Effects of low temperature on aluminum(Ⅲ) hydrolysis:Theoretical and experimental studies

In this study,the effects of low temperature on aluminum(Ⅲ)(Al)hydrolysis were examined both theoretically and experimentally by constructing a solubility diagram for amorphous aluminum hydroxide(Al(OH)_3(am))and a distribution diagram of hydrolyzed Al species.First,thermodynamic data of Al species at 4℃were calculated from that at 25℃.A well confirmed polymeric Al species, AlO_4Al_(12)(OH)_(24)~(7+)(Al_(13)),was involved in building the diagrams and,correspondingly,the non-linear simultaneous equations ...     

Fractionation of residual Al in natural water treatment from reservoir with poly-aluminum-silicate-chloride (PASiC): Effect of OH/Al, Si/Al molar ratios and initial pH

An aluminum fractionation study was conducted for a surface reservoir water treatment to understand the performance of poly-aluminum-silicate-chloride (PASiC) in terms of the residual Al fractions as a function of initial pH. The coagulation performance expressed as turbidity and organic matter removal was established as supporting data. Some extra data were evaluated in terms of the residual Al ratio of the composite PASiC coagulant. The main residual Al sources were the Al fractions derived from the use of PASiC. The turbidity and organic matter removal ability was optimal at initial pH 6.00-7.00, while the concentrations of various residual Al species and the residual Al ratio of PASiC were minimal at an initial pH range of 7.00-8.00. Under the conditions of OH/Al molar ratio = 2.00 and Si/Al molar ratio = 0.05, PASiC had superior coagulation performance and comparatively low residual Al concentrations. The Al fraction in the composite PASiC coagulant seldom remained under such conditions. Experimental data also indicated that the suspended (filterable) Al fraction was the dominant species, and organic-bound or organo-Al complex Al was considered to be the major species of dissolved Al in water treated by PASiC coagulation. Additionally, the dissolved inorganic monomeric Al species dominated the dissolved monomeric Al fraction.     

Al(Ⅲ) speciation distribution and transformation in high concentration PACl solutions

Effects of Al（Ⅲ） concentration and pH on the speciation of Al（Ⅲ） in polyaluminum chloride （PACl） solutions especially on the Al13 fraction were investigated. A series of PACl samples were prepared over the range of Al（Ⅲ） concentration from 0.01 to 2.0 mol/L with the B （OH/Al ratio） value from 1.0 to 2.5 by forced hydrolysis of AICl3. The samples were characterized by ferron assay, pH and 27^Al NMR. It was shown that the Al（Ⅲ） concentration had a dramatic effect on the hydrolysis processes and the species distribution of PACl was in relate to the decrease of pH. The fraction of Al species, Alb （or Al13） decreased and Al0 increased with increase of total Al（Ⅲ） concentration. Under the condition of Al（Ⅲ） 2.0 reel/L, B = 2.5, the pH value was 2.73 and no Al13 could be detected. During diluting and aging, the species distribution evoIved. The Al13 could then be detected again and the amounts increased with time. If the diluted samples were concentrated by freeze dry at -35℃ or heating at 80℃, the pH value and Al13 content would decrease with the increased concentration. It demonstrated that the key factor for formation of Al13 in concentrated PACl was pH value.     

Fluoride removal by Al, Ti, and Fe hydroxides and coexisting ion effect

Batch experiments were conducted to evaluate fluoride removal by Al,Fe,and Ti-based coagulants and adsorbents,as well as the effects of coexisting ions and formation of aluminum–fluoride complexes on fluoride removal by co-precipitation with alum(Al_2(SO_4)_3·18H_2O).Aluminum sulfate was more efficient than the other coagulants for fluoride removal in the pH range between 6 and 8.Nano-crystalline TiO_2 was more effective for fluoride removal than Al and Fe hydroxides in a pH range of 3–5.Coexisting anions in water decreased the removal of fluoride in the order:phosphate(2.5 mg/L) arsenate(0.1 mg/L) bicarbonate(200 mg/L) sulfate(100 mg/L) = nitrate(100 mg/L) silicate(10 mg/L) at a pH of 6.0.The effect of silicate became more significant at pH 7.0.Calcium and magnesium improved the removal of fluoride.Zeta-potential measurements determined that the adsorption of fluoride shifted the PZC of Al(OH)_3 precipitates from 8.9 to 8.4,indicating the chemical adsorption of fluoride at the surface.The presence of fluoride in solution significantly increased the soluble aluminum concentration at pH 6.5.A Visual MINTEQ modeling study indicated that the increased aluminum solubility was caused by the formation of AlF~(2+),AlF~(+2),and AlF_3complexes.The AlF_x complexes decreased the removal of fluoride during co-precipitation with aluminum sulfate.     

