Variations of lead isotopes and airborne particulate concentrations from the Kozani basin,West Macedonia,Greece

The spread and variation in 206Pb/207Pb ratios make Pb isotopes a powerful tool when it comes to detecting trends in airborne particulates originating mainly from power plants. This study was conducted to determine the source of pollution in Kozani area, an affected industrial area. Lead isotopic ratios of air filters under certain meteorological conditions were compared to Pb isotope analyses sampled from lignite mines, but also to Pb isotope analyses of cultivations in soil originating from the reclamation of old abandoned lignite-mines. The particles taken into consideration have an aerodynamic diameter less than 10 microm (PM10). The measurements were carried out in a central part of the town of Kozani, West Macedonia, for one year observation period. The lead isotope values of air filters and of wheat in the Kozani area are between the values of lignite Pb and of Greek gasoline.     

Gas Forming Processes within Lignite Mining Dumps

Abstract

Gas analyses of the soil atmosphere of lignite mining dumps yielded increased contents of carbon dioxide. To get information about the potential sources and the carbon dioxide releasing capacity of the dumps, samples of dump material were investigated for their contents and isotopic compositions of organic and inorganic carbon as well as the carbon dioxide in the soil atmosphere. The contents of organic and inorganic carbon were found to vary depending on type of dump material. The isotopic composition of the organic carbon ranges between ?24.5 and ?26.5‰, which is typical for humous materials. The carbonates are found to be of marine origin (δ¹³C: +0.5 to ?1.1‰). By means of the isotope investigations it could be shown that the carbon dioxide in the lignite mining dump arises from these two different sources. Mixing ratios can be calculated using the isotope balance equation. Both reaction paths are associated with oxygen consumption and do not result in an increased gas pressure within the dump.     

The Global Methane Cycle: Isotopes and Mixing Ratios,Sources and Sinks

Abstract

A review of the global cycle of methane is presented with emphasis on its isotopic composition. The history of methane mixing ratios, reconstructed from measurements of air trapped in ice-cores is described. The methane record now extends back to 420 kyr ago in the case of the Vostok ice cores from Antarctica. The trends in mixing ratios and in δ¹³C values are reported for the two Hemispheres. The increase of the atmospheric methane concentration over the past 200 years, and by 1% per year since 1978, reaching 1.7 ppmv in 1990 is underlined.

The various methane sources are presented. Indeed the authors describe the methane emissions by bacterial activity under anaerobic conditions in wet environments (wetlands, bogs, tundra, rice paddies), in ruminant stomachs and termite guts, and that originating from fossil carbon sources, such as biomass burning, coal mining, industrial losses, automobile exhaust, sea floor vent, and volcanic emissions. Furthermore, the main sinks of methane in the troposphere, soils or waters via oxidation are also reported, and the corresponding kinetic isotope effects.     

Stable isotope ratio method for the characterisation of the poultry house environment

Stable isotope analysis was applied to describe the poultry house environment. The poultry house indoor environment was selected for this study due to the relevant health problems in animals and their caretakers. Air quality parameters including temperature, relative humidity, airflow rate, NH₃, CO₂ and total suspended particles, as well as mean levels of total airborne bacteria and fungi count, were measured. Carbon isotope ratios (¹³C/¹²C) were obtained in size-segregated aerosol particles. The carbon (¹³C/¹²C) and nitrogen (¹⁵N/¹⁴N) isotope ratios were measured in feed, litter, scrapings from the ventilation system, feathers and eggs. Additionally, the distribution of δ¹³C and δ¹⁵N values in different tissues of the chicken was examined. The airborne bacteria and fungi extracted from the air filters collected from poultry farms were grown in the laboratory in media with known isotope values and measured for stable isotope ratios. Analysis of isotope fractionation between microorganisms and their media indicated the applicability of stable isotope analysis in bulk samples for the identification of source material. The analysed examples imply that stable isotope analysis can be used to examine the indoor environment along with its biology and ecology, and serve as an informative bioanalytical tool.     

