Presence Of Natural Organic Matter Research Articles

Investigation of Kinetic, Equilibrium, and Thermodynamic Modeling of Perfluorooctanoic Acid (PFOA) Adsorption in the Presence of Natural Organic Matter (NOM) by Dielectric Barrier Discharge Plasma-Modified Granular Activated Carbon (GAC)

Perfluorooctanoic acid (PFOA) contamination in water sources poses significant environmental and health concerns. The kinetic, equilibrium, and thermodynamic features of PFOA adsorption in the existence of natural organic matter (NOM) were thoroughly investigated in this work using granular activated carbon (GAC) modified by dielectric barrier discharge (DBD) plasma. The impacts of DBD plasma parameters on the adsorption process were systematically examined. The results demonstrated that GAC modified by DBD plasma exhibited enhanced adsorption performance for PFOA, even in the presence of NOM. The optimal condition for plasma-treated GAC was achieved with 20 min of plasma treatment time and 100 W of plasma power, resulting in 92% PFOA removal efficiency in deionized water (DIW) and 97% removal efficiency in Chao Phraya River water (CPRW). A kinetic investigation using the pseudo-first-order model (PFOM), the pseudo-second-order model (PSOM), and the Elovich model (EM) indicated that plasma treatment time and NOM presence influenced the adsorption capacity and rate constants of PFOA with the PSOM having emerged as the most fitting kinetic model. The Langmuir isotherm model indicates monolayer adsorption of PFOA on plasma-treated GAC, with higher maximum adsorption capacity while NOM is present. The Redlich–Peterson and Sips isotherm models indicated varying adsorption capacity and heterogeneity in the adsorption system. The Sips model was determined as the most fitting isotherm model. Furthermore, the favorable and spontaneous character of PFOA adsorption onto plasma-treated GAC was validated by thermodynamic analysis, with endothermic heat absorption during the process. Overall, this comprehensive investigation provides valuable insights into the adsorption characteristics of PFOA in the existence of NOM using GAC modified by DBD plasma.

Role of Ripening in the Deposition of Fragments: The Case of Micro- and Nanoplastics.

Particulate contaminants, such as microplastics (1 μm to 5 mm) and nanoplastics (<1 μm), are disseminated in many terrestrial environments. However, it is still unclear how particles' properties drive their mobility through soils and aquifers due to (i) poor environmental relevance of the model particles that are studied (e.g., spherical and monodisperse) and (ii) the use of packed bed experiments which do not allow a direct observation of deposition dynamics. Using transparent 2D porous media, this study analyzes deposition dynamics of rough polystyrene fragments with irregular shapes and with a size continuum (≈10 nm to 5 μm). Using in situ and ex situ measurements, particle deposition as a function of size was monitored over time under repulsive conditions. In the absence of natural organic matter (NOM), micrometric particles rapidly deposit and promote the physical interception of smaller nanoparticles by creating local porous roughness or obstacles. In the presence of NOM, differences according to particle size were no longer observed, and all fragments were more prone to being re-entrained, thereby limiting the growth of deposits. This work demonstrates the importance of pore surface roughness and porosity of the pore surface for the deposition of colloidal particles, such as microplastics and nanoplastics, under repulsive conditions.

Effect of humic acid on visible light photocatalytic inactivation of bacteriophage f2 with electrospinning Cu-TiO2 nanofibers: insight into the mechanisms.

Photocatalytic disinfection is a promising technology with low cost and high efficiency. However, most of the current studies on photocatalytic disinfection ignore the widespread presence of natural organic matter (NOM) in water bodies, so the incomplete conclusions obtained may not be applicable. Herein, this paper systematically studied the influence of humic acid (HA), one of the most important components of NOM, on the photocatalytic inactivation of bacteriophage f2 with electrospinning Cu-TiO2 nanofibers. We found that with the addition of HA, the light transmittance of the solution at 550 nm decreased from 94 to 60%, and the band gap of the photocatalyst was increased from 2.96 to 3.05 eV. Compared with reacting without HA, the degradation amount of RNA of f2 decreased by 88.7% after HA was added, and the RNA concentration increased from 1.95 to 4.38 ng·μL-1 after the reaction. Hence, we propose mechanisms of the effect of HA on photocatalytic disinfection: photo-shielding, passivation of photocatalysts, quenching of free radicals, and virus protection. Photo-shielding and photocatalyst passivation lead to the decrease of photocatalyst activity, and the reactive oxygen species (ROSs) (·OH, ·O2-, 1O2, H2O2) are further trapped by HA. The HA in water also can protect the shape of phage f2 and reduce the leakage of protein and the destruction of ribonucleic acid (RNA). This work provides an insight into the mechanisms for the influence of HA in photocatalytic disinfection process and a theoretical basis for its practical application.

