Natural Organic Matter Concentration Research Articles

Life Cycle Assessment of Immobilised and Slurry Photocatalytic Systems for Removal of Natural Organic Matter in Water

This study investigates the environmental impacts caused by the scaling up of the photocatalytic purification of drinking water using ultraviolet light-emitting diode technology. The life cycle assessment methodology was utilised to estimate the environmental impacts of two different reactor setups commonly used in lab-scale studies: an immobilised and a suspended TiO2 catalytic system. The functional unit adopted was the treatment of 1 L of water with an initial 7.8 mg/L concentration of natural organic matter, achieving a final 1 mg/L concentration. The use of a suspended photocatalyst was found to have an environmental footprint that was 87% lower than that of the immobilised one. From the sensitivity analysis, the environmental hotspots of the treatment process were the electricity usage and immobilised catalyst production. Therefore, alternative scenarios investigating the use of a renewable electricity mix and recyclable materials were explored to enhance the environmental performance of the photocatalytic treatment process. Using a renewable electricity mix, a decrease of 55% and 15% for the suspended and immobilised catalyst, respectively, was observed. Additionally, the process of recycling the glass used to support the immobilised catalyst achieved a maximum reduction of 22% in the environmental impact from the original scenario, with 100 glass reuses appearing to provide diminishing returns on the environmental impact savings.

Effect and mechanisms of pollutant removal in tetrachloroethylene contaminated water by persulfate-dithionite remediation system

Tetrachloroethylene (PCE) is a common organic pollutant in industrial process, and the scope and extent of PCE pollution to groundwater are increasing in recent years. In this study, an emerging and effective method was used to purify PCE contaminated water by activating persulfate (PS) with dithionite (DTN). The addition ratio of PS and DTN were optimized in the removal of PCE by PS-DTN system and the optimal molar ratio of PS to DTN was 1 to 1 at the maximum PCE removal rate, and it was applicable in the pH range of 3-12. In PCE simulated wastewater, PCE removal rate in PS-DTN system exceeded 90% within 48 hours, which was 66% higher than that in PS-NaOH system, and the degradation process followed pseudo-first-order kinetics with the reaction rate constant being 0.068 h-1. The dominant active species in PS-DTN system was proved to be sulfate radical on PCE degradation based on the radical quenching experiments and ESR analysis. HCO3- and low concentration of natural organic matter (NOM) could promote the removal of PCE, while Cl- and high NOM concentration had no adverse effect on PCE degradation. Few chlorinated intermediates (<2.77%) were produced and the dechlorination rate of PCE reached 95%, indicating a low secondary pollution risk. In simulated groundwater containing aquifer media, PS-DTN system could still degrade PCE to a certain extent, but the non-target reaction triggered by iron minerals on the medium mainly inhibited PCE degradation. The study showed that PS-DTN system was promising in degrading organic pollutants in groundwater.

Degradation of prometryn during UV/persulfate process: Kinetics and disinfection by-product formation

Prometryn is one of the commonly used triazine herbicides and is also widely used for algae removal in aquaculture. This study investigated the degradation kinetics of prometryn via UV/persulfate (PS) oxidation and confirmed its adherence to pseudo-first-order kinetics, with a calculated rate constant (kobs) of 0.2358 min−1. The impact of PS concentration, water matrix (including background ions of Cl− and Br− and natural organic matter (NOM)), and solution pH on prometryn degradation were assessed. Results indicated an increase in prometryn degradation with raising concentrations of PS, Cl−, and Br−, especially evident at a PS concentration of 400 μm where complete degradation was achieved. Conversely, degradation decreased with increasing NOM concentration and pH. Radical scavenging experiments affirmed the promotion of prometryn degradation in UV/PS by both HO• and SO4−•, with SO4−• contributing over 70 % of the total free radical contribution. Evaluation of disinfection by-product (DBP) formation revealed trichloromethane (TCM) as the predominant DBP in non‑bromine water and tribromomethane (TBM) in bromine water. Thus, this study offers a theoretical foundation for UV/PS degradation of triazine herbicides in aqueous environments. The obtained results hold significance for controlling DBPs in subsequent water treatment processes, ensuring the provision of safe drinking water to the public and meeting the sustainable development goal 6.

