Promoting effects of bioplastics and sludge anaerobic co-fermentation for carboxylates production with pH regulation: Insights into the plastic structure, microbial metabolic traits, and adaptive mechanism.

Biodegradable plastics (BPs) are presenting new challenges for their reutilization. This work found that volatile fatty acids (VFAs) production by co-fermentation of BPs with waste activated sludge (WAS) reached 4-37 times of the WAS fermentation alone, which was further amplified by pH regulation (especially alkaline regulation). Moreover, the VFAs composition is highly associated with BPs category. By contrast, the traditional plastic showed a limited effect on the VFAs yield and composition. Alkaline regulation enhanced the breakdown of BPs' ester bonds and boosted WAS disintegration, increasing bioavailable substrates. The hydrolytic-acidogenic anaerobes (i.e., Serpentinicella and Proteiniclasticum) and the major metabolic processes participated in the transformation of BPs and WAS to VFAs were upregulated under alkaline conditions. Further exploration unveiled that quorum sensing and peptidoglycan synthesis played important roles in counteracting alkaline stress and maintaining microbial activity for effective VFAs generation. The works demonstrated the effectiveness of pH-regulated anaerobic co-fermentation for BPs valorization.

Mechanistic insights into Fe3O4-mediated inhibition of H2S gas production in sludge anaerobic digestion.

The addition of iron-based conductive materials has been extensively validated as a highly effective approach to augment methane generation from anaerobic digestion (AD) process. In this work, it was additionally discovered that Fe3O4 notably suppressed the production of hazardous H2S gas during sludge AD. As the addition of Fe3O4 increased from 0 to 20 g/L, the accumulative H2S yields decreased by 89.2 % while the content of element sulfur and acid volatile sulfide (AVS) respectively increased by 55.0 % and 30.4 %. Mechanism analyses showed that the added Fe3O4 facilitated sludge conductive capacity, and boosted the efficiency of extracellular electron transfer, which accelerated the bioprocess of sulfide oxidation. Although Fe3O4 can chemically oxidize sulfide to elemental sulfur, microbial oxidation plays a major role in reducing H2S accumulation. Moreover, the released iron ions reacted with soluble sulfide, which promoted the chemical equilibrium of sulfide species from H2S to metal sulfide. Microbial analysis showed that some SRBs (i.e., Desulfomicrobium and Defluviicoccus) and SOB (i.e., Sulfuritalea) changed into keystone taxa (i.e., connectors and module hubs) in the reactor with Fe3O4 addition, showing that the functions of sulfate reduction and sulfur oxidation may play important roles in Fe3O4-present system. Fe3O4 presence also increased the content of functional genes encoding sulfide quinone reductase and flavocytochrome c sulfidedehydrogenase (e.g., Sqr and Fcc) that could oxidize sulfide to sulfur. The impact of other iron-based conductive material (i.e., zero-valent iron) was also verified, and the results showed that it could also significantly reduce H2S production. These findings provide new insights into the effect of iron-based conductive materials on anaerobic process, especially sulfur conversion.

How Does Triclocarban Affect Sulfur Transformation in Anaerobic Systems?

Triclocarban (TCC), as a typical antimicrobial agent, accumulates at substantial levels in natural environments and engineered systems. This work investigated the impact of TCC on anaerobic sulfur transformation, especially toxic H2S production. Experimental findings revealed that TCC facilitated sulfur flow from the sludge solid phase to liquid phase, promoted sulfate reduction and sulfur-containing amino acid degradation, and largely improved anaerobic H2S production, i.e., 50-600 mg/kg total suspended solids (TSS) TCC increased the cumulative H2S yields by 24.76-478.12%. Although TCC can be partially biodegraded in anaerobic systems, the increase in H2S production can be mainly attributed to the effect of TCC rather than its degradation products. TCC was spontaneously adsorbed by protein-like substances contained in microbe extracellular polymers (EPSs), and the adsorbed TCC increased the direct electron transfer ability of EPSs, possibly due to the increase in the content of electroactive polymer protein in EPSs, the polarization of the amide group C═O bond, and the increase of the α-helical peptide dipole moment, which might be one important reason for promoting sulfur bioconversion processes. Microbial analysis showed that the presence of TCC enriched the organic substrate-degrading bacteria and sulfate-reducing bacteria and increased the abundances of functional genes encoding sulfate transport and dissimilatory sulfate reduction.

