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Advanced organic characterisation methods were used to investigate the suitability of lab-based model compounds as surrogates to mimic the dissolved organic matter (DOM) of both first and second generation fermentation industry effluents. Comparisons to both humic acid and synthetic melanoidin revealed the limitations of using these model organic compounds in treatment studies of biorefinery effluent. Rapid resin fractionation (RRF) of effluent from yeast cultivated on molasses suggests that 64% of the dissolved organic matter is present in the form of very hydrophobic acid (VHPhoA) compounds. Molecular weight distribution by size exclusion chromatography (LC-OCND) and fluorophore specific intensity by fluorescence excitation and emission matrix (FEEM) of the yeast effluent was comparable to signatures from humic acid. This indicates that humic acid would be a suitable model compound for oxidation, adsorption and filtration studies. Differences among the fermentation industry effluents were found to be inherently dependent on both the biochemistry of yeast and processes used. RRF and FEEM spectra of effluent from bioethanol production on cellulosic feed highlighted a preponderance of neutral compounds with fluorophore specific intensity characteristic of non-humic compounds with a higher fraction of neutral compounds (41%) relative to VHPhoA (38%), SHPhoA (16%) and HPhi (5%) moieties. Findings were not consistent with commercial humics, synthetic melanoidins or other cellulosic and lignocellulosic based effluents from Kraft and Thermomechanical pulp mills since the actual pollutants are heavily dependent on the pre-treatment process. This suggests further work is required to develop a model compound for treatment studies of effluent from second generation bio-refineries.

Development of an in situ passive sampler for mercury (Hg), and its toxic form, methylmercury (MeHg), using simple polymer films, was explored for the potential to make an efficient and environmentally relevant monitoring tool for this widespread aquatic pollutant. The sulfur-containing polymers polysulfone (PS), and polyphenylene sulfide (PPS), were found to accumulate both MeHg and inorganic Hg (iHg), whereas polyethylene (PE) sorbed iHg but not MeHg, and polyoxymethylene (POM) and polyethersulfone (PES) films had low affinity for both Hg species. Uptake rates of Hg species into polymers were linear over two weeks, and dissolved organic matter at natural levels had no effect on partitioning of MeHg or iHg to the polymers. Sorption of MeHg to PS and PPS from three estuarine sediments correlated with uptake into diffusive gel-type samplers over time, and in PPS, with accumulation by the estuarine amphipod, Leptocheirus plumulosus. These polymers had lower MeHg adsorption rates, but are simpler to assemble, than diffusive gel-type samplers. Higher contaminant concentrations in polymer and gel-type samplers corresponded with porewater concentrations across sediments, suggesting they sample the dissolved MeHg pool, whereas MeHg levels in amphipods were more elevated with higher bulk sediment MeHg, which may reflect feeding strategy. While polymers with higher affinity for MeHg and iHg are needed for some environmental applications, this work suggests a simple sampling approach has potential for time-integrated, environmentally-meaningful MeHg monitoring in contaminated sediments.

Advanced oxidation methods (e.g., ozonation systems) are used for control of recalcitrant pollutants in secondary petrochemical wastewater. For the selection of the optimal wastewater treatment method, we compared the reactivity characteristics of dissolved organic matter (DOM) in three common ozone treatment processes: single ozone, ozone/H2O2, and ozone/catalyst. The raw and ozonated DOM were fractionated into six fractions using ion exchange resins. Fluorescence spectroscopy and size exclusion chromatography were employed to characterize the fractions. The results showed that the single ozone system transformed hydrophobic components into hydrophilic components, but exhibited low mineralization ability. By contrast, the increase in hydrophilic acid fractions transformed from other fractions in the ozonation process were further mineralized in the ozone/H2O2 and ozone/catalyst systems. Ozone/H2O2 preferentially reduced hydrophobic bases, whereas ozone/catalyst preferentially reduced hydrophilic neutral components. However, ozone/H2O2 exhibited low selectivity in degrading organic compounds of different molecular weights. The highest total organic carbon (TOC) removal efficiency was achieved in the ozone/catalyst system, which promoted the transformation from fulvic acid- and humic acid-like substances into aromatic proteins and soluble microbial by-product-like substances. The single ozone system transformed high-molecular-weight compounds into low-molecular-weight compounds, resulting in an unsatisfactory TOC removal efficiency. By contrast, the ozone/catalyst system selectively removed the residual low-molecular-weight compounds in the reaction with ozone. This might have contributed to the high TOC removal efficiency of the ozone/catalyst treatment. These results can be used by other researchers and engineers to inform the selection of optimal ozone treatment based on wastewater characteristics.