Removal of neonicotinoids present in secondary effluents by ferrate(VI)-based oxidation processes

The persistence in the environment and possible harmful effects of neonicotinoid insecticides have raised some concerns, which have led to the proposal of various measures for their remediation. The aim of this work was to study the elimination of five neonicotinoids (thiamethoxam (THM), imidacloprid (IMI), clothianidin (CLO), thiacloprid (THC), and acetamiprid (ACE)) using ferrate (Fe(VI)) as the oxidizing agent. Firstly, second-order rate constants for the reactions of neonicotinoids with Fe(VI) were determined at different pHs. The most reactive compound was THC, with a rate constant of 400 ± 43 M−1 s−1 at pH 8 (the optimum pH considering the predominance of the most reactive species (HFeO4−) and the decreasing self-decomposition of Fe(VI) with pH), followed by CLO (10.7 ± 1.7 M−1 s−1), THM (9.7 ± 0.7 M−1 s−1), and IMI (2.5 ± 0.6 M−1 s−1). ACE did not significantly react with Fe(VI). The oxidation of the selected pollutants in secondary effluents by Fe(VI) was rather slow, and only THC could be efficiently removed. The presence of natural organic matter (NOM) exerted a negative influence on the removal of the neonicotinoids of moderate reactivity with Fe(VI) (CLO, THM, and IMI). The additional presence of peroxymonosulfate (Fe(VI)/PMS system) slightly increased the removal of neonicotinoids due to the formation of hydroxyl and sulfate radicals. Finally, the application of the Fe(VI)/sulfite system considerably increased the oxidation rate of the selected pollutants, with enhanced formation of hydroxyl and, especially, sulfate radicals. Overall, these results suggest that the Fe(VI)/sulfite system has significant potential to address environmental and health concerns associated with neonicotinoids in water sources with low NOM content.Graphical abstract

Arsenic(III) sorption on organo-ferrihydrite coprecipitates: Insights from maize and rape straw-derived DOM

The mobility of arsenic (As) specie in agricultural soils is significantly impacted by the interaction between ferrihydrite (Fh) and dissolved organic material (DOM) from returning crop straw. However, additional research is necessary to provide molecular evidence for the interaction of toxic and mobile As (As(III)) specie and crop straw-based organo- Fh coprecipitates (OFCs). This study investigated the As(III) sorption behaviours of OFCs synthesized with maize or rape derived-DOM under various environmental conditions and the primary molecular sorption mechanisms using As K-edge X-ray absorption near edge structure (XANES) spectroscopy. According to our findings, pure Fh adsorbed more As(III) relative to the other two OFCs, and the presence of natural organic matter in the OFCs induced more As(III) adsorption at pH 5.0. Findings from this study indicated a maximum As(III) sorption on Ma (53.71 mg g⁻1) and Ra OFC (52.46 mg g⁻1) at pH 5.0, with a sharp decrease as the pH increased from 5.0 to 8.0. Additionally, As K-edge XANES spectroscopy indicated that ∼30% of adsorbed As(III) on the OFCs undergoes transformation to As(V) at pH 7–8. Functional groups from the DOM, such as O–H, COOH, and CO, contributed to As(III) desorption and its oxidation to As(V), whereas ionic strength analysis revealed inner complexation as the dominant As(III) sorption mechanism on the OFCs. Overall, the results indicate that the interaction of natural organic matter (NOM) with As(III) at higher pH promotes As(III) mobility, which is crucial when evaluating As migration and bioavailability in alkaline agricultural soils.

