Effect of drainage on CO2, CH4, and N2O fluxes from aquaculture ponds during winter in a subtropical estuary of China

Aquaculture ponds are dominant features of the landscape in the coastal zone of China.Generally,aquaculture ponds are drained during the non-culture period in winter.However,the effects of such drainage on the production and flux of greenhouse gases(GHGs)from aquaculture ponds are largely unknown.In the present study,field-based research was performed to compare the GHG fluxes between one drained pond(DP,with a water depth of 0.05 m)and one undrained pond(UDP,with a water depth of 1.16 m)during one winter in the Min River estuary of southeast China.Over the entire study period,the mean CO_2flux in the DP was(0.75±0.12)mmol/(m~2·hr),which was significantly higher than that in the UDP of(-0.49±0.09)mmol/(m~2·hr)(p0.01).This indicates that drainage drastically transforms aquaculture ponds from a net sink to a net source of CO_2in winter.Mean CH_4and N_2O emissions were significantly higher in the DP compared to those in the UDP(CH_4=(0.66±0.31)vs.(0.07±0.06)mmol/(m~2·hr)and N_2O=(19.54±2.08)vs.(0.01±0.04)μmol/(m~2·hr))(p0.01),suggesting that drainage would also significantly enhance CH_4and N_2O emissions.Changes in environmental variables(including sediment temperature,p H,salinity,redox status,and water depth)contributed significantly to the enhanced GHG emissions following pond drainage.Furthermore,analysis of the sustained-flux global warming and cooling potentials indicated that the combined global warming potentials of the GHG fluxes were significantly higher in the DP than in the UDP(p0.01),with values of739.18 and 26.46 mg CO_2-eq/(m~2·hr),respectively.Our findings suggested that drainage of aquaculture ponds can increase the emissions of potent GHGs from the coastal zone of China to the atmosphere during winter,further aggravating the problem of global warming.     

Roles of SO2 oxidation in new particle formation events

The oxidation of SO₂ is commonly regarded as a major driver for new particle formation (NPF) in the atmosphere. In this study, we explored the connection between measured mixing ratio of SO₂ and observed long-term (duration > 3 hr) and short-term (duration <1.5 hr) NPF events at a semi-urban site in Toronto. Apparent NPF rates (J₃₀) showed a moderate correlation with the concentration of sulfuric acid ([H₂SO₄]) calculated from the measured mixing ratio of SO₂ in long-term NPF events and some short-term NPF events (Category I) (R² = 0.66). The exponent in the fitting line of J₃₀ ~ [H₂SO₄]ⁿ in these events was 1.6. It was also found that SO₂ mixing ratios varied a lot during long-term NPF events, leading to a significant variation of new particle counts. In the SO₂-unexplained short-term NPF events (Category II), analysis showed that new particles were formed aloft and then mixed down to the ground level. Further calculation results showed that sulfuric acid oxidized from SO₂ probably made a negligible contribution to the growth of >10 nm new particles.     

Roles of SO2 oxidation in new particle formation events

The oxidation of SO₂ is commonly regarded as a major driver for new particle formation (NPF) in the atmosphere. In this study, we explored the connection between measured mixing ratio of SO₂ and observed long-term (duration > 3 hr) and short-term (duration < 1.5 hr) NPF events at a semi-urban site in Toronto. Apparent NPF rates (J₃₀) showed a moderate correlation with the concentration of sulfuric acid ([H₂SO₄]) calculated from the measured mixing ratio of SO₂ in long-term NPF events and some short-term NPF events (Category I) (R² = 0.66). The exponent in the fitting line of J₃₀ ~ [H₂SO₄]ⁿ in these events was 1.6. It was also found that SO₂ mixing ratios varied a lot during long-term NPF events, leading to a significant variation of new particle counts. In the SO₂-unexplained short-term NPF events (Category II), analysis showed that new particles were formed aloft and then mixed down to the ground level. Further calculation results showed that sulfuric acid oxidized from SO₂ probably made a negligible contribution to the growth of > 10 nm new particles.     

