Photochemical Transformation of Dissolved Organic Matter in Surface Water Augmented the Formation of Disinfection Byproducts.

Sunlight may lead to changes in disinfection byproducts (DBPs) formation potentials of source water via transforming dissolved organic matter (DOM); however, the underlying mechanisms behind these changes remain unclear. This work systematically investigated the effect of photochemical transformation of DOM from reservoir water (DOMRe) and micropolluted river water (DOMRi) after 36 h of simulated sunlight irradiation (equivalent to one month under natural sunlight) on DBPs formation. Upon irradiation, high molecular weight (MW) and aromatic molecules tended to be mineralized or converted into low-MW and highly oxidized (O/C > 0.5) ones which might react with chlorine to generate high levels of DBPs, resulting in an elevation in the yields (µg DBP/mg C) of almost all the measured DBPs and the quantities of unknown DBPs in both DOM samples after chlorination. Additionally, DOMRi contained more aromatic molecules susceptible to photooxidation than DOMRe. Consequently, irradiated DOMRi exhibited a greater increase in the formation potentials of haloacetonitriles, halonitromethanes, and specific regulated DBPs, with nitrogenous DBPs being responsible for the overall rise in the calculated cytotoxicity following chlorination. This work emphasized the importance of a comprehensive removal of phototransformation products that may serve as DBPs precursors from source waters, especially from micropolluted source waters.

Combined effects of particle size and humic acid corona on the aggregation kinetics of nanoplastics in aquatic environments.

Nanoplastics (NPs) contaminant in aquatic environments is one of the pressing environmental concerns globally. However, the combined effects of particle size and humic acid (HA) corona on the aggregation behavior of NPs have not been revealed yet. Therefore, this study explored the influence of HA corona on the aggregation kinetics of NPs with three different particle sizes under various water quality conditions. Results showed that in the absence of HA corona, the aggregation kinetic processes of all the three NPs were affected by the repulsive force originating from the hydration layer. Moreover, the smaller the particle size, the more obvious the effect. HA corona played a steric hindrance role for all the three NPs based on the extended-Derjaguin-Landau-Verwey-Overbeek (XDLVO) theory in monovalent solutions, resulting in the impediment of aggregation. Whereas, in divalent solutions, the HA corona of 100 and 200 nm NPs experienced three stages: deformation, electrostatic-patch and bridging; while that of 40 nm NPs underwent electrostatic-patch and steric hindrance. The larger number of HA molecules distributed on 100 and 200 NPs surfaces led to more interactions with Ca2+ and NPs, which was the key factor for HA corona to play more diverse roles. According to the two dimension correlation spectroscopy analysis (2D-COS), the structural change in the interaction between HA and NPs was that the aromatic ring of NPs took precedence, followed by the carbonyl groups of HA. This study provided new insights into the combined effects of HA corona and particle size on the aggregation kinetics of NPs and established a theoretical foundation for predicting and assessing the transport and fate of NPs.

Decomposition of Al13 promoted by salicylic acid under acidic condition: Mechanism study by differential mass spectrometry method and DFT calculation.

Decomposition of the polycation Al13O4(OH)24(H2O)127+ (Al13) promoted by ligand is a vital subject to advance our understanding of natural and artificial occurrence and evolution of aluminum ions, especially in the case of acidic condition that dissolved Al3+ species can be released from the Al-bearing substances. However, the microscopic pathway of synchronous proton-promoted and ligand-promoted decomposition process for Al13 is still in the status of ambiguity. Herein, we applied differential mass spectrometry method and DFT calculation to study the initial detailed process of Al13 decomposition under the presence of proton and salicylic acid (H2Sal). Mass results showed that the mononuclear Al3+-H2Sal complexes dominated the resulting Al species, whereas the monodentate complex Al13HSal6+ was not observed in the spectra. The difference of decomposition levels between the ligand/Al ratio 0.2 and 0.5 cases revealed that proton and ligand performed synergistic effect in initial Al13 decomposition process, and the proton transfer determined the ring closure efficiency. The ring closure reaction is the prerequisite for the collapse of Al13 structure and detachment of the mononuclear complex. DFT calculations reveal that hydrogen bond plays an important role in inducing the formation of chelated complex accompanying proton transfer. Attachment of protons at the bridging OH- can elongate and weaken the critical bond between targeted Al3+ and µ4-O2- resulting from delocalization of electron pairs in the oxygen atom. These results demonstrate the detailed mechanism of Al13 composition promoted by ligand and proton, and provide significant understanding for further application and control of Al13.

