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Flame retardants (FRs) are commonly added to commercial products to achieve flammability resistance. Since most of them are not chemically bonded to the materials, they could be leached to the environment during the production and disposal cycle. These FRs were categorised based on their chemical nature, including brominated, organophosphorus-, mineral- and nitrogen-based. This review summarised the abiotic degradation reactions of these four classes of FRs, with a focus on thermal and photodegradation reactions in environmental and food matrices. Only 24 papers have reported related information on abiotic degradation reactions that could be useful for predicting possible degradation pathways, and most focused on brominated FRs. Most studies also investigated the thermal degradation of FRs under high temperatures (>400 °C), which exceeds the normal cooking temperature at 100–300 °C. For photodegradation, studies have used up to five times the energy typically used in UV radiation during food processing. It is recommended that future studies investigate the fate of these FRs in foods under more realistic processing conditions, to provide a more comprehensive picture of the estimated consumption of FRs and their degradation products from foods, and facilitate a better risk assessment of the use of these novel FRs. [ABSTRACT FROM AUTHOR]

The abiotic transformations of quinolones and tetracyclines facilitated by redox-active minerals has been studied extensively, however limited information is available regarding the antimicrobial activity and toxicity of their resultant transformation products. In this study, we first investigated the mechanisms underlying the transformation of two commonly used antibiotics, ciprofloxacin (CIP) and tetracycline (TC), by the ubiquitous redox soil mineral, birnessite (MnO2). Subsequently, we evaluated the impact of these transformation products on both the growth and activity of the environmental denitrifier Pseudomonas veronii. Following the reaction with birnessite, four transformation products for CIP and five for TC were identified. Remarkably, the antibacterial activity of both CIP and TC was lost upon the formation of transformation products during their interaction with birnessite. This loss of antimicrobial efficacy was associated with specific chemical transformations, such as the opening of the piperazine ring for CIP and hydroxylation and demethylation for TC. Interestingly, denitrifying activity, quantified in terms of nitrate reduction rates, remained unaffected by both CIP and TC at low concentrations that did not impact bacterial growth. However, under certain conditions, specifically at low concentrations of CIP, the second step of denitrification—nitrite reduction—was hindered, leading to the accumulation of nitrite. Our findings highlight that the transformation products induced by the mineral-mediated reactions of CIP or TC lose the initial antibacterial activity observed in the parent compounds. This research contributes valuable insights into the intricate interplay between antibiotics, redox-active minerals, and microbial activity in environmental systems. [ABSTRACT FROM AUTHOR]

As the most widely used polybrominated diphenyl ether, BDE-209 is commonly used in polymer-based commercial and household products. Due to its unique physicochemical properties, BDE-209 is ubiquitous in a variety of environmental compartments and can be exposed to organisms in various ways and cause toxic effects. The present review outlines the current state of knowledge on the occurrence of BDE-209 in the environment, influencing factors, toxicity, and degradation. BDE-209 has been detected in various environmental matrices including air, soil, water, and sediment. Additionally, environmental factors such as organic matter, total suspended particulate, hydrodynamic, wind, and temperature affecting BDE-209 are specifically discussed. Toxicity studies suggest BDE-209 may cause systemic toxic effects on living organisms, reproductive toxicity, embryo-fetal toxicity, genetic toxicity, endocrine toxicity, neurotoxicity, immunotoxicity, and developmental toxicity, or even be carcinogenic. BDE-209 has toxic effects on organisms mainly through epigenetic regulation and induction of oxidative stress. Evidence regarding the degradation of BDE-209, including biodegradation, photodegradation, Fenton degradation, zero-valent iron degradation, chemical oxidative degradation, and microwave radiation degradation is summarized. This review may contribute to assessing the environmental risks of BDE-209 to help develop rational management plans.

The literature data on the abiotic degradation of asphaltenes are the subject of a systematic review. Such degradation may proceed under natural conditions. In particular, the action of sunlight, especially, ultraviolet radiation, initiates photolysis and photooxidation in asphaltenes leading to an increase in their oxygen content, thereby shifting the hydrophilic-lipophilic balance toward hydrophilicity and increased access of the reaction products for subsequent biotic degradation by microorganisms. The action of ionizing radiation does not lead to a significant change in the molecular composition of asphaltenes since they are highly inert to radiation. An exception is found for the irradiation of asphaltenes by intense electron beams, leading to their considerable degradation. [ABSTRACT FROM AUTHOR]

