RESUMEN

Dibromoethane is a widespread, persistent organic pollutant. Biochars are known mediators of reductive dehalogenation by layered FeII-FeIII hydroxides (green rust), which can reduce 1,2-dibromoethane to innocuous bromide and ethylene. However, the critical characteristics that determine mediator functionality are lesser known. Fifteen biochar substrates were pyrolyzed at 600 °C and 800 °C, characterized by elemental analysis, X-ray photo spectrometry C and N surface speciation, X-ray powder diffraction, specific surface area analysis, and tested for mediation of reductive debromination of 1,2-dibromoethane by a green rust reductant under anoxic conditions. A statistical analysis was performed to determine the biochar properties, critical for debromination kinetics and total debromination extent. It was shown that selected plant based biochars can mediate debromination of 1,2-dibromoethane, that the highest first order rate constant was 0.082/hr, and the highest debromination extent was 27% in reactivity experiments with 0.1 µmol (20 µmol/L) 1,2-dibromoethane, ≈ 22 mmol/L FeIIGR, and 0.12 g/L soybean meal biochar (7 days). Contents of Ni, Zn, N, and P, and the relative contribution of quinone surface functional groups were significantly (p < 0.05) positively correlated with 1,2-dibromoethane debromination, while adsorption, specific surface area, and the relative contribution of pyridinic N oxide surface groups were significantly negatively correlated with debromination.

Asunto(s)

RESUMEN

Chemical anthropogenic contaminants in the marine environment pose a substantial threat to sea turtles. The current systematic review quantified the published literature on biomarkers of aquatic contamination in sea turtles. It examined the exposure and potential impacts of pollution at biochemical, molecular, and cellular levels, as indicated by these biomarkers. Eighty-seven primary peer-reviewed papers were included, most of which were published from 2013 onwards. Most studies focused on the species Chelonia mydas (n = 43 papers) and Caretta caretta (n = 36) and used blood samples for biomarker (n = 54) and chemical (n = 38) analyses. Chemical analyses were assessed alongside biomarker analyses in most studies (n = 71). Some studies indicated possible damage to the DNA, cells, oxidative balance, and reproduction of sea turtles associated with chemical contaminants as metals, emerging, and mixtures of organic pollutants. Research gaps and recommendations for future studies were addressed to help understand the toxicity of chemical pollutants in sea turtles. The purpose of this review is to contribute for supporting actions to mitigate the threats posed by pollution to these protected species, as well as to plan new studies in this research field for both conservation and biomonitoring purposes.

RESUMEN

Chemical risk assessments typically focus on single substances, often overlooking real-world co-exposures to chemical mixtures. Mixture toxicology studies using representative mixtures can reveal potential chemical interactions, but these do not account for the unique chemical profiles that occur in the blood of diverse individuals. Here we used the H295R steroidogenesis assay to screen personalized mixtures of 24 persistent organic pollutants (POPs) for cytotoxicity and endocrine disruption. Each mixture was reconstructed at a human exposure relevant concentration (1×), as well as at 10- and 100-fold higher concentration (10×, 100×) by acoustic liquid handling based on measured blood concentrations in a Swedish cohort. Among the twelve mixtures tested, nine mixtures decreased the cell viability by 4-18%, primarily at the highest concentration. While the median and maximum mixtures based on the whole study population induced no measurable effects on steroidogenesis at any concentration, the personalized mixture from an individual with the lowest total POPs concentration was the only mixture that affected estradiol synthesis (35% increase at the 100× concentration). Mixtures reconstructed from blood levels of three different individuals stimulated testosterone synthesis at the 1× (11-15%) and 10× concentrations (12-16%), but not at the 100× concentration. This proof-of-principle personalized toxicity study illustrates that population-based representative chemical mixtures may not adequately account for the toxicological risks posed to individuals. It highlights the importance of testing a range of real-world mixtures at relevant concentrations to explore potential interactions and non-monotonic effects. Further toxicological studies of personalized contaminant mixtures could improve chemical risk assessment and advance the understanding of human health, as chemical exposome data become increasingly available.