Application and environmental impact of loose nanofiltration in surface water treatment

Loose nanofiltration (LNF) membranes with a molecular weight cutoff (MWCO) of about 1000 Da have great potential for high selectivity between natural organic matter (NOM) and mineral salts. Therefore, they are interesting for treatment plants for purifying oligotrophic lake waters with an elevated NOM concentration. This study was conducted to determine the design and operational expenses as well as the environmental impact of an LNF-based drinking water treatment process that removes NOM from Finnish surface water. Two LNF membranes with similar MWCOs were selected, and the results were compared to ultrafiltration, nanofiltration, and conventional treatment. One LNF membrane demonstrated a rejection rate of NOM higher than 95 % and a low rejection rate of hardness at about 40 %, while the other LNF membrane performed similarly to an ultrafiltration membrane. The LNF-based treatment process would increase operational expenses by 53—69 % but at the same time decrease the environmental impact by >18 %. Improved removal of aromaticity and low molecular weight compounds could lower the disinfection byproduct formation potential and microbial growth in the network, thus reducing the required chlorine dosage in the network and possibly bringing further cost savings.

Biofilm-NOM-ferrihydrite synergy facilitate the dissimilatory iron bioreduction

Dissimilatory microbial iron reduction, a key biogeochemical process, influences the cycling of iron, hazardous metals such as arsenic, cadmium and chromium, and natural organic matter (NOM) across diverse environments like soils and aquatic systems. Despite its ecological significance, the interaction between ferrihydrite, NOM, and biofilms, particularly the synergy within these conditions, remains unclear. This study explored the bioreduction of ferrihydrite by Shewanella oneidensis MR-1 biofilms, analyzing how varying concentrations of NOM and electron donor affects this process. We developed a kinetic model to quantify iron transformation, revealing that NOM performs dual functions: as a carbon source and an electron shuttle. In carbon-rich environments, NOM acts as an electron shuttle, while insufficient carbon sources, biofilms metabolize NOM for electron transfer to ferrihydrite. The biofilm's extensive surface area facilitates the coprecipitation of NOM and ferrihydrite, enhancing electron transfer efficiency. The study noted a significant conversion of ferrihydrite into goethite and lepidocrocite, particularly at high C/Fe ratios. Additionally, integrating a coupled reactive-diffusion model, we aimed to predict iron transformation and distribution in biofilm systems. This approach emphasizes the importance of the biofilm-NOM-ferrihydrite synergy in iron biogeochemical cycles and the need for incorporating biofilm dynamics in realistic biogeochemical process models. The findings provide a new insight into the biofilm function in mediating the ferrihydrite bioreduction process in different carbon resources in real scenarios.

Macronutrient and PFOS bioavailability manipulated by aeration-driven rhizospheric organic nanocapsular assembly

Ubiquitous presence of the extremely persistent pollutants, per- and polyfluoroalkyl substances, is drawing ever-increasing concerns for their high eco-environmental risks which, however, are insufficiently considered based on the assembly characteristics of those amphiphilic molecules in environment. This study investigated the re-organization and self-assembly of perfluorooctane sulfonate (PFOS) and macronutrient molecules from rhizospheric organic (RhO) matter induced with a common operation of aeration. Atomic force microscopy (AFM) with infrared spectroscopy (IR)-mapping clearly showed that, after aeration and stabilization, RhO nanocapsules (∼ 1000 nm or smaller) with a core of PFOS-protein complexes coated by “lipid-carbohydrate” layers were observed whereas the capsule structure with a lipid core surrounded by “protein-carbohydrate-protein” multilayers was obtained in the absence of PFOS. It is aeration that exerted the disassociation of pristine RhO components, after which the environmental concentration PFOS restructured the self-assembly structure in a conspicuous “disorder-to-order” transition. AFM IR-mapping analysis of faeces combined with quantification of component uptake denoted the decreased ingestion and utilization of both PFOS and proteins compared with lipids and carbohydrates when Daphnia magna were fed with RhO nanocapsules. RhO nanocapsules acted as double-edged swords via simultaneously impeding the bioaccessibility of hazardous PFOS molecules and macronutrient proteins; and the latter might be more significant, which caused a malnutrition status within merely 48 h. Elucidating the assembly structure of natural organic matter and environmental concentration PFOS, the finding of this work could be a crucial supplementation to the high-dose-dependent eco-effect investigations on PFOS.

