Hydrophobic Dissolved Organic Matter Research Articles

Response mechanism of soil leachate and disinfection by-product formation to extreme precipitation events under continuous drought scenario

In this study, a rainfall simulation device was employed to investigate the response mechanism of soil leachate and disinfection by-products formation potential (DBPsFP) to extreme precipitation events. The results revealed that the aromaticity of dissolved organic matter (DOM) and the concentration of hydrophobic DOM containing aromatic carbon groups in leachate decreased with rising temperature. The humification degree of DOM decreased at 25 °C (99 mm/h), while the humification degree and protein-like level of DOM increased under high temperatures droughts (45 °C and 65 °C). Higher temperatures resulted in the leach of more microbial-derived humus and low molecular phenolic compounds from soil and broadened the range of molecular weight distribution. Increasing temperature increased DBPsFP and DBPs species and caused the precursors of haloacetic acids (HAAs) in leachate to become more hydrophobic, while the precursors of trihalomethanes (THMs) became more hydrophilic. Most importantly, the increased temperature attenuated the rainfall-mediated dilution of organic pollutant concentration, and temperature has a more significant effect than extreme rainfall in DOM abundance and the formation potential (or species) of DBPs. The results help to better understand the impact of climate change on the physicochemical processes of water quality.

Removal performance of dissolved organic matter from municipal secondary effluent by different advanced treatment processes and preventing the formation of disinfection by-products.

Various advanced treatment processes including ultrafiltration (UF), ozonation, enhanced coagulation, and biological aerated filter (BAF) have been applied to reduce dissolved organic matter (DOM) from the secondary effluent of municipal wastewater treatment plants (MWTPs). In this study, DOM were characterized and the relationship between DOM characteristics and disinfection by-products (DBPs) generation was investigated systematically. Results showed that BAF and ozonation processes could significantly affect DOM characteristics in the treated effluents and the following DBP generation. UF and enhanced coagulation reduced the production of DBPs by removing large molecular hydrophobic organics. The removal of low molecule DOM by BAF resulted in a 67.6% reduction in trihalomethanes (THMs) production. Ozonation could oxidize large hydrophobic DOM into small hydrophilic molecules containing aldehyde and ketone groups, leading to 54% increase of halogenated aldehydes (HALs) and halogenated ketones (HKs). Humic acid (HA) was the main organic type in DOM and important precursor for THMs and dichloroacetonitrile (DCAN) formation. The generation of trichloromethane (TCM) showed a significant positive correlation (R2 = 0.987) with the specific ultraviolet absorbance at 254nm (SUVA). Large molecule hydrophobic DOM devoted the most to the formation of carbonaceous disinfection by-products and [Formula: see text]-N content was an important factor affecting the generation of nitrogenous disinfection by-products. These results are important for the optimization of advanced treatment process in MWTPs, and controlling DBPs should consider the removal of low MW hydrophobic DOM and the reduction of SUVA.

Affinity-based alleviation of dissolved organic matter (DOM) on tetracycline toxicity to photosynthesis of green algae Chlorella vulgaris: roles of hydrophilic and hydrophobic DOM.

