Formation Of Non-extractable Residues Research Articles

Identifying bound compounds in non-extractable residues of pesticides in soil by 4-pool kinetic analysis

This study explores the feasibility of identifying bound compounds in non-extractable residues (NERs) of pesticides in soil by 4-pool kinetic analysis. The 4-pools refer to parent compound, metabolites, NERs, and CO2 in 14C-labeled pesticide soil degradation studies. We discovered the following two characteristic 4-pool kinetic behaviors of formation of NERs: (1) if parent compound is bound as NERs, the metabolites (m(t) in % applied radioactivity (AR)) kinetically drive the evolution of CO2 only; and (2) if a metabolite (x) in a sequential degradation pathway is bound as NERs, m(t) is split into m1(t) and m2(t) at the metabolite (x) that is bound as NERs, which kinetically drive the formation of NERs and evolution of CO2 respectively. We developed two (i.e., Parent➔NER and metabolite➔NER) 4-pool models to capture the kinetic behaviors respectively. By fitting the models to a set of 4-pool data, we not only determine whether NERs form from parent compound or metabolites but also identify the bound metabolite (x) by resolving the metabolites into M1(t) and M2(t) (i.e., the variables used to simulate m1(t) and m2(t)) and then matching m1(t) (i.e., the sum of bound metabolite (x) and its metabolite precursors) with M1(t). By applying the models to 14C-labeled parent compound-dosed studies and then sequentially to metabolite-dosed studies for 7 pesticides with ≥70 % AR NERs, we identified the bound compounds, which have the moieties known to be responsible for NERs, are bound as NERs instantaneously when dosed into soil, and account for pH dependency of NER formation.

Non-extractable residues of perfluorooctanoic acid (PFOA) in soil

Perand polyfluoroalkyl substances have gained increased attention due to their persistence, ubiquitous presence in the environment, and toxicity. We hypothesised that the formation of non-extractable residues [NER] occurs in soils and contributes to the overall persistence of these priority pollutants, and that NER formation is controlled by temperature. To test these hypotheses, we used 14C-labelled perfluorooctanoic acid [PFOA] as target compound, added it to two arable soils (Cambisol, Luvisol), and incubated them at 10°C and 20°C in the dark. To support potential co-metabolic decomposition, some samples were additionally fed with glucose to enhance microbial activity. The PFOA residues were then sequentially extracted using 0.01 M CaCl2, followed by accelerated solvent extraction (ASE) with methanol or methanol/acetic acid after 0, 1, 3, 9, 30, 62, and 90 days of incubation. In addition, we monitored the release of 14C into the gas phase as well as [14C]-PFOA-NER after dry combustion and liquid scintillation counting. After 90 days, we found that the [14C]-PFOA content declined in the extraction order of CaCl2 ((bio)available fraction) > ASE (residual fraction) > NER > gas fraction), with most rapid changes occurring in the first 9 days of incubation. NER formation was different in the two soils and reached 5-9% of the applied amount in the Cambisol and Luvisol, respectively. Noteworthy the proportion of 14C-PFOA in the (bio)available fraction remained relatively stable over time at 56-62% of the applied amount, indicating the reversible transfer into this fraction from a bi-exponentially declining residual (ASE) pool. These dissipation patterns were neither influenced by temperature nor by the addition of glucose. We conclude that NER exist for PFOA, but that the majority of PFOA remains in (bio)available form, thus maintaining toxicity and mobility in soil for prolonged periods of time.

Maize (Zea mays L.) Plants Alter the Fate and Accumulate Nonextractable Residues of Sulfamethoxazole in Farmland Soil.

