Abiotic Degradation Research Articles

Determination of organophosphate diesters in facility vegetable soils using ultra-high performance liquid chromatography-electrostatic field orbitrap high resolution mass spectrometry

Organophosphate diesters (Di-OPEs) are biotic or abiotic degradation products of organophosphate esters (OPEs). Current analytical methods focus on detecting Di-OPEs in human urine. Human exposure to Di-OPEs in environmental matrices has not been systematically studied. Soil plays an important role in the environmental migration and transformation of organic pollutants. Previous studies found that OPEs are ubiquitous in soil. However, few studies reported OPEs metabolite pollution in soil, especially in facility vegetable soil. In this study, an ultra-high performance liquid chromatography-electrostatic field orbitrap high resolution mass spectrometry (UPHLC-Orbitrap HRMS) method was developed for the determination of five Di-OPEs (bis(2-chloroethyl) phosphate (BCEP), bis(1,3-dichloro-2-propyl) phosphate (BDCP), di-n-butyl phosphate (DnBP), diphenyl phosphate (DPhP), and bis(2-ethylhexyl) phosphate (DEHP)) in the facility vegetable soil. The pretreatment process and chromatographic and mass spectrometric conditions were optimized in the present study. Comparative study of the purification effects of different solid-phase extraction columns showed that Oasis WAX cartridge had best purification efficiency for the five Di-OPEs. The cartridge was first activated using 3 mL methanol, 3 mL methanol containing 5% (v/v) ammonia, and 3 mL 0.1 mol/L sodium acetate-acetic acid buffer solution. Then, the cartridge was rinsed with 3 mL of 30% (v/v) methanol aqueous solution, and finally eluted using 8 mL methanol containing 5% (v/v) ammonia. The effects of mobile phase (with respect to solvent composition and flow rate) and column temperature on the shape and intensity of chromatographic peaks were studied. The optimized UHPLC conditions were as follows: chromatographic column, Thermo Accucore RP-MS; column temperature, 30 ℃; mobile phase, 0.2 mmol/L ammonium acetate aqueous solution and methanol; flow rate, 0.2 mL/min. In the UHPLC-Orbitrap HRMS experiment, the five Di-OPEs were analyzed in full MS mode with negative ionization. Instrumental parameters, such as sheath gas and auxiliary gas, were optimized to determine the MS conditions. The optimized Orbitrap HRMS conditions were as follows: heating electrospray ionization source (HESI), full MS mode with negative ionization; scan range, m/z 100-500; ion transfer tube temperature, 320 ℃; automatic gain control of target particle count, 1×106; sheath gas flow rate, 8.58 L/min; auxiliary gas flow rate, 17.40 L/min; spray voltage, 3.2 kV; and S-lens voltage, 50 V. The limits of detection and quantification were 0.001-0.047 ng/g and 0.004-0.156 ng/g, respectively. The correlation coefficients of the calibration curve were 0.9985-0.9999. At three spiked levels, 5.0, 25.0, and 50.0 ng/g, the recoveries of the five Di-OPEs ranged from 56.9% to 133.0% with relative standard deviations of 4.4%-18.9%. The established method was applied to the analysis of the five Di-OPEs in 16 facility vegetable soils. The detection frequencies of the five Di-OPEs exceeded 60% in all soil samples, indicating that the Di-OPEs were ubiquitous in the facility vegetable soil. The contents of the five Di-OPEs in the facility vegetable soil samples ranged from 2.53-6.94 ng/g. DnBP (1.37-3.20 ng/g) and DPhP (0.47-2.44 ng/g) were the predominant congeners in the facility vegetable soil samples, accounting for 23.4%-68.8% and 16.3%-35.9% of the five Di-OPEs, respectively. The developed method is simple, sensitive, and reproducible and can be used effectively for the determination of Di-OPEs in soil. The results of this study will be helpful for understanding the environmental behavior of Di-OPEs and their human exposure in facility vegetable soils.

Ethylated analogue of Zingerone: A new and eco-respectful preservative in cosmetics.