The environmental fate and toxic effects of antibiotics such as tetracycline (TC) could be influenced by the ubiquitous dissolved organic matter (DOM). However, DOM from different origins has different hydrophilic and hydrophobic properties. It is still unknown the effects of hydrophilic and hydrophobic DOM on the toxic effect of TC. In this study, DOM with hydrophilicity and hydrophobicity was separated and used to investigate their roles in affecting TC toxicity to the photosynthesis of green algae Chlorella vulgaris. Results showed that 10 mg L-1 TC inhibited the efficiency of photosystem II (PSII) of C. vulgaris using light by hindering electron transfer from QA- to QB/QB-, and the O2 release rate of C. vulgaris decreased by a third after 12-h treatment of 10 mg L-1 TC, while both hydrophilic and hydrophobic DOM (20 mg L-1 TOC) alleviated TC toxicity to the photosynthesis of C. vulgaris. In the presence of hydrophilic or hydrophobic DOM, stable complex of TC-hydrophilic DOM or TC-hydrophobic DOM was formed immediately, due to the good affinity of both DOM for TC. Fourier transform infrared spectroscopy result showed that both hydrophilic and hydrophobic DOM could reduce C=O in TC to C-O, and isothermal titration calorimetry result suggested that reactions of both DOM with TC were exothermic (△H < 0) and spontaneous (△G < 0). Thereinto, the reaction constant (Ka) of TC reacting with hydrophobic DOM (Ka=9.70) was higher than that with hydrophilic DOM (Ka=8.93), indicating hydrophobic DOM with more chemical binding sites and accessible fractions for TC. The present study suggests that DOM, especially the hydrophobic DOM, is an important consideration in the environmental impact assessment of antibiotics.

An autopsy study of hollow fiber and multibore ultrafiltration membranes from a pilot-scale ultra high-recovery filtration system for surface water treatment

The organic fouling characteristics of hollow fiber ultrafiltration (HFUF) and multibore ultrafiltration (MBUF) membranes from long-term ultrafiltration (UF) membrane systems were systemically investigated in this study. The objective was to obtain insights into the fouling behavior of dissolved organic matter (DOM) in a pilot-scale ultra-high-recovery membrane filtration system (p-UHMS) used for surface water treatment. The pilot system consisted of a series of two different UF membranes (1st stage: polyvinylidene fluoride (PVDF) HFUF and 2nd stage: polyethersulfone (PES) MBUF). It was designed to feed the HFUF concentrate to the MBUF membranes to achieve ≥99.5 % total water recovery for surface water treatment, as these advances might enhance the production efficiencies of drinking water. The experimental results confirmed that hydrophobic DOM controlled the formation of HFUF membrane organic fouling, whereas hydrophilic DOM, including polysaccharide-like and protein-like matter, promoted MBUF membrane fouling. These opposing trends were attributed to the hydrophilic characteristics of the MBUF membrane surfaces (contact angle: PVDF = 90–130° and PES ≤ 80°), which reduced the hydrophobic interactions between the UF membrane surfaces and foulants. The performance declines of the MBUF membrane due to fouling layer formation was considerably severer than those of the HFUF membrane, decreasing total permeate water in the p-UHMS. Moreover, the quantity of the desorbed MBUF membrane foulants via 0.1 N NaOH was roughly 7.2 times larger than that of the desorbed HFUF membrane foulants through 0.1 N NaOH, indicating that alkaline-based cleaning agent could much more efficiently recover the performance of the fouled MBUF membranes. Hence, adequate cleaning strategies using alkaline-based agent for the MBUF membrane appeared to be essential for preventing the performance deterioration of the p-UHMS.

Responses of nickel bioavailability and toxicity of Prorocentrum Donghaienses to dissolved organic matter (DOM) fractions incubated in urea

Urea, nickel (Ni) and dissolved organic matter (DOM) from land varied with different sources have a great impact on the offshore ecosystem. The heterogeneity of Ni bioavailability and toxicity of Prorocentrum donghaiense influenced by DOM fractions incubated in urea was investigated in this study. On the occasion, chlorophyll (Chl a) concentration, growth rate, and photosynthesis parameters were monitored to track changes occurring in the test organism. Chl a concentration and photosynthesis parameters in the treatment of hydrophilic DOM (HPI) with Ni-free was significantly higher than that in the control treatment, and similar data were shown in the treatment of hydrophobic DOM（HPO）with the low Ni environment (0.17μmol L−1). However, the opposite phenomena were observed in the treatments of HPO with the higher Ni environment (over 170μmol L−1). Moreover, the EC50 of Ni for P.donghaiense incubated in HPO was relatively lower than that in HPI and control treatment, which implied that HPO elevated the toxicity of Ni. Therefore, the varied DOM compositions because of different origins, as a chelating agent and potential nutrient source in coastal waters, shows the significantly different bioavailability and toxicity of Ni with the increasing inputs of urea, which in turn influences the dynamics of phytoplankton.

