Showing papers in "Environmental Science and Pollution Research in 2015"

Systemic insecticides (neonicotinoids and fipronil): trends, uses, mode of action and metabolites

Abstract: Since their discovery in the late 1980s, neonicotinoid pesticides have become the most widely used class of insecticides worldwide, with large-scale applications ranging from plant protection (crops, vegetables, fruits), veterinary products, and biocides to invertebrate pest control in fish farming. In this review, we address the phenyl-pyrazole fipronil together with neonicotinoids because of similarities in their toxicity, physicochemical profiles, and presence in the environment. Neonicotinoids and fipronil currently account for approximately one third of the world insecticide market; the annual world production of the archetype neonicotinoid, imidacloprid, was estimated to be ca. 20,000 tonnes active substance in 2010. There were several reasons for the initial success of neonicotinoids and fipronil: (1) there was no known pesticide resistance in target pests, mainly because of their recent development, (2) their physicochemical properties included many advantages over previous generations of insecticides (i.e., organophosphates, carbamates, pyrethroids, etc.), and (3) they shared an assumed reduced operator and consumer risk. Due to their systemic nature, they are taken up by the roots or leaves and translocated to all parts of the plant, which, in turn, makes them effectively toxic to herbivorous insects. The toxicity persists for a variable period of time—depending on the plant, its growth stage, and the amount of pesticide applied. A wide variety of applications are available, including the most common prophylactic non-Good Agricultural Practices (GAP) application by seed coating. As a result of their extensive use and physicochemical properties, these substances can be found in all environmental compartments including soil, water, and air. Neonicotinoids and fipronil operate by disrupting neural transmission in the central nervous system of invertebrates. Neonicotinoids mimic the action of neurotransmitters, while fipronil inhibits neuronal receptors. In doing so, they continuously stimulate neurons leading ultimately to death of target invertebrates. Like virtually all insecticides, they can also have lethal and sublethal impacts on non-target organisms, including insect predators and vertebrates. Furthermore, a range of synergistic effects with other stressors have been documented. Here, we review extensively their metabolic pathways, showing how they form both compound-specific and common metabolites which can themselves be toxic. These may result in prolonged toxicity. Considering their wide commercial expansion, mode of action, the systemic properties in plants, persistence and environmental fate, coupled with limited information about the toxicity profiles of these compounds and their metabolites, neonicotinoids and fipronil may entail significant risks to the environment. A global evaluation of the potential collateral effects of their use is therefore timely. The present paper and subsequent chapters in this review of the global literature explore these risks and show a growing body of evidence that persistent, low concentrations of these insecticides pose serious risks of undesirable environmental impacts.

Environmental fate and exposure; neonicotinoids and fipronil

Abstract: Systemic insecticides are applied to plants using a wide variety of methods, ranging from foliar sprays to seed treatments and soil drenches. Neonicotinoids and fipronil are among the most widely used pesticides in the world. Their popularity is largely due to their high toxicity to invertebrates, the ease and flexibility with which they can be applied, their long persistence, and their systemic nature, which ensures that they spread to all parts of the target crop. However, these properties also increase the probability of environmental contamination and exposure of nontarget organisms. Environmental contamination occurs via a number of routes including dust generated during drilling of dressed seeds, contamination and accumulation in arable soils and soil water, runoff into waterways, and uptake of pesticides by nontarget plants via their roots or dust deposition on leaves. Persistence in soils, waterways, and nontarget plants is variable but can be prolonged; for example, the half-lives of neonicotinoids in soils can exceed 1,000 days, so they can accumulate when used repeatedly. Similarly, they can persist in woody plants for periods exceeding 1 year. Breakdown results in toxic metabolites, though concentrations of these in the environment are rarely measured. Overall, there is strong evidence that soils, waterways, and plants in agricultural environments and neighboring areas are contaminated with variable levels of neonicotinoids or fipronil mixtures and their metabolites (soil, parts per billion (ppb)-parts per million (ppm) range; water, parts per trillion (ppt)-ppb range; and plants, ppb-ppm range). This provides multiple routes for chronic (and acute in some cases) exposure of nontarget animals. For example, pollinators are exposed through direct contact with dust during drilling; consumption of pollen, nectar, or guttation drops from seed-treated crops, water, and consumption of contaminated pollen and nectar from wild flowers and trees growing near-treated crops. Studies of food stores in honeybee colonies from across the globe demonstrate that colonies are routinely and chronically exposed to neonicotinoids, fipronil, and their metabolites (generally in the 1–100 ppb range), mixed with other pesticides some of which are known to act synergistically with neonicotinoids. Other nontarget organisms, particularly those inhabiting soils, aquatic habitats, or herbivorous insects feeding on noncrop plants in farmland, will also inevitably receive exposure, although data are generally lacking for these groups. We summarize the current state of knowledge regarding the environmental fate of these compounds by outlining what is known about the chemical properties of these compounds, and placing these properties in the context of modern agricultural practices.

Effect of salinity stress on plants and its tolerance strategies: a review.

Abstract: The environmental stress is a major area of scientific concern because it constraints plant as well as crop productivity. This situation has been further worsened by anthropogenic activities. Therefore, there is a much scientific saddle on researchers to enhance crop productivity under environmental stress in order to cope with the increasing food demands. The abiotic stresses such as salinity, drought, cold, and heat negatively influence the survival, biomass production and yield of staple food crops. According to an estimate of FAO, over 6 % of the world’s land is affected by salinity. Thus, salinity stress appears to be a major constraint to plant and crop productivity. Here, we review our understanding of salinity impact on various aspects of plant metabolism and its tolerance strategies in plants.

