Characterizing properties and environmental behaviors of organic matter in sludge using liquid chromatography organic carbon detection and organic nitrogen detection: A mini-review.

The presence of organic matter in sludge plays a significant role in sludge dewatering, anaerobic sludge digestion, resource (i.e., protein) recovery and pollutants removal (i.e., heavy metals) from sludge, as well as post-application of sludge liquid and solid digestate. This study summarized the current knowledge on using liquid chromatography organic carbon detection and organic nitrogen detection (LC-OCD-OND) for characterization and quantification of organic matter in sludge samples related with sludge treatment processes by fractionating organic matter into biopolymers, building blocks, humic substances, low molecular weight (LMW) acids, low LMW neutrals, and inorganic colloids. In addition, the fate, interaction, removal, and degradation of these fractions in different sludge treatment processes were summarized. A standardized extraction procedure for organic components in different extracellular polymeric substances (EPS) layers prior to the LC-OCD-OND analysis is highly recommended for future studies. The analysis of humic substances using the LC-OCD-OND analysis in sludge samples should be carefully conducted. In conclusion, this study not only provides a theoretical foundation and technical guidance for future experiments and practices in characterizing sludge organic matter using LC-OCD-OND, but also serves as a valuable resource for consulting engineers and other professionals involved in sludge treatment.

Fate of antibiotics and hormones during hydrothermal carbonization of poultry litter: degradation kinetics and toxicity assessment of filtrates and hydrochars.

This study investigated degradation kinetics of five selected organic micropollutants (OMPs) present in poultry litter (namely: sulfadiazine, tetracycline, and doxycycline hyclate (antibiotics); estrone and 17-ß-estradiol (hormones)) during hydrothermal carbonization (HTC) treatment as the temperature stepwise increased to 250 °C. All five pure OMPs were completely degraded before 250 °C was reached during the HTC process. Nevertheless, presence of poultry litter slowed down the degradation of OMPs. Through elemental mass balance calculation, it is noted that after 15 min (temperature less than 137 °C), 69-82% of organic carbon and 50-66% of organic nitrogen initially consisting part of the target antibiotics were fully mineralized. Both HTC filtrates and hydrochars obtained from poultry litter inhibited Escherichia coli and Bacillus subtilis growth. A combination of high salinity, high nutrients, dissolved organic carbon, and other ions in the filtrate as well as the adsorption of OMPs on hydrochars were probably the reason for the high toxicity.

Pretreatment of sludge with sodium iron chlorophyllin-H2O2 for enhanced biogas production during anaerobic digestion.

This study investigated a novel sodium iron chlorophyllin-H2O2 (SIC-H2O2) sludge pretreatment strategy before anaerobic digestion to enhance methane production. The efficiencies and mechanism of the proposed strategy to enhance sludge biodegradability were explored. The SIC-H2O2 pretreatment could enhance the oxidation performance for sludge floc disintegration to dissociate TB-EPS into S-EPS increased SCOD to 521.38 mg/L. The increase of solubilization and release of EPS with the pretreatment facilitate the biogas production at 702 L kg-1 VS, which was 3-folds of the control and significantly higher than other pretreatments. The result of excitation-emission matrix and parallel factor (EEM-PARAFAC) analysis showed that the SIC-H2O2 pretreatment enhanced the dissociation of TB-EPS fractions, especially the protein-like and soluble microbial by-product-like substances. Electron paramagnetic resonance (EPR) results provided evidence for homolytic catalysis H2O2 for the generation OH and the production of high-valent (Por)FeIV(O) intermediates. Synergistic effects of reactive oxygen species (OH, H2O2 and /HO2) and (Por)FeIV(O) enhanced the EPS disintegration during SIC-H2O2 pretreatment. The mixed-acid type fermentation provided continuous VFAs supply under the enrichment of Chloroflexi and Actinobacteria and multiplication Methanosaeta also promoted methane production. This research provides a feasible pretreatment strategy increase sludge biodegradability and enhance biogas production in the anaerobic digestion process.

Deciphering the role of microplastic size on anaerobic sludge digestion: Changes of dissolved organic matter, leaching compounds and microbial community.