Identification of key precursors contributing to the formation of CX3R-type disinfection by-products along the typical full-scale drinking water treatment processes

Identification and characterization of disinfection by-product (DBP) precursors could help optimize drinking water treatment processes and improve the quality of finished water. This study comprehensively investigated the characteristics of dissolved organic matter (DOM), the hydrophilicity and molecule weight (MW) of DBP precursor and DBP-associated toxicity along the typical full-scale treatment processes. The results showed that dissolved organic carbon and dissolved organic nitrogen content, the fluorescence intensity and the SUVA254 value in raw water significantly decreased after the whole treatment processes. Conventional treatment processes were in favor of the removal of high-MW and hydrophobic DOM, which are important precursors of trihalomethane and haloacetic acid. Compared with conventional treatment processes, Ozone integrated with biological activated carbon (O3-BAC) processes enhanced the removal efficiencies of DOM with different MW and hydrophobic fractions, leading to a further decrease in almost all DBP formation potential and DBP-associated toxicity. However, almost 50% of the detected DBP precursors in raw water has not been removed after the coagulation-sedimentation-filtration integrated with O3-BAC advanced treatment processes. These remaining precursors were found to be mainly hydrophilic and low-MW (< 1.0 kDa) organics. Moreover, they would largely contribute to the formation of haloacetaldehydes and haloacetonitriles, which dominated the calculated cytotoxicity. Since current drinking water treatment process could not effectively control the highly toxic DBPs, the removal of hydrophilic and low-MW organics in drinking water treatment plants should be focused on in the future.

Molecular-level investigation into UV-induced transformation of hydrophobic aquatic dissolved organic matter

The ubiquitously present dissolved organic matter (DOM) greatly influence the efficiency of UV-based technologies due to its reactivity to UV irradiation. In this work, UV-induced changes within three hydrophobic DOM fractions isolated from different surface waters were investigated. Analysis on UV absorbance at 254 nm, electron donating capacity, fluorescence intensity and carbon content revealed small changes in DOM bulk properties associated with the UV-induced photochemical reactions. Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) was further used to explore the modification of the molecular distribution based on H/C and O/C ratios, m/z and DBE. The molecular-level investigation revealed that an average of 296 aromatic and lignin-like molecules were degraded, leading to the production of around 306 new molecules. The UV-reactive community were identified as CHO molecules with higher DBE (>10) and carbon number (>25) which could be readily transformed into smaller saturated molecules. Molecules containing nitrogen (N) or sulfur (S) atom, independent of aromaticity and molecular weight (m/z), were also highly UV susceptible and transformed into molecules with larger DBE and m/z. Possible reaction pathways responsible for the observations were discussed. The results indicated that UV-reactivity and subsequent transformation of DOM are remarkably correlated with its molecular composition and characteristics. Though the changes in bulk properties of DOM following UV irradiation were observed to be very small, the significant alteration in its molecular structures would have a profound impact on the UV-based treatment processes.

Chemical Cleaning-Triggered Release of Dissolved Organic Matter from a Sludge Suspension in a Ceramic Membrane Bioreactor: A Potential Membrane Foulant

Ceramic membrane bioreactors (MBRs) have attracted a great deal of interest due to their robustness in the treatment of various kinds of wastewaters. So far, in situ chemical cleaning with sodium hypochlorite (NaClO) has been the most prevalent MBR cleaning method. This study showed that in situ NaClO cleaning in MBRs triggered a significant release of dissolved organic matter (DOM) from a sludge suspension, while the generated DOM could facilitate fouling development, especially irreversible fouling in a ceramic MBR. It was found that biopolymers with a molecular weight (MW) of >10 kDa and humic substances could be effectively rejected by the ceramic membranes. As such, the membrane fouling rate (dTMP/dt) of the supernatant from a NaClO-treated sludge suspension was closely related to the rejected levels of biopolymers and humic substances. However, hydrophobic DOM and low-MW organics (MW < 500 Da) could easily pass through the membranes, indicating an insignificant contribution to the observed membrane fouling. Consequently, this study verified the contributions of DOM released from a sludge suspension after in situ membrane cleaning with NaClO with respect to subsequent membrane fouling development in a ceramic MBR.

