Natural Organic Matter Concentration Research Articles

Natural organic matter source, concentration, and pH influences the toxicity of zinc to a freshwater microalga

Zinc is a contaminant of concern in aquatic environments and is a known toxicant to many aquatic organisms. Dissolved organic matter (DOM) is a toxicity modifying factor for zinc and is an important water chemistry parameter. This study investigated the influence of DOM concentration, source, and water pH on the chronic toxicity of zinc to a freshwater microalga, Chlorella sp. The influence of DOM on zinc toxicity was dependent on both concentration and source. In the absence of DOM, the 72-h EC50 was 112 μg Zn.L−1. In the presence of a DOM high in fulvic-like components, zinc toxicity was either slightly decreased (<4-fold increase in EC10s across 15 mg C.L−1 range) or unchanged (minimal difference in EC50s). In the presence of a DOM high in humic-like (aromatic and high molecular weight) components, zinc toxicity was slightly decreased at the EC10 level and strongly increased at the EC50 level. The influence of pH on zinc toxicity was dependent on the source of DOM present in the water. In the presence of DOM high in humic-like components pH did not influence toxicity. In the presence of DOM high in fulvic-like components, pH had a significant effect on EC50 values. Labile zinc (measured by diffusive gradients in thin-films) followed linear relationships with dissolved zinc but could not explain the changes in observed toxicity, with similar DGT-labile zinc relationships shown for the two DOMs despite each DOM influencing toxicity differently. This indicates changes in toxicity may be unrelated to changes in zinc lability. The results suggest that increased toxicity of zinc in the presence of DOM may be due to direct uptake of Zn-DOM complexes. This study highlights the importance of considering DOM source and characteristics when incorporating DOM into water quality guidelines through bioavailability models.

Nitrite Quantification by Second Derivative Chemometric Models Mitigates Natural Organic Matter Interferences under Chloraminated Drinking Water Distribution System Conditions

Nitrite (NO2−) production in chloraminated drinking water distribution systems (CDWDSs) is among the first bulk water indicators of a nitrification event and is typically quantified using ion chromatography (IC) or colorimetric techniques. NO2− can also be quantified using chemometric models (CMs) formulated using molar absorptivity (Ɛ) and/or ultraviolet absorbance (UVA) spectra, but concerns exist regarding their accuracy and generalizability because of varying source water natural organic matter (NOM), monochloramine (NH2Cl), bromide (Br−), and other species in CDWDSs. We demonstrate that the impact of NOM was mitigated in the second derivative molar absorptivity (Ɛ″) and UVA spectra (UVA″) between 200–300 nm and developed a generalizable CM for NO2− quantification. The Ɛ″+UVA″ CM was calibrated with daily NO2− measurements by IC from five biofilm annular reactor (BAR) tests with feedwater from Fayetteville, Arkansas, USA (FAY1, n = 275) and validated with eight BAR tests (n = 376) with another Fayetteville water (FAY2) and two waters from Dallas, Texas, USA (DAL1 and DAL2). The Ɛ″+UVA″ CM used Ɛ″ for NO2−, nitrate (NO3−), Br−, and NH2Cl at wavelengths of 213-, 225-, 229- and 253 nm, had an adjusted R2 of 0.992 for FAY1 and 0.987 for the other waters, and had a method detection limit (MDL) of 0.050 mg·L−1-N. NO2− challenge samples with three reconstituted NOM types and Br− indicated the Ɛ″+UVA″ CM was generalizable at NOM concentrations like those in the BAR tests (≤ 2.5 mg·L−1-C). The Ɛ″+UVA″ CM accurately simulated NO2− in field tests from two CDWDSs undergoing nitrification, including one with NOM at 3.5 mg·L−1-C, illustrating a practical application of the CM for identifying biological ammonia oxidation.

