Bottom-up approach for the reaction of xenobiotics and their metabolites with model substances for natural organic matter by electrochemistry-mass spectrometry (EC-MS)

Risk assessment of xenobiotics requires a comprehensive understanding of their transformation in the environment. As most of the transformation processes usually involve a redox reaction or a hydrolysis as the first steps of the transformation, we applied an approach that uses an electrochemical cell to investigate model “redox” reactions in aqueous solutions for environmental processes. We investigated the degradation of a variety of xenobiotics from polar to nonpolar and analyzed their degradation products by on-line coupling of electrochemistry with mass spectrometry (EC-MS). Furthermore, we evaluated possible binding reactions with regard to the generation of non-extractable residues with some model substances (catechol, phthalic acid, γ-l-Glutamyl-l-cysteinyl-glycine (GSH) and l-histidine) deduced from a natural organic matter (NOM) structure model and identified possible binding-sites.Whereas typically investigations in soil/water-systems have been applied, we used to our knowledge for the first time a bottom-up approach, starting from the chemicals of interest and different model substances for natural organic matter to evaluate chemical binding mechanisms (or processes) in the EC-MS under redox conditions. Under oxidative conditions, bindings of the xenobiotics with catechol, GSH and histidine were found, but no reactions with the model compound phthalic acid were observed. In general, no chemical binding has yet been found under reductive conditions. In some cases (i.e. benzo[a]anthracene) the oxidation product only underwent a binding reaction, whereas the xenobiotic itself did not undergo any reactions.EC-MS is a promising fast and simple screening method to investigate the environmental behavior of xenobiotics and to evaluate the potential risks of newly synthesized substances.     

Ni adsorption and Ni-Al LDH precipitation in a sandy aquifer: an experimental and mechanistic modeling study

Mining activities and industries have created nickel (Ni) contaminations in many parts of the world. The objective of this study is to increase our understanding of Ni adsorption and Nickel-Aluminium Layered Double Hydroxide (Ni-Al LDH) precipitation to reduce Ni mobility in a sandy soil aquifer. At pH ≥7.2 both adsorption and Ni-Al LDH precipitation occurred. In batch experiments with the sandy soil up to 70% of oxalate-extractable Al was taken up in LDH formation during 56 days. In a long term column experiment 99% of influent Ni was retained at pH 7.5 due to Ni adsorption (≈34%) and Ni-Al LDH precipitation (≈66%) based on mechanistic reactive transport modeling. The subsequent leaching at pH 6.5 could be largely attributed to desorption. Our results show that even in sandy aquifers with relatively low Al content, Ni-Al LDH precipitation is a promising mechanism to immobilize Ni.     

Landfill modelling in LCA - a contribution based on empirical data

Landfills at various stages of development, depending on their age and location, can be found throughout Europe. The type of facilities goes from uncontrolled dumpsites to highly engineered facilities with leachate and gas management. In addition, some landfills are designed to receive untreated waste, while others can receive incineration residues (MSWI) or residues after mechanical biological treatment (MBT). Dimension, type and duration of the emissions from landfills depend on the quality of the disposed waste, the technical design, and the location of the landfill. Environmental impacts are produced by the leachate (heavy metals, organic loading), emissions into the air (CH(4), hydrocarbons, halogenated hydrocarbons) and from the energy or fuel requirements for the operation of the landfill (SO(2) and NO(x) from the production of electricity from fossil fuels). To include landfilling in an life-cycle assessment (LCA) approach entails several methodological questions (multi-input process, site-specific influence, time dependency). Additionally, no experiences are available with regard to mid-term behaviour (decades) for the relatively new types of landfill (MBT landfill, landfill for residues from MSWI). The present paper focuses on two main issues concerning modelling of landfills in LCA: Firstly, it is an acknowledged fact that emissions from landfills may prevail for a very long time, often thousands of years or longer. The choice of time frame in the LCA of landfilling may therefore clearly affect the results. Secondly, the reliability of results obtained through a life-cycle assessment depends on the availability and quality of Life Cycle Inventory (LCI) data. Therefore the choice of the general approach, using multi-input inventory tool versus empirical results, may also influence the results. In this paper the different approaches concerning time horizon and LCI will be introduced and discussed. In the application of empirical results, the presence of data gaps may limit the inclusion of several impact categories and therefore affect the results obtained by the study. For this reason, every effort has been made to provide high-quality empirical LCI data for landfills in Central Europe.     

