Determination of primary and secondary sources of organic acids and carbonaceous aerosols using stable carbon isotopes

Stable carbon isotope ratio (δ¹³C) data can provide important information regarding the sources and the processing of atmospheric organic carbon species. Formic, acetic and oxalic acid were collected from Zurich city in August–September 2002 and March 2003 in the gas and aerosol phase, and the corresponding δ¹³C analysis was performed using a wet oxidation method followed by isotope ratio mass spectrometry. In August, the δ¹³C values of gas phase formic acid showed a significant correlation with ozone (coefficient of determination (r²) = 0.63) due to the kinetic isotope effect (KIE). This indicates the presence of secondary sources (i.e. production of organic acids in the atmosphere) in addition to direct emission. In March, both gaseous formic and acetic acid exhibited similar δ¹³C values and did not show any correlation with ozone, indicating a predominantly primary origin. Even though oxalic acid is mainly produced by secondary processes, the δ¹³C value of particulate oxalic acid was not depleted and did not show any correlation with ozone, which may be due to the enrichment of ¹³C during the gas - aerosol partitioning.The concentrations and δ¹³C values of the different aerosol fractions (water soluble organic carbon, water insoluble organic carbon, carbonate and black carbon) collected during the same period were also determined. Water soluble organic carbon (WSOC) contributed about 60% to the total carbon and was enriched in ¹³C compared to other fractions indicating a possible effect of gas - aerosol partitioning on δ¹³C of carbonaceous aerosols. The carbonate fraction in general was very low (3% of the total carbon).     

Field responses of Prunus serotina and Asclepias syriaca to ozone around southern Lake Michigan

Higher ozone concentrations east of southern Lake Michigan compared to west of the lake were used to test hypotheses about injury and growth effects on two plant species. We measured approximately 1000 black cherry trees and over 3000 milkweed stems from 1999 to 2001 for this purpose. Black cherry branch elongation and milkweed growth and pod formation were significantly higher west of Lake Michigan while ozone injury was greater east of Lake Michigan. Using classification and regression tree (CART) analyses we determined that departures from normal precipitation, soil nitrogen and ozone exposure/peak hourly concentrations were the most important variables affecting cherry branch elongation, and milkweed stem height and pod formation. The effects of ozone were not consistently comparable with the effects of soil nutrients, weather, insect or disease injury, and depended on species. Ozone SUM06 exposures greater than 13 ppm-h decreased cherry branch elongation 18%; peak 1-h exposures greater than 93 ppb reduced milkweed stem height 13%; and peak 1-h concentrations greater than 98 ppb reduced pod formation 11% in milkweed.     

The origin of stable halogenated compounds in volcanic gases

BACKGROUND: Halogenated compounds in the atmosphere are of great environmental concern due to their demonstrated negative effect on atmospheric chemistry and climate. Detailed knowledge of the emission budgets of halogenated compounds has to be gained to understand better their specific impact on ozone chemistry and the climate. Such data are also highly relevant to guide policy decisions in connexion with international agreements about protection of the ozone layer. In selected cases, the relevance of specific emission sources for certain compounds were unclear. In this study we present new and comprehensive evidence regarding the existence and relevance of a volcanic contribution of chlorofluorocarbons (CFCs), hydrofluorocarbons (HFCs), hydrochlorofluorocarbons (HCFCs), halons (bromine containing halo(hydro)carbons), and fully fluorinated compounds (e.g. CF4 and SF6) to the atmospheric budget. METHODS: In order to obtain new evidence of a volcanic origin of these compounds, we collected repeatedly, during four field campaigns covering a period of two years, gases from fumaroles discharging over a wide range of temperatures at the Nicaraguan subduction zone volcanoes Momotombo, Cerro Negro and Mombacho, and analysed them with very sensitive GC/MS systems. RESULTS AND DISCUSSION: In most fumarolic samples certain CFCs, HFCs, HCFCs, halons, and the fully fluorinated compounds CF4 and SF6 were present above detection limits. However, these compounds occur in the fumarole gases in relative proportions characteristic for ambient air. CONCLUSION: This atmospheric fingerprint can be explained by variable amounts of air entering the porous volcanic edifices and successively being incorporated into the fumarolic gas discharges. Recommendation and Outlook. Our results suggest that the investigated volcanoes do not constitute a significant natural source for CFCs, HFCs, HCFCs, halons, CF4, SF6 and NF3.     