Effect of liming on sulfate transformation and sulfur gas emissions in degraded vegetable soil treated by reductive soil disinfestation

Reductive soil disinfestation (RSD), namely amending organic materials and mulching or flooding to create strong reductive status, has been widely applied to improve degraded soils. However, there is little information available about sulfate (SO₄^2 −) transformation and sulfur (S) gas emissions during RSD treatment to degraded vegetable soils, in which S is generally accumulated. To investigate the effects of liming on SO₄^2 − transformation and S gas emissions, two SO₄^2 −-accumulated vegetable soils (denoted as S1 and S2) were treated by RSD, and RSD plus lime, denoted as RSD₀ and RSD₁, respectively. The results showed that RSD₀ treatment reduced soil SO₄^2 − by 51% and 61% in S1 and S2, respectively. The disappeared SO₄^2 − was mainly transformed into the undissolved form. During RSD treatment, hydrogen sulfide (H₂S), carbonyl sulfide (COS), and dimethyl sulfide (DMS) were detected, but the total S gas emission accounted for < 0.006% of total S in both soils. Compared to RSD₀, lime addition stimulated the conversion of SO₄^2 − into undissolved form, reduced soil SO₄^2 − by 81% in S1 and 84% in S2 and reduced total S gas emissions by 32% in S1 and 57% in S2, respectively. In addition to H₂S, COS and DMS, the emissions of carbon disulfide, methyl mercaptan, and dimethyl disulfide were also detected in RSD₁ treatment. The results indicated that RSD was an effective method to remove SO₄^2 −, liming stimulates the conversion of dissolved SO₄^2 − into undissolved form, probably due to the precipitation with calcium.     

Temporal variation of microbial population in a thermophilic biofilter for SO2 removal

The performance of a biofilter relies on the activity of microorganisms during the gas contaminant treatment process. In this study, SO_2 was treated using a laboratory-scale biofilter packed with polyurethane foam cubes(PUFC), on which thermophilic desulfurization bacteria were attached. The thermophilic biofilter effectively reduced SO_2 within 10 months of operation time, with a maximum elimination capacity of 48.29 g/m~3/hr.Temporal shifts in the microbial population in the thermophilic biofilter were determined through polymerase chain reaction-denaturing gradient gel electrophoresis and deoxyribonucleic acid(DNA) sequence analysis. The substrate species and environmental conditions in the biofilter influenced the microbial population. Oxygen distribution in the PUFC was analyzed using a microelectrode. When the water-containing rate in PUFC was over 98%, the oxygen distribution presented aerobic–anoxic–aerobic states along the test route on the PUFC. The appearance of sulfate-reducing bacteria was caused by the anaerobic conditions and sulfate formation after 4 months of operation.     

Influence of phenol on ammonia removal in an intermittent aeration bioreactor treating biologically pretreated coal gasification wastewater

A laboratory-scale intermittent aeration bioreactor was investigated to treat biologically pretreated coal gasification wastewater that was mainly composed of NH_3-N and phenol.The results showed that increasing phenol loading had an adverse effect on NH_3-N removal;the concentration in effluent at phenol loading of 40 mg phenol/(L·day) was 7.3 mg/L, 36.3%of that at 200 mg phenol/(L·day). The enzyme ammonia monooxygenase showed more sensitivity than hydroxylamine oxidoreductase to the inhibitory effect of phenol, with32.2% and 10.5% activity inhibition, respectively at 200 mg phenol/(L·day). Owing to intermittent aeration conditions, nitritation-type nitrification and simultaneous nitrification and denitrification(SND) were observed, giving a maximum SND efficiency of 30.5%.Additionally, ammonia oxidizing bacteria(AOB) and denitrifying bacteria were the main group identified by fluorescent in situ hybridization. However, their relative abundance represented opposite variations as phenol loading increased, ranging from 30.1% to 17.5%and 7.6% to 18.2% for AOB and denitrifying bacteria, respectively.     