Suların Klorla Dezenfeksiyonunda Trihalometan Oluşumuna Hümik Asit ve Bromürün Etkisi

Chlorination is one of the most important methods used in water disinfection. Chlorine reacts with natural organic substances in water and causes the formation of disinfection byproducts that might cause health problems. The predominant by-product of chlorination is trihalomethanes. Humic substances, which make up the majority of natural organic substances, are the primary precursors of trihalomethanes. In this study, the effect of different doses of chlorine on the formation of chloroform, bromodichloromethane, dibromochloromethane and bromoform in the presence of natural organic matter and bromide in drinking water was evaluated. Artificial raw water samples prepared with the addition of 2, 3 and 5 mg/L humic acid representing natural organic matter were subjected to chlorination at doses of 1, 2 and 3 mg/L and analysed on the 0th, 3rd and 7th day. The only trihalomethane formed was chloroform with a concentration of 20.52-131.13 μg/L. Increased humic acid and chlorine levels resulted in increased chloroform content. Free chlorine in the water caused chloroform formation to continue even on the 7th day. Accordingly, the amount of chloroform formed increased with the contact time. While the chlorine dose was constant, increased humic acid resulted in decreased free chlorine. To evaluate the effect of bromide on trihalomethane formation, 200 μg/L bromide was added to 2 mg/L humic acid containing water, and 1 mg/L and 2 mg/L chlorination was applied. At the end of the chlorination process in bromide-free waters, only 23.46-41.90 μg/L of chloroform was formed. In the presence of bromide, chloroform, bromodichloromethane, dibromochloromethane and bromoform were formed and the total trihalomethane level increased to 50.03-85.59 μg/L. While the ratio of brominated trihalomethane increased, the amount of chlorinated species decreased.

The overlooked role of the association between 2-methylisoborneol and natural organic matters in the nanofiltration treatment of authentic water

The presence of natural organic matter (NOM) in surface water and its significance for removing pollutants during nanofiltration (NF) are overlooked since most previous studies were conducted in synthetic water rather than real water. In this paper, using raw water collected from Lake Tai (the third largest lake in China), we investigate the removal of 2-methylisoborneol (2-MIB, one of the most concerned off-flavor compounds in raw water) by NF and analyze the binding behaviors between 2-MIB and NOM, which affect their corresponding migration and removal behaviors of 2-MIB during NF. The results show that the removal of 2-MIB in real raw water is 12.2 ∼ 22.0 % higher than that in pure water (PW). Additionally, we evaluate the increment of the removal of 2-MIB under different backgrounds, which follow the order NOM (17.2 %∼22.0 %) > bovine serum albumin (BSA 16.0 %∼19.1 %) > intracellular organic matter (IOM) of M. aeruginosa (8.3 %∼9.4 %) > sodium carboxymethyl cellulose (CMC 3.9 %∼6.5 %) > humic acid (HA 0.28 %∼0.31 %). These findings demonstrate that the protein-like components in raw water play a major role in binding to 2-MIB, while humic-like components exhibit a weak association with 2-MIB. Overall, the conclusion and findings in this study provide a new perspective on the NOM effect on micropollutant removal during water treatment.

Developing a hybrid model for predicting the reaction kinetics between chlorine and micropollutants in water

Understanding the reactivities of chlorine towards micropollutants is crucial for assessing the fate of micropollutants in water chlorination. In this study, we integrated machine learning with kinetic modeling to predict the reaction kinetics between micropollutants and chlorine in deionized water and real surface water. We first established a framework to predict the apparent second-order rate constants for micropollutants with chlorine by combining Morgan molecular fingerprints with machine learning algorithms. The framework was tuned using Bayesian optimization and showed high prediction accuracy. It was validated through experiments and used to predict the unreported apparent second-order rate constants for 103 emerging micropollutants with chlorine. The framework also improved the understanding of the structure-dependence of micropollutants’ reactivity with chlorine. We incorporated the predicted apparent second-order rate constants into the Kintecus software to establish a hybrid model to profile the time-dependent changes of micropollutant concentrations by chlorination. The hybrid model was validated by experiments conducted in real surface water in the presence of natural organic matter. The hybrid model could predict how much micropollutants were degraded by chlorination with varied chlorine contact times and/or initial chlorine dosages. This study advances fundamental understanding of the reaction kinetics between chlorine and emerging micropollutants, and also offers a valuable tool to assess the fate of micropollutants during chlorination of drinking water.