Resolving natural organic matter and nanoplastics in binary or ternary systems via UV–Vis analysis

Nanoplastics (NPs) and natural organic matter (NOM) are ubiquitous and usually present simultaneously in the environment. Both NPs and NOM can be adsorbed to minerals such as iron-(hydr)oxides, with such interactions being important for controlling their fate in the environment. However, the quantification of NPs and NOM in mixtures remains challenging even under controlled conditions in laboratory studies. In this research, a UV–Vis method was established to quantify concentrations of NOM, such as humic acid (HA) and fulvic acid (FA), and polystyrene NPs (PSNPs) in mixtures. In addition, both original NOM samples and those recovered following adsorptive fractionation using an iron oxide (goethite, α-FeOOH) were mixed separately with PSNPs and their concentrations were further calculated via the developed UV–Vis method. The UV–Vis method performed well (recovery of 100 ± 16 %) with original NOM and PSNPs system at detection limits of 20.8 and 7.4 mgC L−1, respectively. Particularly, for original FA and PSNPs systems with carboxylic groups (PSNPs-COOH, 200 nm), a similar recovery rate could be obtained at detection limits of only 2.5 and 1.9 mgC L−1, respectively. For fractionated NOM and PSNPs systems, detection limits (31.2 mgC L−1 and 27.5 mgC L−1, respectively) are increased to reach the same accuracy. Furthermore, the UV–Vis method can be used to estimate the proportion of HA that is adsorbed to PSNPs. The relative errors are < 13.7 % when the mass ratios of PSNPs and HA was between 1.6:1 and 8:1 and HA concentration was higher than 4.6 mgC L-1. This method developed can be applied to future laboratory research to investigate the interaction between NOM, NPs, and minerals.

Insight into the formation and biological effects of natural organic matter corona on silver nanoparticles in water environment using biased cyclical electrical field-flow fractionation

Natural organic matter (NOM) readily interacts with nanoparticles, leading to the formation of NOM corona structures on their surface. NOM corona formation is closely related to the surface coatings and bioavailability of nanoparticles. However, the mechanism underlying NOM corona formation on silver nanoparticles (AgNPs) remains largely unknown due to the lack of effective analytical methods for identifying the changes in the AgNP surface. Herein, the separation ability of biased cyclical electrical field-flow fractionation (BCyElFFF) for same-sized polyvinyl pyrrolidone-coated and poly(ethylene glycol)-coated silver nanoparticles (AgNPs) with different electrophoretic mobilities was evaluated under various electrical conditions. Then, the mechanism behind the NOM corona formation on these AgNP surfaces was elucidated based on the changes in the elution time and off-line characterization of the collected fractions during their elution time in a BCyElFFF run. Finally, the survival rates of E. coli exposed to polyvinyl pyrrolidone-coated and poly(ethylene glycol)-coated AgNPs with or without NOM collected during repeated BCyElFFF runs were observed to increase with increasing NOM concentration, clearly demonstrating the negative effect of NOM corona structures on the bioavailability of AgNPs. These findings highlight the powerful separation and isolation ability of BCyElFFF in studying the transformation and fate of nanoparticles in aqueous environments.

Effect of Seawater Intrusion on the Formation of Chlorinated and Brominated Trihalomethanes in Coastal Groundwater

Around the world, coastal groundwater is increasingly subject to seawater intrusion (SWI). The quality and characteristics of such waters differ from those of surface and groundwater. In the current study, trihalomethane (THM) formation under varying levels of SWI, natural organic matter (NOM), and chloride-to-bromide (Cl/Br) ratio was evaluated. Different levels of SWI were simulated by mixing deionized water with real seawater (RSW) collected from the Indian Ocean or synthetic seawater (SSW) by varying seawater volumes from 0% to 3%. Humic acid (0 to 5 mg/L) was added to represent NOM at concentrations mimicking natural levels of dissolved organic carbon. The chlorine demand of the simulated water samples was significantly correlated to SWI levels and NOM concentrations. THM concentration in SSW increased from 12.64 µg/L to 105.34 µg/L after 24 h and to 115.8 µg/L after 48 h for an increase from 0% to 3% volume of seawater. For water samples simulated with RSW, maximum THMs after 24 h were 119.2 µg/L, and after 48 h were 126.4 µg/L. An increase in NOM concentration in seawater-intruded water samples resulted in increasing THMs, especially tribromomethane. However, the increment in THMs at higher NOM concentration was lower compared to that at low NOM concentration. Chlorine demand was positively correlated only to tribromomethane. An increase in bromide concentration resulted in lower Cl/Br ratio and a concomitant increase in brominated THMs. The bromine substitution factor corresponding to increasing SWI of 0.25–3% decreased from 2.67 to 1.81 over a reaction time of 24 to 48 h, indicating a shift from TBM dominance to chlorinated THMs.

