Innovative Long-Lasting Catalytic Hydrothermal Reaction for High Efficient Energy Harvest and Carbon Capture from Recalcitrant Wastewater.

Simultaneous recovery of energy and carbon from recalcitrant wastewater has attracted ever-growing interest for water management. However, the existing technologies to break down recalcitrant pollutants are mainly energy and chemical intensive. Here, a novel hydrothermal reaction amended with activated carbon (AC) was demonstrated to enable an unprecedented 99.5% removal of an exemplar difficult-to-degrade contaminant, polyvinyl alcohol (PVA), from wastewater. Meanwhile, an easy-separated hydrochar (C6H7.08O0.99) with an abundance of unsaturated aromatic rings was produced, exhibiting 118.46% of energy yield with a high heating value of 32.9 MJ/kg, outperforming the hydrochar(s) reported to date. The retrieved energy from the hydrochar was able to entirely offset the energy needs for this hydrothermal process. Interestingly, the AC catalyst can sustain in situ reuse over 125 cycles with no evidence of irreversible deactivation. The adjacent carbonyl groups on AC were revealed to provide active sites for dehydrogenation from either the C-H (1.24 Å) or O-H (1.40 Å) bond in PVA, forming hydroxyl groups on AC and highly reactive intermediates (ΔG0 = -11.5 kcal/mol). It was further proved that the free oxygen in the headspace extracted H atoms from the newly formed hydroxyl groups on AC (ΔG0 = -4.7 kcal/mol), thus regenerating the carbonyl sites on AC for the next catalytic hydrothermal dehydrogenation cycles. The long-lasting catalyst reusability and energy self-sufficient approach offer a sustainable route to carbon neutrality in recalcitrant wastewater treatment.

Treatment of industrial ferric sludge through a facile acid-assisted hydrothermal reaction: Focusing on dry mass reduction and hydrochar recyclability performance.

Large amounts of Fenton sludge and waste activated sludge (WAS) are mixed as ferric sludge (FS) in most industrial wastewater treatment plants. The treatment of such waste represents a challenge and quantity-dependent cost, so that a reliable way for FS waste reduction is required. In this study, we develop a facile acid-assisted hydrothermal treatment (HT) for the cost-efficient treatment of hazardous FS waste. Sulfuric acid was dosed at 0.25 mL/g dry solid (DS) to the HT process, which significantly increased the total solid mass reduction (TMR) by 25.1 % and dry mass reduction (DMR) by 104.4 %. The participation of sulfuric acid during the HT process changed the HT reaction pathway from dehydration to demethylation based on the analysis of the derivative thermogravimetric and Van Krevelen diagram. The addition of sulfuric acid improved the release of Fe from FS by 52.9 %, which contributed to the DMR. During the acid-assisted HT, Fe(III) was effectively reduced to Fe(II) within the produced hydrochar, which can be recycled for the Fenton reaction during the degradation of actual industrial wastewater such as pharmaceutical wastewater. Moreover, Sulfuric acid facilitated the generation of sulfonated hydrochar, which was efficient as an adsorbent for the complete removal of some metals such as Cu(II) - cation metal (98.8 %) and Cr(VI) - anion metal (99.9 %). This study firstly provides a novel and reliable approach for hazardous FS reduction and pointed out the recycling of hydrochar as the supplement for the Fenton reaction and adsorbents for some hazardous heavy metals.

Transformation of polyvinyl chloride (PVC) into a versatile and efficient adsorbent of Cu(II) cations and Cr(VI) anions through hydrothermal treatment and sulfonation.

The reuse of waste polyvinyl chloride (PVC) has drawn much attention as it can reduce plastic waste and associated pollution, and provide valuable raw materials and products. In this study, sulfonated PVC-derived hydrochar (HS-PVC) was synthesized by two-stage hydrothermal treatment (HT) and sulfonation, and shown to be a versatile adsorbent. The removal of Cu(II) cations and Cr(VI) anions using HS-PVC reached 81.2 ± 1.6% and 60.3 ± 3.8%, respectively. The first stage of HT was crucial for the dichlorination of PVC and the formation of an aromatic structure. This stage guaranteed the introduction of -SO3H onto PVC-derived hydrochar through subsequent sulfonation. HT intensities (i.e., temperature and time) and sulfonation intensity strongly determined the adsorption capacity of HS-PVC. Competitive adsorption between Cu(II) and Cr(VI) onto HS-PVC was demonstrated by binary and preloading adsorption. The proposed Cu(II) cations adsorption mechanism was electrostatic adsorption, while Cr(VI) were possibly complexed by the phenolic -OH and reduced to Cr(III) cations by CC groups in HS-PVC. In addition, HS-PVC derived from PVC waste pipes performed better than PVC powder for Cu(II) and Cr(VI) removal (＞90%). This study provides an efficient method for recycling waste PVC and production of efficient adsorbents.