RESUMEN

Microbially induced calcium precipitation (MICP) has been extensively discussed as a water treatment method. However, the impact of MICP on the selective adsorption of different organic contaminants in industrial wastewater and the metabolism and growth of bacteria has not been elucidated in detail. In this study, by comparing the differences in the metabolism and removal of bacteria by phenol, bisphenol A (BPA), and tetracycline (TC), it was found that bioprecipitates had significant differences in the adsorption capacity of organic pollutants with different molar volumes. Concurrently, bacteria produced more extracellular polymeric substances (EPS) under the influence of organic pollutants, and the self-protection mechanism of bacteria would reduce the amount of gaseous nitrogen. However, the points on the surface of EPS promoted the process of MICP, and MICP encapsulated bacteria to form precipitates to regulate bacteria in water and further improve the removal of carbon and nitrogen in water through biomineralization. This experiment provides new insights into the selective adsorption of bioprecipitates and its multiple effects on bacteria.

RESUMEN

Chlorinated paraffins (CPs) and microplastics (MPs) are commonly found in deep-sea cold seep sediments, where nitrogen cycling processes frequently occur. However, little is known about their combined effects on sedimentary microbial communities and nitrogen cycling in these environments. This study aimed to investigate the synergistic impacts of CPs and MPs on microbial communities and nitrogen cycling in deep-sea cold seep sediments through microcosm experiments. Our results demonstrated that the presence of CPs and MPs induced significant alterations in microbial community composition, promoting the growth of Halomonas. Furthermore, CPs and MPs were found to enhance nitrification, denitrification and anammox processes, which was evidenced by the higher abundance of genes associated with nitrification and denitrification, as well as increased activity of denitrification and anammox in the CPs and MPs-treatment groups compared to the control group. Additionally, the enhanced influence of CPs and MPs on denitrification was expected to promote nitrate-dependent and sulfate-dependent anaerobic oxidation of methane, thereby resulting in less methane released into the environment. These findings shed light on the potential consequences of simultaneous exposure to CPs and MPs on biogeochemical nitrogen cycling in deep-sea cold seep sediments.

RESUMEN

The advanced oxidation process is an efficient technology for the degradation and detoxification of refractory organics to ensure water safety. However, most researches focus on improving pollutant degradation but overlook carbon emission and resource utilization. In this study, a flow-through electrochemical integrated system was constructed to simultaneously realize bisphenol A (BPA) oxidation into small non-toxic organics and CO2, and generated CO2 coupled with nitrate-containing wastewater conversion to urea and ammonia on a porous cathode (Zr-Fe/CN). The synergistic effect between anodic BPA oxidation with cathodic CO2 and NO3-reduction improves the electron utilization efficiency and thus increasing the BPA degradation, urea yield rate (UYR) and NH3 yield rate (NYR) by 13.4 % 18.4 % and 8.3 %, respectively. Furthermore, the flow-through operation mode significantly increased the mass transfer efficiency and quickly carried generated CO2 from the anode into the cathode to improve CO2 utilization efficiency. Compared to the parallel plate electrode reactor, the BPA degradation efficiency, UYR and NYR in the flow-through reactor increased from 59.46 % to 84.49 % (the initial concentration of BPA was 40 mg/L), 9.94 mmol h-1g-1 to 19.55 mmol h-1g-1, and 80.31 mmol h-1g-1 to 106.06 mmol h-1g-1 within 60 min, respectively. Moreover, the total carbon conversion efficiency (from BPA to urea) increased from 20.2 % to 42.4 % and the total Faraday efficiency (FE) increased from 78.6 % to 96.3 %. This work provides a multi-win strategy of harmless, resource-based and carbon emission reduction for wastewater treatment.

RESUMEN

In this study, hazardous wastes including fluff, dust, and scrubbing sludge were sampled in 2019 from two metal shredding facilities located in Wallonia, Belgium. To assess the extent of the contamination, a global approach combining chemical and biological techniques was used, to better reflect the risks to health and the environment. The samples investigated induced significant in vitro aryl hydrocarbon receptor (AhR) agonistic bioactivities and estrogenic receptor (ERα) (ant)agonistic bioactivities in the respective CALUX (chemical activated luciferase gene expression) bioassays. The mutagenicity of the samples was investigated with the bacterial reverse gene mutation test using the Salmonella typhimurium TA98 and TA100 strains. Except for the sludge sample (site 3), all samples induced a mutagenic response in the TA98 strain (± S9 metabolic fraction) whereas in the TA100 strain (+ S9 metabolic fraction), only the sludge sample (site 2) showed a clear mutagenic effect. The in vivo toxicity/teratogenicity of the shredder wastes was further evaluated with zebrafish embryos. Except for the dust sample (site 2), all samples were found to be teratogenic as they returned teratogenic indexes (TIs) > 1. The high levels of contamination, the mutagenicity, and the teratogenicity of these shredder wastes raise significant concerns about their potential negative impacts on both human health and environment.