Biochar addition supports high digestion performance and low membrane fouling rate in an anaerobic membrane bioreactor under low temperatures

The enhancement effects of biochar to an anaerobic membrane bioreactor (AnMBR) treating sewage at low temperatures was investigated in this study through analyzing organics removal, digestion performance, mixed liquor properties, membrane resistance, and foulant compositions. The chemical oxygen demand (COD) removal efficiency and the COD converted to methane rate increased by more than 12.5% at 10 °C, mainly because of the promotion of biochar to volatile fatty acids degradation. Although biochar caused higher dissolved organic matter (DOM) concentration in the AnMBR, it improved the filtration property of the bulk sludge and absorbed the hydrophobic DOM. The decreased filtration resistance assisted by biochar leads to a prolonged membrane operation duration over 200%. Surface foulants, especially cake foulants, were largely mitigated by the enhanced scouring intensity of mixed liquor at the membrane surface, and hence, decreasing the cake/gel foulants ratio.

Fouling characteristics of dissolved organic matter in fresh water and seawater compartments of reverse electrodialysis under natural water conditions

The fouling characteristics of dissolved organic matter (DOM) in the fresh water and seawater compartments of the reverse electrodialysis (RED) system were investigated under natural water conditions. The salinity gradient power generation was governed monovalent ions whereas multivalent ions strongly contributed to the fouling formation of the ion-exchange membranes (IEMs). The partial deposition of DOM within the membrane pores during its passage from the fresh water compartment to the seawater compartment facilitated the fouling formation of the IEMs. Despite of the similar DOC losses in fresh water (DOC loss = 20%) and seawater (DOC loss = 22%) through the RED system, the colour variations of the anion-exchange membranes (AEMs) and spacers in contact with fresh water were more noticeable than those in contact with seawater. These results indicate that the deposition of hydrophobic DOM components onto the AEM surfaces water may lead to the increases in the pressure drop of the fresh water compartment and the decreases in the power density of the RED system. Therefore, an appropriate pre-treatment strategy capable of mitigating membrane fouling by hydrophobic DOM components seemed to be indispensable to maintain constantly the performance of the RED system under natural water conditions.

Dynamics of the dissolved organic matter in a stream-lake system within an extremely acid to neutral pH range: Agrio-Caviahue watershed.

The Agrio-Caviahue is a natural stream-lake system composed of the Upper Agrio River (UAR) -Lake Caviahue-Lower Agrio River (LAR). The system has a broad pH gradient from extremely acid in the hot spring to almost neutral pH only 60km downstream the source, and varies as a function of the distance. The aim of this study was to analyze the dynamics of the dissolved organic matter (DOM) of this extreme system. For that matter, an absorbance and fluorescence-based characterization was performed on natural water samples and hydrophobic resin DOM extracts during different seasons in nine sampling stations. Between August and December, the hydrological connectivity is maximum due to precipitation and snowmelt, respectively. During these months, the stream that exits the lake governs the chemical characteristics downstream mainly in the period of high connectivity. In contrast, in the dry season when the flow of LAR is minimum, the two major affluents of this river influence its pH and DOM features, and deliver inputs of humified DOM from the wetlands where the tributaries are born. DOM was characterized by having low absorbance. The PARAFAC analysis of the fluorescent DOM (FDOM) validated three fluorescent components in the natural samples (with humic and non-humic features), two of which were also recorded in the extracts, meaning that no additional hydrophobic components were missed under the limit of detection of the fluorometer. The unique features of Agrio-Caviahue DOM resemble those found in DOM from Yellowstone hot springs, both acid and alkaline.