Determining Fe concentration and speciation in waters with high natural organic matter content

Valency, solubility and size of Fe are important controls on quality of natural waters. Recent recognition of the ubiquitous influence of natural organic matter on these, means that wider monitoring of Fe species in waters containing organic matter is required. We assess and develop methods that explicitly recognize this need. We show that for water samples prepared by acidification and filtration for inductively coupled plasma – atomic emission spectroscopy (I.C.P.-A.E.S.) analysis, only 50%–80% of Fe was recovered. This was because acidification coagulated the natural organic matter; Fe could then attach to its surface and/or be entrained as it deposited, both processes prevent Fe entering the I.C.P.-A.E.S. We show that this discrepancy in analysis of Fe – which could also occur and be more significant in analysis of trace metals - is likely to be undetected as the coagulate is unlikely to be observed prior to analysis. Accurate Fe analysis was possible, by I.C.P.-A.E.S. if H2O2 and U.V. light were used to remove organic carbon (O.C.), or by use of proprietary Fe chelators that produce colored complexes (e.g. Palintest LR, Palintest, UK). We also show that reliable resolution of Fe(II) concentration into free Fe(II) and Fe(II) bound to O.C. can be achieved by monitoring the time taken for ferrozine color development. This occurs within 2 s for free Fe(II) but up to 3 days for Fe(II) bound to O.C.

Effect of pH by Manganese Salts and Natural Organic Matter on Nanofiltration Membrane Fouling

This research aimed to determine the removal performance of manganese affected from solution pH of combined manganese salts with natural organic matter (NOM) using commercial nanofiltration (NF) membrane. The filtration experiments were tested under a dead-end filtration test cell. Variational factors used in this study were the types of manganese salts (i.e. manganese chloride (MnCl2), manganese sulfate (MnSO4), and manganese nitrate (Mn(NO3)2)) with the solution pH of 3, 5, and 7, and ionic strength of 0.01 mol/L. Water samples were prepared with NOM concentration of 10 mg/L, while the operating pressure was operated constant at 60 psig. Experimental results found that the MnSO4 salt provided the highest manganese removal efficiency of 95%, while the removal efficiencies of MnCl2 and Mn(NO3)2 were about 84.86% and 70.7%, respectively. Solution fluxes were not significantly different. In the presence of NOM concentration of 10 mg/L, solution pH of 3–7, it was found that low solution pHs for all conditions provided the highest manganese removal. The removals of NOM were relatively high more than 97%. The mathematical fouling model was done with cake filtration model (CFM) due to NOM accumulation on NF membrane surface.

Coagulation Enhanced with Adsorption and Ozonation Processes in Surface Water Treatment

The requirements for water intended for domestic and economic purposes prompt the search for new solutions in surface water treatment technologies. In this study, the enhancement of coagulation processes by connections with adsorption and/or ozonation for surface water treatment was studied. The possibility of a reduction in natural organic matter (NOM) content in modified surface water was analysed regarding changes in colour, turbidity, oxidisability (OXI), total and dissolved organic carbon (TOC, DOC) and absorbance at 254 nm (UV254). Additionally, the changes in copper and zinc ion content during the modified surface water treatments studied were analysed for initial metal concentrations of 0.5 or 1.0 mg/L. Studies of modified surface water were carried out with doses of medium-basicity PAX coagulant (C2) 5 mg/L and PAC 100 mg/L. During the coagulation process, the colour decreased by 86–90%, turbidity by 85–90%, OXI by 65–77%, TOC by 65–76% and UV254 absorbance by 73–84%. The enhancement of coagulation with adsorption and/or ozonation resulted in an increased efficiency of colour and turbidity removal by 2 and 4%, respectively. The highest increase in efficiencies of OXI, TOC, DOC and UV254 removal, by 12, 12, 11 and 11%, was observed for the connection of ozonation with coagulation and adsorption. The efficiency of metal ion removal from modified water observed for the single coagulation process was 58 and 55% for copper and 46 and 43% for zinc, respectively, for initial concentrations of 0.5 and 1.0 mg/L. The intensification of coagulation with ozonation and adsorption resulted in metal removal on the level of 66 and 62% for copper and 62 and 54% for zinc.

