Photochemical Transformation of Dissolved Organic Matter in Surface Water Augmented the Formation of Disinfection Byproducts.

Sunlight may lead to changes in disinfection byproducts (DBPs) formation potentials of source water via transforming dissolved organic matter (DOM); however, the underlying mechanisms behind these changes remain unclear. This work systematically investigated the effect of photochemical transformation of DOM from reservoir water (DOMRe) and micropolluted river water (DOMRi) after 36 h of simulated sunlight irradiation (equivalent to one month under natural sunlight) on DBPs formation. Upon irradiation, high molecular weight (MW) and aromatic molecules tended to be mineralized or converted into low-MW and highly oxidized (O/C > 0.5) ones which might react with chlorine to generate high levels of DBPs, resulting in an elevation in the yields (µg DBP/mg C) of almost all the measured DBPs and the quantities of unknown DBPs in both DOM samples after chlorination. Additionally, DOMRi contained more aromatic molecules susceptible to photooxidation than DOMRe. Consequently, irradiated DOMRi exhibited a greater increase in the formation potentials of haloacetonitriles, halonitromethanes, and specific regulated DBPs, with nitrogenous DBPs being responsible for the overall rise in the calculated cytotoxicity following chlorination. This work emphasized the importance of a comprehensive removal of phototransformation products that may serve as DBPs precursors from source waters, especially from micropolluted source waters.

Facile synthesis of graphene-based hyper-cross-linked porous carbon composite with superior adsorption capability for chlorophenols.

In this work, we proposed a green and cost-effective method to prepare a graphene-based hyper-cross-linked porous carbon composite (GN/HCPC) by one-pot carbonization of hyper-cross-linked polymer (HCP) and glucose. The composite combined the advantages of graphene (GN) and hyper-cross-linked porous carbon (HCPC), leading to high specific surface area (396.93 m2/g) and large total pore volume (0.413 cm3/g). The resulting GN/HCPC composite was applied as an adsorbent to remove 2,4-dichlorophenol (2,4-DCP) from aqueous solutions. The influence of different solution conditions including pH, ionic strength, contact time, system temperature and concentration of humic acid was determined. The maximum adsorption capacity of GN/HCPC composite (calculated by the Langmuir model) could reach 348.43 mg/g, which represented increases of 43.6% and 13.6% over those of the as-prepared pure GN and HCPC, respectively. The Langmuir model and pseudo-second-order kinetic model were found to fit well with the adsorption process. Thermodynamic experiments suggested that the adsorption proceeded spontaneously and endothermically. In addition, the GN/HCPC composite showed high adsorption performance toward other organic contaminants including tetracycline, bisphenol A and phenol. Measurement of the adsorption capability of GN/HCPC in secondary effluent revealed a slight decrease over that in pure water solution. This study demonstrated that the GN/HCPC composite can be utilized as a practical and efficient adsorbent for the removal of organic contaminants in wastewater.

Tracking the transformation pathway of dissolved organic matters (DOMs) in biochars under sludge pyrolysis via reactomics and molecular network analysis.

This work examined the transformation pathways of sludge biochar-derived dissolved organic matters (SBC-derived DOMs) under sludge pyrolysis via FT-ICR-MS-based reactomics and molecular network analysis. Lignin/carboxylic-rich alicyclic molecules, proteins/aliphatic, and lipids of SBC-derived DOMs did not contribute equally to the overall pyrolytic reactions. Reactomics suggested that the pyrolysis reactions of SBC-derived DOMs consist of multiple cascade reactions involving the elimination of assemblages of reactive fragments during each pyrolysis reaction region, and the overall pyrolysis process was divided into three stages according to cascade reaction variations. Especially, cascade reactions at 400-500 °C produced potential environmental risk substances of N-containing, carbonyl-containing, and phenolic compounds. Besides, network analysis unraveled the complexity and number of molecular reaction pairs of SBC-derived DOMs decreased with the increase in pyrolytic temperatures. Keystone molecules and pathways results indicated that the pyrolytic temperature of the sludge pyrolysis process should be controlled at temperatures above 500 °C according to the harmful substances generation pattern in reaction products. Overall, the possible transformation pathways of SBC-derived DOMs during sludge pyrolysis treatment were proposed. This study elucidated the underlying mechanisms in generating SBC-derived DOMs and provided theoretical support for process optimization and harmful substances control of sludge pyrolysis.