Diazinon is an organophosphorus pesticide widely used to control cabbage insects, cotton aphids and underground pests. The continuous application of diazinon in agricultural activities has caused both ecological risk and biological hazards in the environment. Diazinon can be degraded via physical and chemical methods such as photocatalysis, adsorption and advanced oxidation. The microbial degradation of diazinon is found to be more effective than physicochemical methods for its complete clean-up from contaminated soil and water environments. The microbial strains belonging to Ochrobactrum sp., Stenotrophomonas sp., Lactobacillus brevis , Serratia marcescens , Aspergillus niger , Rhodotorula glutinis , and Rhodotorula rubra were found to be very promising for the ecofriendly removal of diazinon. The degradation pathways of diazinon and the fate of several metabolites were investigated. In addition, a variety of diazinon-degrading enzymes, such as hydrolase, acid phosphatase, laccase, cytochrome P450, and flavin monooxygenase were also discovered to play a crucial role in the biodegradation of diazinon. However, many unanswered questions still exist regarding the environmental fate and degradation mechanisms of this pesticide. The catalytic mechanisms responsible for enzymatic degradation remain unexplained, and ecotechnological techniques need to be applied to gain a comprehensive understanding of these issues. Hence, this review article provides in-depth information about the impact and toxicity of diazinon in living systems and discusses the developed ecotechnological remedial methods used for the effective biodegradation of diazinon in a contaminated environment. [ABSTRACT FROM AUTHOR]

Diazinon is an organophosphorus pesticide widely used to control cabbage insects, cotton aphids and underground pests. The continuous application of diazinon in agricultural activities has caused both ecological risk and biological hazards in the environment. Diazinon can be degraded via physical and chemical methods such as photocatalysis, adsorption and advanced oxidation. The microbial degradation of diazinon is found to be more effective than physicochemical methods for its complete clean-up from contaminated soil and water environments. The microbial strains belonging to Ochrobactrum sp., Stenotrophomonas sp., Lactobacillus brevis, Serratia marcescens, Aspergillus niger, Rhodotorula glutinis, and Rhodotorula rubra were found to be very promising for the ecofriendly removal of diazinon. The degradation pathways of diazinon and the fate of several metabolites were investigated. In addition, a variety of diazinon-degrading enzymes, such as hydrolase, acid phosphatase, laccase, cytochrome P450, and flavin monooxygenase were also discovered to play a crucial role in the biodegradation of diazinon. However, many unanswered questions still exist regarding the environmental fate and degradation mechanisms of this pesticide. The catalytic mechanisms responsible for enzymatic degradation remain unexplained, and ecotechnological techniques need to be applied to gain a comprehensive understanding of these issues. Hence, this review article provides in-depth information about the impact and toxicity of diazinon in living systems and discusses the developed ecotechnological remedial methods used for the effective biodegradation of diazinon in a contaminated environment.

Fipronil is a broad-spectrum phenyl-pyrazole insecticide that is widely used in agriculture. However, in the environment, its residues are toxic to aquatic animals, crustaceans, bees, termites, rabbits, lizards, and humans, and it has been classified as a C carcinogen. Due to its residual environmental hazards, various effective approaches, such as adsorption, ozone oxidation, catalyst coupling, inorganic plasma degradation, and microbial degradation, have been developed. Biodegradation is deemed to be the most effective and environmentally friendly method, and several pure cultures of bacteria and fungi capable of degrading fipronil have been isolated and identified, including Streptomyces rochei, Paracoccus sp., Bacillus firmus, Bacillus thuringiensis, Bacillus spp., Stenotrophomonas acidaminiphila, and Aspergillus glaucus. The metabolic reactions of fipronil degradation appear to be the same in different bacteria and are mainly oxidation, reduction, photolysis, and hydrolysis. However, the enzymes and genes responsible for the degradation are somewhat different. The ligninolytic enzyme MnP, the cytochrome P450 enzyme, and esterase play key roles in different strains of bacteria and fungal. Many unanswered questions exist regarding the environmental fate and degradation mechanisms of this pesticide. The genes and enzymes responsible for biodegradation remain largely unexplained, and biomolecular techniques need to be applied in order to gain a comprehensive understanding of these issues. In this review, we summarize the literature on the degradation of fipronil, focusing on biodegradation pathways and identifying the main knowledge gaps that currently exist in order to inform future research. Key points: • Biodegradation is a powerful tool for the removal of fipronil. • Oxidation, reduction, photolysis, and hydrolysis play key roles in the degradation of fipronil. • Possible biochemical pathways of fipronil in the environment are described. [ABSTRACT FROM AUTHOR]

