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)     

Mercury and selenium concentrations in the crab Callinectes arcuatus from three coastal lagoons of NW Mexico

Environmental Science and Pollution Research - Mercury and selenium concentrations and Se:Hg molar ratio in edible muscle and hepatopancreas of the crab Callinectes arcuatus from coastal lagoons of...     

Soil microarthropod communities from Mediterranean forest ecosystems in Central Italy under different disturbances

The aim of this study is to assess soil quality in Mediterranean forests of Central Italy, from evergreen to deciduous, with different types of management (coppice vs. high forest vs. secondary old growth) and compaction impacts (machinery vs. recreational). Soil quality was evaluated studying soil microarthropod communities and applying a biological index (QBS-ar) based on the concept that the higher is the soil quality, the higher will be the number of microarthropod groups well adapted to the soil habitat. Our results confirm that hardwood soils are characterised by the highest biodiversity level among terrestrial communities and by a well-structured and mature microarthropod community, which is typical of stable ecosystems (QBS value, >200). While silvicultural practices and forest composition do not seem to influence QBS-ar values or microarthropod community structure, the index is very efficient in detecting soil impacts (soil compaction due to logging activities). Several taxa (Protura, Diplura, Coleoptera adults, Pauropoda, Diplopoda, Symphyla, Chilopoda, Diptera larvae and Opiliones) react negatively to soil compaction and degradation (QBS value, <150). In particular, Protura, Diplura, Symphyla and Pauropoda, are taxonomic groups linked to undisturbed soil. This index could also be a useful tool in monitoring soil biodiversity in protected areas and in urban forestry to prevent the negative effects of trampling. QBS-ar is a candidate index for biomonitoring of soil microarthropod biodiversity across the landscape to provide guidance for the sustainable management of renewable resource and nature conservation.     

The role of environmental and spatial processes in structuring lake communities from bacteria to fish

We assessed the relative roles of local environmental conditions and dispersal on community structure in a landscape of lakes for the major trophic groups. We use taxonomic presence-absence and abundance data for bacteria, phytoplankton, zooplankton, and fish from 18 lakes in southern Quebec, Canada. The question of interest was whether communities composed of organisms with more limited dispersal abilities, because of size and life history (zooplankton and fish) would show a different effect of lake distribution than communities composed of good dispersers (bacteria and phytoplankton). We examine the variation in structure attributable to local environmental (i.e., lake chemical and physical variables) vs. dispersal predictors (i.e., overland and watercourse distances between lakes) using variation partitioning techniques. Overall, we show that less motile species (crustacean zooplankton and fish) are better predicted by spatial factors than by local environmental ones. Furthermore, we show that for zooplankton abundances, both overland and watercourse dispersal pathways are equally strong, though they may select for different components of the community, while for fish, only watercourses are relevant dispersal pathways. These results suggest that crustacean zooplankton and fish are more constrained by dispersal and therefore more likely to operate as a metacommunity than are bacteria and phytoplankton within this studied landscape.     

Uptake and translocation of metformin, ciprofloxacin and narasin in forage- and crop plants

Transfer of bioactive organic compounds from soil to plants might represent animal and human health risks. Sewage sludge and manure are potential sources for bioactive compounds such as human- and veterinary drugs. In the present study, uptake of the anti-diabetic compound, metformin, the antibiotic agent ciprofloxacin and the anti-coccidial narasin in carrot (Daucuscarota ssp. sativus cvs. Napoli) and barley (Hordeumvulgare) were investigated. The pharmaceuticals were selected in order to cover various chemical properties, in addition to their presence in relevant environmental matrixes. The root concentration factors (RCF) found in the present study were higher than the corresponding leaf concentration factors (LCF) for the three test pharmaceuticals. The uptake of metformin was higher compared with ciprofloxacin and narasin for all plant compartments analyzed. Metformin was studied more explicitly with regard to uptake and translocation in meadow fescue (Festucapratense), three other carrot cultivars (D.carota ssp. sativus cvs. Amager, Rothild and Nutri Red), wheat cereal (Triticumaestivum) and turnip rape seed (Brassicacampestris). Uptake of metformin in meadow fescue was comparable with uptake in the four carrot cultivars (RCF 2-10, LCF approximately 1.5), uptake in wheat cereals were comparable with barley cereals (seed concentration factors, SCF, 0.02-0.04) while the accumulation in turnip rape seeds was as high as 1.5. All three pharmaceuticals produced negative effects on growth and development of carrots when grown in soil concentration of 6-10 mg kg⁻¹ dry weight.     