Hydrolyzed AI（Ⅲ） clusters： Speciation stability of nano-All3

Pure nano-Al13 and aggregates at various concentrations were prepared to examine the particle size e ect 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 di erent 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°C.     

Chemical species distribution and transformation in polyaluminum chemical solutions

The hydrolysis polymerization precipitation process of Al(III) was studied with pH titration method, and the prepared polyaluminum solutions were characterized by various experimental methods: acid depolymerization, timed complex-colorimetric procedure, ultrafiltration, X-ray diffraction and infrared absorption spectrum. The results showed that the chemical species transformation and distribution of Al(III) in the hydrolysis-polymerization process depended on B=(OH/Al) ratio, pH and other factors. By their structures, the chemical species can be divided into three categories of monomeric (Ala), polymeric (Alb), sol or gel precipitates (Alc) and the polymeric species may be further divided into three groups such as linear low polymer (Alb1), linear high polymer (Alb2) and high polymer with cyclic structure (Alb3). The nominal molecular weight of polymeric species obtained by ultrafiltration was about 1000-50000 and most of them failed into a range around 10000. A scheme for the chemical speciation model     

Effects of simulated acid rain on root growth of Cunninghamia lanceolata and Schima superba saplings planted in acidified soil

Results from pot culture (with one-year old Cunninghamia lanceolata and Schima superba) are described. It was found that the biomass production and elongation of C. lanceolata was seriously inhibited at pH 2.0 rain, but for S. superba, was not affected markedly. When pH values of experimental rain were higher than 2.0, the root growth of both species was not adversely affected. Aluminium had already accumulated to some degrees in the roots of both trees, and started to affect the root growth of C. lanceolata at pH 2.0 rain. The soil chemistry was also examined. Increased acidity of experimental rain increased the leaching of Ca and Mg. The Al/Ca mol ratio increased from 0.3 to 0.9 in top soil, and in rhizosphere to 1.5 when the pH values of simulated acid rain were 4.5 to 2.0. In this experiment, NO3- fertilization effect was discovered.     

Estimation and comparison of night-time OH levels in the UK urban atmosphere using two di erent analysis methods

Night-time OH levels have been determined for UK urban surface environments using two methods, the decay and steady state approximation methods. Measurement data from the UK National Environmental Technology Centre archive for four urban sites (Bristol, Harwell, London Eltham and Edinburgh) over the time period of 1996 to 2000 have been used in this study. Three reactive alkenes, namely isoprene, 1,3-butadiene and trans-2-pentene were chosen for the calculation of OH levels by the decay method. Hourly measurements of NO, NO2, O3, CO and 20 VOCs were used to determine night-time OH level using the steady state approximation method. Our results showed that the night-time OH levels were in the range of 1 105–1 106 molecules/cm3 at these four urban sites in the UK. The application of a t-test of these analyses indicated that except Bristol, there was no significant di erence between the OH levels found from the decay and steady state approximation methods. Night-time levels of the OH radical appeared to peak in summer and spring time tracking the night-time O3 levels which also passed through a maximum at this time.     