Effect of aeration rate on composting of penicillin mycelial dreg

Pilot scale experiments with forced aeration were conducted to estimate effects of aeration rates on the performance of composting penicillin mycelial dreg using sewage sludge as inoculation. Three aeration rates of 0.15, 0.50 and 0.90 L/(min·kg) organic matter(OM) were examined. The principal physicochemical parameters were monitored during the 32 day composting period. Results showed that the higher aeration rate of 0.90 L/(min·kg) did not corresponded to a longer thermophilic duration and higher rates of OM degradation;but the lower aeration rate of 0.15 L/(min·kg) did induce an accumulation of NH+4-N contents due to the inhibition of nitrification. On the other hand, aeration rate has little effect on degradation of penicillin. The results show that the longest phase of thermophilic temperatures ≥ 55°C, the maximum NO-3-N content and seed germination, and the minimum C/N ratio were obtained with 0.50 L/(min·kg) OM. Therefore, aeration rates of0.50 L/(min·kg) OM can be recommended for composting penicillin mycelial dreg.     

Denitrification and biofilm growth in a pilot-scale biofilter packed with suspended carriers for biological nitrogen removal from secondary effluent

Tertiary denitrification is an effective method for nitrogen removal from wastewater. A pilot-scale biofilter packed with suspended carriers was operated for tertiary denitrification with ethanol as the organic carbon source. Long-term performance, biokinetics of denitrification and biofilm growth were evaluated under filtration velocities of 6, 10 and 14 m/hr. The pilot-scale biofilter removed nitrate from the secondary effluent effectively, and the nitrate nitrogen (NO₃-N) removal percentage was 82%, 78% and 55% at the filtration velocities of 6, 10 and 14 m/hr, respectively. At the filtration velocities of 6 and 10 m/hr, the nitrate removal loading rate increased with increasing influent nitrate loading rates, while at the filtration velocity of 14 m/hr, the removal loading rate and the influent loading rate were uncorrelated. During denitrification, the ratio of consumed chemical oxygen demand to removed NO₃-N was 3.99–4.52 mg/mg. Under the filtration velocities of 6, 10 and 14 m/hr, the maximum denitrification rate was 3.12, 4.86 and 4.42 g N/(m²·day), the half-saturation constant was 2.61, 1.05 and 1.17 mg/L, and the half-order coefficient was 0.22, 0.32 and 0.24 (mg/L)^1/2/min, respectively. The biofilm biomass increased with increasing filtration velocity and was 2845, 5124 and 7324 mg VSS/m² at filtration velocities of 6, 10 and 14 m/hr, respectively. The highest biofilm density was 44 mg/cm³ at the filtration velocity of 14 m/hr. Due to the low influent loading rate, biofilm biomass and thickness were lowest at the filtration velocity of 6 m/hr.     

Role of secondary aerosols in haze formation in summer in the Megacity Beijing

A field experiment from 18 August to 8 September 2006 in Beijing, China, was carried out. A hazy day was defined as visibility < l0 km and RH (relative humidity) < 90%. Four haze episodes, which accounted for ~ 60% of the time during the whole campaign, were characterized by increases of SNA (sulfate, nitrate, and ammonium) and SOA (secondary organic aerosol) concentrations. The average values with standard deviation of SO₄^2 −, NO₃⁻, NH₄⁺ and SOA were 49.8 (± 31.6), 31.4 (± 22.3), 25.8 (± 16.6) and 8.9 (± 4.1) μg/m³, respectively, during the haze episodes, which were 4.3, 3.4, 4.1, and 1.7 times those in the non-haze days. The SO₄^2 −, NO₃⁻, NH₄⁺, and SOA accounted for 15.8%, 8.8%, 7.3%, and 6.0% of the total mass concentration of PM₁₀ during the non-haze days. The respective contributions of SNA species to PM₁₀ rose to about 27.2%, 15.9%, and 13.9% during the haze days, while the contributions of SOA maintained the same level with a slight decrease to about 4.9%. The observed mass concentrations of SNA and SOA increased with the increase of PM₁₀ mass concentration, however, the rate of increase of SNA was much faster than that of the SOA. The SOR (sulfur oxidation ratio) and NOR (nitrogen oxidation ratio) increased from non-haze days to hazy days, and increased with the increase of RH. High concentrations of aerosols and water vapor favored the conversion of SO₂ to SO₄^2 − and NO₂ to NO₃⁻, which accelerated the accumulation of the aerosols and resulted in the formation of haze in Beijing.     

