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.     

Use of a food web model to evaluate the factors responsible for high PCB fish concentrations in Lake Ellasjøen, a high Arctic Lake

Background, aim, and scope

Lake Ellasjøen, located in the Norwegian high arctic, contains the highest concentrations of polychlorinated biphenyls (PCBs) ever recorded in fish and sediment from high arctic lakes, and concentrations are more than 10 times greater than in nearby Lake Øyangen. These elevated concentrations in Ellasjøen have been previously attributed, in part, to contaminant loadings from seabirds that use Ellasjøen, but not Øyangen, as a resting area. However, other factors, such as food web structure, organism growth rate, weight, lipid content, lake morphology, and nutrient inputs from the seabird guano, also differ between the two systems. The aim of this study is to evaluate the relative influence of these factors as explanatory variables for the higher PCB fish concentrations in Ellasjøen compared with Øyangen, using both a food web model and empirical data.

Methods

The model is based on previously developed models but parameterized for Lakes Ellasjøen and Øyangen using measured data wherever possible. The model was applied to five representative PCB congeners (PCB 105, 118, 138, 153, and 180) using measured sediment and water concentrations as input data and evaluated with previously collected food web data.

Results

Modeled concentrations are within a factor of two of measured concentrations in 60% and 40% of the cases in Lakes Ellasjøen and Øyangen, respectively, and within a factor of 10 in 100% of the cases in both lakes. In many cases, this is comparable to the variability associated with the data as well as the efficacy of the predictions of other food web model applications.

Discussion

We next used the model to quantify the relative importance of five major differences between Ellasjøen and Øyangen by replacing variables representing each of these factors in the Ellasjøen model with those from Øyangen, in separate simulations. The model predicts that the elevated PCB concentrations in Ellasjøen water and sediment account for 49%–58% of differences in modeled fish PCB concentrations between lakes. These elevated sediment and, to a lesser extent, water concentrations in Ellasjøen are due to PCB loadings from seabird guano. However, sediment–water fugacity ratios of PCBs are consistently greater in Ellasjøen compared with Øyangen, which suggests that internal lake processes also contribute to differences in sediment and water concentrations. We hypothesize that the nutrients associated with guano influence sediment–water fugacity ratios of PCBs by increasing the stock of pelagic algae. As both these algae and the guano settle, their organic carbon content is degraded faster than PCBs, which causes an extra magnification step in Ellasjøen before these detrital particles are consumed by benthic organisms, which are in turn consumed by fish. The model predicts that the remaining ～50% of the differences in PCB concentrations observed between the fish of these lakes are due to other subtle differences in their food web structures.

Conclusions

In conclusion, based on the results of a food web model, we found that the most dominant factors influencing the higher PCB fish concentrations in Lake Ellasjøen compared with Øyangen are the higher sediment and water concentrations in Ellasjøen, caused by seabird guano. Together, sediment and water are predicted to account for 49%–58% of differences in fish concentrations between lakes. Although seabird guano provides a source of nutrients to the lake, in addition to contaminants, empirical data and indirect model results suggest that nutrients are not leading to decreased bioaccumulation, in contrast to what has been observed in temperate, pelagic food webs.

Recommendations and perspectives

The results of this study emphasize the importance of considering even small differences in food web structure when comparing bioaccumulation in two lakes; although the food web structures of Ellasjøen and Øyangen differ only slightly, the model predicts that these differences account for most of the remaining ～50% of the differences in PCB fish concentrations between the two lakes. This study further demonstrates the utility of food web models as we were able to predict and tease apart the influence of various factors responsible for the elevated concentrations in the fish from Lake Ellasjøen, which would have been difficult using the field data alone.     