This article describes the eco-design of a new preservative in cosmetics based on bio-inspiration of natural extracts from traditional medicines. In order to reach the multiple specification targets, various structures have been synthesized and evaluated to select the one demonstrating broad antimicrobial spectrum with favorable environmental profile and application potential to a wide variety of formulas. In order to evaluate the antimicrobial activity of the synthesized structures, the method of the challenge test consisting in an artificial contamination of the sample with collection microbial strains and evaluation of the number of revivable microorganisms was used to select the most promising candidate. Validation of its antimicrobial potential was later confirmed on Gram positive and Gram negative bacteria, yeast and mold with measurement of its Minimum Inhibitory Concentration (MIC) in comparison with known preservatives. Environmental impact assessment of the selected candidate was achieved with the help of ready biodegradability and aquatic ecotoxicity tests performed according to appropriate Organization tes a strfor Economic Co-operation and Development (OECD) and European Union (EU) guidelinesy. Bio-inspired from turmeric and ginger extracts, an ethylated analog of Zingerone (EZ) with the chemical name 4-(3-ethoxy-4-hydroxyphenyl)butan-2-one demonstrates the strongest activity on Escherichia coli, Enterococcus faecalis, Pseudomonas aeruginosa and Candida albicans. Moreover, EZ shows a solubility in water two times higher than that of Zingerone thus increasing its interest as a potential preservative. Finally, its assessment of ready biodegradability and aquatic ecotoxicity in OECD-EU tests with a favorable environmental profile confirms its unique interest and fully justifies its use in cosmetic formulas as an eco-respectful preservative. Bio-inspiration based on technologies without noteworthy side effects but also on eco-design, particularly through the use of measures of potential environmental impact very upstream of a development, are two fundamental elements for the launching of new eco-friendly cosmetic ingredients. This approach has thus validated the strong potential of EZ as a preservative of eco-respectful formulas. The selection of EZ is also a very good example of the achievement of two key objectives targeted by cosmetic companies for the development of a novel active ingredient: environmental performance and technical performance.

Evaluation of nanoplastics toxicity in the soil nematode Caenorhabditis elegans by iTRAQ-based quantitative proteomics

Plastic pollution is recognized as a major threat to ecosystems in the 21st century. Large plastic objects undergo biotic and abiotic degradation to generate micro- and nano-sized plastic pieces. Despite tremendous efforts to evaluate the adverse effects of microplastics, a comprehensive understanding of the toxicity of nanoplastics remains elusive, especially at the protein level. To this end, we used isobaric-tag-for-relative-and-absolute-quantitation-based quantitative proteomics to investigate the proteome dynamics of the soil nematode Caenorhabditis elegans in response to exposure to 100 nm polystyrene nanoplastics (PS-NPs). After 48 h of exposure to 0.1, 1, or 10 mg/L PS-NPs, 136 out of 1684 proteins were differentially expressed and 108 of these proteins were upregulated. These proteins were related to ribosome biogenesis, translation, proteolysis, kinases, protein processing in the endoplasmic reticulum, and energy metabolism. Remarkably, changes in proteome dynamics in response to exposure to PS-NPs were consistent with the phenotypic defects of C. elegans. Collectively, our findings demonstrate that disruption of proteome homeostasis is a biological consequence of PS-NPs accumulation in C. elegans, which provides insights into the molecular mechanisms underlying the toxicology of nanoplastics.

Rapid Biotic and Abiotic Transformation of Toxins produced by Ostreopsis. cf. ovata.

