Transformation By-products Research Articles

Solid-Phase Reactivity-Directed Extraction (SPREx): An Alternative Approach for Simultaneous Extraction, Identification, and Prioritization of Toxic Electrophiles Produced in Water Treatment Applications.

Current strategies to assess water quality are ineffective at prioritizing the most toxic chemicals within a treated water sample. Although it is well known that oxidation byproducts (OBPs) from water treatment processes (e.g., chlorination and ozonation) are linked to adverse health outcomes such as skin diseases, reproductive toxicity, and various cancers, we are still unable to account for a large fraction of the toxicity drivers. Previous approaches utilize in vitro or in vivo assays to assess OBPs on an individual basis, which is too time- and resource-intensive considering the countless number of transformation byproducts of unknown toxicities that exist in treated waters. In vitro assays have also been developed to analyze the toxicity of OBPs in environmental mixtures, but these approaches do not provide identification information about the responsible toxicants. Furthermore, an additional challenge for OBP detection arises during the extraction and detection stages of analysis, as certain OBPs are typically lost using traditional extraction methods or are not detectable via liquid-chromatography-high-resolution mass spectrometry (LC-HRMS) without derivatization. To address these issues, we have developed the analytical assay Solid-Phase Reactivity-directed Extraction (SPREx), which aims to provide an all-in-one evaluation for (i) in chemico toxicity screening, (ii) extraction, (iii) detection, and (iv) identification via LC-HRMS. The performance of SPREx was evaluated by testing different nucleophile probes for the capture and detection of 24 different carbonyl compounds, which serve as model electrophiles and are known OBPs that provide unique extraction and detection challenges. SPREx provided distinct advantages for extraction recoveries and was an effective screening tool for carbonyl detection and quantification in complex water matrices such as drinking water and wastewater.

Comparing occurrence of per- and polyfluoroalkyl substances (PFAS) in municipal biosolids and industrial wastewater sludge: A City of Los Angeles study

Biosolids and sludge are what remain after the liquid fraction of wastewater is separated during wastewater treatment. These high organic content matrices are known to contain organic contaminants, a few of which are the hazardous and environmentally persistent per- and polyfluoroalkyl substances (PFAS). The current study investigates whether sludge from a treatment facility serving mostly industrial establishments and biosolids from a facility serving mostly domestic dwellings retain these ‘forever chemicals’ similarly. Using 31 markers covering different classes of PFAS, the sludge was found to contain higher levels of PFAS (869 ± 791 ng/g; 21 of 31) than biosolids (31 ± 7 ng/g, 11 of 31). The most abundant overall was perfluorooctane sulfonic acid (PFOS), mostly in sludge (range: 71–1300 ng/g versus 0–18 ng/g in biosolids). The large PFAS concentration variability in sludge was seasonal and sinusoidal. Sludge, additionally, contained all long chain PFAS, precursors (mostly surfactant ingredients and their transformation byproducts) and short chain PFAS (perhaps because of higher moisture content). By regression, the sludge is shown to consistently contain twice as much PFAS as biosolids when the same amounts are exposed to increasing levels of PFAS. Factors observed to cause differential PFAS retention between sludge and biosolids were moisture (98.6 % and 72.1 %, respectively), chain length, input quality (industrial versus residential) and functional group. Sulfonic acids for instance are one C atom shorter than carboxylates with similar occurrence in sludge and biosolids. More studies are needed to define the roles that organic carbon of sludge/biosolids, water chemistry, temperature and factors not considered here play in partitioning PFAS between the two matrices with respect to inputs. Existing Koc values could not help in explaining observed trends, but the ratio of biosolids-to-influent concentrations was found to correlate positively with PFAS size. Using influent in the ratio, and not effluent, is novel. SynopsisSludge and biosolids are soil amendments; they contain hazardous and persistent PFAS. Methods of decoupling PFAS from these matrices start with understanding matrix-driven PFAS partitioning as shown here.