湖岸缓冲带反硝化作用的研究进展

反硝化作用是湖岸缓冲带去除硝酸盐的重要途径。湖岸缓冲带是联系陆地与湖泊生态系的纽带,不仅为许多动植物提供适宜生境,而且通过反硝化作用能去除地下水中的硝酸盐,提高湖泊水质。概述不同检测反硝化速率的方法,并对比各种方法的优点与缺点。阐述反硝化作用的影响因素：厌氧环境、有机碳、湖岸坡度、缓冲带坡度、pH与温度、硝酸盐浓度。介绍反硝化速率模型的研究开发状况。最后,提出了目前国内外反硝化研究中存在的不足及发展方向。     

新型转式垃圾焚烧过程中脱氯脱硫机理的研究

为了探讨有机垃圾焚烧过程钙基添加剂对HCl,SO_x生成特性的影响,分别在自行设计的中空水冷转式垃圾焚烧炉和固定床加热炉中进行了一系列的实验,研究结果表明新型转式焚烧炉具有强化传热传质特性,能提高HCl、SO_x的脱除率,可抑制有害气体的生成;同时也研究了 HCl,SO₂气体同时存在时,钙基添加剂对脱氯脱硫效率的影响规律。     

Batch sorption dynamics and equilibrium for the removal of lead ions from aqueous phase using activated carbon developed from coffee residue activated with zinc chloride

Lignocellulosic materials are good precursors for the production of activated carbon. In this work, coffee residue has been used as raw material in the preparation of powder activated carbon by the method of chemical activation with zinc chloride for the sorption of Pb(II) from dilute aqueous solutions.The influence of impregnation ratio (ZnCl₂/coffee residue) on the physical and chemical properties of the prepared carbons was studied in order to optimize this parameter. The optimum experimental condition for preparing predominantly microporous activated carbons with high pore surface area (890 m²/g) and micropore volume (0.772 cm³/g) is an impregnation ratio of 100%. The developed activated carbon shows substantial capability to sorb lead(II) ions from aqueous solutions and for relative impregnation ratios of 75 and 100%, the maximum uptake is practically the same. Thus, 75% represents the optimal impregnation ratio.Batch experiments were conducted to study the effects of the main parameters such as contact time, initial concentration of Pb(II), solution pH, ionic strength and temperature. The maximum uptake of lead(II) at 25 °C was about 63 mg/g of adsorbent at pH 5.8, initial Pb(II) concentration of 10 mg/L, agitation speed of 200 rpm and ionic strength of 0.005 M. The kinetic data were fitted to the models of pseudo-first order and pseudo-second order, and follow closely the pseudo-second order model. Equilibrium sorption isotherms of Pb(II) were analyzed by the Langmuir, Freundlich and Temkin isotherm models. The Freundlich model gives a better fit than the others.Results from this study suggest that activated carbon produced from coffee residue is an effective adsorbent for the removal of lead from aqueous solutions and that ZnCl₂ is a suitable activating agent for the preparation of high-porosity carbons.     

Population dynamics and the economics of invasive species management: the greenhouse whitefly in California-grown strawberries

In agriculture, relatively few efficacious control measures may be available for an invasive pest. In the case of a new insect pest, insecticide use decisions are affected by regulations associated with its registration, insect population dynamics, and seasonal market price cycles. We assess the costs and benefits of environmental regulations designed to regulate insecticide applications on an invasive species. We construct a bioeconomic model, based on detailed scientific data, of management decisions for a specific invasion: greenhouse whiteflies in California-grown strawberries. The empirical model integrates whitefly population dynamics, the effect of whitefly feeding on strawberry yields, and weekly strawberry price. We use the model to assess the optimality of alternative treatment programs on a simulated greenhouse whitefly population. Our results show that regulations may lead growers to "under-spray" when placed in an economic context, and provide some general lessons about the design of optimal invasive species control policies.     

Teachers' conceptions of nature and environment in 16 countries

By using an original framework involving complementary statistical approaches, we investigated the environmental attitudes of 6379 pre-service and in-service teachers in 16 countries of Europe and its neighbourhood. To test hypotheses about the nature of environmental attitudes, we examined the variation across groups of individuals (between-class analysis), investigated the independent effects of several candidate explanatory factors (orthogonal analysis), and finally inspected potential relationships between conceptions on a variety of topics (co-inertia analysis).     