The dinoflagellate Ostreopsis cf. ovata produces several families of toxic polyketides. Despite only a few field measurements of these phycotoxins in seawater and aerosols, they are believed to be responsible for dermatitis and the toxic inhalations reported during blooms of this species. Therefore, the stability of these compounds in seawater is essential to understanding the causes of these symptoms, however, this has never been assessed. In the current study, the optimization of a solid phase extraction (SPE) procedure was first performed to ensure the most efficient extraction of all phycotoxins known to be produced by this strain, including the recently described liguriatoxins. The SPE cartridge SDBL® under non acidified conditions offered the best option. The stability of the ovatoxins and the liguriatoxins under biotic and abiotic stress was assessed by exposing the spent medium of a culture of Ostreopsis cf. ovata to its bacterial consortium and natural sunlight. A rapid biotic transformation was detected for both families of compounds. When exposed to bacteria, the half-lives of the ovatoxins were reached before 10 h and at 36 h, 97% of these toxins had been transformed. The half-lives of the liguriatoxins were 10 h under these conditions. Photolysis (abiotic degradation) of the ovatoxins (T1/2 < 36 h) was faster than for the liguriatoxins (T1/2 > 62 h). Although none of the catabolites of these phycotoxins were thoroughly identified, an untargeted metabolomics approach combined with molecular networking highlighted the presence of several compounds exhibiting structural similarities with the ovatoxins. Additional work should confirm the preliminary findings on these potential ovatoxins’ catabolites and their biological properties. The rapid transformation of O. cf. ovata’s phycotoxins introduces questions concerning their presence in seawater and their dispersion in the sea spray aerosols. The compounds involved in the toxic inhalations and dermatitis often experienced by beachgoers may stem from the catabolites of these toxins or even unrelated and as yet unidentified compounds.

Combined remediation effects of biochar and organic fertilizer on immobilization and dissipation of neonicotinoids in soils.

Neonicotinoid (NEO) pesticides have become a potential risk to ecological safety and human health after application. The combined use of biochar and organic fertilizer (OF) is a promising approach to reduce pesticide adverse effects and improve soil fertility in agricultural soils. However, the combined remediation effects of biochar and OF on immobilization and dissipation of NEOs in soils have not previously been systematically investigated. In this study, biochars derived from peanut shell prepared at low/high pyrolysis temperatures (PS400 and PS900) were combined with composted chicken manure (CCM) as an example for OF to remediate contaminated soils toward six typical NEOs, nitenpyram (NIT), thiamethoxam (THIA), clothianidin (CLO), imidacloprid (IMI), acetamiprid (ACE), thiacloprid (THI). Results shown that both biochars and CCM were effective in improving soil sorption capacity and immobilization efficiency. The Freundlich affinity parameters (Kf) of NEOs in soils increased 7.2-12.0 times after the combined remediation of biochar and CCM, and the Kf of six NEOs had negative correlation with their lipophilicity (p<0.05), which followed by THI>ACE ≈ IMI>CLO>THIA>NIT. Meanwhile, NEOs-abiotic degradation was accelerated by biochar, CCM and their combined addition by adjusting soil pH and stimulating hydrolysis action. Biotic degradation was dominant in NEOs dissipation processes in amended soils, and the contribution ratios of biotic degradation (CRbio) were in the range of 25.4-99.0%. The combined use of biochar and CCM selectively stimulated the relative abundance of NEOs-degraders, which simplified abiotic degradation of -NO2-containing NEOs (viz., NIT, THIA, CLO, and IMI), but inhibited -C≡N-containing NEOs (viz., ACE and THI). The combined remediation provided a strategy for immobilizing NEOs and facilitating dissipation of -NO2-containing NEOs in soils. The results in this study provide valuable information for policymakers and decision-makers to choose appropriate soil remediation approaches with respect to the NEO types.

Environmental degradation of human metabolites of cyclophosphamide leads to toxic and non-biodegradable transformation products