Amino-functionalized mesoporous silica-magnetic graphene oxide nanocomposites as water-dispersible adsorbents for the removal of the oxytetracycline antibiotic from aqueous solutions: adsorption performance, effects of coexisting ions, and natural organic matter.

The amino-functionalized mesoporous silica-magnetic graphene oxide nanocomposite (A-mGO-Si) was synthesized and used for oxytetracycline (OTC) removal from water. Various factors like the effects of initial concentration, contact time, and influence of pH were investigated. Selective adsorption experiments in connection with coexisting ions and dissolved organic matter (DOM) were also investigated. In this study, humic acid (HA) and tannic acid (TA) were representative of both hydrophobic and hydrophilic DOM, respectively. Results indicated that A-mGO-Si had an adsorption ability for OTC that was relatively greater than that of virgin magnetic graphene oxide (mGO), graphene oxide (GO), Fe3O4 particles, and SBA-15 mesoporous silica and also showed a better uptake removal capacity for OTC at low initial concentration in comparison with the other adsorbents. The adsorption behavior of OTC onto A-mGO-Si could be described by the pseudo-second-order kinetic model and the Freundlich isotherm model. The electrostatic interaction has no influence on the OTC absorbed when the OTC is in an aqueous medium in its zwitterion form (3.22 < pH < 7.46). At high pH, the weak π-π EDA interactions and hydrogen bonding may manifest themselves, hence causing a lower adsorption capacity. The main adsorption mechanisms were plausibly activated by H-bonding, and π-π EDA interactions, while the electrostatic interaction (cation-π interaction) might be the minor adsorption mechanism. Addition of individually exogenous ions (Na+, Mg2+, NO-, and CO32-) resulted in a decrease of OTC adsorption due to the emergence of a competitive effect. Considering the presence of HA and TA in mixed solute systems, the DOM was likely to form a stronger interaction system with mGO-Si, thereby resulting in an adsorption level which was more competitive in the process at low aqueous phase concentration of OTC. In contrast to the high aqueous phase, the coexistence of DOM could promote OTC adsorption. The phenomenon may reflect the result that a surface complexation mechanism could achieve in adsorptions.

Changes in groundwater dissolved organic matter character in a coastal sand aquifer due to rainfall recharge

Dissolved organic matter (DOM) in groundwater is fundamentally important with respect to biogeochemical reactions, global carbon cycling, heavy metal transport, water treatability and potability. One source of DOM to groundwater is from the transport of organic matter from the vadose zone by rainfall recharge. Changes in precipitation patterns associated with natural climate variability and climate change are expected to alter the load and character of organic matter released from these areas, which ultimately impacts on groundwater quality and DOM treatability. In order to investigate potential changes in groundwater DOM character after rainfall recharge, we sampled shallow groundwater from a coastal peat-rich sand aquifer in New South Wales, Australia, during an extended period of low precipitation (average daily precipitation rate < 1.6 mm day−1 over the 8 months prior to sampling), and after two heavy precipitation events (84 mm day−1 and 98 mm day−1 respectively). We assess changes in DOM composition after correcting for dilution by a novel combination of two advanced analytical techniques: liquid chromatography organic carbon detection (LC-OCD) and negative-ion electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). We also assess changes in water chemistry pre- and post-rainfall. Post-rainfall, we show that the dilution-corrected amount of highly aromatic DOM molecular formulae (i.e. those categorised into the groups polyphenolics and condensed aromatics) were 1.7 and 2.0 times higher respectively than in pre-rainfall samples. We attribute this to the flushing of peat-derived DOM from buried organic material into the groundwater. We also identify that periods of low precipitation can lead to low hydrophilic/HOC ratios in groundwater (median = 4.9, n = 14). Redundancy analysis (RDA) was used to compare the HOC fraction with FT-ICR MS compound groups. We show that HOC has a more aromatic character in pre-rainfall samples, and is less similar to the aromatic groups in post-rainfall samples. This suggests that the decline in water-borne hydrophobics observed post-rainfall could be associated with preferential adsorption of the hydrophobic aromatic DOM, making post-rainfall samples less treatable for potable water supply. Post-rainfall we also observe significant increases in arsenic (leading to concentrations greater than 3 times the World Health Organisation drinking water limit of 10 μg / L). Increases in coastal rainfall due to climate change may therefore alter the composition of groundwater DOM in coastal peatland areas in ways that may impact DOM bioavailability, and increase arsenic concentrations, reducing the ease of water treatment for human consumption. To the best of our knowledge, this is the first study to identify the chemical and molecular changes of shallow groundwater DOM pre-rainfall and post-rainfall in a sedimentary organic carbon rich environment through multiple analytical techniques.