Effects of neonicotinoids and fipronil on non-target invertebrates

Abstract: We assessed the state of knowledge regarding the effects of large-scale pollution with neonicotinoid insecticides and fipronil on non-target invertebrate species of terrestrial, freshwater and marine environments. A large section of the assessment is dedicated to the state of knowledge on sublethal effects on honeybees (Apis mellifera) because this important pollinator is the most studied non-target invertebrate species. Lepidoptera (butterflies and moths), Lumbricidae (earthworms), Apoidae sensu lato (bumblebees, solitary bees) and the section “other invertebrates” review available studies on the other terrestrial species. The sections on freshwater and marine species are rather short as little is known so far about the impact of neonicotinoid insecticides and fipronil on the diverse invertebrate fauna of these widely exposed habitats. For terrestrial and aquatic invertebrate species, the known effects of neonicotinoid pesticides and fipronil are described ranging from organismal toxicology and behavioural effects to population-level effects. For earthworms, freshwater and marine species, the relation of findings to regulatory risk assessment is described. Neonicotinoid insecticides exhibit very high toxicity to a wide range of invertebrates, particularly insects, and field-realistic exposure is likely to result in both lethal and a broad range of important sublethal impacts. There is a major knowledge gap regarding impacts on the grand majority of invertebrates, many of which perform essential roles enabling healthy ecosystem functioning. The data on the few non-target species on which field tests have been performed are limited by major flaws in the outdated test protocols. Despite large knowledge gaps and uncertainties, enough knowledge exists to conclude that existing levels of pollution with neonicotinoids and fipronil resulting from presently authorized uses frequently exceed the lowest observed adverse effect concentrations and are thus likely to have large-scale and wide ranging negative biological and ecological impacts on a wide range of non-target invertebrates in terrestrial, aquatic, marine and benthic habitats.

A review of the direct and indirect effects of neonicotinoids and fipronil on vertebrate wildlife

Abstract: Concerns over the role of pesticides affecting vertebrate wildlife populations have recently focussed on systemic products which exert broad-spectrum toxicity. Given that the neonicotinoids have become the fastest-growing class of insecticides globally, we review here 150 studies of their direct (toxic) and indirect (e.g. food chain) effects on vertebrate wildlife—mammals, birds, fish, amphibians and reptiles. We focus on two neonicotinoids, imidacloprid and clothianidin, and a third insecticide, fipronil, which also acts in the same systemic manner. Imidacloprid and fipronil were found to be toxic to many birds and most fish, respectively. All three insecticides exert sub-lethal effects, ranging from genotoxic and cytotoxic effects, and impaired immune function, to reduced growth and reproductive success, often at concentrations well below those associated with mortality. Use of imidacloprid and clothianidin as seed treatments on some crops poses risks to small birds, and ingestion of even a few treated seeds could cause mortality or reproductive impairment to sensitive bird species. In contrast, environmental concentrations of imidacloprid and clothianidin appear to be at levels below those which will cause mortality to freshwater vertebrates, although sub-lethal effects may occur. Some recorded environmental concentrations of fipronil, however, may be sufficiently high to harm fish. Indirect effects are rarely considered in risk assessment processes and there is a paucity of data, despite the potential to exert population-level effects. Our research revealed two field case studies of indirect effects. In one, reductions in invertebrate prey from both imidacloprid and fipronil uses led to impaired growth in a fish species, and in another, reductions in populations in two lizard species were linked to effects of fipronil on termite prey. Evidence presented here suggests that the systemic insecticides, neonicotinoids and fipronil, are capable of exerting direct and indirect effects on terrestrial and aquatic vertebrate wildlife, thus warranting further review of their environmental safety.

Brake wear particle emissions: a review

Abstract: Traffic-related sources have been recognized as a significant contributor of particulate matter particularly within major cities. Exhaust and non-exhaust traffic-related sources are estimated to contribute almost equally to traffic-related PM10 emissions. Non-exhaust particles can be generated either from non-exhaust sources such as brake, tyre, clutch and road surface wear or already exist in the form of deposited material at the roadside and become resuspended due to traffic-induced turbulence. Among non-exhaust sources, brake wear can be a significant particulate matter (PM) contributor, particularly within areas with high traffic density and braking frequency. Studies mention that in urban environments, brake wear can contribute up to 55 % by mass to total non-exhaust traffic-related PM10 emissions and up to 21 % by mass to total traffic-related PM10 emissions, while in freeways, this contribution is lower due to lower braking frequency. As exhaust emissions control become stricter, relative contributions of non-exhaust sources—and therefore brake wear—to traffic-related emissions will become more significant and will raise discussions on possible regulatory needs. The aim of the present literature review study is to present the state-of-the-art of the different aspects regarding PM resulting from brake wear and provide all the necessary information in terms of importance, physicochemical characteristics, emission factors and possible health effects.

The uptake and bioaccumulation of heavy metals by food plants, their effects on plants nutrients, and associated health risk: a review.

