The concentrated polyaluminum chloride with tailor-made distribution of Al species: synthesis, distribution and transformation of Al species, and coagulation performance.

Production of concentrated polyaluminum chloride (PACl) with the proper distribution of Al species (Ala, Alb, and Alc) is still a challenging issue on both industrial and laboratory scale. Hence, the effects of total aluminum concentration (AlT) at high levels, regular basicity values, and low base injection rates on the distribution of Al species in PACl solutions were investigated using quadratic models. The results confirmed the possibility to synthesize tailor-made PACl solutions with a specified value of either Ala, Alb, or Alc within the range of 22-51%, 4-51%, or 0.5-74%, respectively. For instance, in agreement with the predicted value, a PACl sample rich in both Alb (42,200 ppm) and AlT was produced by applying the basicity of 1.7, AlT of 9.07% as Al2O3, and basification rate of 0.48 ml/h. In addition, the maximum Alc could be acquired by exploiting the highest C, B, and Q values. This condition also minimized both Ala and Alb. The trends of Ala and Alc changes by the increment of basicity were concave and convex, respectively, while Alb showed either a decreasing trend or a concave pattern based on the values of injection rate and AlT. The Alb-rich PACl sample was effectively applied for turbidity removal from synthetic wastewater at various pHs and initial turbidities. At best, residual turbidity of about 1% was observed after the coagulation process. These findings can be constructive for the production and application of tailor-made PACl.

Characteristics and mechanisms of As(III) removal by potassium ferrate coupled with Al-based coagulants: Analysis of aluminum speciation distribution and transformation.

This study was carried out to investigate the enhanced removal of arsenite (As(III)) by potassium ferrate (K2FeO4) coupled with three Al-based coagulants, which focused innovatively on the distribution and transformation of hydrolyzed aluminum species as well as the mechanism of K2FeO4 interacted with different aluminum hydrolyzed polymers during As(III) removal. Results demonstrated that As(III) removal efficiency could be substantially elevated by K2FeO4 coupled with three Al-based coagulants treatment and the optimum As(III) removal effect was occurred at pH 6 with more than 97%. K2FeO4 showed a great effect on the distribution and transformation of aluminum hydrolyzed polymers and then coupled with a variety of aluminum species produced by the hydrolysis of aluminum coagulants for arsenic removal. During enhanced coagulation, arsenic removal by AlCl3 was main through the charge neutralization of in situ Al13 and the sweep flocculation of Al(OH)3, while PACl1 mainly depended on the charge neutralization of preformed Al13 and the bridging adsorption of Al13 aggregates, whereas PACl2 mainly relied on the sweep flocculation of Al(OH)3. This study provided a new insight into the distribution and transformation of aluminum species for the mechanism of As(III) removal by K2FeO4 coupled with different Al-based coagulants.

On the Nature of Extra-Framework Aluminum Species and Improved Catalytic Properties in Steamed Zeolites.

Steamed zeolites exhibit improved catalytic properties for hydrocarbon activation (alkane cracking and dehydrogenation). The nature of this practically important phenomenon has remained a mystery for the last six decades and was suggested to be related to the increased strength of zeolitic Bronsted acid sites after dealumination. We now utilize state-of-the-art infrared spectroscopy measurements and prove that during steaming, aluminum oxide clusters evolve (due to hydrolysis of Al out of framework positions with the following clustering) in the zeolitic micropores with properties very similar to (nano) facets of hydroxylated transition alumina surfaces. The Bronsted acidity of the zeolite does not increase and the total number of Bronsted acid sites decreases during steaming. O5Al(VI)-OH surface sites of alumina clusters dehydroxylate at elevated temperatures to form penta-coordinate Al1O5 sites that are capable of initiating alkane cracking by breaking the first C-H bond very effectively with much lower barriers (at lower temperatures) than for protolytic C-H bond activation, with the following reaction steps catalyzed by nearby zeolitic Bronsted acid sites. This explains the underlying mechanism behind the improved alkane cracking and alkane dehydrogenation activity of steamed zeolites: heterolytic C-H bond breaking occurs on Al-O sites of aluminum oxide clusters confined in zeolitic pores. Our findings explain the origin of enhanced activity of steamed zeolites at the molecular level and provide the missing understanding of the nature of extra-framework Al species formed in steamed/dealuminated zeolites.