Effect of Dissolved Organic Matter on Agglomeration and Removal of CuO Nanoparticles by Coagulation

Engineered nanomaterials (ENMs), such as copper oxide nanoparticles (CuO NPs), are emerging as pollutants extensively used in many commercial and industrial applications, thus raising environmental concerns due to their release into water bodies. It is, therefore, essential to remove these pollutants from water bodies in order to minimize the potential threat to the aquatic environment and human health. The objective of this study was to investigate the removal of CuO NPs from waters by the coagulation process. This study also explored the efficiency of coagulation to remove hydrophobic/hydrophilic dissolved organic matter (DOM) and turbidity with varying polyaluminum chloride (PACl) doses. According to the results, a high concentration of DOM affects both the CuO NPs zeta potential and hydrodynamic diameter, thereby decreasing the agglomeration behavior. At effective coagulation zone (ECR), high removal of CuO NPs (&gt;95%) was observed for all studied waters (hydrophobic and hydrophilic waters), above ECR excess charge induced by coagulant restabilized particles in solution. Furthermore, waters containing hydrophobic DOM and those with high UV254nm values needed more coagulant dose than hydrophilic waters to obtain similar CuO NP removals. The primary mechanism involved in CuO NPs removal might be charge neutralization. These findings suggest that PACl is an effective coagulant in the removal of CuO NPs; however, water characteristics are an influencing factor on the removal performance of ENMs during the coagulation process.

Achieving no spent brine discharge in an anion exchange resin-based fixed-bed process for typical DOM removal

The anion exchange resin (AER) process successfully removed dissolved organic matter (DOM) from various water matrices. To restore AER capacity by routine DOM removal from the regenerant is an attractive strategy to solve the spent brine disposal problem. This study investigated the long-term removal (from the feed) and accumulation (in the inorganic regenerant) characteristics of typical DOM molecules (including anionic pharmaceuticals, short-chain aliphatic acids, humic substances and amino acids) during ˜50 adsorption–regeneration cycles of an AER-based fixed-bed process with the routine physico-chemical purification treatment of the regenerant. All anionic DOM molecules complied with common long-term removal and accumulation mechanisms driven by both electrostatic and non-electrostatic interactions in a multicomponent system, regardless of aromatic structure, hydrophobicity/hydrophilicity, or water solubility. A high anionic DOM removal (˜90%) from the feed could be stably achieved after anionic DOM accumulated in the regenerant was effectively removed (˜80%) by more frequent regenerant-purification treatments. The AER presented here did not selectively remove aromatic and/or hydrophobic DOM molecules from water matrices during the long-term cyclic operation. These findings will enable the development of new designs of AER-based fixed-bed processes for DOM removal from various water matrices.