Biochars derived from wetland biomass have been extensively applied in water and wastewater treatments. This study investigated the quantity and chemical quality of dissolved organic matter (DOM) released from the biochar prepared from the typical wetland plant (Typha orientalis) at different pyrolysis temperatures (300–700 °C) by using fluorescence excitation-emission (EEM) spectrophotometry with parallel factor analysis (PARAFAC) and UV–Visible spectroscopy. The results showed that the content of DOM released from biochars at low pyrolysis temperatures (300–500 °C) was higher than that observed at high pyrolysis temperatures (600–700 °C). The distribution of DOM components (mainly including three humic acid-like substances, one fulvic acid-like substance and one tyrosine-like substance) varied significantly due to the increase of pyrolysis temperatures. The fulvic acid-like material was the key DOM component at the low pyrolysis temperature while the humic acid-like material became dominant at the high temperature. DOM quality indices also indicated that the percentage of the low molecular-weight DOM increased with the decreasing DOC concentration due to the higher temperatures. The results obtained in this study would be beneficial to guide the rational application of biochars in waste treatments.

Herein we systematically examined the roles of water chemistry (pH, dissolved organic carbon (DOC), and divalent cations) and particle surface functionality that control the aqueous stability, aggregation, and toxicity of engineered nanoplastic particles in simulated natural environmental conditions. Model polystyrene latex nanoparticles (PLNPs) with three different functional groups, namely unmodified (uPLNPs), amine-modified (aPLNPs), and carboxyl-modified (cPLNPs), were investigated. Results indicate that the presence of only DOC increased the surface charge and exhibited negligible effects on the size distribution of the PLNPs in aqueous suspensions. The presence of the divalent cations (Ca2+ and Mg2+) was observed to decrease the surface charge and increase the size of the PLNPs. The coexistence of DOC and the divalent cations enhanced the extent of aggregation of the PLNPs in the water columns. The surface modification and pH were sensitive factors influencing the stability of PLNPs during long-term suspension when DOC and the divalent cations coexisted. Direct visual further testified the conclusions on the combined effects of solution and surface chemistry parameters. Furthermore, in situ transmission electron microscope observations revealed that the enhancement of PLNP aggregation in the presence of DOC and the divalent cation was caused by bridge formation. Toxicity test indicated the PLNPs exhibited acute toxicity and physical damage to Daphnia magna. The more complex the solution conditions, the more toxicity the aPLNPs and cPLNPs. Analysis of mode of toxic action implied that the PLNPs mainly caused the accumulation of oxidative damage to the gut of D. magna.

Understanding bioavailable metal behaviour in situ is critical for pollution evaluation and contaminant management in mangrove wetland. Here, the diffusive gradients in thin films technique (DGT) was used for characterizing the (bio)available portions of Cr, Zn, Pb, Cu, Fe and Mn in two mangrove wetlands affected by industrial waste discharges (Jiulong Estuary) and domestic discharges (Zhangjiang Estuary), in Fujian Province, China. In addition, fluorescence excitation emission matrices-parallel factor analysis (EEM-PARAFAC) was applied for characterizing the occurrence and behaviour of dissolved organic matter (DOM) in soil solution, as well as their feasibility for assessing behaviours of metals. The results demonstrated that the combination of DGT and EEM, which are well suitable for studying DOM impacted metal behaviors in mangrove sediments. Discharge of difference wastewater into the mangrove wetlands of Jiulong and Zhangjiang Estuaries, gave rise to the DGT-labile metal concentration of Zn > Cu > Cr > Pb and Zn > Cr > Pb > Cu, respectively. A variety of humic-like fluorescent components was characterized here, providing valuable insights into the chemical composition of DOM in rhizosphere and bulk sediment. Terrestrial humic-like compounds indicated a different binding affinity for heavy metals in mangrove sediments. These findings are useful for the future understanding of the metal speciation and molecular binding mechanisms in such mangrove wetlands.

Microplastics (MPs) have been regarded as a vector for contaminants and greatly affect the migration and fate of hydrophobic organic compounds (HOCs) in marine water. In this study, the sorption behavior of 17β-estradiol (E2) on MPs was investigated in marine water system. The sorption capacity of E2 varied greatly with the chemical structures of MPs. The adsorption or partition contribution of E2 sorption on MPs was well quantified with adsorption-partition dual-mode model mechanism. The hydrophobic partition dominantly regulates the sorption of E2 due to the high crystallinity of MPs and high accessibility of amorphous domain of rubbery MPs. Smaller particle size benefits the sorption of E2 on same kind of MPs. The salinity and dissolved organic matter (DOM) have minor effect on E2 sorption by MPs in real marine water. The result shows that the MPs greatly influence the transportation of E2 and cause potential environmental risk to marine ecosystem.