Effect of natural organic matter on Cr(VI) reduction by reduced nontronite

Fe(II)-bearing clay minerals are abundant in soils and are critical to control the fate of the highly toxic hexavalent chromium (Cr(VI)). Even though the reduction of Cr(VI) by Fe(II)-bearing clay minerals has been extensively studied, the effect of the commonly co-existing natural organic matter (NOM) on this process is poorly understood. This study aimed to understand the kinetics of Cr(VI) reduction by a typical Fe(II)-bearing clay mineral (i.e., reduced nontronite (rNAu-2)) in the presence of Suwannee River NOM and to unveil the possible mechanisms. Cr(VI) reduction experiments were conducted with different NOM concentrations in a range of 0 to 100 mg C L−1 under circumneutral pH. The time-course aqueous-phase measurements and solid-phase characterizations were performed with a combination of wet chemical methods, transmission electron microscopy (TEM), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS) analyses. The results demonstrated that NOM inhibited Cr(VI) reduction overall, mainly due to the decrease of Cr(VI) sorption on rNAu-2 by mineral-bound NOM. Besides the predominant solid Cr(III) species, soluble and mobile Cr(III) complexes were formed during reduction. Interestingly, the reduction rate (k) decreased with the increase of NOM concentration from 0 to 20 mg C L−1, but kept increasing when the concentration of NOM increased from 30 to 100 mg C L−1. The contrary pattern is due to the increasing promotion effects that offset the inhibitory effect caused by competitive sorption between Cr(VI) and NOM. The promotion effects may include weakening the mineral passivation by forming stable aqueous NOM-Cr(III) complexes, accelerating the electron transfer rate by dissolving rNAu-2, and donating electrons through NOM-Fe(II/III) complexes and/or NOM-Cr(V) complexes. This study extends our knowledge of Cr(VI) reduction by clay minerals in organic matter-rich soils and sediments and has important implication for understanding the transport and long-term behavior of Cr in the environment.

Correlation Analysis of the Carboxyl and Carbonyl Groups of Natural Organic Matter and the Formation Potential of Trihalomethanes and Chloral Hydrate

Natural organic matter (NOM) has always been considered the main precursor of disinfection by-products (DBPs) during the chlorine disinfection of drinking water. This research focuses on investigating the correlation between the functional group (carboxyl and carbonyl groups) content of NOM and the formation of trichloromethane (TCM) and chloral hydrate (CH). The quantitative determination of carboxyl groups, carbonyl groups, TCM, and CH were conducted during the drinking water treatment processes with different coagulant dosages and with/without pre-oxidation by KMnO4 or NaClO. The most appropriate coagulant for the removal of conventional components was polyaluminum chloride (PAC), and the dosage was 110 mg/L. Up to 43.7% and 14.5% of the carboxyl and carbonyl groups, respectively, were removed through the coagulation and sedimentation processes, which can be enhanced by increasing PAC dosage. The filtration process further increased the removal rates of these two functional groups to 59.8% and 33.5%, respectively. The formation potential of the TCM and CH decreased as the PAC dosage increased. Pre-oxidation by KMnO4 (0.8-1.0 mg/L) effectively controlled the formation of DBPs while increasing the carboxyl and carbonyl group content. Pre-oxidation by NaClO decreased the formation of TCM rather than CH, and a suitable amount (0.5-1.0 mg/L) decreased the carboxyl and carbonyl groups. It was found that there was a good linear correlation between carboxyl groups and TCM and CH. The linear fit R2 values of the carboxyl groups to TCM and CH were 0.6644 and 0.7957, respectively. The linear fit R2 values of the carbonyl groups to TCM and CH were 0.5373 and 0.7595, respectively.

Toxicity effects of ballast water treated by electrolysis process under different salinity conditions on plankton

The impacts of total residual oxidant (TRO) on ecological health have been of great concern due to their widespread ubiquity in disinfection process. However, little is known about the effects of discharge water produced by electrolysis-based Ballast Water Management System (BWMS) on the toxicity of plankton. The present study was conducted to investigate the effects of TRO at discharge-relevant concentrations on plankton under different salinity conditions. The results showed that brackish water always gave the highest TRO concentrations, which is related to the natural organic matter (NOM) content. TRO exposure significantly (p<0.01) inactivated ≥ 50 μm and 10–50 μm organisms. Biodiversity dropped significantly after TRO exposure, especially in brackish water conditions. Meanwhile, the discharge water still has an impact on plankton after neutralization. Therefore, proper disposal of TRO generated by BWMS is significant to maintain ecological balance and protect native biodiversity.

