Long-range atmospheric transport of three toxaphene congeners across Europe. Modeling by chained single-box FATEMOD program

Background, aims, and scope  Since toxaphene (polychlorocamphene, polychloropinene, or strobane) mixtures were applied for massive insecticide use in the 1960s to replace the use of DDT, some of their congeners have been found at high latitudes far away from the usage areas. Especially polychlorinated bornanes have demonstrated dominating congeners transported by air up to the Arctic areas. Environmental fate modeling has been applied to monitor this phenomenon using parallel zones of atmosphere around the globe as interconnected environments. These zones, shown in many meteorological maps, however, may not be the best way to configure atmospheric transport in air trajectories. The latter could also be covered by connecting a chain of simple model boxes. We aim to study this alternative approach by modeling the trajectory chain using catchment boxes of our FATEMOD model. Polychlorobornanes analyzed in biota of the Barents Sea offered one case to study this modeling alternative, while toxaphene has been and partly still is used massively at southern East Europe and around rivers flowing to the Aral Sea. Materials and methods  Pure model substances of three polychlorobornanes (toxaphene congeners P26, P50, and P62) were synthesized, their environmentally important thermal properties measured by differential scanning calorimetry, as evaluated from literature data, and their temperature dependences estimated by the QSPR programs VPLEST, WATSOLU, and TDLKOW. The evaluated property parameters were used to model their atmospheric long-range transport from toxaphene heavy usage areas in Ukraine and Aral/SyrDarja/AmuDarja region areas, through East Europe and Northern Norway (Finnmarken) to the Barents Sea. The time period used for the emission model was June 1997. Usual weather conditions in June were applied in the model, which was constructed by chaining FATEMOD model boxes of the catchment’s areas along assumed maximal air flow trajectories. Analysis of the three chlorobornanes in toxaphene mixtures function as a basis for the estimates of emission levels caused by its usage. High estimate (A) was taken from contents in a Western product chlorocamphene and low estimate (B) from mean contents in Russian polychloroterpene products to achieve modeled water concentrations. Bioaccumulation to analyzed lipid of aquatic biota at the target region was estimated by using statistical calculation for persistent organic pollutants in literature. Results  The results from model runs A and B (high and low emission estimate) for levels in sea biota were compared to analysis results of samples taken in August 1997 at Barents Sea. The model results (ng g⁻¹ lw): 4–95 in lipid of planktovores and 7–150 in lipid of piscivores, were in fair agreement with the analysis results from August 1997: 21–31 in Themisto libellula (chatka), 26–42 in Boreocadus saida (Polar cod), and 5–27 in Gadus morhua (cod) liver. Discussion  The modeling results indicate that the application of chained simple multimedia catchment boxes on predicted trajectory is a useful method for estimation of volatile airborne persistent chemical exposures to biota in remote areas. For hazard assessment of these pollutants, their properties, especially temperature dependences, must be estimated by a reasonable accuracy. That can be achieved by using measurements in laboratory with pure model compounds and estimation of properties by thermodynamic QSPR methods. The property parameters can be validated by comparing their values at an environmental temperature range with measured or QSPR-estimated values derived by independent methods. The chained box method used for long-range air transport modeling can be more suitable than global parallel zones modeling used earlier, provided that the main airflow trajectories and properties of transported pollutants are predictable enough. Conclusions  Long-range air transport modeling of persistent, especially photo-resistant organic compounds using a chain of joint simple boxes of catchment’s environments is a feasible method to predict concentrations of pollutants at the target area. This is justified from model results compared with analytical measurements in Barents Sea biota in August 1997: three of six modeled values were high and the other three low compared to the analysis results. The order of magnitude level was similar in both modeled (planktovore and piscivore) and observed (chatka and polar cod) values of lipid samples. The obtained results were too limited to firm validation but are sufficient to justify feasibility of the method, which prompts one to perform more studies on this modeling system. Recommendations and perspectives  For assessment of the risk of environmental damages, chemical fate determination is an essential tool for chemical control, e.g., for EU following the REACH rules. The present conclusion of applicability of the chained single-box multimedia modeling can be validated by further studies using analyses of emissions and target biota in various other cases. To achieve useful results, fate models built with databases having automatic steps for most calculations and outputs accessible to all chemical control professionals are essential. Our FATEMOD program catchments at environments and compound properties listed in the database represent a feasible tool for local, regional, and, according our present test results, for global exposure predictions. As an extended use of model, emission estimates can be achieved by reversed modeling from analysis results of samples corresponding to the target area. This article is dedicated to the memory of Professor Alexander B Terentiev (who passed away in November 2006), our true friend. With his Institute of Organo-Element Compounds, Russian Academy of Science, Moscow, he was an important main organizer of the six joint Finnish–Russian seminars (every third year since 1989) on the field (‘Chemistry and Ecology of Organo-Element Compounds’). He prompted us especially to search properties and environmental fates for various polyhalogen compounds. We remember him for his friendly character and great sense of humor.     