Amino acid promoted oxidation of atrazine by Fe3O4/persulfate

In the present study, we demonstrated that the presence of cysteine could remarkably enhance the degradation of atrazine by Fe3O4/persulfate system. The results of electron paramagnetic resonance (EPR) spectra confirmed the combination of cysteine and Fe3O4 exhibited much higher activity on activation of persulfate to generate more SO4•- and •OH than Fe3O4 alone. At pH of 3.0, SO4•- and •OH contributed to about 58.2 % and 41.8 % of atrazine removal respectively, while •OH gradually dominated the oxidation of atrazine from neutral condition to alkaline condition. The co-existing Cl− and HCO3− could quench SO4•-, resulting in the inhibition of atrazine degradation. The presence of low natural organic matters (NOM) concentration (0–2 mg L−1) could enhance the atrazine removal, and high concentration (>5 mg L−1) of NOM restrained the atrazine degradation. During the Cysteine/Fe3O4/Persulfate process, cysteine served as a complexing reagent and reductant. Through acidolysis and complexation, Fe3O4 could release dissolved and surface bound Fe2+, both of which contributed to the activation of persulfate together. Meanwhile, cysteine was not rapidly consumed due to a regeneration process, which was beneficial for maintaining Fe2+/Fe3+ cycle and constantly accelerating the activation of persulfate for atrazine degradation. The reused Fe3O4 and cysteine in the Cysteine/Fe3O4/Persulfate process exhibited high stability for the atrazine degradation after three cycles. The degradation pathway of atrazine included alkylic-oxidation, dealkylation, dechlorination-hydroxylation processes. The present study indicates the novel Cysteine/Fe3O4/Persulfate process might be a high potential for treatment of organic polluted water.

Bacterial inactivation in sunlit surface waters is dominated by reactive species that emanate from the synergy between light, iron, and natural organic matter

In this study, the synergistic and antagonistic effects of Fe species and coexisting natural organic matter (NOM) on the efficacy of solar light disinfection of water are investigated. Different initial iron species (Fe2+/Fe3+) and naturalorganic matter types (Suwannee River-SRNOM, Nordic Reservoir NOM-NDNOM, SR Humic Acid-SRHA, and SR Fulvic Acid-SRFA) were selected. The bactericidal actions of Fe and NOM, alone or in conjunction, were evaluated at various initial iron dosing concentrations, NOM concentrations, irradiation intensities, and pH values. We show that when an appropriate iron (1 ppm Fe2+ or 0.25 ppm Fe3+) and NOM concentration (2 ppm SRNOM or 5 ppm NDNOM) coexisted, synergistic inactivation was observed in the pH range 5.0–8.0. A plausible explanation is that the presence of Fe+NOM significantly promoted the generation of hydroxyl radicals (•OH) and singlet oxygen (1O2), which led to enhanced disinfection rates. These results elucidate the previously understudied effects of ubiquitous elements in natural waters and their impact on solar-mediated bacterial inactivation.

How suitable is the gold-labelling method for the quantification of nanoplastics in natural water?

Abstract Nanoplastics are detected in surface water, yet accurately quantifying their particle number concentrations remains a significant challenge. In this study, we tested the applicability of a gold-labelling method to quantify nanoplastics in natural organic matter (NOM) containing water matrices. Gelatin-coated gold nanoparticles (Au-gel NPs) form conjugates with nanoplastics via electrostatic interaction which produces peak signals which can be translated into particle number concentration using single-particle inductively coupled plasma–mass spectrometry (SP-ICP-MS). We used water samples with various NOM concentrations, with and without the addition of 1 × 107 particle–1 nanoplastics. Our results indicate that nanoplastics in low NOM samples (&amp;lt;1 mg·C L−1) could be successfully quantified. However, in high NOM samples (&amp;gt;15 mg·C L−1), only 13–19% of added nanoplastics were successfully quantified. Further digestion to remove NOM yielded only 10% of spiked nanoplastics. This discrepancy in high NOM samples could likely be attributed to the competition between nanoplastics and NOM existing in the water sample to bind with Au-gel NPs. Our study highlights the suitability of the Au-gel labelling method for quantifying nanoplastics in low NOM water samples. Nevertheless, further optimization, including pre-digestion steps, is essential to apply this method for high NOM water samples effectively.

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.

Tuning nanofiltration membrane performance: OH–MoS2 nanosheet engineering and divalent cation influence on fouling and organic removal

