Degradation of dyes from aqueous solution by Fenton processes: a review

Several industries are using dyes as coloring agents. The effluents from these industries are increasingly becoming an environmental problem. The removal of dyes from aqueous solution has a great potential in the field of environmental engineering. This paper reviews the classification, characteristics, and problems of dyes in detail. Advantages and disadvantages of different methods used for dye removal are also analyzed. Among these methods, Fenton process-based advanced oxidation processes are an emerging prospect in the field of dye removal. Fenton processes have been classified and represented as “Fenton circle”. This paper analyzes the recent studies on Fenton processes. The studies include analyzing different configurations of reactors used for dye removal, its efficiency, and the effects of various operating parameters such as pH, catalyst concentration, H₂O₂ concentration, initial dye concentration, and temperature of Fenton processes. From the present study, it can be conclude that Fenton processes are very effective and environmentally friendly methods for dye removal.     

Photosensitised humic-like substances (HULIS) formation processes of atmospheric significance: a review

Photosensitised reactions can produce compounds that closely resemble the humic-like substances (HULIS) occurring in atmospheric aerosols. The relevant processes have been observed in the laboratory, in both gas–solid systems and the aqueous phase. They involve triplet sensitisers (such as benzophenones, anthraquinones and nitroaromatic compounds, which yield reactive triplet states after sunlight absorption) or photogenerated oxidants like ^?OH, in the presence of substrates that undergo oligomerisation reactions upon oxidation. Formation of higher molecular weight compounds, modification of the wettability properties of organic films and photoproduction of substances with humic-like fluorescence properties have been observed as a consequence of the photosensitised reactions. Ozone plays an important but still not completely clear role in gas–solid systems.     

Teratological effects of pesticides in vertebrates: a review

Abstract

In the last decades, the use and misuse of pesticides in the agriculture have increased, having a severe impact on ecosystems and their fauna. Although the various effects of pesticides on biodiversity have been already documented in several studies, to our knowledge no consistent overview of the impact of pesticides in vertebrates, both terrestrial and aquatic, is available. In this review, we try to present a concise compilation of the teratogenic effects of pesticides on the different classes of vertebrates – mammals, birds, reptiles, amphibians and fish.     

Earthworms,pesticides and sustainable agriculture: a review

The aim of this review is to generate awareness and understand the importance of earthworms in sustainable agriculture and effect of pesticides on their action. The natural resources are finite and highly prone to degradation by the misuse of land and mismanagement of soil. The world is in utter need of a healthy ecosystem that provides with fertile soil, clean water, food and other natural resources. Anthropogenic activities have led to an increased contamination of land. The intensification of industrial and agricultural practices chiefly the utilization of pesticides has in almost every way made our natural resources concave. Earthworms help in a number of tasks that support many ecosystem services that favor agrosystem sustainability but are degraded by exhaustive practices such as the use of pesticides. The present review assesses the response of earthworm toward the pesticides and also evaluates the relationship between earthworm activity and plant growth. We strictly need to refresh and rethink on the policies and norms devised by us on sustainable ecology. In an equivalent way, the natural resources should be utilized and further, essential ways for betterment of present and future livelihood should be sought.     

Environmental properties and effects of nonionic surfactant adjuvants in pesticides: a review

Little is known about the environmental fate of adjuvants after application on the agricultural land. Adjuvants constitute a broad range of substances, of which solvents and surfactants are the major types. Nonionic surfactants such as alcohol ethoxylates (AEOs) and alkylamine ethoxylates (ANEOs) are typically examples of pesticide adjuvants. In view of their chemical structure this paper outlines present knowledge on occurrence, fate and effect on the aquatic and terrestrial environment of the two adjuvants: AEOs and ANEOs.Both AEOs and ANEOs are used as technical mixtures. This implies that they are not one single compound but a whole range of compounds present in different ratios. Structurally both groups of substances have a mutual core with side chains of varying lengths. Each of these compounds besides having the overall ability to distribute between different phases also possesses some single compound behaviour. This is reflected in the parameters describing the fate e.g. distribution coefficient, leaching, run-off, adsorption to soil, degradation and effects of these substances. The adsorption behaviour of ANEOs in contrast to AEOs is particularly variable and matrix dependent due to the ability of the compound to ionise at environmentally relevant pH. Probably because the compounds exceeds high soil adsorption and are easily degradable which is reflected in the low environmental concentrations generally found in monitoring studies. The compounds generally possess low potency to both terrestrial and aquatic organisms. The major environmental problem related to these compounds is the ability to enhance the mobility of other pollutants in the soil column.     