Assessing the environmental risk potential of transformation byproducts formed during fungal enzymatic treatment of a pharmaceutical mixture

The present study advances our understanding of the ecological risk potential associated with pharmaceutical mixtures treated with fungal enzymes. We optimized a submerged bioreactor for fungal enzyme production by testing three fungal species and adjusting the organic loading rate and retention time, yielding enzyme activities exceeding 20 U/L. These fungal enzymes effectively reduced the half-lives of tetracycline and sulfamethoxazole to less than 3 h in a mixture of tetracycline and sulfamethoxazole, using syringaldehyde as an optimized mediator. Analytical chemistry assessments identified transformation products (TPs) generated in situ from the mixture, revealing three novel transformation pathways. Quantitative structure–activity relationship analysis highlighted two TPs with heightened toxicity and prolonged persistence compared to their parent compound. Furthermore, these TPs exhibited distinct environmental mobility characteristics at the liquid–solid interface. Our combined experimental and computational framework allowed for a systematic screening of pharmaceutical residues, considering aspects such as toxicity, mobility, persistence, bioaccumulation, and removal. This approach has practical implications for prioritizing target pollutants in subsequent monitoring and environmental risk assessments.

Toxicity assessment of dioxins and their transformation by-products from inferred degradation pathways

Due to the significant POPs characteristics, dioxins caused concern in public health and environmental protection. Evaluating the toxicity risk of dioxin degradation pathways is critical. OCDD, 1,2,3,4,6,7,8-HpCDD, and 1,2,3,4,6,7,8-HpCDF, which are highly abundant in the environment and have strong biodegradation capabilities, were selected as precursor molecules in this study. Firstly, their transformation pathways were deduced during the metabolism of biometabolism, microbial aerobic, microbial anaerobic, and photodegradation pathways, and density function theory (DFT) was used to calculate the Gibbs free energy to infer the possibility of the occurrence of the transformation pathway. Secondly, the carcinogenic potential of the precursors and their degradation products was evaluated using the TOPKAT modeling method. With the help of the positive indicator (0–1) normalization method and heat map analysis, a significant increase in the toxic effect of some of the transformation products was found, and it was inferred that it was related to the structure of the transformation products. Meanwhile, the strength of the endocrine disrupting effect of dioxin transformation products was quantitatively assessed using molecular docking and subjective assignment methods, and it was found that dioxin transformation products with a higher content of chlorine atoms and molecules similar to those of thyroid hormones exhibited a higher risk of endocrine disruption. Finally, the environmental health risks caused by each degradation pathway were comprehensively assessed with the help of the negative indicator (1–2) standardization method, which provides a theoretical basis for avoiding the toxicity risks caused by dioxin degradation transformation. In addition, the 3D-QSAR model was used to verify the necessity and rationality of this study. This paper provides theoretical support and reference significance for the toxicity assessment of dioxin degradation by-products from inferred degradation pathways.

Electrocatalytic water treatment of per- and polyfluoroalkyl substances reduces adsorbable organofluorine and bioaccumulation potential.

Per- and polyfluoroalkyl substances (PFAS) are pervasive in industrial processes, eliciting public concern upon their release into municipal sewers or the environment. Removing PFAS from the environment has become an urgent need. However, because potential endpoints span from energy-intensive complete mineralization to partial PFAS transformation, understanding and developing metrics for evaluating PFAS treatment can be a challenge. The goal of this study was to evaluate and compare the effectiveness of electrocatalytic degradation of PFAS with boron-doped diamond (BDD) electrodes using four techniques: LC-MS/MS target analysis, fluoride ion (F-), adsorbable organofluorine (AOF), and bioaccumulation potential using lipid-bilayer partition (LBP) tests. After 3 hours of electrocatalysis, >99% perfluorooctanoic acid (PFOA) degradation was achieved and corresponded with 84% conversion to F-, which was substantial - though intentionally not complete - defluorination. For the same 3 hour treatment time, AOF and LBP coefficient were reduced by 95% and 83%, respectively. LBP's detection limit was 2 orders of magnitude higher than that of AOF, so the positive correlation observed between LBP and AOF (r = 0.86) suggests AOF's practical utility as a design metric for assessing bioaccumulation potential of various organofluorine transformation by-products.