Biostimulants in dissolved organic matters recovered from anaerobic digestion sludge with alkali-hydrothermal treatment: Nontarget identification by ultrahigh-resolution mass spectrometry.

Recovering high-value biomaterials from anaerobic digestion sludge (ADS) has attracted considerable attention. However, the molecular features and biological effects of abundant dissolved organic matters (DOMs) in ADS are still unclear, which limits the efficient recycling and application of these bioproducts. This study investigated the molecular composition and transformation of DOMs recovered from ADS through a mild-temperature alkali-hydrothermal treatment (AHT) with ultrahigh-resolution mass spectrometry and energy spectroscopy, and the fertilizing effects of DOMs were evaluated by rice hydroponics. The results indicated that AHT processes significantly promoted the solubilization and release of DOMs from ADS, where most of DOMs molecules remained unchanged and mainly consisted of N-containing compounds with 1-3 N atoms, featuring aromatic or N-heterocyclic rings. Furthermore, AHT processes at pH of 9-10 induced the hydrolysis of partial protein-like substances in DOMs, which was accompanied by formation of heterocyclic-N compounds. Under AHT at pH of 11-12, protein-like and heterocyclic-N substances were increasingly decomposed into amino-N compounds containing 1 or 5 N atoms, while numerous oxygenated aromatic substances with phytotoxicity were degraded and removed from DOMs. Rice hydroponic test verified that ADS-derived DOMs recovered by AHT process at pH of 12 exhibited the highest bioactivity for rice growth, which was attributed to the abundance of amino compounds and humic substances. This study proposed a novel process for the recovery of high-quality liquid organic fertilizer from ADS through AHT process, which can further enrich the technical options available for the safe utilization of sludge resources.

Dissolved organic matter transformation mechanisms and process optimization of wastewater sludge hydrothermal humification treatment for producing plant biostimulants.

Understanding the composition, transformation and bioactivity of dissolved organic matter (DOM) at the molecular level is crucial for investigating the hydrothermal humification process of wastewater sludge and producing ecological fertilizers. In this study, DOM transformation pathways under alkali-thermal humification treatment (AHT) were characterized by Fourier transform-ion cyclotron resonance mass spectrometry (FT-ICR MS) in conjunction with molecular reaction network analysis. The effects of DOM on plant growth were examined using hydroponics and transcriptomic analysis. In the wastewater sludge humification process, AHT produced maximum amounts of protein (3260.56 mg/L) and humic acid (5788.24 mg/L) after 12 h. FT-ICR MS results indicated that protein-like structures were prone to continuous oxidation and were ultimately transformed into aromatic N-containing compounds resembling humic substances. Several reactive fragments (such as -C2H2O2, -C3H4O2, and -C4H6O2) formed by the Maillard reaction (MR) were identified as potential precursors to humic acid (HA). In terms of biological effects, DOM12h showed the highest rice germination and growth activity, whereas that produced by AHT for a longer period (> 12 h) displayed phytotoxicity owing to the accumulation of toxic substances. Plant biostimulants (such as amino acids and HAs) in DOM improved energy metabolism and carbohydrate storage in rice seedlings by upregulating the "starch and sucrose metabolism" pathways. Toxic substances (such as pyrrole, pyridine, and melanoidin) in DOM can activate cell walls formation to inhibit abiotic stimuli in rice seedlings through the biosynthesis of phenylpropanoid pathway. These findings provide a theoretical basis for optimizing sludge hydrothermal humification and recovering high-quality liquid fertilizers.