The fate of sulfonamide antibiotics in farmlands is crucial for food and ecological safety, yet it remains unclear. We used [phenyl-U-14C]-labeled sulfamethoxazole (14C-SMX) to quantitatively investigate the fate of SMX in a soil-maize system for 60 days, based on a six-pool fate model. Formation of nonextractable residues (NERs) was the predominant fate for SMX in unplanted soil, accompanied by minor mineralization. Notably, maize plants significantly increased SMX dissipation (kinetic constant kd = 0.30 day-1 vs 0.17 day-1), while substantially reducing the NER formation (92% vs 58% of initially applied SMX) and accumulating SMX (40%, mostly bound to roots). Significant NERs (maximal 29-42%) were formed via physicochemical entrapment (determined using silylation), which could partially be released and taken up by maize plants. The NERs consisted of a considerable amount of SMX formed via entrapment (1-8%) and alkali-hydrolyzable covalent bonds (2-12%, possibly amide linkage). Six and 10 transformation products were quantified in soil extracts and NERs, respectively, including products of hydroxyl substitution, deamination, and N-acylation, among which N-lactylated SMX was found for the first time. Our findings reveal the composition and instability of SMX-derived NERs in the soil-plant system and underscore the need to study the long-term impacts of reversible NERs.

Impact of different sterilisation techniques on sorption and NER formation of test chemicals in soil

Standard OECD tests are used to generate data on biodegradation (OECD 307) and sorption (OECD 106) of test chemicals in soil. In such tests, data on abiotic degradation using sterile samples are utilised to investigate any losses due to abiotic processes. The data from sterile samples are also used to interpret results and findings of non-sterile samples, especially in the context of sorption and non-extractable residue (NER) formation. However, to ensure the comparability of the data obtained from sterile and non-sterile experiments, effects of sterilisation on the soil matrix should be minimal. The objective of this study was to investigate the efficiencies of different sterilisation techniques and the impact of the sterilisation on sorption and NER formation in soil. In this study, experiments in accordance with OECD 307 and OECD 106 guidelines were performed with two soils covering wide range of soil characteristics and treated with the three sterilisation techniques autoclaving, gamma(γ)-radiation and adding 1% (w/w) sodium azide. As a test item, 14C-labelled phenanthrene and bromoxynil was used for OECD 307 test, whereas non-labelled phenanthrene and atrazine was used for OECD 106. The sterilisation efficiencies were investigated using traditional viable plate count and molecular approaches (RNA extraction method). The results suggest that none of the tested techniques resulted in completely sterilised soil with autoclaving being the most efficient technique. Adding sodium azide led to most inefficient sterilisation and a significant increase (0.56 units) in soil pH. OECD 307 results showed differences in NER formation of the test chemicals, especially for soil poisoning and γ-radiation, which could be due to inefficient sterilisation and/or change in soil physico-chemical properties. OECD 106 results suggest that none of the sterilisation techniques considerably affected sorption behaviour of the test chemicals. Based on our results, we recommend autoclaving as most suitable sterilisation technique.

Fate of sulfamethoxazole in wetland sediment under controlled redox conditions

Redox condition is an important controlling factor for contaminant removal in constructed wetlands; however, the redox-sensitivity of antibiotic removal in wetland sediments under controlled conditions with specific electron acceptors remains unclear. Here, using a 14C radioactive tracer, we explored fate of sulfamethoxazole (SMX) in a wetland sediment slurry under oxic, nitrate-reducing, iron-reducing, and methanogenic conditions. In the sterile treatment, unlike the comparable SMX dissipation from the water phase under four redox conditions, non-extractable residues (NERs) of SMX was highest formed in the sediment under oxic condition, mainly in sequestered and ester/amide-linked forms. Microorganisms markedly promoted SMX transformation in the slurry. The dissipation rate of SMX and its transformation products (TPs) followed the order: oxic ≈ iron-reducing > methanogenic >> nitrate-reducing conditions, being consistent with the dynamics of microbial community in the sediment, where microbial diversity was greater and networks connectivity linking dominant bacteria to SMX transformation were more complex under oxic and iron-reducing conditions. Kinetic modeling indicated that the transformation trend of SMX and its TPs into the endpoint pool NERs depended on the redox conditions. Addition of wetland plant exudates and sediment dissolved organic matter at environmental concentrations affected neither the abiotic nor the biotic transformation of SMX. Overall, the iron-reducing condition was proven the most favorable and eco-friendly for SMX transformation, as it resulted in a high rate of SMX dissipation from water without an increase in toxicity and subsequent formation of significant stable NERs in sediment. Our study comprehensively revealed the abiotic and biotic transformation processes of SMX under controlled redox conditions and demonstrated iron-reducing condition allowing optimal removal of SMX in constructed wetlands.