Effects of dietary supplementation with medicinal plant mixtures and immunostimulants on the immune response, antioxidant capacity, and hepatopancreatic health of Chinese mitten crab (Eriocheir sinensis).

Introduction: This study aimed to evaluate the efficiency of tea polyphenols (TP) and medicinal plant mixtures (Astragalus membranaceus + Lonicera japonica, Rheum officinale Bail + Scutellaria baicalensis + Platycladus orientalis) combined with astaxanthin (AST), benzoic acid (BA), and yeast complex on the health status of Eriocheir sinensis. Method: A total of 630 crabs (male crabs: 41.51 ± 1.63 g; female crabs: 47.27 ± 0.79 g) were randomly distributed into seven groups with three replicates (male: female, 1:1). These crabs were fed as follows for 8 weeks: basal diet (M1), M2 (M1 + 100 mg/kg TP), M3 (M1 + 2.0 g/kg A. membranaceus + 20 g/kg L. japonica), M4 (M1 + 2.5 g/kg R. officinale Bail + 1.5 g/kg S. baicalensis + 1.0 g/kg P. orientalis), and M5, M6, M7 (M2, M3 and M4 with 600 mg/kg AST +1.0 g/kg BA + 20 mg/kg yeast complex added, respectively). Results and discussion: The results showed that the activities of acid phosphatase (ACP), alkaline phosphatase (AKP), and lysosome (LZM) in the hemolymph were significantly increased in M5, M6, and M7 (P < 0.05), and the highest phagocytosis index (PI) and LZM activity were observed in M7 of female crabs. Moreover, the antioxidant indicators superoxide dismutase (SOD), glutathione (GSH), glutathione peroxidase (GPx), and catalase (CAT) of hepatopancreas were also significantly improved in M5, M6, and M7 (P < 0.05), while the malondialdehyde (MDA) contents showed an opposite trend. Furthermore, a morphological examination also showed the improved histological structure of hepatopancreas in M7, especially as seen in the clear lumens, no vacuolation, and integrity of the basal membrane of the hepatopancreatic tubule. Taken together, these results suggested that 2.5 g/kg R. officinale Bail, 1.5 g/kg S. baicalensis, and 1.0 g/kg P. orientalis in combination with 600 mg/kg AST, 1.0 g/kg BA, and 20 mg/kg yeast complex could improve the non-specific immunity, antioxidant capacity, and hepatopancreatic health of E. sinensis.

The resistance of hydrogenotrophic methanogenic microorganisms to ofloxacin in sludge anaerobic digestion process.

Ofloxacin (OFL) is a commonly used antibiotic that can enter wastewater treatment plants and be adsorbed by the sludge, resulting in a high OFL concentration in sludge and affecting the subsequent sludge anaerobic digestion process. However, the micro mechanisms involved in this process have not been thoroughly studied. Therefore, this study focuses on the effect of OFL on the sludge anaerobic digestion of sludge to provide such support. The experimental results showed that the maximal methane yield decreased from 277.7 to 164.7 mL/g VSS with the OFL concentration increased from 0 to 300 mg/L. Additionally, OFL hindered the intermediate biochemical processes of hydrolysis, acidogenesis, acetogenesis, and acetoclastic methanogenesis. However, it promoted hydrogenotrophic methanogenesis process, using H2 as substrate, with the concentration of 300 mg/L OFL was 5.54 fold methane production of that in the control. Further investigation revealed that the negative effect of OFL was likely due to the induction of reactive oxygen species, which led to a decrease in cell activity and interference with the activity of key enzymes. Microbiological analysis revealed that OFL reduced the relative abundance of hydrolysis and acidogenesis bacteria, and Methanosaeta archaea, while increasing the relative abundance of hydrogenotrophic methanogenesis microorganism from 36.54% to 51.48% as the OFL concentration increase from 0 to 300 mg/L.