Molecular composition and chemodiversity of dissolved organic matter in wastewater sludge via Fourier transform ion cyclotron resonance mass spectrometry: Effects of extraction methods and electrospray ionization modes.

High-resolution mass spectrometry was extensively applied in molecular composition and transformation pathways of dissolved organic matter (DOM) in wastewater sludge treatments. Sample pretreatment methods and electrospray ionization (ESI) modes significant affect the accuracy of molecular characterization for DOM. This study investigated the effects of pretreatment methods (styrene divinyl benzene polymer (PPL), octadecyl (C18), and electrodialysis (ED)) on molecular characteristics of DOM in two typical wastewater sludges (waste activated sludge (WAS) and anaerobic digestion sludge (ADS)) analyzed by FT-ICR MS in both positive ESI (ESI (+)) and negative ESI (ESI (-)) modes. The results indicated that ED pretreatment exhibited the highest recovery rate of 70% ‒ 95% for sludge-derived DOM. ED and PPL performed well in recovering the different sludge-derived DOM with a high similarity of molecular characteristics (e.g., lipids, proteins/aliphatic, and lignins/CRAM-like), and the C18 method was ineffective in extracting carbohydrates, unsaturated hydrocarbons, and amino sugars. In addition, compared with single ESI (-) analysis mode, the molecular number identified by ESI (+) analysis mode was increased by 200%, especially, more unsaturated hydrocarbons and N-containing compounds were detected. Except for biogenic DOM, plenty of emerging containments (ECs) in sludge-derived DOM were identified; ESI (-) mode was more effectively in recognizing the alkyl benzene sulfonic acids (e.g., anionic surfactants); and ESI (+) mode was more effectively for plasticizers identification, for example, dioctyl terephthalate and dibutyl phthalate. This study illustrated that ED pretreatment coupled with FT-ICR MS in dual ESI modes could give more insights in complexed molecular information for DOM in wastewater sludge, and provides a theoretical basis for subsequent sludge treatments and disposals.

Coupling effect of DOM and microbe on arsenic speciation and bioavailability in tailings soil after the addition of different biologically stabilized sludges.

Dissolved organic matter (DOM) and microbes co-mediate the transformation of heavy metals in soil. However, few previous studies have investigated the effects of interaction between DOM and microbes on the transformation and bioavailability of heavy metals in tailings soil at the molecular level after the addition of organic wastes. This study used co-occurrence network analysis based on Fourier-transform ion cyclone resonance mass spectrometry and high-throughput sequencing to investigate the molecular mechanisms of different bio-stabilized sludge addition on arsenic fraction transformation and bioavailability in tailings soil. It was found that sludge amendments decreased the arsenic bioavailable fraction from 3.62% to 1.74% and 1.68% and promoted humification of DOM in soil. The extra inorganic salt ions introduced with sludge desorb the adsorbed As(V) into soil solution. Specifically, bio-stabilized sludge increased the contents of labile compounds that provided nutrients for microbial metabolism and shaped the microbial community composition into a more copiotrophic state, which increased the abundance of As(V)-reducing bacteria and then converted the As(V) into As(III) and precipitated as As2S3. This work innovatively explores the transformation mechanisms of As fractions through the perspectives of microbial community and DOM molecular characterization, providing an important basis for the remediation of As-contaminated soil using biosolids.

The molecular characteristics of DOMs derived from bio-stabilized wastewater activated sludge and its effect on alleviating Cd-stress in rice seedlings (Oryza sativa L.).

