A Simple Field Method to Determine Mercury Volatilization from Soils (3 pp)

Background Estimations of gaseous mercury volatilization from soils are often complex, stationary and expensive. Our objective was to develop a mobile and more simple, easy to handle and more cost-effective field method allowing rapid estimates of potential Hg emissions from soils. Methods. The study site is located in Germany, about 100 kilometers south-westerly of Berlin and influenced by the river Elbe and its tributary Saale river. The site is representative for a lot of other floodplain locations at the river Elbe and highly polluted with Hg and other heavy metals. For our study we developed a system consisting of a glass chamber gas, two gold traps, a battery operated pump and a gas meter. Adsorbed total gaseous mercury (TGM) in the gold traps was determined by use of atomic absorption spectrometry (AAS). Results and Discussion. In contrast to the common used flux chambers we designed a chamber without inlet and named it gas suck up chamber (GSC). TGM fluxes determined with the GSC showed a very close linear correlation (r = 0.993) between the TGM content in the gold traps and the corresponding pumped gas volume. The TGM adsorbed, increased proportional with increasing gas volume indicating homogenous concentrations of gaseous mercury in the soil air sucked. In contrast to the commonly used dynamic flux chamber with the aim of precisely measuring actual fluxes of Hg from a defined soil area, we focused on developing of a measurement system which will allow rapid estimates of potential Hg emissions of a site. Earlier research at the study site indicated a high potential for releasing volatile Hg from the soil to the atmosphere. Indeed, due to the high Hg content of the soil significant amounts of TGM could be detected and no shortage was reached. Conclusion. Our initial measurements are still too few in number neither to generalize the achieved results nor discuss controlling factors and processes. However, we are pleased to communicate that the developed GSC is well suited to become an effective sampling set up to rapidly estimate the magnitude of Hg volatilization from soils. Outlook. Further measurements at other polluted locations are necessary to verify the GSC method. In addition the use of a mercury analyzer instead of gold traps is planned for faster risk assessments.     

Passivsammler zur Wasseruntersuchung

Zusammenfassung  Durch r?umlich integrale Bestimmung der Schadstofffrachten [1] und zeitlich integrales Monitoring mit Schadstoff-Dosimetern [1] l?sst sich Topographie und Bewegung von Schadstofffahnen im Grundwasser bestimmen. Konventionelle Methoden der Entnahme und Untersuchung von Wasserproben sind ungeeignet zur Erfüllung dieser Anforderungen. Sorptionsaktive Passivsammler, die für entsprechende Untersuchungen in der Gasphase konzipiert sind, eignen sich nicht zur Aquiferuntersuchung. Die Passivsammler zur Untersuchung im ungest?rten Aquifer sind zentraler Bestandteil eines Systems von Probenahme- und Messsonden, das die Autoren für das Monitoring chemischer und hydraulischer Wasser-Parameter entwickelt haben. Mit den Passivsammlern lassen sich die relativen Schadstofffrachten in beliebig enger tiefenorientierter Anordnung der Messpunkte und auch zeitlich integriert zur Gewinnung von vertikalen relativen Schadstofffracht-Profilen ermitteln. Organische und anorganische relative Schadstofffrachten k?nnen damit bestimmt werden. Die gaiasafe-Passivsammler sind einfach handhabbar und lassen sich nach standardisierten chemischen Analysenmethoden auswerten. Damit erfüllen sie eine Reihe wesentlicher Anforderungen an das zielführende Monitoring von Schadstofffahnen. Die Passivsammler sind auch geeignet für die In-situ-Untersuchung von ruhigen und bewegten Gew?ssern auch in gro?er Tiefe z.B. Abw?sserkan?le, Kl?ranlagen, Flüsse und Meere und insbesondere zum Nachweis von Kontaminanten und Spurenstoffen in Wasserproben. Online First: 10. 01. 2001     

