Degradation Of Parent Compound Research Articles

Nitrite leads to the formation of N-nitrosodimethylamine during sulfate radical oxidation of dimethylamine compounds

Sulfate radical (SO4•−) advanced oxidation processes (SR-AOPs) are efficient for degrading a broad spectrum of contaminants. This study demonstrates that the existence of environmentally relevant concentrations of nitrite (NO2−) can lead to the formation of N-nitrosodimethylamine (NDMA), a probable human carcinogen, when heat activated peroxydisulfate (heat/PDS) is applied to address contaminants with dimethylamine moieties, such as tetracyclines. NO2− effectively competes with tetracyclines for SO4•− at a high second-order reaction rate constant of 8.8 × 108 M−1s−1, thus suppressing the degradation. Simultaneously, SO4•− reacts with NO2− to form the nitrogen dioxide radical (NO2•) which rapidly dimerizes to a potent nitrosating agent named dinitrogen tetroxide (N2O4). N2O4, in turn, attacks the dimethylamine moiety in tetracyclines via nucleophilic substitution, contributing to the degradation of parent compounds and generating an active intermediate that quickly decomposes to NDMA, along with the release of R+ and NO3−. The released R+ can be further oxidized by SO4•− to form phenolic intermediates which combine with NO2• to generate nitrated products. When 5 μM oxytetracycline (OTC) was treated with 0.5 mM PDS in the presence of 20 μM NO2− at 60 °C, the highest formation of NDMA was 0.045 μM in 1 h. NDMA formation was also observed for other compounds with dimethylamine moieties, such as methylene blue, phenylurea herbicides, etc., with the molar yield ranging from 0.07 to 3.53 %, negatively related to the R-N bond dissociation energy of the precursors. These findings suggest that NDMA can be commonly generated when SO4•− is applied to the degradation of dimethylamine pollutants in wastewater treatment or groundwater remediation where NO2− ubiquitously exists, which may pose a serious threat to the aquatic environment.

Promotive Effects of Chloride and Sulfate on the Near-Complete Destruction of Perfluorocarboxylates (PFCAs) in Brine via Hydrogen-tuned 185-nm UV Photolysis: Mechanisms and Kinetics.

Hydrogen-tuned 185 nm vacuum ultraviolet (VUV/H2) photolysis is an emerging technology to destroy per- and polyfluoroalkyl substance (PFAS) in brine. This study discovered the promotive effects of two major brine anions, i.e., chloride and sulfate in VUV/H2 photolysis on the hydrated electron (eaq-) generation and perfluorocarboxylates (PFCAs) destruction and established a kinetics model to elucidate the promotive effects on the steady-state concentration of eaq- ([eaq-]ss). Results showed that VUV/H2 achieved near-complete defluorination of perfluorooctanoic acid (PFOA) in the presence of up to 1000 mM chloride or sulfate at pH 12. The defluorination rate constant (kdeF) of PFOA peaked with a chloride concentration at 100 mM and with a sulfate concentration at 500 mM. The promotive effects of chloride and sulfate were attributed to an enhanced generation of eaq- via their direct VUV photolysis and conversion of additionally generated hydroxyl radical to eaq- by H2, which was supported by a linear correlation between the predicted [eaq-]ss and experimentally observed kdeF. The kdeF value increased from pH 9 to 12, which was attributed to the speciation of the H·/eaq- pair. Furthermore, the VUV system achieved >95% defluorination and ≥99% parent compound degradation of a concentrated PFCAs mixture in a synthetic brine, without generating any toxic perchlorate or chlorate.

Concentration identification and endpoint-oriented health risk assessments on a broad-spectrum of organic compounds in atmospheric fine particles: A sampling experimental study in Beijing, China