Adsorption-desorption of organic micropollutants by powdered activated carbon and coagulant in drinking water treatment

The addition of powdered activated carbon (PAC) and a coagulant during the coagulation-flocculation process is an easy and common option for tackling pollution peaks from organic micropollutants (OMPs) in the production of drinking water. However, the adsorption-desorption mechanisms during this process have not been thoroughly explored. Thus, this research aims to study the mechanisms involved and the impact of the operating conditions when PAC and coagulant are simultaneous used. A commercial PAC with a BET-specific surface area of 961 m2/g, and ferric chloride (FeCl3) were added simultaneously to three different waters spiked with 15 OMPs (pesticides and pharmaceuticals). Different parameters such as PAC and coagulant dosage, pH, contact time and the nature/content of the natural organic matter (NOM) were examined. Results showed that using coagulant + PAC reduced OMP adsorption efficiency, whereas increasing PAC dosage and extending contact time enhanced OMP removal efficiency. Furthermore, a high concentration of NOM affected micropollutant adsorption by competing for adsorption sites. This study highlights for the first time an unexpected phenomenon that significantly affects overall efficiency: i.e. OMPs adsorbed during the slow mixing step that desorbed during the sedimentation step. Desorption sometimes reduced by >30 % the overall efficiency of OMP removal. The parameters that affected efficiency loss were pH, contact time, NOM concentration, and PAC and FeCl3 dosage. Some operational adaptations could be considered regarding these parameters to avoid or reduce desorption, making the process more cost-effective.

Seasonal variations of natural organic matter (NOM) in surface water supplied to two coal-fired power stations.

Global issues such as pollution and global warming have resulted in changes in water characteristics over the past 20years. Natural organic matter (NOM) which is a major component in water systems has shown an increase globally. This increase in NOM concentration has negatively affected both water treatment processes and drinking water quality. It is subsequently critical to understand the seasonal variations and composition of NOM to be able to address issues related to NOM. In this study, techniques such as ultraviolet-visible spectroscopy, total organic carbon and liquid chromatography-organic carbon detection (LC-OCD) were used for characterisation and quantification of NOM. Two coal-fired power stations were selected for this study with each power station receiving water from a different source, i.e. power station A receives water from the Vaal River and power station B from the Nkomati River. Results from this study demonstrated that composition and concentration of NOM from these two water sources varied seasonally. Characterisation of NOM using the LC-OCD indicated that the different fractions of NOM, i.e. low molecular weight neutrals, low molecular weight acids, building blocks, humic substances and biopolymers, varied seasonally. The dissolved organic carbon concentration and specific ultraviolet absorbance values of the raw water at both power stations showed an increment amid the wet seasons and a decrease amid the dry seasons.

Performance study of fly-ash-derived coagulant in removing natural organic matter from drinking water: synthesis, characterization, and modelling.

This study is an attempt to develop a liquid coagulant using fly ash (FAC) for removing natural organic matter (NOM) from drinking water systems. Acid-alkali leaching and polymerization technique was used for developing FAC. Characterization of FAC was performed using Fourier-transform infrared spectroscopy (FESEM), field emission scanning electron microscopy (FTIR), and X-ray diffraction (XRD) to assess the surface morphology and functional groups present. FE SEM analysis revealed uneven, coarse, and irregular structure with numerous pores, an indicative of their high adsorption capacity. XRD study revealed that Al, Fe, and Si are the major constituent group of FAC. FAC demonstrated excellent potential in removing THMs precursors: dissolved organic carbon (84.46%), UV254 (90.57%), and turbidity (96.85%) from the drinking water systems. Charge neutralization followed by adsorption is the main mechanism behind NOM removal. Moreover, FAC also showed good capability in minimizing the reactivity of NOM (ASI-72.86%) towards THM formation. FAC proved to be a good alternative for conventional coagulant used in drinking water treatment and can be effectively used for reducing NOM content of raw water which leads to the formation of THMs on chlorination.