The present study assessed the ready biodegradability of the prodrug cyclophosphamide (CPA) and its stable human metabolites in the closed bottle test (CBT). The results of the CBT showed that only the main human metabolite, carboxyphosphamide (CXP), was biodegradable to a certain extent (23 ± 2.4 % ThODNH3). All other metabolites showed neither biodegradation under these conditions nor were any toxic effects on the inoculum observed. Yet, HRMSn results revealed partial primary elimination of all human metabolites and formation of 25 new transformation products. Abiotic degradation via SNi and SN2 reactions was proposed as the main degradation pathway during the CBT. The main degradation products were assigned as 3-(2-chloroethyl)oxazolidin-2-one (COAZ), cytotoxic N-2-chloroethylaziridine (CEZ) and nor‑nitrogen mustard (NNM), an analogue of the chemical warfare agent HN2. While the acute ecotoxicity of the detected products is widely unknown, many have already been reported in medical literature to be either mutagenic, genotoxic, cytotoxic or carcinogenic and may therefore cause a greater risk than their precursors. QSAR models predicted that 16 of them are mutagenic and genotoxic, thus classifying the majority of the chemicals as potential environmental hazards. The central intermediates during the degradation process were proposed as CEZ and its corresponding aziridinium ion. However, other degradation products may occur depending on the type and strength of nucleophiles present in the matrices. Overall, the results demonstrated the importance to include human metabolites in the evaluation of the environmental fate of pharmaceuticals and their risk assessment especially when investigating prodrugs. The results underline the importance of identifying possible degradation products of metabolites, as they can be more toxic than related parent compounds and metabolites and can cause a greater risk to the environment and humans.

Biodegradability under marine conditions of bio-based and petroleum-based polymers as substitutes of conventional microparticles

Plastic microbeads have been produced at very large scales since several decades for cosmetics and personal care products, a large amount of which is being directly transported in the oceans. To better understand their biodegradability in marine environment and evaluate their possible replacement by biodegradable polymers, seven polymer types were studied including three conventional petroleum-based polymers (PE, PMMA, and PCL), two bio-based polymers (PLA and PHBV), and two natural products (rice seeds and apricot kernel). We used several innovative approaches by both the experimental design and the set of multidisciplinary techniques to follow the successive steps of biodegradation together with abiotic degradation under seawater conditions. Congruent signs of biodegradability were observed by oxygen consumption, weight loss, and modification of molecular weight, 1H NMR, and mass spectrometry profiles. We found that microparticles made of PHBV, PCL, rice, and to a lesser extent apricot were biodegradable under our conditions, while not microparticles made of PE, PMMA, and PLA. Taking into consideration of the industrial application, PHBV could be the potential material to replace the conventional microbeads, since the material is resistant to hydrolysis, but susceptible to microbial degradation, as shown by the 1H NMR results. This study provides the first time arguments for the use of biodegradable substitutes to replace conventional microbeads to support the recent legislative rules aiming to reduce the pollution by primary microplastics in the oceans.

Feasibility Analysis Upon Optimal Pollutant Degradation via Compartmental Modeling

Due to a lack of plausible kinetic modeling for contaminant attenuation, this study first proposed a “bi-exponential disposition” model to demonstrate the feasibility of wide-ranging applications for the biotic and abiotic degradation of pollutant(s). As a consequence of under-determined systems of bisphenol A (BPA) degradation via advanced oxidation processes (AOPs), a previous study proposed asymptotic approximation singular perturbation for kinetic modeling. The present study extended this model to provide the key performance indicator (KPI); namely, the area under the time course (AUC) of pollutant concentrations from time zero to the endpoint (i.e., AUC0→tf), quantitatively revealing the most promising strategy for pollutant (bio)degradation. Compared to the typical KPI (percentage of pollutant removal), AUC better illustrated the overall efficiency. Compartmental modeling predicted maximal pollutant mitigation through optimal schemes of operation for global optimization. The feasibility of adopting AUC for system prediction was confirmed in cases of azo and anthraquinone dye biodecolorization and acetaminophen (APAP), glyphosate, and bisphenol A (BPA) degradation. Regarding azo dye biodecolorization, the AUC and SDRmax indicated the need to consider cell concentrations. Compartment kinetics could be used for the serial acclimation of anthraquinone dye removal. Moreover, compartmental assessment upon glyphosate and acetaminophen abiotic degradation was also feasible for further applications. To minimize the AUC for optimal degradation of A⇌k3k1B→k2C, the maximal forward rate constants k1 and k2 and minimal backward rate constant k3 should be satisfied simultaneously. Thus, this AUC approach might be broadened to demonstrate overall optimization via Pontryagin’s maximum principle.