Reactivity of chromophoric dissolved organic matter (CDOM) to sulfate radicals: Reaction kinetics and structural transformation

Sulfate radical (SO4•−) has been extensively studied as a promising alternative in advanced oxidation processes (AOPs) for water treatment. However, little is known about its reactivity to the ubiquitous dissolved organic matter (DOM) in water bodies. SO4•− would selectively react with electron rich moieties in DOM, known as chromophoric DOM (CDOM), due to its light absorbing property. In this study, the reactivity and typical structural transformation of CDOM with SO4•− was investigated. Four well characterized hydrophobic DOM fractions extracted from different surface water sources were selected as model CDOM. SO4•− was produced through the activation of peroxymonosulfate (PMS) by Co(II) ions at pH 8 in borate buffer. The reactivity of CDOM was studied based on the decrease in its ultraviolet absorbance at 254 nm (UVA254) as a function of time. The reactivity of CDOM changed with time where fast and slow reacting CDOMs (i.e., CDOMfast and CDOMslow) were clearly distinguished. A second-order rate constant of CDOMfast with SO4•− was calculated by plotting UVA254 decrease versus PMS exposure; where a Rct value (i.e., ratio of sulfate radical exposure to PMS exposure) was calculated using pCBA as a probe compound. The transformation of CDOM was studied through the analysis of the changes in UVA254, electron donating capacity, fluorescence intensity, and total organic carbon. A transformation pathway leading to a significant carbon removal was proposed. This new knowledge on the kinetics and transformation of CDOM would ultimately assist in the development and operation of SO4•−-based water treatment processes.

Aggregation of TiO2 and Ag nanoparticles in soil solution – Effects of primary nanoparticle size and dissolved organic matter characteristics

The colloidal stability of nanoparticles NP in soil solution is important to assess their potential effects on ecosystems. The aim of this work was to elucidate the interactions between initial particle size di, particle number concentration (N0) as well as the characteristics of dissolved organic matter (DOM) for stabilizing Ag NP and TiO2 NP.In batch experiments using time-resolved dynamic light scattering (DLS), we investigated the aggregation of TiO2 NP (79 nm, 164 nm) and citrate-stabilised Ag NP (73 nm, 180 nm) in Ca2+ solution (2 mM) and two soil solutions, one extracted from a farmland and one from a floodplain soil (each containing 2 mM Ca2+).Our results demonstrate that the initial particle size and the particle number concentration affected aggregation more strongly in the presence of DOM than without DOM. The composition of DOM also affected aggregate size: NP formed larger aggregates in the presence of hydrophilic DOM than in the presence of hydrophobic DOM. Hydrophilic DOM showed a larger charge density than hydrophobic DOM. If Ca2+ is present, it may bridge DOM molecules, which may lead to greater NP destabilization. The results demonstrate that DOM interaction with NP may not only vary for different DOM characteristics (i.e. charge density) but may also be influenced by the presence of multivalent cations and different NP material; thus the effect of DOM on NP colloidal stability is not uniform.

Transformation of dissolved organic matter during advanced coal liquefaction wastewater treatment and analysis of its molecular characteristics

Coal liquefaction wastewater (CLW) contains numerous toxic and biorefractory organics. A series of advanced treatment processes were designed to remove the dissolved organic matter (DOM) from CLW. Here, the reactivity and state of the DOM in the treatment train were studied in relation to its chemical composition by a Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) analysis. Within an isobaric group, the raw CLW possessed a high average double-bond equivalent (DBEwa) and low H/Cwa values with the N- and S-containing compounds accounting for approximately 77% of the raw CLW, which represented lignin (73.6%) and condensed aromatic structures (19.8%). In addition, the flotation process removed some hydrophobic DOM compounds with highly unsaturated states, which were biorefractory compounds. Ozonation and catalytic oxidation processes preferentially removed the highly unsaturated compounds and produced more oxidized molecules. The biofiltration process impacted the organics composition by consuming oxygen-rich substances, whereas the anoxic/oxic (A/O) process converted the reactive compounds into newly formed compounds through the loss of hydrogen (unsaturation) from the original compounds. The membrane bioreactor (MBR) process was more efficient in removing the N-containing compounds with higher unsaturated states. The compounds resistant to the applied CLW treatment processes were characterized by lower molecular weights (approximately 250–350 Da), higher oxidation states (O/S > 6), numerous carboxylic groups, and non-biodegradable features.