Pesticides have been used in the field of agriculture ever since their role in protection of crops from pests which include four different categories namely insects, mites, rodents and animals has been identified. Organophosphate pesticides are one of the most extensively applied insecticides in the field of agriculture such that around 40% of all the pesticides that are produced and used commercially belong to this category. The main toxicological effect of these pesticides when exposed to a living being encompasses the irremediable inhibition of the acetylcholinesterase (AChE) enzyme which is involved in the neurotransmission of signals and hence its inhibition causes impairment of the respiratory tract and neuromuscular transmission. Apart from being used as a pesticide, organophosphates have also been applied as herbicides to some extent. The residues of these highly toxic chemicals have found route into the underground water system by seeping into the ground, in rivers where the agricultural run off water is disposed, and in the air when sprayed on the crops hence posing a threat to all the living strata exposed to these chemicals in various ways which are discussed further. Many significant studies have been carried out in order to evaluate the health risks associated with these pesticides which commonly include acute neurological disorders. This review emphasizes on the toxicological effects of organophosphate pesticides and the recent methods of detection that are used to identify trace amounts of organophosphate pesticides along with strategies which are used for their degradation.

[Display omitted] As the most widely used polybrominated diphenyl ether, BDE-209 is commonly used in polymer-based commercial and household products. Due to its unique physicochemical properties, BDE-209 is ubiquitous in a variety of environmental compartments and can be exposed to organisms in various ways and cause toxic effects. The present review outlines the current state of knowledge on the occurrence of BDE-209 in the environment, influencing factors, toxicity, and degradation. BDE-209 has been detected in various environmental matrices including air, soil, water, and sediment. Additionally, environmental factors such as organic matter, total suspended particulate, hydrodynamic, wind, and temperature affecting BDE-209 are specifically discussed. Toxicity studies suggest BDE-209 may cause systemic toxic effects on living organisms, reproductive toxicity, embryo-fetal toxicity, genetic toxicity, endocrine toxicity, neurotoxicity, immunotoxicity, and developmental toxicity, or even be carcinogenic. BDE-209 has toxic effects on organisms mainly through epigenetic regulation and induction of oxidative stress. Evidence regarding the degradation of BDE-209, including biodegradation, photodegradation, Fenton degradation, zero-valent iron degradation, chemical oxidative degradation, and microwave radiation degradation is summarized. This review may contribute to assessing the environmental risks of BDE-209 to help develop rational management plans. [ABSTRACT FROM AUTHOR]

Organophosphorus pesticides (OPPs), a kind of effective insecticide, have attracted extensive attention of researchers because of the high toxicity and refractory character of their degradation products. Given the ubiquity of manganese dioxide (MnO 2) and bisulfite (HSO 3 −) in environmental media, the abiotic degradation of several typical OPPs by the MnO 2 -HSO 3 - reaction system was investigated in batch experiments. As a representative OPP, methyl parathion (MP) was chosen to be the focus of the study. The removal rate of MP was remarkably improved by adding bisulfite (HSO 3 −) to the MnO 2 single-reaction system, and the oxidation product methyl paraoxon was below the detection limit. The primary active substances generated from the reaction system were determined to be Mn(III) species by adding excess radical scavengers or complexants (methanol and pyrophosphate) to the reaction system. On the basis of the metabolic products of MP identified by liquid chromatography–high-resolution mass spectrometry (LC/HRMS) and gas chromatography–mass spectrometry (GC/MS), the transformation pathway of MP in the MnO 2 -HSO 3 - reaction system was elicited, which included the predominant processes of hydrolysis and oxidation. Furthermore, the typical OPPs with different structures were also degraded efficiently by the reaction system because of the oxidative degradation of Mn(III). This study offers significative information related to the abiotic oxidation of manganese minerals and the fate and dissipation of OPPs in the actual environment. Image 1 • HSO 3 − significantly enhanced the abiotic degradation of methyl parathion by MnO 2. • The primary active substance was determined to be Mn(III) in the MnO 2 -HSO 3 - reaction system. • Transformation pathway of MP was elicited according to the identified products. • Many OPPs with different structures were also degraded efficiently by the reaction system. [ABSTRACT FROM AUTHOR]