Impact of organic matter on transformation during thermal remediation of pyrene-contaminated substrates

Thermal remediation (TR) is a broadly applicable technology that is effective at removing volatile and semi-volatile contaminants from soil. However, TR can be costly and inefficient in practice, with underlying removal and transformation mechanisms poorly understood. To better understand the role organic matter plays in removal, a series of experiments was performed with a humic substance, humic modified silica, and a natural soil in the presence of pyrene from 100 to 500 °C and compared to prior experiments using pure minerals. Detection of by-products confirmed that pyrene was removed by transformation in addition to volatilization. Oxidation via hydroxyl radical formation and reductive hydrogenation were both indicated as possible reaction mechanisms promoted by organic matter. Because the presence of bulk water did not impact the extent of pyrene degradation or transformation, it is hypothesized that hydroxyl radicals were produced from soil organic matter functional groups, such as carboxyl and phenol groups, and possibly bound water at elevated temperatures in dry experiments. Additionally, the average oxidation state of carbon in detected by-products increased with temperature in experiments with humic modified silica and soil but not humic substance alone, though the extent of degradation did not significantly change. This shift in oxidation state may indicate that attachment of organic matter to another surface may increase interaction between reactive species. The results of this study show that contaminant transformation in soils during TR significantly contributes to removal, even at temperatures lower than those used in traditional treatment. This information will help to guide the design and operation of TR systems, potentially reducing energy requirements and highlighting the necessity of testing for transformation by-products.

Weathering alters the profile of trace metals and organic compounds in leachates and bioavailability extracts from microplastics of trail running shoes

Microplastics (MPs) from rubber outsoles of trail running shoes may contribute significantly to contamination in protected areas. In the natural environment, weathering processes can damage MP molecular structure and alter the mobility of inorganic and organic compounds used as additives in rubber. In this study, we characterised changes in the surface morphology, functional groups, and thermal stability of MPs weathered on and below the soil surface over 12 weeks, and analysed inorganic and organic additives in leachates (0.01M CaCl2) and bioaccessibility extracts (ethyl acetate). Weathering conditions included UVC irradiation at 25 °C and 80% soil moisture. Microplastics on the soil surface exhibited cracking, fragmentation, and increased extractability of zinc, sulphur, titanium and fatty acids. Microplastics below the soil surface were not significantly physically or chemically altered, however zinc leachability increased following extended weathering by up to 155%. Bioaccessibility of thiol, aromatic and cyclic organic additives decreased from both surface and sub-surface MPs over the 12 week weathering period, but there was evidence of an increase in transformation by-products. Microplastic toxicity may be significantly altered by environmental conditions and MP weathering. It is critical ecotoxicological studies use weathered MPs to assess impacts on rare and endemic species found in protected spaces.

Multivariate effect of inorganic wastewater matrix on the removal of pesticides by solar photo-Fenton

An amount of works has reported the effect of wastewater matrix composition on pollutants removal by different AOPs. The biggest challenge is that each wastewater source has a challenging composition (organic and inorganic compounds, pollutants, etc.) and not only the concentration of all these species but also the interaction between them may affect the effectiveness of the studied process. This work has been carried out to evaluate the photo-degradation kinetics of six different pesticides (flutriafol, imidacloprid, myclobutanil, pirimicarb, thiamethoxam and triadimenol) by solar photo-Fenton (SPF) process at acidic pH. First, oxidant concentration (H2O2) was optimized with an actual WWTP effluent. Then, the process was validated with two different secondary and tertiary WWTP effluents, in which main intermediate transformation by-products were identified. Finally, the effect of the inorganic water matrix components (bicarbonate, chloride, sulphate, nitrate and phosphate) was evaluated by a multivariate analysis. Once H2O2 has been optimized at 30 mg L−1, the photo-degradation efficiency of pesticides in real wastewater samples was compared. DOC content of both secondary and tertiary WWTP effluents was dropped by 67%. The identification of the main intermediate transformation by-products (such as 1H-1,2,4-triazole, desmethyl-formamido pirimicarb, thiamethoxam urea, chloronicotinic acid and imidacloprid urea) was reviewed. Following, the multivariate analysis on pesticides photo-degradation, generally, predicted four significant effects in common for the studied pesticides: a positive effect (interaction bicarbonate/nitrate) and three negative ones (chloride, phosphate and the interaction chloride/sulphate); among others. In addition, optimum values of inorganic ion concentrations, to obtain an optimum desirability on studied pesticides removal by SPF at acidic pH, were also evaluated.

Leaves are a Source of Biogenic Persistent Free Radicals.

