Tracing sources of atmospheric sulphur using epiphytic lichens

The overall objective of this work was to measure the spatial variation of sulphur isotopic composition of lichens across the island of Newfoundland in order to assess the degree to which the atmosphere is being affected by long-range transport of anthropogenic sulphur from eastern North America, and/or local pollution sources. A contour map (based on over 80 composite samples of the lichen Alectoria sarmentosa) illustrates the spatial distribution of sulphur isotopic composition of the Newfoundland atmosphere. It shows a gradient of delta(34)S of sulphur in lichen, decreasing from the coast to the interior of the island. It also shows local anomalies corresponding to the city of St. John's, the Come-By-Chance Oil Refinery, mining areas and fossil-fuel powered pulp and paper mills in central and western Newfoundland. The study strongly suggests that the isotopic composition of sulphur in the Newfoundland atmosphere is influenced more by the ocean (sea salt sulphate) and local anthropogenic activities in the province, than by long-range transport of continental North American sulphate.     

Atmospheric Pb isotopic composition and trace metal concentration as revealed by epiphytic lichens:: an investigation related to two altitudinal sections in Eastern France

During Fall 1996, epiphytic lichens were collected along altitudinal sections in two areas of France (the Vosges mountains in the North-East, and the Alps, in Haute-Savoie) in order to verify any geographic distribution of atmospheric metals on a small scale. These lichens have various Pb isotopic compositions (²⁰⁶Pb/²⁰⁷Pb=1.126–1.147) which are correlated with the altitude of sampling. Lichens sampled near valleys display isotopic ratios significantly less radiogenic than those sampled at several hundred to thousand meters of altitude. In the Vosges sections, Pb concentrations and isotopic compositions of lichens may be used to define three zones: (1) valley: Pb-rich and non-radiogenic ratios, (2) transition: low-Pb and intermediate isotopic compositions, (3) mountain: heterogeneous Pb concentrations but more radiogenic and homogeneous Pb isotopic composition. Other metals (Zn, Cu, Cd, As), when normalised one to another, are not fractionated between these zones and display homogeneous relative abundance along the altitudinal sections of both sites. Variation of ²⁰⁶Pb/²⁰⁷Pb ratios with altitude is interpreted in terms of mixing of at least two pollution sources: one being the petrol (leaded and/or unleaded) combustion, and the other being of industrial origin. The latter is characterised by a more radiogenic isotopic composition. The Pb isotopic composition of flue gas residues from different municipal solid waste combustors in the Rhine valley and in other areas of France would suggest that these plants might be an important source of industrial Pb in the atmosphere. If the average industrial Pb in France has a ²⁰⁶Pb/²⁰⁷Pb close to 1.15, between 60 and 80% of the total Pb in lichens from the Rhine valley would come from gasoline combustion, whereas 85–90% of the Pb would have an industrial origin in lichens from higher altitude in the Vosges mountains. Although lichens from the Alps were collected at higher altitude, the percentage of industrial Pb for these lichens would be slightly lower (65%). Major winds and convection winds in the different valleys must then play an important role in term of distribution of atmospheric Pb in function of altitude.     

Sulphur isotopic investigation of a polluted raised bog and the uptake of pollutant sulphur by Sphagnum

The sulphur content and sulphur isotopic composition of Sphagnum as well as anionic compositions and sulphur isotope ratios of rainwater inputs and bog waters have been measured at Thorne Moors, a raised bog in eastern England. Rainwater sulphate isotopic composition shows the sulphur input at this site to be dominated by anthropogenic pollution from fossil fuel burning. Strong depletion of sulphate (low SO4(2-)/Cl-) and enrichment in 34S in sulphate occurs at depth in the bog porewaters due to bacterial sulphate reduction. Some surface waters have low SO4(2-)/Cl-) and are 34S enriched due to removal of sulphate by downward diffusion into a sulphate-reducing zone. Other sites have high SO4(2-)/Cl-) which appears to result from oxidation of organically bound sulphur in the peat. Sulphur is present in Sphagnum at around 0.2% by weight and is depleted by 0 to -9 per thousand in the heavier 34S isotope compared to sulphate. Comparison with similar data from pristine coastal sites shows that sulphur incorporation into Sphagnum is enhanced in the polluted site (as Sphagnum sulphur concentrations are higher at lower total sulphur inputs) and that sulphur incorporation is accompanied by a smaller isotopic shift than in the pristine sites. The data support a model of preferential incorporation of partially reduced sulphur species (probably HSO3-) into Sphagnum. In pristine sites these are only available as oxidation products of sulphide formed by sulphate reduction and are 32S depleted. In polluted sites this source is augmented by sulphur(IV) species in atmospheric inputs and the resultant mixture is less depleted in 32S. Thus, in the polluted sites more HSO3- is available for uptake and the isotopic shift between Sphagnum and aqueous sulphur species is smaller.     