Tris (2-chloroethyl) phosphate presence inhibits methane production from anaerobic digestion: Alterations in organic matter transformation, cell physiological status, and microbial community.

Organophosphate flame retardants (OPFRs) are widely used in consumer products, leading to their unavoidable release into the environment, especially accumulation in anaerobic environments and posing potential risks. This study focused on Tris(2-chloroethyl) phosphate (TCEP), a representative OPFR, to investigate its effects on carbon transformation and methane production in anaerobic digestion. Increasing TCEP concentrations from control to 16 mg/L resulted in decreased cumulative methane yield (from 235.4 to 196.3 mL/g COD) and maximum daily methane yield (from 40.8 to 16.17 mL/(g COD·d)), along with an extended optimal anaerobic digestion time (from 15 to 20 days). Mechanistic analysis revealed TCEP binding to tyrosine-like proteins in extracellular polymeric substances, causing cell membrane integrity impairment. The TCEP-caused alteration of the physiological status of cells was demonstrated to be a significant contribution to the inhibited bioprocesses including acidogenesis, acetogenesis, and methanogenesis. Illumina Miseq sequencing showed TCEP decreasing the relative abundance of acidogens (58.8 % to 46.0 %) and acetogens (7.1 % to 5.0 %), partly shifting the methanogenesis pathway from acetoclastic to hydrogenotrophic methanogenesis. These findings enhance understanding of TCEP's impact on anaerobic digestion, emphasizing the environmental risk associated with its continued accumulation.

Exposure of polyethylene microplastics affects sulfur migration and transformation in anaerobic system.

Polyethylene (PE) microplastic, which is detected in various environmental media worldwide, also inevitably enters wastewater treatment plants, which may have an impact on anaerobic processes in wastewater treatment. In this work, the effect of PE microplastics on anaerobic sulfur transformation was explored. Experimental results showed that PE microplastics addition at 0.1%- 0.5% w/w promoted H2S production by 14.8%-27.4%. PE microplastics enhanced the release of soluble organic sulfur and inorganic sulfate, and promoted the bioprocesses of organosulfur compounds hydrolysis and sulfate reduction. Mechanism analysis showed that PE microplastics increased the content of electroactive components (e.g., protein and humic acids) contained in extracellular polymeric substances (EPS). In particular, PE microplastics increased the proportion and the dipole moment of α-helix, an important component involved in electron transfer contained in extracelluar protein, which provided more electron transfer sites and promoted the α-helix mediated electron transfer. These enhanced the direct electron transfer ability of EPSs, which might explain why PE microplastics facilitated the bioprocesses of organosulfur compounds hydrolysis and sulfate reduction. Correspondingly, metagenomic analysis revealed that PE microplastics increased the relative abundance of S2- producers (e.g., Desulfobacula and Desulfonema) and the relative abundance of functional genes involved in anaerobic sulfur transformation (e.g., PepD and cysD), which were beneficial to H2S production in anaerobic system.

Mitigation of Triclocarban Inhibition in Microbial Electrolysis Cell-Assisted Anaerobic Digestion.

Triclocarban (TCC), as a widely used antimicrobial agent, is accumulated in waste activated sludge at a high level and inhibits the subsequent anaerobic digestion of sludge. This study, for the first time, investigated the effectiveness of microbial electrolysis cell-assisted anaerobic digestion (MEC-AD) in mitigating the inhibition of TCC to methane production. Experimental results showed that 20 mg/L TCC inhibited sludge disintegration, hydrolysis, acidogenesis, and methanogenesis processes and finally reduced methane production from traditional sludge anaerobic digestion by 19.1%. Molecular docking revealed the potential inactivation of binding of TCC to key enzymes in these processes. However, MEC-AD with 0.6 and 0.8 V external voltages achieved much higher methane production and controlled the TCC inhibition to less than 5.8%. TCC in the MEC-AD systems was adsorbed by humic substances and degraded to dichlorocarbanilide, leading to a certain detoxification effect. Methanogenic activities were increased in MEC-AD systems, accompanied by complete VFA consumption. Moreover, the applied voltage promoted cell apoptosis and sludge disintegration to release biodegradable organics. Metagenomic analysis revealed that the applied voltage increased the resistance of electrode biofilms to TCC by enriching functional microorganisms (syntrophic VFA-oxidizing and electroactive bacteria and hydrogenotrophic methanogens), acidification and methanogenesis pathways, multidrug efflux pumps, and SOS response.