Comparing ameliorative effects of biomass ash and alkaline slag on an acidic Ultisol under artificial Masson pine: A field experiment.

Forest soil acidification caused by acid deposition is a serious threat to the forest ecosystem. To investigate the liming effects of biomass ash (BA) and alkaline slag (AS) on the acidic topsoil and subsoil, a three-year field experiment under artificial Masson pine was conducted at Langxi, Anhui province in Southern China. The surface application of BA and AS significantly increased the soil pH, and thus decreased exchangeable acidity and active Al in the topsoil. Soil exchangeable Ca2+ and Mg2+ in topsoil were significantly increased by the surface application of BA and AS, while an increase in soil exchangeable K+ was only observed in BA treatments. The soil acidity and active Al in subsoil were decreased by the surface application of AS. Compared with the control, soluble monomeric and exchangeable Al in the subsoil was decreased by 38.0% and 29.4% after 3 years of AS surface application. There was a minimal effect on soluble monomeric and exchangeable Al after the application of BA. The soil exchangeable Ca2+ and Mg2+ in the subsoil increased respectively by 54% and 141% after surface application of 10 t ha-1 AS. The decrease of soil active Al and increase of base cations in subsoil were mainly attributed to the high migration capacity of base cations in AS. In conclusion, the effect of surface application of AS was superior to BA in ameliorating soil acidity and alleviating soil Al toxicity in the subsoil of this Ultisol.

Profiles of and variations in aluminum species in PAC-MC used for the removal of blooming microalgae.

Polyaluminum chloride modified clay (PAC-MC) is a safe and efficient red tide control agent that has been studied and applied worldwide. Although it is well known that the distribution of hydrolytic aluminum species in PAC affects its flocculation, little is known about the influence of particulars aluminum species on the microalgae removal efficiency of PAC-MC; this lack of knowledge creates a bottleneck in the development of more efficient MCs based on aluminum salts. The ferron method was used in this study to quantitatively analyze the distributions of and variations in different hydrolytic aluminum species during the process of microalgae removal by PAC-MC. The results showed that Ala, which made up 5%-20% of the total aluminum, and Alp, which made up 15%-55% of the total aluminum, significantly affected microalgae removal, with Pearson's correlation coefficients of 0.83 and 0.89, respectively. Most of the aluminum in the PAC-MC sank rapidly into the sediments, but the rate and velocity of settlement were affected by the dose of modified clay. The optimal dose of PAC-MC for precipitating microalgae was determined based on its aluminum profile. These results provide guidance for the precise application of PAC-MC in the control of harmful algal blooms.

Stray particles as the source of residuals in sand filtrate: Behavior of superfine powdered activated carbon particles in water treatment processes.

Although superfine powdered activated carbon has excellent adsorption properties, it is not used in conventional water treatment processes comprising coagulation-flocculation, sedimentation, and sand filtration (CSF) due to concerns about its residual in treated water. Here, we examined the production and fate of very fine carbon particles with lacking in charge neutralization as a source of the residual in sand filtrate after CSF treatment. Almost all of the carbon particles in the water were charge-neutralized by coagulation treatment with rapid mixing, but a very small amount (≤0.4% of the initial concentration) of very fine carbon particles with a lesser degree of charge neutralization were left behind in coagulation process. Such carbon particles, defined as stray carbon particles, were hardly removed by subsequent flocculation and sedimentation processes, and some of them remained in the sand filtrate. The concentration of residual carbon particles in the sand filtrate varied similarly with that of the stray carbon particles. The stray and residual carbon particles were similarly smaller than the particles before coagulation treatment, but the residual carbon particles had less charge neutralization than the stray carbon particles. The turbidity of water samples collected after sedimentation was not correlated with the residual carbon concentration in the sand filtrate, even though it is often used as an indicator of treatment performance with respect to the removal of suspended matter. Based on these findings, we suggest that reduction of the amount of stray particles should be a performance goal of the CSF treatment. Examining this concept further, we confirmed that the residence time distributions in the coagulation and flocculation reactors influenced the concentration of stray carbon particles and then the residual carbon particle concentration in sand filtrate, but found that the effect was dependent on coagulant type. A multi-chambered-reactor configuration lowered both the stray carbon particle concentration after coagulation treatment and the residual carbon particle concentration in sand filtrate compared with a single-chambered reactor configuration. When a normal basicity PACl that consisted mainly of monomeric Al species was used, the stray carbon particle concentration was decreased during coagulation process and then gradually decreased during subsequent flocculation process because the monomeric Al species were transformed to colloidal Al species via polymeric Al species. In contrast, when a high-basicity PACl that consisted mostly of colloidal Al species was used, coagulation treatment largely decreased the stray carbon particle concentration, which did not decrease further during subsequent flocculation process. These findings will be valuable for controlling residual carbon particles after the CSF treatment.