Hydrochemical and isotopic effects associated with petroleum fuel biodegradation pathways in a chalk aquifer

Hydrochemical data, compound specific carbon isotope analysis and isotopic enrichment trends in dissolved hydrocarbons and residual electron acceptors have been used to deduce BTEX and MTBE degradation pathways in a fractured chalk aquifer. BTEX compounds are mineralised sequentially within specific redox environments, with changes in electron acceptor utilisation being defined by the exhaustion of specific BTEX components. A zone of oxygen and nitrate exhaustion extends approximately 100 m downstream from the plume source, with residual sulphate, toluene, ethylbenzene and xylene. Within this zone complete removal of the TEX components occurs by bacterial sulphate reduction, with sulphur and oxygen isotopic enrichment of residual sulphate (epsilon(s) = -14.4 per thousand to -16.0 per thousand). Towards the plume margins and at greater distance along the plume flow path nitrate concentrations increase with delta15N values of up to +40 per thousand indicating extensive denitrification. Benzene and MTBE persist into the denitrification zone, with carbon isotope enrichment of benzene indicating biodegradation along the flow path. A Rayleigh kinetic isotope enrichment model for 13C-enrichment of residual benzene gives an apparent epsilon value of -0.66 per thousand. MTBE shows no significant isotopic enrichment (delta13C = -29.3 per thousand to -30.7 per thousand) and is isotopically similar to a refinery sample (delta13C = -30.1 per thousand). No significant isotopic variation in dissolved MTBE implies that either the magnitude of any biodegradation-induced isotopic fractionation is small, or that relatively little degradation has taken place in the presence of BTEX hydrocarbons. It is possible, however, that MTBE degradation occurs under aerobic conditions in the absence of BTEX since no groundwater samples were taken with co-existing MTBE and oxygen. Low benzene delta13C values are correlated with high sulphate delta34S, indicating that little benzene degradation has occurred in the sulphate reduction zone. Benzene degradation may be associated with denitrification since increased benzene delta13C is associated with increased delta15N in residual nitrate. Re-supply of electron acceptors by diffusion from the matrix into fractures and dispersive mixing is an important constraint on degradation rates and natural attenuation capacity in this dual-porosity aquifer.     

Sulphur isotope composition of epiphytic and terricolous lichens and pine bark in Finland

The sulphur isotope composition of the epiphytic lichens, Hypogymnia physodes (L.) Nyl and Pseudevernia furfuracea (L.) Zopf, of the terricolous lichens, Cladina sp. and Peltigera aphthosa (L.) Willd., and of pine bark, at 31 sites in Finland, appeared to be dependent on lichen and tree species. The negative correlation of sulphur isotope composition with sulphur content was highly significant (P<0.001) in H. physodes and significant (P<0.01) in Pseudevernia furfuracea and Peltigera aphthosa. No correlation between the sulphur isotope composition and sulphur content was found for Cladina sp. and pine bark. The sulphur isotope compositions displayed statistically significant regional variation from south to north. Microenvironmental factors were considered, including phorophyte species and the chemical form of sulphur.     

Analysis of anaerobic BTX biodegradation in a subarctic aquifer using isotopes and benzylsuccinates