Nonsenescent and senescent leaves of selected coniferous and broadleaf plants contained substantial levels of naturally occurring persistent free radicals (PFRs). These biogenic PFRs (BPFRs) were stable and persistent despite multiple wetting and drying cycles, implying that BPFRs can leach and sorb on soil particles. Results suggest that endogenous chemicals in plants and their transformation byproducts can stabilize unpaired electrons in leaves under ambient conditions. Thus, the vast amount and perpetual supply of leaf litter is an unaccounted natural source of BPFRs. If toxic, inhaling and accidentally ingesting fine soil dust and powder from degraded leaf litter may increase our environmental and health burdens to PFRs. We expect that this finding will generate more studies on natural sources of PFRs, establish their properties, and distinguish them from those formed from combustion and thermal processes.

Transformation and toxicity studies of UV filter diethylamino hydroxybenzoyl hexyl benzoate in the swimming pools

Diethylamino hydroxybenzoyl hexyl benzoate (DHHB), an ultraviolet (UV) filter, can be found in sunscreens and other personal care products and thus can be introduced into swimming pools through the swimmers. In outdoor pools, DHHB will inevitably interact with free chlorine and sunlight. Therefore, the mechanism of solar‑chlorine chemical transformation of DHHB, as well as the environmental risk, were investigated in this work. In chlorinated with solar (Cl + solar) process, free chlorine was the dominant contributor to 85% of the DHHB degradation, while hydroxyl radicals and reactive chlorine species contributed only 15% because of low free radical generation and fast DHHB and free chlorine reaction rates. Scavenging matrices, such as Cl−, NH4+, and dissolved organic matter (DOM), inhibited the degradation of DHHB in the Cl + solar process, while Br−, HCO3–, NO3–, and urea promoted DHHB degradation. DHHB degradation was inhibited in tap water swimming pool samples, while it was enhanced in seawater pool samples by the Cl + solar process. Seven transformation by-products (TBPs) including mono-, dichlorinated, dealkylate, and monochloro-hydroxylated TBPs were identified. Three degradation pathways, chlorine substitution, chlorine and hydroxyl substitution, and dealkylation were proposed for DHHB transformation in the Cl + solar process. Both Quantitative structure-activity relationship and Aliivibrio fischeri toxicity tests demonstrated increased toxicity for the chlorinated TBPs. A risk assessment of the DHHB and its TBPs suggested that both DHHB and its chlorinated TBPs pose a significant health risk.

Electrooxidation of Phenol on Boron-doped Diamond and Mixed-metal Oxide Anodes: Process Evaluation, Transformation By-products, and Ecotoxicity

Phenolic pollutants raise health and environmental concerns due to their widespread occurrence in industrial wastewaters. Electrooxidation was studied for phenol degradation in different supporting electrolytes: NaCl, Na2SO4, H2SO4. Experiments were performed at constant current density 20 mA cm−2. Two anode materials were tested ‒ boron-doped diamond (BDD) and mixed-metal oxide (MMO). Degradation process and its impact was investigated from technological, analytical, and ecotoxicological viewpoints. Removal efficiency was monitored by phenol index spectrophotometric method and phenol removal quantified with HPLC-DAD. Additionally, transformation by-products were tracked with GC-MS and LC-MS, as well as ion chromatography. Finally, ecotoxicity was investigated using Daphnia magna. Electrooxidation was efficient and had low energy consumption. The use of BDD anode led to higher removal efficiencies and induced more progressive degradation to simple organic acids, compared to MMO. Selection of electrolyte affected degradation pathways and detoxification pattern. Treatment by BDD in NaCl led to complete phenol removal in 30 min, but undesired chlorinated aromatic by-products were formed. Treatment in sulphate medium led to slower processes irrespective of pH, but less problematic by-products with minimal ecotoxicological impact emerged. By using multi-aspect methodology, this study reevaluates phenol electrooxidative degradation and contributes to better understanding of electrooxidation performance in water treatment.

Degradation of benzothiazole by the UV/persulfate process: Degradation kinetics, mechanism and toxicity