Here the role of microplastic size on dissolved organic matter, leaching compounds and microbial community during anaerobic sludge digestion was evaluated. Compared to that without the addition of polyvinyl chloride (PVC), during the 30 days' incubation, the anaerobic sludge digestion by adding PVC at the size of 75 µm and the concentration of 2.4 g/g volatile solids (VS) showed a 8.5% lower cumulative methane production, while a 17.9% higher cumulative methane production was noted by adding PVC at the size of 3000 µm and the concentration of 2.4 g/g VS. A long-term fed-batch laboratory-scale fermenter test for 147 days further testified, that higher removal efficiencies of total solids, volatile solids, and total chemical oxygen demand, and higher methane production were noted by adding PVC (2.4 g/g VS, 3000 µm) into the fermenter. More interestingly, higher concentrations of proteins, polysaccharides, volatile fatty acids, and soluble microbial by-products component were noted in the liquid phase of sludge drawn from the fermenter added with PVC since the biomass therein showed higher efficiencies of solubilization, hydrolysis, acidification, and methanogenesis. Moreover, as identified from the fermenter added with PVC, dibutyl phthalate (DBP) was the most predominant leaching phthalates compound, although the biomass therein showed a 93.4% anaerobic biodegradability of DBP. The leaching of DBP drove the predominance of microbial community towards Synergistota and Methanosaeta. More irregular elliptical shallow dimples were noted on the PVC surface after 147 days' incubation, accompanied with abundances of Proteobacteria, Actinobacteriota, Chloroflexi, Methanosaeta and Methanobacterium. The results from this study showed that the size of microplastic was a crucial factor in evaluating its impact on anaerobic sludge digestion.

Recirculation of reject water in deep-dewatering process to influent of wastewater treatment plant and dewaterability of sludge conditioned with Fe2+/H2O2, Fe2+/Ca(ClO)2, and Fe2+/Na2S2O8: From bench to pilot-scale study.

Deep dewatering of sewage sludge pretreated with advanced oxidation processes (AOPs) is a strategy for efficient sludge reduction and subsequent disposal. The pretreatment and dewatering performance of sludge conditioned with three types of AOPs (Fe2+/H2O2, Fe2+/Ca(ClO)2, and Fe2+/Na2S2O8), compared with sludge conditioned with traditional conditioner (Fe3+/CaO), were investigated in both bench and pilot-scale tests. All of those conditioner systems could reduce the water content of dewatered sludge cake to below 60 wt% in bench-scale (about 16 kg raw sludge per round) and pilot-scale (approximate 800 kg raw sludge per round) diaphragm filter press dewatering. Compared with raw sludge, the deep-dewatering filtrate after different conditioning and dewatering processes had higher ammonia nitrogen (NH4+-N) and chemical oxygen demand (COD) contents due to the degradation of organic matter, and much lower total phosphorus (TP) content due to the formation of iron phosphate precipitate. A better biodegradability (i.e. higher BOD5/COD ratio) was found in the deep-dewatering filtrate of sludge conditioned with Fe2+/H2O2 (25.2 %) and Fe2+/Ca(ClO)2 (17.4 %). Most of the heavy metals (Cr, Cu, Ni, and Pb) (>79 wt%) have remained in the dewatered sludge cake, and most of the Cl element (>90 wt%) in the sludge pretreated by Fe2+/Ca(ClO)2 and Fe3+/CaO was kept in the filtrate, rather than the dewatered sludge cake. Based on the pilot-scale experimental results, if all the filtrate in the deep-dewatering process returned to the influent of WWTP, the loading ratios of TP, NH4+-N, COD in the four conditioner systems were less than 3 wt%. The above results proved that the AOPs conditioned sludge could achieve deep-dewatering in pilot-scale and the direct recirculation of deep-dewatering filtrate to the influent of wastewater treatment plant was feasible.

Enhancing waste activated sludge dewaterability by reducing interaction energy of sludge flocs.