Understanding the complicate chemical components in atmospheric fine particulate matter (PM2.5) helps policy makers for pollutants control track progress and identify disparities in overall health risks. However, till now, information on accurate component detection, source identification, and effect-oriented risk assessment is scarce, especially for the simultaneous analysis of a broad-spectrum of compounds. In this study, a high-throughput target method was employed to distinguish the occurrence and characteristics of 152 chemicals: phthalate esters (PAEs), organophosphate esters (OPEs), carboxylic acid esters (CAEs), nitrophenols (NPs), nitrogen heterocyclic compounds (NHCs), per- and poly-fluoroalkyl substances (PFASs), triclosan and its derivatives (TCSs), and organosulfates (OSs) in ambient PM2.5 collected from Beijing, China. Detection frequencies of 77 targeted compounds were >50 %. Total concentrations of all compounds ranged from 33.1 to 745 ng/m3. The median concentration of ∑PAEs (108 ng/m3) was the highest, followed by ∑CAEs (12.2 ng/m3) and ∑NPs (10.1 ng/m3). Organophosphate diesters (di-OPEs) and TCSs were reported for the first time in ambient PM2.5. The pollutants mainly originated from the local industrial production, release of building materials, and environmental degradation of parent compounds. Based on absorption, distribution, metabolism, excretion, and toxicity (ADMET)-oriented risk evaluations, we found that bis (2-ethylhexyl) phthalate, diisobutyl phthalate, dibutyl phthalate, and di (2-ethylhexyl) adipate have high health risks. Additionally, the high oxidative stress potential of 4-nitrocatechol and the strong blood-brain barrier penetration potential of triclosan cannot be ignored. Our study will facilitate the evaluations of specific health outcomes and mechanisms of pollutants, and suggestion of pollutants priority control to reduce human health hazards caused by atmospheric particles.

Toxicological approaches as tool to assess the effects of a mixture of photocatalytic degradation products originated from the unregulated neonicotinoid acetamiprid employing a terrestrial organism (Eisenia andrei)

Acetamiprid (ACT) has been detected in several water sources in Latin America. The presence of its degradation products in the environment is not negligible and transformation products (TPs) significantly contribute to environmental health risks. Although advanced oxidative processes are promising for the treatment of this neocotinoid, effects of these are still unknown. In this context, the effects of a mixture of photocatalytic degradation products resulting from an ACT treatment for 90 min employing TiO2/UV on cytotoxicity and oxidative stress parameters in Eisenia andrei earthworms in acute and chronic experiments using typical Latin American soil were assessed. Acute contact tests were performed (72 h) using a filter paper moistened with an ACT solution and a chronic test was performed using Oxisoil (200 g) moistened with an ACT solution for 45 days. Catalase (CAT) and glutathione-S-transferase (GST) activities, reduced glutathione (GSH) levels and cytotoxicity (cellular eleocyte and amoebocyte assessments) were investigated. Over 75 % of ACT was degraded within the first 15 min of treatment, with levels below the limit of detection after 60 min. The acute test revealed greater cytotoxic effects associated with the effluents treated for T0 and T15 min, with decreased cell density noted after 48 h of exposure, in addition to CAT induction (in all treatments) and GST induction following T0, T15 and T90 min exposures. Concerning the chronic assay, decreases in cell density (T0, T15, T60 and T90 min) and viability (T0, T60 and T90 min) were observed after 45 days, in addition to induced CAT activity following T0, T15 and T60 exposures and GST induction following the T60 min exposure. Reduced glutathione levels were unaltered, comprising the least sensitive biomarker among the investigated parameters to the treated effluent exposures. The mixture of ACT degradation products can cause toxic effects to non-target organisms, despite parent compound degradation, alerting for the need for ecotoxicological tests to prove decreased effluent toxicity, in addition to the improvement of degradation techniques.

Degradation of emerging per- and polyfluoroalkyl substances (PFAS) using an electrochemical plug flow reactor

In recent years, shorter-chain fluorinated compounds have been manufactured as alternatives to legacy per- and polyfluoroalkyl substances (PFAS) after a global ban on some long-chain PFAS. This study is the first to investigate the degradability of emerging PFAS by an electrochemical plug flow reactor (EPFR). Ten different emerging PFAS, representing classes of fluorotelomer alcohol, perfluoroalkyl ether carboxylate, polyfluoroalkyl ethersulfonic acids, perfluoroalkyl ether/polyether carboxylates, perfluoroether sulfonate, N-alkyl perfluoroalkylsulfonamido carboxylate, fluoroalkyl phosphonic acid, and perfluoro alkane sulfonamide were investigated. The process kinetics was performed. The degradation of parent compounds increased with increasing retention time (RT). At 45.2 min of RT, the degradation of parent compounds ranged between 68%−100% with a current density of 17.2 mA/cm2. A linear increase in pseudo-first order rate constants was observed for all PFAS with increasing current density from 5.7 to 28.7 mA/cm2 (R2 > 0.91). The effect of pH, natural organic matter, and bicarbonate on the degradation, defluorination, and fluorine mass balance are reported. Alkaline pH (11) caused a decrease in degradation for all PFAS. While the presence of natural organic matter (NOM) significantly decreased the degradation and defluorination processes, the presence of bicarbonate at all studied concentrations (25, 50, and 100 mg/L) did not affect the process efficiency. The defluorination reduced to 34% from 81% with 15 mg/L NOM. The unknown/undetected fluorine fraction also increased in the presence of 15 mg/L NOM indicating the formation of NOM-PFAS complexes. Additionally, C2-C8 perfluoro carboxylic acids (PFCAs), one perfluoro sulfonic acid (PFSA), two H-PFCAs, and 4:2 fluorotelomer sulfonate (FTS) were identified as degradation byproducts in suspect screening. The electrical energy per order for PFAS ranged between 1.8 and 19.4 kWh/m3. This study demonstrates that emerging types of PFAS can potentially be degraded using an EPFR with relatively low electrical energy requirements.

