Cyclooctane tropospheric degradation initiated by reaction with Cl atoms

Goal, Scope and Background Within the non-methane hydrocarbons, alkanes constitute the largest fraction of the anthropogenic emissions of volatile organic compounds. For the case of cyclic alkanes, tropospheric degradation is expected to be initiated mainly by OH reactions in the gas phase. Nevertheless, Cl atom reaction rate constants are generally one order of magnitude larger than those of OH. In the present work, the reaction of cyclooctane with Cl atoms has been studied within the temperature range of 279–333 K. Methods The kinetic study has been carried out using the fast flow tube technique coupled to mass spectrometry detection. The reaction has been studied under low pressure conditions, p=1 Torr, with helium as the carrier gas. Results The measured room temperature rate constant is very high, k=(2.63±0.54)×10⁻¹⁰ cm³molecule⁻¹s⁻¹, around 20 times larger than that for the corresponding OH reaction. We also report the results of the rate coefficients obtained at different temperatures: k = (3.5±1.2)×10⁻¹⁰ exp[(−79±110)/T] cm³ molecule⁻¹ s⁻¹ within the range of 279–333 K. This reaction shows an activation energy value close to zero. Discussion Quantitative formation of HCl has been observed, confirming the mechanism through H-atom abstraction. The reactivity of cyclic alkanes towards Cl atoms is clearly dependent on the number of CH₂ groups in the molecule, as is shown by the increase in the rate constant when the length of the organic chain increases. This increase is very high for the small cyclic alkanes and it seems that the reactions are approaching the collision-controlled limit for cyclohexane and cyclooctane. Conclusions These results show that gas-phase reaction with Cl in marine or coastal areas is an efficient sink (competing with the gas phase, OH initiated degradation) for the Earth’s emissions of cyclooctane, with a Cl-based lifetime ranging from 11 to 2000 hours, depending on the location and time of day. Recommendations and Perspectives Cl and OH fast reactions with cyclooctane are expected to define the lifetime of cyclooctane emissions to the atmosphere. The degradation of cyclooctane occurs in a short period of time and consequently (under conditions of low atmospheric mass transport), close to the emission sources enabling a significant contribution to local effects, like the formation of photochemical smog. ESS-Submission Editor: Prof. Dr. Gerhard Lammel (lammel@recetox.muni.cz)     

Are two resources really better than one? Some unexpected results of the availability of substitutes

The possibility of exploiting multiple resources is usually regarded as positive from both the economic and the environmental point of view. However, resource switching may also lead to unsustainable growth and, ultimately, to an equilibrium condition which is worse than the one that could have been achieved with a single resource. We developed a dynamic model where users exploit multiple resources and have different levels of preference among them. In this setting, exploiting multiple resources leads to worse outcomes in both economic and ecological terms than the single resource case under a wide range of parameter configurations. Our arguments are illustrated using two empirical situations, namely oil drilling in the North Sea and whale hunting in the Antarctic.     

Catalytic upgrading of higher 1-alkenes from polyethylene thermal cracking by modified Wacker oxidation

The economic success of feedstock recycling procedures for plastic wastes is increasingly demanding the conversion of the starting residue into more valuable chemicals. Thermal cracking of polyethylenes leads to the preparation of equimolar mixtures of n-paraffins and 1-alkenes within the C₂–C₁₀₀ range. These 1-olefins can be catalytically upgraded by selective oxidation processes to more valuable products (e.g., ketones and fatty acids) with different uses such as polar waxes, cetane improvers, varnishes, and printer inks. The results obtained on oxidation in a modified Wacker system of a model 1-olefin (1-dodecene) as well as of a distillate cut (C₁₀–C₂₅) of the product from the thermal cracking of urban polyethylene waste are described.     

Minimum viable metapopulation size, extinction debt, and the conservation of a declining species.