Natural organic matter (NOM) present in surface water causes severe organic fouling of nanofiltration (NF) membranes employed for the production of potable water. Calcium (Ca2+) and magnesium (Mg2+) are alkaline earth metals present in natural surface water and severely exacerbate organic fouling owing to their ability to cause charge neutralization, complexation, and bridging of NOM and the membrane surface. Hence, it is of practical significance to engineer membranes with properties suitable for addressing organic fouling in the presence of these cations. This study employed OH-functionalized molybdenum disulphide (OH–MoS2) nanosheets as nanofillers via the interfacial polymerization reaction to engineer NF membranes for enhanced removal of NOM and fouling mitigation performance. At an optimized concentration of 0.010 wt.% of OH–MoS2 nanosheet, the membrane was endowed with higher hydrophilicity, negative charge and rougher membrane morphology which enhanced the pure water permeance by 46.33% from 11.2 to 16.39 L m−2 h−1 bar−1 while bridging the trade-off between permeance and salt selectivity. The fouling performance was evaluated using humic acid (HA) and sodium alginate (SA), which represent the hydrophobic and hydrophilic components of NOM in the presence of 0, 0.5, and 1 mM Ca2+ and Mg2+, respectively, and the performance was benchmarked with control and commercial membranes. The modified membrane exhibited normalized fluxes of 95.09% and 93.26% for HA and SA, respectively, at the end of the 6 h filtration experiments, compared to the control membrane at 89.71% and 74.25%, respectively. This study also revealed that Ca2+ has a more detrimental effect than Mg2+ on organic fouling and NOM removal. The engineered membrane outperformed the commercial and the pristine membranes during fouling tests in the presence of 1 mM Ca2+ and Mg2+ in the feed solution. In summary, this study has shown that incorporating OH–MoS2 nanosheets into membranes is a promising strategy for producing potable water from alternative water sources with high salt and NOM contents.

A UVA light-emitting diode microreactor for the photocatalytic degradation of humic acids and the control of disinfection by-products formation potential

Chlorination is one of the most applied technologies for drinking water disinfection. However, the generation of disinfection by-products (DBPs) in the chlorination process is threatening drinking water safety, especially when the concentration of natural organic matter (NOM) is high in source water. Climate change increases the fluctuation of NOM in source water, which further challenges water safety in small and rural communities. In this study, environmental microfluidics was introduced to a UVA-LED photocatalytic oxidation system for a rapid oxidation of NOM. The results showed that HA adsorption and degradation, and DOC degradation were more favored in low pH. At pH 5, 56.9% of HA and 58.1% of dissolved organic carbon (DOC) were removed in 3.4 min by the microreactor. DBP formation potential was efficiently reduced, with the highest reduction of THM and HAA formation potentials by 76% and 70.7%, respectively. Compared with the bottle reactor, the degradation rate constants of HA and DOC by UVA-LED microreactor were increased by 2.99 – 15.8 times, and 6.8 – 170.2 times, respectively. Homogenous irradiation and rapid mass transfer in the microreactor accelerated the inhibited oxidation of HA in acidic and base solutions and increased the apparent quantum yields of photocatalysis. Further, the microfluidic photocatalytic oxidation was much more efficient in the reduction of DPBs formation potential in a source water sample. The process was rapid and had low chemical and energy consumption. Approaches on system scale-up, system simplification, and energy conservation would increase potential of microfluidic photocatalytic oxidation in water purification for households and small communities.

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 and ionic strength (CaCl2) affect transport, retention and remobilization of silica encapsulated DNA colloids (DNAcol) in saturated sand columns

In the terrestrial environment, interactions between natural organic matter (NOM) and colloids can lead to the formation of an environmental corona around colloids, influencing their transport behaviour and, ultimately, their ecotoxicity. We used a synthetically designed colloid tagged with DNA (DNAcol) as a surrogate for natural colloids and investigated its transport in saturated sand columns. We varied the concentrations of NOM and ionic strength (CaCl2), to better understand the transport and release of DNAcol in porous media under both steady and transient porewater chemistry conditions. In addition, we aimed to understand the main factors that control deposition and release of DNAcol under tested conditions. To induce transient chemistry, we replaced the injection solution containing NOM and/or CaCl2 with Milli-Q water. The results showed that the deposition rate of DNAcol was inversely proportional to the concentration of NOM. The deposition rate increased significantly even under low ionic strength (CaCl2) conditions of tested conditions. Notably, the influence of NOM on the transport of DNAcol was most pronounced at the lowest range of [Ca2+]/DOC ratios, and the attachment of DNAcol to the sand grains was negligible. Moreover, the results showed while the DLVO theory captured the general trend of experimental results, it significantly underestimated the deposition of DNAcol in the presence of CaCl2. Under transient porewater chemistry conditions, colloid remobilization was observed upon flushing the column with Milli-Q water, leading to a secondary peak in the breakthrough curves. We observed that under transient porewater chemistry conditions, when the ionic strength of the solution was 10 mM, the magnitude of the remobilization peak was more significant compared to conditions with 1 mM ionic strength. Our work emphasized the complex interplay between water quality on the one hand and deposition and release of colloidal matter in saturated porous media on the other hand.