Sorptive removal of dissolved organic matter in biologically-treated effluent by functionalized biochar and carbon nanotubes: Importance of sorbent functionality

The sorptive removal of dissolved organic matter (DOM) in biologically-treated effluent was studied by using multi-walled carbon nanotube (MWCNT), carboxylic functionalised MWCNT (MWCNT-COOH), hydroxyl functionalized MWCNT (MWCNT-OH) and functionalized biochar (fBC). DOM was dominated by hydrophilic fraction (79.6%) with a significantly lower hydrophobic fraction (20.4%). The sorption of hydrophobic DOM was not significantly affected by the sorbent functionality (∼10.4% variation) and sorption capacity followed the order of MWCNT > MWCNT-COOH > MWCNT-OH > fBC. In comparison, the sorption of hydrophilic fraction of DOM changed significantly (∼37.35% variation) with the change of sorbent functionality with adsorption capacity decreasing as MWCNT-OH > MWCNT-COOH > MWCNT > fBC. Furthermore, the affinity of adsorbents toward a hydrophilic compound (dinitrobenzene), a hydrophobic compound (pyrene) and humic acid was also evaluated to validate the proposed mechanisms. The results provided important insights on the type of sorbents which are most effective to remove different DOM fractions.

Soil organic amendments: impacts on sorption of organophosphate pesticides on an alluvial soil

Soil organic carbon enrichment by addition of organic amendments (OAs) is a common agricultural and gardening practice. Such amendments can cause ambiguous environmental effects; it could enhance the sorption of pesticides by increasing soil organic carbon content, and on the contrary, dissolved organic matter (DOM) from OAs could facilitate their leaching. This study evaluated the influence of OAs, mixed waste compost, and dried goat organic manure on the sorption of organophosphates, dichlorvos, and chlorpyrifos. Soil (15 cm depth) was collected from an agricultural field and stored. Dissolved organic matter (DOM) extracted from the amendments and the amended soils was characterized by fluorescence spectroscopy and Fourier transform infrared spectroscopy (FT-IR). Initially, studies were carried out to evaluate the effect of DOM from organic amendments (OA-DOM) and dissolved humic acids (HAs) as model DOM on the sorption of selected pesticides. In the later part, OAs (2.5 and 5% w/w) were added to the soil, and sorption experiments were carried out using amended soil to understand the combined effects of insoluble and soluble organic carbon fraction. As dichlorvos sorption was found to be very low, desorption experiments were conducted only for chlorpyrifos using 0.01 M CaCl2 and DOM solutions. The spectroscopic characterization of OA-DOM revealed that it mainly contained large amounts of highly humified and aromatic material. OA-DOM and HAs had a similar effect on pesticide sorption leading to a slight but not significant increase in dichlorvos sorption while a substantial reduction in chlorpyrifos sorption was observed. Surface tension analysis highlighted that OA-DOM and HAs might have caused greater solubilization of chlorpyrifos, thus reducing sorption. Further, it also promoted greater desorption of adsorbed chlorpyrifos. These results seem to be related to the humified and aromatic nature of OA-DOM and HAs, determining the interactions between hydrophobic chlorpyrifos and DOM. On the contrary, the addition of OAs to soil promoted greater chlorpyrifos and dichlorvos sorption, but a clear correlation between increase in soil organic carbon and pesticide sorption could not be established. The study highlighted that the net effect of OA application was an increase in pesticide sorption that depended on the nature of DOM and pesticide properties. The interactions of hydrophobic chlorpyrifos with DOM can lead to a significant reduction in sorption to such an extent that the sorption in the presence of substantial DOM concentration can be less than the sorption without it.