A key question facing conservation biologists is whether declines in species' distributions are keeping pace with landscape change, or whether current distributions overestimate probabilities of future persistence. We use metapopulations of the marsh fritillary butterfly Euphydryas aurinia in the United Kingdom as a model system to test for extinction debt in a declining species. We derive parameters for a metapopulation model (incidence function model, IFM) using information from a 625-km2 landscape where habitat patch occupancy, colonization, and extinction rates for E. aurinia depend on patch connectivity, area, and quality. We then show that habitat networks in six extant metapopulations in 16-km2 squares were larger, had longer modeled persistence times (using IFM), and higher metapopulation capacity (lambdaM) than six extinct metapopulations. However, there was a > 99% chance that one or more of the six extant metapopulations would go extinct in 100 years in the absence of further habitat loss. For 11 out of 12 networks, minimum areas of habitat needed for 95% persistence of metapopulation simulations after 100 years ranged from 80 to 142 ha (approximately 5-9% of land area), depending on the spatial location of habitat. The area of habitat exceeded the estimated minimum viable metapopulation size (MVM) in only two of the six extant metapopulations, and even then by only 20%. The remaining four extant networks were expected to suffer extinction in 15-126 years. MVM was consistently estimated as approximately 5% of land area based on a sensitivity analysis of IFM parameters and was reduced only marginally (to approximately 4%) by modeling the potential impact of long-distance colonization over wider landscapes. The results suggest a widespread extinction debt among extant metapopulations of a declining species, necessitating conservation management or reserve designation even in apparent strongholds. For threatened species, metapopulation modeling is a potential means to identify landscapes near to extinction thresholds, to which conservation measures can be targeted for the best chance of success.     

Historical record of mercury contamination in sediments from the Babeni Reservoir in the Olt River,Romania

Background, aim and scope

Mercury (Hg) is a ubiquitous and hazardous contaminant in the aquatic environment showing a strong biomagnification effect along the food chain. The most common transfer path of Hg to humans is contaminated fish consumption. In severely exposed humans, Hg poisoning may lead to damage in the central nervous system. Thus, it is important to examine current and past contamination levels of Hg in aquatic milieu. The Olt River is the largest Romanian tributary of the Danube River. The use of Hg as an electrode in a chlor-alkali plant contributed to the contamination of the aquatic environment in the Rm Valcea region. The purpose of this study was to compare the current state of Hg contamination with the past contamination using a historical record obtained from a dated sediment core from one of the Olt River reservoirs (Babeni) located downstream from the chlor-alkali plant. To our knowledge, no published data on Hg contamination in this region are available. The Babeni Reservoir was selected for this study because it is situated downstream from the chlor-alkali plant, whilst the other reservoirs only retain the pollutants coming from the upstream part of the watershed. Preliminary analyses (unpublished) showed high Hg concentrations in the surface sediment of the Babeni Reservoir. One core was taken in the upstream Valcea Reservoir to provide a local background level of Hg concentrations in sediments.

Results and discussion

Sediment texture was uniform in the cores from both reservoirs. Laminated sediment structure, without any obvious discontinuities, was observed. Hg concentrations in the sediment core from the Valcea Reservoir were low and constant (0.01–0.08 mg/kg). In Babeni Reservoir sediments, Hg concentrations were very high in the deeper core section (up to 45 mg/kg in the longest core) and decreased to lower concentrations toward the top of the cores (1.3–2.4 mg/kg). This decrease probably reflects technological progress in control of emissions from the Hg-cell-based chlor-alkali industry. Two strong peaks could be distinguished in older sediments. The mean rate of sedimentation (5.9 cm/year) was calculated from the depth of the ¹³⁷Cs Chernobyl peak. This was in good agreement with the sedimentation rate estimated at this site from a bathymetric study. Assuming a constant sedimentation rate, the two Hg peaks would reflect two contamination events in 1987 and 1991, respectively. However, it is also possible that the two peaks belong to the same contamination event in 1987 but were separated by a sediment layer richer in sand and silt. This layer had a low Hg concentration, which can be interpreted as a mass deposition event related to a major flood bringing Hg-free sediments.

Conclusions

Whilst the chlor-alkali plant partly switched to a cleaner technology in 1999, no obvious decrease of Hg concentrations was observed in recent decade. Results from the sediment core reflected the historical trend of Hg release from the chlor-alkali plant, revealed important contamination episodes and confirmed a legacy of contamination of Hg in recent sediments even if the concentrations of Hg decreased toward the surface due to a more efficient emission control.