Nitrogen-fertilizer addition to an agricultural soil enhances biogenic non-extractable residue formation from 2-13C,15N-glyphosate

Glyphosate and nitrogen (N) or (P) phosphorus fertilizers are often applied in combination to agricultural fields. The additional P or N supply to microorganisms might drive glyphosate degradation towards sarcosine/glycine or aminomethylphosphonic acid (AMPA), and consequently determine the speciation of non-extractable residues (NERs): harmless biogenic NERs (bioNERs) or potentially hazardous xenobiotic NERs (xenoNERs). We therefore investigated the effect of P or N-fertilizers on microbial degradation of glyphosate and bioNER formation in an agricultural soil. Four different treatments were incubated at 20 °C for 75 days as follows; I: no fertilizer (2-13C,15N-glyphosate only, control), II: P-fertilizer (superphosphate + 2-13C,15N-glyphosate, effect of P-supply), III: N-fertilizer (ammonium nitrate + 2-13C,15N-glyphosate, effect of N-supply) and IV: 15N-fertilizer (15N-ammonium nitrate + 2-13C-glyphosate, differentiation between microbial assimilations of 15N: 15N-fertilizer versus 15N-glyphosate). We quantified 13C or 15N in mineralization, extractable residues, NERs and in amino acids (AAs). At the end, mineralization (36–41 % of the 13C), extractable 2-13C,15N-glyphosate/2-13C-glyphosate (0.42–0.49 %) &15N-AMPA (1.2 %), and 13C/15N-NERs (40–43 % of the 13C, 40–50 % of the 15N) were comparable among treatments. Contrastingly, the 15N-NERs from 15N-fertlizer amounted to only 6.6 % of the 15N. Notably, N-fertilizer promoted an incorporation of 13C/15N from 2-13C,15N-glyphosate into AAs and thus the formation of 13C/15N-bioNERs. The 13C/15N-AAs were as follows: 16–21 % (N-fertilizer) > 11–13 % (control) > 7.2–7.3 % (P-fertilizer) of the initially added isotope. 2-13C,15N-glyphosate was degraded via the sarcosine/glycine and AMPA simultaneously in all treatments, regardless of the treatment type. The percentage share of bioNERs within the NERs in the N-fertilized soil was highest (13C: 80–82 %, 15N: 100 %) compared to 53 % (13C &15N, control) and to only 30 % (13C &15N, P-fertilizer). We thus concluded simultaneous N & glyphosate addition to soils could be beneficial for the environment due to the enhanced bioNER formation, while P & glyphosate application disadvantageous since it promoted xenoNER formation.

The Interaction of Pesticides with Humin Fractions and Their Potential Impact on Non-Extractable Residue Formation.

The constant influx of pesticides into soils is a key environmental issue in terms of their potential retention in the soil, thus reducing their negative impact on the environment. Soil organic matter (SOM) is an important factor influencing the environmental fate of these substances. Therefore, the aim of this research was to assess the chemical behavior of pesticides (flufenacet, pendimethalin, α-cypermethrin, metazachlor, acetamiprid) toward stable soil humin fractions (HNs) as a main factor affecting the formation of non-extractable residues of agrochemicals in soil. This research was conducted as a batch experiment according to OECD Guideline 106. For this purpose, HNs were isolated from eight soils with different physicochemical properties (clay content = 16-47%, pHKCl = 5.6-7.7, TOC = 13.3-49.7 g·kg-1, TN = 1.06-2.90 g·kg-1, TOC/TN = 11.4-13.7) to reflect the various processes of their formation. The extraction was carried out through the sequential separation of humic acids with 0.1 M NaOH, and then the digestion of the remaining mineral fraction with 10% HF/HCl. The pesticide concentrations were detected using GC-MS/MS. The pesticides were characterized based on the different sorption rates to HNs, according to the overall trend: metazachlor (95% of absorbed compound) > acetamiprid (94% of absorbed compound) > cypermethrin (63% of partitioning compound) > flufenacet (39% of partitioning compound) > pendimethalin (28% of partitioning compound). Cypermethrin and metazachlor exhibited the highest saturation dynamic, while the other agrochemicals were much more slowly attracted by the HNs. The obtained sorption kinetic data were congruous to the pseudo-first-order and pseudo-second-order models related to the surface adsorption and interparticle diffusion isotherm. The conducted research showed that the processes of pesticide sorption, apart from physicochemical phenomena, are also affected by the properties of the pollutants themselves (polarity, KOC) and the soil properties (SOM content, clay content, and pHKCl).

