Transformation of copper oxide nanoparticles as affected by ionic strength and its effects on the toxicity and bioaccumulation of copper in zebrafish embryo.

This study aimed to investigate the transformation of copper oxide nanoparticles (CuO NPs) in aquatic environments under different ionic strength and further examine its effects on copper toxicity and bioaccumulation by monitoring the responses and uptake behaviours of zebrafish embryo. Ionic strength (IS) was simulated according to surface water (1.5 mM), groundwater (15 mM), and wastewater (54 mM), representing low-, mid-, and high-IS water, respectively. At the highest exposure of 10 mg CuO/L, zebrafish larvae mortality was increased from 21.3% to 33.3%, when IS decreased from 54 to 1.5 mM. Low-IS solution also caused the highest numbers of delayed hatching embryo (81.3%) and opaque yolk deformation (36.3%). Copper bioaccumulation markedly increased when larvae were exposed to low-IS water (35%) relative to high-IS water (15%). Exposing to low-IS particularly enhanced copper uptake (~15 ng Cu/g inside embryo), facilitating the copper accumulation in the heart of larvae, whereas aggregated CuO NPs (>500 nm) in mid- and high-IS water were blocked from the embryo and found abundantly in the body axis and tail. Results indicate that CuO NPs in low-IS solutions rapidly form the relatively small CuO NP aggregates with a high copper dissolution, which would pose great concern for aquatic organisms.

Algal removal from cyanobacteria-rich waters by preoxidation-assisted coagulation-flotation: Effect of algogenic organic matter release on algal removal and trihalomethane formation.

The cyanobacteria-bloom in raw waters frequently causes an unpredictable chemical dosing of preoxidation and coagulation for an effective removal of algal cells in water treatment plants. This study investigated the effects of preoxidation with NaOCl and ClO2 on the coagulation-flotation effectiveness in the removal of two commonly blooming cyanobacteria species, Microcystis aeruginosa (MA) and Cylindrospermopsis raciborskii (CR), and their corresponding trihalomethane (THM) formation potential. The results showed that dual dosing with NaOCl plus ClO2 was more effective in enhancing the deformation of cyanobacterial cells compared to single dosing with NaOCl, especially for CR-rich water. Both preoxidation approaches for CR-rich water effectively reduced the CR cell count with less remained dissolved organic carbon (DOC), which benefited subsequent coagulation-flotation. However, preoxidation led to an adverse release of algogenic organic matter (AOM) in the case of MA-rich water. The release of AOM resulted in a poor removal in MA cells and a large amount of THM formation after oxidation-assisted coagulation-flotation process. The reduction in THM formation potential of CR-rich waters is responsible for effective algae and DOC removal by alum coagulation. It is concluded that the species-specific characteristic of cyanobacteria and their AOM released during chlorination significantly influences the performance of coagulation-flotation for AOM removal and corresponding THM formation.

Nitrate removal and extracellular polymeric substances of autohydrogenotrophic bacteria under various pH and hydrogen flow rates.

In recent years there has been an increasing interest in the use of autohydrogenotrophic bacteria to treat nitrate from wastewater. However, our knowledge about the characteristics of extracellular polymeric substances (EPS) releasing by these activities is not yet very advanced. This study aimed to investigate the change in EPS compositions under various pH values and hydrogen flow rates, taking into consideration nitrogen removal. Results showed that pH7.5 and a hydrogen flow rate of 90mL/min were the optimal operating conditions, resulting in 100% nitrogen removal after 6hr of operation. Soluble and bound polysaccharides decreased, while bound proteins increased with increasing pH. Polysaccharides increased with increasing hydrogen flow rate. No significant change of bound proteins was observed at various hydrogen flow rates.

Effects of C/N ratio on nitrate removal and floc morphology of autohydrogenotrophic bacteria in a nitrate-containing wastewater treatment process.