Effects of crop straw biochars on aluminum species in soil solution as related with the growth and yield of canola (Brassica napus L.) in an acidic Ultisol under field condition.

The toxicity of aluminum (Al) to plants in acidic soils depends on the Al species in soil solution. The effects of crop straw biochars on Al species in the soil solution, and canola growth and yield were investigated in this study. In a long-term field experiment, there were four treatments, which were a control, rice straw biochar (RSB), canola straw biochar (CSB), and peanut straw biochar (PSB). The soil solution was collected in situ, the Al species were identified, and the relationships between the concentration of phytotoxic Al and canola growth and yield were evaluated. The results showed that applying the three biochars resulted in significant decreases in the concentrations of total Al, monomeric Al, and monomeric inorganic Al (P < 0.05). The Al3+, Al-OH, and Al-SO4 proportions of the total Al also decreased. The abilities of the different biochars to reduce dissolved Al followed the order PSB > CSB > RSB, which was consistent with the alkalinity of these biochars. Application of the biochars significantly decreased the concentration of phytotoxic Al (Al3+ + Al-OH), which improved canola growth and increased the canola seed and straw yields. Plant height, leaf number per plant, area per leaf, chlorophyll content, and canola yield were negatively correlated with the Al3+ + Al-OH concentrations. Therefore, the results showed that crop straw biochars can be used to ameliorate soil acidity and alleviate Al toxicity in acidic soils, and that peanut straw biochar is the best amendment for acidic soils.

Toxicity of soil labile aluminum fractions and aluminum species in soil water extracts on the rhizosphere bacterial community of tall fescue.

Different forms of aluminum (Al) in soil can be toxic to plants and the bacterial community. In our previous study, the distribution and toxicity to plants of soil Al species and soil labile Al fractions were examined. However, the toxicity of different forms of Al on the bacterial community has not been completely studied. In this study, five soil samples (pH: 4.92, 6.17, 6.62, 6.70, 8.51) were collected from Lichuan, China. Tall fescue was planted in rhizosphere boxes with those soils for 120 days. The toxicity of soil Al species and soil labile Al fractions on the bacterial community of near-rhizosphere (NR) soils and far-rhizosphere (FR) soils were analyzed. The effect of different forms of Al on bacterial community between NR and FR soils was small, but the difference was obvious according to the different spatial distribution of samples. An individual bacterial community has eosinophilia, and most bacterial communities are tolerant of heavy metals (e.g., Cu, Zn, Cd). The toxicity of exchangeable Al has a strong effect on the bacterial community. Meanwhile, the toxicity of Al3+ to the bacterial community is strong. In this study, the key finding was that the toxicity of the Al-F- complex toward the bacterial community and plants was different. AlF2+, AlF2+, AlF3, and AlF4- are toxic for the bacterial community, and the correlation decreases with the addition of F-. This finding is of considerable significance to the treatment of acid-contaminated soil and the study of the tolerance mechanism of plants toward Al.

Speciation matching mechanisms between orthophosphate and aluminum species during advanced P removal process.

Aluminum (Al) salts are widely used as coagulants to remove phosphorus (P) in water treatment. However, the relationship between P and Al species and the underlying coagulation mechanisms is rarely studied. Currently, water eutrophication is a serious issue, and therefore advanced P removal is extremely necessary. Herein, the orthophosphate removal behavior of Al coagulants with various species distributions was investigated. The results showed that AlCl3·6H2O (AC) had a more pronounced P removal efficiency than polyaluminum chloride (PACl). Medium (Alb or Al13) and high polymeric species (Alc) played a more significant role in removing P than monomeric species (Ala). During coagulation, adsorption onto flocs was the dominant P removal mechanism, which could be categorized as multilayer adsorption. Although the adsorption kinetics showed that physical adsorption best described the adsorption mechanism for AC and PACl, it is worth noting that chemical adsorption also occurred during P removal by AC because of the formation of the AlPO4 precipitate. This could be because of the strong complex adsorption between the in situ Al13 species and P. Based on the excellent P removal performance, we believe these findings will have a large potential for application in advanced P removal in water treatment.