Fate of bisphenol A (BPA) in a flooded soil-rice system

In this study, 14C-tracers were used to investigate the fate of BPA in flooded soil with or without rice plants during a complete growing period. In flooded soil, the dissipation of BPA (half-life 14.8 d) was accompanied by its mineralization (8.4% of the initially applied radioactivity) and the formation of non-extractable residues (NERs) in amounts (79.5%) similar to that formed under oxic conditions. The growth of rice significantly accelerated the dissipation of BPA in flooded soil, resulting in a reduction in both the half-life (5.6 d) and the amount of NERs (35.8%). Two non-polar metabolites were detected both in unplanted and in rice-planted soil. At rice harvest, 57.1% of the radioactivity had accumulated in rice plants, mainly as NERs (54.2%) rather than as extractable radioactivity (2.7%), and mainly in roots (34.5 ± 1.4%), stems (9.4 ± 1.1%), and leaves (8.8 ± 0.6%), with trace amounts in seeds (3.6 ± 0.3%) and seed shells (0.7 ± 0.05%). Our study thus demonstrates that the oxic-anoxic interface stimulates the dissipation of BPA in flooded soil. The link between the releasing of NERs in flooded soil and the uptake of BPA metabolites by rice should be considered in environmental risk assessments of agroecosystems.

Low-temperature thermally enhanced bioremediation of polycyclic aromatic hydrocarbon-contaminated soil: Effects on fate, toxicity and bacterial communities

Remediation of polycyclic aromatic hydrocarbon (PAH)-contaminated soil using thermal desorption technology typically requires very high temperatures, necessitating coupled microbial treatment for energy and cost reduction. This study investigated the fate and toxicity of PAHs as well as the responses of microbial communities following thermal treatment within a low temperature range. The optimal temperature for PAH mineralization was 20–28 °C, within the growth range of most mesophilic microorganisms. By contrast, 50 °C treatment almost completely inhibited PAH mineralization but resulted in the greatest detoxification effect particularly for cardiotoxicity and nephrotoxicity. A potential increase in toxicity was observed at 28 °C. Co-metabolism and non-extractable residue formation may play an interdependent role in thermally enhanced bioremediation. Moreover, alterations in bacterial communities were strongly associated with PAH mineralization and zebrafish toxicity, revealing that soil microorganisms play a direct role in PAH mineralization and served as ecological receptors reflecting changes in toxicity. Network analysis revealed that Firmicutes formed specific ecological communities at high temperature, whereas Acidobacteria and Proteobacteria act as primary PAH degraders at moderate temperature. These findings will enable better integration of strategies for thermal and microbial treatments in soil remediation.

Soil drying legacy does not affect phenanthrene fate in soil but modifies bacterial community response

Alteration of the structure of soil microbial communities following the elimination of hydrophobic organic pollutants (e.g., polycyclic aromatic hydrocarbons, PAHs) is generally assessed using DNA-based techniques, and soil is often required to dry prior to pollutant addition, to facilitate a better mix when establishing microcosms. However, the drying practice may have a legacy effect on soil microbial community structure, which would in turn influence the biodegradation process. Here, we used 14C-labeled phenanthrene to examine the potential side effects of precedent short-term drought events. The results indicate that the drying practice had legacy effects on soil microbial community structure, illustrated by irreversible shifts in the communities. The legacy effects had no significant impact on phenanthrene mineralization and non-extractable residue formation. However, they altered the response of bacterial communities to PAH degradation, leading to a decrease in the abundance of potential PAH degradation genes plausibly attributed to moderately abundant taxa. Based on a comparison of the varied effects of different drying intensity levels, an accurate description of microbial responses to phenanthrene degradation strongly relies on the establishment of stable microbial communities before PAH amendment. Concurrent alterations in the communities resulting from environmental perturbation could greatly mask minor alterations from the degradation of recalcitrant hydrophobic PAH. In practice, to minimize the legacy effects, a soil equilibration step with a reduced drying intensity is indispensable.