The effects of C/N ratio of a nitrate-containing wastewater on nitrate removal performed by autohydrogenotrophic bacteria as well as on the morphological parameters of floc such as floc morphology, floc number distribution, mean particle size (MPS), aspect ratio and transparency were examined in this study. The results showed that the nitrate reduction rate increased with increasing C/N ratio from 0.5 to 10 and that the nitrogen removal of up to 95% was found at the C/N ratios of higher than 5 (between 0.5-10). Besides, high C/N ratio values reflected a corresponding high nitrite accumulation after 12-hr operation, and a fast decreasing rate of nitrite in the rest of operational time. The final pH values increased with the C/N ratio increasing from 0.5 to 2.5, but decreased with the C/N ratio increasing from 2.5 to 10. There were no significant changes in floc morphology with the MPSs ranging from 35 to 40µm. Small and medium-sized flocs were dominant in the sludge suspension, and the number of flocs increased with the increasing C/N ratios. Furthermore, the highest apparent frequency of 10% was observed at aspect ratios of 0.5 and 0.6, while the transparency of flocs changed from 0.1 to 0.7.

Electrochemical decolorization of dye wastewater by surface-activated boron-doped nanocrystalline diamond electrode.

Complex organics contained in dye wastewater are difficult to degrade and often require electrochemical advanced oxidation processes (EAOPs) to treat it. Surface activation of the electrode used in such treatment is an important factor determining the success of the process. The performance of boron-doped nanocrystalline diamond (BD-NCD) film electrode for decolorization of Acid Yellow (AY-36) azo dye with respect to the surface activation by electrochemical polarization was studied. Anodic polarization found to be more suitable as electrode pretreatment compared to cathodic one. After anodic polarization, the originally H-terminated surface of BD-NCD was changed into O-terminated, making it more hydrophilic. Due to the oxidation of surface functional groups and some portion of sp(2) carbon in the BD-NCD film during anodic polarization, the electrode was successfully being activated showing lower background current, wider potential window and considerably less surface activity compared to the non-polarized one. Consequently, electrooxidation (EO) capability of the anodically-polarized BD-NCD to degrade AY-36 dye was significantly enhanced, capable of nearly total decolorization and chemical oxygen demand (COD) removal even after several times of re-using. The BD-NCD film electrode favored acidic condition for the dye degradation; and the presence of chloride ion in the solution was found to be more advantageous than sulfate active species.

Selective dissolution of zinc and lead from duplex ß-phase brasses in low and high conductivity water.

This study provides insights regarding the selective metal leaching of brass in various tap water conditions, which benefits water utilities to predict the potential of metal released from brass water meters. The long-term time-dependent selective metal dissolution of brass with various ß phase fractions have not previously been investigated. In this study, a 201-d immersion experiment was carried out in low and high conductivity tap water (LCTW and HCTW, respectively). Three commercialized brass samples in different ß phase fractions (ß = 51%, ß = 43%, ß = 39%), named brass 51, brass 43, and brass 39, respectively, were used. The results showed that brass 51 had the most negative corrosion potential (-0.17 V) and the lowest polarization resistance (8.5 kΩ) compared to brass 43 and brass 39 (-0.04 V and 10.1-14.7 kΩ, respectively) in LCTW. This trend was verified by the 201-d immersion experiment in which brass 51 exhibited the highest zinc leaching rate (21-30 µg L-1 cm-2 d-1), followed by brass 43 and brass 39 (16-23 µg L-1 cm-2 d-1) in both waters. The leaching amounts of lead and copper were extremely low compared to zinc. In LCTW, the uniform corrosion (UC) mechanism dominated from day 1 to day 120. Afterwards, UC was replaced by the galvanic corrosion (GC) mechanism, with the selective leaching coefficient of Zn over Cu (SZn/Cu) increasing from 10 to 25 to 40-80. In HCTW, however, the SZn/Cu reached 300-1000, and the transition of UC to GC occurred earlier on day 30 due to the rapid formation of the ZnO layer on the brass surface that hindered the ion attack.

Destabilization of polystyrene nanoplastics with different surface charge and particle size by Fe electrocoagulation.