Abiotic plastic leaching contributes to ocean acidification

Ocean acidification and plastic pollution are considered as potential planetary boundary threats for which crossing certain thresholds could be very harmful for the world's societies and ecosystems well-being. Surface oceans have acidified around 0.1 units since the Industrial Revolution, and the amount of plastic reaching the ocean in 2018 was quantified to 13 million metric tonnes. Currently, both ocean threats are worsening with time. Plastic leaching is known to alter the biogeochemistry of the ocean through the release of dissolved organic matter. However, its impact in the inorganic chemistry of the seawater is less studied. Here we show, from laboratory experiments, that abiotic plastic degradation induces a decrease in seawater pH, particularly if the plastic is already aged, as that found in the ocean. The pH decrease is enhanced by solar radiation, and it is probably induced from a combination of the release of organic acids and the production of CO2. It is also related to the amount of leached dissolved organic carbon, with higher acidification as leaching increases. In coastal areas, where plastic debris accumulates in large quantities, plastic leaching could lead to a seawater pH decrease up to 0.5 units. This is comparable to the projected decrease induced in surface oceans by the end of the twenty-first century for the most pessimistic anthropogenic emissions scenarios.

Identification and toxicity towards aquatic primary producers of the smallest fractions released from hydrolytic degradation of polycaprolactone microplastics.

Bioplastics are thought as a safe substitute of non-biodegradable polymers. However, once released in the environment, biodegradation may be very slow, and they also suffer abiotic fragmentation processes, which may give rise to different fractions of polymer sizes. We present novel data on abiotic hydrolytic degradation of polycaprolactone (PCL), tracking the presence of by-products during 132 days by combining different physicochemical techniques. During the study a considerable amount of two small size plastic fractions were found (up to∼6mg of PCL by-product/g of PCL beads after 132 days of degradation); and classified as submicron-plastics (sMPs) from 1μm to 100nm and nanoplastics (NPs, <100nm) as well as oligomers. The potential toxicity of the smallest fractions, PCL by-products < 100nm (PCL-NPs+PCL oligomers) and the PCL oligomers single fraction, was tested on two ecologically relevant aquatic primary producers: the heterocystous filamentous nitrogen-fixing cyanobacterium Anabaena sp. PCC 7120, and the unicellular cyanobacterium Synechococcus sp. PCC 7942. Upon exposure to both, single and combined fractions, Reactive Oxygen Species (ROS) overproduction, intracellular pH and metabolic activity alterations were observed in both organisms, whilst membrane potential and morphological damages were only observed upon PCL-NPs+PCL oligomers exposure. Notably both PCL by-products fractions inhibited nitrogen fixation in Anabaena, which may be clearly detrimental for the aquatic trophic chain. As conclusion, fragmentation of bioplastics may render a continuous production of secondary nanoplastics as well as oligomers that might be toxic to the surrounding biota; both PCL-NPs and PCL oligomers, but largely the nanoparticulate fraction, were harmful for the two aquatic primary producers. Efforts should be made to thoroughly understand the fragmentation of bioplastics and the toxicity of the smallest fractions resulting from that degradation.

Major metabolites of NBPT degradation pathways contribute to urease inhibition in soil.

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 6d (NBPTO), 3d (NBPT) and ≤1d (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 2d 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.

Quantification of a Sulfated Marine-Inspired Antifouling Compound in Several Aqueous Matrices: Biodegradation Studies and Leaching Assays from Polydimethylsiloxane Coatings.