Green alga Chlamydomonas reinhardtii can effectively remove diclofenac from the water environment – A new perspective on biotransformation

The use of unicellular algae to remove xenobiotics (including drugs) from wastewaters is one of the rapidly developing areas of environmental protection. Numerous data indicate that for efficient phycoremediation three processes are important, i.e. biosorption, bioaccumulation, and biotransformation. Although biosorption and bioaccumulation do not raise any serious doubts, biotransformation is more problematic since its products can be potentially more toxic than the parent compounds posing a threat to organisms living in a given environment, including organisms that made this transformation. Thus, two questions need to be answered before the proper algae strain is chosen for phycoremediation, namely what metabolites are produced during biotransformation, and how resistant is the analyzed strain to a mixture of parent compound and metabolites that appear over the course of culture? In this work, we evaluated the remediation potential of the model green alga Chlamydomonas reinhardtii in relation to non-steroidal anti-inflammatory drugs (NSAIDs), as exemplified by diclofenac. To achieve this, we analysed the susceptibility of C. reinhardtii to diclofenac as well as its capability to biosorption, bioaccumulation, and biotransformation of the drug. We have found that even at a relatively high concentration of diclofenac the algae maintained their vitality and were able to remove (37.7%) DCF from the environment. A wide range of phase I and II metabolites of diclofenac (38 transformation products) was discovered, with many of them characteristic rather for animal and bacterial biochemical pathways than for plant metabolism. Due to such a large number of detected products, 18 of which were not previously reported, the proposed scheme of diclofenac transformation by C. reinhardtii not only significantly contributes to broadening the knowledge in this field, but also allows to suggest possible pathways of degradation of xenobiotics with a similar structure. It is worth pointing out that a decrease in the level of diclofenac in the media observed in this study cannot be fully explained by biotransformation (8.4%). The mass balance analysis indicates that other processes (total 22%), such as biosorption, a non-extractable residue formation, or complete decomposition in metabolic cycles can be involved in the diclofenac disappearance, and those findings open the prospects of further research.

Effect of Applying an Organic Amendment on the Persistence of Tebuconazole and Fluopyram in Vineyard Soils

The persistence of fluopyram and tebuconazole has been studied in different crops and agricultural soils. However, the behaviour of these fungicides may be altered when they are applied as a combined formulation in organically amended vineyard soils under field conditions. The purpose of this study is to evaluate the effect of applying spent mushroom substrate (SMS) or this residue re-composted with ophite (SMS + OF) on the adsorption, dissipation, and mobility of the fungicides fluopyram and tebuconazole in vineyard soils. Triplicate 10 m2 plots per treatment were set up in two different vineyard soils in the eastern La Rioja region: silt loam (ARN1) and sandy loam (ARN2), respectively, with low organic carbon (OC) content. The organic residues SMS and SMS + OF were applied at doses of 25 and 100 Mg ha−1. The adsorption distribution coefficients (Kd) increased when SMS and SMS + OF were applied, especially at the higher dose (100 Mg ha−1). The dissipation curve of both compounds fitted a two-phase kinetic model, with a very fast initial dissipation rate, followed by slower prolonged dissipation during the second phase. The dissipation half-lives (DT50) ranged between 4.7 and 26.3 days for fluopyram and between 2.3 and 6.3 days for tebuconazole in the different soils, increasing for fluopyram in the ARN1 amended with SMS and SMS + OF. The fungicide residues at 15–30 cm depth were lower in the unamended and amended sandy loam soil (ARN2), indicating that fungicides are dissipated mainly in the topsoil. The results indicate different dissipation mechanisms for both fungicides, as the adsorption by soil OC prevented the dissipation of fluopyram but facilitated the dissipation of tebuconazole, probably due to the formation of non-extractable residues.

