratory and contamination. It was capable of fast removing 76–94 % of the total petroleum hydrocarbons including 25 alkanes (C₁₁–C₃₅) and 16 US EPA priority polycyclic aromatic hydrocarbons from soils at room temperature. The partial least squares analysis indicated that the solvent extraction efficiencies were positively correlated with soil organic matter, cation exchange capacity, moisture, pH, and sand content of soils, while negative effects were observed in the properties reflecting the molecular size (e.g., molecular weight and number of carbon atoms) and hydrophobicity (e.g., water solubility, octanol–water partition coefficient, soil organic carbon partition coefficient) of hydrocarbons. The high concentration of weathered crude oil at the order of 10⁵ mg kg^?1 in this study was demonstrated adverse for solvent extraction by providing an obvious nonaqueous phase liquid phase for hydrocarbon sinking and increasing the sequestration of soluble hydrocarbons in the insoluble oil fractions during weathering. A full picture of the mass distribution and transport mechanism of petroleum contaminants in soils will ultimately require a variety of studies to gain insights into the dynamic interactions between environmental indicator hydrocarbons and their host oil matrix.     

Radioactive isotopes in atmospheric aerosols over Russia and the Sea of Japan following nuclear accident at Fukushima Nr. 1 Daiichi Nuclear Power Station in March 2011

Artificial radionuclides, such as iodine-131 (¹³¹I), cesium-134 (¹³⁴Cs), and cesium-137 (¹³⁷Cs), as well as natural isotopes of beryllium-7 (⁷Be) and potassium-40 (⁴⁰K) have been registered in atmospheric aerosols over Vladivostok selected from 11 March to 17 June 2011. Additionally, ¹³⁴Cs and ¹³⁷Cs were detected in atmospheric aerosols over Tomsk selected from 16 March to 17 June 2011. Artificial radionuclides were also discovered in atmospheric wet depositions sampled in Vladivostok from 3 to 17 May 2011. Moreover, these radionuclides have been registered in atmospheric aerosols over the sea surface of the Sea of Japan selected from 3 to 31 May 2011 during an expedition of the “Nadezhda” sailing ship. From 18 March to 15 April, an increase in concentrations of atmospheric aerosols over Vladivostok from 108.8 to 321.5 μg/m³ has been registered. It was accompanied by increased activity concentrations of ¹³⁴Cs, ¹³⁷Cs, and the ¹³¹I. During the period from 18 March to 15 April, activity concentrations of ¹³⁷Cs and ¹³⁴Cs in atmospheric aerosols increased 100 times compared with the minimum detectable concentration (MDC) level and peaked in the weekly sample gathered from 8 to 15 April (145.0 and 105.3 μBq/m³, respectively). Variability of concentrations of natural isotopes of ⁷Be and ⁴⁰K was not greater than 1 order of magnitude throughout the sampling period. Maximal values of ¹³⁷Cs and ¹³⁴Cs concentrations (1,281.5?±?141 and 384.4?±?42.3 μBq/m³, respectively) in Tomsk were reached in samples taken from 1 to 2 April. For the atmospheric aerosol samples from the Sea of Japan, the largest concentration of ¹³¹I (392.3?±?215.7 μBq/m³) was detected from 13 to 19 May, while all other samples had much lower concentration values. Synoptic analysis of back trajectories movement of air masses showed that the radioactive cloud came to Vladivostok from the regions of Siberia and northeastern part of China. Synoptic analysis for Tomsk showed that during the period of maximal activity concentrations (1–9 April), air masses were arriving from the European part of Russia and north of Kazakhstan.     

Concentrations,atmospheric partitioning,and air–water/soil surface exchange of polychlorinated dibenzo-p-dioxin and dibenzofuran along the upper reaches of the Haihe River basin,North China

Polychlorinated dibenzo-p-dioxin and dibenzofuran (PCDD/PCDF) were overall measured and compared in ambient air, water, soils, and sediments along the upper reaches of the Haihe River of North China, so as to evaluate their concentrations, profiles, and to understand the processes of gas–particle partitioning and air–water/soil exchange. The following results were obtained: (1) The average concentrations (toxic equivalents, TEQs) of 2,3,7,8-PCDD/PCDF in air, water, sediment, and soil samples were 4,855 fg/m³, 9.5 pg/L, 99.2 pg/g dry weight (dw), and 56.4 pg/g (203 fg TEQ/m³, 0.46 pg TEQ/L, 2.2 pg TEQ/g dw, and 1.3 pg TEQ/g, respectively), respectively. (2) Although OCDF, 1,2,3,4,6,7,8-HpCDF, OCDD, and 1,2,3,4,6,7,8-HpCDD were the dominant congeners among four environmental sinks, obvious discrepancies of these congener and homologue patterns of PCDD/PCDF were observed still. (3) Significant linear correlations for PCDD/PCDF were observed between the gas–particle partition coefficient (K _p) and the subcooled liquid vapor pressure (P _L ⁰) and octanol–air partition coefficient (K _oa). (4) Fugacity fraction values of air–water exchange indicated that most of PCDD/PCDF homologues were dominated by net volatilization from water into air. The low-chlorinated PCDD/PCDF (tetra- to hexa-) presented a strong net volatilization from the soil into air, while high-chlorinated PCDD/PCDF (hepta- to octa-) were mainly close to equilibrium for air–soil exchange.     

Stable carbon isotope ratio in atmospheric CO2 collected by new diffusive devices

In this paper, stable carbon isotope ratios (δ ¹³C) were determined in the atmosphere by using a Ca-based sorbent, CaO/Ca₁₂Al₁₄O₃₃ 75:25 w/w, for passively collecting atmospheric CO₂, in both field and laboratory experiments. Field measurements were conducted in three environments characterized by different carbon dioxide sources. In particular, the environments under consideration were a rather heavily trafficked road, where the source of CO₂ is mostly vehicle exhaust, a rural unpolluted area, and a private kitchen where the major source of CO₂ was gas combustion. Samplers were exposed to the free atmosphere for 3 days in order to allow collection of sufficient CO₂ for δ¹³C analysis, then the collected CO₂ was desorbed from the adsorbent with acid treatment, and directly analyzed by nondispersive infrared (NDIR) instrument. δ ¹³C results confirmed that the samplers collected representative CO₂ samples and no fractionation occurred during passive trapping, as also confirmed by an appositely designed experiment conducted in the laboratory. Passive sampling using CaO/Ca₁₂Al₁₄O₃₃ 75:25 w/w proved to be an easy and reliable method to collect atmospheric carbon dioxide for δ ¹³C analysis in both indoor and outdoor places.