Recent advances in selective catalytic oxidation of nitric oxide (NO-SCO) in emissions with excess oxygen: a review on catalysts and mechanisms

Environmental Science and Pollution Research - Nitric oxides (NOx, which mainly include more than 90% NO) are one of the major air pollutants leading to a series of environmental problems, such as...     

Evaluation and comparison of advanced oxidation processes for the degradation of 2,4-dichlorophenoxyacetic acid (2,4-D): a review

Environmental Science and Pollution Research - Organochlorine pesticides have generated public concern worldwide because of their toxicity to human health and the environment, even at low...     

The environmental risks of neonicotinoid pesticides: a review of the evidence post 2013

Neonicotinoid pesticides were first introduced in the mid-1990s, and since then, their use has grown rapidly. They are now the most widely used class of insecticides in the world, with the majority of applications coming from seed dressings. Neonicotinoids are water-soluble, and so can be taken up by a developing plant and can be found inside vascular tissues and foliage, providing protection against herbivorous insects. However, only approximately 5% of the neonicotinoid active ingredient is taken up by crop plants and most instead disperses into the wider environment. Since the mid-2000s, several studies raised concerns that neonicotinoids may be having a negative effect on non-target organisms, in particular on honeybees and bumblebees. In response to these studies, the European Food Safety Authority (EFSA) was commissioned to produce risk assessments for the use of clothianidin, imidacloprid and thiamethoxam and their impact on bees. These risk assessments concluded that the use of these compounds on certain flowering crops poses a high risk to bees. On the basis of these findings, the European Union adopted a partial ban on these substances in May 2013. The purpose of the present paper is to collate and summarise scientific evidence published since 2013 that investigates the impact of neonicotinoids on non-target organisms. Whilst much of the recent work has focused on the impact of neonicotinoids on bees, a growing body of evidence demonstrates that persistent, low levels of neonicotinoids can have negative impacts on a wide range of free-living organisms.     

Cyclodextrin inclusion: catalytic effects on the degradation of organophosphorus pesticides in neutral aqueous solution.

alpha-, beta and gamma-Cyclodextrins were found to have promotive inclusion-catalytic effects on the degradation of organophosphorus pesticides solubilized in neutral aqueous media. Pesticide degradations were especially accelerated in such systems as alpha-cyclodextrin plus diazinon and beta-cyclodextrin plus chloropyrifos. The above findings are in contrast with the inhibitive catalytic effects of cyclodextrins on pesticide degradations in alkaline media. Cyclodextrin catalytic effects found here were considerably affected by differences in the substitutional and hetero-cyclic properties of the aromatic rings of pesticides and also by the sizes of cyclodextrin cavities.     

Effects of the ultraviolet-B radiation (UV-B) on conifers: a review

The current knowledge on conifer responses to enhanced ultraviolet-B (UV-B) radiation is mainly based on greenhouse or growth chamber experiments of one growing season in duration. However, the biomass losses observed in greenhouses do not occur in field-grown trees in their natural habitats. Moreover, the majority of the 20 conifer species studied have been 1-year-old seedlings, and no studies have been undertaken on mature trees. Fully grown needles, with their glaucous waxy surfaces and thick epidermal cells with both soluble and wall-bound UV-B screening metabolites, are well protected against UV-B radiation. However, it is not known whether these are sufficient protectants in young emerging needles or during the early spring period of high UV-B levels reflected from snow. In order to understand all the mechanisms that result in the protection of conifer needles against UV-B radiation, future research should focus on the epidermal layer, separating the waxes, cuticle and epidermal and hypodermal cells. Parallel studies should consist of wall-bound and soluble secondary metabolite analysis, antioxidant measurements and microscopic observations.     