Efficient degradation of venlafaxine using intimately coupled high-active crystal facets exposed TiO2 and biodegradation system: Kinetic studies, biofilm stress behavior and transformation mechanism.

Intimately coupled photocatalysis and biodegradation (ICPB) system is a potential wastewater treatment technology, of which TiO2-based ICPB system has been widely studied. There are many ways to improve the degradation efficiency of the ICPB process, but no crystal facet engineering method has been reported yet. In this work, a new ICPB system coated with NaF-TiO2 exposing high energy facets was designed to degrade biorecalcitrant psychotropic drug - venlafaxine (VNF). Initially, the TiO2 crystal surface was modified with NaF, resulting in the formation of NaF-TiO2 with a 14.4% increase in the exposure ratio of (001). The contribution rate of ·OH was increased by 9.5%, and the contribution rate of h+ was increased by 33.2%. Next, NaF-TiO2 was loaded onto the surface of the sponge carrier, and then the ICPB system was constructed after about 15 days of biofilm formation. After the ICPB system was acclimated with VNF, the removal rate of COD decreased significantly (the lowest was 62.7%), but that of ammonia nitrogen remained at 50.5 ± 6.0% and the extracellular polymeric substance (EPS) secretion increased by 84.1 mg/g VSS. According to the high throughput results, at the phylum level, Proteobacteria and Chloroflexi together maintain the nitrogen removal capability and structural stability of the ICPB system. The relative abundance of Bacteroidota was significantly increased by 14.2%, suggesting that there may be some correlation between Bacteroidota and certain metabolites of the anti-depressant active ingredients. At the genus level, the Thauera (3.1%∼11.5%) is the major bacterial group that secretes EPS, protecting biofilm against external influences. Most of the changes in microorganisms are consistent with the decontamination properties and macroscopic appearance of EPS in the ICPB system. Finally, the degradation efficiency of ICPB system for VNF was investigated (92.7 ± 3.8%) and it was mostly through hydroxylation and demethylation pathways, with more small molecular products detected, providing the basis for biological assimilation of VNF. Collectively, the NaF-TiO2 based ICPB system would be lucrative for the future degradation of venlafaxine.

The Impact of Bisphenol A on the Anaerobic Sulfur Transformation: Promoting Sulfur Flow and Toxic H2S Production.

Bisphenol A (BPA), as a typical leachable additive from microplastics and one of the most productive bulk chemicals, is widely distributed in sediments, sewers, and wastewater treatment plants, where active sulfur cycling takes place. However, the effect of BPA on sulfur transformation, particularly toxic H2S production, has been previously overlooked. This work found that BPA at environmentally relevant levels (i.e., 50-200 mg/kg total suspended solids, TSS) promoted the release of soluble sulfur compounds and increased H2S gas production by 14.3-31.9%. The tryptophan-like proteins of microbe extracellular polymeric substances (EPSs) can spontaneously adsorb BPA, which is an enthalpy-driven reaction (ΔH = -513.5 kJ mol-1, ΔS = -1.60 kJ mol-1K -1, and ΔG = -19.52 kJ mol-1 at 35 °C). This binding changed the composition and structure of EPSs, which improved the direct electron transfer capacity of EPSs, thereby promoting the bioprocesses of organic sulfur hydrolysis and sulfate reduction. In addition, BPA presence enriched the functional microbes (e.g., Desulfovibrio and Desulfuromonas) responsible for organic sulfur mineralization and inorganic sulfate reduction and increased the abundance of related genes involved in ATP-binding cassette transporters and sulfur metabolism (e.g., Sat and AspB), which promoted anaerobic sulfur transformation. This work deepens our understanding of the interaction between BPA and sulfur transformation occurring in anaerobic environments.