Turnover of dissolved organic carbon fuels nocturnal CO2 emissions from a headwater catchment reservoir, Southeastern China: Effects of ecosystem metabolism on source partitioning of CO2 emissions.

Dam reservoirs in headwater catchments, as critical zones for their proximity to terrestrial sources, play important roles in dissolved organic carbon (DOC) cycling. However, the effects of ecosystem metabolism (EM) on DOC cycling are not well known. Here, in-situ diurnal and monthly observations were conducted to measure EM (including gross primary production (GPP), ecosystem respiration (ER) and heterotrophic respiration (HR)), DOC turnover and CO2 emissions in a headwater catchment reservoir in Southeastern China in 2020. Our study showed the nocturnal CO2 emission rate was about twice as high as in daytime, and was strongly driven by EM. The values for DOC turnover velocity ranged from 0.10 to 1.59 m/day, and the average DOC turnover rate was 0.13 day-1, with the average removal efficiency of 12%. The contribution of respired DOC to daily CO2 emissions ranged from 17% to 61%. The accumulated efficiencies were estimated to be 13% for the selected 15 reservoirs throughout the Changjiang River network, corresponding to about 0.34 Tg C/year of the respired DOC. The modified CO2 flux was 0.75 Tg C/year, and respired DOC accounted for about 45% of total emitted CO2 from the 15 larger reservoirs. Our research emphasizes the necessity of incorporating the effects of EM into studies of reservoir DOC removal and CO2 emissions.

Removal of microorganic pollutants in aquatic environment: The utilization of Fe(VI).

Microorganic pollutants (MOPs) in aquatic environment with low levels but high toxicity are harmful to ecosystem and human health. Fe(VI) has a dual-functional role in oxidation and coagulation, and can effectively remove MOPs, heavy metal, phosphate, particulates and colloids. Moreover, Fe(VI) can combine with traditional coagulants, or use as a pretreatment for membrane treatment because of its characters to generate nanoparticles by degradation in water. Based on the relevant toxicity experiments, Fe(VI) had been proved to be safe for the efficient treatment of MOPs. For better utilization of Fe(VI), its oxidation and coagulation mechanisms are summarized, and the knowledge about the control parameters, utilization methods, and toxicity effect for Fe(VI) application are reviewed in this paper. pH, different valences of iron, environmental substances, and other parameters are summarized in this study to clarify the important factors in the treatment of MOPs with Fe(VI). In the future study, aiming at cost reduction in Fe(VI) preparation, transportation and storage, enhancement of oxidation in the intermediate state, and better understanding the mechanism between interface and Fe(VI) oxidation will help promote the application of Fe(VI) in the removal of MOPs. This study offers guidelines for the application and development of Fe(VI) for the treatment of MOPs in aquatic environment.

Effect of low-temperature thermal drying on malodorous volatile organic compounds (MVOCs) emission of wastewater sludge: The relationship with microbial communities.

Sludge treatment processes are the main source of nuisance odors in wastewater treatment plants. Apart from well-known odorants such as NH3 and H2S, malodorous volatile organic compounds (MVOCs) contribute largely to nuisance odors but are less concerned. In this work, the emission of MVOCs from wastewater sludges at different processing stages was measured, and the effects of dewatering and low-temperature thermal drying on the generation of sludge odor were investigated. The MVOCs were analyzed by olfactory measurements, headspace gas chromatography-coupled ion mobility spectrometry (HS-GC-IMS), and headspace solid-phase microextraction gas chromatography-mass spectrometry (HS-SPME-GC-MS). Low-temperature thermal drying treatment changed the odor categories and increased the odor intensity (OI) from moderate level (8-9) for raw sludges to strong (>10) for dried sludge. The odor emission capacity of MVOCs, namely the concentration of MVOCs, increased for dried sludge. The major odorants of sludge after different processes included 2-MIB, geosmin, dimethyl disulfide (DMDS), dimethyl trisulfide (DMTS), hexanal, and decanal according to their odor activity values (OAVs). The bacterial community structures showed a correlation with the key MVOC odorants. Specifically, there was a significant positive correlation between the concentration of key odorants and the relative abundance of the phyla of Actinobacteria and Chloroflexi. Thus, low-temperature thermal drying had a significant effect on odor formation by acting on the microbial community of sludge.

