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.

Microplastics affect rice (Oryza sativa L.) quality by interfering metabolite accumulation and energy expenditure pathways: A field study.

Microplastic accumulation in agricultural soils can stress plants and affects quality of the products. Current research on the effects of microplastics on plants is not consistent and the underlying mechanisms are yet unknown. Here, the molecular mechanisms of the stress response were investigated via metabolomic and transcriptomic analyses of rice Oryza sativa L. II Y900 and XS123 under the exposure of polystyrene microplastics (PS-MPs) in a field study. Distinct responses were obtained in these two rice subspecies, showing decreased head rice yield by 10.62% in Y900 and increase by 6.35% in XS123. The metabolomics results showed that PS-MPs exposure inhibited 29.63% of the substance accumulation-related metabolic pathways and 43.25% of the energy expenditure-related metabolic pathways in the Y900 grains; however, these related pathways were promoted in the XS123 grains. The transcriptomics results indicated that the expression of genes encoding proteins involved in the tricarboxylic acid cycle in the Y900 grains was inhibited, but it was enhanced in the XS123 grains. The XS123 subspecies could response against microplastic exposure stress through the metabolite accumulation and energy expenditure pathways, while the Y900 could not. The results provide insight into the perturbation of rice grains in farmlands with microplastics contamination.

Metabolomics revealing the response of rice (Oryza sativa L.) exposed to polystyrene microplastics.

Large amounts of microplastics accumulate in the agricultural soil. Microplastics would stress the crops but the underlying mechanism remains unclear. Herein, a laboratory exposure and field trials were carried out to investigate the response of rice (Oryza sativa L. II You. 900) to stress induced by polystyrene microplastics (PS-MPs) using a metabolomic approach. After laboratory exposure for 21 days, the decreases in shoot biomass of rice exposed to low, medium and high doses of PS-MPs were 13.1% (CV = 4.1%), 18.8% (CV = 3.7%), and 40.3% (CV = 9.2%), respectively, while the antioxidant enzymes showed an inverted upper-U shape when exposed to PS-MPs. A total of 24 samples from three exposure dose levels were included in the metabolic analysis. The metabolites of 12 amino acids, 16 saccharides, 26 organic acids and 17 others (lipids and polyols) in leaves decreased after the exposure to both 50 mg L-1 and 250 mg L-1 PS-MPs doses with hydroponically-cultured. The inhibition of perturbed biological pathway causes the biosynthesis of amino acids, nucleic acids, fatty acids and some secondary metabolites decreased which indicate that the energy expenditure exceeded the substance accumulation. In order to further validate the effects of PS-MPs on rice leaves obtained from the laboratory-scale experiments, a field-trial experiment was conducted. After 142 days of cultivation in farmland, the results with a maximum of 25.9% lower biomass in the crops exposed with PS-MPs. As such, the presence of PS-MPs may affect rice production by altering the metabolic systems of rice. Long-term exposure of PS-MPs to rice might be a potential risk to rice safety and quality.

Citric acid assisted Fenton-like process for enhanced dewaterability of waste activated sludge with in-situ generation of hydrogen peroxide.

Fenton's reagent has been widely used to enhance sludge dewaterability. However, drawbacks associated with hydrogen peroxide (H2O2) in Fenton's reagents exist, since it is a hazardous chemical and shows carcinogenicity, explosivity, instability, and corrosivity. Moreover, initial acidification and subsequent neutralization are needed as optimal conditions for homogeneous Fenton conditioning and final filtrate discharge. In this study, a Fenton-like process for the enhanced dewaterability of waste activated sludge with in-situ generation of H2O2 and without extra pH adjustment was firstly proposed, namely citric acid (CA)-assisted oxygen activation in an air/nano zero-valent iron (nZVI) system and chemical re-coagulation with polydiallyldimethylammonium chloride (PDMDAAC). Using the response surface methodology (RSM), the optimal doses of CA, nZVI, and PDMDAAC were determined to be 13, 33, and 9 mg g-1 dry solids (DS), respectively. This composite conditioner showed a good dewatering capability compared with the raw sludge, e.g. the capillary suction time decreased from 130.0 to 9.5 s. The enhanced sludge dewaterability was further confirmed by laboratory-scale diaphragm filter press dewatering tests, which produced a lower cake moisture content compared with the raw sludge, and the final pH of the filtrate was close to neutrality. The citric acid promoted the production of H2O2 and Fe(II)/Fe(III) species, the degradation of protein in tightly-bound extracellular polymeric substances, and the decomposition of protein-N in the solid phase of sludge, resulting a greater conversion of bound water to free water. The results of electron spin resonance indicated that the hydroxyl radicals were mainly responsible for the decomposition of proteinaceous compounds. The subsequent chemical re-coagulation with PDMDAAC can make the zeta potential of sludge samples less negative, reduce the repulsive electrostatic interactions, and agglomerate the smaller particles into larger aggregates, thus enhancing sludge dewaterability.