Exposure assessment of pesticides in a shallow groundwater of the Tagus vulnerable zone (Portugal): a multivariate statistical approach (JCA)

Purpose

To assess groundwater exposure to pesticides, in agricultural areas of ??Ribatejo?? region (Portugal), and the influence of some key factors in that exposure, field, laboratory and modelling studies were carried out.

Methods

The study was performed in maize, potato, sugar beet, tomato and vegetables agricultural areas, located in a shallow aquifer, with pesticides use and, in most cases, with irrigation practices. Pesticides used in the studied agricultural areas and having leaching potential were selected, being considered also other pesticides included in priority lists, defined in Europe. Evaluation of groundwater exposure to pesticides was carried out by successively: (1) groundwater sampling in seven campaigns over the period 2004?C2006; (2) pesticide analysis [including isolation and concentration from the groundwater samples and further determination by gas chromatography?Cmass spectrometry (GC?CMS) of 14 herbicides, four insecticides and two metabolites]; and (3) analysis and discussion of the results by applying joint correspondence analysis (JCA).

Results

From the 20 pesticides and metabolites selected for the study, 11 were found in groundwater. Pesticides and metabolites most frequently detected were atrazine, alachlor, metolachlor, desethylatrazine, ethofumesate, ??-endosulfan, metribuzine, lindane and ??-endosulfan. The results showed that groundwater exposure to pesticides is influenced by local factors??either environmental or agricultural, as precipitation, soil, geology, crops and irrigation practices. Spring and autumn were more associated with the detection of pesticides being more likely to observe mixtures of these compounds in a groundwater sample in these transition seasons.

Conclusions

This work evidences the importance of models, which evaluate pesticides environmental behaviour, namely their water contamination potential (as Mackay multicompartimental fugacity model) and, specially, groundwater contamination potential (as GUS and Bacci and Gaggi leaching indices), in pesticide selection. Moreover, it reveals the importance to adapt proper statistical methods according to level of left-censored data. Using JCA was still possible to establish relations between pesticides and their temporal trend in a case study where there were more than 80% of data censored. This study will contribute to the Tagus river basin management plan with information on the patterns of pesticide occurrence in the alluvial aquifer system.     

Degradation of atrazine by modified stepwise-Fenton's processes

The removal of atrazine (ATZ) by stepwise Fenton's processes (stepwise-FP) was studied and the system models were developed through the examination of reaction kinetics. The study compared the performance of the removal of ATZ by conventional FP with stepwise-FP, where the total dose of H(2)O(2) was split and inputted into the system at different times and/or quantities. The performance of stepwise-FP was found to be better than that of conventional FP. This was probably due to the minimization of the peak concentration of H(2)O(2) in the solution, which reduced the probability that valuable H(2)O(2) and hydroxyl radicals would be consumed in forming weaker radicals. The reaction kinetics of the decay of ATZ in stepwise-FP was found to be a two-stage process; and in each stage, fast decay followed by stagnant decay was observed. Two characterized constants (the initial decay rate and the oxidative capacity) were introduced and were found to be useful in quantifying the stepwise-FP. The models for predicting stepwise-FP with respect to different dosing times and/or asymmetrical doses were developed, and were found to be very useful for evaluating the system performance and/or for process design.     

Foliar washoff of pesticides (FWOP) model: Development and evaluation

Abstract

The Foliar Washoff of Pesticides (FWOP) Model was developed to provide an empirical simulation of pesticide washoff from plant leaf surfaces as influenced by rainfall amount. To evaluate the technique, simulations by the FWOP Model were compared to those by the foliar washoff algorithm of the Chemical, Runoff and Erosion from Agricultural Management Systems (CREAMS) Model. The two algorithms were linked individually to the Pesticide Runoff Simulator (PRS) for the comparison. Five years of test data from a Mississippi watershed were used to evaluate six insecticides (carbaryl, profenofos, methyl parathion, permethrin, phorate, and toxaphene).

Initially, the FWOP model was used to evaluate the relative impact of chemical distribution (foliage versus soil) on the subsequent foliar washoff and soil surface contributions to runoff losses. Results indicated that runoff losses were low If all of the insecticide was applied to the foliage whereas high losses occurred if applied only to the soil. When an assumed application was distributed between the plant and soil (i.e., 90% to foliage and 10% to soil), predicted runoff losses compared well with observed field data (<3% of the application rate).