Chemisch-analytische Untersuchung von Arsenkampfstoffen und ihren Metaboliten

Zusammenfassung  Arsenkampfstoffe sind in der Umwelt persistent und kontaminieren bis heute Boden und Grundwasser. In diesem Beitrag werden die chemischen Reaktionen der Arsenkamptstoffe Diphenylarsinchlorid (CLARK I), Phenylarsindichlorid (PFIFFIKUS), Ethylarsindichlorid (DICK) sowie von Chlorvinylarsinverbindungen (LEWISITE) dargestellt. Die M?glichkeiten der chemisch-analytischen Erfassung dieser chemischen Kampfstoffe als Originalsubstanzen und als Thiol-Derivate werden pr?sentiert.      

In situ biodegradation determined by carbon isotope fractionation of aromatic hydrocarbons in an anaerobic landfill leachate plume (Vejen,Denmark)

Concentrations and isotopic compositions (13C/12C) of aromatic hydrocarbons were determined in eight samples obtained from the strongly anoxic part of the leachate plume downgradient from the Vejen Landfill (Denmark), where methanogenic, sulfate-reducing and iron-reducing conditions were observed. Despite the heterogeneous distribution of the compounds in the plume, the isotope fractionation proved that ethylbenzene and m/p-xylene were subject to significant biodegradation within the strongly anoxic plume. The isotope fractionation factors (alphaC) for the degradation of the m/p-xylene (1.0015) and ethylbenzene (1.0021) obtained from the field observations were similar to factors previously determined for the anaerobic degradation of toluene and o-xylene in laboratory experiments, and suggest that in situ biodegradation is one major process controlling the fate of these contaminants in this aquifer. The isotope fractionation determined for 1,2,4-trimethylbenzene and 2-ethyltoluene suggested in situ biodegradation; however, the isotopic composition did not correlate well with the respective concentration as expressed by the Rayleigh equation. Some other compounds (1,2,3-trimethylbenzene, o-xylene, naphthalene and fenchone) did not show significant enrichments in delta13C values along the flow path. The compound concentrations were too low for accurate isotope analyses of benzene, toluene, 1- and 2-methylnaphthalene, while interferences in the chromatography made it impossible to evaluate the isotopic composition for 4-ethyltoluene, 1,3,5-trimethylbenzene and camphor.In addition to demonstrating the potential of assessing isotopic fractionation as a means for documenting the in situ biodegradation of complex mixtures of aromatic hydrocarbons in leachate plumes, this study also illustrates the difficulties for data interpretation in complex plumes and high analytical uncertainties for isotope analysis of organic compounds in low concentration ranges.     

Role of climate, crown position, tree age and altitude in calculated ozone flux into needles of Picea abies and Pinus cembra: a synthesis

Ozone (O(3)) flux into Norway spruce (Picea abies) and cembran pine (Pinus cembra) needles was estimated under ambient conditions at six rural sites between 580 and 1950 m a.s.l. We also assessed age-related differences in O(3) flux by examining changes in leaf conductance across the life span of Norway spruce. At the leaf level O(3) flux into the needles was effectively controlled by stomatal conductance and, hence by factors such as temperature, irradiance and humidity, which control stomatal conductance. Seasonal variations in O(3) flux were mainly attributed to the course of the prevailing temperature. During the growing season, however, data have emphasised leaf-air vapour pressure difference as the environmental factor most likely to control stomatal conductance and O(3) flux into the needles. In the sun crown stomatal conductance averaged over the growing season decreased with increasing tree age from 42.0+/-3.5 mmol O(3) m(-2) s(-1) in 17-year-old trees to 7.1+/-1.0 mmol O(3) m(-2) s(-1) in 216-year-old trees, indicating that O(3) concentration in the substomatal cavities is higher in young than in old trees. Independent from tree age stomatal conductance and O(3) flux were approximately 50% lower in shade needles as compared to sun-exposed needles. Stomatal conductance was also greater in the current flush (24+/-5.6 mmol O(3) m(-2) s(-1)) and in 1-year old needles (16+/-4 mmol O(3) m(-2) s(-1)) than in older needle age classes (12+/-1 mmol O(3) m(-2) s(-1), averaged across the four older needle age classes). In trees similar in age (60-65 years old) average O(3) flux into sun needles increased from 0.55+/-0.36 nmol m(-2) s(-1) at the valley floor to 0.9 nmol m(-2) s(-1) in 1950 m a.s.l. Cumulative O(3) uptake during the vegetation period increased from 11.4+/-1.7 mol m(-2) in the valley to 14 mol m(-2) at the alpine timberline. Although stomatal conductance provides the principal limiting factor for O(3) flux, additional field research is necessary in order to improve our understanding concerning the quantitative 'physiological threshold dose' which internally can be active and can have adverse effects of O(3) on forest trees.     