Abstract: Heavy metal contamination is a globally recognized environmental issue, threatening human life very seriously. Increasing population and high demand for food resulted in release of various contaminants into environment that finally contaminate the food chain. Edible plants are the major source of diet, and their contamination with toxic metals may result in catastrophic health hazards. Heavy metals affect the human health directly and/or indirectly; one of the indirect effects is the change in plant nutritional values. Previously, a number of review papers have been published on different aspects of heavy metal contamination. However, no related information is available about the effects of heavy metals on the nutritional status of food plants. This review paper is focused upon heavy metal sources, accumulation, transfer, health risk, and effects on protein, amino acids, carbohydrates, fats, and vitamins in plants. The literature about heavy metals in food plants shows that both leafy and nonleafy vegetables are good accumulators of heavy metals. In nonleafy vegetables, the bioaccumulation pattern was leaf > root ≈ stem > tuber. Heavy metals have strong influence on nutritional values; therefore, plants grown on metal-contaminated soil were nutrient deficient and consumption of such vegetables may lead to nutritional deficiency in the population particularly living in developing countries which are already facing the malnutrition problems.

The effect of excess copper on growth and physiology of important food crops: a review

Abstract: In recent years, copper (Cu) pollution in agricultural soils, due to arbitrary use of pesticides, fungicides, industrial effluent and wastewater irrigation, present a major concern for sustainable agrifood production especially in developing countries. The world’s major food requirement is fulfilled through agricultural food crops. The Cu-induced losses in growth and yield of food crops probably exceeds from all other causes of food safety and security threats. Here, we review the adverse effects of Cu excess on growth and yield of essential food crops. Numerous studies reported the Cu-induced growth inhibition, oxidative damage and antioxidant response in agricultural food crops such as wheat, rice, maize, sunflower and cucumber. This article also describes the toxic levels of Cu in crops that decreased plant growth and yield due to alterations in mineral nutrition, photosynthesis, enzyme activities and decrease in chlorophyll biosynthesis. The response of various crops to elevated Cu concentrations varies depending upon nature of crop and cultivars used. This review could be helpful to understand the Cu toxicity and the mechanism of its tolerance in food crops. We recommend that Cu-tolerant crops should be grown on Cu-contaminated soils in order to ameliorate the toxic effects for sustainable farming systems and to meet the food demands of the intensively increasing population.

Isotherm, kinetic, and thermodynamic studies on Hg(II) adsorption from aqueous solution by silica- multiwall carbon nanotubes

Abstract: Silica combined with 2% multiwall carbon nanotubes (SiO2-CNT) was synthesized and characterized. Its sorption efficacy was investigated for the Hg(II) removal from an aqueous solution. The effect of pH on the percentage removal by the prepared material was examined in the range from 3 to 7. The adsorption kinetics were well fitted by using a pseudo-second-order model at various initial Hg(II) concentrations with R (2) of >0.99. The experimental data were plotted using the interparticle diffusion model, which indicated that the interparticle diffusion is not the only rate-limiting step. The data is well described by the Freundlich isotherm equation. The activation energy (Ea) for adsorption was 12.7 kJ mol(-1), indicating the process is to be physisorption. Consistent with an endothermic process, an increase in the temperature resulted in increasing mercury removal with a ∆H(o) of 13.3 kJ/mol and a ∆S(o) 67.5 J/mol K. The experimental results demonstrate that the combining of silica and nanotubes is a promising alternative material, which can be used to remove the mercury from wastewaters.

Causal relationship between CO 2 emissions, real GDP, energy consumption, financial development, trade openness, and urbanization in Tunisia

Abstract: The aim of this paper is to examine the causal relationship between CO2 emissions, real GDP, energy consumption, financial development, trade openness, and urbanization in Tunisia over the period of 1971-2012. The long-run relationship is investigated by the auto-regressive distributed lag (ARDL) bounds testing approach to cointegration and error correction method (ECM). The results of the analysis reveal a positive sign for the coefficient of financial development, suggesting that the financial development in Tunisia has taken place at the expense of environmental pollution. The Tunisian case also shows a positive monotonic relationship between real GDP and CO2 emissions. This means that the results do not support the validity of environmental Kuznets curve (EKC) hypothesis. In addition, the paper explores causal relationship between the variables by using Granger causality models and it concludes that financial development plays a vital role in the Tunisian economy.

Effets des néonicotinoïdes et du fipronil sur les invertébrés

Abstract: We assessed the state of knowledge regarding the effects of large-scale pollution with neonicotinoid insecticides and fipronil on non-target invertebrate species of terrestrial, freshwater and marine environments. A large section of the assessment is dedicated to the state of knowledge on sublethal effects on honeybees (Apis mellifera) because this important pollinator is the most studied non-target invertebrate species. Lepidoptera (butterflies and moths), Lumbricidae (earthworms), Apoidae sensu lato (bumblebees, solitary bees) and the section “other invertebrates” review available studies on the other terrestrial species. The sections on freshwater and marine species are rather short as little is known so far about the impact of neonicotinoid insecticides and fipronil on the diverse invertebrate fauna of these widely exposed habitats. For terrestrial and aquatic invertebrate species, the known effects of neonicotinoid pesticides and fipronil are described ranging from organismal toxicology and behavioural effects to population-level effects. For earthworms, freshwater and marine species, the relation of findings to regulatory risk assessment is described. Neonicotinoid insecticides exhibit very high toxicity to a wide range of invertebrates, particularly insects, and field-realistic exposure is likely to result in both lethal and a broad range of important sublethal impacts. There is a major knowledge gap regarding impacts on the grand majority of invertebrates, many of which perform essential roles enabling healthy ecosystem functioning. The data on the few non-target species on which field tests have been performed are limited by major flaws in the outdated test protocols. Despite large knowledge gaps and uncertainties, enough knowledge exists to conclude that existing levels of pollution with neonicotinoids and fipronil resulting from presently authorized uses frequently exceed the lowest observed adverse effect concentrations and are thus likely to have large-scale and wide ranging negative biological and ecological impacts on a wide range of non-target invertebrates in terrestrial, aquatic, marine and benthic habitats.