In this research, the degradation of seven different micropollutants (MPs) and the formation of their transformation products (TPs) have been assessed during the application of different advanced oxidation processes: photolytic and photocatalytic activation of peroxymonosulfate (PMS) and persulfate (PS). The results were compared with those obtained from the photolytic experiments using hydrogen peroxide (H2O2) as oxidant. A significant abatement of almost all MPs was achieved, even with very low UV-C contact time (9 and 28 s). The degradation of atenolol (ATN) and caffeine (CFN) ranged from 84 to 100% with a dose of 0.5 mM of any oxidant. The efficiencies for bisphenol-A (BPA), carbamazepine (CBZ), diclofenac (DCF), ibuprofen (IBP), and sulfamethoxazole (SMX) varied depending on the oxidation system and operating conditions (oxidant dose and UV-C contact time), leading to the photolysis of PMS to higher efficiencies than PS and H2O2. In all cases, the abatement of MPs ranged from 63 to 83%, even with the lowest PMS dosage. Moreover, the addition of Fe(II) as a catalyst enhanced the removal efficiency, reaching almost total removal, especially over CBZ, DCF, and IBP. The Dissolved Organic Carbon (DOC) removal ranged between 44 and 62%, suggesting the transformation of MPs in intermediate compounds. The identification of transformation products was carried out for each micropollutant and each oxidation treatment, being observed some transformation products specific of oxidation by sulfate radicals. For example, m/z 165.0432 only appeared after PMS/Fe(II)/UV-C on the degradation of BFA, m/z 251.082 appeared after photolytic activation of PMS and PS on CBZ removal, and m/z 128.0452 was observed after any sulfate radical oxidation treatment, but not after photolysis of H2O2.

This study presents the impacts of TiO2 nanoparticles (TNPs) amendment on plant growth, phosphorus (P) content, and dissolved organic matter (DOM) composition in the rhizosphere. For this work, wheat plants (Galaxy-2013) were exposed to soil amended by different amounts of TNPs (i.e., 0, 50, and 100 mg TNP/kg of soil) for 40 days and harvested. The maximum increase in the shoots and roots lengths reached 15.9 ± 0.3% and 3.8 ± 0.3% respectively, which was concurrent with improved P content in the plants. Compared with the control, the P content in the shoots and roots was enriched by 23.4% and 17.9% at 50 mg TNP/kg of soil respectively. The increased electrical conductivity (EC) and decreased pH of the rhizosphere implied that the added TNPs might induce the enhancement of the P dissolution. Fluorescence spectroscopy revealed the increase of microbial activity as depicted by the humification index (HIX) changing from 0.88 ± 0.02 to 0.92 ± 0.01, with increasing TNPs amendments. Excitation-emission matrix coupled with parallel factor analysis (EEM-PARAFAC) showed the presence of four fluorescent components (C1 to C4) in the rhizosphere. Three of them (C1-C3) were related to humic-like substances, while the C4 was associated with protein-like fluorescence. EEM-PARAFAC results revealed the degradation of C4, and the enhancement of the other three components, which supported the stimulation of microbial activity by the TNPs amendment. This study provided new insights into the relation between improved phytoavailble P in plants and the changes in the rhizosphere soil solution chemistry and the DOM composition upon TNPs amendments.

The batch experiments were conducted to understand sorption process of bithionol (BIT) in yellow soil (YS) and red soil (RS), while column leaching experiments were performed to evaluate the leaching behavior of BIT and levamisole (LEV) in the tested soils. The adsorption and desorption data fitted well with the Freundlich isotherms (R2 ≥ 0.94). The distribution coefficient of BIT in the YS and RS were 104 and 98.3 L/kg, respectively. Hysteresis was observed for bithionol desorption in the YS and RS, with hysteresis coefficient of 0.917 and 0.928, respectively. Dissolved organic matter (DOM) addition and acid condition enhanced the adsorption of BIT in the soil. Both BIT and LEV showed poor leaching potential in the tested soils. More than 80% of BIT and LEV remained in the surface soil layer and the amount of the two target compounds in the leachates accounted for less than 1% of overall recovery. DOM showed little influence on the concentration of BIT and LEV in the leachates collected at different time. The results could fill the gap on the behavior of BIT and LEV in soil under laboratory conditions.

The effect of waterborne ingredient on ecosystem has been of great interest. In the present study, the evaluation method using algal photosynthesis inhibition assay with dual-channel pulse amplitude modulation (PAM) system was established for a series of water samples to elucidate the potential effect of the total body of organic compounds including natural organic matter (NOM) on aquatic ecosystems. The more sensitive and less time-consuming monitoring method compared with algal growth inhibition assay was suggested, especially considering inorganic and coloring constituents. Algal photosynthesis inhibition activity was detected with high sensitivity for photosystem II (PSII) inhibitors, whereas the IC10 of the other chemicals was over the environmental standard concentration for Chlamydomonas moewusii (Chlorophyceae) and Pheodactylum tricornutum (Diatomea). The photosynthesis inhibition activity of Lake Biwa dissolved organic matter (LBDOM) and fulvic acid (LBFA) was significantly detected at ≥10 times the concentration and >10 mgC L−1, respectively, whereas prominent activity was confirmed for Suwannee River NOM (SRNOM) on the river original concentration (>30 mgC L−1) for both algae. Significant inhibition activity was detected in both algae at least in twice-concentration for water samples from a wastewater treatment pilot plant. There was no great difference in the activity between sewage secondary effluent and its filtrate with ultrafiltration (UF), and physically washing water for the UF membrane.