Ecology and characterization of yeasts from aquatic regions of South Florida

Mycological investigations, entailing over 400 samples from 120 separate collection stations, of the composite aquatic regions of southern Florida and adjacent areas have been developed. A collection of over 1000 yeasts, representing more than 50 taxa, has been characterized and studied. Highest yeast densities were found in freshwaters with the recovery of yeasts per sample decreasing from 100% to approximately 70% with lowered organic content, increasing salinity and remoteness from land. Average cell population densities, variety of species, and particularly the number of sexual yeasts, decreased in saline samples. The isolation media used were evaluated and have been discussed in terms of yeast densities obtained. Stritly oxidative species of Candida, Cryptococcus, and Rhodotorula and the sexual yeast, Debaryomyces hansenii, were the most widespread in all the habitas studied and the predominant forms in water of relatively low organic content. Selective survival of certain yeasts in the various aquatic environments was suggested. Definite distributional patterns were exhibited by various taxa and the possible existence of indicator species wa suggested. The systematics of the fungi have been reviewed at length and the significance of strain differences considered and discussed as related to the unique characteristics of the various ecological habitats.     

Dietary-induced responses in the phagotrophic flagellate Oxyrrhis marina

Primary producers may be limited by different nutrients as well as by light availability, which in turn affects their quality as food for higher trophic levels. Typically, algae with high C:N and/or C:P ratios are low-quality food for consumers. Heterotrophic protists are important grazers on these autotrophes, but despite their importance as grazers, knowledge of food quality effects on heterotrophic protists is sparse. In the present study, we examined how differently grown Rhodomonas salina (nutrient replete, N-limited and P-limited) affected the phagotrophic flagellate Oxyrrhis marina. The functional response of O. marina (based on ingested biovolume) did not show significant differences between food sources, thus food uptake was independent of food quality. O. marina was weakly homoeostatic which means that its C:N:P ratio still reflected the elemental composition of its food to some extent. Food quality had a significantly negative effect on the numerical response of O. marina. Whereas N-limited R. salina and nutrient replete R. salina resulted in similar growth rates, P-limited algae had a significantly negative effect on the specific growth rate of O. marina. Hence, the lack of elemental phosphorus of O. marina feeding on P-limited algae caused a reduction in growth. Thus, despite their weaker homoeostasis, heterotrophic protists are also affected by high C:P food in a similar way to crustacean zooplankton.     

Application of headspace analysis and AOX-measurement to leachate from hazardous waste landfills

The applicability of headspace analysis for the quantitation of volatile organic compounds in leachates from hazardous waste landfills is investigated with respect to standard stability, leachate stability and reproducibility. Between the corresponding data sets, deviations at about 10 % are observed. Besides the analysis of the volatile leachate components, the sum parameters POX and AOX are determined for the leachate samples. From the POX-data, good agreements with the total organic chlorine determined by headspace analysis are received. For determination of AOX, two different methods are applied to the leachates and discussed with respect to the high concentrations of POX determined in all leachate samples.     

Correlations between mutagenic activity of organic extracts of airborne particulate matter, NOx and sulphur dioxide in southern Germany: results of a two-year study

Goals, Scope and Background Among other substances, sulphur dioxide (SO2), nitric oxide (NO) and nitrogen dioxide (NO2) are parameters which are routinely measured to describe basic air quality. Organic extracts of airborne particulate matter contain mutagenic chemical compounds of different origins. The aim of the study was to find correlations between routine monitoring data and mutagenic activity of organic extracts of simultaneously drawn samples.Methods Specimens were collected over a period of two years at 8 sampling sites in south-west Germany. Simultaneously, concentrations of NO, NO2, and SO2 were measured on-line within the framework of the official air monitoring network of Baden-Württemberg, Germany. Dust samples were collected for biotesting using high volume air samplers equipped with glass fibre filters. After sampling was completed, filters were extracted and samples were prepared for biological testing. Mutagenic activity was tested by means of the plate incorporation assay (Ames test) using S. typhimurium TA98 and TA100 tester strains. During the first year of the study, all tests have been performed with and without metabolic activation. Additionally, a series of tests has been performed in parallel with TA98 and TA98NR.Results and Discussion Comparison of Ames test data obtained with and without metabolic activation indicates no statistically significant difference between both methods. Therefore, during the second year of the study, all tests have been performed without metabolic activation. Average yearly activities at the sampling sites were between 1 und 27 Revertants per m³ (Rev/m³). High activities were preferably found at congested sites (Karlsruhe, up to 95 Rev/m³). However, peak values of over 100 Rev/m³ were found in other places where pollution by traffic is significantly lower. The reason for these high level values is not evident. Tests performed using TA98NR tester strain indicate a significant share (average 31%) of compounds requiring activation by nitroreductase for mutagenic activity. Average mutagenic activity can be correlated to routine monitoring parameters. Comparison of averaged data for particular sampling sites indicates significant correlation between nitric oxide and mutagenic activity in TA98 (r²=0.90), while correlation between nitrogen dioxide (0.84) or sulphur dioxide (0.52) and mutagenic activity is weaker. For TA100, correlations are generally weaker than for TA98. Comparison of data for mutagenic activity and routine monitoring data of distant sites being sampled simultaneously shows parallel behaviour.Conclusions Results from this study show that mutagenic activity can be compared to seasonal and local variations of gaseous indicator air pollutants. Tester strain TA98 generally shows the best correlations. Although pollution by particle-bound mutagenic substances is significantly higher during the cold season than during summer on average, mutagenic activity of airborne dust is not a continuous effect. During winter, peak levels as well as low pollution periods can occur. Even during winter time mutagenic activity can reach very low levels typical for summertime. Comparison of results for distant sampling sites where samples have been collected simultaneously indicate that “classical” indicators of air pollution and bacterial mutagenicity of organic extracts from airborne particulate matter are influenced by connected effects. Seasonal trend of mutagenic activity, in particular, is similar to the concentrations of nitrogen oxide. NO is a strong indicator for vehicle exhaust gases. It is concluded that the average mutagenic activity at particular sites can be estimated using NO concentrations as an indicator.     