Recommendations and perspectives

Although the Hg concentrations in Babeni Reservoir sediments were extremely high in the late eighties and they remain one order of magnitude higher in the surface sediments than in sediments from the upstream reservoir, little is known about the transfer of Hg to the biota and human population. Our initial measurements indicate the presence of monomethyl-Hg (MMHg) in pore water, but further studies are necessary to evaluate fluxes of MMHg at the sediment–water interface. Samples of fish and hair from various groups of the local population were recently collected to evaluate the potential hazard of Hg contamination to human health in the Rm Valcea region.

     

Spatial and temporal variability of atmospheric mercury concentrations emitted from a coal-fired power plant in Mexico

Atmospheric mercury in the environment as a result of the consumption of fossil fuels, such as coal used in electricity generation, has gained increased attention worldwide because of its toxicity, atmospheric persistence, and bioaccumulation. Determining or predicting the concentration of this pollutant in ambient air is essential for determining sensitive areas requiring health protection. This study investigated the spatiotemporal variability of gaseous elemental mercury (GEM) concentrations and its dry deposition surrounding the Presidente Plutarco Elías Calles (CETEPEC) coal-fired power plant, located on Mexico’s Pacific coast. The CALPUFF dispersion model was applied on the basis of the daily consumption of coal during 2013 for each generating unit in the power plant and considering the local scale. The established 300-ng/m³ annual average risk factor considered by the U.S. Department of Health and Human Services (U.S. DHHS) and Integrated Risk Information System (IRIS) must not be exceeded to meet satisfactory air quality levels. An area of 65 × 60 km was evaluated, and the results show that the risk level for mercury vapor was not exceeded because the annual average concentration was 2.8 ng/m³. Although the predicted risk level was not exceeded, continuous monitoring studies of GEM and of particulates in the atmosphere, soil, and water may be necessary to identify the concentration of this pollutant, specifically that resulting from coal-fired power plants operated in environmental areas of interest in Mexico. The dry mercury deposition was low in the study area; according to the CALPUFF model, the annual average was 1.40E?2 ng/m²/sec. These results represent a starting point for Mexico’s government to implement the Minamata Convention on Mercury, which Mexico signed in 2013.

Implications: The obtained concentrations of mercury from a bigger coal-fired plant in Mexico, through the application of the CALPUFF dispersion model by the mercury emissions, are below the level recommended according to the US Department of Health and Human Services and Integrated Risk Information System. These results provide evidence of important progress in the planning and installation to the future of monitoring mercury stations in the area of interest.     

Mercury human exposure through fish consumption in a reservoir contaminated by a chlor-alkali plant: Babeni reservoir (Romania)

Purpose  

Chlor-alkali plants are one of the most important point sources of mercury to aquatic environment. The problem of Hg contamination has been studied in a region, Rm Valcea (Romania), impacted by the wastewater discharge of a chlor-alkali plant. The purpose of the present study is to evaluate the current status of mercury pollution in the Babeni reservoir (Olt River) and the exposure of local population via fish consumption to mercury originating from the chlor-alkali plant.     

<Emphasis Type="Italic">Alexandrium catenella</Emphasis> (Dinophyceae), a toxic ribotype expanding in the NW Mediterranean Sea

The presence of the paralytic shellfish poisoning (PSP) dinoflagellate Alexandrium catenella in the north western (NW) Mediterranean Sea has been known since 1983. From this date on, the species has spread along the Spanish and Italian coastlines. Information concerning A. catenella isolates in the NW Mediterranean Sea was gained through phylogenetic studies. Twenty established toxic cultures of A. catenella taken from various NW Mediterranean Sea locations were analysed by nucleotide sequencing of the 5.8S rDNA and internal transcribed spacer regions. These rDNA ribosomal markers resulted useful in delineating the phylogenetic position of this species in the genus Alexandrium as well as in determining relationships between A. catenella isolates from different geographic areas. The phylogenetic position of the Mediterranean A. catenella ribotype, when compared to the “Alexandrium tamarense/catenella/fundyense species complex”, fits this species complex well. All the Mediterranean A. catenella isolates were constituted by only one genetic ribotype. By comparing the isolate sequences with those of other geographic areas, it revealed that the Mediterranean A. catenella ribotype was closely related to the A. catenella from Japan, Western Pacific Ocean. It was also evident that in temperate Japanese waters, a genetic variability was detected within A. catenella isolates; in fact, all strains resulted divergent showing as many as 15 mutational steps. The possibility that A. catenella has been recently introduced into the Mediterranean basin from temperate Asian areas is discussed.