Isotope Abundance Ratios of Sr In Wine Provenance Determinations,in A Tree-Root Activity Study,and Of Pb in A Pollution Study on Tree-Rings

Abstract

In this contribution, the various and fundamentally different uses and applications of isotope signatures (of both heavy and light elements) are discussed. Examples are given for the successful use of ⁸⁷Sr/⁸⁶Sr in uncovering fraud in wine trade. Also, in an experiment related to “Waldsterben”, ⁸⁷Sr/⁸⁶Sr analyses reveal rather unexpected responses of spruces and maple-trees to mechanical damage of their roots. In another study, from ²⁰⁶Pb/²⁰⁷Pb (and ²⁰⁸Pb/²⁰⁷Pb) analyses of tree growth-rings it is demonstrated that they do not accurately record lead burdens in the environment. This is contrary to current views on the subject of tree-rings as reliable banks of past heavy metal pollutions of the biosphere. Furthermore, new perspectives of applications of isotopes in biological tissues, including those of cosmogenic and nucleogenic origin will be shortly outlined.     

Nitrogen Isotope Ratios in Different Compartments of a Mixed Stand of Spruce,Larch and Beech Trees and of Understorey Vegetation Including Fungi

Abstract

Natural nitrogen isotope ratios were measured in different compartments (needles or leaves and twigs of different age classes and crown positions, roots and soil of different horizons) of spruce (Picea abies), larch (Larix decidua) and beech (Fagus sylvatica) trees in an 11-year-old mixed stand in the Fichtelgebirge, NE Bavaria, Germany. In addition, samples of understorey vegetation (mainly ericaceous shrubs and grass) and of ectomycorrhizal and saprophytic fungi were analyzed. The δ¹⁵N values found for all samples ranged between ?7.5 and + 4.5‰. No significant differences were found for the nitrogen isotope ratios of the three tree species despite of their evergreen versus deciduous foliage and despite of their different rooting depth. Ericaceous shrubs had the most negative and fungi and soil from the mineral horizon the most positive δ¹⁵N values. Positive δ¹⁵N values of the fungi indicate their ability to utilize organic soil nitrogen, but the data do not unequivocally show that plants forming mycorrhizas profit from this organic nitrogen source.     

Continuous measurements of stable isotopes of carbon dioxide and water vapour in an urban atmosphere: isotopic variations associated with meteorological conditions

Isotope ratios of carbon dioxide and water vapour in the near-surface air were continuously measured for one month in an urban area of the city of Nagoya in central Japan in September 2010 using laser spectroscopic techniques. During the passages of a typhoon and a stationary front in the observation period, remarkable changes in the isotope ratios of CO₂ and water vapour were observed. The isotope ratios of both CO₂ and water vapour decreased during the typhoon passage. The decreases can be attributed to the air coming from an industrial area and the rainout effects of the typhoon, respectively. During the passage of the stationary front, δ¹³C–CO₂ and δ¹⁸O–CO₂ increased, while δ²H–H₂Ov and δ¹⁸O–H₂Ov decreased. These changes can be attributed to the air coming from rural areas and the air surrounding the observational site changing from a subtropical air mass to a subpolar air mass during the passage of the stationary front. A clear relationship was observed between the isotopic CO₂ and water vapour and the meteorological phenomena. Therefore, isotopic information of CO₂ and H₂Ov could be used as a tracer of meteorological information.     

Influence of Nitrogen,Water and Competition on Carbon Isotope Ratios (δ13C) in a CAM Plant (Crassula argentea)

Abstract

Leaf carbon isotope ratios (δ¹³C), an indicator of long-term intercellular carbon dioxide concentration, and also stem and root carbon isotope ratios were measured on the obligate CAM species Crassula argentea cultivated in pure and mixed cultures with the succulent C₃ Peperomia obtusifolia in open-air conditions under two different levels of nitrogen and water supply.

As expected, a diminished water supply and a relatively dry and hot summer climate cause a shift of δ¹³C values to a less strong ¹³C discrimination (less negative δ¹³C values). A diminished nitrogen supply causes a shift of the δ¹³C values in direction of a higher ¹³C discrimination (more negative δ¹³C values), particularly in the leaves. Competition causes also an increased ¹³C discrimination, especially valid for shoot axes.

The shift of ¹³C/¹²C isotope ratios in case of nitrogen deficiency is discussed to be a result of a decreased PEPCase activity in the night.     