Benzothiazole, a high-production chemical used in domestic and industrial applications, possesses a persistent nature and is ubiquitous in aquatic environments; this study aims to investigate benzothiazole degradation by utilizing a UV-activated persulfate process (UV/persulfate). The results demonstrated that the UV/persulfate process can efficiently degrade benzothiazole in deionized water (the pseudo-first-order degradation rate constant (kobs) was 0.0847 min−1 under the experimental conditions of [benzothiazole]0 = 10 mg/L, [persulfate]0 = 150 mg/L and initial solution pH = 7). kobs and persulfate dose (18.75 to 150 mg/L) exhibited a linearly proportional relationship (R2 = 0.9696). The optimal benzothiazole degradation rate occurred at pH 7 (kobs = 0.0847 min−1) compared with those at pH 3 (kobs = 0.0516 min−1) and 11 (kobs = 0.0450 min−1). The presence of common water constituents (HCO3–, Cl–, NO3– and dissolved organic matter) had an inhibitory effect on benzothiazole degradation. Radical scavenger experiments showed that both SO4•– and •OH were involved in benzothiazole degradation, with SO4•– playing a relatively predominant role. The second-order rate constant between SO4•– and benzothiazole was 2.1 × 109 M−1 s−1. Two transformation byproducts of benzothiazole degradation were detected, which were generated through the dihydroxylation and trihydroxylation reactions of benzothiazole. During the UV/persulfate process, the toxicity (Microtox®) increased and then declined within 60 min of reaction time. The results suggested that the UV/persulfate process is an efficient way to remove benzothiazole from water.

Metformin Contamination in Global Waters: Biotic and Abiotic Transformation, Byproduct Generation and Toxicity, and Evaluation as a Pharmaceutical Indicator.

Metformin is the first-line antidiabetic drug and one of the most prescribed medications worldwide. Because of its ubiquitous occurrence in global waters and demonstrated ecotoxicity, metformin, as with other pharmaceuticals, has become a concerning emerging contaminant. Metformin is subject to transformation, producing numerous problematic transformation byproducts (TPs). The occurrence, removal, and toxicity of metformin have been continually reviewed; yet, a comprehensive analysis of its transformation pathways, byproduct generation, and the associated change in adverse effects is lacking. In this review, we provide a critical overview of the transformation fate of metformin during water treatments and natural processes and compile the 32 organic TPs generated from biotic and abiotic pathways. These TPs occur in aquatic systems worldwide along with metformin. Enhanced toxicity of several TPs compared to metformin has been demonstrated through organism tests and necessitates the development of complete mineralization techniques for metformin and more attention on TP monitoring. We also assess the potential of metformin to indicate overall contamination of pharmaceuticals in aquatic environments, and compared to the previously acknowledged ones, metformin is found to be a more robust or comparable indicator of such overall pharmaceutical contamination. In addition, we provide insightful avenues for future research on metformin.

The efficient degradation of diclofenac by ferrate and peroxymonosulfate: performances, mechanisms, and toxicity assessment.

In this study, the degradation efficiency and reaction mechanisms of diclofenac (DCF), a nonsteroidal anti-inflammatory drug, by the combination of ferrate (Fe(VI) and peroxymonosulfate (PMS) (Fe(VI)/PMS) were systematically investigated. The higher degradation efficiency of DCF in Fe(VI)/PMS system can be obtained than that in alone persulfate (PS), Fe(VI), PMS, or the Fe(VI)/PS process at pH 6.0. DCF was efficiently removed in Fe(VI)/PMS process within a wide range of pH values from 4.0 to 8.0, with higher degradation efficiency in acidic conditions. The increasing reaction temperature (10 to 30 ℃), Fe(VI) dose (6.25 to 100µM), or PMS concentration (50 to 1000µM) significantly enhanced the DCF degradation. The existences of HCO3¯, Cl¯, and humic acid (HA) obviously inhibited the DCF removal. Electron paramagnetic resonance (EPR), free radical quenching, and probing experiments confirmed the existence of sulfate radicals (SO4•¯), hydroxyl radicals (•OH), and Fe(V)/ Fe(IV), which are responsible for DCF degradation in Fe(VI)/PMS system. The variations of TOC removal ratio reveal that the adsorption of organics with ferric particles, formed in the reduction of Fe(VI), also were functioned in the removal process. Sixteen DCF transformation byproducts were identified by UPLC-QTOF/MS, and the toxicity variation was evaluated. Consequently, eight reaction pathways for DCF degradation were proposed. This study provides theoretical basis for the utilization of Fe(VI)/PMS process.