Mobility in the context of exposure-based assessment of chemicals for drinking water resourceprotection.

In order to protect European Union (EU) drinking water resources from chemical contamination, criteria for identifying persistent, mobile, and toxic (PMT) chemicals and very persistent and very mobile (vPvM) chemicals under the EU REACH Regulation were proposed by the German Environment Agency (Umweltbundesamt-UBA). Additionally, new hazard classes for PMT and vPvM substances in the revised EU classification, labeling, and packaging (CLP Regulation) are intended. Therefore, a reliable approach in theidentificationof potential drinking water resource contaminants is needed. The scientific basis of the property-based PMT/vPvM criteria, focusing on mobility, which dictates the migration of chemicaldrinking water sources, was evaluated, and a critical analysis of the deviation of sorption metrics from simple behavior was carried out. Based on our evaluation, a Koc may be used for nonionic substances on a screening level only, requiring a higher tier assessment. It is considered inappropriate for hydrophilic and ionizable chemicals, particularly for soils with low organic carbon contents. The nonextractable residue formation is complex and not well understood but remains significant in limiting the mobility of chemicals through soils and sediments. In order to inform the EU commission's work on the introduction of new hazard classes for PMT and vPvM substances into the European legislation, the derivation of a tiered approach is proposed,which utilizes the weight of evidence available, with adoption of appropriate higher tier models commensurate with the nature of the substance and the data available. Integr Environ Assess Manag 2023;19:775-791. © 2022 The Authors. Integrated Environmental Assessment and Management published by Wiley Periodicals LLC on behalf of Society of Environmental Toxicology & Chemistry (SETAC).

Effect of Cu2+ on the Laccase-Inducted Formation of Non-Extractable Residues of Tetrabromobisphenol A in Humic Acids.

We used 14C-radiolabelling to study the non-extractable residues (NERs) formation of tetrabromobisphenol A (TBBPA) in a humic acid (HA) suspension under catalysis of laccase in the presence of copper. When entering the suspension after TBBPA adsorbing to HA supramolecular associates, Cu2+ at low concentrations (even without toxicity to laccase) significantly reduced the amount and first-order kinetic constant of the NER formation, while Cu2+ had no significant effect on the formation after it was complexed with HA. The inhibition effect of Cu2+ on the NER formation is explained to be attributed to the prevention of laccase-induced oxidation of TBBPA in the voids of HA associates by complexation of Cu2+ with periphery molecules of the associates. The results provide insights into varying effects of heavy metals on the environmental fate of organic contaminants and suggest that co-existing heavy metals could increase their environmental risk by reducing their NER formation.

Fate of 14C-labelled ionic organic chemicals in a water-sediment system and surface water.

The persistence assessment of organic chemicals is based on neutral reference substances. Therefore, our study aimed at investigating the influence of a chemical charge on the degradation of organic compounds in a water-sediment system (OECD 308) and surface water (OECD 309). We used radiolabelled 4-n-dodecylbenzenesulfonic acid sodium salt (14C-DS-, anionic), 4-n-dodecylbenzyltrimethylammonium chloride (14C-DA+, cationic) and 4-n-dodecylphenol (14C-DP, non-ionic) which are structurally similar except their charges. After 120 days of incubation in a water-sediment system, 68% (14C-DS-), 6% (14C-DA+) and 63% (14C-DP) of the applied radioactivity (AR) were mineralized. The formation of non-extractable residues (NER) after 120 days was highest for 14C-DA+ (33% AR), followed by 14C-DS- (19% AR) and 14C-DP (14% AR). Dissipation half-lives (DT50) at 12°C decreased as follows: 14C-DA+ (346 days) ≫ 14C-DS- (47 days)>14C-DP (30 days). After 60 days of incubation in surface water with suspended sediment, mineralization of 14C-DS-, 14C-DA+ and 14C-DP accounted for 63%, 7% and 58% AR, respectively. Highest NER formation was observed for 14C-DP (21% AR), followed by 14C-DA+ (14% AR) and 14C-DS- (9% AR). DT50 (12°C) decreased as follows: 14C-DA+ (45 days)>14C-DP (3 days)>14C-DS- (2 days). We showed that a positive charge reduces the degradability of organic chemicals in both test systems. From a scientific point of view, simulation studies following OECD 309 should always be complimented by tests with high sorption capacity, e.g. OECD 308 and OECD 307 tests in order to assess the degradation of a compound, especially in case of cationic organic compounds.