Tree age dependence and within-canopy variation of leaf gas exchange and antioxidative defence in Fagus sylvatica under experimental free-air ozone exposure

We characterized leaf gas exchange and antioxidative defence of two-year-old seedlings and 60-year-old trees of Fagus sylvatica exposed to ambient (1 x O3) or two-fold ambient (2 x O3) O3 concentrations (maximum of 150 ppb) in a free-air canopy exposure system throughout the growing season. Decline in photosynthesis from sun-exposed to shaded conditions was more pronounced in adult than juvenile trees. Seedling leaves and leaves in the sun-exposed canopy had higher stomatal conductance and higher internal CO2 concentrations relative to leaves of adult trees and leaves in shaded conditions. There was a weak overall depression of photosynthesis in the 2 x O3 variants across age classes and canopy positions. Pigment and tocopherol concentrations of leaves were significantly affected by canopy position and tree age, whereas differences between 1 x O3 and 2 x O3 regimes were not observed. Glutathione concentrations were significantly increased under 2 x O3 across both age classes and canopy levels. Seedlings differed from adult trees in relevant physiological and biochemical traits in ozone response. The water-soluble antioxidative systems responded most sensitively to 2 x O3 without regard of tree age or canopy position.     

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.     

Diffusive boundary layers and photosynthesis of the epilithic algal community of coral reefs

The effects of mass transfer resistance due to the presence of a diffusive boundary layer on the photosynthesis of the epilithic algal community (EAC) of a coral reef were studied. Photosynthesis and respiration of the EAC of dead coral surfaces were investigated for samples from two locations: the Gulf of Aqaba, Eilat (Israel), and One Tree Reef on the Great Barrier Reef (Australia). Microsensors were used to measure O₂ and pH at the EAC surface and above. Oxygen profiles in the light and dark indicated a diffusive boundary layer (DBL) thickness of 180–590 μm under moderate flow (~0.08 m s^?1) and >2,000 μm under quasi-stagnant conditions. Under light saturation the oxygen concentration at the EAC surface rose within a few minutes to 200–550% air saturation levels under moderate flow and to 600–700% under quasi-stagnant conditions. High maximal rates of net photosynthesis of 8–25 mmol O₂ m^?2 h^?1 were calculated from measured O₂ concentration gradients, and dark respiration was 1.3–3.3 mmol O₂ m^?2 h^?1. From light–dark shifts, the maximal rates of gross photosynthesis at the EAC surface were calculated to be 16.5 nmol O₂ cm^?3 s^?1. Irradiance at the onset of saturation of photosynthesis, E _k, was <100 µmol photons m^?2 s^?1, indicating that the EAC is a shade-adapted community. The pH increased from 8.2 in the bulk seawater to 8.9 at the EAC surface, suggesting that very little carbon in the form of CO₂ occurs at the EAC surface. Thus the major source of dissolved inorganic carbon (DIC) must be in the form of HCO₃ ^?. Estimates of DIC fluxes across the DBL indicate that, throughout most of the daytime under in situ conditions, DIC is likely to be a major limiting factor for photosynthesis and therefore also for primary production and growth of the EAC.