Adsorption of antibiotics onto low-grade charcoal in the presence of organic matter: Batch and column tests

Antibiotics contaminate diverse ecosystems and threaten human health. In ecosystems including water, sediment, and soil, the amount of antibiotics present is tiny compared to the amount of natural organic matter. However, most studies have ignored the co-presence of natural organic matter in the adsorption of target antibiotics. In this study, we quantitatively evaluated the effect of co-presenting natural organic matter on the adsorption of sulfamethazine (SMZ) through batch and column experiments using low-grade charcoal, an industrial by-product. SMZ was used as a model antibiotic compound and humic acid (HA) was used to represent natural organic matter. The co-presence of 2000 mg/L HA (400 times the concentration of SMZ) lowered the adsorption rate of SMZ from 0.023 g/mg·min to 0.007 g/mg·min, and the maximum adsorption capacity from 39.8 mg/g to 15.6 mg/g. HA blocked the charcoal's pores and covered its surface adsorption sites, which dramatically lowered its capacity to adsorb SMZ. Similar results were obtained in the flow-through column experiments, where the co-presence of natural organic matter shortened the lifetime of the charcoal. As a result, the co-presence of a relatively high concentration of natural organic matter can inhibit the adsorption of SMZ and likely other antibiotic compounds, and thus the presence of natural organic matter should be accounted for in the design of adsorption processes to treat antibiotics in water.

Microplastics' Shape and Morphology Analysis in the Presence of Natural Organic Matter Using Flow Imaging Microscopy.

Ubiquitous microplastics in urban waters have raised substantial public concern due to their high chemical persistence, accumulative effects, and potential adverse effects on human health. Reliable and standardized methods are urgently needed for the identification and quantification of these emerging environmental pollutants in wastewater treatment plants (WWTPs). In this study, we introduce an innovative rapid approach that employs flow imaging microscopy (FlowCam) to simultaneously identify and quantify microplastics by capturing high-resolution digital images. Real-time image acquisition is followed by semi-automated classification using customized libraries for distinct polyethylene (PE) and polystyrene (PS) microplastics. Subsequently, these images are subjected to further analysis to extract precise morphological details of microplastics, providing insights into their behavior during transport and retention within WWTPs. Of particular significance, a systematic investigation was conducted to explore how the presence of natural organic matter (NOM) in WWTPs affects the accuracy of the FlowCam's measurement outputs for microplastics. It was observed that varying concentrations of NOM induced a more curled shape in microplastics, indicating the necessity of employing pre-treatment procedures to ensure accurate microplastic identification when utilizing the FlowCam. These observations offer valuable new perspectives and potential solutions for designing appropriate treatment technologies for removing microplastics within WWTPs.

Natural Organic Matter Removal in Surface Water Treatment via Coagulation—Current Issues, Potential Solutions, and New Findings

Considerable changes have been observed in surface waters’ quality in recent years. They include an increase in dissolved organic carbon (DOC) concentrations, as well as a shift of natural organic matter (NOM) composition in favor of low molecular weight (LMW), and they are expected to occur on a wider scale in the future. Those predictions are particularly worrying given the importance of surface water as the main potable water source for numerous communities across the globe. Conventional methods of surface water treatment for drinking purposes mostly focus on the process of coagulation. The progressing changes in the quality of surface waters, however, render the conventional treatment via coagulation inefficient. The issue of the presence of natural organic matter in drinking water sources, its anticipated changes, and the related treatment problems are all complex and pressing matters that need addressing. This paper aims to provide a critical review of recent findings regarding NOM removal via coagulation in reference to the current NOM-related issues and their potential solutions. The paper discusses the application of different types of coagulants, and their respective advantages and disadvantages. Coagulation-integrated processes including adsorption, membrane filtration, biological processes, and oxidation are also addressed. Lastly, insights on the future approach to the discussed issues and conclusions are presented.

A Perspective on Removal of Cyanotoxins from Water Through Advanced Oxidation Processes.