Characterizing a Major Urban Stream Restoration Project: Nine Mile Run (Pittsburgh,Pennsylvania, USA)

Urban stream restoration continues to be used as an ecological management tool, despite uncertainty about the long‐term sustainability and resilience of restored systems. Evaluations of restoration success often focus on specific instream indicators, with limited attention to the wider basin or parallel hydrologic and geomorphic process. A comprehensive understanding of urban stream restoration progress is particularly important for comparisons with nonurban sites as urban streams can provide substantial secondary benefits to urban residents. Here, we utilize a wide range of indicators to retrospectively examine the restoration of Nine Mile Run, a multi‐million dollar stream restoration project in eastern Pittsburgh (Pennsylvania, USA). Examination of available continuous hydrological data illustrates the high cost of failures to incorporate the data into planning and adaptive management. For example, persistent extreme flows drive geomorphic degradation threatening to reverse hydrologic connections created by the restoration and impact the improved instream biotic communities. In addition, human activities associated with restoration efforts suggest a positive feedback as the stream restoration has focused effort on the basin beyond the reach. Ultimately, urban stream restoration remains a potentially useful management tool, but continued improvements in post‐project assessment should include examination of a wider range of indicators.     

The influence of age on volunteer contributions in a nonprofit organization

This study examines the role of chronological age and age diversity in relation to the effects of organizational influences on the contributions of 458 volunteers in 74 geographically dispersed teams of a large nonprofit organization. The results indicate that the quality of member selection has a greater positive influence on in‐role performance for older rather than younger volunteers that the quality of training for group members has a greater positive influence on in‐role performance for volunteers who are less dissimilar in age from others in the group, and that the positive effects of chronological age on helping behaviors depend on the mean age of the group such that it is stronger for groups with older age means. The findings are discussed along with their practical implications. Copyright © 2007 John Wiley & Sons, Ltd.     

The development of self‐efficacy during aviation training

Given that self‐efficacy has been shown to be positively related to training outcomes, a better understanding of factors that affect self‐efficacy in complex training contexts is needed. This study examined the development of self‐efficacy in a flight‐training programme. Results indicate that training performance and self‐esteem predicted self‐efficacy for post‐training flight performance. Furthermore, prior flight experience moderated the relationships between training performance and self‐efficacy, and between self‐esteem and self‐efficacy. Implications regarding the development of self‐efficacy and the design of training programmes are discussed. Copyright © 2000 John Wiley & Sons, Ltd.     

Net Ecosystem Production of Boreal Larch Ecosystems on the Yenisei Transect

The study was carried out in the Turukhansk Research Station of Yenisei Transect (65^°46^′N, 89^°25^′E). Larch (Larix gmelinii (Rupr.) Rupr.) is the dominant overstory tree species. The research has been conducted on four permanent test plots in same-age mature (110-year old) and overmature (380-year old) post-fire larch stands of green moss and lichen groups of forest type. Carbon cycle parameters were assessed based on a biometric method. Quantitative analysis of carbon pools and fluxes shows that net ecosystem production of north taiga larch stands averages 32% of net primary production. Sink of atmospheric CO₂ makes 1.22 and 0.74 t C ha^{− 1} year^{− 1} for mature and overmature green moss larch stands, and 0.65 and 0.35 t C ha^{− 1} year^{− 1} for lichen type. Net carbon sink in the tree layer make up 9% of net primary production carbon, ground vegetation – 15%, and dead plant residues accumulation – 8% of atmospheric carbon uptake via photosynthesis.     

Toxaphene chemistry: separation and characterisation of selected enantiomers of the Polychloropinene mixtures

The primary goal for the study presented here was the preparation and characterisation of enantiomeric pure chlorobornane standards (Toxaphene). In this context, we partially modeled the procedure for Polychloropinene production in the former USSR. The initial reaction was ionic addition of hydrogen chloride to (1S)-alpha-pinene resulting predominantly in (1S)-2-endo-chlorobornane. Further photochlorination gave mixtures of chlorinated terpenes with different average content of Cl per molecule. The resulting mixtures were separated on a silica-gel column and a number of known hepta to decachlorobornanes were identified in fractions with the help of NMR and GC (using electron capture and mass spectrometric detection)--but in very unusual ratios as compared to the technical Toxaphene mixture formerly produced by Hercules (USA). Also several previously unknown congeners were isolated or detected. Three of the isolated congeners were obtained in crystalline state and X-ray crystallography showed their enantiomeric purity.     

Hydrogeochemistry and stable isotopes in radon-rich thermal waters of Belokurikha (Altai,Russia)

Environmental Science and Pollution Research - The first integrated isotope and chemistry results have been obtained for radon-rich thermal waters from the Belokurikha field which are used at a...