To recycle fertilizing contents in wastewater activated sludge (WAS) is attracting increasing interest. Dissolved organic matters (DOMs) in WAS with high content are biologically active. In this work, the molecular composition of DOMs derived from two typical bio-stabilized WAS (DOMBWS), aerobic composting (DOMACS) and anaerobic digestion (DOMADS), were analyzed. The mitigative effect and molecular mechanisms of DOMBWS on rice seedlings (Oryza sativa L.) under Cd-stress were investigated. Our study indicated that DOMBWS significantly alleviated Cd-stress and facilitated growth recovery of rice seedlings with distinct absorption mechanisms. DOMACS, primarily composed of CHO class with low molecular weight rich in carboxyl groups, forming labile Cd-DOM complexes, which promoted Cd-absorption of rice seedlings. While DOMADS comprised large molecular weight of CHON class interacted with Cd to produce stable macromolecular complexes in the form of microaggregates, consequently reducing Cd-absorption. At transcriptional level, DOMBWS restored auxin signal transduction and phenylpropanoid biosynthesis pathways in root cells, and got the expression of glutathione S-transferase well. Besides, DOMACS significantly promoted the metabolism of amino acids to alleviate phytotoxicity, while DOMADS improved the DNA repair function of rice seedlings. These findings provided novel insights into land-use of bio-stabilized WAS for remediation of heavy metals contaminated soils and food security.

Fractionation, molecular composition, and biological effects of organic matter in bio-stabilization sludge with implication to land utilization.

Bioactive organic compounds (BOCs) contained in bio-stabilized products of waste activated sludge (WAS) have attracted considerable attention, as they can enhance the fertilizing effect of WAS in land applications. This study investigated the molecular composition and plant-growth-promoting mechanisms of various BOCs in the bio-stabilized products of WAS. After stepwise fractionation, aerobic composting sludge (ACS) and anaerobic digestion sludge (ADS) were chemically fractioned into five subcomponents, namely dissolved organic matter (DOM) (C1), weakly interacted organic matter (OM) (C2), metal-bonded OM (C3), NaOH-extracted OM (C4), and strongly interacted OM (C5), in sequence. The results showed that fatty acids and carboxylic acid (CAs) present in ACS C2 promoted plant growth and enhanced the ability of plants against stresses by upregulating pathways related to "carbohydrate metabolism," "lipid metabolism," "amino acid metabolism," and "phenylpropanoid biosynthesis." However, in ACS C4, plenty of amino acids could promote plant growth via upregulating "carbohydrate metabolism" and "amino acid metabolism" pathways. As an important precursor, aromatic amino acids inside ACS C4 also stimulated the production of indoleacetic acids. In ADS C1, amino sugar and phytohormone were the major BOCs causing the up-regulation of "carbohydrate metabolism" and AAA catabolism in "amino acid metabolism" pathways. CAs enriched in ADS C2 stimulated plant growth through "amino acid metabolism" pathway. In summary, alkali extraction can recycle a large proportion of BOCs with low environmental risk from the bio-stabilization products of WAS. The results from this study provide scientific guidance for safe and value-added resource utilization of bio-stabilization products of WAS in land applications.

Molecular transformation of dissolved organic matter and formation pathway of humic substances in dredged sludge under aerobic composting.

Using Fourier transform-ion cyclotron resonance mass spectrometry (FT-ICR MS) and molecular reaction network analysis, this study investigated molecular transformation of dissolved organic matter (DOM) and formation pathway of humic substances (HS) in dredged sludge during aerobic composting. The results showed that macromolecular N-containing compounds in dredged sludge are abundantly transformed into unsaturated and aromatic oxygenated compounds, exhibiting physicochemical properties similar to those of humus. Especially, N-containing compounds with one nitrogen atom are susceptible to oxidative deamination. Furthermore, assemblages of reactive fragments (e.g., -C7H8O2, -C10H12O2, -C2H2O2, and -C4H6O2) were identified as potential precursors to HS formed by the following reactions: starting with protein deamination and desulfurization, lignin delignification cascaded, finally decarbonylation occurred. This work provides novel insight for optimizing the process of stabilization and humification of dredged sludge.

Photochemical transformation mechanisms of dissolved organic matters (DOM) derived from different bio-stabilization sludge.