In aquatic systems, dissolved organic matter (DOM) plays an important role in regulating the reactivity and transport of environmental pollutants. Fluorescence excitation-emission matrix (EEM) analysis combined with fluorescence regional integration (FRI) and parallel factorial analysis (PARAFAC) were applied to investigate the composition, humification degree and depth-dependent variation of DOM in Lake Baihua, China. The results showed that humic-like materials with more than 60% of percentage fluorescence response (Pi,n) were dominant in DOM. The molecular complexity and structural condensation of PARAFAC components showed the order of C1 (humic-like components) > C3 (protein-like components) > C4 (fulvic-like components) > C2 (fulvic-like components). The lower maximum fluorescence intensities (Fmax) of components in surface layers were attributed to photo-oxidation of DOM by radiation. With depths less than 16 m, the Fmax increases and decreases were attributed to accumulation of recalcitrant humic substances and microbial/abiotic degradation of particulate DOM, respectively. A combination of biological and humification indices could be used as indicators for distinguishing different degrees of humification and sources of DOM. DOM from Lake Baihua mainly originated from an aquatic bacterial source that consisted of an important/intermediate autochthonous component with a weak humic character. The fluorescence indices of PI,n/PII,n, PI+II+IV,n/PIII+V,n, C2, C1/C2 and C2/(C3+C4) were more suitable to determine the humification degree. Stronger humic characters and higher humification degree for DOM were present at depths of 10–13 m. The fluorescence spectroscopy combined with fluorescence indices is convenient to investigate depth-dependent DOM characteristics and to assess water quality or pollution risk in lake systems.

Estrogens are of environmental concern because disruptive effect on biological functions at levels as low as ng/L. Wastewater treatment plant effluent is a significant source of estrogens in aquatic environment. Ferric ions (Fe3+)-saturated montmorillonite has been shown to effectively remove 17β-estradiol (βE2), a common estrogen, from pure water by catalyzing formation of insoluble βE2 oligomers on mineral surfaces. We investigated the effects of reaction temperature, dissolved organic matter, pH, and common cations, on Fe3+-saturated montmorillonite-surface catalyzed βE2 polymerization, and the removal of this estrogen from three different secondary wastewater effluents with more complicated matrixes. Highest βE2 removal occurred at near neutral pH and it increased with increasing treatment temperatures. Presence of common cations in the water did not affect the reaction efficiency. Dissolved organic matter at 15 mg C/L slightly lowered the βE2 removal efficiency as compared to that in pure water. Regardless of the source of wastewater effluents, βE2 removal efficiency of ∼40% was achieved using the dosage of Fe3+-saturated montmorillonite similar to that tested for the aqueous phases with simpler matrix. Doubling this dosage resulted in removal of ∼80% of βE2 from a tested secondary wastewater effluent within 30 min reaction. For wastewater with complex matrixes at the commonly reported βE2 levels which are magnitudes lower than the tested concentration in our study, this dosage would provide sufficient available reaction sites for the surface-catalyzed βE2 polymerization. This study demonstrated that Fe3+-saturated montmorillonite is a promising material for effective removal of phenolic estrogen compounds from domestic wastewater effluents.

The electron transfer capacities (ETC) of dissolved organic matter (DOM) are related to their hydrophobicity. However, the underlying mechanism is poorly understood. The DOM was extracted from chicken manure compost, and fractionated into four fractions based on hydrophobicity, i.e., hydrophobic acid (HOA), hydrophobic base (HOB), hydrophilic matter (HIM) and acid insoluble matter (AIM) fractions. The composition, structure and ETC of the four fractions were measured using spectral technology and electrochemical methods. The results showed that the HOA and AIM fractions consisted mainly of fulvic- and humic-like substances, the HOB fraction comprised mainly organic nitrogen compounds, and the HIM was mainly composed of carbohydrates and protein-like matter. The electron donating capacities (EDC) and electron accepting capacities (EAC) of the four fractions were in the range of 616.90-5224.66 and 7.30-191.20 μmoL/g(C), respectively, The HOB fraction exhibited the highest EDC among the four fractions, followed by the HOA, AIM and HIM fractions. The EAC of the four fractions was characterized by the order of AIM, HOB, HOA and HIM. The tryptophan- and humic-like substances and organic nitrogen compounds accounted for the EDC, whereas the carboxyl group on aromatic substance responsible for the EAC.

In this study, the removal of Cr (VI) was examined in the presence of bio-produced Fe (II) from hematite, sulfate and dissolved organic matter by Geobacter sulfurreducens. The adaptation results of G. sulfurreducens showed that cells growth was stimulated up to 576 μM of Cr (VI) concentration. The first-order rate and electron transfer rate in each step during Cr (VI) reduction by G. sulfurreducens in the presence of hematite was clearly modeled and calculated. For Cr (VI) reduction rate, both separately dissolved and adsorbed bio-produced Fe (II) were faster than G. sulfurreducens although bio-produced Fe (II) contributed only 20% to total Cr (VI) removal in a combined system containing Cr (VI), hematite and G. sulfurreducens. The electron transfer rate from G. sulfurreducens to hematite (R2) to produce Fe (II) was a limited step and electron transfer rate from acetate to Cr (VI) (1.8 μeq L−1 h−1) by G. sulfurreducens was much higher than that to hematite (0.272 μeq L−1 h−1, producing Fe (II)). Cr (VI) reduction was enhanced in the presence of SO42− due to sulfate boost cells growth. AQDS enhanced Cr (VI) reduction by serving as an electron shuttle thus accelerating the electron transfer rate.