In situ biodegradation of benzene, toluene, and xylenes in a petroleum hydrocarbon contaminated aquifer near Fairbanks, Alaska was assessed using carbon and hydrogen compound specific isotope analysis (CSIA) of benzene and toluene and analysis of signature metabolites for toluene (benzylsuccinate) and xylenes (methylbenzylsuccinates). Carbon and hydrogen isotope ratios of benzene were between -25.9 per thousand and -26.8 per thousand for delta13C and -119 per thousand and -136 per thousand for delta2H, suggesting that biodegradation of benzene is unlikely at this site. However, biodegradation of both xylenes and toluene were documented in this subarctic aquifer. Biodegradation of xylenes was indicated by the presence of methylbenzylsuccinates with concentrations of 17-50 microg/L in three wells. Anaerobic toluene biodegradation was also indicated by benzylsuccinate concentrations of 10-49 microg/L in the three wells with the highest toluene concentrations (1500-5000 microg/L toluene). Since benzylsuccinate typically accounts for a very small fraction of the toluene present in groundwater (generally <1 mol%), the signature metabolite approach works best at higher toluene concentrations when it is not constrained by detection limits. In wells with lower toluene concentrations (410-640 microg/L), carbon and hydrogen isotopic values were enriched by up to approximately 2 per thousand for delta13C and approximately 70 per thousand for delta2H. This evidence of isotopic fractionation verifies the effects of biodegradation in these low concentration wells where metabolites may already be below detection limits. The combined use of signature metabolite and CSIA data is particularly valuable given the challenge of verifying biodegradation in subarctic environments where degradation rates are typically much slower than in temperate environments.     

Chemical response of transplanted lichen Canomaculina pilosa to different emission sources of air pollutants

The lichen Canomaculina pilosa was transplanted to 21 sampling sites, plus two controls sites in a north-western area of Córdoba City, Argentina. The transplantation sites were set according to traffic levels, industry condition and distances from the power plant. On the transplanted lichens chlorophyll a, chlorophyll b, phaeophytin a, soluble proteins, hydroperoxy-conjugated dienes, malondialdehyde concentration and sulphur accumulation were determined. A pollution index was calculated for each sampling site. The present study provides information about chemical parameters showing variations as the response of C. pilosa to different emission sources of air pollutants. The C. pilosa chemical response was mainly associated to industries. Significant higher values were observed in phaeophytin a/chlorophyll a ratio, sulphur content and pollution index values in lichen material transplanted at sites with industry. For the distance from the power plant category, only the hydroperoxy-conjugated dienes concentration showed significant differences. For the different traffic levels no significant variations were observed for any of the chemical parameters quantified.     

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.     

Lichens as biomonitors of uranium in the Balkan area

The contribution of the conflict of 1999 to the environmental levels of uranium in the Balkan area was evaluated by means of lichens used as biomonitors. The average U concentration found in lichens in the present study was in line with the values reported for lichens from other countries and well below the levels found in lichens collected in areas with natural or anthropogenic sources of U. Measurement of isotopic ratios 235U/238U allowed to exclude the presence of depleted uranium. According to these results, we could not detect widespread environmental contamination by depleted uranium in the Balkan area.     

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.     

Ammonium and nitrate tolerance in lichens

Since lichens lack roots and take up water, solutes and gases over the entire thallus surface, these organisms respond more sensitively to changes in atmospheric purity than vascular plants. After centuries where effects of sulphur dioxide and acidity were in the focus of research on atmospheric chemistry and lichens, recently the globally increased levels of ammonia and nitrate increasingly affect lichen vegetation and gave rise to intense research on the tolerance of lichens to nitrogen pollution. The present paper discusses the main findings on the uptake of ammonia and nitrate in the lichen symbiosis and to the tolerance of lichens to eutrophication. Ammonia and nitrate are both efficiently taken up under ambient conditions. The tolerance to high nitrogen levels depends, among others, on the capability of the photobiont to provide sufficient amounts of carbon skeletons for ammonia assimilation. Lowly productive lichens are apparently predisposed to be sensitive to excess nitrogen.     

A comparison of blue crab and bivalve delta15N tissue enrichment in two North Carolina estuaries

Stable isotope analyses (delta(15)N) were used to examine invertebrate tissue enrichment in two North Carolina estuaries with differing amounts of nutrient loading. Bivalves collected from a nutrient sensitive estuary yielded a significant difference in mean nitrogen isotopic composition of tissue (10.4 per thousand+/-0.82; N=66) compared to bivalves collected from a less nutrient sensitive estuary (6.4 per thousand+/-0.63; N=45). Similarly, blue crabs from nutrient sensitive sites had a nitrogen isotopic composition of 11.4 per thousand (+/-1.3, N=77), which was significantly different (P<0.001) than the tissue of less nutrient sensitive blue crabs (9.6 per thousand+/-0.6; N=77). The results showed that an inverse relationship exists between invertebrate tissue enrichment and indicators of water quality across estuarine sites. This study suggests that a relationship may exist between nutrient sources and subsequent energy transfer to estuarine consumers in two North Carolina estuaries.     