Potential role of phytohormones and plant growth-promoting rhizobacteria in abiotic stresses: consequences for changing environment.

Abstract: Plants are sessile beings, so the need of mechanisms to flee from unfavorable circumstances has provided the development of unique and sophisticated responses to environmental stresses. Depending on the degree of plasticity, many morphological, cellular, anatomical, and physiological changes occur in plants in response to abiotic stress. Phytohormones are small molecules that play critical roles in regulating plant growth and development, as well as stress tolerance to promote survival and acclimatize to varying environments. To congregate the challenges of salinity, temperature extremes, and osmotic stress, plants use their genetic mechanism and different adaptive and biological approaches for survival and high production. In the present attempt, we review the potential role of different phytohormones and plant growth-promoting rhizobacteria in abiotic stresses and summarize the research progress in plant responses to abiotic stresses at physiological and molecular levels. We emphasized the regulatory circuits of abscisic acid, indole acetic acid, cytokinins, gibberellic acid, salicylic acid, brassinosteroids, jasmonates, ethylene, and triazole on exposure to abiotic stresses. Current progress is exemplified by the identification and validation of several significant genes that enhanced crop tolerance to stress in the field. These findings will make the modification of hormone biosynthetic pathways for the transgenic plant generation with augmented abiotic stress tolerance and boosting crop productivity in the coming decades possible.

Bisphenol A, nonylphenols, benzophenones, and benzotriazoles in soils, groundwater, surface water, sediments, and food: a review

Abstract: Contaminants of emerging concern (CECs) are not commonly monitored in the environment, but they can enter the environment from a variety of sources. The most worrying consequence of their wide use and environmental diffusion is the increase in the possible exposure pathways for humans. Moreover, knowledge of their behavior in the environment, toxicity, and biological effects is limited or not available for most CECs. The aim of this work is to edit the state of the art on few selected CECs having the potential to enter the soil and aquatic systems and cause adverse effects in humans, wildlife, and the environment: bisphenol A (BPA), nonylphenol (NP), benzophenones (BPs), and benzotriazole (BT). Some reviews are already available on BPA and NP, reporting about their behavior in surface water and sediments, but scarce and scattered information is available about their presence in soil and groundwater. Only a few studies are available about BPs and BT in the environment, in particular in soil and groundwater. This work summarizes the information available in the literature about the incidence and behavior of these compounds in the different environmental matrices and food. In particular, the review focuses on the physical-chemical properties, the environmental fate, the major degradation byproducts, and the environmental evidence of the selected CECs.

Risks of large-scale use of systemic insecticides to ecosystem functioning and services

Abstract: Large-scale use of the persistent and potent neonicotinoid and fipronil insecticides has raised concerns about risks to ecosystem functions provided by a wide range of species and environments affected by these insecticides. The concept of ecosystem services is widely used in decision making in the context of valuing the service potentials, benefits, and use values that well-functioning ecosystems provide to humans and the biosphere and, as an endpoint (value to be protected), in ecological risk assessment of chemicals. Neonicotinoid insecticides are frequently detected in soil and water and are also found in air, as dust particles during sowing of crops and aerosols during spraying. These environmental media provide essential resources to support biodiversity, but are known to be threatened by long-term or repeated contamination by neonicotinoids and fipronil. We review the state of knowledge regarding the potential impacts of these insecticides on ecosystem functioning and services provided by terrestrial and aquatic ecosystems including soil and freshwater functions, fisheries, biological pest control, and pollination services. Empirical studies examining the specific impacts of neonicotinoids and fipronil to ecosystem services have focused largely on the negative impacts to beneficial insect species (honeybees) and the impact on pollination service of food crops. However, here we document broader evidence of the effects on ecosystem functions regulating soil and water quality, pest control, pollination, ecosystem resilience, and community diversity. In particular, microbes, invertebrates, and fish play critical roles as decomposers, pollinators, consumers, and predators, which collectively maintain healthy communities and ecosystem integrity. Several examples in this review demonstrate evidence of the negative impacts of systemic insecticides on decomposition, nutrient cycling, soil respiration, and invertebrate populations valued by humans. Invertebrates, particularly earthworms that are important for soil processes, wild and domestic insect pollinators which are important for plant and crop production, and several freshwater taxa which are involved in aquatic nutrient cycling, were all found to be highly susceptible to lethal and sublethal effects of neonicotinoids and/or fipronil at environmentally relevant concentrations. By contrast, most microbes and fish do not appear to be as sensitive under normal exposure scenarios, though the effects on fish may be important in certain realms such as combined fish-rice farming systems and through food chain effects. We highlight the economic and cultural concerns around agriculture and aquaculture production and the role these insecticides may have in threatening food security. Overall, we recommend improved sustainable agricultural practices that restrict systemic insecticide use to maintain and support several ecosystem services that humans fundamentally depend on.