This perspective discusses the challenges associated with the removal of cyanotoxins from raw water sources for drinking water treatment and the emergence of sulfate radical-based advanced oxidation processes (SR-AOPs) as an effective treatment technique. The advantage of SR-AOPs is that they can be activated using a variety of methods, including heat, UV radiation, and transition metal catalysts, allowing for greater flexibility in treatment design and optimization. In addition, the byproducts of SR-AOPs are less harmful than those generated by •OH-AOPs, which reduces the risk of secondary contamination. SR-AOPs generate sulfate radicals (SO4 •-) that are highly selective to certain organic contaminants and have lower reactivity to background water constituents, resulting in higher efficiency and selectivity of the process. The presence of natural organic matter and transition metals in the natural water body increases the degradation efficiency of SR-AOPs for the cyanotoxins. The bromate formation is also suppressed when the water contaminated with cyanotoxins is treated with SR-AOPs.

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

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

Polymer based on beta-cyclodextrin for the removal of bisphenol A, methylene blue and lead(II): Preparation, characterization, and investigation of adsorption capacity

A bioadsorbent was prepared by applying a green facile synthesis route, using water as solvent and beta-cyclodextrin (βCD), citric acid (CA), and polyethylene glycol (PEG) as raw materials. The synthesis parameters were optimized, and the prepared βCD-CA-PEG polymer was thoroughly characterized. With FT-IR analysis, the formation of the new polymeric structure based on a network with ester bonds between βCD, PEG, and citric acid was detected. The increase in thermal stability revealed by the TGA analysis confirmed further the polymerization. The XRD and SEM analyses demonstrated that the original structure of βCD was changed, and a new amorphous structure was formed. The results of the SEM and BET analyses showed that the polymer has relatively low surface area and porosity. The zeta potential study revealed that the polymer has a negative surface charge at a pH range of 3–10. The swelling test showed moderate water uptake, suggesting good hydrophilicity and flexibility of the polymer’s network, thus enhancing the interaction with pollutants’ molecules. Regarding the adsorption performance of the βCD-CA-PEG polymer, bisphenol A (BPA), methylene blue (MB), and lead (Pb(II)) were rapidly and efficiently removed from aqueous solutions. The adsorption processes followed the pseudo-second-order kinetic model for all pollutants in both mono-pollutant and multi-pollutant systems. Furthermore, BPA and Pb(II) adsorption equilibrium data were well simulated by the Langmuir model, while MB adsorption fitted well to the Sips model. The presence of natural organic matter (humic acid) or the increased ionic strength (addition of NaCl) did not significantly impact the adsorption capacity. Finally, the polymer could be easily regenerated at room temperature and retained its good adsorption performance even after five adsorption–desorption cycles. The prepared βCD-CA-PEG polymer can pose an efficient alternative adsorptive in water and wastewater treatment targeting several pollutant categories, including specific organic micropollutants, cationic dyes and heavy metals.

Impact of Natural Organic Matter Competition on the Adsorptive Removal of Acetochlor and Metolachlor from Low-Specific UV Absorbance Surface Waters.

Although activated carbon adsorption is a very promising process for the removal of organic compounds from surface waters, the removal performance for nonionic pesticides could be adversely affected by co-occurring natural organic matter. Natural organic matter can compete with pesticides during the adsorption process, and the size of natural organic matter affects the removal of pesticides, as low-molecular-weight organics directly compete for adsorbent sites with pesticides. This study aims to investigate the competitive impact of low-molecular-weight organics on the adsorptive removal of acetochlor and metolachlor by four commercial powdered activated carbons. The adsorption features of selected powdered activated carbons were evaluated in surface water samples collected from the influent stream of the filtration process having 2.75 mg/L organic matter and 0.87 L/mg-m specific UV absorbance. The adsorption kinetics and capacities were examined by employing pseudo-first-order, pseudo-second-order, and intraparticle diffusion kinetic models and modified Freundlich and Langmuir isotherm models to the experimental data. The competitive removal of acetochlor and metolachlor in the presence of natural organic matter was evaluated for varied powdered activated carbon dosages on the basis of UV and specific UV absorbance values of adsorbed organic matter. The adsorption data were well represented by the modified Freundlich isotherm, as well as pseudo-second-order kinetics. The maximum organic matter adsorption capacities of the modified Freundlich isotherm were observed to be 120.6 and 127.2 mg/g by Norit SX Ultra and 99.5 and 100.6 mg/g by AC Puriss for acetochlor- and metolachlor-containing water samples, respectively. Among the four powdered activated carbons, Norit SX Ultra and AC Puriss provided the highest natural organic matter removal performances with 76 and 72% and 71 and 65% for acetochlor- and metolachlor-containing samples, respectively. Similarly, Norit SX Ultra and AC Puriss were very effective for adsorbing aromatic organics with higher than 80% specific UV absorbance removal efficiency. Metolachlor was almost completely removed by higher than 98% by Norit SX Ultra, Norit SX F Cat, and AC Puriss, even at low adsorbent dosages. However, an adsorbent dose of 100 mg/L and above should be added for all powdered activated carbons, except for Norit SX F Cat, for achieving an acetochlor removal performance of higher than 98%. The competition between low-molecular-weight organics (low-specific UV absorbance) and acetochlor and metolachlor was more apparent at low adsorbent dosages (10-75 mg/L).