How to efficiently improve waste activated sludge (WAS) dewaterability is a common challenge in WAS treatment and management throughout world. The interaction energy of sludge flocs is of great importance for sludge dewaterability. In this study, the relationship among the repulsive force of sludge flocs, hydrophilic/hydrophobic characteristics of sludge flocs, and sludge dewaterability have been quantitatively and qualitatively investigated based on extended Derjaguin-Landau-Verwey-Overbeek theory for the first time. The energy barrier of sludge flocs has good correlations with sludge dewaterability (p < 0.05). Trivalent cations (Al3+ and Fe3+) and Fenton's reagent reduced the interfacial free energy (ΔG) from 9.4 mJ/m2 of raw sludge to -34.2 (Al3+), -60.5 (Fe3+), and -63.2 (Fenton) mJ/m2, respectively, indicating that the hydrophilic surfaces of the sludge flocs converted to hydrophobic (△G < 0), and decreasing Lewis acid-base interaction energy (WAB) of sludge flocs. In addition, most of the trivalent cations (Al3+ and Fe3+) were attached to sludge flocs, leading to neutralize negative charges and mitigate electrostatic interaction energy (WR) of sludge flocs. The reduction of WAB and WR eliminated energy barrier of sludge flocs and repulsive force between sludge flocs. In comparison, monovalent (Na+ and K+) and bivalent (Ca2+ and Mn2+) cations cannot completely change the hydrophilic surface characteristic and negative charge of sludge flocs. The existed energy barrier prevented sludge flocs to agglomerate with each other, thus resulting in a worse dewaterability. This study illustrated that reducing interaction energy of sludge flocs played a critical role to improve sludge dewaterability.

Enhanced quorum sensing of anode biofilm for better sensing linearity and recovery capability of microbial fuel cell toxicity sensor.

MFC toxicity sensor has major hindrances that limit its practical application, such as the poor concentration-response relationship and inferior recovery capability after high toxicity shock. Till now, the direct influence of intrinsic properties on the performance of MFC toxicity sensor has not been well understood. Quorum sensing (QS) is a cell-to-cell communication strategy that indirectly affects the intrinsic properties of electroactive biofilms. In this work, commercially available QS autoinducers (AHLs) were applied to MFC toxicity sensor to manipulate anode biofilm for better sensing performance. The results showed that the addition of AHLs (C6-HSL, 3-OXO-C12-HSL) led to higher sensing linearity to a wider range of Pb2+. The voltage of MFC sensors with AHLs addition fully recovered even after 10 mg/L Cu2+ shock, indicating an enhanced recovery capability of MFC toxicity sensor. It was found that higher live/dead cells ratio and increased exoelectrogen Geobacter abundance were responsible for the superior sensing linearity and recovery capability of MFC toxicity sensor. Our work presented a novel and effective way to advance the process of MFC toxicity sensor application from the perspective of EABs.

Improvement of sludge dewaterability by ammonium sulfate and the potential reuse of sludge as nitrogen fertilizer.

A novel method to enhance sludge dewaterability with ammonium sulfate ((NH4)2SO4) was proposed, and the potential reuse of dewatered sludge cake and filtrate as nitrogen fertilizers was evaluated. Compared with raw sludge, 87.91% reduction of capillary suction time (CST) and 88.02% reduction of specific resistance to filtration (SRF) after adding 80% (m/m) (NH4)2SO4 were achieved, with 38.49% of protein precipitated simultaneously. The (NH4)2SO4 dose destroyed cell membrane, resulting in the release of intracellular water by converting bound water into free water, thus enhancing sludge dewaterability. In the solid phase, the content of protein-N increased, and larger protein aggregates were formed. The (NH4)2SO4 dose destroyed the hydration shell, making proteins to exhibit hydrophobic interactions, and to be aggregated, and precipitated from the liquid phase. When incubated Pennisetum alopecuroides L. with the dewatered sludge cake and filtrate after dewatering and conditioning with (NH4)2SO4, the germination rate of grass seed and shoot lengths both increased while compared with those incubated with dewatered sludge cake and filtrate of the raw sludge. This study might provide insights into sustainable sludge treatment by integrating sludge dewatering and the potential reuse of dewatered sludge cake and filtrate as nitrogen fertilizer via treatment with (NH4)2SO4.

Facile and Cost-Effective Approach for Copper Recovery from Waste Printed Circuit Boards via a Sequential Mechanochemical/Leaching/Recrystallization Process.