Bio-stabilization sludge contains numerous dissolved organic matter (DOM) that could enter aquatic environments by soil leaching after sludge land use, but a clear understanding of their photochemical behavior is still lacking. In this study, we systematically investigated the photoactivity and photochemical transformation of aerobic composting sludge-derived DOM (DOMACS) and anaerobic digestion sludge-derived DOM (DOMADS) by using multispectral analysis coupled with Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). The results indicated that DOMACS and DOMADS have a higher proportion of highly unsaturated and phenolic compounds (HuPh)with high DBEwa, but the different polyphenols (Polyph) abundance of them, causing the different photoactivity between them. DOMACS had much higher apparent quantum yields (AQY) for triplet states of dissolved natural organic matter (3DOM*) and hydroxyl radical (•OH) but slightly lower AQY for singlet oxygen (1O2) than DOMADS under simulated sunlight conditions. As the irradiation time increased, HuPh and Polyph (associated with humic-like substances) contained in DOMACS (DOMADS) decreased by 12.0% (14.1%) and 3.0% (0.2%), respectively, with concurrent decrease in average molecular weight and aromaticity moieties, resulting in more generation of aliphatic compounds. Furthermore, based on 27 types of photochemical transformation reactions, DOMACS containing higher fractions of O10-15 and N1-3Oy class preferred dealkyl group and carboxylic acid reactions, whereas DOMADS composed of more N4Oy and S2Oy fragments preferred oxygen addition and anmine reactions. Consequently, photochemical transformations reduced the Cd (II) ion activity in the presence of DOMACS (DOMADS). This study is believed to unveil the photochemical transformation of bio-stabilization sludge-derived DOM and its impact on pollutants' fate in the aquatic environment.

Molecular composition and biotoxicity effects of dissolved organic matters in sludge-based carbon: Effects of pyrolysis temperature.

Sludge pyrolysis carbonization has shown potential to convert sludge biomass into multifunctional carbon materials. However, ecological risks of dissolved organic matters (DOMs) with obscure molecular characteristics retaining in sludge-based carbons (SBCs) have received little attention. This study investigated the impact of pyrolysis temperatures on the molecular conversion and biotoxicity effects of DOMs in SBCs. The results revealed that DOMs in SBCs300-400 were mainly derived from depolymerization of biopolymers and the polycondensation and cyclization of small intermediate molecules, which mainly consisted of aromatic CHON compounds with 1-3 N atoms, featuring high unsaturation and molecular weights. High-temperature pyrolysis (500-800 °C) promoted the decomposition and ring-opening of aromatic CHON compounds into saturated aliphatic CHO compounds with 2-4 O atoms in SBCs500-800. Noteworthily, SBCs300-400-derived DOMs showed relatively strong biotoxicity on the growth and development of wild-type zebrafish embryos, pakchoi seeds, and Vibrio qinghaiensis Q67, which was significantly related to aromatic amines, phenols, and heterocyclic-N compounds in DOMs of SBCs300-400. SBCs500-800-derived DOMs were mainly straight-chain fatty acids and showed no observable acute biotoxicity. This study highlights the negative impact of DOMs in SBCs on the ecological environment, and provides the theoretical basis for controlling toxic byproducts in sludge pyrolysis process.

Changes in molecular structure of extracellular polymeric substances (EPS) with temperature in relation to sludge macro-physical properties.