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Abstract Antibiotics discharged to the environment constitute a main concern for which different treatment alternatives are being studied, some of them based on antibiotics removal or inactivation using by-products with adsorbent capacity, or which can act as catalyst for photo-degradation. But a preliminary step is to determine the general characteristics and magnitude of the degradation process effectively acting on antibiotics. A specific case is that of sulfonamides (SAs), one of the antibiotic groups most widely used in veterinary medicine, and which are considered the most mobile antibiotics, causing that they are frequently detected in both surface- and ground-waters, facilitating their entry in the food chain and causing public health hazards. In this work we investigated abiotic and biotic degradation of three sulfonamides (sulfadiazine –SDZ-, sulfachloropyridazine –SCP-, and sulfamethazine –SMT-) in aqueous media. The results indicated that, in filtered milliQ water and under simulated sunlight, the degradation sequence was: SCP > SDZ ≈ SMT. Furthermore, the rate of degradation clearly increased with the raise of pH: at pH 4.0, half-lives were 1.2, 70.5 and 84.4 h for SCP, SDZ and SMT, respectively, while at pH 7.2 they were 2.3, 9.4 and 13.2 h for SCP, SMT and SDZ. The addition of a culture medium hardly caused any change in degradation rates as compared to experiments performed in milliQ water at the same pH value (7.2), suggesting that in this case sulfonamides degradation rate was not affected by the presence of some chemical elements and compounds, such as sodium, chloride and phosphate. However, the addition of bacterial suspensions extracted from a soil and from poultry manure increased the rate of degradation of these antibiotics. This increase in degradation cannot be attributed to biodegradation, since there was no degradation in the dark during the time of the experiment (72 h). This indicates that photo-degradation constitutes the main removal mechanism for SAs in aqueous media, a mechanism that in this case was favored by humic acids supplied with the extracts from soil and manure. The overall results could contribute to the understanding of the environmental fate of the three sulfonamides studied, aiding to program actions that could favor their inactivation, which is especially relevant since its dissemination can involve serious environmental and public health risks. Highlights • Photo-degradation was the main degradation process for the three sulfonamides studied. • Increased pH favored degradation under simulated sunlight in filtered milliQ water. • Soil and poultry manure extracts (bacterial suspensions) further increased photo-degradation. [ABSTRACT FROM AUTHOR]

Polyethylene (PE) is the most abundant synthetic, petroleum-based plastic materials produced globally, and one of the most resistant to biodegradation, resulting in massive accumulation in the environment. Although the microbial degradation of polyethylene has been reported, complete biodegradation of polyethylene has not been achieved, and rapid degradation of polyethylene under ambient conditions in the environment is still not feasible. Experiments reported in the literature suffer from a number of limitations, and conclusive evidence for the complete biodegradation of polyethylene by microorganisms has been elusive. These limitations include the lack of a working definition for the biodegradation of polyethylene that can lead to testable hypotheses, a non-uniform description of experimental conditions used, and variations in the type(s) of polyethylene used, leading to a profound limitation in our understanding of the processes and mechanisms involved in the microbial degradation of polyethylene. The objective of this review is to outline the challenges in polyethylene degradation experiments and clarify the parameters required to achieve polyethylene biodegradation. This review emphasizes the necessity of developing a biochemically-based definition for the biodegradation of polyethylene (and other synthetic plastics) to simplify the comparison of results of experiments focused for the microbial degradation of polyethylene.

In this study, degradation affinities of 14 antibiotics and one metabolite were determined in batch experiments. A modelling framework was applied to decrypt potential ranges of abiotic, biotic and photolytic degradation coefficients. In detail, we performed batch experiments with three different sewages in the dark at 7 °C and 22 °C. Additionally, we conducted further batch experiments with artificial irradiation and different dilutions of the sewage at 30 °C – de novo three different sewages were used. The batch experiments were initially spiked with a stock solution with 14 antibiotics and one metabolite to increase background concentrations by 1 μg L −1 for each compound. The final antibiotic concentrations were sub-inhibitory with regard to sewage bacteria. The here presented modelling framework based on the Activated Sludge Model No. 3 in combination with adsorption and desorption processes. The model was calibrated with monitored standard sewage compounds before antibiotic degradation rates were quantified. The model decrypted ranges of abiotic, biotic and photolytic degradation coefficients. In detail, six antibiotics were not abiotic degradable at 7 °C, five antibiotics not at 22 °C and only 2 antibiotics at 30 °C. Finally, nine antibiotics were not significantly biodegradable at 7 °C and 22 °C. The model determined the link between adsorption characteristics and biodegradation rates. In detail, the rate was significantly affected by the bio-solid partition coefficient and the duration until adsorption was balanced. All antibiotics and the metabolite were photolytic degradable. In general, photolytic degradation was the most efficient elimination pathway of presented antibiotics except for the given metabolite and penicillin antibiotics. [ABSTRACT FROM AUTHOR]