Spatial pattern of China's rural digital economy based on subjective-Objective evaluation: Evidence from 2085 counties.

The rural digital economy plays an essential role in China's industrial upgrading, transformation, and urban-rural integration. To determine the state of China's rural digital economy, we constructed a county-level evaluation system using the subjective-objective evaluation method and calculated the digital economic levels of 2085 counties. Then, we analyzed the spatial distribution characteristics, spatial autocorrelation pattern, spatial disequilibrium degree, and spatial driving force of the rural digital economy at the county level using spatial analysis technology and a self-organizing feature mapping model. The results are as follows: 1) Compared with the real economy, the agglomeration effect of the digital economy was more obvious, and the economic gradient was more significant. Specifically, the dense high-value regions formed a continuous belt on the eastern coast from the Beijing-Tianjin area to the Pearl River Delta, opposite the dense low-value regions in the west. 2) There were significant differences in the rural digital economy within cities or provinces. Intraregional differences were not necessarily linked to the overall digital economy level because central and northeastern China presented a more balanced rural digital economy. 3) Digital network performance, e-commerce level, and economic vitality were identified as the core factors influencing the rural digital economy.

Effects of Mixtures of Engineered Nanoparticles and Cocontaminants on Anaerobic Digestion.

The widespread application of nanotechnology inevitably leads to an increased release of engineered nanoparticles (ENPs) into the environment. Due to their specific physicochemical properties, ENPs may interact with other contaminants and exert combined effects on the microbial community and metabolism of anaerobic digestion (AD), an important process for organic waste reduction, stabilization, and bioenergy recovery. However, the complicated interactions between ENPs and other contaminants as well as their combined effects on AD are often overlooked. This review therefore focuses on the co-occurrence of ENPs and cocontaminants in the AD process. The key interactions between ENPs and cocontaminants and their combined influences on AD are summarized from the available literature, including the critical mechanisms and influencing factors. Some sulfides, coagulants, and chelating agents have a dramatic "detoxification" effect on the inhibition effect of ENPs on AD. However, some antibiotics and surfactants increase the inhibition of ENPs on AD. The reasons for these differences may be related to the interactive effects between ENPs and cocontaminants, changes of key enzyme activities, adenosine triphosphate (ATP) levels, reactive oxygen species (ROS) production, and microbial communities. New scientific opportunities for a better understanding of the coexistence in real world situations are converging on the scale of nanoparticles.

Benzethonium chloride affects short chain fatty acids produced from anaerobic fermentation of waste activated sludge: Performance, biodegradation and mechanisms.

Benzethonium chloride (BZC) is viewed as a promising disinfectant and widely applied in daily life. While studies related to its effect on waste activated sludge (WAS) anaerobic fermentation (AF) were seldom mentioned before. To understand how BZC affects AF of WAS, production of short chain fatty acids (SCFAs), characteristics of WAS as well as microbial community were evaluated during AF. Results manifested a dose-specific relationship of dosages between BZC and SCFAs and the optimum yield arrived at 2441.01 mg COD/L with the addition of 0.030 g/g TSS BZC. Spectral results and protein secondary structure variation indicated that BZC denatured proteins in the solid phase into smaller proteins or amino acids with unstable structures. It was also found that BZC could stimulate the extracellular polymeric substances secretion and reduce the surface tension of WAS, leading to the enhancement of solubilization. Beside, BZC promoted the hydrolysis stage (increased by 7.09 % to 0.030 g/g TSS BZC), but inhibited acetogenesis and methanogenesis stages (decreased by 6.85 % and 14.75 % to 0.030 g/g TSS BZC). The microbial community was also regulated by BZC to facilitate the enrichment of hydrolytic and acidizing microorganisms (i.e. Firmicutes). All these variations caused by BZC were conducive to the accumulation of SCFAs. The findings contributed to investigating the effect of BZC on AF of WAS and provided a new idea for the future study of AF mechanism.