RESUMEN

Environmental MPs are complex mixtures of plastic polymers and sorbed chemical pollutants with high degrees of heterogeneity, particularly in terms of particle size, morphology and degree of weathering. Currently, limitations exist in sampling sufficient amounts of environmental particles for laboratory studies to assess toxicity endpoints with statistical rigor and to examine chemical pollutant interactions. This study seeks to bridge this gap by investigating environmental plastic particle mimetics and pollutant-polymer interactions by mixing polymer particles with persistent organic pollutants (POPs) at set concentrations over time. Solutions containing combinations of polymers including polystyrene (PS), polypropylene (PP), polyethylene terephthalate (PET), and polyamide (PA) and POPs including 2,3,7,8 -Tetrachlorodibenzo-p-dioxin (TCDD), bisphenol A (BPA), and atrazine, were stirred for up to 19 weeks and monitored using assays to test for aryl hydrocarbon (AhR) and estrogen receptor (ER) activity which are cell signaling pathways impacted by environmental pollutants. TCDD induced AhR activity decreased over time in the presence of PS in a surface area dependent manner. BPA and atrazine also exhibited AhR antagonist activity in the presence of TCDD. The addition of BPA slowed the loss of activity but atrazine did not, suggesting that polymer chemistry impacts interactions with POPs. We also observed potential differences in TCDD sorption with different plastic polymers and that higher concentrations of PS particles may inhibit BPA-induced estrogen receptor activation. These results emphasize the need for additional understanding of how POPs and polymer chemistry impacts their interaction and toxicity.

RESUMEN

The characteristic of semi-volatility enables persistent organic pollutants (POPs) almost ubiquitous in the environment. There is increasing concern about the potential risks of exposure to POPs due to their lipophilicity and readily bioaccumulation. Lipid droplets (LDs) are highly dynamic lipid storage organelles, alterations of intracellular LDs play a vital role in the progression of many prevalent metabolic diseases, such as type 2 diabetes (T2D) and nonalcoholic fatty liver disease (NAFLD). This article systematically reviewed the biological processes involved in LDs metabolism, the role of LDs proteins and LDs in metabolic diseases, and summarized updating researches on involvement of POPs in the progression of LDs-related metabolic diseases and potential mechanisms. POPs might change the physiological functions of LDs, also interfere the processes of adipogenesis and lipolysis by altering LDs synthesis, decomposition and function. However, further studies are still needed to explore the underlying mechanism of POPs-induced metabolic diseases, which can offer scientific evidences for metabolic disease prevention.

RESUMEN

Variable importance is a key statistical issue in exposure mixtures, as it allows a ranking of exposures as potential targets for intervention, and helps to identify bad actors within a mixture. In settings where mixtures have many constituents or high between-constituent correlations, estimators of importance can be subject to bias or high variance. Current approaches to assessing variable importance have major limitations, including reliance on overly strong or incorrect constraints or assumptions, excessive model extrapolation, or poor interpretability, especially regarding practical significance. We sought to overcome these limitations by applying an established doubly-robust, machine learning-based approach to estimating variable importance in a mixtures context. This method reduces model extrapolation, appropriately controls confounding, and provides both interpretability and model flexibility. We illustrate its use with an evaluation of the relationship between telomere length, a measure of biologic aging, and exposure to a mixture of polychlorinated biphenyls (PCBs), dioxins, and furans among 979 US adults from the National Health and Nutrition Examination Survey (NHANES). In contrast with standard approaches for mixtures, our approach selected PCB 180 and PCB 194 as important contributors to telomere length. We hypothesize that this difference could be due to residual confounding in standard methods that rely on variable selection. Further empirical evaluation of this method is needed, but it is a promising tool in the search for bad actors within a mixture.