During recent years, carbonyl sulfide (COS), a trace gas with a similar diffusion pathway into leaves as carbon dioxide (CO), but with no known 'respiration-like' leaf source, has been discussed as a promising new approach for partitioning net ecosystem-scale CO fluxes into photosynthesis and respiration. The utility of COS for flux partitioning at the ecosystem scale critically depends on the understanding of non-leaf sources and sinks of COS. This study assessed the contribution of the soil to ecosystem-scale COS fluxes under simulated drought conditions at temperate grassland in the Central Alps. We used transparent steady-state flow-through chambers connected to a quantum cascade laser spectrometer to measure the COS and CO gas exchange between the soil surface and the atmosphere. Soils were a source of COS during the day, emissions being mainly driven by incoming solar radiation and to a lesser degree soil temperature. Soil water content had a negligible influence on soil COS exchange and thus the drought and control treatment were statistically not significantly different. Overall, daytime fluxes were large (12.5 ± 13.8 pmol m s) in their magnitude and consistently positive compared to the previous studies, which predominantly used dark chambers. Nighttime measurements revealed soil COS fluxes around zero, as did measurements with darkened soil chambers during daytime reinforcing the importance of incoming solar radiation. Our results suggest that abiotic drivers play a key role in controlling in situ soil COS fluxes of the investigated grassland. [ABSTRACT FROM AUTHOR]

Biochar is used as a new type of fertilizer in agriculture; however, its effect on the fate of fumigants in soil is not fully understood. The objective of this study was to investigate the effects of biochar on methyl isothiocyanate (MITC) degradation in soil in laboratory incubation experiments, including the effects of biochar composition, amendment rate, moisture, temperature, soil sterilization and soil type. The dissipation pathways of MITC in biochars included adsorption and chemical degradation. The adsorption of MITC by biochars was positively correlated with the specific surface area (SSA) of the biochar. Biochar with a high SSA and low H/C value (such as biochar type BC-1) reduced MITC degradation in soil substantially; following BC-1 amendment, the degradation rate was 73.9% slower than in unamended soil. The degradation of MITC was positively correlated with the H/C value of biochar, and MITC degradation in soil increased 2.2–31.1 times following amendment with biochars with higher H/C values (e.g. biochar types BC-3–6). The biochar with the lowest organic matter and low H/C value did not affect the fate of MITC in soil. Biochars affect abiotic degradation processes more than biodegradation. When soil samples had a higher water content (> 10%), higher temperature (40 °C), and lower organic matter, the addition of BC-1 biochar reduced MITC degradation substantially; and this did not change significantly when the amendment rate increased. However, BC-4 biochar accelerated MITC degradation with increasing amendment rate, increasing temperature, and decreasing soil water content. The differences in degradation rates due to soil type were minimized by amendment with BC-4, but significant differences in BC-1. The results showed that the rational use of biochar has the potential to reduce MITC emission by accelerated degradation and adsorption. [ABSTRACT FROM AUTHOR]

The aim of this paper was to study the effects of temperature and irradiance on the photodegradation state of killed phytoplankton cells. For this purpose, killed cells of the diatom Chaetoceros neogracilis RCC2022 were irradiated (photosynthetically active radiation) at 36 and 446 J · s−1 · m−2 (for the same cumulative dose of irradiation energy) and at two temperatures (7°C and 17°C). Analyses of specific lipid tracers (fatty acids and sterols) revealed that low temperatures and irradiances increased photooxidative damages of monounsaturated lipids (i.e., palmitoleic acid, cholesterol and campesterol). The high efficiency of type II photosensitized degradation processes was attributed to: (i) the relative preservation of the sensitizer (chlorophyll) at low irradiances allowing a longer production of singlet oxygen and (ii) the slow diffusion rate of singlet oxygen through membranes at low temperatures inducing more damages. Conversely, high temperatures and irradiances induced (i) a rapid degradation of the photosensitizer and a loss of singlet oxygen by diffusion outside the membranes (limiting type II photosensitized oxidation), and (ii) intense autoxidation processes degrading unsaturated cell lipids and oxidation products used as photodegradation tracers. Our results may explain the paradoxical relationship observed in situ between latitude and photodegradation state of phytoplankton cells. [ABSTRACT FROM AUTHOR]