Sulphur and Oxygen Isotopes in Sulphates in Natural Waters: (2) Deep-Waters from Horizons Below Baltic Sea Floor

Abstract

In this paper we consider deep waters from horizons located under the Baltic-Sea bottom. The samples were taken twice from wells bored in Hel peninsula. The δ¹⁸O and δD values of these waters show their glacial origin since they have significantly low values (δ¹⁸O from ?14 to ?11 whereas the modern groundwaters in Gdańsk area have ?10%₀). In contrast to surface waters the sulphates dissolved in these deep waters have rather high and uniform δ¹⁸O values which are correlated with δ¹⁸O of H₂O but not correlated with δ³⁴S. The isotope patterns may be explained assuming that the waters are very old, in which the slow process of oxygen isotope exchange at low temperatures, but extended in time, could enrich the sulphate in heavier oxygen isotopes.     

Isotope analyses of the lake sediments in the Plitvice Lakes,Croatia

The analyses of radioactive isotopes ¹⁴C, ¹³⁷Cs and ²¹⁰Pb, and stable isotope ¹³C were performed in the sediment cores, top 40 cm, taken in 2011 from karst lakes Pro??e and Kozjak in the Plitvice Lakes National Park, central Croatia. Frozen sediment cores were cut into 1 cm thick layers and dried. ¹⁴C activity in both carbonate and organic fractions was measured using accelerator mass spectrometry technique with graphite synthesis. ¹³⁷Cs, ²¹⁰Pb, ²¹⁴Pb and ²¹⁴Bi were measured by low level gamma spectrometry method on ORTECHPGe detector with the efficiency of 32%. Distribution of ¹⁴C activity from both lakes showed increase of the ¹⁴C activity in the top 10–12 cm in both carbonate and organic fractions as a response to thermonuclear bomb-produced ¹⁴C in the atmosphere in the sixties of the 20th century. Anthropogenically produced ¹³⁷Cs was also observed in sediment profiles. Sedimentation rates for both lake sediments were estimated based on the unsupported ²¹⁰Pb activity. Different ¹⁴C activity of the carbonate fraction (63–80 pMC, percent of modern carbon) and organic fraction (82–93 pMC) is the result of geochemical and biological processes of the sediment precipitation in the lake waters. This is also confirmed by the δ ¹³ C values of both fractions. Carbon isotope composition, a ¹⁴ C and δ ¹³ C, was compared with the lake sediments from the same lakes collected in 1989 and 2003.     

Sulfur Isotopic Composition of Mangroves

Abstract

Sulfur isotope ratios of mangrove leaves of 19 species were compared to discuss the species-specific characteristics of sulfur uptake and assimilation. The members of Rhizophora and Bruguiera always show remarkable enrichments of the light isotope, giving negative δ³⁴S values in most cases. The elaborated root systems of such species seem to be closely related to their sulfur absorbing systems as an adaptation to their anaerobic soil conditions.     

Oxygen and nitrogen isotopic composition of nitrate in commercial fertilizers,nitric acid,and reagent salts

Nitrate is a key component of synthetic fertilizers that can be beneficial to crop production in agro-ecosystems, but can also cause damage to natural ecosystems if it is exported in large amounts. Stable isotopes, both oxygen and nitrogen, have been used to trace the sources and fate of nitrate in various ecosystems. However, the oxygen isotope composition of synthetic and organic nitrates is poorly constrained. Here, we present a study on the N and O isotope composition of nitrate-based fertilizers. The δ¹⁵N values of synthetic and natural nitrates were 0?±?2?‰ similar to the air N₂ from which they are derived. The δ¹⁸O values of synthetic nitrates were 23?±?3?‰, similar to air O₂, and natural nitrate fertilizer δ¹⁸O values (55?±?5?‰) were similar to those observed in atmospheric nitrate. The Δ¹⁷O values of synthetic fertilizer nitrate were approximately zero following a mass-dependent isotope relationship, while natural nitrate fertilizers had Δ¹⁷O values of 18?±?2?‰ similar to nitrate produced photochemically in the atmosphere. These narrow ranges of values can be used to assess the amount of nitrate arising from fertilizers in mixed systems where more than one nitrate source exists (soil, rivers, and lakes) using simple isotope mixing models.     