Dissipation of a mix of priority PAHs in soils by using availability enhancers. Effect of aging and pollutant interactions.

A remediation strategy using three non-toxic availability enhancers (two cyclodextrins and a rhamnolipid biosurfactant) was applied to various soils artificially contaminated with a mix of Polycyclic Aromatic Hydrocarbons (PAHs) considered priority pollutants at two levels of contamination: only with 7 low molecular weight PAHs (LMW PAHs, 5 with 3-ring and 2 with 4-ring - fluoranthene and pyrene) or with 14 PAHs (from 3 to 6 rings). Natural attenuation of PAHs in all soils showed degradation capacity for the LMW PAHs, with a final content of LMW PAHs <5% of their initial concentration. Conversely, the rest of PAHs (high molecular weight PAHs, HMW) remained in the soils (61% - 83.5%), indicating abiotic dissipation of HMW PAHs due to formation of non-extractable residues in soils. The influence of the presence of HMW PAHs on the degradation of the 7 LMW PAHs was also tested, showing a general decrease in the time to obtain 50% dissipation (DT50), statistically significant for acenaphthene, acenaphthylene and fluorene. Availability enhancers showed different effects on PAHs dissipation. 2-hydroxypropyl-β-cyclodextrin (HP) decreased DT50 of some of the lighter PAHs, whereas the rhamnolipid (RL) caused a slight DT50 increase due to its initial toxicity on native soil microorganisms, but showing later high degradation rate for LMW PAHs. On the contrary, randomly methylated-β-cyclodextrin (RAMEB) slowed down PAHs degradation due to its high adsorption onto soil surface, blocking the desorption of PAHs from the soils. The high number of experimental factors not studied simultaneously before (soil type, co-contamination, availability enhancers and incubation time) allowed to conduct a statistical analysis which supported the conclusions reached. Principal Component Analysis separated the studied PAHs in 3 groups, in relation with their molecular weight and Kow. The first principal component was related with LMW PAHs, and separate the inefficient RAMEB from the other availability enhancers.

Formation and nature of non-extractable residues of emerging organic contaminants in humic acids catalyzed by laccase

Formation of non-extractable residues (NERs) is the major fate of most environmental organic contaminants in soil, however, there is no direct evidence yet to support the assumed physical entrapment of NERs (i.e., type I NERs) inside soil humic substances. Here, we used 14C-radiotracer and silylation techniques to analyze NERs of six emerging and traditional organic contaminants formed in a suspension of humic acids (HA) under catalysis of the oxidative enzyme laccase. Laccase induced formation of both type I and covalently bound NERs (i.e., type II NERs) of bisphenol A, bisphenol F, and tetrabromobisphenol A to a large extent, and of bisphenol S (BPS) and sulfamethoxazole (SMX) to a less extent, while no induction for phenanthrene. The type I NERs were formed supposedly owing to laccase-induced alteration of primary (active groups) and secondary (conformation) structure of humic supramolecules, contributing surprisingly to large extents (23.5%–65.7%) to the total NERs, particularly for BPS and SMX, which both were otherwise not transformed by laccase catalysis. Electron-withdrawing sulfonyl group and bromine substitution significantly decreased amount and kinetics of NER formation, respectively. This study provides the first direct evidence for the formation of type I NERs in humic substances and implies a “Trojan horse” effect of such NERs in the environment.