Greenhouse gas emissions from oilfield-produced water in Shengli Oilfield, Eastern China

Greenhouse gas(GHG) emissions from oil and gas systems are an important component of the GHG emission inventory. To assess the carbon emissions from oilfield-produced water under atmospheric conditions correctly, in situ detection and simulation experiments were developed to study the natural release of GHG into the atmosphere in the Shengli Oilfield,the second largest oilfield in China. The results showed that methane(CH4) and carbon dioxide(CO2) were the primary gases released naturally from the oilfield-produced water.The atmospheric temperature and release time played important roles in determining the CH4 and CO2emissions under atmospheric conditions. Higher temperatures enhanced the carbon emissions. The emissions of both CH4 and CO2from oilfield-produced water were highest at 27°C and lowest at 3°C. The bulk of CH4 and CO2was released from the oilfield-produced water during the first release period, 0–2 hr, for each temperature, with a maximum average emission rate of 0.415 g CH4/(m3·hr) and 3.934 g CO2/(m3·hr), respectively. Then the carbon emissions at other time periods gradually decreased with the extension of time. The higher solubility of CO2 in water than CH4 results in a higher emission rate of CH4 than CO2over the same release duration. The simulation proved that oilfield-produced water is one of the potential emission sources that should be given great attention in oil and gas systems.     

Effects of elevated atmospheric CO2 concentration and temperature on the soil profile methane distribution and diffusion in rice–wheat rotation system

The aim of this experiment was to determine the impacts of climate change on soil profile concentrations and diffusion effluxes of methane in a rice–wheat annual rotation ecosystem in Southeastern China. We initiated a field experiment with four treatments: ambient conditions (CKs), CO₂ concentration elevated to ~ 500 μmol/mol (FACE), temperature elevated by ca. 2°C (T) and combined elevation of CO₂ concentration and temperature (FACE + T). A multilevel sampling probe was designed to collect the soil gas at four different depths, namely, 7 cm, 15 cm, 30 cm and 50 cm. Methane concentrations were higher during the rice season and decreased with depth, while lower during the wheat season and increased with depth. Compared to CK, mean methane concentration was increased by 42%, 57% and 71% under the FACE, FACE + T and T treatments, respectively, at the 7 cm depth during the rice season (p < 0.05). Mean methane diffusion effluxes to the 7 cm depth were positive in the rice season and negative in the wheat season, resulting in the paddy field being a source and weak sink, respectively. Moreover, mean methane diffusion effluxes in the rice season were 0.94, 1.19 and 1.42 mg C/(m²·hr) in the FACE, FACE + T and T treatments, respectively, being clearly higher than that in the CK. The results indicated that elevated atmospheric CO₂ concentration and temperature could significantly increase soil profile methane concentrations and their effluxes from a rice–wheat field annual rotation ecosystem (p < 0.05).     

Ozone concentrations, flux and potential effect on yield during wheat growth in the Northwest-Shandong Plain of China