Guiding principles for rewilding

There has been much recent interest in the concept of rewilding as a tool for nature conservation, but also confusion over the idea, which has limited its utility. We developed a unifying definition and 10 guiding principles for rewilding through a survey of 59 rewilding experts, a summary of key organizations’ rewilding visions, and workshops involving over 100 participants from around the world. The guiding principles convey that rewilding exits on a continuum of scale, connectivity, and level of human influence and aims to restore ecosystem structure and functions to achieve a self-sustaining autonomous nature. These principles clarify the concept of rewilding and improve its effectiveness as a tool to achieve global conservation targets, including those of the UN Decade on Ecosystem Restoration and post-2020 Global Biodiversity Framework. Finally, we suggest differences in rewilding perspectives lie largely in the extent to which it is seen as achievable and in specific interventions. An understanding of the context of rewilding projects is the key to success, and careful site-specific interpretations will help achieve the aims of rewilding.     

The toxicology of climate change: Environmental contaminants in a warming world

Climate change induced by anthropogenic warming of the earth's atmosphere is a daunting problem. This review examines one of the consequences of climate change that has only recently attracted attention: namely, the effects of climate change on the environmental distribution and toxicity of chemical pollutants. A review was undertaken of the scientific literature (original research articles, reviews, government and intergovernmental reports) focusing on the interactions of toxicants with the environmental parameters, temperature, precipitation, and salinity, as altered by climate change. Three broad classes of chemical toxicants of global significance were the focus: air pollutants, persistent organic pollutants (POPs), including some organochlorine pesticides, and other classes of pesticides. Generally, increases in temperature will enhance the toxicity of contaminants and increase concentrations of tropospheric ozone regionally, but will also likely increase rates of chemical degradation. While further research is needed, climate change coupled with air pollutant exposures may have potentially serious adverse consequences for human health in urban and polluted regions. Climate change producing alterations in: food webs, lipid dynamics, ice and snow melt, and organic carbon cycling could result in increased POP levels in water, soil, and biota. There is also compelling evidence that increasing temperatures could be deleterious to pollutant-exposed wildlife. For example, elevated water temperatures may alter the biotransformation of contaminants to more bioactive metabolites and impair homeostasis. The complex interactions between climate change and pollutants may be particularly problematic for species living at the edge of their physiological tolerance range where acclimation capacity may be limited. In addition to temperature increases, regional precipitation patterns are projected to be altered with climate change. Regions subject to decreases in precipitation may experience enhanced volatilization of POPs and pesticides to the atmosphere. Reduced precipitation will also increase air pollution in urbanized regions resulting in negative health effects, which may be exacerbated by temperature increases. Regions subject to increased precipitation will have lower levels of air pollution, but will likely experience enhanced surface deposition of airborne POPs and increased run-off of pesticides. Moreover, increases in the intensity and frequency of storm events linked to climate change could lead to more severe episodes of chemical contamination of water bodies and surrounding watersheds. Changes in salinity may affect aquatic organisms as an independent stressor as well as by altering the bioavailability and in some instances increasing the toxicity of chemicals. A paramount issue will be to identify species and populations especially vulnerable to climate–pollutant interactions, in the context of the many other physical, chemical, and biological stressors that will be altered with climate change. Moreover, it will be important to predict tipping points that might trigger or accelerate synergistic interactions between climate change and contaminant exposures.     