Organophosphate esters in soils of Beijing urban parks: Occurrence, potential sources, and probabilistic health risks

Organophosphate esters (OPEs) are an emerging contaminant widely distributed in the soil. OPEs have drawn increasing attention for their biological toxicity and possible threat to human health. This research investigated the pollution characteristics of two typical OPEs, organophosphate triesters (tri-OPEs) and organophosphate diesters (di-OPEs), in soils of 104 urban parks in Beijing. The median concentrations of Σ11tri-OPEs and Σ8di-OPEs were 157 and 17.9 ng/g dw, respectively. Tris(2-chloroisopropyl) phosphate and bis(2-ethylhexyl) phosphate were the dominant tri-OPE and di-OPE, respectively. Consumer materials (such as building insulation and decorative materials), traffic emissions, and reclaimed water irrigation may be critical sources of tri-OPEs in urban park soils. Di-OPEs mainly originated from the degradation of parent compounds and industrial applications. Machine learning models were employed to determine the influencing factors of OPEs and predict changes in their concentrations. The predicted OPEs concentrations in Beijing urban park soils in 2025 and 2030 are three times and five times those in 2018, respectively. According to probabilistic health risk assessment, non-carcinogenic and carcinogenic risks of OPEs can be negligible for children and adults. Our results could inform measures for preventing and controlling OPEs pollution in urban park soils.

Comprehensive Dissipation of Azadirachtin in Grapes and Tomatoes: The Effect of Bacillus thuringiensis and Tentative Identification of Unknown Metabolites.

Neem oil is a biopesticide normally applied together with Bacillus thuringiensis (Bt). However, neither its dissipation nor the influence of Bt has been previously evaluated. In this study, dissipation of neem oil was investigated when it was applied alone or together with Bt at 3 and 22 °C. A methodology involving solid-liquid extraction and liquid chromatography-high-resolution mass spectrometry was developed for that purpose. The method was validated obtaining recoveries from 87 to 103%, with relative standard deviations lower than 19% and limits of quantification from 5 to 10 μg/kg. Azadirachtin A (AzA) dissipation was fit to a single first order, being faster when neem oil was applied together with Bt and at 22 °C (RL50 = 12-21 days) than alone and at 3 °C (RL50 = 14-25 days). Eight related compounds were found in real samples with similar dissipation curves compared to AzA, and five unknown metabolites were identified in degraded samples, with increasing concentrations during parent compound degradation.

Photocatalytic sol-gel/P25 TiO2 coatings for water treatment: Degradation of 7 selected pharmaceuticals

The effect of different water matrices on the photocatalytic degradation of dissolved pharmaceuticals was explored. The focus was on the degradation efficiencies in wastewater effluent from a bioreactor and water effluent from a central wastewater treatment plant and comparing the results with degradation in deionized H2O. The compounds tested included: oxytetracycline, marbofloxacin, ibuprofen, diclofenac, phenytoin, ciprofloxacin, sulfamethoxazole. For the experiments performed in this study, a compact packed-bed photocatalytic reactor was used in which the hybrid TiO2 photocatalyst (sol-gel/P25) was deposited on ∼3 mm glass beads. As expected, the reactions proceed more slowly in wastewater than in deionized water, yet it is shown that removal of the compounds from the water is still possible even when other organic molecules are present. Total organic carbon measurements have shown that complete mineralization takes place albeit at slower rates than the initial degradation of parent compounds. The results show that an acidic pH can increase the reaction rates and the adsorption on the photocatalyst surface. Analyses of the degradation intermediates were performed using tandem liquid chromatography triple-quadrupole mass spectrometry system. Additionally, X-ray absorption spectroscopy was applied to get insight into the local structure of the photocatalyst before and after use. Understanding the effects that different wastewater compositions have on photocatalytic reactions will help to refine the potential applications of the technology.