Variations in NOM during floc aging: Effect of typical Al-based coagulants and different particle sizes.

Most studies on the interaction between coagulation and NOM (natural organic matter) currently focus on pollutant removal and coagulant species distribution, while studies on floc aging are lacking. Investigation onto the effects of floc aging could guide further processes that utilize flocs, such as densadeg sludge recirculation, floc predeposition for ultrafiltration, sludge condensation, and other traditional sludge reflux processes. In this study, flocs generated by Al13 and AlCl3 in microparticle- and nanoparticle-containing water were investigated, and the effect of floc aging on NOM was quantified based on several organic matter characterization techniques. Flocs absorb and release organics during aging. The flocs generated from micro-SiO2 have a significant absorbing effect for LWM-N (low-molecular-weight neutral substances) and protein-like substances, while the absorption of NOM by flocs generated from nano-SiO2 is insignificant. HS (humic substances) with high aromaticity are released during floc aging. From the molecular perspective, the molecules released during floc aging are those with higher double bond equivalents and higher aromaticity, while the absorbed molecules are those with lower double bond equivalents and lower aromaticity. 2D-COS (two-dimensional correlation spectroscopy) demonstrated that the flocs generated by Al13 and AlCl3 had the same organic release patterns but different intensities, while the flocs generated in the micro-SiO2 and nano-SiO2 systems had different organics release patterns. Abundant aluminum hydrolysates with low polymerization and amorphous Al(OH)3 would be produced from AlCl3 during the coagulation process and then undergo hydroxyl­bridging reaction and crystallization during floc aging, thus releasing more HS with high aromaticity into the supernatant; in comparison, prehydrolyzed Al13 produces a more stable floc and releases less HS during aging. The flocs produced by nano-SiO2 and Al-based coagulants release higher aromaticity HS into the water than those produced by micro-SiO2, which may be related to the formation of more highly polymerized degree hydrolysates and nanocrystalline Al(OH)3 in the nano-SiO2 system. The flocs generated in water with micro-SiO2 may contain a large amount of Al-OH and have a loose structure, thus further absorbing NOM, such as protein-like substances and LWM-N. In contrast, the flocs generated from nano-SiO2 possess abundant adsorbed water and a denser structure; thus, organic matter cannot be absorbed stably.

Aggregation, settling characteristics and destabilization mechanisms of nano-particles under different conditions.

An abundance of nano-particles have been exposed to water environment. Owing to the particle size effects, nano-particles are inclined to absorb harmful substances and increase their levels of toxicity. In this study, the existence state, aggregation and settlement characteristics of nano-particles in the natural water are studied. Influenced by the structural layer repulsion, nano-particles have higher stability in natural water. When coagulants were added, nano-particles could effectively aggregate with slow flocculation speed and relatively small flocs size without hydraulic shearing due to the significant effect of Brownian motion. It is worth noting that the aggregated flocs formed by Brownian motion showed high strength and strong ability to resist hydraulic disturbance, and thus the flocs were harder to break. This is because the combination among nano-particles under hydraulic shearing is the result of a single-point chain-to-chain aggregation mode, while that under the Brownian motion is the result of multi-points face-to-face aggregation mode. Therefore, in the process of re-flocculation, flocs formed by the Brownian motion were more compact. This study provides a new view in nano-particles treatment for both the in-situ treatment process of natural water body and the regular water treatment plants.

Enhanced chemodiversity, distinctive molecular signature and diurnal dynamics of dissolved organic matter in streams of two headwater catchments, Southeastern China.