The recovery of copper (Cu0) from waste printed circuit boards (WPCBs) is a great challenge as a result of its heterogeneous structural properties, with a mixture of metals, epoxy resin, and fiberglass. In this study, a three-step sequential process, including mechanochemical processing, water leaching, and recrystallization, for Cu0 recovery from WPCB powder is reported. Potassium persulfate (K2S2O8), instead of acid/alkali reagents, was employed as the sole reagent in the cupric sulfate (CuSO4) regeneration process. Complete oxidation of Cu0 in the WPCBs to copper oxide (CuO) and CuSO4 was first achieved during mechanochemical processing with K2S2O8 as the solid oxidant, and the K2S2O8 was simultaneously converted to sulfate compounds [K3H(SO4)2] via a solid-solid reaction with epoxy resin (C nH mO y) as the hydrogen donator under mechanical force. The rapid leaching of Cu species in the forms of CuO and CuSO4 was therefore easily realized with pure water as a nontoxic leaching reagent. The kinetics of the leaching process of Cu species was confirmed to follow the shrinking nucleus model controlled by solid-film diffusion. Finally, CuSO4·5H2O was successfully separated by cooling crystallization of the hot saturated solution of sulfate salt [K2Cu(SO4)2·6H2O]. An efficient conversion of Cu0 to CuSO4·5H2O product, for WPCB recycling, was therefore established.

A micromilled microgrid sensor with delaminated MXene-bismuth nanocomposite assembly for simultaneous electrochemical detection of lead(II), cadmium(II) and zinc(II).

A delaminated MXene-bismuth (Bi@d-Ti3C2) nanocomposite was synthesized for the construction of a microgrid electrochemical sensor via mechanical milling. The Bi@d-Ti3C2 nanocomposite was synthesized by accumulation of Bi(III) on the surface of delaminated Ti3C2 nanosheets through electrostatic attraction and subsequent in-situ growth of bismuth nanorods. Under optimized experimental conditions, the sensor exhibits (a) linear responses to Pb(II), Cd(II) and Zn(II) in the concentration range from 1 to 20 µg L-1, (b) well separated peak potentials at -0.54 V, -0.76 V and - 1.15 V vs. Ag/AgCl, (c) sensitivities of 0.98, 0.84 and 0.60 µA L µg-1, and (d) detection limits of 0.2, 0.4 and 0.5 µg L-1, respectively. This performance is attributed to the uniform dispersion of Bi nanorods on electrically conductive delaminated Ti3C2 MXene, and to the enhanced diffusion due to the microgrid structure. Graphical abstractSchematic representation of a microgrid sensor based on delaminated MXene-bismuth (Bi@d-Ti3C2) nanocomposite for the simultaneous electrochemical determination of Pb(II), Cd(II) and Zn(II).

An Emission-Free Vacuum Chlorinating Process for Simultaneous Sulfur Fixation and Lead Recovery from Spent Lead-Acid Batteries.

Spent lead-acid battery recycling by using conventional technologies is usually accompanied by releases of lead-containing wastewater as well as emissions of sulfur oxides and lead particulates that may potentially cause secondary pollution. This study developed a vacuum chlorinating process for simultaneous sulfur fixation and high-purity lead chloride (PbCl2) recovery from spent lead paste by using calcium chloride (CaCl2) and silicon dioxide (SiO2) as reagents. The process train includes pretreatment, simultaneous PbCl2 production and sulfur fixation, and PbCl2 volatilization. The pretreatment eliminated chlorine emission from direct chlorinating reaction of PbO2 in the initial S-paste (PbSO4/PbO2/PbO/Pb). During the subsequent PbCl2 production and sulfur fixation step, lead compounds in the P-paste (PbSO4/PbO) was converted to volatile PbCl2, and sulfur was simultaneously fixed to the solid residues in the form of CaSO4 to eliminate the emission of sulfur oxides. The final step, PbCl2 volatilization under vacuum, is a physical phase-transformation process of ionic crystals, following a zeroth-order kinetic model. A cost estimate indicates a profit of USD $ 8.50/kg PbCl2. This process offers a novel green lead recovery alternative for spent lead-acid batteries with environmental and economic benefits.

Simulation on flow field and gas hold-up of a pilot-scale oxidation ditch by using liquid-gas CFD model.