ICP-MS determination of lead isotope ratios in legal and counterfeit cigarette tobacco samples

A method for the determination of Pb isotope ratios (IR) in cigarette tobacco by quadrupole inductively coupled plasma mass spectrometry (Q-ICP-MS) has been developed and applied to tobacco samples from genuine and counterfeit cigarettes obtained in the USA. The IR ²⁰⁷Pb/²⁰⁶Pb, ²⁰⁸Pb/²⁰⁶Pb, ²⁰⁶Pb/²⁰⁴Pb, ²⁰⁷Pb/²⁰⁴Pb and ²⁰⁸Pb/²⁰⁴Pb were measured using a Q-ICP-MS instrument. Two certified reference materials, grown in the USA and Bulgaria, were also analysed for comparison with the tobacco samples, as were tobacco samples from cigarettes obtained in Pakistan and China. The precision of the results was sufficient to distinguish between the counterfeit and genuine USA cigarettes. All of the genuine cigarettes and both reference materials, grown in different regions, were statistically distinct based on the measured ratios. The counterfeit cigarettes were indistinguishable from the reference material grown in Bulgaria. The technique shows promise as a method for identifying counterfeit cigarettes, possibly determining the source region.     

Accuracy and precision of a laser-spectroscopy approach to the analysis of δ2H and δ18O in human urine

The isotope ratio analysis of body water often involves large sample numbers and lengthy sample processing. Here we demonstrate the ability of isotope ratio infrared spectroscopy (IRIS) to rapidly and accurately analyse the isotope ratios of water in urine. We analysed water extracted from human urine using traditional isotope ratio mass spectrometry (IRMS) and compared those values with IRIS-analysed extracted water and un-extracted urine. Regression analyses for δ²H and δ¹⁸O values between (1) extracted water analysed via IRMS and IRIS and (2) urine and extracted water analysed via IRIS were significant (R ²=0.99). These results indicate that cryogenic distillation of urine was not required for an accurate estimate of the isotopic composition of urine when using IRIS.     

Record of Nile seasonality in Nubian neonates

The oxygen isotope compositions of bones (n?=?11) and teeth (n?=?20) from 12 Sudanese individuals buried on Sai Island (Nubia) were analysed to investigate the registration of the evolution of the Nile environment from 3700 to 500 years BP and the potential effects of ontogeny on the oxygen isotope ratios. The isotopic compositions were converted into the composition of drinking water, ultimately originating from the Nile. δ¹⁸O values decrease during ontogeny; this is mainly related to breastfeeding and physiology. Those of neonates present very large variations. Neonates have a very high bone turnover and are thus able to record seasonal δ¹⁸O variations of the Nile waters. These variations followed a pattern very similar to the present one. Nile δ¹⁸O values increased from 1.4 to 4.4?‰ (Vienna Standard Mean Ocean Water) from the Classic Kerma (～3500 BP) through the Christian period (～1000 BP), traducing a progressive drying of Northeast Africa.     

Development of Methods to Measure Carbon Isotope Ratios of Bacterial Biomarkers in the Environment

Abstract

The δ¹³C value of bacterial carbon is an important parameter in microbial ecology for studying the carbon flow within a microbial community and for the identification of ecological important strains involved in the mineralization of certain carbon pools in the environment. In our study, biomarkers were isolated from bacteria from a microbial consortium derived from two chemostats and δ¹³C values were measured. Similar isotope ratios between biomarkers such as fatty acids and outer membrane protein, biomass and substrate were observed. The δ¹³C analyses of outer membrane protein F of Pseudomonas and biomarker fatty acids were combined to follow bacterial assimilation of ¹³C labelled 4-chlorocatechol. This new approach was also used in the environment where soil samples were cultivated with different ¹³C traced substrates.

The isotopic analyses of bacterial biomarkers indicated that carbons of histidine were widely incorporated into bacterial biomarkers, in contrast to 4-chlorocatechol which was less often used as a substrate. Results indicate that by isolating bacterial biomarkers and measuring their δ¹³C values, activities of microbial communities in a complex environmental sample can be determined. This new method has the potential to elucidate individual carbon sources for individual bacterial taxa in microbial ecology.     