Resource utilization of chicken manure to produce biochar for effective removal of levofloxacin hydrochloride through peroxymonosulfate activation: The synergetic function of graphitization and nitrogen functionality

Transforming hazardous livestock manure into biochar as an advanced oxidation processes catalyst is a two-in-one strategy to treat waste by waste. In this work, a self-modified biochar catalyst obtained from chicken manure is developed for peroxymonosulfate activation to degrade levofloxacin hydrochloride. The deterioration rate of levofloxacin hydrochloride reached 89% in 40 min, after three cycles of the catalyst, the LFX still maintained 52% degradation rate. And under low levofloxacin hydrochloride concentration, the degradation rate can reach 99% within 40 min. Apart from catalyst characterization and optimization, the effects of catalyst, peroxymonosulfate, levofloxacin hydrochloride, co-existing anions, and natural organic matter concentrations during the reaction are investigated. Additionally, the quenching experiments and electron spin resonance spectroscopy both reveal the reaction mechanism. As the graphitic nitrogen combined with the sp2-hybridized carbon in biochar was highly electronegative, thus appealing electrons from neighboring carbon networks, making the adjoining carbon atoms to be positively charged, which facilitated the degradation process. The oxidative degradation of levofloxacin hydrochloride was ascribed to non-radical routes including surface-bound radicals, h+ and 1O2 mediated oxidation, the contribution rates were 91%, 93.5%, and 96.8%, respectively. Moreover, possible degradation pathways of levofloxacin hydrochloride are studied by Density Functional Theory (DFT) and LC-MS analysis. This work provides a novel method to produce chicken manure biochar by self-modified chicken manure during biochar pyrolysis for peroxymonosulfate activation in organic contaminations abatement and reveals the combined effect of graphitization and nitrogen functionalization while providing new ideas for the resource utilization of chicken manure.

Performance assessment and optimization of forward osmosis–low pressure ultrafiltration hybrid system using machine learning for rhodamine B removal

Here, an in-series forward osmosis-low pressure ultrafiltration membrane system was devised for water treatment. Response surface methodology (RSM) and artificial neural network (ANN) machine learning techniques were applied to evaluate this system's performance and optimization with respect to water flux and rhodamine B (RhB) removal. The effects of initial feed solution (FS) concentration, draw solution (DS) concentration, initial feed pH, and natural organic matter (NOM) concentrate were examined using a central composite design. Models developed using RSM and ANN could successfully fit and predict the data with >99.5 % accuracy. DS and FS concentrations were the most influential factors on water flux and RhB removal, respectively. Statistical parameters demonstrated that ANN approach (water flux = 98.46 % and RhB removal = 99.85 %) was more reliable than RSM; it also better predicted system performance (water flux = 95.06 %; RhB removal = 97.01 %). The predicted optimum conditions for water flux and RhB removal were FS concentration = 47.01 mg L−1, DS concentration = 4.91 M, initial pH = 10.99, and NOM concentration = 7.97 mg L−1. Under these conditions, RSM and ANN models predicted water fluxes of 16.37 L m−2 h−1 and 16.38 L m−2 h−1, respectively, and RhB removal of 99.99 % and 99.95 %, respectively.

Electrocoagulation of peatland runoff: Statistical optimization and economic analysis

Irish peatlands play a crucial role in delivering drinking water sources to large conurbations. However, peatland runoff contains a high concentration of natural organic matter (NOM), which is problematic for drinking water treatment as it decreases the effectiveness of conventional treatment and can lead to the formation of suspected carcinogenic disinfection by-products (DBPs). In this study, a low-cost and highly efficient electrocoagulation (EC) unit has been used to treat raw peatland runoff. EC processes were designed, evaluated and optimized via the response surface methodology (RSM). Total operation cost was calculated after the RSM process. Box-Behnken design (BBD) was employed in RSM to analyse the effect of the applied voltage, reaction time, and electrolyte (NaCl) addition on the removal of total organic carbon (TOC) and colour at 465 nm. Two second order polynormal equation models were fitted with a high R2 of 0.93 (TOC) and 0.96 (colour). The highest removal performance (88.44 % of TOC and 98.93 % of colour) was observed when the applied voltage and reaction time were at their middle level (i.e. 3 V and 35 min). The optimum values of operating variables obtained by the multi-objective optimization were a NaCl concentration of 130.4 mg/L, an applied voltage of 2.0 V and a reaction time of 47.0 min. Under these conditions, 85.2 % of TOC and 98.1 % of true colour (at 465 nm) was removed in the laboratory at an operating cost of 0.50 €/m3, representing a higher TOC and colour removal and lower total operating cost than previous studies. The cost of NaCl contributed the most of the three factors to the total cost of the treatment process.

