Heterogeneous uptake of octamethylcyclotetrasiloxane (D4) and decamethylcyclopentasiloxane (D5) onto mineral dust aerosol under variable RH conditions

We have carried out kinetic studies to characterize the heterogeneous decay of octamethylcyclotetrasiloxane (D₄) and decamethylcyclopentasiloxane (D₅) in the presence of representative mineral dust aerosol in order to obtain a better understanding of the atmospheric fate of these siloxanes. The heterogeneous chemistry of D₄ and D₅ with various mineral dusts was studied in an environmental aerosol reaction chamber using FTIR absorption spectroscopy to monitor the reaction. The apparent heterogeneous uptake coefficient, γ_app, for D₄ and D₅ with various mineral dusts was measured under dry conditions and as a function of relative humidity (RH). In addition, the effect of initial D₄ and D₅ concentration on the rate and yield of the reaction was examined. The uptake coefficient, γ_app, for D₄ and D₅ was similar for the most reactive aerosols tested, with kaolinite ≈hematite > silica. Limited uptake onto carbon black and calcite surfaces was observed for either siloxane. Reaction with hematite and kaolinite resulted in multilayer coverages, suggesting extensive polymerization of D₄ and D₅ on the aerosol surface.     

A modeling assessment of association between East Asian summer monsoon and fate/outflow of α-HCH in Northeast Asia

Using a dynamic numerical atmospheric transport model for organochlorine pesticides (OCPs), the relationship between the East Asian summer monsoon and the fate of α-hexachlorocyclohexane (α-HCH), a banned OCP, in the atmosphere over Northeast Asia was investigated and assessed. The modeled temporal and spatial patterns and variability of α-HCH air concentrations during the summer months of 2005 revealed a strong link between this chemical in the atmosphere over Northeast Asia and the East Asian summer monsoon. At lower atmospheric levels, easterly and southeasterly winds blowing from relatively cold ocean surface convey α-HCH air concentration from southeast China to northeast China. A monsoon front extending from southeast China to Japan, characterized by a strong wind convergence, carried the air concentration to a high elevation of the atmosphere where it was delivered by southerly monsoon flow to northern China and North Pacific Ocean. This summer monsoon associated northward atmospheric transport caused a reversal of the soil/air exchange from outgassing to net deposition during spring–summer period. The modeled wet deposition fluxes of α-HCH agreed well with the changes in the typical summer monsoon rain bands, designated as Meiyu in China, Changma in Korea, and Baiu in Japan. The major wet deposition flux paralleled with the monsoon front as well as the monsoon rain bands. The temporal change in the fluxes exhibits abrupt northward advances, which is associated with a stepwise northward and northeastward advance of the East Asian summer monsoon. The modeled α-HCH outflow in the atmosphere from China occurs mostly in the summer months and through northeast China, featured strongly by the evolution of the summer month. This study suggests that the East Asian summer monsoon provides a major atmospheric pathway and summer outflows to α-HCH over East Asia.     

Concentrations,seasonal variations,and transport of carbonaceous aerosols at a remote Mountainous region in western China

Carbonaceous aerosol concentrations were determined for total suspended particle samples collected from Muztagh Ata Mountain in western China from December 2003 to February 2006. Elemental carbon (EC) varied from 0.004 to 0.174 μg m^?3 (average = 0.055 μg m^?3) while organic carbon (OC) ranged from 0.12 to 2.17 μg m^?3 and carbonate carbon (CC) from below detection to 3.57 μg m^?3. Overall, EC was the least abundant fraction of carbonaceous species, and the EC concentrations approached those in some remote polar areas, possibly representing a regional background. Low EC and OC concentrations occurred in winter and spring while high CC in spring and summer was presumably due to dust from the Taklimakan desert, China. OC/EC ratios averaged 10.0, and strong correlations between OC and EC in spring–winter suggest their cycles are coupled, but lower correlations in summer–autumn suggest influences from biogenic OC emissions and secondary OC formation. Trajectory analyses indicate that air transported from outside of China brings ～0.05 μg m^?3 EC, ～0.42 μg m^?3 OC, and ～0.10 μg m^?3 CC to the site, with higher levels coming from inside China. The observed EC was within the range of loadings estimated from a glacial ice core, and implications of EC-induced warming for regional climate and glacial ice dynamics are discussed.     