Electro-Fenton treatment of a complex pharmaceutical mixture: Mineralization efficiency and biodegradability enhancement

Combination of the electro-Fenton process with a post-biological treatment could represent a cost-effective solution for application of electrochemical advanced oxidation processes. The objective of this study was to assess this treatment strategy in the case of a complex pharmaceutical mixture. First, main operating parameters ([Fe2+] and current) of the electro-Fenton process were optimized. An optimal concentration of 0.2 mM of Fe2+ was obtained for mineralization of the pharmaceutical mixture. An optimal current of 400 mA was also obtained for degradation of caffeine and 5-fluorouracil in the mixture. However, mineralization of the effluent was continuously improved when increasing the current owing to the promotion of mineralization of organic compounds at the BDD anode. Besides, energy efficiency was decreased at prolonged treatment time because of mass transport limitation. Interestingly, it was observed a strong biodegradability enhancement of the solution after short treatment times (<3 h) at 500 and 1000 mA, which can be related to the degradation of parent compounds into more biodegradable by-products. The need for an acclimation time of the biomass to the pre-treated effluent was also emphasized, most probably because of the formation of some toxic by-products as observed during acute toxicity tests. Therefore, a biological post-treatment could represent a cost-effective solution for the removal of biodegradable residual organic compounds as well as for the removal of nitrogen released from mineralization of organic compounds under the form of NO3− and NH4+ during electro-Fenton pre-treatment.

Metabolic profile and behavior of clethodim and spirotetramat in herbs during plant growth and processing under controlled conditions

Herbs may contain pesticide residues which are an important discriminator of food security and food quality. The challenge of the research was to assess the fate of the herbicide clethodim (CLE) and the insecticide spirotetramat (SPI) applied in herbs (BBCH 11-21) during herb growth and processing under controlled greenhouse trial conditions. The metabolic profile of CLE and SPI and their degradation products in basil (Ocimum basilicum L.), peppermint (Mentha × piperita L.) and sage (Salvia officinalis L.) was also presented. The half-lives of CLE and SPI in herbs were 1.10–1.56 days and 0.51–0.83 days, respectively. The terminal residues of SPI (SPI-enol, SPI-ketohydroxy, SPI-monohydroxy and SPI-enol-glucoside) and CLE (CLE-sulfone and CLE-sulfoxide) in herbal matrices were measured below EU maximum residue limits. In this paper, we aimed to assess the impact of washing and dehydratation pretreatment and calculated processing factors (PFs) which can be applied to more accurate food safety assessments. The PF values of CLE and SPI after drying prior washing was below 1 indicating reduction of initial residues. Drying process without washing demonstrated increases of SPI concentrations (PF up to 1.50). The lowest PFs were obtained when raw herbal plants were washed before drying showing almost complete degradation of parent compound (93–99%).

Functional categories of microbial toxicity resulting from three advanced oxidation process treatments during management and disposal of contaminated water

Large volumes of contaminated water are produced via intentional and unintentional incidents, including terrorist attacks, natural disasters and accidental spills. Contaminated waters could contain harmful chemicals, which present management and disposal challenges. This study investigates three Advanced Oxidation Processes (AOPs) - UV/H2O2, O3/H2O2, and electrochemical oxidation using a boron-doped diamond (BDD) anode - to treat eleven contaminants including herbicides, pesticides, pharmaceuticals, and flame retardant compounds. To address treatment and toxicity concerns, this study focuses on the resulting microbial toxicity via Microtox® toxicity and Nitrification Inhibition tests. The results suggest four functional Microtox® toxicity categories upon AOP treatment, which are useful for streamlining AOP selection for specific applications. Except for one compound, the O3/H2O2 and UV/H2O2 AOPs achieved, within experimental error, 100% parent compound degradation during 2 h of treatment for all contaminants, as well as Microtox® toxicities that declined below 10% by the end of the treatment. In addition, anodic oxidation with a BDD electrode exhibited slower degradation and some increases in Microtox® toxicity. Only one compound exhibited above 50% Nitrification Inhibition, indicating the robustness of activated sludge to many contaminated and AOP-treated waters. These results indicate that AOP pre-treatment can be a viable strategy to facilitate drain disposal of contaminated waters, but that eco-toxicity may remain a concern.