Nanoplastics (NPs) discharged from wastewater could pose a major threat to organisms in aquatic environments. Effective removal of NPs by the current conventional coagulation-sedimentation process is not yet satisfactory. This study aimed to investigate the destabilization mechanism of polystyrene NPs (PS-NPs) with different surface properties and sizes (i.e., 90 nm, 200 nm, and 500 nm) by Fe electrocoagulation (EC). Two types of PS-NPs were prepared by a nanoprecipitation method using sodium dodecyl sulfate and cetrimonium bromide solutions to produce negatively-charged SDS-NPs and positively-charged CTAB-NPs. For both NPs, obvious floc aggregation from 7 µm to 14 µm was observed only at pH 7 with particulate Fe accounted for >90 %. At pH 7, Fe EC removed 85.3 %, 82.8 %, and 74.7 % of the negatively-charged SDS-NPs at small-, mid-, and large-sizes from 90 nm, 200 nm, to 500 nm, respectively. Small-size SDS-NPs(90 nm) were destabilized through physical adsorption on the surface of Fe flocs, while the main removal mechanism of mid- and large-SDS-NPs(200 nm and 500 nm) involved the enmeshment of large Fe flocs. Compared to SDS-NPs(200 nm and 500 nm), Fe EC performed similar destabilization behavior to two CTAB-NPs(200 nm and 500 nm), but it resulted in much lower removal rates of 54.8 % - 77.9 %. The Fe EC also exhibited no removal (<1 %) ability toward the small-size and positively-charged CTAB-NPs(90 nm) due to insufficient formation of effective Fe flocs. Our results provide insight into the destabilization of PS in nano-scale with different sizes and surface properties, which clarifies the behavior of complex NPs in a Fe EC-system.

The effect of feed salinity on the biofouling dynamics of seawater desalination.

A persistent cell labeling dye and a novel microbial counting method were used to explore the effects of salinity on a microbial population in a reverse osmosis (RO) desalination system, and these clearly distinguished microbial cell multiplication from cell adherence. The results indicated that microbial multiplication is more active at the front of a seawater RO pressure vessel, while adhesion dominates the back of the vessel. A severe reduction in RO permeate flux and total dissolved solid (TDS) rejection were detected at low salinity, attributed to marked cell multiplication and release of extracellular polymeric substances, whilst a relatively stable flux was observed at medium and high salinity. The results from PCR-DGGE revealed the variation in microbial species distribution on the membrane with salinity. The results imply the critical role of membrane modification in biofouling mitigation in the desalination process.

Impact of sludge retention time on sludge characteristics and microbial community in MBR.

In this study, the impact of sludge retention time (SRT) on sludge characteristics and microbial community and the effect on membrane fouling in membrane bioreactor (MBR) was investigated. The results show that MBR with longer SRT has less fouling propensity, in agreement with other studies, despite the fact that the MBR with longer SRT contained higher MLSS and smaller particle size. However, much more soluble microbial products (SMPs) were released in MBR with shorter SRT. More slime on the membrane surface was observed in MBR with shorter SRT while sludge cakes formed on the membrane surface in MBR with longer SRT. The results show that SMP contributes to the severe fouling observed in MBR with shorter SRT, which is in agreement with other studies showing that SMPs were the major foulants in MBR. Under different SRTs of operation, the bacterial community structures of the sludge obtained by use of polymerase chain reaction-denaturing gradient gel electrophoresis (PCR-DGGE) were almost identical, but those on the membrane surface differed substantially. It suggests that, although SRT has impact on sludge characteristics, it doesn't affect the microbial community in the suspension.

Hydrolyzed Al(III) clusters: speciation stability of nano-Al13.

Pure nano-Al13 and aggregates at various concentrations were prepared to examine the particle size effect of coagulation with inorganic polymer flocculant. The property and stability of various species formed were characterized using Infrared, 27Al-NMR, photo correlation spectroscopy (PCS), and Ferron assay. Results showed that concentration and temperature exhibited different roles on the stability of Al13. The quantity of Alb species analyzed by ferron assay in the initial aging period corresponded well with that of Al13, which has been confirmed in a dimension range of 1-2 nm by PCS. Al13 solutions at high concentrations (0.5-2.11 mol/L) were observed to undergo further aggregation with aging. The aggregates with a wide particle size distribution would contribute to the disappeared/decreased Al13 basis on the 27Al-NMR spectrum, whereas a part of Al13 would still remain as Alb. At low concentrations, Al13 solution was quite stable at normal temperature, but lost its stability quickly when heating to 90 degrees C.