US EPA Method 521 employs activated carbon-based solid phase extraction (SPE) cartridges for analyzing N-nitrosamines. The analysis of N-nitrosamines and their chloramine-reactive and ozone-reactive precursors in nitrified municipal secondary effluent revealed the potential for NDMA to form as an artefact during the analysis. As samples passed through the SPE cartridge, the activated carbon mediated the reaction of nitrite with dimethylamine to form NDMA. The reaction was not significant with tertiary amines. Artefactual NDMA formation was important for nitrite concentrations >0.2 mg/L as N in the Biological Nitrogen Removal (BNR) process effluent. However, it is difficult to define a general threshold for nitrite concentrations, because the importance of the reaction also depends on secondary amine concentrations, which are usually poorly characterized. Pre-treatment of samples with sulfamic acid to destroy nitrite mitigated the artefact. This artefact did not affect NDMA analysis in a nitrified effluent from another facility, likely due to low dimethylamine concentrations. This artefact also did not affect the analysis of primary effluent, due to the lack of nitrite, or the analysis of other N-nitrosamines, likely due to the lack of their secondary amine precursors. Because chloramination does not significantly degrade nitrite, this artefact could affect the analysis of chloramine-reactive N-nitrosamine precursors. Because ozonation rapidly degrades nitrite, it should not affect the analysis of ozone-reactive precursors. However, ozonation at 0.8 mg ozone/mg dissolved organic carbon resulted in significant degradation of all N-nitrosamines, even though simultaneous NDMA formation from ozone-reactive precursors resulted in a net increase in NDMA concentration.

Composting is a major sludge-treatment method and bulking agents are very important in sludge composting. In this study, ceramsite and activated alumina balls were chosen as recyclable bulking agents for sludge composting. Variations in the temperature, pH, electrical conductivity, organic matter, dissolved organic carbon, moisture content, and heavy metals were detected during composting with different bulking-agent treatments as well as differences in the germination index values. The results showed that both bulking agents could ensure the maturity of the compost; further, ceramsite treatment resulted in the best water removal efficiency. According to the sequential extraction procedure, both ceramsite and activated alumina balls could stabilize Cd but they also increased the mobility of Zn. After comparing the effects of different particle sizes of ceramsite on composting, 20 mm was determined to be the most optimal value. Additionally, the recovery rates of ceramsite and activated alumina balls were 96.9% and 99.9%, respectively.

In this study, the influences of feedstock and pyrolysis temperature on carbon fractions of biochar were investigated. Four types of organic wastes (rice straw (RS), pine wood (PW), pig manure (PM) and sewage sludge (SS)) were pyrolyzed at different temperatures (300 °C, 400 °C, 500 °C, 600 °C and 700 °C). Biochar produced at low temperature exhibited high yields, high dissolved organic carbon (DOC) content and unstable organic carbon content. In contrast, biochar formed at high temperature showed high C content and C stability with a low O/C and H/C ratios. In addition, the biochar pyrolyzed from PW contained the lowest DOC of the four biochar types. The properties of DOC fractions (F1, F2 and F3) released from biochar differed depending on feedstock, pyrolysis temperatures, and extraction procedures. The highest specific ultraviolet absorbance at 254 nm of the F1 and F2 fractions were observed for RS biochar, suggesting that more aromatic organic matter was present in sequentially extracted fractions of RS biochar than in extracts from the other biochars. In addition, the hot water extracts (F2) mostly showed higher aromaticity than cold water extracts (F1). The stability of biochars was greatly enhanced at pyrolysis temperatures >500 °C. If the biochars produced in this study were to be used for carbon sequestration in soil, the first priority should be PW, followed in order by RS and PM.

Chlorination of coastal (CS) and deep ocean (DO) seawater was accompanied by a prominent decrease (of up to 70%) of the intensity of its emission which was measured using a 315 nm excitation wavelength. Deconvolution of the emission spectra of CS and DO seawater showed that these spectra comprised three Gauss-shaped bands. The intensities of two of these bands decreased rapidly as the halogenation proceeded. For both DO and CS seawater, two stages of changes of their fluorescence were observed. The first stage in which the relative changes of the fluorescence intensity (ΔF/F) were between zero to 0.30 and 0.40 was not accompanied by the release of individual disinfection byproduct (DBP) species. For ΔF/F values above the corresponding thresholds, the relative changes of fluorescence intensity were well correlated with the concentrations of individual DBP species such as trihalomethanes and haloacetonitriles. R2 values for CHBr3, CHBr2Cl and CHBrCl2 formed in DO seawater were 0.83, 0.80 and 0.68, respectively while for CS seawater, the corresponding R2 values were 0.91, 0.93 and 0.92. The presented data demonstrate that the intrinsic chemistry of DBP formation and dissolved organic matter (DOM) halogenation in seawater can be well quantified based on the examination of changes of its fluorescence. This approach can also be employed for practical monitoring of changes of properties of marine DOM and generation of DBPs in desalination, marine aquaculture and other processes.