Evaluating filterability of different types of sludge by statistical analysis: The role of key organic compounds in extracellular polymeric substances.

An investigation was conducted for 20 different types of sludge in order to identify the key organic compounds in extracellular polymeric substances (EPS) that are important in assessing variations of sludge filterability. The different types of sludge varied in initial total solids (TS) content, organic composition and pre-treatment methods. For instance, some of the sludges were pre-treated by acid, ultrasonic, thermal, alkaline, or advanced oxidation technique. The Pearson's correlation results showed significant correlations between sludge filterability and zeta potential, pH, dissolved organic carbon, protein and polysaccharide in soluble EPS (SB EPS), loosely bound EPS (LB EPS) and tightly bound EPS (TB EPS). The principal component analysis (PCA) method was used to further explore correlations between variables and similarities among EPS fractions of different types of sludge. Two principal components were extracted: principal component 1 accounted for 59.24% of total EPS variations, while principal component 2 accounted for 25.46% of total EPS variations. Dissolved organic carbon, protein and polysaccharide in LB EPS showed higher eigenvector projection values than the corresponding compounds in SB EPS and TB EPS in principal component 1. Further characterization of fractionized key organic compounds in LB EPS was conducted with size-exclusion chromatography-organic carbon detection-organic nitrogen detection (LC-OCD-OND). A numerical multiple linear regression model was established to describe relationship between organic compounds in LB EPS and sludge filterability.

Variations in physical, chemical and biological properties in relation to sludge dewaterability under Fe (II) - Oxone conditioning.

The mechanism of Fe (II) - oxone conditioning to improve sludge dewaterability was investigated in this study. Five different types of sludge were tested, including raw sludge (Group 1: mixed primary and secondary sludge, waste activated sludge and anaerobic digested sludge) and pretreated sludge with prior solubilisation (Group 2: ultrasonic or thermal pretreated sludge). After Fe (II) - oxone conditioning, the concentrations of dissolved organic carbon, protein and polysaccharide of soluble extracellular polymeric substances (SB EPS) increased for Group 1, but decreased for Group 2. For all types of sludge investigated, the related organic compounds of loosely bound (LB) and tightly bound (TB) EPS decreased with Fe (II) - oxone conditioning, and increased sludge filterability showed strong and positive correlation with the removal of low molecular weight protein and neutrals in LB EPS. Fe (II) - oxone was very effective in disintegrating cell membrane and caused potential cell lysis, as indicated by increased percentage of damaged microbial cells. From this study, the mechanism of Fe (II) - oxone conditioning was proposed and can be divided into two steps: (1) Oxidation step - sulfate radicals degraded organic compounds in LB and TB EPS in sludge and transformed bound water to free water that was trapped in TB and LB EPS; It also damaged cells membrane and may help to release intracellular water content. Sludge flocs were broken into smaller particles; (2) Coagulation step - Fe (III), generated from the oxidation step can act as a coagulant to agglomerate smaller particles into larger ones and reduce the repulsive electrostatic interactions. Combined effects from above two steps can greatly improve sludge filterability.

Characterization of key organic compounds affecting sludge dewaterability during ultrasonication and acidification treatments.

This study investigated the mechanism and effects of ultrasonic pretreatment followed by acidification on sludge dewaterability through looking at the changes of extracellular polymeric substances (EPS) content, composition and stratification. The results suggested sludge filterability was closely correlated with quantity of protein (R = 0.94, p < 0.01) and polysaccharide (R = 0.97, p < 0.01) present in loosely bound EPS rather than in soluble and tightly bound EPS. The fractions of polymers, especially tryptophan-like proteins and microbial by-product like material at molecular weight of 106-5 × 107 Da, were the key compounds related to sludge filterability. Ultrasonication may increase biopolymers concentrations that in turn deteriorate sludge filterability as evidenced at high ultrasonic power conditions. However, the subsequent acidification can reduce the concentrations of these organic compounds, reduce negative zeta potential, and increase floc size, thus increase sludge filterability. Combined ultrasonic-acid pretreamtent was more effective than the acidification treatment alone in reducing the concentrations of macromolecular compounds that may deteriorate sludge filterability.