Ecotoxicity studies of two atrazine nanoformulations: From the evaluation of stability in media to the effects on aquatic organisms

In the field of agriculture, nanopesticides have been developed as an alternative to the conventional pesticides, being more efficient for pest control. However, before their widespread application it is essential to evaluate their safe application and no environmental impacts. In this paper, we evaluated the toxicological effects of two kinds of atrazine nanoformulations (ATZ NPs) in different biological models (Raphidocelis subcapitata, Danio rerio, Lemna minor, Artemia salina, Lactuca sativa and Daphnia magna) and compared the results with nanoparticle stability over time and the presence of natural organic matter (NOM). The systems showed different characteristics for Zein (ATZ NPZ) (184 ± 2 nm with a PDI of 0.28 ± 0.04 and zeta potential of (30.4 ± 0.05 mV) and poly(epsilon-caprolactone (ATZ PCL) (192 ± 3 nm, polydispersity (PDI) of 0.28 ± 0.28 and zeta potential of −18.8 ± 1.2 mV) nanoparticles. The results showed that there is a correlation between nanoparticles stability and the presence of NOM in the medium and Environmental Concentrations (EC) values. The stability loss or an increase in nanoparticle size result in low toxicity for R. subcapitata and L. minor. For D. magna and D. rerio, the presence of NOM in the medium reduces the ecotoxic effects for ATZ NPZ nanoparticles, but not for ATZ NPs, showing that the nanoparticles characteristics and their interaction with NOM can modulate toxic effects. Nanoparticle stability throughout the evaluation must be considered and become an integral part of toxicity protocol guidelines for nanopesticides, to ensure test quality and authentic results regarding nanopesticide effects in target and non-target organisms.

Influence of the aqueous matrix on the degradation of cyanotoxins by CWPO: A study on the Iberian Peninsula freshwaters

The increasing occurrence of toxic cyanobacterial blooms worldwide represents a critical health and environmental risk. Catalytic wet peroxide oxidation (CWPO) has emerged as an efficient and environmentally friendly technology for the removal of cyanotoxins in water. Nevertheless, its effectiveness has just been demonstrated in deionized water or simple synthetic aqueous matrices. In this work, the effect of the different components of the aqueous matrix on the CWPO of cyanotoxins was deeply evaluated considering the widespread properties of the Iberian Peninsula freshwaters. The presence of Cl-, HCO3- and SO42- ions reduced the oxidation rate of cylindrospermopsin (CYN) up to 70–80% at the highest concentrations tested (2000, 250 and 500 mg L−1 for Cl-, HCO3- and SO42-, respectively) due to their hydroxyl radical scavenging capacity. The presence of natural organic matter (NOM) resulted in a similar outcome (oxidation rate reduction up to 90% at the highest concentration tested, 20 mg L−1), but in this case due to the consumption of hydroxyl radicals in competition with CYN oxidation. The presence of NO3- and H2PO4- did not show any significant effect on CYN oxidation. Similarly, the presence of cyanobacteria (Chrysosporum ovalisporum, 50 µg chlorophyll-a L−1) did not appreciably affect the CYN oxidation rate. These results were consistent with those obtained by evaluating the impact of real aqueous matrices from drinking water treatment plants (DWTPs) located in Castilla y León and Extremadura regions (Spain) on CWPO performance. This knowledge is key to the implementation of the technology for the treatment of surface waters affected by toxic cyanobacterial blooms.