RESUMEN

In the state of New South Wales (NSW), Australia, recent legislative action has focused on identifying key threats to the marine estate. We used a systematic literature review to evaluate the knowledge status of the effects of estuarine outflows on coastal marine ecosystems, within the environmental, hydrological, and physicochemical context of NSW waters. Results focussed on studies that measured outcomes for marine biota (n = 56). Trace elements and organochlorines were the most frequently studied contaminant types, with reported biological concentrations often below guideline values but detected at the highest concentrations adjacent to urban sources. Few studies measured the impacts of legacy and emerging contaminants to animal health, or the flow on effects to marine ecosystems in NSW. Our review highlights key biological and geographical data gaps in estuarine outflow research in NSW, particularly of the impact on ecosystems of exported carbon and nutrients to the oligotrophic waters of NSW.

RESUMEN

Although the ovarian reserve is constituted in utero, the literature on the effects of persistent organic pollutants (POPs) during this vulnerable period on the ovarian reserve later in life is limited. We investigated whether cord blood concentrations of POPs were associated with decreased anti-Müllerian hormone (AMH, a marker of the ovarian reserve) levels in girls at the age of 12. We included 239 girls from the French mother-child PELAGIE cohort. POP concentrations of 14 organochlorine pesticides, 17 polychlorinated biphenyls (PCBs), 5 polybrominated diphenyl ethers, and 9 per-polyfluoroalkyl substances were measured on cord blood sampled at birth. During a follow-up study at 12 years old, blood samples were collected to measure AMH levels. Single-exposure associations were examined with multivariable linear regression models adjusted a priori for potential confounders. Stratification on menarche status was also performed. Mixture effects were investigated using quantile g-computation and Bayesian kernel machine regression. Overall, 16 POPs were measured in at least 30% of samples. No significant associations were found in multivariable linear regressions, except for the third tercile of exposure to PCB 180 which was statistically significantly associated with an increase in AMH levels at 12 years old (Tercile 2 v. Tercile 1: 0.13 ng/mL, 95% CI = -0.29, 0.56; Tercile 3 v. Tercile 1: 0.51 ng/mL, 95% CI = 0.02, 0.99). Additionally, in post-menarcheal girls (N = 104) only, the second tercile of p,p'-DDE was statistically significantly associated with decreased AMH levels at 12 years old (Tercile 2 v. Tercile 1: -0.61 ng/mL, 95% CI = -1.16, -0.05, Tercile 3 v. Tercile 1: 0.02 ng/mL, 95% CI = -0.51, 0.54). Both mixture models returned null associations. Despite the limited associations observed in this study, we recommend exploring these associations in larger mother-child cohorts and at older ages.

RESUMEN

As an electrochemical advanced oxidation process, the electro-Fenton (EF) process has gained significant importance in the treatment of wastewater and persistent organic pollutants in recent years. As recently reported in a bibliometric analysis, the number of scientific publications on EF have increased exponentially since 2002, reaching nearly 500 articles published in 2022 (Deng et al., 2022). The influence of the main operating parameters has been thoroughly investigated for optimization purposes, such as type of electrode materials, reactor design, current density, and type and concentration of catalyst. Even though most of the studies have been conducted at a laboratory scale, focusing on fundamental aspects and their applications to degrade specific pollutants and treat real wastewater, important large-scale attempts have also been made. This review presents and discusses the most recent advances of the EF process with special emphasis on the aspects more closely related to future implementations at the large scale, such as applications to treat real effluents (industrial and municipal wastewaters) and soil remediation, development of large-scale reactors, costs and effectiveness evaluation, and life cycle assessment. Opportunities and perspectives related to the heterogeneous EF process for real applications are also discussed. This review article aims to be a critical and exhaustive overview of the most recent developments for large-scale applications, which seeks to arouse the interest of a large scientific community and boost the development of EF systems in real environments.