A liquid-gas two-phase computational fluid dynamics (CFD) model was developed to simulate flow field and gas hold-up in a pilot-scale oxidation ditch (OD). The volume of fluid (VOF) model and the mass flow inlet boundary condition for gas injection were introduced in this model. The simulated values of the flow velocities and the gas hold-up were verified by experimental measurements in the pilot-scale OD. The results showed that the gas hold-up at test-site 3, immediately downstream of the surface aerator, was the highest among all three test-sites. Most of the gas existed in the upper portion of the ditch and was close to the inner side of the channel. Based on the liquid-gas two-phase CFD model, three operating conditions with different setting height ratios of the submerged impellers were simulated. The simulated results suggested that the setting heights of the submerged impellers have significant impacts on the flow velocity distribution. Lowering the setting height could increase the flow velocity in the pilot-scale OD. An optimal setting height ratio of 0.273 was proposed, which would be beneficial for minimizing sludge sedimentation, especially near the inner side of the curve bend.

Role of Micronutrients on Dyeing Wastewater Treatment in Activated Sludge Process.

Adequate individual supplements of Zn, Co and Mo increased chemical oxygen demand (COD) removal and specific oxygen uptake rates during activated sludge treatment of dyeing wastewater, while overdoses of micronutrients can decrease metabolic rates. The effects of combing Zn, Co, and Mo at different doses were investigated using response surface methodology, with a second order polynomial equation: Y = 78.19+ 0.17X1 + 37.33 X2 + 20.20X3 - 5.58X1X2 - 63.05 X2X3, where Y means COD removal rate (%), X1 means Co concentration, X2 means Zn concentration, X3 means Mo concentration. The maximum COD removal efficiency of 89.41% was achieved with doses of 0.02 mg/L Co, 0.24 mg/L Zn and 0.45 mg/L Mo. Both the combinations of Zn-Co and Zn-Mo acted antagonistically for COD removal efficiency, and the combination of Co-Mo was negligible to COD removal efficiency. Doses of micronutrients, particularly Zn, Co and Mo, were beneficial for microbial shift towards Planctomyces and Bacteroidetes.

Impact of undissociated volatile fatty acids on acidogenesis in a two-phase anaerobic system.

This study investigated the degradation and production of volatile fatty acids (VFAs) in the acidogenic phase reactor of a two-phase anaerobic system. 20 mmol/L bromoethanesulfonic acid (BESA) was used to inhibit acidogenic methanogens (which were present in the acidogenic phase reactor) from degrading VFAs. The impact of undissociated volatile fatty acids (unVFAs) on "net" VFAs production in the acidogenic phase reactor was then evaluated, with the exclusion of concurrent VFAs degradation. "Net" VFAs production from glucose degradation was partially inhibited at high unVFAs concentrations, with 59%, 37% and 60% reduction in production rates at 2190 mg chemical oxygen demand (COD)/L undissociated acetic acid (unHAc), 2130 mg COD/L undissociated propionic acid (unHPr) and 2280 mg COD/L undissociated n-butyric acid (unHBu), respectively. The profile of VFAs produced further indicated that while an unVFA can primarily affect its own formation, there were also unVFAs that affected the formation of other VFAs.

Determination of the archaeal and bacterial communities in two-phase and single-stage anaerobic systems by 454 pyrosequencing.

2-Phase anaerobic digestion (AD), where the acidogenic phase was operated at 2day hydraulic retention time (HRT) and the methanogenic phase at 10days HRT, had been evaluated to determine if it could provide higher organic reduction and methane production than the conventional single-stage AD (also operated at 12days HRT). 454 pyrosequencing was performed to determine and compare the microbial communities. The acidogenic reactor of the 2-phase system yielded a unique bacterial community of the lowest richness and diversity, while bacterial profiles of the methanogenic reactor closely followed the single-stage reactor. All reactors were predominated by hydrogenotrophic methanogens, mainly Methanolinea. Unusually, the acidogenic reactor contributed up to 24% of total methane production in the 2-phase system. This could be explained by the presence of Methanosarcina and Methanobrevibacter, and their activities could also help regulate reactor alkalinity during high loading conditions through carbon dioxide production. The enrichment of hydrolytic and acidogenic Porphyromonadaceae, Prevotellaceae, Ruminococcaceae and unclassified Bacteroidetes in the acidogenic reactor would have contributed to the improved sludge volatile solids degradation, and ultimately the overall 2-phase system's performance. Syntrophic acetogenic microorganisms were absent in the acidogenic reactor but present in the downstream methanogenic reactor, indicating the retention of various metabolic pathways also found in a single-stage system. The determination of key microorganisms further expands our understanding of the complex biological functions in AD process.