Except for toxaphene, the FWOP model generally predicted less washoff and subsequent runoff losses than the CREAMS approach. Simulated toxaphene washoff losses were in good agreement with observed field data. Statistical comparisons of the two modeling approaches using the Kolmogorov‐Smirnov test showed differences in the two cumulative frequency distributions for washoff but smaller differences for runoff. Average 5‐year runoff losses, however, were greater using the CREAMS approach—by factors of 2, 3, and 3 for profenofos, methyl parathion and phorate, respectively.

Results from this study will be useful for upgrading current exposure assessment models to more accurately address foliar washoff losses of pesticides as well as for assessing the impact of foliar‐applied chemicals on environmental quality.     

Use,exposure, and environmental impacts of pesticides in Pakistan: a critical review

Environmental Science and Pollution Research - The excessive use of pesticides is posing major threats to humans and the environment. However, the environmental exposure and impact of pesticides in...     

Effects of atmospheric ammonia (NH3) on terrestrial vegetation: a review

At the global scale, among all N (nitrogen) species in the atmosphere and their deposition on to terrestrial vegetation and other receptors, NH3 (ammonia) is considered to be the foremost. The major sources for atmospheric NH3 are agricultural activities and animal feedlot operations, followed by biomass burning (including forest fires) and to a lesser extent fossil fuel combustion. Close to its sources, acute exposures to NH3 can result in visible foliar injury on vegetation. NH3 is deposited rapidly within the first 4-5 km from its source. However, NH3 is also converted in the atmosphere to fine particle NH4+ (ammonium) aerosols that are a regional scale problem. Much of our current knowledge of the effects of NH3 on higher plants is predominantly derived from studies conducted in Europe. Adverse effects on vegetation occur when the rate of foliar uptake of NH3 is greater than the rate and capacity for in vivo detoxification by the plants. Most to least sensitive plant species to NH3 are native vegetation > forests > agricultural crops. There are also a number of studies on N deposition and lichens, mosses and green algae. Direct cause and effect relationships in most of those cases (exceptions being those locations very close to point sources) are confounded by other environmental factors, particularly changes in the ambient SO2 (sulfur dioxide) concentrations. In addition to direct foliar injury, adverse effects of NH3 on higher plants include alterations in: growth and productivity, tissue content of nutrients and toxic elements, drought and frost tolerance, responses to insect pests and disease causing microorganisms (pathogens), development of beneficial root symbiotic or mycorrhizal associations and inter species competition or biodiversity. In all these cases, the joint effects of NH3 with other air pollutants such as all-pervasive O3 or increasing CO2 concentrations are poorly understood. While NH3 uptake in higher plants occurs through the shoots, NH4+ uptake occurs through the shoots, roots and through both pathways. However, NH4+ is immobile in the soil and is converted to NO3- (nitrate). In agricultural systems, additions of NO3- to the soil (initially as NH3 or NH4+) and the consequent increases in the emissions of N2O (nitrous oxide, a greenhouse gas) and leaching of NO3- into the ground and surface waters are of major environmental concern. At the ecosystem level NH3 deposition cannot be viewed alone, but in the context of total N deposition. There are a number of forest ecosystems in North America that have been subjected to N saturation and the consequent negative effects. There are also heathlands and other plant communities in Europe that have been subjected to N-induced alterations. Regulatory mitigative approaches to these problems include the use of N saturation data or the concept of critical loads. Current information suggests that a critical load of 5-10 kg ha(-1) year(-1) of total N deposition (both dry and wet deposition combined of all atmospheric N species) would protect the most vulnerable terrestrial ecosystems (heaths, bogs, cryptogams) and values of 10-20 kg ha(-1) year(-1) would protect forests, depending on soil conditions. However, to derive the best analysis, the critical load concept should be coupled to the results and consequences of N saturation.     