Pyrethroid pesticide metabolite, 3-PBA, in soils: method development and application to real agricultural soils.

3-Phenoxybenzoic acid (3-PBA) is a shared metabolite of several synthetic pyrethroid pesticides (SPs) resulting from environmental degradation of parent compounds and thus occurs frequently as a residue in samples. Hence, the importance of 3-PBA evaluation after pyrethroid application. There is a gap of analytical methods to determine 3-PBA in soil samples. Therefore, an analytical method that combines the solid-phase extraction (SPE) and gas chromatography-mass spectrometry (GC/MS) detection has been developed for the determination of 3-PBA in soil samples. The analytical method was validated in terms of linearity, sensitivity, intra- and inter-day batch precisions, recoveries, and quantification limits. An SPE method using a Strata X cartridge allows obtaining limits of detection and quantification equal to 4.0 and 13.3ngg-1, respectively. Under optimized conditions, the method average recovery levels ranged from 70.3 to 93.5% with a relative standard deviation below 3.4%. Method intra- and inter-day precision was under 5.0 and 4.8%, respectively. The developed method was applied to 11 agricultural soil samples in the north of Portugal. The developed methodology allowed for the determination of the pyrethroid metabolite, 3-PBA, in agricultural soil samples at levels of few ngg-1. Graphical abstract ᅟ.

Electrolyte selection and microbial toxicity for electrochemical oxidative water treatment using a boron-doped diamond anode to support site specific contamination incident response

Intentional and unintentional contamination incidents, such as terrorist attacks, natural disasters, and accidental spills, can result in large volumes of contaminated water. These waters may require pre-treatment before disposal and assurances that treated waters will not adversely impact biological processes at wastewater treatment facilities, or receiving waters. Based on recommendations of an industrial workgroup, this study addresses such concerns by studying electrochemical advanced oxidation process (EAOP) pre-treatment for contaminated waters, using a boron-doped diamond (BDD) anode, prior to discharge to wastewater treatment facilities. Reaction conditions were investigated, and microbial toxicity was assessed using the Microtox® toxicity assay and the Nitrification Inhibition test. A range of contaminants were studied including herbicides, pesticides, pharmaceuticals and flame retardants. Resulting toxicities varied with supporting electrolyte from 5% to 92%, often increasing, indicating that microbial toxicity, in addition to parent compound degradation, should be monitored during treatment. These toxicity results are particularly novel because they systematically compare the microbial toxicity effects of a variety of supporting electrolytes, indicating some electrolytes may not be appropriate in certain applications. Further, these results are the first known report of the use of the Nitrification Inhibition test for this application. Overall, these results systematically demonstrate that anodic oxidation using the BDD anode is useful for addressing water contaminated with refractory organic contaminants, while minimizing impacts to wastewater plants or receiving waters accepting EAOP-treated effluent. The results of this study indicate nitrate can be a suitable electrolyte for incident response and, more importantly, serve as a baseline for site specific EAOP usage.

English

Bacteria were isolated by enrichment culture technique from groundnut (Arachis hypogaea L.) soils and tested for their ability to degrade monocrotophos in mineral salts medium under aerobic conditions in the laboratory. Based on some of the morphological and 16S rRNA gene sequence analysis, the isolates were identified as Rhodococcus phenolicus strain MCP1 and Rhodococcus ruber strain MCP-2. The initial (0-day) recovery of monocrotophos in the culture medium was 94%; and by the end of 4th day, about 21% of added monocrotophos was lost from the uninoculated medium. By the end of 1st, 2nd, 3rd and 4th day 13, 20, 24, 30% and 18, 33, 37, 45% of monocrotophos was degraded, by R. phenolicus strain MCP1 and R. ruber strain MCP-2 respectively, when the mineral salts medium was supplemented with monocrotophos as a C source. Simultaneously 12, 22, 26, 30% and 18, 26, 37, 40% of N-methylacetoacetamide a metabolite of monocrotophos was recovered in the media inoculated with the R. phenolicus strain MCP1 and R. ruber strain MCP-2 respectively, during the same period. Decrease in the amount of monocrotophos with a concomitant increase in the level of N-methylacetoacetamide clearly indicates the degradation of parent compound. Key words: Monocrotophos; N-methylacetoacetamide, biodegradation; isolation, identification.