Methyl parathion, a widely used insecticide around the world, has aroused gradually extensive concern of researchers due to its degradation product such as methyl paraoxon, with higher toxicity for mammals and more recalcitrant. Given the ubiquity of manganese dioxide (MnO 2 ) in soils and aquatic sediments, the abiotic degradation of methyl parathion by α-MnO 2 was investigated in batch experiments. It was found that methyl parathion was decomposed up to 90% by α-MnO 2 in 30 h and the removal efficiency of methyl parathion depended strongly on the loading of α-MnO 2 and pH value in the solution where the reactions followed pseudo-first-order model well. The coexisting metal ions (such as Ca 2+ , Mg 2+ and Mn 2+ ) weakened markedly the degradation of methyl parathion by α-MnO 2 . However, the effect of dissolved organic matter (HA-Na) on reaction rates presented two sides: to improve hydrolysis rate but deteriorate oxidation rate of methyl parathion. Based on the degradation products identified by gas chromatography–mass spectrometer (GC/MS) and liquid chromatography high-resolution mass spectrometer (LC/HRMS), both hydrolysis and oxidation processes were proposed to be two predominant reaction mechanisms contributing to methyl parathion degradation by α-MnO 2 . This study provided meaningful information to elucidate the abiotic dissipation of methyl parathion by manganese oxide minerals in the environment. [ABSTRACT FROM AUTHOR]

Compound-specific isotope analysis (CSIA) is a powerful tool to track contaminant fate in groundwater. However, the application of CSIA to chlorinated ethanes has received little attention so far. These compounds are toxic and prevalent groundwater contaminants of environmental concern. The high susceptibility of chlorinated ethanes like 1,1,1-trichloroethane (1,1,1-TCA) to be transformed via different competing pathways (biotic and abiotic) complicates the assessment of their fate in the subsurface. In this study, the use of a dual C–Cl isotope approach to identify the active degradation pathways of 1,1,1-TCA is evaluated for the first time in an aerobic aquifer impacted by 1,1,1-TCA and trichloroethylene (TCE) with concentrations of up to 20 mg/L and 3.4 mg/L, respectively. The reaction-specific dual carbon–chlorine (C–Cl) isotope trends determined in a recent laboratory study illustrated the potential of a dual isotope approach to identify contaminant degradation pathways of 1,1,1-TCA. Compared to the dual isotope slopes (Δδ 13 C/Δδ 37 Cl) previously determined in the laboratory for dehydrohalogenation/hydrolysis (DH/HY, 0.33 ± 0.04) and oxidation by persulfate (∞), the slope determined from field samples (0.6 ± 0.2, r 2 = 0.75) is closer to the one observed for DH/HY, pointing to DH/HY as the predominant degradation pathway of 1,1,1-TCA in the aquifer. The observed deviation could be explained by a minor contribution of additional degradation processes. This result, along with the little degradation of TCE determined from isotope measurements, confirmed that 1,1,1-TCA is the main source of the 1,1-dichlorethylene (1,1-DCE) detected in the aquifer with concentrations of up to 10 mg/L. This study demonstrates that a dual C–Cl isotope approach can strongly improve the qualitative and quantitative assessment of 1,1,1-TCA degradation processes in the field. [ABSTRACT FROM AUTHOR]

Urea is the most commonly used nitrogen fertilizer worldwide. However, depending on soil and environmental conditions, high nitrogen losses can occur due to gaseous ammonia emissions. Urease inhibitors like N -(n -butyl)thiophosphoric triamide (NBPT) reduce these losses by blocking the urease enzyme, which catalyzes urea hydrolysis. With the increasing use of NBPT its environmental fate and features of urease inhibition become increasingly important. This study aimed to further elucidate major NBPT degradation pathways and related urease inhibition in soil. This was investigated in a 14-d incubation experiment using practice-relevant application rates of NBPT and four of its metabolites N -(n -butyl)phosphoric triamide (NBPTO), diamido phosphoric acid (DAP), diamido thiophosphoric acid (DATP) and rac - N -(n -butyl)thiophosphoric diamide (NBPD), covering three postulated degradation pathways. Additionally, the urease inhibition by these compounds was determined and further investigated in 2-h tests. The latter provided dose-response curves, showing that all substances inhibited urease, with NBPTO being the most effective. Inhibition of urease in NBPT-spiked soil was also largely, but not completely, attributed to NBPTO formed within the test period. In 14-d incubation tests, all investigated compounds dissipated quickly by >90% within 6 d (NBPTO), 3 d (NBPT) and ≤1 d (DAP, DATP and NBPD). Extensive oxidation of NBPT to NBPTO and subsequent minor formation of DAP was identified as the preferred degradation pathway. Abiotic degradation processes in sterile soil corresponded to 65–90% of total degradation in microbial active soil. Furthermore, pseudo-first order dissipation kinetics were retarded in sterile soil. Urease activity, calculated as a percentage of activity in the urea-fertilized control, was lowest after about 2 d when NBPTO was spiked to soil (17.9%), followed by NBPT (35.7%), DATP (51.3%), NBPD (54.0%), and DAP (54.4%). This shows that urease inhibition depends on the interplay of NBPT and its degradation products. [Display omitted] • A completed scheme for NPBT degradation is postulated. • The soil fate and effects on urease of NBPT and four metabolites were investigated. • NBPT and its metabolites NBPTO, DATP, NBPD and DAP all inhibit urease. • One out of three postulated degradation pathways of NBPT was analytically confirmed. • Dissipation is dominated by abiotic processes and secondarily by microbial degradation. [ABSTRACT FROM AUTHOR]