Determination of hydroxyl radicals with salicylic acid in aqueous nitrate and nitrite solutions

The qualitative and quantitative analyses of reactive oxygen species are essential to determine their steady-state concentration and related reaction mechanisms in environmental aquatic systems. In this study, salicylic acid was employed as an innovative molecular probe of hydroxyl radical(OH) generated in aqueous nitrate and nitrite solutions through photochemical reactions. Kinetic studies showed that the steady-state concentrations of OH in aqueous NO3^-(10 mmol/L, pH=5) and NO2^ (10 mmol/L, pH=5) solutions under ultraviolet irradiation were at a same magnitude, 10v-15 mol/L. Apparent quantum yields of OH at 313 nm were measured as 0.011 and 0.07 for NO3^- and NO2^ respectively, all comparable to the results of previous studies.     

Characterization of aliphatic hydrocarbons in deep subsurface soils near the outskirts of Beijing, China

Thirty-nine deep subsurface soils( 150—180 cm depth) near the outskirts of Beijing were investagated. The concentrations including n-alkanes from C13 to C36, pristane and phytane were in the range of 0.60 to 170.10μg/g, with a median value of 4.26. Carbon preference index values for n-alkanes ranged from 1.08 to 2.98, with a median value of 1.48. The percentage contribution of “wax” nalkanes was in the range of 6.03%--46.22%. A predominance of odd/even carbon n-alkanes and unresolved complex mixtures with different shapes and ranges were frequently observed. Factor analysis reduced the data set into three principal components and confirming contributions from low ( 19.58% ), medium ( 20.49% ) molecular weight species and long-chain n-alkanes (43.41% ), respectively.Molecular biomarkers such as pristane, phytane, hopanes and steranes were detected. Based on the principal component analysis, the concentration profiles and molecular markers, it was found that the aliphatic hydrocarbons were from both biogenic and anthropogenic sources.     

Spatial variations of aluminum species in drinking water supplies in Xi’an studied applying geographic information system

This article aimed to investigate the variation of aluminum species and the effects of coagulant type and water quality on aluminum speciation in drinking water.Statistical analysis showed that the concentration of total aluminum(AlT) of drinking water in Xi'an ranged from 0.051 to 0.417 mg/L and the concentration of AlT in about 24.7% studied samples was higher than the currently recommended value(0.2 mg/L).The areas fed by surface water plants had a larger portion(39.4%) of samples over the recommended value.In drinking water treated by alum coagulant,the average concentration of monomeric aluminum(Ala) was higher than that in water treated by poly aluminum chlorine(PACl) and poly aluminum ferric chloride(PAFC).The average concentrations of polynuclear aluminum(Alb) and colloidal/suspended aluminum(Alc) in the drinking water treated by alum were lower than those in water treated by PACl and PAFC.There was a notable decrease in AlT along with the delivery pipeline away from the plants,with an average decline of about 36 μg/(L·km).Besides coagulant type,water quality also could afflect aluminum speciation.In drinking water without orthophosphate,the concentrations of Ala and AlT were positively correlated with pH;while,in drinking water with orthophosphate,the concentrations of Ala and AlT were negatively correlated with pH.The addition of orthophosphate salts in the drinking water treatment process would be an effective method for aluminum control in pH range 6.5-8.2.     

Identification of sources of lead in the atmosphere by chemical speciation using X-ray absorption near-edge structure (XANES) spectroscopy

Sources of Pb pollution in the local atmosphere together with Pb species, major ions, and heavy metal concentrations in a size-fractionated aerosol sample from Higashi-Hiroshima(Japan) have been determined by X-ray absorption near-edge structure(XANES) spectroscopy, ion chromatography, and ICP-MS/AES, respectively. About 80% of total Pb was concentrated in fine aerosol particles. Lead species in the coarse aerosol particles were PbC2O4, 2PbCO3·Pb(OH)2, and Pb(NO3)2, whereas Pb species in the fine aerosol particles were PbC2O4, PbSO4, and Pb(NO3)2. Chemical speciation and abundance data suggested that the source of Pb in the fine aerosol particles was different from that of the coarse ones. The dominant sources of Pb in the fine aerosol particles were judged to be fly ash from a municipal solid waste incinerator and heavy oil combustion. For the coarse aerosol particles, road dust was considered to be the main Pb source. In addition to Pb species, elemental concentrations in the aerosols were also determined. The results suggested that Pb species in size-fractionated aerosols can be used to identify the origin of aerosol particles in the atmosphere as an alternative to Pb isotope ratio measurement.     