Carbon and nitrogen composition and stable isotope as potential indicators of source and fate of organic matter in the salt marsh of the Changjiang Estuary, China

Elemental (TOC, TN, C/N) and stable carbon and nitrogen isotopic (delta(13)C, delta(15)N) compositions were measured for surface sediments, three sediment vibrocores, plants, and suspended particulate matter (SPM) collected from salt marsh of the Changjiang Estuary. The purpose of this study is to characterize the sources of organic matter in sediments and to further elucidate the factors influencing the isotope signature in the salt marsh. Our results indicate that organic matter preserved in the sediments is predominantly controlled by the particulate organic matter in the Changjiang Estuary. The in situ contribution of marsh plants carbon to sediment organic matter is clearest in the high marsh, where the low delta(13)C of the plants (-28.1 per thousand) is reflected by a sediment delta(13)C (-24.7 per thousand) lower than values found for the low marsh and bare flat sediments (-23.4 per thousand and -23.0 per thousand, respectively). The effect of grain size on the spatial difference of isotope composition in the marsh sediments is insignificant, based on the observation that similar isotope values are found in different size particles, both for delta(13)C and delta(15)N. Nutrient utilization by plant assimilation, however, shows great impact on the surface sediment delta(15)N composition, due to the isotope fractionation. With extensive plant coverage and the consequent low surface water nitrate concentration, delta(15)N values of the high marsh surface sediments show (15)N enrichment.     

Anthropogenic inputs of boron into urban atmosphere: Evidence from boron isotopes of precipitations in Guiyang City,China

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 SO₄^2? 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.     

Lichens as an integrating tool for monitoring PAH atmospheric deposition: A comparison with soil, air and pine needles

The aim of this study was to validate lichens as biomonitors of PAH atmospheric deposition; for that, an inter-comparison between the PAH profile and concentrations intercepted in lichens with those of air, soil and pine needles was performed. The study was conducted in a petro-industrial area and the results showed that PAH profiles in lichens were similar to those of the air and pine needles, but completely different from those of soils. Lichens accumulated higher PAH concentrations when compared to the other environmental compartments and its concentrations were significantly and linearly correlated with concentrations of PAHs in soil; we showed that a translation of the lichen PAHs concentrations into regulatory standards is possible, fulfilling one of the most important requirements of using lichens as biomonitors. With lichens we were then able to characterize the air PAHs profile of urban, petro-industrial and background areas.     

The distinctive isotopic signature of plant-derived chloromethane: possible application in constraining the atmospheric chloromethane budget

Chloromethane (CH(3)Cl) is the most abundant halocarbon in the atmosphere. Although largely of natural origin it is responsible for around 17% of chlorine-catalysed ozone destruction. Sources identified to date include biomass burning, oceanic emissions, wood-rotting fungi, higher plants and most recently tropical ferns. Current estimates reveal a shortfall of around 2 million ty(-1) in sources versus sinks for the halocarbon. It is possible that emissions from green plants have been substantially underestimated. A potentially valuable tool for validating emission flux estimates is comparison of the delta13C value of atmospheric CH(3)Cl with those of CH(3)Cl from the various sources. Here we report delta13C values for CH(3)Cl released by two species of tropical ferns and show that the isotopic signature of CH(3)Cl from pteridophytes like that of CH(3)Cl from higher plants is quite different from that of CH(3)Cl produced by biomass burning, fungi and industry. delta13C values for CH(3)Cl produced by Cyathea smithii and Angiopteris evecta were respectively -72.7 per thousand and -69.3 per thousand representing depletions relative to plant biomass of 42.3 per thousand and 43.4 per thousand. The characteristic isotopic signature of CH(3)Cl released by green plants should help constrain their contribution to the atmospheric burden when reliable delta13C values for all other major sources of CH(3)Cl are obtained and a globally averaged delta13C value for atmospheric CH(3)Cl is available.     