Modification on biochars for applications: A research update.

Biochars are the solid product of biomass under pyrolysis or gasification treatment, whose wholesale prices are lower than commercial activated carbons and other fine materials now in use. The employment of biochars as a renewable resource for field applications, if feasible, would gain apparent economic niche. Modification using physical or chemical protocol to revise the surface properties of biochar for reaching enhanced performances of target application has attracted great research interests. This article provided an overview of biochar application, particularly with the respect to the use of modified biochar as preferred soil amendment, adsorbent, electrochemical material, anaerobic digestion promotor, and catalyst. Based on literature works the current research trends and the prospects and research needs were outlined.

The recovery of sulfuric acid from spent piranha solution over a dimensionally stable anode (DSA) Ti-RuO2 electrode.

Piranha solution is a highly acidic mixture of sulfuric acid and hydrogen peroxide. The present study aimed at developing a dimensionally stable anode (DSA), made of titanium metal foil coated with Ruthenium Dioxide (RuO2), for the electrochemical oxidation of hydrogen peroxide in the presence of strong sulfuric acid under ambient conditions. Results showed that hydrogen peroxide in the piranha solution was fully degraded in 5 h under a constant current of 2 A (or current density of 0.32 A-cm-2). The oxidation kinetics of hydrogen peroxide followed the Langmuir-Hinshelwood model. The observed rate constant was a function of applied current. The initial current efficiency was 17.5% at 0.5 A (or 0.08 A-cm-2) and slightly decreased to about 13.5% at applied current between 1.3 and 1.5 A (or current density of 0.208 and 0.24 A-cm-2). Results showed the capability and feasibility of the electrochemical oxidation process for the recovery of sulfuric acid from the spent piranha solution in semiconductor industrial installations or general laboratories.

Bromide-intrusion into Chlorella sp. and Microcystis aeruginosa growing environments: Its impacts on algal growth and the formation potential of algal-derived DBPs upon chlorination.

Due to the negative impact of climate change and anthropogenic activities, bromide intrusion into algae-impacted freshwater becomes a new challenge for safe drinking water supply worldwide, as bromide and algal organic matter are important disinfection byproduct (DBP) precursors. However, the influences of this phenomenon on algal precursor dynamic and their derived DBPs have to date received little attention. This study examined the effects of bromide intrusion on algal intra- (IOM) and extra-cellular (EOM) precursors during the growth of two freshwater algae Chlorella sp. and Microcystis aeruginosa. Both algae were well-adapted to Br-intrusion, and no significant effect on their growth and their IOM and EOM precursor characteristics was statistically found (p > 0.05). Notwithstanding, this phenomenon apparently added bromide ions into the algal-EOM solution, which resulted in a linear uptake of bromide by IOM. Under Br-intrusion from 0-4 mg/L (Br0-Br4), 15-60% (on average) of the initial bromide additions remained in the algal EOM. By contrast, only an average of ~1.5-2.4% of the additional bromide was taken up by the IOM, resulting in an elevation of brominated DBPs (Br-DBPs) upon chlorination, especially for those samples collected in the late exponential and declined growth phases. When Br0 shifted to Br4, the %Br-DBP yields from both IOM and EOM increased by more than 75%, with a corresponding increasing the total DBP yield of ~30%. The toxic potencies of all chlorinated Br-containing IOM/EOM were thus magnified, by over one order magnitude greater than the non-Br IOM/EOM at Br0. These results are highly significant for understanding the potential risks of Br-intrusion and algal blooming in raw water quality prior to chlorination.

Recycling of spent filter backwash water using coagulation-assisted membrane filtration: effects of submicrometre particles on membrane flux.