The development of marine-inspired compounds as non-toxic antifouling (AF) agents has been pursued in the last years. Sulfur is the third most common element in seawater. Sulfur is present in oxygenated seawater as sulfate anion (SO42−), which is the most stable combination of sulfur in seawater, and several promising AF secondary metabolites with sulfate groups have been described. However, sulfated compounds proved to be an analytical challenge to quantify by HPLC. Taking these facts into consideration, this work presents the development and validation of a method for the quantification of gallic acid persulfate (GAP) in seawater and ultrapure water matrix, based on hydrophilic interaction liquid chromatography (HILIC). This method was used to evaluate GAP stability following several abiotic and biotic degradation assays, and to quantify its release in seawater from room-temperature-vulcanizing polydimethylsiloxane commercial coating. GAP was very stable in several water matrices, even at different pH values and in the presence/absence of marine microorganisms and presented a leaching value lower than 0.5%. This work discloses HILIC as an analytical method to overcome the difficulties in quantifying sulfated compounds in water matrices and highlights the potential of GAP as a promising long-lasting coating.

Fate and transport of tetracycline and ciprofloxacin and impact on nitrate reduction activity in coastal sediments from the Seine Estuary, France.

Fluoroquinolones and tetracyclines are frequently detected antibiotics in aquatic sediments. In this study, the transport of ciprofloxacin (CIP) and tetracycline (TET) was investigated in sediments from the Seine Estuary (France), under nitrate reducing conditions. Dynamic flow experiments showed that although TET and CIP strongly interacted with the sediment components through adsorption and (bio)-chemical transformation, they kept their antimicrobial activities. Less nitrate reduction was observed during the first period of breakthrough, while TET and CIP were absent in the column effluent. Batch experiments with freeze-dried vs fresh sediments showed that adsorption and abiotic degradation are the major removal processes, while microbe-driven transformation is of less importance. Whereas TET is to a large extent chemically transformed and little adsorbed in the sediment, CIP was less transformed and more adsorbed, most likely due to the great reactivity of TET with redox-active mineral surfaces. Our findings show the strong capacity of natural sediment to retain and transform antibiotics, while still maintaining their antimicrobial activity or inhibitory effect of nitrate reducing activity.

Gold Mine Wooden Artefacts: Multianalytical Investigations for the Selection of Appropriate Consolidation Treatments.

Environmental conditions present in mines generally are very favourable to decay; high temperature, high humidity, variable oxygen content, numerous metal-wood connections and the presence of a high content of inorganic compounds typical of mines have a significant impact on the biotic and abiotic degradation factors. The state of conservation of wooden artefacts from the Złoty Stok (Poland) gold mine was investigated using a multi-analytical approach. The aim was to select the conservation treatments that would stop decay and improve the conditions and dimensional stability of the wood. FT-IR and Py-GC/MS were used to assess the state of preservation of lignocellulosic material. ED-XRF and SEM-EDS were used to determine—and XRD to identify crystalline phases—salts and minerals in the wood structure or efflorescence on the surface. Highly degraded lignocellulosic material that had undergone depolymerisation and oxidation was found to be severely contaminated by iron-based mineral substances, mainly pyrite, and in some cases greigite and magnetite. The presence of inorganic salts made it difficult to choose the best consolidating material to reduce the level of decay and improve the dimensional stability of the wood.

Statistical enchainment of ester/ether and carbonate cleavable bonds to control copolymers’ erosion rate and trigger environment-specific degradation

Polymers containing ester bonds undergo abiotic degradation independently from the surrounding environment as long as the hydrolytic conditions are provided. The hydrolysis of the ester bonds leads a bulk degradation of the polymeric matrix which, contrary to surface erosion, is unpredictable. The enchainment of diverse degradability functions was sought to expand the scope of the degradation mechanism and achieve a more predictable profile of the mass loss.The copolymerization of trimethylene carbonate and p-dioxanone enabled the synthesis of one class of copolymers with controllable erosion rate and susceptible to three degradation pathways depending on the surrounding environment. The synthetic strategy used organocatalysts and allowed the synthesis at room temperature of both random and block copolymers in high yield and with molar mass, Mn, in the range 12–22 kg mol−1. The composition and microstructure of the random copolymers were regulated by varying the monomers’ ratio. Diverse cleavable groups, i.e., ester/ether and carbonate bonds, were statistically incorporated along the same polymer chain to yield materials able to degrade under hydrolytic, oxidative and enzymatic conditions. Bulk degradation was the mechanism that took place under hydrolytic conditions, while the oxidative and enzymatic environments lead to surface erosion. The rate of mass loss of the random copolymers was regulated by varying the composition. These results showed how the statistical incorporation of different degradable bonds could pave the way to diverse and more predictable degradation pathways than simple hydrolysis by taking advantages of the surrounding environment to trigger surface erosion.