87Sr/86Sr in Saxon Mineral and Spa Waters

Abstract

Understanding and preserving the genesis of natural mineral and spa waters is a matter of keen interest. Under a complex analysis programme, ⁸⁷Sr/⁸⁶Sr ratios (as well as other isotopes) were measured in such waters at various sites in Saxony, producing values ranging between 0.708 and 0.731. The strontium isotope ratio was found to be closely linked to the flow patterns and variations in the chemical composition of water. The ⁸⁷Sr/⁸⁶Sr ratio can thus be used as an indicator to characterize groundwater-rock interaction and hence the variation of flow paths. It is especially useful for differentiating waters in a lithologically heterogeneous aquifer system. However, it has to be applied together with other methods and different samples from the same area should be compared.     

Isotope variations in white-tailed kites from various habitats in California: Possible limitations in assessing prey utilization and population dynamics

White-tailed kite (Elanus leucurus) populations in the 1930s were close to extirpation in the United States. But by the 1940s, an upward trend towards recovery was apparent and continued to their current stable population levels. These dramatic fluctuations in kite numbers may have been related to changes in rodent prey populations due to the conversion of native habitats to agriculture. To address this question, we evaluated the use of stable isotope analysis in determining if a shift in diet could be isotopically differentiated in current and historic kite populations. We first compared δ ¹³C, δ ¹⁵N, and δ ³⁴S values from present-day kite flight feathers and prey fur samples from four locations in California. The total ranges of isotope values for kite and their rodent prey were similar within each site. Carbon isotope values ranged from m 27.1 to m 22.2 in Arcata, m 26.1 to m 16.9 in Davis, m 27.0 to m 15.0 in Cosumnes, and m 28.2 to m 11.6 in Santa Barbara. Nitrogen isotope values ranged from 3.2 to 15.7 in Arcata, 2.8 to 12.7 in Davis, 4.0 to 15.7 in Cosumnes, and 1.7 to 20.0 in Santa Barbara. Sulfur isotope values ranged from m 7.8 to 12.4 in Arcata, m 1.1 to 9.2 in Davis, 0.7 to 10.9 in Cosumnes, and m 8.6 to 15.6 in Santa Barbara. Carbon, nitrogen, and sulfur isotope values at each site reflect typical trophic enrichments due to physiological processes. At each site, δ ¹³C and δ ¹⁵N values reflected the influence of a predominantly C₃ or a mixed C₃/C₄ plant community. Sulfur isotope values reflect the influence of predominant marine or terrestrial sulfur sources at each site. However, variability in isotope values may limit the usefulness of such analyses for addressing prey utilization and population dynamics.     

PB- Und Sr-Isotopensignaturen AlS Herkunftsindikatoren Für Anthropogene Und Geogene Kontaminationen

Abstract

In isotope geochemistry, natural differences in isotope abundance ratios of heavy elements (e.g. Sr, Nd, Pb) allow the use of specific isotopic signatures as tracers for these and genetically related elements. Examples of such applications in the field of anthropogeochemistry will be presented for lead and strontium.     

Nitrogen isotope fractionation factors (α) measured and estimated from the volatilisation of ammonia from water at pH 9.2 and pH 8.5

ABSTRACT

This paper examines the nitrogen isotope fractionation factors (α) associated with the volatilisation of ammonia from water under controlled conditions at two pH values (8.5 and 9.2). This experiment assumed the continuous removal of ammonia at a single purge rate of 10?mL air min^?1. The fractionation resulting from the removal of total ammonia from the water into an acid trap was named the observed isotope fractionation factor (α_obs), and it was measured as 1.019 (±0.0025) at pH 8.5 and 1.030 (±0.0025) at pH 9.2. The observed isotope fractionation factor includes the equilibrium isotope fractionation factor (α_eq) and the kinetic isotope fractionation factor (α_kin), each one mathematically derived from the experimental data. The equilibrium and kinetic isotope fractionation factors were estimated as α_eq?=?1.036 (±0.0014) and α_kin?=?1.050 (±0.003), respectively. Our results are compared to other previously measured and estimated fractionation factors.