Enhanced Oxidation of Antibiotics by Ferrate Mediated with Natural Organic Matter: Role of Phenolic Moieties.

The increasing presence of antibiotics in water sources threatens public health and ecosystems. Various treatments have been previously applied to degrade antibiotics, yet their efficiency is commonly hindered by the presence of natural organic matter (NOM) in water. On the contrary, we show here that nine types of NOM and NOM model compounds improved the removal of trimethoprim and sulfamethoxazole by ferrate(VI) (FeVIO42-, Fe(VI)) under mild alkaline conditions. This is probably associated with the presence of phenolic moieties in NOMs, as suggested by first-order kinetics using NOM, phenol, and hydroquinone. Electron paramagnetic resonance reveals that NOM radicals are generated within milliseconds in the Fe(VI)-NOM system via single-electron transfer from NOM to Fe(VI) with the formation of Fe(V). The dominance of the Fe(V) reaction with antibiotics resulted in their enhanced removal despite concurrent reactions between Fe(V) and NOM moieties, the radicals, and water. Kinetic modeling considering Fe(V) explains the enhanced kinetics of antibiotics abatement at low phenol concentrations. Experiments with humic and fulvic acids of lake and river waters show similar results, thus supporting the enhanced abatement of antibiotics in real water situations.

A systematic study on adsorptive removal of arsenic using low cost adsorbents with or without the presence of NOM

Arsenic is a toxic and bio-accumulating element in water bodies, especially in drinking water sources.One of the methods used to remove arsenic from drinking water is adsorption. NOM (natural organic matter), which is ubiquitous in natural aquatic environments, can inhibit arsenic adsorption by competing with arsenic for adsorbent surface sites. The main objectives of this study were to investigate the competitive adsorption between NOM and arsenic using low-cost adsorbents. For this purpose, batch adsorption experiments were carried out in synthetic and natural water using pumice, steel slag and red mud as low cost adsorbents.The highest arsenic removal efficiencies obtained with steel slag, pumice and red mud were 95, 95 and 50 %, respectively without the presence of NOM. The results showed that the presence of NOM caused a significant reduction in arsenic adsorption for all tested adsorbents and 20-30% less arsenic removal efficiency was obtained in natural water compared to the removal efficiencies obtained in synthetic water. The maximum adsorption capacities obtained in synthetic water with all tested adsorbents vary between 1.6 -3.05 mgAs/g, while the maximum adsorption capacities obtained in natural water vary between 0.9-1.2 mgAs/g. All these findings indicate that NOM can hinder the uptake of arsenic by all tested adsorbents. Moreover, the arsenic adsorption in natural water were modelled by Langmuir, Freundlich and modified Freundlich. The results showed that the arsenic adsorption data were well fitted by modified Freundlich isotherm with R2 values between 0.87 and 0.90.

Trihalomethanes formation potential of polluted tropical river water and its correlation with UV-Vis spectral ratio: A case study in Citarum River, Indonesia

The presence of natural organic matter (NOM) and anthropogenic organic matter (AOM) in polluted river water leads to the formation of carcinogenic disinfection by-products (DBPs) during the water chlorination process. This study aimed to determine trihalomethanes (THMs) formation, as the regulated DBPs, in polluted tropical river water. The samples were taken from the Citarum River, Bandung, Indonesia. The NOM and AOM were characterized using UV254, UV355, and ultraviolet-visible (UV-Vis) spectral ratio while DBPs formation was determined using THM4 formation potential. In several sampling points, the THM4 formation potential of the samples exceeded the USEPA regulation standards and had high toxicity (LC50) values. On the other hand, other sampling points had small THM4 formations. Also, the THM4 formation potential was found to have a great correlation with the spectral ratio, especially A280/A350 UV absorbances that could be further used as a surrogate parameter of THM4 formation. Citarum River, as a water source, needs sufficient treatment to remove the DBPs precursors to provide healthy and clean potable water.