Formation potential and speciation characteristics of two important groups of disinfection byproducts (DBPs), namely, trihalomethanes (THMs) and haloacetic acids (HAAS), during Cl2 and ClO2 treatment of water samples collected from three different sources, namely, sea, river, and reservoir, were investigated with reference to key controlling parameters. Formation of inorganic DBPs such as chlorate and chlorite was evaluated. Dissolved organic carbon (DOC) and UV absorbance (UV254) of the sea, river, and reservoir samples were 3.35 ± 0.05, 3.12 ± 0.05, and 3.23 ± 0.05 mg/L and 0.062 ± 0.01, 0.074 ± 0.01, and 0.055 ± 0.01 cm−1, respectively. For Cl2 and ClO2 treatments, the respective formation potential of THMs and HAAs from the three water sources studied exhibited unidentical trend suggesting that higher THM formation was not necessarily associated with higher HAA formation. On chlorination, the concentrations of total HAAs formed were 9.8 μg/L (sea), 12.8 μg/L (river), and 20.6 μg/L (reservoir) and total THM yields were 38.3 μg/L (sea), 18.8 μg/L (river), and 21.5 μg/L (reservoir) for a Cl2 dose of 1 mg/L and 30 min reaction time. The trend of formation of THMs and HAAs for Cl2 treatment was similar to that for ClO2 treatment. However, the amount of HAAs (3.5 μg/L (sea), 1.8 μg/L (river), and 1.9 μg/L (reservoir)) and THMs (not detected) formed was much lower than that formed during chlorination. Regardless of source water type, di-HAAs were the most favored HAAs, followed by tri-HAAs with a small amount of mono-HAAs formed for both Cl2 and ClO2 treatment. Chlorination yielded more THMs than HAAs, whereas it was reverse for chlorine dioxide treatment. Irrespective of treatment with ClO2 or Cl2, seawater samples showed the highest bromine incorporation percentage (BIP) in both THMs and HAAs followed by that for river and reservoir water samples. HAAs were found to be always associated with lower amount of BIP than THMs.

This study evaluated the performance of a pilot-scale hybrid constructed wetland system for secondary effluent and investigated bulk organic matter characteristics. The hybrid constructed wetland consisted of a vertical-flow (VF) bed followed by a horizontal-flow (HF) bed. We also investigated the effects of hydraulic loading rates and influent organic load on the performance of the pilot-scale VF-HF hybrid constructed wetland. The results showed a high removal efficiency for suspended solids (>95%) and organic matter as determined by total organic carbon (>98.5%) and dissolved organic carbon (>70%), but no significant change in nitrogen removal was observed. The wetland treatment efficiency for suspended solids and organic matter showed a good buffer capacity even when hydraulic loading rates increased from 750 to 1500 L m−2 d−1 and 500–1000 L m−2 d−1 during the VF and HF stages, respectively. Moreover, there was no significant change in the performance when influent organic load increased eight-fold. Fluorescence excitation-emission matrix and liquid chromatography-organic carbon detection (LC-OCD) were used to investigate the dissolved organic matter characteristics in the hybrid VF-HF constructed wetland. Fluorescence excitation-emission matrix spectroscopy showed that both protein- and humic-like substances did not significantly change in the effluent when hydraulic loading rates and organic load increased by two- and eight-fold, respectively. Biopolymers determined using LC-OCD were effectively removed via the VF and HF stage wetlands, indicating the occurrence of biodegradation. Fluorescence excitation-emission matrix spectroscopy and LC-OCD provided the fate of dissolved organic matter characteristics in the hybrid VF-HF constructed wetland.

The widespread use of halogenated flame retardants in recent years has led to the accumulation of TBBPA in water, which may cause potential harm to living organisms. The phototransformation of the flame retardant TBBPA in alkaline saline water under simulated sunlight irradiation was investigated. The effects of abiotic factors such as the initial concentration of TBBPA, chloride ion concentration, solution pH, inorganic anions and cations, dissolved organic matter (DOM) were studied. The results showed that the phototransformation rate of TBBPA accelerated with the decrease of the initial concentration of TBBPA, the increase of chloride ion concentration and solution pH. The scavenging experiments showed that •OH, 1O2, O2•- and 3TBBPA* all participated in the phototransformation of TBBPA. The presence of NO3-, CO32-, SO42-, Mg2+, Ca2+, Fe3+ and fulvic acid (FA) all inhibited the phototransformation of TBBPA in the present study. The phototransformation products of TBBPA were detected by liquid chromatography-mass spectrometry (LC-MS), and the phototransformation pathways were proposed. This is the first report on the photo-induced generation of halogen exchange products from TBBPA in saline solutions, which will contribute to a better understanding of the environmental behavior and risks of BFRs in water.