Effects of Fireplace Use on Forest Vegetation and Amount of Woody Debris in Suburban Forests in Northwestern Switzerland

Urban forests are popular recreation areas in Europe. Several of these temperate broad-leaved forests also have a high conservation value due to sustainable management over many centuries. Recreational activities, particularly the use of fireplaces, can cause extensive damage to soil, ground vegetation, shrubs, and trees. Firewood collection depletes woody debris, leading to a loss of habitat for specialized organisms. We examined the effects of fireplace use on forest vegetation and the amount of woody debris by comparing disturbed and control plots in suburban forests in northwestern Switzerland. At frequently used fireplaces, we found reduced species densities in the ground vegetation and shrub layer and changes in plant species composition due to human trampling within an area of 150–200 m². Picnicking and grilling also reduced the height and changed the age structure of shrubs and young trees. The amount of woody debris was lower in disturbed plots than in control plots. Pieces of wood with a diameter of 0.6–7.6 cm were preferentially collected by fireplace users. The reduction in woody debris volume extended up to a distance of 16 m from the fire ring, covering an area of 800 m² at each picnic site. In order to preserve the ecological integrity of urban forests and to maintain their attractiveness as important recreation areas, we suggest depositing logging residues to be used as firewood and to restrict visitor movements near picnic sites.     

Garnering input for recycling communication strategies at a Big Ten University

With increasing environmental challenges confronting our planet, colleges and universities are trying different approaches for minimizing their adverse environmental impacts. Among the approaches being used to revitalize campus sustainability efforts, new waste management strategies have included attempts to improve campus-recycling programs. This paper presents select findings from a comprehensive study at a large, Tier I university aimed at, among other things, informing university administration and decision makers working on the planning and implementation of a new campus-wide recycling facility and program. The researchers used a mixed-method approach to help them develop an understanding of the campus community's (1) perceived barriers to recycling, (2) recycling knowledge, (3) program preferences, and (4) environmental attitudes. The results from a web-based survey (n = 3896, RR1 = 24.9%) suggest, communication efforts for recycling programming should focus more on messages concerning what, how, and where to recycle rather than messages on why to recycle. Furthermore, the results suggest recycling-related publicity approaches should differentiate their mode and content for different segments of the community.     

Gas/particle partitioning of atmospheric PCDD/Fs in a satellite town in Eastern China

Gas/particle partitioning of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in ambient air was investigated in a satellite town in Eastern China from April 2007 to January 2008 comprehending large temperature variations (from 3 to 34 °C, daily average). Molecular weight, molecular structure and ambient temperatures are the three major factors that govern the gas/particle partitioning of atmospheric PCDD/Fs throughout the year. Generally, good agreements were obtained (except for winter) between measured particulate fractions and theoretical estimates of both the Junge–Pankow adsorption model and Harner Bidleman absorption model using different sets of subcooled liquid vapor pressure and octanol–air partition coefficient (K_oa), respectively. Models utilizing estimates, derived from gas chromatographic retention indices (GC-RIs), are more accurate than that of entropy-based. Moreover, during winter, the K_oa-based model using the GC-RIs approach performs better on lower chlorinated PCDD/Fs than that of -based. Furthermore, possible sources of mismatch between measured and predicted values in winter (3–7 °C) were discussed. Gas adsorption artifact was demonstrated to be of minor importance for the phenomena observed. On the other hand, large deviations of slopes (m_r) and intercepts (b_r) in logK_p vs. plots from theoretical values are observed in the literature data and these are found to be linearly correlated with ambient temperatures (P<0.001) in this study. This indicates that the non-equilibrium partitioning of PCDD/Fs in winter may be significantly influenced by the colder temperatures that may have slowed down the exchange between gaseous and particulate fractions.     