Comparison of different phosphate species adsorption by ferric and alum water treatment residuals

As safe byproducts of drinking water treatment processes,ferric and alum water treatment residuals(FARs) have the potential to be new phosphate(P) immobilization materials.In this study,batch experiments were conducted to investigate and compare the adsorption characteristics of three P species by FARs.The results showed that the kinetic processes of different P species’ adsorption by FARs could be described by a pseudo second-order model.The ranking list of the initial adsorption rates with respect to different phosphates was pyrophosphate,phytate,orthophosphate,hexametaphosphate and glycerophosphate.Of the six models considered,the two-site Langmuir model most effectively described the adsorption characteristics of the various P species.Upon fitting the results,the maximum adsorption capacities were determined to be 40.24 mg/g for phytate,18.04 mg/g for pyrophosphate,17.14 mg/g for orthophosphate,15.86 mg/g for hexametaphosphate and 10.81 mg/g for glycerophosphate.In addition,the adsorption processes of the different P species were spontaneous endothermic processes and were favored at lower pH values.The pH dependency was found to be especially true for orthophosphate,where the adsorption capacity decreased by 1.22 mg/g with an increase in pH from 5 to 9.Fractionation of the adsorbed P species from the FARs demonstrated that Al-P and Fe-P were the dominating forms,constituting approximately 80%-90% of the total P fractions,which indicated that the adsorbed P species had a low leaching risk and could stably exist in the FARs.Therefore,the FARs could be effective in controlling pollution in water caused by different P species.     

Arsenic species in electronic cigarettes: Determination and potential health risk

Human exposure to contaminants from electronic cigarettes(e-cigarettes) and the associated health effects are poorly understood.There has been no report on the speciation of arsenic in e-liquid(solution used for e-cigarettes) and aerosols.We report here determination of arsenic species in e-liquids and aerosols generated from vaping the e-liquid.Seventeen e-liquid samples of major brands,purchased from local and online stores in Canada and China,were analyzed for arsenic species using high-performance liquid chromatography and inductively coupled plasma mass spectrometry.Aerosols condensed from vaping the eliquids were also analyzed and compared for arsenic species.Six arsenic species were detected,including inorganic arsenate(iAs~Ⅴ),arsenite(iAs~Ⅲ),monomethylarsonic acid(MMA),and three new arsenic species not reported previously.In e-liquids,iAs~Ⅲ was detected in 59%,iAs~Ⅴ in 94%,and MMA in 47% of the samples.In the condensate of aerosols from vaping the e-liquids,iAs~Ⅲ was detected in 100%,iAsv in 88%,and MMA in 13% of the samples.Inorganic arsenic species were predominant in e-liquids and aerosols of e-cigarettes.The concentration of iAs~Ⅲ in the condensate of aerosols(median 3.27 μg/kg) was significantly higher than that in the e-liquid(median 1.08 μg/kg) samples.The concentration of inorganic arsenic in the vaping air was approximately 3.4 μg/m~3,which approaches to the permissible exposure limit(10 μg/m~3) set by the United States Occupational Safety and Health Administration(OSHA).According to the Environmental Protection Agency's unit risk factor(4.3 × 10~(-3) per μg/m~3) for inhalation exposure to inorganic arsenic in the air,the estimated excess lung cancer risk from lifetime exposure to inorganic arsenic in the ecigarette vaping air(3.4 μg/m~3),assuming e-cigarette vaping at 1% of the time,is as high as1.5 × 10~(-4).These results raise health concerns over the exposure to arsenic from electronic cigarettes.     