RESUMEN

Homogenous advanced oxidation processes (AOPs) based on transition metal catalysts toward the activation of H2O2 to hydroxyl radical (•OH) have been widely applied to organic pollutants removal, such as Fenton and Fenton-like processes. These transition metal catalysts mostly flocculate as the pH increases. It's worth noting that the formed transition metal flocs are complex heterogeneous aggregations with active substances, providing diverse reaction spaces and interfaces. However, it is a challenge to distinguish the roles of transition metal flocs in the organic pollutants removal from homogeneous catalytic reactions. Herein, we unveiled a pathway for the long-lasting removal of organic pollutants via Cr flocs adsorbed with •OH (HO•-Cr flocs) using a stepwise method. First, adsorbed •OH (•OHads) within the HO•-Cr flocs was proved to be the active site forming hydrogen bond (H-bond) and van der Waals force with organic pollutants. Then, the presence of switchable electron transfer between Cr and OH groups within the HO•-Cr flocs was revealed, contributing to the persistent existence of •OHads and consequently ensuring the long-lasting organics removal. Further, this removal pathway of organic pollutants was confirmed during the leather wastewater treatment. These findings will complement a different pathway for organic pollutants removal via transition metal flocs and extend the lifetime of homogeneous AOPs based on transition metal catalysts, providing significant implications for their design and optimization.

RESUMEN

Human activities related to agriculture and industrial development result in the emission of different types of pollutants in the environment. The phytosanitary pressure depends on the time of the year, the type of habitat, and the used treatments. Wildlife, particularly ungulates, can be exposed to pesticides and trace metals through their herbivorous diet directly impregnated by the environmental contamination. Wild game thus plays a sentinel role but can also represent a risk for human health by exposing venison consumers to these contaminants. The present study explored this dual problem in two types of habitat: forests and agricultural plains located in North-eastern France. Samples of liver and muscle were taken from ten roe deer, five caught on the forests and five others in the plains, to determine contaminant levels. There was no significant difference in contamination of roe deer livers according to the habitat for three trace metals (chromium, nickel, and copper), while lead concentrations were higher in samples from the plain (0.85 vs. 0.74 mg·kg-1 dry matter DM; P < 0.01). Conversely, zinc concentrations were higher in forest roe deer (110 vs. 95 mg·kg-1 DM; P < 0.05). Cadmium concentrations did not differ significantly between the two habitats, but forest samples showed strong inter-individual variability, with some values close to those observed on the plains and others higher (1.8 vs. 0.3 mg·kg-1 DM for forest and plain, respectively; P = 0.11). Mercury was not detected in any sample. The majority of pesticides investigated were not detected. Only a few pesticides were in trace amount (from 1 to 8 µg·kg-1 fresh matter), either in the liver (e.g., heptachlor and oxychlordane) or in both tissues, liver and muscle (e.g., pyridalyl). Some compounds were only detected in plain (e.g., cypermethrin and fenpropidin) and others in forest (piperonyl butoxide and pyridalyl) samples. Analyses mainly detected insecticides in samples taken from forests and agricultural plains. Fungicides and a few herbicides were mainly detected in plain sampled animals. Pesticides and copper concentrations in roe deer tissues were lower than maximum residue levels established for farm (copper) or wild terrestrial (pesticides) animals. Cadmium concentrations were also lower than the maximum level for most samples, except for some forest roe deer. However, both forest and plain roe deer exceeded the maximum level for lead in liver. Human exposure was simulated according to different amounts of meat consumed and compared with toxicological reference values. This study highlighted an overall low risk to human health for both pesticides, copper and lead, with more reservations about cadmium for some roe deer shot in forest. The differences in roe deer contamination between forests and agricultural plains for some trace elements and organic pollutants confirmed the sentinel role of this species.

RESUMEN

Despite their global ban in 2001, persistent organic pollutants (POPs) remain detectable in marine species, posing ongoing environmental and health risks. Current use pesticides (CUPs) like chlorpyrifos and chlorothalonil, along with polycyclic aromatic hydrocarbons (PAHs), also contaminate coastal areas, affecting human health. This study assessed POPs, CUPs and PAHs in bivalves, gastropods, polychaetes, crustaceans, and echinoderms from an Atlantic Patagonian harbor. Concentrations of organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs), and polybrominated diphenyl ethers (PBDEs) ranged from

Asunto(s)

RESUMEN

Phenol, quinoline, and pyridine, commonly found in industrial wastewater, disrupt the nitrification process, leading to nitrite accumulation. This study explores the potential mechanisms through which these biotoxic organic compounds affect nitrite accumulation, using metagenomic and molecular docking analyses. Despite increasing concentrations of these compounds from 40 to 160 mg/L, ammonia nitrogen removal was not hindered, and stable nitrite accumulation rates exceeding 90 % were maintained. Additionally, these compounds inhibited nitrite-oxidizing bacteria (NOB) and enriched ammonia-oxidizing bacteria (AOB) in situ. As the concentration of these compounds rose, protein (PN) and polysaccharide (PS) concentrations also increased, along with a higher PN/PS ratio. Metagenomic analysis further revealed an increase in hao relative abundance, while microbial community analysis showed increased Nitrosomonas abundance, which contributed to nitrite accumulation stability. Molecular docking indicated that these compounds have lower binding energy with hydroxylamine oxidoreductase (HAO) and nitrate reductase (NAR), theoretically supporting the observed sustained nitrite accumulation.