Perfluoroalkyl and polyfluoroalkyl substances in consumer products

Abstract: Perfluoroalkyl and polyfluoroalkyl substances (PFAS) are used in a wide range of products of all day life. Due to their toxicological potential, an emerging focus is directed towards their exposure to humans. This study investigated the PFAS load of consumer products in a broad perspective. Perfluoroalkyl sulfonic acids (C4, C6-C8, C10-PFSA), carboxylic acids (C4-C14-PFCA) and fluorotelomer alcohols (4:2, 6:2; 8:2 and 10:2 FTOH) were analysed in 115 random samples of consumer products including textiles (outdoor materials), carpets, cleaning and impregnating agents, leather samples, baking and sandwich papers, paper baking forms and ski waxes. PFCA and PFSA were analysed by HPLC-MS/MS, whereas FTOH were detected by GC/CI-MS. Consumer products such as cleaning agents or some baking and sandwich papers show low or negligible PFSA and PFCA contents. On the other hand, high PFAS levels were identified in ski waxes (up to about 2000 μg/kg PFOA), leather samples (up to about 200 μg/kg PFBA and 120 μg/kg PFBS), outdoor textiles (up to 19 μg/m(2) PFOA) and some other baking papers (up to 15 μg/m(2) PFOA). Moreover, some test samples like carpet and leather samples and outdoor materials exceeded the EU regulatory threshold value for PFOS (1 μg/m(2)). A diverse mixture of PFASs can be found in consumer products for all fields of daily use in varying concentrations. This study proves the importance of screening and monitoring of consumer products for PFAS loads and the necessity for an action to regulate the use of PFASs, especially PFOA, in consumer products.

Mechanisms of silicon-mediated alleviation of drought and salt stress in plants: a review.

Abstract: Drought and salinity are the main abiotic stresses limiting crop yield and quality worldwide. Improving food production in drought- and salt-prone areas is the key to meet the increasing food demands in near future. It has been widely reported that silicon (Si), a second most abundant element in soil, could reduce drought and salt stress in plants. Here, we reviewed the emerging role of Si in enhancing drought and salt tolerance in plants and highlighted the mechanisms through which Si could alleviate both drought and salt stress in plants. Silicon application increased plant growth, biomass, photosynthetic pigments, straw and grain yield, and quality under either drought or salt stress. Under both salt and drought stress, the key mechanisms evoked are nutrient elements homeostasis, modification of gas exchange attributes, osmotic adjustment, regulating the synthesis of compatible solutes, stimulation of antioxidant enzymes, and gene expression in plants. In addition, Si application decreased Na+ uptake and translocation while increased K+ uptake and translocation under salt stress. However, these mechanisms vary with plant species, genotype, growth conditions, duration of stress imposed, and so on. This review article highlights the potential for improving plant resistance to drought and salt stress by Si application and provides a theoretical basis for application of Si in saline soils and arid and semiarid regions worldwide. This review article also highlights the future research needs about the role of Si under drought stress and in saline soils.

Impact of nanoparticles on human and environment: review of toxicity factors, exposures, control strategies, and future prospects

Abstract: Nanotechnology has revolutionized the world through introduction of a unique class of materials and consumer products in many arenas. It has led to production of innovative materials and devices. Despite of their unique advantages and applications in domestic and industrial sectors, use of materials with dimensions in nanometers has raised the issue of safety for workers, consumers, and human environment. Because of their small size and other unique characteristics, nanoparticles have ability to harm human and wildlife by interacting through various mechanisms. We have reviewed the characteristics of nanoparticles which form the basis of their toxicity. This paper also reviews possible routes of exposure of nanoparticles to human body. Dermal contact, inhalation, and ingestion have been discussed in detail. As very limited data is available for long-term human exposures, there is a pressing need to develop the methods which can determine short and long-term effects of nanoparticles on human and environment. We also discuss in brief the strategies which can help to control human exposures to toxic nanoparticles. We have outlined the current status of toxicological studies dealing with nanoparticles, accomplishments, weaknesses, and future challenges.

Coal fly ash as a resource for rare earth elements.

Abstract: Rare earth elements (REE) have been recognised as critical raw materials, crucial for many clean technologies. As the gap between their global demand and supply increases, the search for their alternative resources becomes more and more important, especially for the countries which depend highly on their import. Coal fly ash (CFA), which when not utilised is considered waste, has been regarded as the possible source of many elements, including REE. Due to the increase in the energy demand, CFA production is expected to grow, making research into the use of this material a necessity. As Poland is the second biggest coal consumer in the European Union, the authors have studied different coal fly ashes from ten Polish power plants for their rare earth element content. All the fly ashes have a broadly similar distribution of rear earth elements, with light REE being dominant. Most of the samples have REE content relatively high and according to Seredin and Dai (Int J Coal Geol 94: 67–93, 2012) classification can be considered promising REE raw materials.

Selected issues related to the toxicity of ionic liquids and deep eutectic solvents--a review

Abstract: Green Chemistry plays a more and more important role in implementing rules of sustainable development to prevent environmental pollution caused by technological processes, while simultaneously increasing the production yield. Ionic liquids (ILs) and deep eutectic solvents (DESs) constitute a very broad group of substances. Apart from many imperfections, ILs and DESs have been the most promising discoveries in the world of Green Chemistry in recent years. The main advantage of ILs is their unique physicochemical properties—they are very desirable from the technological point of view, but apart from these benefits, ILs appear to be highly toxic towards organisms from different trophic levels. DES areas of usage are very spread, because they cover organic synthesis, extraction processes, electrochemistry, enzymatic reactions and many others. Moreover, DESs seem to be a less toxic alternative to ionic liquids. New possibilities of applications and future development trends are sought and presented, including such important solutions of life branches as pharmaceuticals’ production and medicine.