Release kinetics of vanadium from vanadium(Ⅲ, Ⅳ and Ⅴ) oxides: Effect of pH,temperature and oxide dose

Batch experiments were performed to derive the rate laws for the proton-promoted dissolution of the main vanadium(Ⅲ, Ⅳ and Ⅴ) oxides at pH 3.1–10.0. The release rates of vanadium are closely related to the aqueous pH, and several obvious differences were observed in the release behavior of vanadium from the dissolution of V_2O_5 and vanadium(Ⅲ, Ⅳ) oxides. In the first 2 hr, the release rates of vanadium from V_2O_3 were r = 1.14·([H~+])~0.269 at pH 3.0–6.0 and r = 0.016·([H~+])~(-0.048) at pH 6.0–10.0; the release rates from VO_2 were r = 0.362·([H~+])~0.129 at pH 3.0–6.0 and r = 0.017·([H~+])~(-0.097) at pH 6.0–10.0; and the release rates from V_2O_5 were r = 0.131·([H~+])-~(0.104) at pH 3.1–10.0. The release rates of vanadium from the three oxides increased with increasing temperature, and the effect of temperature was different at pH 3.8, pH 6.0 and pH 7.7. The activation energies of vanadium(Ⅲ, Ⅳ and Ⅴ) oxides(33.4–87.5 kJ/mol) were determined at pH 3.8, pH 6.0 and pH 7.7, showing that the release of vanadium from dissolution of vanadium oxides follows a surface-controlled reaction mechanism. The release rates of vanadium increased with increasing vanadium oxides dose,albeit not proportionally. This study, as part of a broader study of the release behavior of vanadium, can help to elucidate the pollution problem of vanadium and to clarify the fate of vanadium in the environment.     

Influence of environmental factors on arsenic accumulation and biotransformation using the aquatic plant species Hydrilla verticillata

Hydrilla verticillata(waterthyme) has been successfully used for phytoremediation in arsenic(As) contaminated water.To evaluate the effects of environmental factors on phytoremediation,this study conducted a series of orthogonal design experiments to determine optimal conditions,including phosphorus(P),nitrogen(N),and arsenate(As(Ⅴ))concentrations and initial pH levels,for As accumulation and biotransformation using this aquatic plant species,while also analyzing As species transformation in culture media after 96-hr exposure.Analysis of variance and the signal-to-noise ratio were used to identify both the effects of these environmental factors and their optimal conditions for this purpose.Results indicated that both N and P significantly impacted accumulation,and N was essential in As species transformation.High N and intermediate P levels were critical to As accumulation and biotransformation by H.verticillata,while high N and low P levels were beneficial to As species transformation in culture media.The highest total arsenic accumulation was(197.2±17.4) μg/g dry weight when As(V) was at level 3(375μg/L),N at level 2(4 mg/L),P at level 1(0.02 mg/L),and pH at level 2(7).Although H.verticillata is highly efficient in removing As(Ⅴ) from aquatic environments,its use could be potentially harmful to both humans and the natural environment due to its release of highly toxic arsenite.For cost-effective and ecofriendly phytoremediation of As-contaminated water,both N and P are helpful in regulating As accumulation and transformation in plants.     

Characterization of particle number size distribution and new particle formation in Southern China

Knowledge of particle number size distribution(PND) and new particle formation(NPF)events in Southern China is essential for mitigation strategies related to submicron particles and their effects on regional air quality,haze,and human health.In this study,seven field measurement campaigns were conducted from December 2013 to May 2015 using a scanning mobility particle sizer(SMPS) at four sites in Southern China,including three urban sites and one background site.Particles were measured in the size range of15-515 nm,and the median particle number concentrations(PNCs) were found to vary in the range of 0.3× 10~4-2.2 × 10~4 cn~(-3) at the urban sites and were approximately 0.2 × 10~4 cm~(-3) at the background site.The peak diameters at the different sites varied largely from 22 to 102 nm.The PNCs in the Aitken mode(25-100 nm) at the urban sites were up to 10 times higher than they were at the background site,indicating large primary emissions from traffic at the urban sites.The diurnal variations of PNCs were significantly influenced by both rush hour traffic at the urban sites and NPF events.The frequencies of NPF events at the different sites were0%-30%,with the highest frequency occurring at an urban site during autumn.With higher SO_2 concentrations and higher ambient temperatures being necessary,NPF at the urban site was found to be more influenced by atmospheric oxidizing capability,while NPF at the background site was limited by the condensation sink.This study provides a unique dataset of particle number and size information in various environments in Southern China,which can help understand the sources,formation,and the climate forcing of aerosols in this quickly developing region,as well as help constrain and validate NPF modeling.     