Construction of multiple crosslinked networks for the preparation of high-performance lignin-containing cellulose nanofiber reinforced polyvinyl alcohol films.

Polyvinyl alcohol (PVA) film, a promising alternative to non-biodegradable plastic packaging films for food and medical packaging, is limited by poor water resistance. In this work, a simple solvent evaporation self-assembly was used to construct a nanophase separation structure to establish dense interfacial hydrogen bonding, covalent bonding and iron metal ion coordination interactions between lignin-containing cellulose nanofibers (LCNFs) and PVA matrix to improve the interfacial force and solve the problem of poor compatibility of LCNFs in PVA. The iron ion (Fe3+) coordination tended to combine with the more active lignin phenolic hydroxyl group to construct the nanophase separation structure. Covalent crosslinking of glutaraldehyde (GA) improved the interfacial compatibility of PVA/LCNF films, enhanced the interfacial bonding and formed a homogeneous structure. The multi-nanophase structures improved the strength and elastic modulus of the PVA/LCNF film and provided the films with extremely low water absorption, water vapor transmission rate and excellent UV-shielding. Compared with pure PVA film, PVA-10L-5Fe-3GA film had about 106.9 % higher tensile strength, 93.9 % lower water absorption and 93.4 % lower mass loss, 69.8 % lower water vapor transmission coefficient, and was able to shield UV at 200-400 nm, which is highly expected to be used in packaging films.

Rapid Construction of Vinyl Indomorphans by Rhenium Catalysis.

Here, an efficient route for accessing the vinylindomorphan skeleton is achieved by rhenium(I) catalysis. This transformation involves the condensation of indoles and alkyne-linked cyclohexanones, followed by intramolecular annulation to build the [3.3.1] bicyclic structure. This protocol complements the synthesis of the structurally complex heterocycles bearing a vinyl indole moiety. In addition, the selected products exhibited moderate cytotoxicity toward human A549 cells.

Efficient photo-driven ion pump through slightly reduced vertical graphene oxide membranes.

Solar energy can be harvested using biological light-driven ion pumps for the sustainability of life. It remains a significant challenge to develop high-performance artificial light-driven ion pumps for solar energy harvesting in all solid-state materials. Here, we exploit the benefits of short channel lengths and efficient light absorption to demonstrate efficient photo-driven ion transport in slightly reduced vertical graphene oxide membranes (GOMs). Remarkably, this photo-driven ion pump exhibits excellent ability, countering a 10-fold electrolyte concentration gradient. We propose a plausible mechanism where light illumination enhances the electric potential of ion channels on GOMs triggered by the separation of photoexcited charge carriers between the sp2 and sp3 carbon clusters. This results in the establishment of an electric potential difference across the effective ion channels composed of sp3 carbon clusters, thus driving the directional transport of cations from the illuminated side to the non-illuminated side. The promising results of this study provide new possibilities for the application of vertical 2D nanofluidic membranes in areas such as artificial photosynthesis, light harvesting, and water treatment.

Pretreatment of free nitrous acid combined with calcium hypochlorite for enhancement of hydrogen production in waste activated sludge.

A variety of variables limit the recovery of resources from anaerobic fermentation of waste activated sludge (WAS), hence pretreatment strategies are necessary to be investigated to increase its efficiency. A combination of free nitrous acid (FNA) and calcium hypochlorite [Ca(ClO)2] was employed in this investigation to significantly improve sludge fermentation performance. The yields of cumulative hydrogen for the blank and FNA treatment group were 1.09 ± 0.16 and 7.36 ± 0.21 mL/g VSS, respectively, and 6.59 ± 0.24 [0.03 g Ca(ClO)2/g TSS], 7.75 ± 0.20 (0.06), and 8.58 ± 0.22 (0.09) mL/g VSS for the Ca(ClO)2 groups. The co-treatment greatly boosted hydrogen generation, ranging from 39.97 ± 2.26 to 76.20 ± 4.78 % as compared to the solo treatment. Mechanism analysis demonstrated that the combined treatment disturbed sludge structure and cell membrane permeability even more, which released more organic substrates and enhanced biodegradability of fermentation broth. This paper describes a unique strategy to sludge pretreatment that expands the use of Ca(ClO)2 and FNA in anaerobic fermentation, with implications for sludge disposal and energy recovery.