It is crucial to study the presence of transformation products (TPs) of emerging contaminants that can be potentially found in the environment after biological or chemical degradation. This review focuses on the potential and shortcomings of high-resolution mass spectrometry (HRMS) to identify these TPs, with emphasis on recent developments in mass analyzers, data evaluation, and compound identification workflows and applications. Advances in HRMS technologies, including direct introduction or in-line chromatographic separation modes, ionization techniques, mass analyzers, and detection methods, have led to powerful tools to assess the molecular changes and the opening of new horizons to identify unknown molecules. Advances in HRMS pertaining to the generation of analytical data for the main methods to identify TPs, including nontargeted and targeted approaches as they are applied to elucidate the structure of TPs, are also discussed. [ABSTRACT FROM AUTHOR]

A comprehensive review of quantitative structure-activity relationships (QSAR) allowing the prediction of the fate of organic compounds in the environment from their molecular properties was done. The considered processes were water dissolution, dissociation, volatilization, retention on soils and sediments (mainly adsorption and desorption), degradation (biotic and abiotic), and absorption by plants. A total of 790 equations involving 686 structural molecular descriptors are reported to estimate 90 environmental parameters related to these processes. A significant number of equations was found for dissociation process (pKa), water dissolution or hydrophobic behavior (especially through the KOWparameter), adsorption to soils and biodegradation. A lack of QSAR was observed to estimate desorption or potential of transfer to water. Among the 686 molecular descriptors, five were found to be dominant in the 790 collected equations and the most generic ones: four quantum-chemical descriptors, the energy of the highest occupied molecular orbital (EHOMO) and the energy of the lowest unoccupied molecular orbital (ELUMO), polarizability (α) and dipole moment (μ), and one constitutional descriptor, the molecular weight. Keeping in mind that the combination of descriptors belonging to different categories (constitutional, topological, quantum-chemical) led to improve QSAR performances, these descriptors should be considered for the development of new QSAR, for further predictions of environmental parameters. This review also allows finding of the relevant QSAR equations to predict the fate of a wide diversity of compounds in the environment. [ABSTRACT FROM AUTHOR]

Elevated ultraviolet ( UV) radiation has been demonstrated to stimulate litter decomposition. Despite years of research, it is still not fully understood whether the acceleration in litter degradation is primarily attributed to abiotic photodegradation or the combined effects of abiotic photodegradation and microbial decomposition. In this study, we used meta-analysis to synthesize photodegradation studies and compared the effects of UV radiation on litter decomposition between abiotic and biotic conditions. We also conducted a microcosm experiment to assess the effects of UV radiation on litter biodegradability and microbial activity. Overall, our meta-analysis found that under abiotic photodegradation, UV radiation reduced the remaining litter mass by 1.44% (95% CI: 0.85% to 2.08%), did not affect the remaining lignin and increased the dissolved organic carbon ( DOC) concentration by 14.01% (1.49-23.67%). Under combined abiotic photodegradation and microbial decomposition, UV radiation reduced the remaining litter mass and lignin by 1.60% (0.04-3.58%) and 16.07% (9.27-24.23%), respectively, but did not alter DOC concentration. UV radiation had no significant impact on soil microbial biomass carbon ( MBC), but it reduced microbial respiration by 44.91% (2.26-78.62%) and altered the composition of the microbial community. In addition, UV radiation reduced nitrogen (N) immobilization by 19.44% (4.77-37.92%). Our microcosm experiment further indicated that DOC concentration and the amount of respired C in UV-treated litter increased with UV exposure time, suggesting that longer UV exposure resulted in greater biodegradability. Overall, our study suggested that UV exposure could increase litter biodegradability by increasing the microbial accessibility of lignin, as well as the labile carbon supply to microbes. However, the remaining litter mass was not different between the abiotic and biotic conditions, most likely because the positive effect of UV radiation on litter biodegradability was offset by its negative effect on microbial activity. Our results also suggested that UV radiation could alter the N cycle during decomposition, primarily by inhibiting N immobilization. [ABSTRACT FROM AUTHOR]