Ozone (O₃) concentration and flux (F_o) were measured using the eddy covariance technique over a wheat field in the Northwest-Shandong Plain of China. The O₃-induced wheat yield loss was estimated by utilizing O₃ exposure-response models. The results showed that: (1) During the growing season (7 March to 7 June, 2012), the minimum (16.1 ppbV) and maximum (53.3 ppbV) mean O₃ concentrations occurred at approximately 6:30 and 16:00, respectively. The mean and maximum of all measured O₃ concentrations were 31.3 and 128.4 ppbV, respectively. The variation of O₃ concentration was mainly affected by solar radiation and temperature. (2) The mean diurnal variation of deposition velocity (V_d) can be divided into four phases, and the maximum occurred at noon (12:00). Averaged V_d during daytime (6:00–18:00) and nighttime (18:00–6:00) were 0.42 and 0.14 cm/sec, respectively. The maximum of measured V_d was about 1.5 cm/sec. The magnitude of V_d was influenced by the wheat growing stage, and its variation was significantly correlated with both global radiation and friction velocity. (3) The maximum mean F_o appeared at 14:00, and the maximum measured F_o was − 33.5 nmol/(m²·sec). Averaged F_o during daytime and nighttime were − 6.9 and − 1.5 nmol/(m²·sec), respectively. (4) Using O₃ exposure-response functions obtained from the USA, Europe, and China, the O₃-induced wheat yield reduction in the district was estimated as 12.9% on average (5.5%–23.3%). Large uncertainties were related to the statistical methods and environmental conditions involved in deriving the exposure-response functions.     

Remarkable promotion effect of trace sulfation on OMS-2 nanorod catalysts for the catalytic combustion of ethanol

OMS-2 nanorod catalysts were synthesized by a hydrothermal redox reaction method using MnSO₄ (OMS-2-SO₄) and Mn(CH₃COO)₂ (OMS-2-AC) as precursors. SO₄^2 −-doped OMS-2-AC catalysts with different SO₄^2 − concentrations were prepared next by adding (NH₄)₂SO₄ solution into OMS-2-AC samples to investigate the effect of the anion SO₄^2 − on the OMS-2-AC catalyst. All catalysts were then tested for the catalytic oxidation of ethanol. The OMS-2-SO₄ catalyst synthesized demonstrated much better activity than OMS-2-AC. The SO₄^2 − doping greatly influenced the activity of the OMS-2-AC catalyst, with a dramatic promotion of activity for suitable concentration of SO₄^2 − (SO₄/catalyst = 0.5% W/W). The samples were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), inductively coupled plasma optical emission spectroscopy (ICP-OES), NH₃-TPD and H₂-TPR techniques. The results showed that the presence of a suitable amount of SO₄^2 − species in the OMS-2-AC catalyst could decrease the Mn–O bond strength and also enhance the lattice oxygen and acid site concentrations, which then effectively promoted the catalytic activity of OMS-2-AC toward ethanol oxidation. Thus it was confirmed that the better catalytic performance of OMS-2-SO₄ compared to OMS-2-AC is due to the presence of some residual SO₄^2 − species in OMS-2-SO₄ samples.     

Composition and source apportionment of dust fall around a natural lake

The aim of this study was to determine the source apportionment of dust fall around Lake Chini, Malaysia. Samples were collected monthly between December 2012 and March2013 at seven sampling stations located around Lake Chini. The samples were filtered to separate the dissolved and undissolved solids. The ionic compositions(NO-3, SO2-4, Cl-and NH+4) were determined using ion chromatography(IC) while major elements(K, Na, Ca and Mg) and trace metals(Zn, Fe, Al, Ni, Mn, Cr, Pb and Cd) were determined using inductively coupled plasma mass spectrometry(ICP-MS). The results showed that the average concentration of total solids around Lake Chini was 93.49 ± 16.16 mg/(m2·day). SO2-4, Na and Zn dominated the dissolved portion of the dust fall. The enrichment factors(EF) revealed that the source of the trace metals and major elements in the rain water was anthropogenic, except for Fe. Hierarchical agglomerative cluster analysis(HACA) classified the seven monitoring stations and 16 variables into five groups and three groups respectively. A coupled receptor model, principal component analysis multiple linear regression(PCA-MLR), revealed that the sources of dust fall in Lake Chini were dominated by agricultural and biomass burning(42%),followed by the earth's crust(28%), sea spray(16%) and a mixture of soil dust and vehicle emissions(14%).     