Asunto(s)

RESUMEN

Advanced oxidation processes (AOP) stood out as an efficient alternative for the treatment of organic contaminants. In this work, there were proposed syntheses of mixed catalysts of pyrite and graphene oxide and pyrite and zinc oxide to treat a mixture of the drugs atenolol and propranolol in aqueous solution through the photo-Fenton process with ultraviolet radiation. The efficiency of the methodologies used in the syntheses was confirmed through different characterization analyses. It was verified that the pyrite and zinc oxide catalyst led to the best contaminant degradation percentages with values equal to 88 and 84% for the groups monitored at the wavelengths (λ) of 217 and 281 nm. The degradation kinetics presented a good fit to the kinetic model proposed by Chan and Chu (2003) with R2 equal to 0.99, indicating a pseudo-first-order degradation profile. Finally, toxicity tests were carried out with two types of seeds, watercress and cabbage, for the solution before and after treatment. The cabbage seeds showed a reduction in germination percentages for the samples after treatments, while no toxicity was observed for watercress ones. This highlights the importance of evaluating the implications caused by products in relation to different organisms representing the biota.

RESUMEN

Polycyclic aromatic hydrocarbons (PAHs), such as phenanthrene (PHE), are common pollutants found in coastal areas where shrimp farming is developed. Even though PAHs can have adverse effects on physiology, shrimp can detoxify and metabolize toxic compounds and neutralize the reactive oxygen species (ROS) produced during this process. This requires the activation of multiple antioxidant enzymes, including peroxiredoxin 6 (Prx6). Prx6 uses glutathione (GSH) to reduce phospholipid hydroperoxides, a function shared with GSH peroxidase 4 (GPx4). Prx6 has been scarcely studied in crustaceans exposed to pollutants. Herein, we report a novel Prx6 from the shrimp Penaeus vannamei that is abundantly expressed in gills and hepatopancreas. To elucidate the involvement of Prx6 in response to PAHs, we analyzed its expression in the hepatopancreas of shrimp sub-lethally exposed to PHE (3.3 µg/L) and acetone (control) for 24, 48, 72, and 96 h, along with GPx4 expression, GSH-dependent peroxidase activity, and lipid peroxidation (indicated by TBARS). We found that GPx4 expression is not affected by PHE, but Prx6 expression and peroxidase activity decreased during the trial. This might contribute to the rise of TBARS found at 48 h of exposure. However, maintaining GPx4 expression could aid to minimize lipid damage during longer periods of exposure to PHE.

Asunto(s)

RESUMEN

Although enhancing the catalytic oxidation activity is a hotspot in thermal-driven catalytic disposal of persistent organic pollutants, few studies have managed to improve catalysts' water-resistance properties. Herein, we developed Fe2-xMnxO3 perovskite to boost the catalytic oxidation of hexabromocyclododecane under humidity by modulating its super-exchange interaction (SEI, Fe3+ + Mn3+ → Fe2+ + Mn4+). Fe0.4Mn1.6O3, with the strongest SEI, exhibits the biggest oxidation rate-constant, which is 3 times higher than that of commonly used Fe2O3 without SEI. Notably, unlike Fe2O3 which deactivates at a relative humidity of 5 %. Fe0.4Mn1.6O3 maintains its activity and is even boosted by 22 % compared to dry conditions. Mechanistic insights reveal that SEI between Fe and Mn enhances the reactivity of Mn4+- linked Olatt by lowering the reductive temperature from Mn4+ to Mn3+. Meanwhile, SEI promotes the adsorption of the associatively adsorbed H2O (HOH-type water) by reducing adsorption energy, thereby facilitating the formation of hydroxyl species, which are crucial for the oxidation process under humidity.