Relationship between epiphytic lichens, trace elements and gaseous atmospheric pollutants

A study was conducted to determine the joint effect of gaseous atmospheric pollutants and trace elements on epiphytic lichens. We used our data to test the hypothesis that lichens are generally insensitive to toxic effects of trace elements, and can therefore be used as accumulator organisms to estimate concentrations of these elements in the environment. In a field study in The Netherlands the abundance of epiphytic lichen species was estimated, and their supporting bark was collected. Concentrations of a range of trace elements were determined in the bark, and concentrations of atmospheric trace gases were estimated at the sites of collection. Multivariate statistics were used to determine the relation between the abundance of the species and pollutant concentrations. Atmospheric SO2 and NO2 appeared to be the most important factors determining lichen biodiversity. Nearly all species were sensitive to these compounds. The effect of the other trace elements was very slight; only Sb had a significantly negative effect on the abundance of a few species. It is concluded that lichens can safely be used as accumulator organisms in pollution studies, provided that concentration in lichen thalli reflect atmospheric concentrations.     

Determination of baseline element composition of lichens using samples from high elevations

The results of a survey aimed at providing baseline element composition of lichens from unpolluted or very low polluted areas are reported. Lichen samples collected at high elevation areas in Himalayas (Nepal), Mt. Kenya (Kenya) and the Alps (Italy) were analyzed for their trace element content, mostly by INAA, allowing for a multi-element analysis. The elemental composition of lichen samples was essentially influenced by natural occurrence, mainly airborne soil dust. However, also anthropogenic input determined by long-distance atmospheric transport of pollutants was involved for some highly volatile elements such as Br, Cd and Sb. To avoid the influence of soil contamination and air pollution, and obtain baseline concentrations to be used as reference (the "natural" elemental composition of lichens), the average of the lowest concentrations is suggested.     

Gaseous Pollutants in St. Louis and Other Cities

During the fall of 1972, a study was undertaken to characterize gaseous air pollutants in the St. Louis metropolitan area. Information obtained in this study will be used in planning air pollution modeling studies to be carried out over the next 4 or 5 years under the Regional Air Pollution Study (RAPS) of the Environmental Protection Agency. From analyses of roadway samples, it was found that certain compounds in automotive emissions such as acetylene, carbon monoxide, o-xylene, ethylene, and 2-methylpentane occur in consistent proportions to other compounds. The concentrations of these indicator compounds in atmospheric samples were used to estimate the amounts of other hydrocarbons present that are attributable to automotive related emissions. Methane, ethane, and propane were found to originate principally from nonautomotive sources, both at St. Louis University and the St. Louis CAMP station. Similar concentrations were found in urban and non-urban areas. A comparison of ethylene-CO and propyl-ene-CO ratios in urban and non-urban areas indicates that CO can serve as an indicator of transport of urban pollutants. Sunlight irradiations of captured air samples showed increasing ozone production with increasing initial concentrations of hydrocarbons and nitrogen oxides. Substantial ozone and peroxyacetyl nitrate were formed from a total non-methane hydrocarbon concentration of only ¹/₄ ppm C.     

Ecological condition of forests around the eastern part of the Gulf of Finland

The effects of air pollutants on forests around the eastern part of the Gulf of Finland were studied by measurement of the sulphur and calcium content of pine needles and evaluation of the ecological conditions of pine forests. Several parameters for pine trees and their needles were chosen as well as the species composition and condition of epiphytic lichens. Very high pine needle S- and Ca-contents were measured in the vicinity of the Narva and Slantsy plants. In this region both the acid and basic pollutant load is massive, partly neutralizing each other. It is suggested that the total load will, sooner or later, cause unexpected environmental damage. Wide 'lichen desert' areas were detected around Narva and Slantsy. Near the margins of these areas extraordinary epiphytes on pines were observed namely Xanthoria parietina (L.) Th.Fr. and red-coloured green alga Trentepohlia umbrina. They are regarded as indicators of alkaline pollution. The lowest pine needle S- and Ca-contents of the study area were measured in south-eastern Finland. The condition of pine forests and their needles was, however, better on the neighbouring Karelian Isthmus although the species number of epiphytic lichens was very low and the condition of the lichens was poor. It is suggested that these most sensitive indicators of air pollutants are damaged by pollutants from St Petersburg and Narva. Vast virgin forests of the Karelian Isthmus act as pollutant sinks reducing the effect of pollutants on trees. On the Finnish side intensive forest management has been carried on for many decades making forests and trees more sensitive to pollutants.