Green Toxicology: a strategy for sustainable chemical and material development

Green Toxicology refers to the application of predictive toxicology in the sustainable development and production of new less harmful materials and chemicals, subsequently reducing waste and exposure. Built upon the foundation of “Green Chemistry” and “Green Engineering”, “Green Toxicology” aims to shape future manufacturing processes and safe synthesis of chemicals in terms of environmental and human health impacts. Being an integral part of Green Chemistry, the principles of Green Toxicology amplify the role of health-related aspects for the benefit of consumers and the environment, in addition to being economical for manufacturing companies. Due to the costly development and preparation of new materials and chemicals for market entry, it is no longer practical to ignore the safety and environmental status of new products during product development stages. However, this is only possible if toxicologists and chemists work together early on in the development of materials and chemicals to utilize safe design strategies and innovative in vitro and in silico tools. This paper discusses some of the most relevant aspects, advances and limitations of the emergence of Green Toxicology from the perspective of different industry and research groups. The integration of new testing methods and strategies in product development, testing and regulation stages are presented with examples of the application of in silico, omics and in vitro methods. Other tools for Green Toxicology, including the reduction of animal testing, alternative test methods, and read-across approaches are also discussed.     

Human impacts on fire occurrence: a case study of hundred years of forest fires in a dry alpine valley in Switzerland

Forest fire regimes are sensitive to alterations of climate, fuel load, and ignition sources. We investigated the impact of human activities and climate on fire occurrence in a dry continental valley of the Swiss Alps (Valais) by relating fire occurrence to population and road density, biomass removal by livestock grazing and wood harvest, temperature and precipitation in two distinct periods (1904–1955 and 1956–2006) using generalized additive modeling. This study provides evidence for the role played by humans and temperature in shaping fire occurrence. The existence of ignition sources promotes fire occurrence to a certain extent only; for example, high road density tends to be related to fewer fires. Changes in forest uses within the study region seem to be particularly important. Fire occurrence appears to have been negatively associated with livestock pasturing in the forest and wood harvesting, in particular during the period 1904–1955. This study illustrates consistently how fire occurrence has been influenced by land use and socioeconomic conditions. It also suggests that there is no straightforward linear relationship between human factors and fire occurrence.     

Impacts of interannual climate variability on past and future forest composition

Numerous analyses of the possible impacts of future climatic changes on tree species composition have been published for both lowland and high-elevation forests. Most of these studies were based on the application of forest "gap" models, and the vast majority of them considered only changes in the average of climatic parameters over time. In this study, we use a unique data set on reconstructed past climatic variations to analyse forest dynamics simulated by the forest gap model ForClim. This analysis forms the basis for a systematic exploration of the ecological effects of changing means vs. changing variability of climate on central European forests. A reconstruction of historical climate covering the last 470 years in the Swiss lowlands (ClimIndex) is extrapolated to a transect across the alpine (cold) treeline and used to simulate the influence of climate variations on the time scale of decades on forest biomass and tree species composition at both sites. While the simulation at the low-elevation site shows little sensitivity to climate variations, the results from upper subalpine forests suggest that two major dieback events would have occurred at elevations above the current but below the climatic tree line, induced by clusters of exceptionally cold summers. The results are in agreement with available dendrochronological data and with documentary evidence on massive negative impacts on flora and fauna at high elevations during these periods. We conclude that ForClim is capable of capturing the effects on tree population dynamics of climate variability at these sites as reconstructed from the ClimIndex record. A factorial design is used to address the sensitivity of ForClim to changes of the long-term averages vs. changes of the variability of monthly temperature and precipitation data. To this end, the simulated tree species composition of near-natural forests is examined along a climate gradient in Europe. The results indicate that there are three types of forest response: (1) little sensitivity to both kinds of change, (2) strong sensitivity to changes in the means, but little sensitivity to changing variability, and (3) strong sensitivity to changing variability at least in parts of the examined climate space. Half of the cases investigated fall under the third category, suggesting that emphasis should be placed on also assessing the sensitivity of ecosystems to future changes in climate variability rather than on changes of average values alone. Electronic Publication     

Modelling Change in Ground Vegetation Response to Acid and Nitrogen Pollution, Climate Change and Forest Management at in Sweden 1500–2100 a.d.

The ForSAFE model, designed for modelling biogeochemical cycles (water, acidity, base cation, nitrogen and carbon) in terrestrial ecosystems, was modified with a vegetation response module (VEG), incorporating the effects of: nitrogen pollution, acidification, soil moisture, temperature, wind chill exposure, light and shading by trees, grazing by animals, competition between plants, above ground for light and below ground for water and nutrients. The model calculates the response of number ground vegetation plant groups. The integrated model was tested and validated at integrated level II forest monitoring sites across Sweden, four have been shown here, and used to assess the effect of acidification and nitrogen pollution in relation to factors such as climate change, forest management and changing grazing pressure. The response functions have been derived from single-factor experiments and integrated through the model structure for use on whole systems. The tests with the model suggest that the ground vegetation composition is reasonably well predicted, that much research remains before the model is fully tested and operational, and that the model may serve as a tool for assessing impacts of climate change, acid rain and forest management on plant biodiversity in forested areas.     

X-ray absorption and photoelectron spectroscopy investigation of selenite reduction by Fe-bearing minerals

The long-lived radionuclide ⁷⁹Se is one of the elements of concern for the safe storage of high-level nuclear waste, since clay minerals in engineered barriers and natural aquifer sediments strongly adsorb cationic species, but to lesser extent anions like selenate (Se^VIO₄²⁻) and selenite (Se^IVO₃²⁻). Previous investigations have demonstrated, however, that Se^IV and Se^VI are reduced by surface-associated Fe^II, thereby forming insoluble Se⁰ and Fe selenides. Here we show that the mixed Fe^II/^III (hydr)oxides green rust and magnetite, and the Fe^II sulfide mackinawite reduce selenite rapidly (< 1 day) to FeSe, while the slightly slower reduction by the Fe^II carbonate siderite produces elemental Se. In the case of mackinawite, both S^−II and Fe^II surface atoms are oxidized at a ratio of one to four by producing a defective mackinawite surface. Comparison of these spectroscopic results with thermodynamic equilibrium modeling provides evidence that the nature of reduction end product in these Fe^II systems is controlled by the concentration of HSe⁻; Se⁰ forms only at lower HSe⁻ concentrations related to slower HSeO₃⁻ reduction kinetics. Even under thermodynamically unstable conditions, the initially formed Se solid phases may remain stable for longer periods since their low solubility prevents the dissolution required for a phase transformation into more stable solids. The reduction by Fe²⁺-montmorillonite is generally much slower and restricted to a pH range, where selenite is adsorbed (pH < 7), stressing the importance of a heterogeneous, surface-enhanced electron transfer reaction. Although the solids precipitated by the redox reaction are nanocrystalline, their solubility remains below 6.3 × 10^− 8 M. No evidence for aqueous metal selenide colloids nor for Se sorption to colloidal phases was found. Since Fe^II phases like the ones investigated here should be ubiquitous in the near field of nuclear waste disposals as well as in the surrounding aquifers, mobility of the fission product ⁷⁹Se may be much lower than previously assumed.