Membrane separation technology has been widely used for recycling of spent filter backwash water (SFBW) in water treatment plant. Membrane filtration performance is subject to characteristics of the particles in the SFBW. A bench-scale microfiltration (MF) coupled with pre-coagulation was set up to evaluate the recovery efficiency of SFBW. Effect of particle size distribution and zeta potential of the coagulated SFBW on the membrane filtration as well as the coagulation strategies were investigated. Pore clogging was more severe on the membrane with 1.0 mum pore size than on the membrane with 0.5 mum pore size due to the fact that submicrometre particles are dominant and their diameters are exactly closed to the pore size of the MF membrane. Pre-settling induced more severe irreversible fouling because only the submicrometre particles in the water become predominant after settling, resulting in the occurrence of more acute pore blocking of membrane. By contrast, pre-coagulation mitigates membrane fouling and improves membrane flux via enlarging particle size on membrane surface. The variations of zeta potential in response to coagulant dosing as well as fractal dimension were also compared with the performance of the subsequent filtration. The result showed that pre-coagulation induced by charge neutralization at the optimum dosage where the zeta potential is around zero leads to the optimal performance of the subsequent membrane filtration for SFBW recycling. At such condition, the fractal dimension of coagulated flocs reached minimum.

Glucose fermentation with biochar-amended consortium: microbial consortium shift.

The effects of adding biochar rice husk (R), white popinee (WP), bamboo (BB), or coconut (CT) on microbial community in fermentation broths from glucose were investigated. The added biochars acted as biofilm carriers on which Sporolactobacillus spathodeae, Clostridium sensu stricto 11 sp., Clostridium sensu stricto 12 sp., Clostridium sensu stricto 1 sp., and Clostridium sensu stricto 5 sp. were enriched. Fermentation reactions substantially increased the amounts of acid-producers in biofilm. The homoacetogens, Clostridium carboxidivorans and Clostridium drakei, were identified in the biofilm in the first two batches of fermentation with biochars as electron conductors between acid-producers and homoacetogens to assist homoacetogenesis. The heterotrophic bacteria overcompeted the acid-producers in the biofilm in long-term fermentation.

Characteristics of low and high SUVA precursors: Relationships among molecular weight, fluorescence, and chemical composition with DBP formation.

Disinfection by-products (DBPs) formed upon water treatment is an emerging issue worldwide. While monitoring of DBP precursors can easily be achieved for high specific UV absorbance (SUVA) organic (>6 L/mg·m), low and extremely low SUVA precursors (<2 L/mg·m) are difficult to monitor or even to predict their DBP formation behaviour. This study investigated the relationships among NOM characteristics, such as molecular weight (MW), fluorescence, and chemical composition, with DBP formation resulting from the chlorination of relatively high and low SUVA precursors. High SUVA precursors were formed by C-rich substances (82-85% of total mass) corresponding with high C/N and C/O (>100 and >5, respectively). Such precursors exhibited the fluorescence of long-wavelength humic-like signal and occurred at a high MW range (>30 kDa). By contrast, low SUVA precursors were either N-rich and/or O-rich substances, associated with much lower carbon content (40-70%). Low SUVA, N-rich precursors particularly also occurred at a high MW region (>100 kDa) and produced a strong protein-like fluorescence signal. When SUVA values of O-rich precursors were extremely low (<1 L/mg·m) they were accompanyied by short-wavelength humic-like fluorescence. During DBP tests, high SUVA produced only high yields of carbonaceous DBPs (e.g trichloromethane, haloacetic acids, haloketones), whereas low SUVA N-rich precursors yielded high levels of both C and NDBPs (e.g. haloacetonenitrile, chloropicrin). By contrast, extremely low SUVA precursors produced significantly low levels of both C and NDBPs (total < 30 µg/mgC). Furthermore, 19 of 20 regression models of DBP formation using log-transformed MW gave R2 = 0.50-0.97. The strong regressions and correlations of NOM characteristics with DBPs in this study provide a better understanding of the influence of precursors characteristics on DBP monitoring, especially for low SUVA NOM.

Glucose fermentation with biochar amended consortium: Sequential fermentations.

The aim of this work was to study sequential batch fermentation of glucose with a biological consortium amended with nine different biochars or with an activated carbon. The glucose fermentation was enhanced by carbon amendment, with activated carbon being more effective than biochars as cell carriers and electron conductors between functional species. The volatile fatty acid distributions were shifted in the consumption of the produced H2 and CO2. The types of biochars were irrelevant to glucose glycolysis and the subsequent H2 and CO2 consumption reactions. Biofilm growth affects the detailed mechanisms occurred in fermentation broth to the yielded volatile fatty acid distributions.