Oxidation of artificial sweetener sucralose by advanced oxidation processes: a review

Sucralose, a chlorinated carbohydrate, has shown its increased use as an artificial sweetener and persistently exists in wastewater treatment plant effluents and aquatic environment. This paper aims to review possible degradation of sucralose and related carbohydrates by biological, electrochemical, chemical, and advanced oxidation processes. Biodegradation of sucralose in waterworks did not occur significantly. Electrochemical oxidation of carbohydrates may be applied to seek degradation of sucralose. The kinetics of the oxidation of sucralose and the related carbohydrates by different oxidative species is compared. Free chlorine, ozone, and ferrate did not show any potential to degrade sucralose in water. Advanced oxidation processes, generating highly strong oxidizing agent hydroxyl radicals (^?OH), have demonstrated effectiveness in transforming sucralose in water. The mechanism of oxidation of sucralose by ^?OH is briefly discussed.     

Degradation of some biorecalcitrant pesticides by homogeneous and heterogeneous photocatalytic ozonation

Photo-Fenton/ozone (PhFO) and TiO2-photocatalysis/ozone (PhCO) coupled systems are used as advanced oxidation processes for the degradation of the following biorecalcitrant pesticides: alachlor, atrazine, chlorfenvinfos, diuron, isoproturon and pentachlorophenol. These organic compounds are considered Priority Hazardous Substances by the Water Framework Directive of the European Commission. The degradation process of the different pesticides, that occurs through oxidation of the organic molecules by means of their reaction with generated OH radical, follows a first and zero-order kinetics, when PhFO and PhCO are applied, respectively. These two Advanced Oxidation Processes, together with the traditional ozone+UV, have been used to investigate TOC reduction of the different pesticide aqueous solutions. The best results of pesticide mineralization are obtained when PhFO is applied; with the use of this advanced oxidation process the aqueous pesticide solutions become detoxyfied except in the case of atrazine and alachlor aqueous solutions for which no detoxification is achieved at the experimental conditions used in the work, at least after 2 and 3 h of treatment, respectively.     

Effect of organophosphorus (dimethoate) and pyrethroid (deltamethrin) pesticides on semen characteristics in rabbits

The present study was undertaken to determine the effect of chronic treatment with two sublethal doses of Dimethoate (organo-phosphorus) or Deltamethrin (pyrethroid) on body weight and semen characteristics in adult male rabbits. Pesticide treatment resulted in a decline in body weight, libido, ejaculate volume, sperm concentration and semen initial fructose; and an increase in abnormal and dead sperm and methylene blue reduction time. In this regard Dimethoate showed greater effects than Deltamethrin. The hazardous effect of these pesticides on semen quality continued during the post-treatment period, and was dose-dependent. This deleterious effect on sperm formation together with the decline in libido suggest a decrease in testosterone secretion by pesticide treatment.     

Perspectives of using fungi as bioresource for bioremediation of pesticides in the environment: a critical review

Pesticides are used for controlling the development of various pests in agricultural crops worldwide. Despite their agricultural benefits, pesticides are often considered a serious threat to the environment because of their persistent nature and the anomalies they create. Hence removal of such pesticides from the environment is a topic of interest for the researchers nowadays. During the recent years, use of biological resources to degrade or remove pesticides has emerged as a powerful tool for their in situ degradation and remediation. Fungi are among such bioresources that have been widely characterized and applied for biodegradation and bioremediation of pesticides. This review article presents the perspectives of using fungi for biodegradation and bioremediation of pesticides in liquid and soil media. This review clearly indicates that fungal isolates are an effective bioresource to degrade different pesticides including lindane, methamidophos, endosulfan, chlorpyrifos, atrazine, cypermethrin, dieldrin, methyl parathion, heptachlor, etc. However, rate of fungal degradation of pesticides depends on soil moisture content, nutrient availability, pH, temperature, oxygen level, etc. Fungal strains were found to harbor different processes including hydroxylation, demethylation, dechlorination, dioxygenation, esterification, dehydrochlorination, oxidation, etc during the biodegradation of different pesticides having varying functional groups. Moreover, the biodegradation of different pesticides was found to be mediated by involvement of different enzymes including laccase, hydrolase, peroxidase, esterase, dehydrogenase, manganese peroxidase, lignin peroxidase, etc. The recent advances in understanding the fungal biodegradation of pesticides focusing on the processes, pathways, genes/enzymes and factors affecting the biodegradation have also been presented in this review article.