Removal of Pb(II) ions from aqueous solution using activated tea waste: Adsorption on a fixed-bed column

An inexpensive and effective adsorbent was developed from waste tea leaves for the dynamic uptake of Pb(II). Characterization of the adsorbents showed a clear change between physico-chemical properties of activated tea waste and simply tea waste. The purpose of this work was to evaluate the potential of activated tea waste in continuous flow removal of Pb(II) ions from synthetic aqueous effluents. The performance of the system was evaluated to assess the effect of various process variables, viz., of bed height, hydraulic loading rate and initial feed concentration on breakthrough time and adsorption capacity. The shape of the breakthrough curves was determined for the adsorption of Pb(II) by varying different operating parameters like hydraulic loading rate (2.3–9.17 m³/h m²), bed height (0.3–0.5 m) and feed concentration (2–10 mg/l). An attempt has also been made to model the data generated from column studies using the empirical relationship based on the Bohart–Adams model. There was an acceptable degree of agreement between the data for breakthrough time calculated from the Bohart–Adams model and the present experimental study with average absolute deviation of less than 5.0%. The activated tea waste in this study showed very good promise as compared with the other adsorbents available in the literature. The adsorbent could be suitable for repeated use (for more than four cycles) without noticeable loss of capacity.     

The whole relationship between environmental variables and firm performance: Competitive advantage and firm resources as mediator variables

The examination of the possible direct link between environmental protection and firm performance in the literature has generally produced mixed results. The present paper contributes to the literature by using the resource-based view as a mediating process in this relationship. The study specifically tests whether or not the resource-based view of the firm mediates the positive relationships of proactive environmental management and improved environmental performance with competitive advantage, which also has consequences for financial performance. We also check the possible link between the adoption of a pioneering approach and good environmental management practices. Our findings support that early investment timing and intensity in environmental issues impact on the adoption of a proactive environmental management, which in turn helps to improve environmental performance. The findings also show that a firm's resources and competitive advantage act as mediator variables for a positive relationship between environmental protection and financial performance. This contribution is original because the present paper develops a comprehensive whole picture of this path process, which has previously only been partially discussed in the literature. In addition, this study clarifies a relevant point in the literature, namely that the effect of environmental protection on firm performance is not direct and can vary depending on the sector considered. Whereas competitive advantage in relation to costs influences financial performance in the IPPC law sector, the relevant influence in the hotel sector comes from competitive advantage through differentiation.     

How good is GLASOD?

The Global Assessment of Soil Degradation (GLASOD) has been the most influential global appraisal of land quality in terms of environmental policy. However, its expert judgments were never tested for their consistency and could not be reproduced at unvisited sites, while the relationship between the GLASOD assessments of land degradation and the social and economic impact of that degradation remains unclear. Yet, other methodologies that could respond to urgent calls for an updated assessment of the global environmental quality are not operational or, at best, in progress. Therefore, we evaluate the reliability and social relevance of the GLASOD approach and assess its candidacy for new global environmental assessments. The study concentrates on the African continent, capitalizing on new GIS data to delineate and define the characteristics of GLASOD map units. Consistency is tested by comparing expert judgments on soil degradation hazard for similar combinations of biophysical conditions and land use. Reproducibility is evaluated by estimating an ordered logit model that relates the qualitative land degradation classes to easily available information on explanatory variables, the results of which can be used to assess the land degradation at unvisited sites. Finally, a cross-sectional analysis investigates the relation between GLASOD assessments and crop production data at sub-national scale and its association with the prevalence of malnutrition. The GLASOD assessments prove to be only moderately consistent and hardly reproducible, while the counter-intuitive trend with crop production reveals the complexity of the production-degradation relationship. It appears that increasing prevalence of malnutrition coincides with poor agro-productive conditions and highly degraded land. The GLASOD approach can be improved by resolving the differences in conceptualization among experts and by defining the boundaries of the ordered classes in the same units as independent, quantitative land degradation data.