Enhancing acidogenic fermentation of waste activated sludge via urea hydrogen peroxide pretreatment: Performance and mechanisms.

Improving the anaerobic treatment performance of waste activated sludge (WAS) to achieve resource recovery is an indispensable requirement to reduce carbon emissions, minimize and stabilize biosolids. In this study, a novel strategy by using urea hydrogen peroxide (UHP) to enhance SCFAs production through accelerating WAS disintegration, degrading recalcitrant substances and alleviating competitive suppression of methanogens. The SCFAs production and acetate proportion rose from 436.9 mg COD/L and 31.3% to 3102.6 mg COD/L and 54.1%, respectively, when UHP grew from 0 to 80 mg/g TSS. Mechanism investigation revealed that OH, O2 and urea were the major contributors to accelerate WAS disintegration with the sequence of OH> O2 > urea. Function microbes related to acidification and genes associated with acetate production ([EC:2.3.1.8] and [EC:2.7.2.1]) were upregulated while genes encoding propionic acid production ([EC:6.4.1.3] and [EC:6.2.1.1]) were downregulated. These results raised the application prospects of UHP in WAS resource utilization.

Revealing an unrecognized role of free ammonia in sulfur transformation during sludge anaerobic treatment.

Free ammonia (FA), the unionized form of ammonium, is presented in anaerobic fermentation of waste activated sludge (WAS) at high levels. However, its potential role in sulfur transformation, especially H2S production, during WAS anaerobic fermentation process was unrecognized previously. This work aims to unveil how FA affects anaerobic sulfur transformation in WAS anaerobic fermentation. It was found that FA significantly inhibited H2S production. With an increase of FA from 0.04 to 159 mg/L, H2S production reduced by 69.9%. FA firstly attacked tyrosine-like proteins and aromatic-like proteins in sludge EPSs, with CO groups being responded first, which decreased the percentage of α-helix/(ß-sheet + random coil) and destroyed hydrogen bonding networks. Cell membrane potential and physiological status analysis showed that FA destroyed membrane integrity and increased the ratio of apoptotic and necrotic cells. These destroyed sludge EPSs structure and caused cell lysis, thus strongly inhibited the activities of hydrolytic microorganisms and sulfate reducing bacteria. Microbial analysis showed that FA reduced the abundance of functional microbes (e.g., Desulfobulbus and Desulfovibrio) and genes (e.g., MPST, CysP, and CysN) involved in organic sulfur hydrolysis and inorganic sulfate reduction. These findings unveil an actually existed but previously overlooked contributor to H2S inhibition in WAS anaerobic fermentation.

Simultaneous oxidation of roxarsone and adsorption of released arsenic by FeS-activated sulfite.

The conventional oxidation-adsorption methods are effective for the removal of roxarsone (ROX) but are limited by complicated operation, toxic residual oxidant and leaching of toxic metal ions. Herein, we proposed a new approach to improve ROX removal, i.e., using the FeS/sulfite system. Experimental results showed that approximately 100% of ROX (20 mg/L) was removed and more than 90% of the released inorganic arsenic (As(V) dominated) was adsorbed on FeS within 40 min. This FeS/sulfite system was a non-homogeneous activation process, and SO4·-, ·OH and 1O2 were identified as reactive oxidizing species with their contributions to ROX degradation being 48.36%, 27.97% and 2.64%, respectively. Based on density functional theory calculations and HPLC-MS results, the degradation of ROX was achieved by C-As breaking, electrophilic addition, hydroxylation and denitrification. It was also found that the released inorganic arsenic was adsorbed through a combination of outer-sphere complexation and surface co-precipitation, and the generated arsenopyrite (FeAsS), a precursor to ecologically secure scorodite (FeAsO4·2H2O), was served as the foundation for further inorganic arsenic mineralization. This is the first attempt to use the FeS/sulfite system for organic heavy metal removal, which proposes a prospective technique for the removal of ROX.