Over a three-year field trial, the impacts of composted and raw gentamicin fermentation waste (GFW) application to land on residual soil gentamicin levels, physicochemical properties, bacterial community composition, and antibiotic resistance genes (ARGs) were assessed. In the saline-alkali soil tested, GFW application decreased electrical conductivity (EC) and pH. Importantly, there was no measurable long-term accumulation of gentamicin as a result of GFW addition. Changes in the abundance of Bacillus was primarily associated with degradation of gentamicin in soil, whereas wider (i.e. more general) shifts in bacterial communities over the treatments was linked to alteration of soil physicochemical properties, particularly pH, total nitrogen, dissolved organic carbon, EC, NO3−-N and NH4+-N. Compared with other treatments, soils receiving composted GFW harbored more types of ARGs and significantly higher (P

This study aimed to clarify that long-term leguminous grass mulching (crown vetch (CV) and white clover (WC)) and gramineous grass (orchardgrass (OG)) drive the distribution of soil aggregates and are associated with dissolved organic matter (DOM) components. Excitation emission spectroscopy and parallel factor analysis (EEM-PARAFAC) were used to evaluate the influence of different grass mulches among aggregates. The results indicated that legumes had a more significant impact on the distribution of aggregates and DOM content than gramineae grass mulching. Leguminous grass mulching significantly increased the proportion of macroaggregates250 μm (74.65%-83.50%) and aggregates associated with dissolved organic carbon (DOC), especially in microaggregates250 μm (172.27 mg kg

A hybridization of managed aquifer recharge (MAR) with pre-oxidation processes was conducted in this study to investigate changes in dissolved organic matter characteristics and the attenuation of selected trace organic contaminants (TrOCs). Potassium permanganate, chlorine, and ozone treatments were used for pre-oxidation, which effectively attenuated some TrOCs, particularly the combination of MAR with ozone achieved 84-99% attenuation. The pre-oxidation step using potassium permanganate showed high removal of carbamazepine (96%). Moreover, MAR was also combined with nanofiltration (NF) as a multi-barrier concept for the removal of persistent TrOCs after MAR. A short-chain polyfluoroalkyl substance (PFAS) was effectively removed after combining MAR columns with NF membranes. Thus, pre-oxidation coupled with MAR followed by NF could potentially enhance the removal of selected TrOCs.

In the presence of dissolved organic matter, the mechanism of algal bioaccumulation of different metals is complex, and its significance goes far beyond the alga-metal binary system. In the presence of 10 and 20 mg L−1 fulvic acid (FA), the maximum tolerance concentrations of Chlorella pyrenoidosa to Ni were 0.25 and 0.26 mmol L−1, and to Zn were 0.62 and 0.68 mmol L−1, respectively. Within the maximum tolerance concentration ranges, the bioaccumulation behaviors of Ni and Zn were systematically compared in the presence of FA. The presence of FA shortened the adsorption equilibrium time and decreased the maximum bioaccumulation capacity of Ni and Zn. The bioaccumulation mechanism of Ni by C. pyrenoidosa was more inclined to monolayer adsorption, while the bioaccumulation mechanism of Zn was more inclined to multilayer adsorption. More details were revealed after the bioaccumulated metals were separated into adsorption and internalization states by 0.01 M EDTA elution. The presence of FA decreased more adsorbed Zn than the adsorbed Ni, due to the different competitive roles of FA in the ternary system of Ni and Zn, but the presence of FA increased the internalized Ni might due to the stronger complexation of Ni-FA. This research indicated that algae had unique bioaccumulation mechanisms for different metals in the presence of FA, which is of great significance to accurately evaluate the ecological risk posed by heavy metals.

Biochars were produced from pine feedstock pretreated with aqueous base, NaOH, at pH 9 and 11, and alkali and alkaline earth metals (AAEMs) Na, K, Ca, and Mg at 10−3 and 1 M. The effects of base and AAEM feedstock pretreatment on biochar surface area, pore size distribution, and adsorption capacity of two organic micropollutants (OMPs), 2,4-dichlorophenoxyacetic acid and sulfamethoxazole, from surface water with background dissolved organic matter (DOM) were evaluated. Base pretreatment significantly increased surface area within micropores ( 2 nm in diameter. The catalytic activity of AAEMs, assessed by generation of non-micropore surface area, decreased in the following order: Ca > K > Na > Mg. All pretreated biochars outperformed untreated biochar for OMP adsorption. Biochar pretreated by aqueous base at pH 11 showed over an order of magnitude increase in OMP adsorption, nearly matching the performance of commercial activated carbon. OMP adsorption from surface water was positively correlated with biochar micropore surface area and negatively correlated with non-micropore surface area, which was linked to higher levels of DOM competition. Base and AAEM pretreatment of biochar feedstocks can increase OMP adsorption for water treatment applications by tuning pore structure and surface area.