The role of bromides upon electrochemical mineralization of bisphenol A with boron-doped diamond anode

Anodic oxidation with boron-doped diamond (BDD) has been regarded as outstanding option for wastewater treatment. However, in the presence of halide, the extreme promise of the technology may be hampered by the formation of toxic halogenated by-products. While the behaviors of chloride are relatively understood, little is currently known about the role of bromide and its effect on the generation of brominated transformation by-products (BTPs). Herein, we reported for the first time the bromide-mediated electrochemical mineralization of bisphenol A with BDD anodes. Firstly, we employed statistical methodology to determine the impacts of the main operating variables on the mineralization performance, and the novel and peculiar roles of bromides during the electrolytic oxidations were identified. Next, LC/MS analysis was used to identify the reaction intermediates, and plenty of BTPs (including oligomers of complex structures) were thus detected. Detailed transformation mechanisms responsible for the BTPs were also proposed. Lastly, we used ECOSAR program to determine the ecological toxicity of all detected by-products, and the structure-toxicity relation involved was discussed. Overall, the above results are of particular interest to understand BTPs formation mechanism in electrochemical oxidation processes, which as well provide guidelines to minimize potential risks of BDD technology for phenolic wastewater treatment.

Superior visible light-mediated catalytic activity of a novel N-doped, Fe3O4-incorporating MgO nanosheet in presence of PMS: Imidacloprid degradation and implications on simultaneous bacterial inactivation

Impressive Imidacloprid (IMD) degradation and bacterial inactivation were attained through the photocatalytic activation of peroxymonosulfate (PMS) via a novel, N-doped MgO@Fe3O4, under visible light. After complete characterization (XPS, XRD, FT-IR, FE-SEM, EDX, HRTEM, DRS, BET, VSM, and EIS), using [PMS]=75 mg/L, [N-MgO@Fe3O4]=150 mg/L at pH=5.6, around 95% of 10 mg/L IMD was degraded within 60 min; highly synergic interactions between the various catalytic routes were revealed. Extensive scavenger tests and EPR studies revealed that SO4•-, HO•, and 1O2 are generated and play a key role in IMD degradation. Tap water experiments proceeded unhindered, and only the presence of high HCO3- and PO43- concentration resulted in a decrease in the IMD degradation efficiency, while negligible leaching, magnetization, notable separation, and reusability properties were well-preserved for six repetitive cycles. Finally, E. coli disinfection was achieved before IMD degradation, possibly affected by its transformation byproducts. The overall efficacy of N-MgO@Fe3O4 indicated the potential for implementation in contaminated waters.

Advanced electrochemical oxidation applied to benzodiazepine and carbamazepine removal: Aqueous matrix effects and neurotoxicity assessments employing rat hippocampus neuronal activity

Benzodiazepines and carbamazepine are mental disorder treatment-related contaminants of emerging concern (CECs) routinely detected in water bodies. Electrochemical oxidation (EO) processes have been proven effective in reducing CECs levels, although the toxic effects of residual compounds formed after EO are still scarcely studied. Herein, ultrapure water (UP), surface water (SW), municipal wastewater (MWW), and industrial pharmaceutical wastewater (IWW) were spiked with four benzodiazepines (alprazolam, clonazepam, diazepam, lorazepam) and carbamazepine (100 μg L−1 each) and treated by an EO process employing two electrodes: a platinum-coated titanium (Ti/Pt) and a boron-doped diamond (BDD). Neurotoxicity tests were performed by exposing rat hippocampus slices to EO-treated waters to investigate the effects of residual compounds on neuronal activity. The EO results indicate that both electrodes were efficient in completely removing the studied drugs from UP and SW, but that <50 % removal was achieved for MWW. For IWW, total organic carbon (up to 71 %) and total nitrogen (up to 82 %) removals were achieved at 1000 A m−2. UP exposure significantly reduced ROS production, likely due to the presence of transformation by-products. SW and MWW EO-treated waters led to slight neurotoxicity. Decreased neurotoxicity was mainly observed for the IWW after EO using both the BDD and Ti/Pt anodes. A ROS production evaluation following the application of several untreated effluent cycles demonstrated that long-term effects may alter cell functionality and that recovery responses decrease over time.