A decision framework for possible remediation of contaminated sediments in the River Kymijoki, Finland

Background, aim, and scope  The paper describes the spatial contamination of the River Kymijoki, South-Eastern Finland, and the coastal region of the Gulf of Finland with PCDD/Fs and mercury. The findings of ecotoxicologial and human health studies are also reported, including environmental and human risk assessments. Sediments from the River Kymijoki, draining into the Gulf of Finland, have been heavily polluted by the pulp and paper industry and by chemical industries. A wood preservative, known as Ky-5, was manufactured in the upper reaches of the river between 1940 and 1984 causing severe pollution of river sediments with polychlorinated dibenzo-p-dioxins (PCDD) and dibenzofurans (PCDF). Moreover, the sediments have been polluted with mercury (Hg) from chlor-alkali production and the use of Hg as a slimicide in pulp and paper manufacturing. Materials and methods  An extensive sediment survey was conducted as well as sediment transport modeling, toxicity screening of sediment invertebrates, and a survey of contaminant bioaccumulation in invertebrates and fish. Studies on human exposure to PCDD/Fs and the possible effects on hypermineralization of teeth as well as an epidemiological study to reveal increased cancer risk were also conducted. An assessment of the ecological and human health risks with a null hypothesis (no remediation) was undertaken. Results  The sediment survey revealed severe contamination of river and coastal sediments with PCDD/Fs and Hg. The total volume of contaminated sediments was estimated to reach 5 × 10⁶ m³ and hot spots with extremely high concentrations (max 292,000 ng g⁻¹ or 1,060 ng I-TEQ g⁻¹ d.w.) were located immediately downstream from the pollution source (approximately 90,000 m³). Sediment contamination was accompanied by changes in benthic assemblages, but direct effects were masked by many factors. The fish showed only slightly elevated PCDD/F levels in muscle, but orders of magnitude higher in the liver compared with reference freshwater sites and the Baltic Sea. The concentrations in human fat did not reveal high human exposure in the Kymijoki area in general and was lower than in sea fishermen. The relative risk for total cancer among farmers was marginally higher (RR = 1.13) among those living close to the river, compared with farmers living further away, and the possibility of increased cancer risk cannot be ruled out. A conservative risk assessment revealed that the present probability of exceeding the WHO upper exposure limit of 4 pg WHO-TEQ kg⁻¹ d⁻¹ for PCDD/Fs and DL-PCBs was 6%. The probability of exceeding the WHO limit value of 0.23 μg kg⁻¹ d⁻¹ for methyl mercury was estimated to be notably higher at 62%. Based on these studies and the estimated risks connected with different remediation techniques a general remediation plan with cost benefit analysis was generated for several sub-regions in the river. Dredging, on-site treatment, and a close disposal of the most contaminated sediments (90,000 m³) was suggested as the first phase of the remediation. The decision regarding the start of remediation will be made during autumn 2008. Conclusions  The sediments in the River Kymijoki are heavily polluted with PCDD/Fs and mercury from earlier chlorophenol, chlor-alkali, and pulp and paper manufacturing. A continuous transport of contaminants is taking place to the Gulf of Finland in the Baltic Sea. The highly increased PCDD/F and Hg levels in river sediments pose an ecotoxicological risk to benthic fauna, to fish-eating predators and probably to human health. The risks posed by mercury exceed those from PCDD/Fs and need to be evaluated for (former) chlor-alkali sites and other mercury releasing industries as one basis for remediation decision making. Recommendations and perspectives  The studies form the basis of a risk management strategy and a plan for possible remediation of contaminated sediments currently under consideration in the Southeast Finland Regional Environment Centre. It is recommended that a detailed restoration plan for the most seriously contaminated areas should be undertaken. Based on current knowledge, the restoration of the whole river is not feasible, considering the current risk caused by the contaminated sediment in the river and the costs of an extensive restoration project. The experiences gained in the present case should be utilized in the evaluation of PCDD/F- and mercury-contaminated sites in other countries. The case demonstrates that the historic reservoirs are of contemporary relevance and should be addressed, e.g., in the national implementation plans of the Stockholm Convention. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Epiphytische Flechten im Wandel von Immissionen und Klima ? Ergebnisse einer Vergleichskartierung 1989/2007 in Nordwestdeutschland