The widespread use of per- and polyfluoroalkyl substances (PFASs)-related products such as aqueous film-forming foams (AFFF) has led to increasing contamination of groundwater systems. The concentration of PFASs in AFFF-impacted groundwater can be several orders of magnitude higher than the drinking water standard. There is a need for a sustainable and effective sorbent to remove PFASs from groundwater. This work aims to investigate the sorption of PFASs in groundwater by biochar column. The specific objectives are to understand the influences of PFASs properties and groundwater chemistry to PFASs sorption by biochar. The PFASs-spiked Milli-Q water (including 19 PFASs) and four aqueous film-forming foams (AFFF)-impacted groundwater were used. The partitioning coefficients (log Kd) of long chain PFASs ranged from 0.77 to 4.63 while for short chain PFASs they remained below 0.68. For long chain PFASs (C ≥ 7), log Kd increased by 0.5 and 0.8 for each CF2 moiety of PFCAs and PFSAs, respectively. Dissolved organic matter (DOM) was the most influential factor in PFASs sorption over pH, salinity, and specific ultraviolet absorbance (SUVA). DOM contained hydrophobic compounds and metal ions which can form DOM-PFASs complexes to provide more sorption sites for PFASs. The finding is useful for executing PFASs remediation by biochar filtration column, especially legacy long chain PFASs, for groundwater remediation.

Quantitative characterization of dissolved organic matter (DOM) in various aquatic ecosystems has become of increasing importance as its transformation plays a key role in inland water carbon, yet few studies have quantified water DOM inputs to storage lakes for water quality control and safety assurance. This study assessed the quantity and quality of DOM in 21 inflow rivers of Nansi Lake as the important storage lake of large-scale water transfer projects by using excitation-emission matrix spectroscopy coupled with parallel factor analysis (EEM-PARAFAC) and ultraviolet–visible (UV–Vis) spectroscopy. The results showed that DOM contents varied significantly with an average value of 5.8 mg L−1 in different inflow rivers, and three fluorescence substances (including UVC humic-like, UVA humic-like and tyrosine-like components) were identified by EEM-PARAFAC. The distribution of the DOM components was distinctively different among sampling sites, and UVA humic-like component mainly dominated in Nansi Lake. Meanwhile, DOM components with higher aromaticity and molecular weight were found in the west side of lake. Fluorescence spectral indexes manifested that the source of DOM was mainly from allochthonous or terrestrial input. Moreover, significant correlations between water quality and DOM characteristics were observed in Nansi Lake. These findings would be beneficial to understand the biogeochemical role and impact of DOM in inflowing rivers in the water-quality monitoring and control of storage lakes.

In petroleum refineries, the electric desalting, distillation, and stripping processes could generate large amounts of wastewaters that contain toxic substances. In this study, eight wastewater samples were collected from the three typical refining processes for comprehensive chemical characterization of the dissolved organic matter (DOM) using excitation emission matrix fluorescence spectroscopy, gas chromatography-mass spectrometry, and Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). Results showed that protein-like components and benzene were ubiquitous in all these wastewaters. Oxygen-containing volatile organic compounds had higher contents in crude distillation and stripping wastewater than those in electric desalting wastewater. Among the three refinery processes, molecular composition of DOM in the stripping wastewater had the highest complexity. The Ox and OxSy class species assigned from the negative-ion electrospray ionization FT-ICR MS were dominant in all wastewaters. The OxS2 class species which were effectively removed during stripping treatment had highest relative abundance in stripping influent. These results are instructive to guide the development of “divide and conquer” and would improve the treatment and management of refinery wastewater streams.

Change in water quality was investigated with laboratory-scale ozone-biological activated carbon filters using copper-modified granular activated carbon (Cu/GAC) and unmodified granular activated carbon (GAC). In the first seven days of the experimental period, Cu/GAC removed organic matter more efficiently owing to its enhanced adsorption capacity. As the running time increased, the amount of disinfection by-products (DBPs), dissolved organic carbon, and extracellular polymeric substances (EPS) increased sharply in the effluent of the Cu/GAC filter (CCW). More importantly, the EPS suspended in the CCW exhibited weaker flocculating efficiency and hydrophobicity, causing more active chemical reactions between chlorine and EPS substances. The copper species significantly limited the microbial biomass (0.01 nmol/L adenosine triphosphate) but stimulated the secretion of significant amounts of EPS by microorganisms for self-protection. Furthermore, the microbial community in the bulk water was successfully shaped by Cu/GAC, resulting in a continuous supply of EPS-derived DBP precursors and a sharp rise in chlorine consumption in the downstream drinking water distribution. Therefore, use of modified GAC materials, similar to Cu/GAC, as carrier materials for biological activated carbon (BAC) treatment remains controversial, despite enhanced pollutant adsorption capacity. This is the first study to reveal the mechanism of BAC-modified materials for water quality stability. The study potentially contributes to a comprehensive understanding of the effects of biofilm transformation and microbial community succession on drinking water quality. These results showed that tap water safety risks could be reduced by improving BAC pretreatment in drinking water treatment plants.