Assessing the micro-phytoplankton response to nitrate in Comau Fjord (42°S) in Patagonia (Chile), using a microcosms approach

Anthropogenic (aquaculture) changes in environment nutrient concentrations may affect phytoplankton (biomass and taxa composition) in marine coastal waters off the Chilean Patagonia. The effects of adding nitrate (NO₃ ^?) to natural phytoplankton assemblages were evaluated considering biomass, cell abundance, and taxonomic composition. Microcosm experiments were performed in the spring, summer, and winter in the Comau Fjord located in Subantarctic Patagonia. At the end of the experiments, NO₃ ^? decreased rapidly and was undetectable in treatments, indicating a strong NO₃ ^? deficiency associated with an exponential increase in Chl-a concentrations, particulate organic nitrogen, and carbon in these treatments. Moreover, given the depleted nitrate concentrations of the spring and summer experiments, the micro-phytoplankton taxa structure shifted from mixed diatom and dinoflagellate assemblages (Ceratium spp., Dinophysis spp., Coscinodiscus sp., Rhizosolenia pungens) to assemblages dominated by blooms of the classic chain-forming diatoms found in temperate and cold waters such as Chaetoceros spp., Skeletonema spp., and Thalassiosira spp. Thus, nitrogen sources (i.e., nitrate, ammonia) may influence phytoplankton abundance and biomass accumulation dynamics in the northern section of Patagonia. It also emphasizes the importance of diatom taxa in regards to the short-term response of phytoplankton to changing environmental nutrient conditions due to natural (decreasing freshwater stream flow) and anthropogenic (aquaculture) events. This situation may be one of the future scenarios in the Patagonian fjords, thus stressing the needs for active environmental monitoring and impact assessment.     

Resolving the Conflict Between Ecosystem Protection and Land Use in Protected Areas of the Sierra Madre de Chiapas,Mexico

Livelihoods of people living in many protected areas (PAs) around the world are in conflict with biodiversity conservation. In Mexico, the decrees of creation of biosphere reserves state that rural communities with the right to use buffer zones must avoid deforestation and their land uses must become sustainable, a task which is not easily accomplished. The objectives of this paper are: (a) to analyze the conflict between people’s livelihoods and ecosystem protection in the PAs of the Sierra Madre de Chiapas (SMC), paying special attention to the rates and causes of deforestation and (b) to review policy options to ensure forest and ecosystem conservation in these PAs, including the existing payments for environmental services system and improvements thereof as well as options for sustainable land management. We found that the three largest PAs in the SMC are still largely forested, and deforestation rates have decreased since 2000. Cases of forest conversion are located in specific zones and are related to agrarian and political conflicts as well as growing economic inequality and population numbers. These problems could cause an increase in forest loss in the near future. Payments for environmental services and access to carbon markets are identified as options to ensure forest permanence but still face problems. Challenges for the future are to integrate these incentive mechanisms with sustainable land management and a stronger involvement of land holders in conservation.     

Growth and life span of the small octopus Octopus tehuelchus in San Matías Gulf (Patagonia): three decades of study

Phenotypic plasticity in response to environmental variability is one of the main characteristics of cephalopods. This study compares growth and life span of Octopus tehuelchus in different coastal environments of San Matías Gulf (Patagonia) at three different periods. The progression of maturity jointly with modal progression analysis and the detection of hatchlings in the natural environment were used to differentiate cohorts and assign ages. Growth was described using the oscillatory von Bertalanffy growth model. Within San Antonio Bay, O. tehuelchus seems to have the most favourable conditions for an extended spawning season and the development of two sub-annual cohorts. O. tehuelchus growth is strongly seasonal with slow growth rates during winter. There were differences in the growth pattern between sites and particularly between sub-annual cohorts in San Antonio Bay. The growth pattern in each site seems to be similar along the last 26 years. The results of our study make evident the variability and plasticity of O. tehuelchus in response to the environment.     

Anaerobic nonylphenol ethoxylate degradation coupled to nitrate reduction in a modified biodegradability batch test

The aim of this work was to elucidate the role of nitrate as a terminal electron acceptor on the biodegradation of NPEO. We have characterized the products of NPEO degradation by mixed microbial communities in anaerobic batch tests by means of HPLC, ¹H NMR and GC–MS. Anaerobic degradation of NPEO was strictly dependent on the presence of nitrate. Within seven days of anoxic incubation, NP2EO appeared as the major degradation product. After 21 days, NP was the main species detected, and was not degraded further even after 35 days. Nitrate concentration decreased in parallel with NPEO de-ethoxylation. A transient accumulation of nitrite was observed within the time period in which NP formation reached its maximum production. The observed generation of nonylphenol coupled to nitrate reduction suggests that the microbial consortium possessed an alternate pathway for the degradation of NPEO, which was not accessible under aerobic conditions.     

Dietary habits associated with the presence of organochlorine pesticides in human milk

Abstract

This study aims to establish the relationship between the consumption of certain foods and the presence of organochlorine pesticides in human milk. A total of 167 samples of breastmilk were collected. Sample analysis was carried out by gas chromatography with electron capture detector. Pesticide concentrations (op’DDT, pp’DDT, pp’DDE, Σ-DDT, HCB, β-HCH) were grouped by consumption level of fish, dairy products, meat, eggs, and seafood and then were compared to each other. The odds ratio (OR) was calculated between the concentration of pesticides (higher and/or lower than median) and the exposure variable (high consumption). The results indicated low median concentrations of HCB, β???HCH, op’DDT and pp’DDT, whose fluctuations and trends between different frequencies of food consumption were not significant. pp’DDE and Σ???DDT values according to the increase in consumption of fish were significantly increased. Women with high fish consumption have a higher risk of high concentrations of pp’DDE and Σ-DDT (OR: high consumption: 5.6 (1.3–23.6). A protective effect was observed in the consumption of dairy products (β-HCH and op’DDT), meat (HCB), and seafood (pp’DDT). These results suggest that it is possible that the consumption of fish, dairy products, meat, and seafood influences the presence of organochlorine pesticides in the studied population.