Effect of ciprofloxacin on the one-stage partial nitrification and anammox biofilm system: A multivariate analysis focusing on size-fractionated organic components.

The impact of ciprofloxacin (CIP) in the partial nitrification and anammox biofilm system was investigated by multivariate analysis, focusing on size-fractionated organic components. The CIP dose of 10 µg/L did not inhibit the total nitrogen (TN) removal efficiency, even though the abundance of antibiotic resistant genes (ARGs) (i.e., qnrD, qnrB, qnrA, qnrS, and arcA) was elevated. However, a gradual higher CIP dosing up to 100 µg/L inhibited the TN removal efficiency, while the abundance of ARGs was still increased. Moreover, both the TN removal efficiency and the abundant ARGs were dwindled at 470 µg/L of CIP. As the CIP dose increased from 0 to 100 µg/L, the abundance of high molecular weight (MW) fractions (14,000 to 87,000 Da; 1000 to 14,000 Da) and humic/fulvic acid-like components in the soluble extracellular polymeric substances (HSS) decreased, with more increases of low MW (84-1000 Da; less than 84 Da) fractions and soluble microbial by-products in soluble extracellular polymeric substances (SMPS). Continuously increasing the CIP dose till 470 µg/L, an inverse trend of the changes of these organic components was noted, along with clear reductions of the microbial diversity and richness, and the abundance of key functional genes responsible for nitrogen removal. The predominance of functional gene amoA (related with ammonia oxidizing bacteria) was more significantly with more distribution of SMPS with relatively low MW and less distribution of HSS with relatively high MW, as well as polymer decomposing microorganisms such as Bryobacteraceae and the unclassified Saprospirales.

Visualization of water transfer channel in sludge dewatering conditioned with skeleton builders by X-ray micro-computed tomography.

Skeleton builders were normally deemed to improve the high porosity and newly-generated permeability of sludge cakes by building water transfer channel during high pressure filtration, thus enhancing sludge dewaterability. However, currently a direct visualization proof of water transfer channel was still lacking. This study provided the direct proof for visualizing water transfer channel in dewatered sludge cakes conditioned with a typical skeleton builder (i.e., phosphogypsum (PG)) by X-ray micro-computed tomography (micro-CT) for the first time. After the addition of PG, the pixel value and image luminance increased significantly, indicating the presence of high density substances from both two-dimensional (2D) cross section and three-dimensional (3D) reconstruction CT images. Moreover, the CT numbers showed strong and negative correlations with specific resistance to filtration (SRF) (R = - 0.99, p < 0.05), capillary suction time (CST) (regression coefficient (R) = - 0.87, probability (p) < 0.05), and water content of the dewatered sludge cake (R = - 0.99, p < 0.05), respectively. These results indicated that the X-ray micro-CT could be a potential technique for analyzing the water distribution in sludge samples conditioned with skeleton builders.

Effect of thermochemical treatment of sewage sludge on its phosphorus leaching efficiency: Insights into leaching behavior and mechanism.

Thermochemical conversion, including hydrothermal processing, pyrolysis and incineration, has become a promising technology for sewage sludge (SS) treatment and disposal. Furthermore, acid leaching is considered as an effective method to recover phosphorus (P) from SS and its thermochemical treatment products. This study has investigated the potential of P reclamation from SS and its thermochemical derivatives, including hydrochar (HC), biochar (BC), and SS incinerated ash (SA). Comparative analyses of physicochemical properties of these derivatives revealed a decrease in hydroxyl and aromatic groups and an increase in aliphatic and oxygen-containing functional groups in HC and BC. Leaching experiments using 1 M sulfuric acid (H2SO4) and 1 M oxalic acid (C2H2O4) suggested that H2SO4 slightly outperformed C2H2O4 in terms of P leaching efficiency. HC achieved 79.1 % optimal leaching efficiency in 60 min using H2SO4, while BC, SS, and SA required 360 min to achieve comparable efficiency. SS and BC reached optimal leaching efficiency at 74.1 % and 76.2 % in H2SO4, while SA achieved 80.9 % in C2H2O4. Importantly, HC and SA are more favorable for P extraction using acid leaching, whereas BC tends to be a potential P carrier. Time-dependent kinetics revealed a two-stage leaching process, i.e., fast and slow reaction stages. Shrinking core model indicates product layer diffusion as the primary rate-limiting step in both stages. Overall, these fundamental insights play an important role in practical P recovery through acid leaching of SS derived residues after thermochemical treatment.