Effects of Polycyclic Aromatic Hydrocarbon Mixtures on Degradation, Gene Expression, and Metabolite Production in Four Mycobacterium Species.

Polycyclic aromatic hydrocarbons (PAHs) are widespread environmental contaminants that are hazardous to human health. It has been demonstrated that members of the Mycobacterium genus are among the most effective degraders of PAHs, but few studies have focused on the degradation of PAH mixtures. In this study, single and mixed PAH metabolism was investigated in four phylogenetically distinct Mycobacterium species with respect to (i) parent compound degradation, (ii) bacterial growth, (iii) catabolic gene expression, and (iv) metabolite production. Synergistic and antagonistic effects on four model PAH compounds (benzo[a]pyrene, pyrene, fluoranthene, and phenanthrene) characterized degradation of mixtures in a strain- and mixture-dependent manner. The mixture of pyrene and phenanthrene, in particular, resulted in antagonized degradation by three out of four bacterial species, and further studies were narrowed to investigate the degradation of this mixture. Antagonistic effects persisted over time and were correlated with reduced bacterial growth. Antagonized degradation of PAH was not caused by preferential degradation of secondary PAHs, nor were mixture compounds or concentrations toxic to cells growing on sugars. Reverse transcription-PCR (RT-PCR) studies of the characterized catabolic pathway of phenanthrene showed that in one organism, antagonism of mixture degradation was associated with downregulated gene expression. Metabolite profiling revealed that antagonism in mixture degradation was associated with the shunting of substrate through alternative pathways not used during the degradation of single PAHs. The results of this study demonstrate metabolic differences between single and mixed PAH degradation with consequences for risk assessment and bioremediation of PAH-contaminated sites. Mycobacterium species are promising organisms for environmental bioremediation because of their ubiquitous presence in soils and their ability to catabolize aromatic compounds. PAHs can be degraded effectively as single compounds, but mixed substrates often are subject to degradative inhibition, which may explain the persistence of these pollutants in soils. Single and mixed PAH degradation by diverse Mycobacterium species was compared, with associated bacterial growth, gene expression, and metabolite production. The results demonstrate that antagonism characterized degradation in a strain- and mixture-dependent manner. One strain that was versatile in its pathway use of single chemicals also efficiently degraded the mixture, whereas antagonism in other the strains was associated with altered metabolic profiles, indicating unusual pathway use. The impacts of this work on risk assessment and bioremediation modeling studies indicate the need to account for mixture-generated intermediates and to recognize mixture degradation as a property distinct from that of PAH substrate range.

Suspect screening of emerging pollutants and their major transformation products in wastewaters treated with fungi by liquid chromatography coupled to a high resolution mass spectrometry

A new approach for the screening of 33 pharmaceuticals and 113 of their known transformation products in wastewaters was developed. The methodology is based on the analysis of samples by liquid chromatography coupled to high resolution mass spectrometry (HRMS) followed by data processing using specific software and manual confirmation. A home-made library was built with the transformation products reported in literature for the target pharmaceuticals after treatment with various fungi. The method was applied to the search of these contaminants in 67 samples generated along treatment of wastewaters with white-rot fungus Trametes versicolor. The screening methodology allowed the detection of different transformation products (TPs) generated from degradation of parent compounds after fungal treatment. This approach can be a useful tool for the rapid screening and tentative detection of emerging contaminants during water treatment in both full and batch-scale studies when pure standards are not available.

Fate and degradation kinetics of nonylphenol compounds in aerobic batch digesters

Nonylphenol (NP) compounds are toxic and persistent chemicals that are not fully degraded either in natural or engineered systems. Current knowledge indicates that these compounds concentrate in sewage sludge. Therefore, investigating the degradation patterns and types of metabolites formed during sludge treatment are important for land application of sewage sludge. Unfortunately, the information on the fate of nonylphenol compounds in sludge treatment is very limited. This study aims to investigate the biodegradation patterns of nonylphenol diethoxylate (NP2EO) in aerobic batch digesters. For this purpose, two NP2EO spiked and two control laboratory aerobic batch digesters were operated. The spiked digester contained 3 mg/L NP2EO in the whole reactor content. The compounds of interest (parent compound and expected metabolites) were extracted with sonication and analyzed by gas chromatography-mass spectrometry (GC–MS) as a function of time. Results showed that, following the day of spike, NP2EO degraded rapidly. The metabolites observed were nonylphenol monoethoxylate (NP1EO), NP and dominantly, nonylphenoxy acetic acid (NP1EC). The mass balance over the reactors indicated that the total mass spiked was highly accounted for by the products analyzed. The time dependent analysis indicated that the parent compound degradation and daughter product formation followed first order kinetics. The digester performance parameters analyzed (VS and COD reduction) indicated that the spike of NP2EO did not affect the digester performance.