Dissolved organic matter (DOM) is a complicated assembly of organic molecules, including thousands of molecules with various structures and properties. However, how the stream DOM sources respond to carbon compositions and the transformation processes remains unclear. In this study, the chemical characteristics and spectral and mass spectrometry (FT-ICR MS) of DOM were analyzed. Six sampling points of headwater stream (HWSs) were sampled, and an effluent polluted stream (WSR) and a main stream of the Changjiang River (DT) were also sampled for comparison. In situ degradation experiments and FT-ICR MS analysis were also performed to observe the dynamic processes of DOM in HWS. The results showed that the anthropogenic markers of sewage (i.e. sulfur (S) compounds and marker from antibiotics and estrogen) in HWS were higher than those in DT. The molecular weight decreased while the degradation products (S-containing compounds and unsaturated compounds (HU)) increased after in situ degradation due to the influence of both the photodegradation and biodegradation process. In addition, the KMD plots showed that the DOM homologue intensities in range 400-600 Da changed significantly after demethylation by biodegradation. The components of highly refractory substances and the degradation degree of DOM in DT was higher than that in HWS. We extracted the refractory DOM pool in HWS, which was mainly small molecular with molecular weights < 600 Da. These molecular will be difficult to remove in traditional drinking water treatment processes and easily produced disinfection byproducts (DBPs). This study emphasized the necessity of identifying the sources and transformation processes of DOM in HWS and clarified the types and characteristics of DOM that should be considered in future drinking water treatment.

Deprotonation and aggregation of Al13 under alkaline titration: A simulating study related to coagulation process.

Unraveling the transformation of coagulants and their interaction with contaminants at the micro-level is vital to advancing our understanding of the coagulation mechanism. To the best of our knowledge, the coagulation effectiveness of [AlO4Al12(OH)24(H2O)12]7+ (Al13), regarded as the dominant species in polyaluminum chloride (PACl), is highly related to its aggregation characteristic, but the detailed process of Al13 aggregation in coagulation time scale was not well studies. Here we systematically studied the deprotonation and aggregation processes of Al13 by alkaline titration to simulate the reaction in coagulation case. By reacting with OH-, Al13 can continuously lose protons regardless of pH until its positive charge was well neutralized. The initial Al13 aggregates (Al13agg) appeared at B of 2.70 and large Al13agg was generated by coalescence of small initial Al13agg. Most Al13 polycations kept their main structure unchanged during aggregation and part was decomposed into monomers or oligomers. Density functional theory (DFT) results reveal that Al13 becomes unstable after deprotonation, but the aggregation of Al13 bridged by Al monomers can stabilize the polycations. Al13 needs to be hydrolyzed before interacting with colloidal particles, but particles can promote the aggregation of Al13 by weakening the repulsion force between the polymers. Strong and compact flocs can be generated induced by in-situ aggregation of Al13 in neutral and alkaline conditions. This study can provide a deep understanding about the role of Al13agg in removing particles and instruct the development of new efficient coagulants against the various water qualities.

Advances in micro interfacial phenomena of adsorptive micellar flocculation: Principles and application for water treatment.

Among various aqua remediation technologies, separation aims at cleaning pollutants by isolating them despite their destruction; solutes can also be recovered after the process. Adsorptive micellar flocculation (AMF) has been known as an important surfactant-based technique to separate poorly water-soluble hazardous pollutants from aqua media as an efficient and energy-intensive replacement for other surfactant-based techniques, as such AMF should be known. AMF is based on the partitioning of solutes gradient from bulk solution into the nanosized smart anionic surfactant micelle followed by flocculation. However, unlike coagulation/flocculation or adsorption, AMF is not viable for the production of drinking water in water utilities due to the loss of surfactant monomers. Unfortunately, it can be used as a reservoir or for the recycling/recovery of organic pollutants (intermediates) (ions, organics/bioactive, dyes, etc.), even at high concentrations. The performance of AMF depends on various parameters, and this review briefly summarizes the existing researches on different pollutants removal by AMF and material recovery/recycling. This includes operating condition factors (surfactants, flocculants, surfactant-flocculant or surfactant-pollutant concentration ratio, and water conditions chemistry). Because varieties of micro interfacial phenomena other than physical interactions occur in a versatile micellar environment in the AMF process, emphases are given to adsorptive oxidation, micellar catalysis, selectivity. Furthermore, for the first time, this review gives an overview of understanding the state-of-the-art multifunctional nano amphiphile-based AMF that behaves mimetic to aquatic organisms in the process of pollutant removal. The efficiency of AMF, including recycling concentrated solution without noticeable deterioration, as an auxiliary resource/income for the next cycle, signifies economic viability, versatility, and manifold applications in aqua remediation. Significance, ways to achieve enhanced process efficiency, as well as challenges and future opportunities in wastewater treatment, are also highlighted.