Preferential interactions of surface-bound engineered single stranded DNA with highly aromatic natural organic matter: Mechanistic insights and implications for optimizing practical aquatic applications

Engineered short-chain single stranded DNA (ssDNA) are emerging materials with various environmental applications, such as aptasensor, selective adsorbent, and hydrological tracer. However, the lack of fundamental understanding on the interactions of such materials with natural organic matter (NOM) hinders the improvement of their application performance in terms of sensitivity, selectivity, and stability. In this study, we investigated the interactions of ssDNA (four strands with systematically varied length and sequence) with two humic acids (Suwannee River humic acid (SRHA) and Aldrich humic acid (AHA)) and two humic-like NOM present in local aquatic matrices (ROM in river water and WOM in wastewater). Detailed, molecular level interaction mechanisms were obtained by probing the colloidal stability of the ssDNA-coated gold nanoparticles, coupled with product characterization using a suite of microscopic and spectroscopic techniques. Our study revealed that π-π interactions and divalent cation bridging were the major mechanisms for ssDNA-NOM interactions. ssDNA preferentially interacted with NOM with high aromaticity (AHA > SRHA/WOM/ROM). With divalent cations present (especially Ca2+), even a small amount of AHA could completely shield ssDNA, whereas the extent of shielding by SRHA/WOM/ROM depended on the relative content of ssDNA and NOM and whether bridges formed. The extent of shielding of ssDNA by NOM provides a potential answer to the reported conflicting effects of natural water matrices on the performance of DNA-based sensors. Taken together, our findings provide insights into the transformations of engineered ssDNA under environmentally relevant conditions as well as implications for their performance optimization in practical aquatic applications (e.g., from DNA design to pretreatment strategy).

Impacts of algal organic matter and humic substances on microcystin-LR removal and their biotransformation during the biodegradation process

The application of bioaugmentation (i.e., injection of contaminant-degrading microorganisms) has shown its potential to remove harmful cyanotoxins like microcystin-LR (MC-LR) from drinking water sources. However, the natural organic matter (NOM) present in both natural and engineered water systems might affect the bacterial biodegradation of MC-LR. Therefore, for the successful application of bioaugmentation for MC-LR removal in water treatment, it is important to understand NOM effects on MC-LR biodegradation. In this study, the impact of NOM [algal organic matter (AOM) and humic substances (HS)] on MC-LR biodegradation was evaluated in the presence of varying concentrations of NOM by monitoring MC-LR biodegradation kinetics. The changes in NOM composition during MC-LR biodegradation were also characterized by a five-component Parallel factor (PARAFAC) model using 336 excitation-emission matrix (EEM) spectra collected at different sampling points. Our results showed decreases in MC-LR biodegradation rate of 1.6-and 3.4-fold in the presence of AOM and HS, respectively. The expression of the functional mlrA gene exhibited a similar trend to the MC-LR degradation rate at different NOM concentrations. EEM-PARAFAC analyses and NOM molecular size fractionation results indicated a relatively greater production of terrestrial humic-like components (57%) and a decrease of protein-like components. Two-dimensional correlation spectroscopy (2D-COS) analyses further confirmed that low molecular weight protein-like components were initially utilized by bacteria, followed by the formation of higher molecular weight humic-like components, likely due to microbial metabolism.

Highly efficient microplastics removal from water using in-situ ferrate coagulation: Performance evaluation by micro-Fourier-transformed infrared spectroscopy and coagulation mechanism

Generation of microplastics (MPs), as a result of the increasing amount of plastic waste from human activities, is an emerging global concern that potentially threatens human health due to its intrinsic toxicity and ability to transfer pollutants. We examined the flocculation/coagulation for efficiently removing MPs (here, polyethylene (PE) and polyethylene terephthalate (PET)) in water by applying in-situ ferrate treatment, which exploits easy preparation and reduces toxic sludge production but has high coagulation efficiency. The PE and PET removal efficiency was evaluated by measuring the amounts of PE and PET in the as-treated supernatant using microscope equipped Fourier-transformed infrared spectroscopy. Overall, in-situ ferrate coagulation removed >80 % of PE and PET in a range of ∼0.9–3.6 mg/L of coagulant dose. In particular, >99 % of PE was removed with 2.7 mg/L coagulants, whereas PET removal efficiency reached 75 % at the highest dose (3.6 mg/L ferrate). However, the presence of organic humic acid (HA) significantly enhanced PET removal efficiency, reaching >99 % at the highest dose (3.6 mg/L ferrate). According to the mechanism study, HA remarkably promoted charge neutralization at low doses, corresponding to the zeta potential reaching zero. In particular, PE and PET exhibited different floc formations owing to ferrate coagulation. Ferrate closely and tightly adhered to the surface of PET, indicating that in-situ ferrate induced the adsorption of MPs. Based on the removal test and mechanism study, in-situ ferrate flocculation/coagulation processes are highly efficient for removing MPs in surface water containing low concentrations of natural organic matter. In the real surface natural water condition, >98 % of MPs removal efficiency was achieved by - twofold decreased ferrate dose (1.8 mg/L) without microfiltration membrane process.