Impact of engineered nanoparticles on the activity, abundance, and diversity of soil microbial communities: a review.

Abstract: This report presents an exhaustive literature review of the effects of engineered nanoparticles on soil microbial communities. The toxic effects on microbial communities are highly dependent on the type of nanoparticles considered. Inorganic nanoparticles (metal and metal oxide) seem to have a greater toxic potential than organic nanoparticles (fullerenes and carbon nanotubes) on soil microorganisms. Detrimental effects of metal and metal oxide nanoparticles on microbial activity, abundance, and diversity have been demonstrated, even for very low concentrations ( 250 mg kg−1), representing a worst case scenario. Considering that most of the available literature has analyzed the impact of an acute contamination of nanoparticles using high concentrations in a single soil, several research needs have been identified, and new directions have been proposed. The effects of realistic concentrations of nanoparticles based on the concentrations predicted in modelization studies and chronic contaminations should be simulated. The influence of soil properties on the nanoparticle toxicity is still unknown and that is why it is crucial to consider the ecotoxicity of nanoparticles in a range of different soils. The identification of soil parameters controlling the bioavailability and toxicity of nanoparticles is fundamental for a better environmental risk assessment.

Worldwide integrated assessment on systemic pesticides

Abstract: In July 2009, a group of entomologists and ornithologists met at Notre Dame de Londres, a small village in the French department of Herault, as a result of an international enquiry amongst entomologists on the catastrophic decline of insects (and arthropods in general) all over Europe. They noted that a perceptible and gradual decline of insects, as part of the general impoverishment of the natural environment, had set in from the 1950s onwards. Amongstmany others, they recognized as root causes of this decline the intensification of agriculture with its accompanying loss of natural habitats and massive use of pesticides and herbicides, the manifold increase in roads and motorized traffic as well as a continent-wide nocturnal light pollution and nitrogen deposition. They equally agreed that a further degradation of the situation, a steeper decline in insect populations, had started in the decade 1990–2000. This first began inwestern Europe, followed by eastern and southern Europe, is nowadays apparent in the scarcity of insects splattered on windscreens of motorcars and squashed against their radiators and is best documented in the decline of butterflies and the global disorders amongst honey bees. They concluded that these phenomena reflected the now general collapse of Europe’s entomofauna. They also noted that the massive collapse of different species, genera and families of arthropods coincided with the severe decline of populations of different insectivorous bird species up to now considered as “common” such as swallows and starlings. On the basis of existing studies and numerous observations in the field as well as overwhelming circumstantial evidence, they came to the hypothesis that the new generation of pesticides, the persistent, systemic and neurotoxic neonicotinoids and fipronil, introduced in the early 1990s, are likely to be responsible at least in part for these declines. They, therefore, issued the Appeal of Notre Dame de Londres under the heading “No Silent Spring again” referring to Rachel Carson’s book “Silent Spring” then published almost half a century ago:

Lipids and proteins--major targets of oxidative modifications in abiotic stressed plants.

Abstract: Stress factors provoke enhanced production of reactive oxygen species (ROS) in plants. ROS that escape antioxidant-mediated scavenging/detoxification react with biomolecules such as cellular lipids and proteins and cause irreversible damage to the structure of these molecules, initiate their oxidation, and subsequently inactivate key cellular functions. The lipid- and protein-oxidation products are considered as the significant oxidative stress biomarkers in stressed plants. Also, there exists an abundance of information on the abiotic stress-mediated elevations in the generation of ROS, and the modulation of lipid and protein oxidation in abiotic stressed plants. However, the available literature reflects a wide information gap on the mechanisms underlying lipid- and protein-oxidation processes, major techniques for the determination of lipid- and protein-oxidation products, and on critical cross-talks among these aspects. Based on recent reports, this article (a) introduces ROS and highlights their relationship with abiotic stress-caused consequences in crop plants, (b) examines critically the various physiological/biochemical aspects of oxidative damage to lipids (membrane lipids) and proteins in stressed crop plants, (c) summarizes the principles of current technologies used to evaluate the extent of lipid and protein oxidation, (d) synthesizes major outcomes of studies on lipid and protein oxidation in plants under abiotic stress, and finally, (e) considers a brief cross-talk on the ROS-accrued lipid and protein oxidation, pointing to the aspects unexplored so far.

Superoxide dismutase—mentor of abiotic stress tolerance in crop plants

Abstract: Abiotic stresses impact growth, development, and productivity, and significantly limit the global agricultural productivity mainly by impairing cellular physiology/biochemistry via elevating reactive oxygen species (ROS) generation. If not metabolized, ROS (such as O2 •−, OH•, H2O2, or 1O2) exceeds the status of antioxidants and cause damage to DNA, proteins, lipids, and other macromolecules, and finally cellular metabolism arrest. Plants are endowed with a family of enzymes called superoxide dismutases (SODs) that protects cells against potential consequences caused by cytotoxic O2 •− by catalyzing its conversion to O2 and H2O2. Hence, SODs constitute the first line of defense against abiotic stress-accrued enhanced ROS and its reaction products. In the light of recent reports, the present effort: (a) overviews abiotic stresses, ROS, and their metabolism; (b) introduces and discusses SODs and their types, significance, and appraises abiotic stress-mediated modulation in plants; (c) analyzes major reports available on genetic engineering of SODs in plants; and finally, (d) highlights major aspects so far least studied in the current context. Literature appraised herein reflects clear information paucity in context with the molecular/genetic insights into the major functions (and underlying mechanisms) performed by SODs, and also with the regulation of SODs by post-translational modifications. If the previous aspects are considered in the future works, the outcome can be significant in sustainably improving plant abiotic stress tolerance and efficiently managing agricultural challenges under changing climatic conditions.