Recycling sludge-derived hydrochar to facilitate advanced denitrification of secondary effluent: Role of extracellular electron transfer.

Sludge-derived hydrochar (SDHC) was recycled to enhance the denitrification of secondary effluent. Under different carbon to nitrogen (C/N) ratios, the nitrogen removal efficiency (NRE) and carbon source efficiency (CSE) of denitrification coupled with SDHC (DN-SDHC) were distinctly higher than that of denitrification alone (DN). Moreover, at the C/N ratios of 3.0-3.2 and 5.8-5.9, the nitrogen removal rate (NRR) of DN-SDHC was 3.6- and 1.5-fold that of DN, respectively. The characterization of SDHC before and after used in denitrification indicated that the metal ions and functional groups did not participate in denitrification. Although SDHC has no redox capacity to donate electron for denitrification, its higher conductivity enabled the acceleration of extracellular electron transfer from carbon source to denitrifiers. The abundance of denitrifying community and functional genes was synchronously promoted by SDHC. Especially, the significant increase of nosZ gene encoding nitrous oxide reductase was conducive to mitigating the emission of N2O greenhouse gas.

Removal of harmful algae by Shigella sp. H3 and Alcaligenes sp. H5: algicidal pathways and characteristics.

Application of algicidal bacteria is a promising technology to control harmful algal blooms (HABs). In this study, algicidal bacteria strains Shigella sp. H3 and Alcaligenes sp. H5 were obtained via two different isolation methods from the same lake water sample, with optimal algicidal efficiencies 96% and 74% against algae mixture. The Shigella sp. H3 and Alcaligenes sp. H5 lysed algae cells through cells-to-cells direct contact and secretion of algicidal metabolites, respectively. The stronger algicidal capability of Shigella sp. H3 was also attributable to its higher efficiency for triggering reactive oxygen species, which led to broken down of the antioxidant system and more severe damage to the bacterial cells. The antioxidant enzyme activities in Alcaligenes sp. H5 group were still expressed because of its relatively weaker algicidal capability and some intact algal cells were remained. The liquid carbohydrates from algal lysis in both groups increased significantly, whereas the quantities of liquid protein decreased, which might be assimilated by algicidal bacteria. Nonetheless, the whole algicidal process resulted in the increase of total released organic matters content. This study revealed the algicidal pathways of diverse bacterial strains, and the possible secondary environmental problem caused by the algal released organic matters should be considered when applying bacteria to control HABs.

Influence of cell lysis by Fenton oxidation on cryptic growth in sequencing batch reactor (SBR): Implication of reducing sludge source discharge.

The cell lysis-cryptic growth was implemented by Fenton oxidation in sequencing batch reactor. Optimizing sludge lysis condition could maximize the release of nutrients and sludge disintegration degree. After Fenton oxidation, the extracellular polymeric substance was obviously destroyed with the sludge average particle decreased from 64 µm to 36 µm. After 5% of the settled sludge in sequencing batch reactor (SBR) was oxidized by Fenton and then returned to SBR, the mixed liquor suspended solids (MLSS) decreased by 19.3% at the end of 35 days operation, the average mixed liquor volatile suspended solids/mixed liquor suspended solids (MLVSS/MLSS) was promoted by 13.3% during the entire operation. Returning lysed sludge had no significant influence on the organics and nitrogen removal, but the total phosphorus removal was distinctly enhanced by generating FePO4 precipitate. Additionally, returning lysed sludge suppressed nitrifying bacteria and promoted denitrifying bacteria slightly. Consequently, the cell lysis-cryptic growth for reducing sludge source discharge from wastewater biological treatment could be achieved on the premise of ensuring effluent quality.

Suspension stability and aggregation of multi-walled carbon nanotubes as affected by dissolved organic matters extracted from agricultural wastes.

Dissolved organic matters (DOMs) extracted from wheat straw (SDOM) and cow manure (MDOM) were used to investigate their effects on the suspension stability and aggregation of multi-walled carbon nanotubes (MWCNTs). Two types of DOM can effectively disperse and stabilize the MWCNTs. At initial MWCNT concentration of 500 mg/L, suspended MWCNT concentration ranged from 8.0 to 17.9 mg/L as DOM were varied from 50 to 200 mg/L dissolved organic carbon (DOC). The critical coagulation concentration (CCC) values were estimated to be 41.4 mM NaCl and 5.3 mM CaCl2 in the absence of DOM. The presence of SDOM and MDOM significantly retarded the aggregation rate of MWCNTs. The CCC values increased to 120 mM NaCl and 14.8 mM CaCl2 at SDOM concentration of 20 mg/L DOC. Due to its higher aromaticity and molecular weight, MDOM showed higher ability to stabilize MWCNTs, with CCC values of 201 mM and 15.8 mM at 20 mg/L DOC. These findings revealed that DOMs originated from agricultural wastes will have great impact on the dispersion and stabilization of MWCNTs, thus their fate in the aquatic environment.