Low-toxicity natural pyrite on electro-Fenton catalytic reaction in a wide pH range.

The resource utilization of natural pyrite not only reduces secondary pollution but also brings certain environmental benefits. However, the green and efficient use of pyrite presents certain challenges. In this study, a novel electro-Fenton (EF) system was constructed utilizing copper modified graphite felt (GF/Cu) as cathode and natural pyrite (com-FeS2) as catalyst. The results demonstrated that the system exhibited a remarkable stability over an extensive pH range (3.0-10.0) and remained effective even under adverse environmental conditions, such as high salinity or elevated antibiotic concentration. After optimizing the reaction conditions, 0.2 mM sulfamerazine (SMZ) was almost completely degraded within 1.5 h. The results highlighted the catalytic role of Fe(II) on the com-FeS2 surface. Combined with quenching experiments and quantitative analysis of reactive oxygen species (ROS), the removal of SMZ was primarily attributed to the generation of •OH, ordered by 1O2 > â€¢O2- > â€¢OHads, a possible degradation pathway was proposed by HR-LC-MS. The biological toxicity after the reaction was detected, and the introduction of polyvinylpyrrolidone (PVP) was beneficial to reduce the biological toxicity of iron dissolution. This work provides new insights into the green and efficient resource utilization of natural pyrite and significantly expands the pH applicability range of the Fenton process, demonstrating the large-scale industrial application potential of pyrite.

Behavior of organic components and the migration of heavy metals during sludge dewatering by different advanced oxidation processes via optical spectroscopy and molecular fingerprint analysis.

A comparative study of the different advanced oxidation processes (Fe(II)-Oxone, Fe(II)-H2O2, and Fe(II)-NaClO) was carried out herein to analyze the characteristics of organic components and the migration of heavy metals in waste activated sludge. With the Fe(II)-Oxone and Fe(II)-H2O2 treatments, sludge dewaterability was significantly improved, however, sludge dewaterability was deteriorated by the Fe(II)-NaClO treatment. The enhanced sludge dewaterability by the Fe(II)-Oxone and Fe(II)-H2O2 treatments was strongly correlated with the shifted organic components, particularly proteins, in soluble extracellular polymeric substances (S-EPS), while the deteriorated sludge dewaterability by the Fe(II)-NaClO treatment was strongly correlated with the over release of organic components from bound EPS (B-EPS) to S-EPS. For both the Fe(II)-Oxone and Fe(II)-H2O2 treatments, the radicals preferentially attacked humic acid-like organic components over the protein-like organic components in S-EPS, while for the Fe(II)-NaClO treatment, interestingly, the radicals preferentially attacked the protein-like organic components in both S-EPS and B-EPS. The hydrophilic functional groups like phenolic OH and CO of polysaccharides may be more preferentially migrated to S-EPS of sludge by the Fe(II)-NaClO treatment compared to the other two treatments. With the Fe(II)-Oxone and Fe(II)-H2O2 treatments, the proportion of aliphatic compounds as well as the much oxygenated organic components with a low desaturation and a low molecular weight increased. While with the Fe(II)-NaClO treatment, the proportion of low oxygenated organic components with a high desaturation and a high molecular weight increased. The concentration of total organic carbon, particularly the concentration of proteins, may be the key factor determining the shift of Zn and Cu from sludge solid to liquid phase, along with the high oxidation extent of organic components and close binding to CHOS and CHON compounds as indicated by density functional theory (DFT) calculation. This study systematically revealed the simultaneous sludge dewatering and migration of heavy metals when the role of organic components was factored into herein.