Positively charged microporous ceramic membrane for the removal of Titan Yellow through electrostatic adsorption

To develop a depth filter based on the electrostatic adsorption principle, positively charged microporous ceramic membrane was prepared from a diatomaceous earth ceramic membrane.The internal surface of the highly porous ceramic membrane was coated with uniformly distributed electropositive nano-Y_2O_3 coating. The dye removal performance was evaluated through pressurized filtration tests using Titan Yellow aqueous solution. It showed that positively charged microporous ceramic membrane exhibited a flow rate of 421 L/(m~2·hr) under the trans-membrane pressure of 0.03 bar. Moreover it could effectively remove Titan Yellow with feed concentration of 10 mg/L between pH 3 to 8. The removal rate increased with the enhancement of the surface charge properties with a maximum rejection of 99.6%. This study provides a new and feasible method of removing organic dyes in wastewater. It is convinced that there will be a broad market for the application of charged ceramic membrane in the field of dye removal or recovery from industry wastewater.     

Synthesis,crystal structure,photodegradation kinetics and photocatalytic activity of novel photocatalyst ZnBiYO4

ZnBiYO₄ was synthesized by a solid-state reaction method for the first time. The structural and photocatalytic properties of ZnBiYO₄ were characterized by X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy and UV–Vis diffuse reflectance. ZnBiYO₄ crystallized with a tetragonal spinel structure with space group I41/A. The lattice parameters for ZnBiYO₄ were a = b = 11.176479 Å and c = 10.014323 Å. The band gap of ZnBiYO₄ was estimated to be 1.58 eV. The photocatalytic activity of ZnBiYO₄ was assessed by photodegradation of methyl orange under visible light irradiation. The results showed that ZnBiYO₄ had higher catalytic activity compared with N-doped TiO₂ under the same experimental conditions using visible light irradiation. The photocatalytic degradation of methyl orange with ZnBiYO₄ or N-doped TiO₂ as catalyst followed first-order reaction kinetics, and the first-order rate constant was 0.01575 and 0.00416 min^− 1 for ZnBiYO₄ and N-doped TiO₂, respectively. After visible light irradiation for 220 min with ZnBiYO₄ as catalyst, complete removal and mineralization of methyl orange were observed. The reduction of total organic carbon, formation of inorganic products, SO₄^2 − and NO₃⁻, and evolution of CO₂ revealed the continuous mineralization of methyl orange during the photocatalytic process. The intermediate products were identified using liquid chromatography–mass spectrometry. The ZnBiYO₄/(visible light) photocatalysis system was found to be suitable for textile industry wastewater treatment and could be used to solve other environmental chemical pollution problems.     

A hydroxyl radical detection system using gas expansion and fast gating laser-induced fluorescence techniques

An OH radical measurement instrument based on Fluorescence Assay by Gas Expansion(FAGE)has been developed in our laboratory.Ambient air is introduced into a low-pressure fluorescence cell through a pinhole aperture and irradiated by a dye laser at a high repetition rate of 8.5 k Hz.The OH radical is both excited and detected at 308 nm using A-X(0,0)band.To satisfy the high efficiency needs of fluorescence collection and detection,a 4-lens optical system and a self-designed gated photomultiplier(PMT)is used,and gating is actualized by switching the voltage applied on the PMT dynodes.A micro channel photomultiplier(MCP)is also prepared for fluorescence detection.Then the weak signal is accumulated by a photon counter in a specific timing.The OH radical excitation spectrum range in the wavelength of 307.82–308.2 nm is detected and the excited line for OH detection is determined to be Q_1(2)line.The calibration of the FAGE system is researched by using simultaneous photolysis of H_2O and O_2.The minimum detection limit of the instrument using gated PMT is determined to be 9.4×10~5molecules/cm~3,and the sensitivity is 9.5×10~(-7)cps/(OH·cm~(-3)),with a signal-to-noise ratio of 2 and an integration time of 60 sec,while OH detection limit and the detection sensitivity using MCP is calculated to be 1.6×10~5molecules/cm~3and 2.3×10~(-6)cps/(OH·cm~(-3)).The laboratory OH radical measurement is carried out and results show that the proposed system can be used for atmospheric OH radical measurement.     