Removal mechanisms of erythromycin by microalgae Chlorella pyrenoidosa and toxicity assessment during the treatment process

Microalgae-based biotechnology for antibiotic removal has received increasing attention as an economical and green method. This study investigated the removal mechanism of erythromycin by Chlorella pyrenoidosa and its correlation with the ecotoxic responses of microalgae. The degradation products (DPs) were identified, and their toxicity was predicted. The results indicated that only 4.04 %, 6.28 % and 23.53 % of erythromycin were left after 21-day microalgae treatment in 0.1, 1.0 and 10 mg/L treatments, respectively. Biodegradation contributed 48.62–67.01 %, 16.67–52.32 % and 6.42–24.82 %, while abiotic degradation contributed 8.76–29.61 %, 5.19–41.39 %, and 16.55–51.22 % to erythromycin attenuation in 0.1, 1.0, and 10 mg/L treatments, respectively. The growth and physiological-biochemical parameters of microalgae were slightly affected in low concentration treatment, which may be the main reason that biodegradation was the prominent removal mechanism. By contrast, oxidative damage in high concentration treatment inhibited the cell growth and chlorophyll content of microalgae, which hindered erythromycin biodegradation. In addition, eleven erythromycin degradation products (DPs) were identified during microalgae treatment of 21 days. Seven DPs including DP717, DP715, DP701A, DP701B, DP657, DP643, and DP557, represented higher toxicity to aquatic organisms than erythromycin.

Influence of the nature of pro-oxidants on the photooxidation of polyethylene blown films

In an attempt to reduce the accumulation of polymeric waste in the environment, such as plastic bags, the use of pro-oxidants has been adopted in polyolefins, including polyethylene (PE), which is one of the most used polymers in film production. The incorporation of this additive to PE film aims to accelerate its oxidation in the process of abiotic degradation, generating oxygenated groups that can facilitate the biotic degradation. Commercial pro-oxidants are commonly organic salts of transition metals. However, their use can lead to a secondary problem, the inappropriate accumulation of transition metals at the site where the polymeric waste was deposited and, for this reason, it has been sought pro-oxidants metals free and that can also be biodegraded. In this context, this work aimed to evaluate the photodegradation of PE blown films obtained by extrusion using a commercial pro-oxidant, d2w™, an alternative organic pro-oxidant, benzoin, and also a standard film, without pro-oxidant. After undergoing 96 and 144 h of UV light exposure, the blown films were evaluated by dilute solution viscometry, FTIR and SEM analysis. The results showed that the pro-oxidants lead to the formation of more macromolecular fragments containing carbonyl groups than in the standard PE film. The film extruded with benzoin showed greater fragmentation, which may be associated with a greater reduction in the average viscosimetric molar mass, therefore, this additive being a promising organic substance in the induction of photooxidation, as demonstrated by the other results obtained by FTIR and SEM.