Sequential sorption of lead and cadmium in three tropical soils

It is important to examine mechanisms of Pb and Cd sorption in soils to understand their bioavailability. The ability of three tropical soils to retain Pb, Cd, and Ca was evaluated. The objectives of this study were to (1) determine the extent to which soil sorption sites are metal specific, (2) investigate the nature of reactions between metals and soil surfaces, and (3) identify how metals compete for sorption sites when they are introduced to soils sequentially or concurrently. Lead was shown to be much less exchangeable than Cd and inhibited Cd sorption. Cadmium had little effect on Pb sorption, though both Ca and Cd inhibited the adsorption of Pb at exchange sites. Lead appears to more readily undergo inner-sphere surface complexation with soil surface functional groups than either Cd or Ca. Thus, regardless of when Pb is introduced to a soil, it should be less labile than Cd.     

Determination of anthropogenic boundary depth in industrially polluted soil and semi-quantification of heavy metal loads using magnetic susceptibility

This study focuses on magnetic susceptibility processing and analysis towards fast and cost-efficient discrimination and semi-quantification of anthropogenic heavy metal loads in soil. Spatial variability of magnetic susceptibility was investigated on sets of soil cores from both “polluted” and “less polluted” forest soil close to a steel mill near Leoben, Austria. Test sites of ∼10 m² represent “site scale” dimensions. Statistical analysis of magnetic data provides a boundary depth indicating the transition from the “polluted” to the deeper, “unpolluted” zone in contaminated natural soil. Introduction of a block master curve simplifies the complex variations of individual curves, and represents magnetic susceptibility at “site scale”. For linking the block master curve to heavy metals we only require magnetic susceptibility data from one soil core and heavy metal data from two sub-samples from the same core. Our optimized magnetic susceptibility data processing scheme provides an applicable tool to semi-quantify anthropogenic heavy metal loads in soil.     

Evaluation of the community multiscale air quality (CMAQ) model version 4.5: Sensitivities impacting model performance; Part II—particulate matter

This paper is Part II in a pair of papers that examines the results of the Community Multiscale Air Quality (CMAQ) model version 4.5 (v4.5) and discusses the potential explanations for the model performance characteristics seen. The focus of this paper is on fine particulate matter (PM_2.5) and its chemical composition. Improvements made to the dry deposition velocity and cloud treatment in CMAQ v4.5 addressing compensating errors in 36-km simulations improved particulate sulfate (SO₄²⁻) predictions. Large overpredictions of particulate nitrate (NO₃⁻) and ammonium (NH₄⁺) in the fall are likely due to a gross overestimation of seasonal ammonia (NH₃) emissions. Carbonaceous aerosol concentrations are substantially underpredicted during the late spring and summer months, most likely due, in part, to a lack of some secondary organic aerosol (SOA) formation pathways in the model. Comparisons of CMAQ PM_2.5 predictions with observed PM_2.5 mass show mixed seasonal performance. Spring and summer show the best overall performance, while performance in the winter and fall is relatively poor, with significant overpredictions of total PM_2.5 mass in those seasons. The model biases in PM_2.5 mass cannot be explained by summing the model biases for the major inorganic ions plus carbon. Errors in the prediction of other unspeciated PM_2.5 (PM_Other) are largely to blame for the errors in total PM_2.5 mass predictions, and efforts are underway to identify the cause of these errors.     

Control of Emissions Through Efficient Use of Atmospheric Dispersion—a Forecast System

Fuel use limitations present a dilemma to both suppliers and users in that fuel with high sulfur content may be prohibited, even though during much of the year meteorological conditions may provide sufficent dispersion to maintain acceptable air quality levels. To make most efficient use of available fuels, a system of varying emissions according to atmospheric parameters is suggested. Objective forecasts of meteorological conditions in terms of dispersion effects can be used to monitor fuel use according to the atmosphere’s ability to disperse pollutants successfully.     

The Utilization of Optimum Meteorological Conditions for the Reduction of Los Angeles Automotive Pollution

Advantage can be taken of optimum conditions of turbulent mixing to decrease the intensity of automobile-caused pollution in the Los Angeles Basin. Changing the summertime peak traffic hours—delaying the morning rush by one hour—will result in an improvement of 24 percent for an eight-hour day, in terms of oxidant concentrations. Greater improvements (up to 54 percent) are possible by use of seven or six-hour days, should they be found to be economically feasible.