Comparison of the formation of aldehydes and carboxylic acids in ozonated and electrochemically treated surface water

This study compared effects of conventional ozonation and electrochemical oxidation (EO) on the formation of aldehydes and aliphatic carboxylic acids produced via the oxidation of natural organic matter (NOM) present in a low-mineralized surface water with a relatively low NOM concentration. Conventional ozonation and EO were effective in degrading the aromatic moiety of NOM characterized by the absorbance at 254 nm. Yields of aliphatic carboxylic acids in the ozone treated water were dominated by formate, acetate and oxalate, while no acetate was observed in the case of EO treatment. The speciation of aldehydes was similar in the case of ozonation and EO treatment, but the aldehydes yields were notably higher for ozonation. The presence of the elevated carbonate concentration moderated the changes in disinfection by-products (DBPs) concentration in the EO treated water due to the interception of ∙OH by HCO3−, while it did not affect ozonation treatment. This study allows gaining more insights into the nature of processes characteristic and optimization of disinfections based on ozonation and EO methods.

Identifying key residual aluminum species responsible for aggravation of nanofiltration membrane fouling in drinking water treatment

Residual aluminum has been identified as one of the key foulants responsible for nanofiltration (NF) membrane fouling in drinking water treatment. However, the extent to which each species of residual aluminum contributes to membrane fouling and the underlying mechanisms are not yet clear. In this study, various pretreatments were applied to a lake water, which generated feed waters of different residual aluminum and species distribution. It was found that Ala (monomeric and oligomeric aluminum species) were mainly in the form of complexes (Ala-NOM) with natural organic matter (NOM), with proportions greater than 70%. The membrane fouling experiments showed that NF operation was sensitive to the presence of Ala, in which a small increase in the Ala concentration of the order of tens of μg/L could greatly aggravate membrane fouling. In contrast, Alb and Alc (intermediately and highly polymeric aluminum species) did not contribute substantially to the membrane fouling process. The membrane fouling potential of Ala increased with increasing coexisting NOM concentration. Results showed that Ala and NOM have a synergistic relationship during membrane fouling. More rigorously, Ala-NOM, rather than Ala itself, are therefore the key residual aluminum species that aggravate NF membrane fouling. The Ala produced by polyaluminum chloride (PACl) had a higher membrane fouling potential than that produced by AlCl3, which was due to the lower polymerization degree of Ala and the more stable complexes with NOM formed when PACl was used. Use of AlCl3 as a coagulant would therefore mitigate NF membrane fouling caused by residual aluminum.

Alkaline aging significantly affects Mn(II) adsorption capacity of polypropylene microplastics in water environments: Critical roles of natural organic matter and colloidal particles

Most microplastic particles may undergo various aging in water environments. In this work, surface physicochemical properties were firstly compared among pristine polypropylene (PP-pris) microplastics, and two aged ones obtained after pretreated with HCl (PP-acid) and NaOH (PP-alka). When compared with PP-pris and PP-acid, PP-alka had a much stronger Mn(II) adsorption capacity. The results regarding the role of natural organic matter and colloidal particle concentrations on adsorption demonstrated that for water solutions either containing kaolin or not, humic acid (HA) had significantly negative influence on Mn(II) adsorption capacity of PP-alka due to their complexation and competition effects, and its negative influence became enhanced with increasing kaolin concentrations. Besides, established conceptual models of adsorption were applied to comprehensively explore adsorption mechanisms of PP-alka for Mn(II) in the coexistence of HA and kaolin. An important suggestion was that in complicated adsorption-reactor system, great numbers of microplastics-kaolin heteroaggregates might be formed via ion bridging of Mn(II) and/or polymer bridging of HA. So these formed aggregates were possible to re-organize themselves, under pre-set vibration-speed conditions, for achieving a more stable structure. As a consequence, Mn(II) adsorption behaviors would be affected by changes in steric-hindrance effects of HA molecules and surface charge distribution of resultant heteroaggregates.