Performance assessment and microbial diversity of two pilot scale multi-stage sub-surface flow constructed wetland systems

This study assessed the performance and diversity of microbial communities in multi-stage sub-surface flow constructed wetland systems(CWs). Our aim was to assess the impact of configuration on treatment performance and microbial diversity in the systems. Results indicate that at loading rates up to 100 g BOD5/(m2·day), similar treatment performances can be achieved using either a 3 or 4 stage configuration. In the case of phosphorus(P), the impact of configuration was less obvious and a minimum of 80% P removal can be expected for loadings up to 10 g P/(m2·day) based on the performance results obtained within the first16 months of operation. Microbial analysis showed an increased bacterial diversity in stage four compared to the first stage. These results indicate that the design and configuration of multi-stage constructed wetland systems may have an impact on the treatment performance and the composition of the microbial community in the systems, and such knowledge can be used to improve their design and performance.     

Influences of anion concentration and valence on dispersion and aggregation of titanium dioxide nanoparticles in aqueous solutions

Dispersion and aggregation of nanoparticles in aqueous solutions are important factors for safe application of nanoparticles. In this study, dispersion and aggregation of nano-TiO₂ in aqueous solutions containing various anions were investigated. The influences of anion concentration and valence on the aggregation size, zeta potential and aggregation kinetics were individually investigated. Results showed that the zeta potential decreased from 19.8 to − 41.4 mV when PO₄^3 − concentration was increased from 0 to 50 mg/L, while the corresponding average size of nano-TiO₂ particles decreased from 613.2 to 540.3 nm. Both SO₄^2 − and NO₃⁻ enhanced aggregation of nano-TiO₂ in solution. As SO₄^2 − concentration was increased from 0 to 500 mg/L, the zeta potential decreased from 19.8 to 1.4 mV, and aggregate sizes increased from 613.2 to 961.3 nm. The trend for NO₃⁻ fluctuation was similar to that for SO₄^2 − although the range of variation for NO₃⁻ was relatively narrow. SO₄^2 − and NO₃⁻ accelerated the aggregation rapidly, while PO₄^3 − did so slowly. These findings facilitate the understanding of aggregation and dispersion mechanisms of nano-TiO₂ in aqueous solutions in the presence of anions of interest.     

Effect of non-solvent additives on the morphology, pore structure, and direct contact membrane distillation performance of PVDF-CTFE hydrophobic membranes

Four common types of additives for polymer membrane preparation including organic macromolecule and micromolecule additives, inorganic salts and acids, and the strong non-solvent H2 O were used to prepare poly(vinylidene fluoride-co-chlorotrifluoroethylene)(PVDF-CTFE) hydrophobic flat-sheet membranes. Membrane properties including morphology, porosity, hydrophobicity, pore size and pore distribution were investigated, and the permeability was evaluated via direct contact membrane distillation(DCMD) of 3.5 g/L Na Cl solution in a DCMD configuration. Both inorganic and organic micromolecule additives were found to slightly influence membrane hydrophobicity. Polyethylene glycol(PEG),organic acids, Li Cl, Mg Cl2, and Li Cl/H2 O mixtures were proved to be effective additives to PVDF-CTFE membranes due to their pore-controlling effects and the capacity to improve the properties and performance of the resultant membranes. The occurrence of a pre-gelation process showed that when organic and inorganic micromolecules were added to PVDF-CTFE solution, the resultant membranes presented a high interconnectivity structure. The membrane prepared with dibutyl phthalate(DBP) showed a nonporous surface and symmetrical cross-section. When H2 O and Li Cl/H2 O mixtures were also used as additives, they were beneficial for solid–liquid demixing, especially when Li Cl/H2 O mixed additives were used. The membrane prepared with 5% Li Cl + 2% H2 O achieved a flux of24.53 kg/(m2·hr) with 99.98% salt rejection. This study is expected to offer a reference not only for PVDF-CTFE membrane preparation but also for other polymer membranes.