Foliar application with nano-silicon alleviates Cd toxicity in rice seedlings

Abstract: Nanofertilizers may be more effective than regular fertilizers in improving plant nutrition, enhancing nutrition use efficiency, and protecting plants from environmental stress. A hydroponic pot experiment was conducted to study the role of foliar application with 2.5 mM nano-silicon in alleviating Cd stress in rice seedlings (Oryza sativa L. cv Youyou 128) grown in solution added with or without 20 μM CdCl2. The results showed that Cd treatment decreased the growth and the contents of Mg, Fe, Zn, chlorophyll a, and glutathione (GSH), accompanied by a significant increase in Cd accumulation. However, foliar application with nano-Si improved the growth, Mg, Fe, and Zn nutrition, and the contents of chlorophyll a of the rice seedlings under Cd stress and decreased Cd accumulation and translocation of Cd from root to shoot. Cd treatment produced oxidative stress to rice seedlings indicated by a higher lipid peroxidation level (as malondialdehyde (MDA)) and higher activities of antioxidant enzymes such as superoxide dismutase (SOD), peroxidase (POD), and catalase (CAT), and a lower GSH content. However, those nano-Si-treated plants had lower MDA but higher GSH content and different antioxidant enzyme activities, indicating a higher Cd tolerance in them. The results suggested that nano-Si application alleviated Cd toxicity in rice by decreasing Cd accumulation, Cd partitioning in shoot and MDA level and by increasing content of some mineral elements (Mg, Fe, and Zn) and antioxidant capacity.

Human health risk assessment of heavy metals in tropical fish and shellfish collected from the river Buriganga, Bangladesh

Abstract: Although fish, crustacean, and shellfish are significant sources of protein, they are currently affected by rapid industrialization, resulting in increased concentrations of heavy metals. Accumulation of heavy metals (V, Cr, Mn, Ni, Cu, Zn, As, Se, Mo, Ag, Cd, Sb, Ba, and Pb) and associated human health risk were investigated in three fish species, namely Ailia coila, Gagata youssoufi, and Mastacembelus pancalus; one crustacean (prawn), Macrobrachium rosenbergii; and one Gastropoda, Indoplanorbis exustus, collected from the Buriganga River, Bangladesh. Samples were collected from the professional fishermen. Cu was the most accumulated metal in M. rosenbergii. Ni, As, Ag, and Sb were in relatively lower concentrations, whereas relatively higher accumulation of Cr, Mn, Zn, and Se were recorded. Mn, Zn, and Pb were present in higher concentrations than the guidelines of various authorities. There were significant differences in metal accumulation among different fish, prawn, or shellfish species. Target hazard quotient (THQ) and target cancer risk (TR) were calculated to estimate the non-carcinogenic and carcinogenic health risks, respectively. The THQ for individual heavy metals were below 1 suggesting no potential health risk. But combined impact, estimated by hazard index (HI), suggested health risk for M. pancalus consumption. Although consumption of fish at current accumulation level is safe but continuous and excess consumption for a life time of more than 70 years has probability of target cancer risk.

Conclusions of the Worldwide Integrated Assessment on the risks of neonicotinoids and fipronil to biodiversity and ecosystem functioning

Abstract: The side effects of the current global use of pesticides on wildlife, particularly at higher levels of biological organization: populations, communities and ecosystems, are poorly understood (Kohler and Triebskorn 2013). Here, we focus on one of the problematic groups of agrochemicals, the systemic insecticides fipronil and those of the neonicotinoid family. The increasing global reliance on the partly prophylactic use of these persistent and potent neurotoxic systemic insecticides has raised concerns about their impacts on biodiversity, ecosystem functioning and ecosystem services provided by a wide range of affected species and environments. The present scale of use, combined with the properties of these compounds, has resulted in widespread contamination of agricultural soils, freshwater resources, wetlands, non-target vegetation and estuarine and coastal marine systems, which means that many organisms inhabiting these habitats are being repeatedly and chronically expose...

EDTA enhanced plant growth, antioxidant defense system, and phytoextraction of copper by Brassica napus L

