Inhibition of phosphorus removal performance in activated sludge by Fe(III) exposure: transitions in dominant metabolic pathways.

Introduction: Simultaneous chemical phosphorus removal process using iron salts (Fe(III)) has been widely utilized in wastewater treatment to meet increasingly stringent discharge standards. However, the inhibitory effect of Fe(III) on the biological phosphorus removal system remains a topic of debate, with its precise mechanism yet to be fully understood. Methods: Batch and long-term exposure experiments were conducted in six sequencing batch reactors (SBRs) operating for 155 days. Synthetic wastewater containing various Fe/P ratios (i.e., Fe/P = 1, 1.2, 1.5, 1.8, and 2) was slowly poured into the SBRs during the experimental period to assess the effects of acute and chronic Fe(III) exposure on polyphosphate-accumulating organism (PAO) growth and phosphorus metabolism. Results: Experimental results revealed that prolonged Fe(III) exposure induced a transition in the dominant phosphorus removal mechanism within activated sludge, resulting in a diminished availability of phosphorus for bio-metabolism. In Fe(III)-treated groups, intracellular phosphorus storage ranged from 3.11 to 7.67 mg/g VSS, representing only 26.01 to 64.13% of the control. Although the abundance of widely reported PAOs (Candidatus Accumulibacter) was 30.15% in the experimental group, phosphorus release and uptake were strongly inhibited by high dosage of Fe(III). Furthermore, the abundance of functional genes associated with key enzymes in the glycogen metabolism pathway increased while those related to the polyphosphate metabolism pathway decreased under chronic Fe(III) stress. Discussion: These findings collectively suggest that the energy generated from polyhydroxyalkanoates oxidation in PAOs primarily facilitated glycogen metabolism rather than promoting phosphorus uptake. Consequently, the dominant metabolic pathway of communities shifted from polyphosphate-accumulating metabolism to glycogen-accumulating metabolism as the major contributor to the decreased biological phosphorus removal performance.

Photochemical transformation and immobilization of thallium in the presence of iron and arsenic: Mechanistic insights from the coupled formation of arsenate complexes.

Despite the occurrence of thallium (Tl) in the acidic mining-affected areas being highly positively correlated with iron (Fe) and arsenic (As), the effects of the two accompanying elements on Tl redox transformation and immobilization remain largely unknown. Here, we investigated the photochemical redox kinetics and immobilization efficiency of Tl for a wide range of As/Fe and As/Tl ratios under acidic conditions. We provided the first experimental confirmation of the complexation of Tl(III) with As(V) by the spectrophotometric method and revealed the role of Tl(III)-As(V) complexes in decreasing the photoreduction rate of Tl(III) under sunlight. Additionally, the negative impact of colloidal Fe(III)-As(V) and Fe(III)-As(III) complexes formation on decreasing photoactive Fe(III) speciation and thus the apparent quantum yield of •OH was highlighted, which consequently hindered the oxidative conversion of Tl(I) to Tl(III). We rationalize the kinetics results by developing the model which quantitatively describes the photochemistry of Tl. Furthermore, we demonstrated the colloid-facilitated immobilization of Tl(III) through the formation of Tl(III)-As(V) clusters and surface adsorption onto the complexes. This study broadens the mechanistic understanding of redox transformation and immobilization potential of Tl and aids in assessing Tl speciation as well as its coupled transformation with Fe and As species in the sunlit water environment.

Improving mesophilic anaerobic digestion of food waste by side-stream thermophilic reactor: Activation of methanogenic, key enzymes and metabolism.

Anaerobic digestion (AD) is a favorable way to convert organic pollutants, such as food waste (FW), into clean energy through microbial action. This work adopted a side-stream thermophilic anaerobic digestion (STA) strategy to improve a digestive system's efficiency and stability. Results showed that the STA strategy brought higher methane production as well as higher system stability. It quickly adapted to thermal stimulation and increased the specific methane production from 359 mL CH4/g·VS to 439 mL CH4/g·VS, which was also higher than 317 mL CH4/g·VS from single-stage thermophilic anaerobic digestion. Further exploration of the mechanism of STA using metagenomic and metaproteomic analysis revealed enhanced activity of key enzymes. The main metabolic pathway was up-regulated, while the dominant bacteria were concentrated, and the multifunctional Methanosarcina was enriched. These results indicate that STA optimized organic metabolism patterns, comprehensively promoted methane production pathways, and formed various energy conservation mechanisms. Further, the system's limited heating avoided adverse effects from thermal stimulation, and activated enzyme activity and heat shock proteins through circulating slurries, which improved the metabolic process, showing great application potential.

Light- and H2O2-Mediated Redox Transformation of Thallium in Acidic Solutions Containing Iron: Kinetics and Mechanistic Insights.