Potential Climate Change Impacts on the Abiotic Degradation of Acyl-Homoserine Lactones in the Fluctuating Conditions of Marine Biofilms

Marine biofilms are functional communities that shape habitats by providing a range of structural and functional services integral to coastal ecosystems. Impacts of climate change on biological aspects of such communities are increasingly studied, but impacts on the chemicals that mediate key interactions of biofilm organisms have largely been overlooked. Acyl-homoserine lactones (AHLs), crucial bacterial signals within biofilms, are known to degrade through pH and temperature-dependent hydrolysis. However, the impact of climate change on AHLs and thus on biofilm form and function is presently unknown. This study investigates the impact of changes in pH and temperature on the hydrolysis rate, half-life time and quantitative abundance of different AHLs on daily and seasonal timescales for current conditions and future climate change scenarios.We established the mathematical relationships between pH, hydrolysis rates/half-life times and temperature, which revealed that natural daily pH-driven changes within biofilms cause the greatest fluctuations in AHL concentration (up to 9-fold). Season-dependant temperature enhanced or reduced the observed daily dynamics, leading to higher winter and lower summer concentrations and caused a shift in timing of the highest and lowest AHL concentration by up to two hours. Simulated future conditions based on climate change projections caused an overall reduction of AHL degradation and led to higher AHL concentrations persisting for longer across both the daily and seasonal cycles.This study provides valuable quantitative insights into the theoretical natural dynamics of AHL concentrations. We highlight critical knowledge gaps on the scale of abiotic daily and seasonal fluctuations affecting estuarine and coastal biofilms and on the biofilms’ buffering capacity. Detailed experimental studies of daily and seasonal dynamics of AHL concentrations and assessment of the potential implications for a suite of more complex interactions are required. Substantial fluctuations like those we show in this study, particularly with regards to concentration and timing, will likely have far reaching implications for fundamental ecosystem processes and important ecosystem services such as larval settlement and coastal sediment stabilisation.

Forward and back diffusion of reactive contaminants through multi-layer low permeability sediments

Contaminants stored in the low permeability sediments will continue to threaten the adjacent shallow groundwater system after the aquifer is remediated. Understanding the storage and discharge behavior of contaminants in the aquitards is essential for the efficient remediation of contaminated sites, but most of the previous analytical studies focused on nonreactive solutes in a single homogenous aquitard. This study presents novel analytical solutions for the forward and back diffusion of contaminants through multi-layer low permeability sediments considering abiotic and biotic environmental degradation. Three representative source depletion patterns (i.e., instantaneous, linear, and exponential patterns) were selected to describe the dissolution of dense non-aqueous phase liquids (DNAPL) in the aquifer more realistically. At the forward diffusion stage, the mass storage of contaminants in the aquitards with the instantaneous pattern is the largest, nearly twice that with the exponential pattern. A simple equivalent homogeneous model is generally adopted in the risk assessment. However, relative to the proposed multi-layer model, it will significantly underestimate the onset of the back-diffusion of heterogeneous aquitards and overestimate the persistence of aquifer plumes. The previously-reported semi-infinite boundary assumption is also not applicable, with a maximum error of over 200% in the long-term prediction of back diffusion behavior of a thin aquitard. Moreover, when the degradation half-life is less than 16 years, less than 10% of the contaminants stored in the aquitards will diffuse into the overlying aquifer, suggesting that biostimulation or bioaugmentation can effectively mitigate back-diffusion risk. Overall, the proposed diffusion-reaction coupled model with multi-layer media is of great value and high demand in predicting the back-diffusion behavior of heterogeneous aquitards and guiding the soil bioremediation.

Plastic pollution fosters more microbial growth in lakes than natural organic matter

Plastic debris widely pollutes freshwaters. Abiotic and biotic degradation of plastics releases carbon-based substrates that are available for heterotrophic growth, but little is known about how these novel organic compounds influence microbial metabolism. Here we found leachate from plastic shopping bags was chemically distinct and more bioavailable than natural organic matter from 29 Scandinavian lakes. Consequently, plastic leachate increased bacterial biomass acquisition by 2.29-times when added at an environmentally-relevant concentration to lake surface waters. These results were not solely attributable to the amount of dissolved organic carbon provided by the leachate. Bacterial growth was 1.72-times more efficient with plastic leachate because the added carbon was more accessible than natural organic matter. These effects varied with both the availability of alternate, especially labile, carbon sources and bacterial diversity. Together, our results suggest that plastic pollution may stimulate aquatic food webs and highlight where pollution mitigation strategies could be most effective.