Abstract: Copper (Cu) is an essential micronutrient for normal plant growth and development, but in excess, it is also toxic to plants. The present study investigated the influence of ethylenediaminetetraacetic acid (EDTA) in enhancing Cu uptake and tolerance as well as the morphological and physiological responses of Brassica napus L. seedlings under Cu stress. Four-week-old seedlings were transferred to hydroponics containing Hoagland's nutrient solution. After 2 weeks of transplanting, three levels (0, 50, and 100 μM) of Cu were applied with or without application of 2.5 mM EDTA and plants were further grown for 8 weeks in culture media. Results showed that Cu alone significantly decreased plant growth, biomass, photosynthetic pigments, and gas exchange characteristics. Cu stress also reduced the activities of antioxidants, such as superoxide dismutase (SOD), peroxidase (POD), ascorbate peroxidase (APX), and catalase (CAT) along with protein contents. Cu toxicity increased the concentration of reactive oxygen species (ROS) as indicated by the increased production of malondialdehyde (MDA) and hydrogen peroxide (H2O2) in both leaves and roots. The application of EDTA significantly alleviated Cu-induced toxic effects in B. napus, showing remarkable improvement in all these parameters. EDTA amendment increased the activity of antioxidant enzymes by decreasing the concentrations of MDA and H2O2 both in leaves and roots of B. napus. Although, EDTA amendment with Cu significantly increased Cu uptake in roots, stems, and leaves in decreasing order of concentration but increased the growth, photosynthetic parameters, and antioxidant enzymes. These results showed that the application of EDTA can be a useful strategy for phytoextraction of Cu by B. napus from contaminated soils.

Cadmium toxicity in Maize (Zea mays L.): consequences on antioxidative systems, reactive oxygen species and cadmium accumulation.

Abstract: Increased cadmium (Cd) accumulation in soils has led to tremendous environmental problems, with pronounced effects on agricultural productivity. Present study investigated the effects of Cd stress imposed at various concentrations (0, 75, 150, 225, 300, 375 μM) on antioxidant activities, reactive oxygen species (ROS), Cd accumulation, and productivity of two maize (Zea mays L.) cultivars viz., Run Nong 35 and Wan Dan 13. Considerable variations in Cd accumulation and in behavior of antioxidants and ROS were observed under Cd stress in both maize cultivars, and such variations governed by Cd were concentration dependent. Exposure of plant to Cd stress considerably increased Cd concentration in all plant parts particularly in roots. Wan Dan 13 accumulated relatively higher Cd in root, stem, and leaves than Run Nong 35; however, in seeds, Run Nong 35 recorded higher Cd accumulation. All the Cd toxicity levels starting from 75 μM enhanced H2O2 and MDA concentrations and triggered electrolyte leakage in leaves of both cultivars, and such an increment was more in Run Nong 35. The ROS were scavenged by the enhanced activities of superoxide dismutase, peroxidase, catalase, ascorbate peroxidase, and glutathione peroxidase in response to Cd stress, and these antioxidant activities were higher in Wan Dan 13 compared with Run Nong 35 at all Cd toxicity levels. The grain yield of maize was considerably reduced particularly for Run Nong 35 under different Cd toxicity levels as compared with control. The Wan Dan 13 was better able to alleviate Cd-induced oxidative damage which was attributed to more Cd accumulation in roots and higher antioxidant activities in this cultivar, suggesting that manipulation of these antioxidants and enhancing Cd accumulation in roots may lead to improvement in Cd stress tolerance.

Does financial development reduce environmental degradation? Evidence from a panel study of 129 countries.

Abstract: The purpose of this study is to explore the effect of financial development on CO2 emission in 129 countries classified by the income level. A panel CO2 emission model using urbanisation, GDP growth, trade openness, petroleum consumption and financial development variables that are major determinants of CO2 emission was constructed for the 1980–2011 period. The results revealed that the variables are cointegrated based on the Pedroni cointegration test. The dynamic ordinary least squares (OLS) and the Granger causality test results also show that financial development can improve environmental quality in the short run and long run due to its negative effect on CO2 emission. The rest of the determinants, especially petroleum consumption, are determined to be the major source of environmental damage in most of the income group countries. Based on the results obtained, the investigated countries should provide banking loans to projects and investments that can promote energy savings, energy efficiency and renewable energy to help these countries reduce environmental damage in both the short and long run.

Occurrence and distribution of sulfonamides, tetracyclines, quinolones, macrolides, and nitrofurans in livestock manure and amended soils of Northern China

Abstract: A feasible and rapid analysis for the simultaneous determination of sulfonamides (SAs), tetracyclines (TCs), fluoroquinolones (FQs), macrolides (MACs) and nitrofurans (NFs) in livestock manure and soils was established by solid-phase extraction (SPE)-ultra-performance liquid chromatography (UPLC)-tandem mass spectrometry (MS/MS). A total of 32 manure and 17 amended soil samples from the Liaoning and Tianjin areas in Northern China were collected for analysis. The largest detected frequencies and concentrations in manure samples were those of TCs (3326.6 ± 12,302.6 μg/kg), followed by FQs (411.3 ± 1453.4 μg/kg), SAs (170.6 ± 1060.2 μg/kg), NFs (85.1 ± 158.1 μg/kg), and MACs (1.4 ± 4.8 μg/kg). In general, veterinary antibiotics (VAs) were detected with higher concentrations in swine and chicken manure than in cattle manure, reflecting the heavy usage of VAs in swine and chicken husbandry in the studied area. Furthermore, higher residues of antibiotics were found in piglet and fattening swine manure than in sow manure. In addition, TCs were the most frequently (100 %) detected antibiotics in amended soil with higher concentrations (up to 10,967.1 μg/kg) than any other VAs. The attenuation of SAs was more obvious than TCs in amended soil after fertilization, which can most likely be attributed to the stronger sorption of TCs than SAs to soil organic matter through cation exchange. This study illustrated the prevalence of TCs detected in both animal manure and fertilized agricultural soils in Northern China, which may increase the risk to human health through the food chain. Thus, TCs should be given more attention in the management of veterinary usage in livestock husbandry.