Adapting direct filtration to increasing source water dissolved organic carbon using clarification and granular activated carbon

AbstractChanging source water quality namely through increasing natural organic matter (NOM) concentration challenges surface water treatment, especially direct filtration. We conducted a pilot‐scale assessment of various adaptation strategies (e.g., clarification, granular activated carbon [GAC] filtration) for direct filtration facilities under the stress of rising NOM levels. Recognizing that changing source water can impact broader aspects of treatment, we considered the implications of Fe and Mn removal via KMnO4 pre‐oxidation. GAC media showed promise as an adaptation strategy, providing ~60% removal of dissolved organic carbon (DOC), and a significant reduction in disinfection by‐product formation potential (DBPfp). However, KMnO4 pretreatment showed limited Mn and Fe removal, and filters with GAC media released dissolved Mn at up to ~30% of prefilter levels. These data suggest that using GAC may come with the risk of poor Mn removal performance if Mn is not removed during pretreatment. This work highlights the complexities anticipated under emerging climate pressures and emphasizes the need for comprehensive treatment solutions that consider factors beyond NOM.

Influence of natural organic matters on fate of polystyrene nanoplastics in porous media

Natural organic matters (NOMs) are widely present in aqueous environments. The effect of NOMs on the fate of nanoplastics that are gradually receiving widespread attention in porous media needs to be noticed, but relevant research is lacking. To fill this gap, the present study focused on elucidating the influence of NOMs and metal cations with varying concentrations upon the transport, long-term release, and particle fracture of polystyrene nanoplastics (PS-NPs) in saturated porous media. The adsorption, transport, long-term release, and particle fracture tests were conducted. A mathematical model and the Derjaguin-Landau-Verwey-Overbeek (DLVO) theory were used in this research. NOMs could adsorb onto PS-NPs leading to a reduction in the PS-NPs' zeta potential and an increase in the energy barrier and steric hindrance between PS-NPs and quartz sand, ultimately facilitating the transport of PS-NPs through porous media. On the other hand, an increase in concentration and valence of metal ions enhanced the PS-NPs' zeta potential, resulting in PS-NPs' aggregation and increased size when NOMs were present. This reduced the energy barrier between porous media and PS-NPs, resulting in increased blocking and straining, allowing decreased PS-NPs' transport. Long-term release tests demonstrated release ability and mobilities of PS-NPs decreased as the enhanced NOM concentration, addition of metal cations, and decreased valence of metal ions, in agreement with the transport test findings. In the research about particle fracture, NOMs were found to inhibit the fracture of PS-NPs by adsorbing on their surface to protect them from fracture. Metal cations and increased metal cation valence promoted the fracture of released PS-NPs when NOMs were present by promoting NOM aggregation and thus hindering the protection of NOMs for the nanoplastics.

Linking water quality, fouling layer composition, and performance of reverse osmosis membranes

Fouling of polyamide membranes during reverse osmosis (RO) is a major challenge for adopting membrane technologies to treat highly contaminated waters, especially those containing organic foulants (e.g., natural organic matter (NOM), polysaccharides) and dominant cations (e.g., sodium, magnesium, calcium). This work combines bench-scale membrane fouling experiments with detailed characterization of feedwater chemistry and fouling layer composition/morphology to reveal fundamental mechanisms of (in)organic fouling during RO. Divalent cations are shown to promote fouling by hydrophobic NOM containing aromatic and carboxyl groups, while NOM fouling in the presence of a monovalent cation, sodium, occurs by smaller fulvic acids containing larger fractions of carboxyl groups and other oxygen-rich moieties. Calcium-carboxyl bridging occurs in solution and near the membrane surface to induce NOM aggregation on nanometer length scales. In complex waters containing foulant mixtures, co-fouling by calcium-carboxyl bridging and CaCO3 precipitation influence membrane performance at longer timeframes. However, the flux decline observed for the co-fouling mechanism was less significant than the sum of its parts, suggesting both synergistic and antagonistic fouling mechanisms should be considered in membrane design/operation. These results encourage the design of pretreatment processes to reduce concentrations of multivalent ions and hydrophobic NOM in RO feedwaters, and of membrane materials to limit attachment/deposition of aggregates to/on polyamide surfaces.