Formation of Al30 aggregates and its correlation to the coagulation effect.

Al30 is the polycation with the highest degree of polymerization and surface charge in the currently known structural aluminum species. It shows excellent coagulation performance in water treatment process, and has the characteristics of wide application range of pH and dosage. pH value is one of the most important factors affecting the aggregation and coagulation process of Al30, but the influence of Al30 aggregation reaction on its coagulation effect is still unclear. Therefore, this article reports the deprotonation and aggregation reaction of Al30 by adjusting the basicity (B) of the solution, particularly to further understand the coagulation mechanism of Al30 under different conditions. The results showed that in the base titration process, when B < 2.86 in 0.01 M Al30 solution as AlT (the concentration of total Al), deprotonation and preliminary aggregation mainly occurred; when B > 2.86, the size of Al30 aggregates (Al30agg) increased rapidly, forming gels and gradually transforming into Al(OH)3. In this process, in addition to the reduction of electrostatic repulsion induced by Al30 deprotonation, the oligomers generated by the partial dissociation of Al30 also play the role of bridging-connection. Under the experimental titration conditions, the Al30agg always maintained a positive zeta potential. In addition, Al30 can deprotonate and aggregate at lower pH, which is an important reason for its unique coagulation characteristics. The larger structure size of Al30 also made it easy to form branched aggregates, so that it can play an effective role in a wider dosage range without destabilization of colloids. This study gives an insight in the advancement of coagulants and promotes the industrial application and commercialization of functional coagulants based on polyaluminum.

Coagulation removal of phosphorus from a southern China reservoir in different stages of algal blooms: Performance evaluation and AlP matching principle analysis.

Due to excessive nutrient discharge, many reservoirs in southern China suffer from eutrophication and harmful algal blooms. Several methods for phosphorus (P) removal have been proposed, including coagulation, adsorption, and biological methods. Among these methods, coagulation is preferable because of its quick effect, simple operation, and low cost. To investigate the effect and mechanism of coagulation on dephosphorization in reservoir water, the performances of Al-based (AlCl3 and polyaluminum chloride (PACl)) and Fe-based coagulants (FeCl3 and FeSO4) were evaluated in this work. For reservoir water with a total phosphorus (TP) concentration of approximately 0.080 mg/L, aluminum salts showed stable advantages in dephosphorization. AlCl3 reduced the TP level by over 90% when treating the water sample collected at the initial stage of algal blooms, and PACl reduced by over 80% during the blooming stage. To reveal the dephosphorization mechanism and AlP matching principle, synthesized water samples were prepared and treated with AlCl3 and [AlO4Al12(OH)24(H2O)12]7+ (Al13). While simulating the water quality characteristics of reservoir water, important influencing factors were considered. The factors include P content (dissolved phosphorus (DP) and particulate phosphorus (PP)), pH, and extracellular organic matter (EOM). The pH was set to 7.66 and 8.29, with PP proportion set to 20%, 50%, and 80%. Simulated water treatment results indicated that, except for the coagulants species, pH significantly affected the dephosphorization efficiency. Moreover, the effects of P speciation and EOM were confirmed. Based on the coagulation performance and coagulation product characterization, chemical precipitation and inner-sphere complexation were estimated to be the most predominant way that DP and PP match with Al and were efficiently removed by Al-based coagulants.

Influence of particle size on the aggregation behavior of nanoparticles: Role of structural hydration layer.