Micropollutant transformation and toxicity: Electrochemical ozonation versus biological metabolism

Environmental water sources are constantly polluted by anthropogenic compounds, not always minimized by conventional water treatment methods to remove these compounds at the micro- and nano-range. The absolute concentrations of a suite of seven representative environmental micropollutants were compared pre- and post-treatment with both ozone and microbial biofilms, in terms of removal efficiencies and toxicity assays. Both synthetic micropollutant mixes and environmental water samples were evaluated. The study started with two representative micropollutants (carbamazepine, CBZ, and sulfamethoxazole, SMX), and broadened into a suite of pollutants, evaluating whole-sample eco-toxicological footprints. An ozone concentration of 4.24 ± 0.27 mg/L in tap water, resulted in an 87.9% and 96.5% removal of CBZ and SMX, respectively, within 1 min. Despite almost immediate removal of parent micropollutants by oxidation, endocrine disruption potential (anti-estrogenicity) of CBZ and SMX required up to 240 min of ozone treatment to show no assay effect. A broader suite of micropollutants in more complex environmental matrices showed scavenging of ozone (2.95 ± 0.17–0.25 ± 0.03 mg/L) and varying micropollutant recalcitrance to oxidation. Lower matrix pollution led to lower reduction in eco-toxicity. Microbial degradation of CBZ and SMX (56% and 70% versus 19% and 79%, respectively, in duplicate biofilms) by nutrient-limited biofilms showed less removal than ozonation, with marked variation due to the stochastic nature of biofilm sloughing. Microbial degradation of CBZ and SMX resulted in an increase of &gt;90% in both estrogenicity and Aliivibrio inhibition. The results obtained from this study address a gap in understanding the removal efficiency of micropollutants, where the removal process often receives more attention than the comparative reduction of toxicological effects. This shift from a controlled laboratory environment to real-world scenarios also provided comparative insights into the removal of micropollutants and the eco-toxicity of the transformation by-products of each process.

Solar-light driven photodegradation of antimicrobials, their transformation by-products and antibiotic resistance determinants in treated wastewater

This study aimed to assess the possibility of using solar light-driven photolysis and TiO2-based photocatalysis to remove (1) antibiotic residues, (2) their transformation products (TPs), (3) antibiotic resistance determinants, and (4) genes identifying the indicator bacteria in a treated wastewater (secondary effluent). 16 antimicrobials belonging to the different classes and 45 their transformation by-products were selected for the study. The most susceptible to photochemical decomposition was tetracycline, which was completely removed in the photocatalysis process and in more than 80% in the solar light-driven photolysis. 83.8% removal (on average) was observed using photolysis and 89.9% using photocatalysis in the case of the tested genes, among which the genes sul1, uidA, and intI1 showed the highest degree of removal by both methods. The study revealed that applied methods promisingly remove the tested antibiotics, their TPs and genes even in such a complex matrix including treated wastewater and photocatalysis process had a higher removal efficiency of antibiotics, TPs and genes tested. Moreover, the high percentage removal of the intI1 gene (>93%) indicates the possibilities of use of the solar light-driven photolysis and TiO2-based photocatalysis in minimizing the antibiotic resistance genes transfer by mobile genetic elements.

Combined Analytical Study on Chemical Transformations and Detoxification of Model Phenolic Pollutants during Various Advanced Oxidation Treatment Processes.

Advanced oxidation processes (AOPs) have been introduced to deal with different types of water pollution. They cause effective chemical destruction of pollutants, yet leading to a mixture of transformation by-products, rather than complete mineralization. Therefore, the aim of our study was to understand complex degradation processes induced by different AOPs from chemical and ecotoxicological point of view. Phenol, 2,4-dichlorophenol, and pentachlorophenol were used as model pollutants since they are still common industrial chemicals and thus encountered in the aquatic environment. A comprehensive study of efficiency of several AOPs was undertaken by using instrumental analyses along with ecotoxicological assessment. Four approaches were compared: ozonation, photocatalytic oxidation with immobilized nitrogen-doped TiO2 thin films, the sequence of both, as well as electrooxidation on boron-doped diamond (BDD) and mixed metal oxide (MMO) anodes. The monitored parameters were: removal of target phenols, dechlorination, transformation products, and ecotoxicological impact. Therefore, HPLC–DAD, GC–MS, UHPLC–MS/MS, ion chromatography, and 48 h inhibition tests on Daphnia magna were applied. In addition, pH and total organic carbon (TOC) were measured. Results show that ozonation provides by far the most suitable pattern of degradation accompanied by rapid detoxification. In contrast, photocatalysis was found to be slow and mild, marked by the accumulation of aromatic products. Preozonation reinforces the photocatalytic process. Regarding the electrooxidations, BDD is more effective than MMO, while the degradation pattern and transformation products formed depend on supporting electrolyte.