Zusammenfassung   Hintergrund, Ziel und Zweck Borkenbewohnende (epiphytische) Flechten reagieren sehr empfindlich auf verschiedene Umwelteinflüsse wie Stoffgehalte in der Atmosph?re und Temperaturen. Sie haben als Bioindikatoren für Luftverunreinigungen einen hohen Stellenwert bei Umweltuntersuchungen. Basierend auf einer 1989 durchgeführten Kartierung borkenbewohnender (epiphytischer) Flechten in einem landwirtschaftlich intensiv genutzten Raum Nordwestdeutschlands erfolgte 2007 eine Wiederholungsuntersuchung. Dabei galt es, m?gliche Ver?nderungen der Immissionssituation und des Klimas zu erkennen. Material und Methoden Die Studie basiert auf einer vergleichenden Kartierung epiphytischer Flechten von 355 Tr?gerb?umen an 45 Monitoringpunkten. Die angewandte Methode orientiert sich an der 1989 angewandten halb-quantitativen Erfassung. Ergebnisse Es stellten sich gravierende Ver?nderungen in der Vegetation rindenbewohnender Flechten heraus. Insgesamt war eine Erh?hung der Artenzahl an nahezu allen Monitoringpunkten festzustellen. Es wurde eine sehr starke Abnahme s?uretoleranter Arten und eine deutliche Zunahme basen- und n?hrstofffordernder Flechtenarten festgestellt. Darüber hinaus zeigte sich eine deutliche Zunahme w?rmeliebender Flechtenarten mit einem Verbreitungsschwerpunkt in Südeuropa bei gleichzeitigem Rückgang von Arten mit einem boreal-montanem Verbreitungsschwerpunkt. Diskussion Die festgestellte Entwicklung steht im Einklang mit überregionalen Beobachtungen. Sie wird im Wesentlichen auf eine gro?r?umig ver?nderte Immissionssituation, d. h. einer Abnahme der atmosph?rischen SO₂-Belastung und Zunahme der Ammoniakbelastung zurückgeführt. Ebenso treten deutliche Auswirkungen der Klimaerw?rmung hervor. Schlussfolgerungen Mit relativ geringem Untersuchungsaufwand lie?en sich Ver?nderungen bei den epiphytischen Flechten in den letzten 18 Jahren aufzeigen. Diese sind relevant für die Beurteilung regional und kleinr?umig ver?nderter Umweltbedingungen, die auch für andere Organismen und ?kosysteme l?ngerfristig von gro?er Bedeutung sind. Empfehlungen und Ausblick Unter Verwendung standardisierter Methoden vermitteln epiphytische Flechten ein differenziertes Bild der Luftbelastungssituation in Ballungsr?umen und in landwirtschaftlich genutzten Regionen. Darüber hinaus sind sie offensichtlich gute Indikatoren für Temperatur?nderungen ihrer Umgebung. Weiterer Forschungsbedarf besteht für die Verwendung epiphytischer Flechten zum Biomonitoring von Klimaver?nderungen.      

New best estimates for radionuclide solid–liquid distribution coefficients in soils. Part 3: miscellany of radionuclides (Cd,Co, Ni,Zn, I,Se, Sb,Pu, Am,and others)

New best estimates for the solid–liquid distribution coefficient (K_d) for a set of radionuclides are proposed, based on a selective data search and subsequent calculation of geometric means. The K_d best estimates are calculated for soils grouped according to the texture and organic matter content. For a limited number of radionuclides this is extended to consider soil cofactors affecting soil–radionuclide interaction, such as pH, organic matter content, and radionuclide chemical speciation. Correlations between main soil properties and radionuclide K_d are examined to complete the information derived from the best estimates with a rough prediction of K_d based on soil parameters. Although there are still gaps for many radionuclides, new data from recent studies improve the calculation of K_d best estimates for a number of radionuclides, such as selenium, antimony, and iodine.