More and more attention has been paid to the aggregation behavior of nanoparticles, but little research has been done on the effect of particle size. Therefore, this study systematically evaluated the aggregation behavior of nano-silica particles with diameter 130-480 nm at different initial particle concentration, pH, ionic strength, and ionic valence of electrolytes. The modified Smoluchowski theory failed to describe the aggregation kinetics for nano-silica particles with diameters less than 190 nm. Besides, ionic strength, cation species and pH all affected fast aggregation rate coefficients of 130 nm nanoparticles. Through incorporating structural hydration force into the modified Smoluchowski theory, it is found that the reason for all the anomalous aggregation behavior was the different structural hydration layer thickness of nanoparticles with various sizes. The thickness decreased with increasing of particle size, and remained basically unchanged for particles larger than 190 nm. Only when the distance at primary minimum was twice the thickness of structural hydration layer, the structural hydration force dominated, leading to the higher stability of nanoparticles. This study clearly clarified the unique aggregation mechanism of nanoparticles with smaller size, which provided reference for predicting transport and fate of nanoparticles and could help facilitate the evaluation of their environment risks.

Pre-aggregation of Al13 in optimizing coagulation for removal of humic acid.

The effective removal of humic acid (HA) by coagulation has been extensively investigated for water treatments. However, the limitations of pH variation and excessive residual aluminum issues were still factors needed to be considered. In this study, to investigate the coagulation mechanism for removing HA by Al13 and optimize Al13 operation for removing HA, Al13 and preformed Al13 aggregates (Al13agg) were applied to remove HA at different pH conditions. The results showed that preformed Al13agg exhibited superior HA removal performance than Al13 due to its wide pH range and low residual Al level. During coagulation, Al13 and Al13agg interacted with HA in their original status, but the DSlope325-375 difference implied that the complexation capacity between HA and Al13agg was stronger than Al13. The new peaks of HPSEC representing larger molecular weight substances were formed under acidic and neutral conditions, which indicated that HA firstly aggregated into larger complexed molecules by interacting with Al13 or its hydrolysates and was subsequently removed by forming large flocs which was completely different from Al13agg situation. Therefore, the different coagulation mechanisms played the roles in HA removal for Al13 and Al13agg which were studied in this paper. It was believed that the complexation and charge neutralization effects dominated coagulation process for Al13 while sweep flocculation and adsorption coagulation were main driving force for Al13agg in HA removing. This work provides significant understanding of HA removal by Al13 and Al13agg coagulation, which can help to design and optimize the high efficiency coagulant based on Al polycations.

Removal of phenolic contaminants from water by in situ coated surfactant on Keggin-aluminum nanocluster and biodegradation.

Recent water treatment plants require multi-process techniques to remove contaminants from aqua media. In this study, we investigate the novel, in situ coated sodium dodecylsulphate (SDS), on kegging Al30 nanocluster as a single water treatment alternative for the removal of phenolic contaminants and suspension. FTIR, TEM-EDX and Zeta potential analysis characterized the nanocluster decoration. The resulting property was examined by emission (λ-max) of the molecular probe, the online aggregate image of fluorescence microscopy, and mixing isochrone, fat-soluble dye solubilization. The coated media was examined as nearly resembling the hydrophobicity of 1-octanol. The elemental line scanning and mapping showed different morphologies of floc depending on the SDS concentration. The material was found to follow Brownian motion to enmesh suspended particles like a ladder, and served as entrapper for small organic contaminants by the sorbed SDS aggregate, based on their log KO/W. About 85% and ≥95% removal archived for contaminants with the least and highest KO/W value, respectively. The residual solutes in the supernatant were well decomposed by using a bacterial agent. One-step removal (less footprint) and ease of operation make this approach an environmentally compatible and cost-effective alternative for the large-scale treatment process.

The difference of aggregation mechanism between microplastics and nanoplastics: Role of Brownian motion and structural layer force.