Identification of transformation products (TPs) of emerging pollutants is challenging, due to the vast number of compounds, mostly unknown, the complexity of the matrices and their often low concentrations, requiring highly selective, highly sensitive techniques. We compile background information on biotic and abiotic formation of TPs and analytical developments over the past five years. We present a database of biotic or abiotic TPs compiled from those identified in recent years. We discuss mass spectrometric (MS) techniques and workflows for target, suspect and non-target screening of TPs with emphasis on liquid chromatography coupled to MS (LC-MS). Both low- and high-resolution (HR) mass analyzers have been applied, but HR-MS is the technique of choice, due to its high confirmatory capabilities, derived from the high resolving power and the mass accuracy in MS and MS/MS modes, and the sophisticated software developed. [ABSTRACT FROM AUTHOR]

As some of the most promising alternatives to traditional non-degradable materials, photodegradable materials have advantages of environmental benignity and rapid degradation under simple conditions. In this work, nontoxic TiO 2 and cost-effective g-C 3 N 4 have been compounded in a weight of 9:1 to form a photocatalytic additive with high activity. A 25 wt% loading of this photocatalytic additive has been incorporated into the polyacrylonitrile (PAN) by centrifugal electrospinning to prepare an abiotic degradable PAN material. Our results showed that the PAN chain could be almost fully degraded within 90 h in an aqueous medium under simulated sunlight in the absence of microorganisms. Product analysis implied that degradation of the PAN chain mainly involved the breaking of –CN and C–C bonds by radicals, followed by oxidation of terminal groups to carboxyl and gradual mineralization to CO 2 and H 2 O. This design strategy may provide new insight for the production and degradation mechanism of photodegradable polymer. [Display omitted] • A PAN material can be abiotic biodegraded completely under sunlight. • The heterojunction structure of TiO 2 /g-C 3 N 4 greatly improved photocatalytic activity. • A new opinion to solve microplastic pollution in water environment is proposed. • The photodegradation mechanism of PAN is systematically analyzed. [ABSTRACT FROM AUTHOR]

Abstract: The feasibility of promoting degradation of pyrene and phenanthrene (PHE) at the surface of soil minerals is demonstrated. Samples of magnetite, birnessite, Na-montmorillonite and Cu-montmorillonite (Cu-Mt) were loaded with pyrene and PHE. While no significant degradation of the PAHs was observed on Na-montmorillonite, birnessite or magnetite, considerable degradation took place on Cu-Mt loaded with pyrene (60±2% in 24h). The initial load of pyrene affected the extent of degradation, with the highest degradation rate observed at a load of 1000μg/g clay mineral. Pyrene degradation on Cu-Mt was inhibited by grinding the loaded mineral as well as by wetting it. Loading PHE on Cu-Mt resulted in little degradation of the PAH, but when the clay mineral was loaded with pyrene and PHE together, the degradation of pyrene was enhanced as compared to its degradation in the absence of PHE. The degradation of PHE may be inhibited by its higher ionization potential which reduces its tendency to participate in electron transfer reactions. The observed difference between the two PAHs in their affinity to various sites on the mineral's surface may also contribute to the disparity in their tendency to degrade at the surface. In experiments performed on soil samples mixed with Cu-Mt and loaded with the PAHs, patterns of degradation similar to those on the mineral itself were observed, but with lower degradation rates than those on neat Cu-Mt. LC–MS analysis revealed that pyrene underwent on Cu-Mt oxidation as well as dimerization. Elemental analysis conducted by SEM–EDS, revealed that both PHE and pyrene displayed a higher affinity to the edges of the clay mineral particles than to their planar surfaces. PHE displayed a higher affinity than pyrene to Cu-Mt, both at the planar surfaces and at the edges of the particles of the clay mineral. The surface sites which displayed the highest affinity to the PAHs were not catalytically active and hence, loading Cu-Mt with a PHE and pyrene mixture resulted in saturation of the more strongly adsorbing sites with PHE and the diversion of more pyrene molecules to the catalytically active sites. [Copyright &y& Elsevier]