Buffer strip effect on terbuthylazine, desethyl-terbuthylazine and S-metolachlor runoff from maize fields in Northern Italy

The effectiveness of a 6 m wide vegetative buffer strip for reducing runoff of S-metolachlor, terbuthylazine and desethyl-terbuthylazine was studied in 2007–2008 in Northern Italy. Two cultivated fields, with and without the buffer strip, were compared. Residues of the chemicals were investigated in runoff water collected after runoff events and their dissipation in the soil was studied. The highest concentration of the chemicals in water occurred in samples collected from the unbuffered field at the first runoff events. Losses of terbuthylazine and S-metolachlor in runoff waters were particularly high in 2007 (2.6% and 0.9% of the amount applied, respectively). Soil half-life of terbuthylazine and S-metolachlor ranged between 12.1 and 8.9 days and 16 and 7 days, respectively. The presence of desethyl-terbuthylazine was related to parent compound degradation. The buffer strip allowed an important reduction of chemical content in water (>90%), in particular during the first runoff events.

Assessing the potential for algae and macrophytes to degrade crop protection products in aquatic ecosystems

Rates of pesticide degradation in aquatic ecosystems often differ between those observed within laboratory studies and field trials. Under field conditions, a number of additional processes may well have a significant role, yet are excluded from standard laboratory studies, for example, metabolism by aquatic plants, phytoplankton, and periphyton. These constituents of natural aquatic ecosystems have been shown to be capable of metabolizing a range of crop protection products. Here we report the rate of degradation of six crop protection products assessed in parallel in three systems, under reproducible, defined laboratory conditions, designed to compare aquatic sediment systems which exclude macrophytes and algae against those in which macrophytes and/or algae are included. All three systems remained as close as possible to the Organisation for Economic Co-operation and Development (OECD) 308 guidelines, assessing degradation of parent compound in the total system in mass balanced studies using ((14) C) labeled compounds. We observed, in all cases where estimated, significant increases in the rate of degradation in both the algae and macrophyte systems when compared to the standard systems. By assessing total system degradation within closed, mass balanced studies, we have shown that rates of degradation are enhanced in water/sediment systems that include macrophytes and algae. The contribution of these communities should therefore be considered if the aquatic fate of pesticides is to be fully understood.

Photodegradation and toxicity changes of antibiotics in UV and UV/H 2O 2 process

The photodegradation of three antibiotics, oxytetracycline (OTC), doxycycline (DTC), and ciprofloxacin (CIP) in UV and UV/H 2O 2 process was investigated with a low-pressure UV lamp system. Experiments were performed in buffered ultrapure water (UW), local surface water (SW), and treated water from local municipal drinking water treatment plant (DW) and wastewater treatment plant (WW). The efficiency of UV/H 2O 2 process was affected by water quality. For all of the three selected antibiotics, the fastest degradation was observed in DW, and the slowest degradation occurred in WW. This phenomenon can be explained by R OH,UV, defined as the experimentally determined OH radical exposure per UV fluence. The R OH,UV values represent the background OH radical scavenging in water matrix, obtained by the degradation of para-chlorobenzoic acid (pCBA), a probe compound. In natural water, the indirect degradation of CIP did not significantly increase with the addition of H 2O 2 due to its effective degradation by UV direct photolysis. Moreover, the formation of several photoproducts and oxidation products of antibiotics in UV/H 2O 2 process was identified using GC–MS. Toxicity assessed by Vibrio fischer (V. fischer), was increased in UV photolysis, for the photoproducts still preserving the characteristic structure of the parent compounds. While in UV/H 2O 2 process, toxicity increased first, and then decreased; nontoxic products were formed by the oxidation of OH radical. In this process, detoxification was much easier than mineralization for the tested antibiotics, and the optimal time for the degradation of pollutants in UV/H 2O 2 process would be determined by parent compound degradation and toxicity changes.