Fate of sulfamethoxazole in compost, manure and soil amended with previously stored organic wastes

Application of organic wastes as soil fertilizers represents an important route of agricultural soil contamination by antibiotics such as sulfamethoxazole (SMX). Soil contamination may be influenced by the storage time of organic wastes before soil spreading. The objective of this work was to study the fate of SMX in two organic wastes, a co-compost of green waste and sewage sludge and a bovine manure, which were stored between 0 and 28 days, then incorporated in an agricultural soil that has never received organic waste and monitored for 28 days under laboratory conditions. Organic wastes were spiked with 14C-labelled SMX at two concentrations (4.77 and 48.03 mg kg−1 dry organic waste). The fate of SMX in organic wastes and soil-organic waste mixtures was monitored through the distribution of radioactivity in the mineralised, available (2-hydroxypropyl-β-cyclodextrin extracts), extractable (acetonitrile extracts) and non-extractable fractions. SMX dissipation in organic wastes, although partial, was due to i) incomplete degradation, which led to the formation of metabolites detected by high performance liquid chromatography, ii) weak adsorption and iii) formation of non-extractable residues. Such processes varied with the organic wastes, the manure promoting non-extractable residues, and the compost leading to an increase in extractable and non-extractable residues. Short storage does not lead to complete SMX elimination; thus, environmental contamination may occur after incorporating organic wastes into soil. After addition of organic wastes to the soil, SMX residues in the available fraction decreased quickly and were transferred to the extractable and mostly non-extractable fractions. The fate of SMX in the soil also depended on the organic wastes and on the prior storage time for manure. However the fate of SMX in the organic wastes and soil-organic waste mixtures was independent on the initial spiked concentration.

Degradation, transformation, and non-extractable residue formation of nitrated nonylphenol isomers in an oxic soil

Nitrated nonylphenols (NNPs) are main metabolites of the endocrine-disrupting nonylphenols in soil, yet their fate is unknown. Here, using four NNP isomers (NNP111, NNP112, NNP65, and NNP38), the degradation pattern of NNPs was investigated in an oxic soil for 266 days. Specifically, NNP111 was 14C-labeled to facilitate investigating its degradation, transformation, and non-extractable residue (NER) formation. NNPs degradation was isomer-specific with the decreasing order of half-life: NNP111 (126 days) > NNP112 (76 days) > NNP65 (14 days) > NNP38 (8.4 days), providing direct evidence of the greater persistence of NNPs in soil than their parent NPs. At the end of the incubation, 8.5 %, 7.3 %, and 39.9 % of 14C-NNP111 was mineralized, transformed to 2-amino-NP111, and formed NERs in active soil, respectively. In contrast, NERs in sterilized soils were significantly lower, amounting to 15.1 % and 17.3 % in autoclaved and γ-irradiated soil, respectively. The majority of the NERs (>70 %) were in humin fraction, in which type I NER was the predominant (>90 %) mode for NER formation. Our results provide comprehensive knowledge on the fate of NNPs in soil, demonstrating that isomer-specific behavior, transformation products of NNPs, and NER formation should be considered when evaluating environmental fate and risks of NNPs.

Influence of Tubificidae Limnodrilus and electron acceptors on the environmental fate of BDE-47 in sediments by (14)C-labelling

2,2′,4,4′-tetrabromodiphenyl ether (BDE-47) was difficult to degrade in sediments. In this study, the environmental behavior of BDE-47 with/without the effect of benthos (Tubificidae Limnodrilus) and electron acceptors in sediments was investigated using C-14 tracer. Generally, extractable residues of BDE-47 were dominant in sediment and posed high environment risk. The amount of non-extractable residues (NERs) accounted for 39.0% of initial radioactivity in oxic sediments was significantly higher than those in anoxic sediments (17.6%). Most of NERs were localized in the humin fraction and presented as sequestrated forms. Under oxic conditions, the present of Limnodrilus significantly increased the proportion of NERs in sediment. Limnodrilus accumulated 34.2% of initial radioactivity. Under anoxic conditions, the addition of iron (Ⅲ) [Fe(III)], sulfate and nitrate reduced the environmental risk of BDE-47 with the increase of NERs formation, while manganese (IV) [Mn(IV)] addition had no effect on the formation of NERs. The present of Limnodrilus and electron acceptors promoted the production of metabolites. Meanwhile, BDE-47 changed the microbial community structure of sediments. These findings indicated that the environmental behavior and risk of BDE-47 was affected by benthos and electron acceptors, and the high proportion of sequestrated NERs posed high bioactivity and toxic threat to ecological environment.