Dark fermentation production of volatile fatty acids from glucose with biochar amended biological consortium.

Effects of adding biochars on dark fermentation production of volatile fatty acids (VFAs) from glucose were investigated. Nine biochars were synthesized and applied, together with an activated carbon, as the testing amendment to enhance preferable fermentation. Biochars were porous materials with internal pores and excess surface functional groups, which would lead to enrichment of acetate over butyrate in the VFA production. Biochar coconut and biochar longan shell showed excess functional groups and high bulk internal crystallinity, presented 109.6% and 71.8% enrichments of acetate production, respectively. The syntrophic growth of fermentative bacteria and homoacetogens on biochar surfaces via direct interspecies electron transfer mechanism was assumed to interpret the noted enhanced acetate production. The excess functional groups on biochar surface to facilitate biofilm development and the high crystallinity of biochar bulk to ease electron transfer favored the production of acetate.

Fluorescent and molecular weight dependence of THM and HAA formation from intracellular algogenic organic matter (IOM).

This study (i) examined the formation of two major carbonaceous disinfection by-products (C-DBPs), trihalomethanes (THMs) and haloacetic acids (HAAs), during the chlorination of intracellular algogenic organic matter (IOM) extracted from two commonly blooming algae M. aeruginosa (MA) and Chlorella sp. (CH), and (ii) investigated the roles and relationships of fluorescent and molecular weight (MW) properties on/with IOM-derived THMs and HAAs. The extracted IOM samples were separated into different MW fractions by centrifugal devices with membrane support with MW cut-offs of 100, 30, 10, 3, and 1 kDa. We observed an overall reduction of C-DBPs with a decrease of IOM-MW from >100 kDa to <1 kDa. Of six fractionated IOM, a large fraction (>100 kDa) contributed the largest amount to the MW distribution of IOM, accounting for 33 and 42% of the total dissolved organic carbon (DOC) of MA and CH, respectively. It also had the highest-yielding potential to produce significant levels of THMs and HAAs, and total C-DBPs over other small MW fractions. Although small MW fractions (>10 kDa) contributed around 50% of the total DOC, they made an insignificant contribution (>20%) to the THMs, HAAs, and overall C-DBPs. Furthermore, the decrease of IOM MW caused a shift from the domination of HAA formation to THM formation, especially when MW was <10 kDa. By canonical correspondent analysis, the relationship of IOM-derived THMs and HAAs with IOM properties was examined. In particular, large fractions of IOM, exhibiting aromatic protein- (AP) and soluble microbial product- (SMP) like fluorescence, are favorable for the formation of HAAs, whereas small MW fractions of IOM with HA- and FA-like fluorescence preferentially tends to form THMs. Our findings evidently show the strong dependence of IOM-derived THMs and HAAs on the fluorescent and MW properties. Therefore, the characterization of MW and fluorescent properties can provide the advantages in the control of algae-derived DBPs upon the chlorination of eutrophic water.

A dual TiO2/Ti-stainless steel anode for the degradation of orange G in a coupling photoelectrochemical and photo-electro-Fenton system.

A dual-anode consists of stainless steel and TiO2/Ti electrodes is used to study the kinetics of the degradation of hazardous chemicals exemplified by azo dye orange G (OG) using a coupling photoelectrochemical catalytic and photoelectro-Fenton (PEC/PEF) system. Concurrent generation of hydroxyl radicals on the TiO2/Ti photocatalyst and in-situ generation of Fenton reagents on the stainless steel electrode greatly enhances the performance of the PEC/PEF electrodes over that of the PEC and the PEF alone process. The efficiency of the PEC/PEF process is a function of Fe2+ and H2O2 concentration OH⋅ in the solution bulk, which promotes the oxidative degradation of OG and its byproducts. The mean carbon oxidation state (COS) is estimated to reflect the degree of mineralization. Based on the pseudo first-order kinetics with respect to OH, OG, Fe2+, the corresponding reaction rates is established. UV-Vis spectrometry reveals the presence of four major intermediates, which helps establish the OG degradation pathways.