Extracellular polymeric substances (EPS) are important components of activated sludge, whose content and composition have important effects on the macro-physical properties of sludge. In this study, the response of EPS in sludge to temperature (-40-200 °C) was systematically investigated using XAD resin fractionation, variable-temperature infrared spectra (VTIS) and two-dimensional correlation spectroscopy (2D-COS). The relationships between the molecular structure of EPS and the macro-physical properties (rheological property and dewatering performance) of waste activated sludge (WAS) at varying temperature were also established. During the freezing treatment, the solubilization of biopolymers and destruction of the hydrophilic functional groups (hydroxy, amino and carboxyl) resulted in the production of small organic matters, which enhanced EPS hydrophobicity and reduced electrostatic repulsion of sludge, and subsequent dewaterability improvement. For the hydrothermal treatment, the EPS transformation showed a two-stages reaction including stage I (70-120 °C) and stage II (>120 °C). Stage I (70-120 °C), a plenty of hydrophilic functional groups (hydroxy, amino and carboxyl) in EPS were exposed via the solubilization of biopolymers, which enhanced electrostatic repulsion of sludge and EPS hydrophilicity, and subsequence in deterioration of sludge dewaterability and fluidity. However, at stage II (>120 °C), the high temperature caused hydrolyzation of macromolecular organic matters in completely, in which the secondary structure of the protein was destroyed, causing the peptide chain to unfold. In addition, the reduction of α-helix and ß-sheet content and intensified Maillard reaction decreased electrostatic repulsion of sludge, thus resulted in the improvement of sludge dewaterability and fluidity. This study enriched the theoretical basis of the optimal control of sludge treatment based on temperature regulation.

Preparation of composite sludge carbon-based materials by LDHs conditioning and carbonization and its application in the simultaneous removal of dissolved organic matter and phosphate in sewage.

In this work, a novel carbon-based hydrotalcite-like compounds materials (LDO-SBCs) were prepared by coupling layered double hydroxides (LDHs) conditioning and pyrolytic carbonization, and characterized by X-ray diffraction (XRD), Thermogravimetric Analyzer (TGA), X-ray photoelectron spectroscopy (XPS) and Brunner-Emmet-Teller (BET) measurements. The synthesized LDO-SBCs composites were used in wastewater treatment for simultaneous removal of phosphate and dissolved organic matter (DOM). The adsorption of DOM and phosphate were well conformed to pseudo-second-order mode. Adsorption equilibrium was better fitted by Langmuir model for phosphate, while Freundlich model for DOM. Compared with the raw sludge carbon, the removal efficiency of DOM and phosphate by LDO-SBCs were increased by 8% and 13%, respectively. Based on the fluorescence spectrum and parallel factor analysis (PARAFAC), LDO-SBCs performed well in promoting the removal of protein substances (TPN and APN). Pore filling, hydrogen bonding, electrostatic adsorption and surface complexation might be dominant in the adsorption of DOM, while, surface complexation and ion exchange between the LDO layers were mainly responsible for the adsorption of phosphate. The difference of adsorption capacity of LDO-SBCs was related to the superior channel structure of composite materials and the composition of interlayer anions of LDO.

Understanding synergistic mechanisms of ferrous iron activated sulfite oxidation and organic polymer flocculation for enhancing wastewater sludge dewaterability.

The bound water in waste activated sludge (WAS) is trapped in extracellular polymeric substances (EPS) in the form of gel-like structure, leading to a great challenge in the sludge deep dewatering. Traditional flocculation conditioning is unable to destroy EPS and ineffective to remove the bound water in WAS. In this study, we employed integration of Fe(II)-sulfite oxidation and polyacrylamide flocculation (F/S-PAM) treatment for removing the bound water and improving sludge dewaterability under aerobic conditions. Meanwhile, the floc microstructure and EPS properties were examined to understand the mechanisms of F/S-PAM conditioning. F/S produced SO3·- radicals which could decompose the EPS in sludge, releasing bound water into free water. In addition, the formed Fe(III) from F/S led to re-coagulation of decomposed EPS, and C=O groups of tryptophan played the leading role in Fe-EPS association binding, causing transformation of the secondary structure of proteins (especially ß-sheets and α-helices). Then, the introduction of PAM caused re-flocculation of disintegrated sludge flocs, enhancing the sludge filterability. This work provides a novel and cost-effective method for efficient removal of bound water in sludge, and subsequence improvement in sludge dewaterability.