In recent years, microplastics (MPs) and nanoplastics (NPs) have attracted worldwide attention because of the potential risks they pose to aquatic environments, but there are few studies on the difference of aggregation mechanism between MPs and NPs. In this study, 100 nm and 1 µm polystyrene plastics were selected as models to explore the aggregation mechanism of MPs/NPs under different aquatic environments. The influence of ion species and concentrations on the aggregation behaviors and kinetics were systematically investigated to predict the effects of water quality on the occurrence form of MPs and NPs based on DLVO theory and revised modified Smoluchowski theory. Results showed concentration, valence and hydrated ability of cations jointly affected the aggregation behavior of NPs. The critical coagulation concentration ratio of cations were consistent with Schulze-Hardy rules. But the different aggregation rate coefficients of same valent cations were ascribed to the structural layer force. Anion species played a role in the reaction-controlled regime by producing hydrogen ions to neutralize negative charges on NPs surfaces. Due to the strong Brownian motion and structural layer force, NPs would be stable in freshwater but preferentially aggregated when transport through brackish water, estuaries, eutrophication and high hardness areas and sea water, forming the accumulation hot spots of NPs in the sediment. While for MPs, physical process controlled the aggregation mechanism of them, leading to high stability in natural water and eventually transporting into marine environments. This study provided a theoretical foundation for assessing the transport, distribution, fate and ecological risks of MPs and NPs in realistic aquatic environments.

Profiling and characterization of odorous volatile compounds from the industrial fermentation of erythromycin.

Complaints caused by odors from the fermentation production of pharmaceuticals are common in China. The elimination of odor remains a challenge for the pharmaceutical industry to meet the increasingly strict environment regulations. Erythromycin is a representative antibiotic produced by microbial fermentation. The fermentation exhaust gas of erythromycin fermentation has an unpleasant odor, but the composition of the key odorants has not been identified. The major odorants from the fermentation production of erythromycin API were analyzed by electronic nose, olfactory measurements, gas chromatography-coupled ion mobility spectrometry (GC-IMS) and gas chromatography-mass spectrometry (GC-MS) analysis. Two compounds, 2-methylisoborneol (2-MIB) and geosmin, were identified as the major odorants of erythromycin fermentation. These had not been detected before using only GC-MS analysis of exhaust gas. Aldehydes, including hexanal, octanal, decanal, and benzaldehyde, also contribute to the odor. The composition analysis of odorants using the fermentation broth headspace was more efficient and reliable, considering the significant dilution effect of exhaust gas. The concentration of 2-MIB and geosmin in the fermentation broth greatly exceeded their odor thresholds. The production of major odorants started in the early fermentation stage and became significant in the middle stage (30-70 h). Due to the extremely low odor thresholds of 2-MIB and geosmin, advanced purification may require deodorization of erythromycin fermentation exhaust gas.

Optimized coagulation pathway of Al13: Effect of in-situ Aggregation of Al13.

The coagulation mechanism for removing particles by Al13 has been extensively investigated for water treatments. It was widely accepted that Al13 played important roles in coagulation mainly by charge neutralization and electrostatic patch. However, the discovery of Al13 aggregates (Al13agg) in flocs indicated that the real coagulation process should be different from the previous understanding, including when Al13agg were generated and how it interacted with negative particles. The aggregation process of Al13 during coagulation and its micro-interfacial effect on particle coagulation remains to be explored. In this study, to investigate the aggregation of Al13 and its effect on coagulation performance, two parallel coagulation jar tests were conducted on silica suspensions by preformed Al13agg and Al13, respectively. The results showed that optimized coagulation for particle removal by Al13 occurred from pH 7 to pH 9, which was dominated by the in-situ aggregation of Al13. The results confirmed that Al13agg were both present in flocs generated in two tests, however, the morphology and distribution of surface Al of flocs were different for two tests. The in-situ formed Al13agg covered all over the silica particles in flocs, resulting in compact structure with rough surfaces, while the preformed Al13agg mainly distributed on joint sites between particles, generating denser flocs with smooth surfaces. This difference verified that the in-situ aggregation of Al13 was the key factor to optimized particle coagulation. The overall optimized particle coagulation by Al13 should undergo the following pathway: charge neutralization - in-situ aggregation of Al13 - inter-particle bridging.