LIMPACT: Ein Expertensystem zur Absch?tzung der Pflanzenschutzmittel-Belastung kleiner Flie?gew?sser mittels der Makroinvertebraten-Fauna

Zusammenfassung  Die Entwicklung, der Aufbau und die Evaluierung eines biologischen Indikatorsystems für die Pflanzenschutzmittel-Belastung in kleinen Flie?gew?ssern wird vorgestellt. In Flie?gew?ssern mit landwirtschaftlichem Einzugsgebiet stuft das Expertensystem LIMPACT die Belastung in vier Klassen ‘unbelastet/nicht nachgewiesen’, ‘gering’, ‘mittel’ und ‘hoch’ belastet ein. Eingangsdaten sind dabei die Abundanzdaten der benthischen Makroinvertebraten-Fauna zu vier Terminen im Jahresverlauf (M?rz/April; Mai/Juni; Juli/August; September/Oktober) und neun physikalisch-chemische bzw. morphologische Flie?gew?sserparameter. Die Wissenbasis wurde mit dem Shellbaukasten D3 aufgebaut und enth?lt 921 Regeln zum etablieren oder de-etablieren einer Bewertungsklasse. Es wurden 39 Arten und Taxa analysiert und dabei 13 positive und 24 negative Indikatorspezies definiert. Positive Indikatorarten zeigen eine hohe Belastung durch hohe Abundanzen an, w?hrend negative Indikatorarten durch eine hohe Abundanz eine Belastung ausschlie?en und unbelastete B?che anzeigen. Die Datenbasis enthielt 157 j?hrliche Untersuchungen und wurde auch zur Evaluierung eingesetzt. Die korrekte Klassifikationsrate liegt bei 66,7–85,5% der F?lle. Die meisten verbleibenden F?llen werden nicht falsch eingestuft, sondern infolge der konservativen Bewertung bei geringer Datengrundlage nicht klassifiziert. Online First: 31.05.2002     

Dynamic studies on the mobility of trace elements in soil and sediment samples influenced by dumping of residues of the flood in the Mulde River region in 2002

In the analysis of soil samples, batch sequential extraction procedures are traditionally used for the fractionation of trace elements to access their mobility and potential risk for the contamination of groundwater. In the present work a continuous-flow technique has been used that enables not only the fast and efficient leaching of trace elements but as well as time-resolved studies on the mobilization of arsenic and selected heavy metals in different forms to be made. Rotating coiled columns (RCC) earlier used mainly in countercurrent chromatography have been successfully applied to the dynamic leaching of heavy metals from soils contaminated by flooding sludge's. The sample was retained in a PTFE rotating column as the stationary phase whereas aqueous solutions were continuously pumped through. The contents of elements were determined by on-line coupling of RCC and inductively coupled plasma atomic emission spectrometry (ICP-AES). This enables real-time data on the leaching process to be obtained. Dynamic and traditional batch procedures were compared. It has been shown that the aqueous elution under centrifugal forced conditions is much more effective for the mobilization of heavy metals. Hence, the dynamic leaching is characterized by a substantially more intensive interaction between solid and water and is besides substantially more time-saving than the conventional batch procedure. The RCC procedure was also employed for preliminary leaching studies with a simulated "acid rain". In comparison with the water leaching, the mobilization of heavy metals and arsenic from soil samples with employment of simulated acid rain as eluent was less effective.     

Decomposition of buried corpses,with special reference to the formation of adipocere

The unrestrained decomposition of a corpse involves the consecutive processes of autolysis, putrefaction and decay. Ideally, decomposition is completed within the regular resting time (15–25 years) and leads to the entire skeletalisation of the corpse. Adipocere, a greyish fatty substance formed during decomposition, is regarded as a spontaneous inhibition of post-mortem changes; it makes the corpse almost entirely resistant to decomposition and makes it impossible to use the same graves again. This creates problems for local governments with regard to the generally growing demand for burial ground.Apart from corpse-specific characteristics (e.g. sex, age, physique, cause of death), method of burial (e.g. material of the coffin, depth of grave, individual or mass grave, clothing) and time of burial, the conditions of the resting place (geology, topography, soil properties and frequency of use, air, water, and heat budget), in particular, have a special impact on adipocere formation. This study summarises the present knowledge on this phenomenon, combining results gained both in forensic medicine and in geosciences.