TiO2 nanotubes as solid-phase extraction adsorbent for the determination of polycyclic aromatic hydrocarbons in environmental water samples

An analytical method based on TiO2 nanotubes solid-phase extraction (SPE) combined with gas chromatography (GC) was established for the analysis of seven polycyclic aromatic hydrocarbons (PAHs): acenaphtylene, acenaphthene, anthracene, fluorene, phenanthrene, fluoranthene and pyrene. Factors a ecting the extraction e ciency including the eluent type and its volume, adsorbent amount, sample volume, sample pH and sample flow rate were optimized. The characteristic data of analytical performance were determined to investigate the sensitivity and precision of the method. Under the optimized extraction conditions, the method showed good linearity in the range of 0.01–0.8 g/mL, repeatability of the extraction (RSD were between 6.7% and 13.5%, n = 5) and satisfactory detection limits (0.017–0.059 ng/mL). The developed method was successfully applied to the analysis of surface water (tap, river and dam) samples. The recoveries of PAHs spiked in environmental water samples ranged from 90% to 100%. All the results indicated the potential application of titanate nanotubes as solid-phase extraction adsorbents to pre-treat water samples.     

Characteristics of isothermal adsorption and desorption of aluminum ion to/from humic acids

The adsorption and desorption characteristics of Al3+ to/from humic acids at di erent pH, ionic strength, and temperature were studied by the C-25 glucosan-gel chromatography method. The results showed that the maximum adsorption amount (Qmax) and adsorption constant (k) increased, whereas, the absolute value of standard thermodynamic molar free energy change ( G0 m) decreased with the increase of pH at constant ionic strength and temperature. With ionic strength increasing from 0 to 0.15 mol/L, Qmax and k increased and the absolute value of G0 m decreased at constant pH and temperature. High temperature was unfavorable for the adsorption reaction, as indicated by the dramatic decrease of Qmax and the absolute value of G0 m with an increase in temperature. The standard thermodynamic molar free energy change ( G0 m) and the standard thermodynamic enthalpy change ( H0m ) of the adsorption reaction were both negative, suggesting that adsorption reaction was spontaneous and exothermic. The desorption rate of HA-Al3+ complex accelerated with the decrease of pH, and a significant linear relationship could be obtained between pH and the desorption rates of Al3+ from humic acids. These results demonstrated that the Al3+ adsorption reaction was a “biphase” reaction, and adsorption occurred at both the interior and exterior adsorption sites of humic acids.     

Catalytic combustion of soot over ceria-zinc mixed oxides catalysts supported onto cordierite

Modified substrates as outer heterogeneous catalysts was employed to reduce the soot generated from incomplete combustion of diesel or diesel/biodiesel blends, a process that harms the environment and public health. The unique storage properties of ceria(CeO2) makes it one of the most efficient catalysts available to date. Here, we proposed that ceria-based catalysts can lower the temperature at which soot combustion occurs; more specifically, from 610℃ to values included in the diesel exhausts operation range(300–450℃). The sol-gel method was used to synthesize mixed oxide-based catalysts(CeO2:ZnO); the resulting catalysts were deposited onto cordierite substrates. In addition, the morphological and structural properties of the material were evaluated by XRD, BET, TPR-H2, and SEM. Thermogravimetric(TG/DTA) analysis revealed that the presence of the catalyst decreased the soot combustion temperature by 200℃ on average, indicating that the oxygen species arise at low temperatures in this situation, promoting highly reactive oxidation reactions. Comparative analysis of soot emission by diffuse reflectance spectroscopy(DRS) showed that catalyst-impregnated cordierite samples efficiently oxidized soot in a diesel/biodiesel stationary motor: soot emission decreased by more than 70%.