The redox transformation between the oxidation states of thallium (Tl(I) and Tl(III)) is the key to influencing its toxicity, reactivity, and mobility. Dissolved iron (Fe) is widely distributed in the environment and coexists at a high level with Tl in acidic mine drainages (AMDs). While ultraviolet (UV) light and H2O2 can directly (by inducing Tl(III) reduction) and indirectly (by inducing Fe(III) to form reactive intermediates) impact the redox cycles of Tl in Fe(III)-containing solutions, the kinetics and mechanism remain largely unclear. This study is the first to investigate the UV light- and H2O2-mediated Tl redox kinetics in acidic Fe(III) solutions. The results demonstrate that UV light and H2O2 could directly reduce Tl(III) to Tl(I), with the extent of reduction dependent on the presence of Fe(III) and the solution pH. At pH 3.0, Tl(I) was completely oxidized to Tl(III), which can be ascribed to the generation of hydroxyl radicals (•OH) from the Fe(III) photoreduction or Fe(III) reaction with H2O2. The kinetics of Tl(I) oxidation were strongly affected by the Fe(III) concentration, pH, light source, and water matrix. Kinetic models incorporating Tl redox kinetics with Fe redox kinetics were developed and satisfactorily interpreted Tl(III) reduction and Tl(I) oxidation under the examined conditions. These findings emphasize the roles of the UV light- and H2O2-driven Fe cycles in influencing the redox state of Tl, with implications for determining its mobility and fate in the environment.

Distinct granulation pathways of aerobic granular sludge under poly aluminum chloride enhancement.

Aerobic granular sludge (AGS), a novel strategy for nutrient removal which exhibits compact structure, good settleability, and resilience against high organic load, has been considered as a highly potential wastewater treatment technology. However, the long start-up period for granulation prevented its widespread development. In this study, the distinct pathways of PAC-enhanced AGS granulation were systematically investigated. Four identical sequencing batch reactors (SBR) with different PAC dosages (with 0, 50, 100, 400 mg/L effective Al3+ respectively) were applied. It was observed that the presence of PAC accelerated granules formation, promoted mechanical strength as well as denitrification rate of granules, and thus notably enhanced removal efficacies of COD, NH4+-N, NO2- and NO3-. According to the dissolved oxygen (DO) distribution inside the sludge and the denitrification rate (SDNR) measurements, distinguishing structures of granules under different PAC addition were discovered. Comparatively, AGS under low PAC addition (i.e., 50 mg/L) resulted in the largest granule size, the biggest anaerobic zone and the highest denitrification rate. Presumably, for the system with the low PAC addition (50 mg/L), appropriate aluminum ions (Al3+) neutralized part of the negative charge on the microorganism surface, thereby promoting cells aggregation. In contrast, a high dosage of PAC (400 mg/L) induced excessive Al3+ absorbed on the cell surface after neutralization, which increased the repulsive force between microorganisms, leading to more cavities and channels existed inside the granules. Therefore, granules under low PAC dosage (i.e., 50 mg/L) presented large anaerobic zone and high denitrification rate, thus favored the best internal structure and nutrients removal efficiencies.

Influence of dissolved black carbon on the aggregation and deposition of polystyrene nanoplastics: Comparison with dissolved humic acid.

Dissolved black carbon (DBC), widely found in soil and water environments is likely to affect the transport of nanoplastics in aquatic environments. The aggregation and deposition behaviors of fresh and aged polystyrene nanoplastics (PSs) with and without DBC in NaCl solution were investigated by time-resolved dynamic light scattering (DLS) and quartz crystal microbalance with dissipation monitoring equipment (QCM-D) techniques. The results suggest that DBC can screen the surface charges of PSs by interacting with PSs through hydrogen bonding, hydrophobic interactions and π-π interactions, although they were negatively charged. DBC promoted the aggregation of PSs under relatively low ionic strengths, and it minimally affected the stability of PSs under high ionic strength. Deposition experiments showed that both DBC in salt solution and DBC adsorption on silica surface facilitated the deposition of fresh PSs while HA inhibited both deposition processes. After aging, PSs were more stable, and the effects of DBC and HA were weakened. This study investigated the influence mechanism of DBC on the aggregation and deposition behaviors, which provides new insights into the stability and transport of PSs in complex aquatic environments.

Removal of trace mercury (II) from aqueous solution by in situ MnO(x) combined with poly-aluminum chloride.

Removal of trace mercury from aqueous solution by Mn (hydr)oxides formed in situ during coagulation with poly-aluminum chloride (PAC) (in situ MnO(x) combined with PAC) was investigated. The efficiency of trace mercury removal was evaluated under the experimental conditions of reaction time, Mn dosage, pH, and temperature. In addition, the ionic strength and the initial mercury concentration were examined to evaluate trace mercury removal for different water qualities. The results clearly demonstrated that in situ MnO(x) combined with PAC was effective for trace mercury removal from aqueous solution. A mercury removal ratio of 9.7 µg Hg/mg Mn was obtained at pH 3. Furthermore, at an initial mercury concentration of 30 µg/L and pH levels of both 3 and 5, a Mn dosage of 4 mg/L was able to lower the mercury concentration to meet the standards for drinking water quality at less than 1 µg/L. Analysis by Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy suggests that the hydroxyls on the surface of Mn (hydr)oxides are the active sites for adsorption of trace mercury from aqueous solution.