Distribution and phytotoxicity of soil labile aluminum fractions and aluminum species in soil water extracts and their effects on tall fescue.

Soil acidification can alter the biogeochemistry of ecosystems and adversely affect biota; however, there are still many debates about the toxicity of aluminum (Al) fractions and Al species in soil:water extracts to plants. In this study, five crude soils with different pH values (4.92-8.51) were collected, seeded with tall fescue and grown in rhizosphere boxes for 120 days. Then, soil properties, labile Al fractions and Al species in soil:water extracts were determined, and their toxicities to plants were analyzed. Our study showed that a stable exchangeable Al fraction (ExAl) pool exists and is supplied by other labile Al fractions. Dissolution of Al from adsorbed hydroxyl-Al fraction (HyAl) and organic-Al fraction (OrAl) may play important roles in soil Al toxicity, as HyAl and OrAl account for major parts of soil labile Al. Additionally, Al3+ and mononuclear hydroxyl-Al species in soil:water extracts have few effects to plants. Nevertheless, high negative correlations were found between Al-F- complexes and tall fescue biomass, indicating their toxicity in the natural soil environment. Thus, in many cases, Al3+ toxicity should not be emphasized because of its lower activity in soil water extracts. Moreover, toxicities of AlF3(aq) and AlF4- to plants should be emphasized, because they have been confirmed in soil water extracts in this study.

[Effect of Cr(â ¥) on Coagulation Process of Different Coagulants].

In this study, the effect of Cr(Ⅵ) in industrial wastewater on the coagulation of different aluminum forms under the influence of different particle concentrations was investigated. The coagulation efficiency was determined by examining the removal rate of turbidity, residual aluminum, and residual chromium and by using the residual pH value, zeta potential, and floc properties of the coagulation to reveal the coagulation mechanism of Cr(Ⅵ) in water under different turbidities. The experimental results show that under low turbidity conditions, Cr(Ⅵ) greatly influences the coagulation process of highly polymerized Alb, yet has no obvious effect on oligomeric Ala. Under high turbidity conditions, particulate matter will adsorb part of the Cr(Ⅵ) in high turbidity water, thus reducing its interaction with Alb. The main role Alb plays in coagulation is charge neutralization. It plays the same role in the stability of the particles and floc regeneration. The main role of Alc formed by hydrolysis of Ala is bridging effects and sweep flocculation, which plays an important role in floc production and strength factor. At the same time, the existence of Cr(Ⅵ) enhances the strength factor of Al13 flocs, but the consumption of some of the positive charge will lead to a reduction in the floc recovery factor.

Adsorption Neutralization Model and Floc Growth Kinetics Properties of Aluminum Coagulants Based on Sips and Boltzmann Equations.

Single-molecule aluminum salt AlCl3, medium polymerized polyaluminum chloride (PAC), and high polymerized polyaluminum chloride (HPAC) were prepared in a laboratory. The characteristics and coagulation properties of these prepared aluminum salts were investigated. The Langmuir, Freundlich, and Sips adsorption isotherms were first used to describe the adsorption neutralization process in coagulation, and the Boltzmann equation was used to fit the reaction kinetics of floc growth in flocculation. It was novel to find that the experimental data fitted well with the Sips and Boltzmann equation, and the significance of parameters in the equations was discussed simultaneously. Through the Sips equation, the adsorption neutralization reaction was proved to be spontaneous and the adsorption neutralization capacity was HPAC > PAC > AlCl3. Sips equation also indicated that the zeta potential of water samples would reach a limit with the increase of coagulant dosage, and the equilibrium zeta potential values were 30.25, 30.23, and 27.25 mV for AlCl3, PAC, and HPAC, respectively. The lower equilibrium zeta potential value of HPAC might be the reason why the water sample was not easy to achieve restabilization at a high coagulant dosage. Through the Boltzmann equation modeling, the maximum average floc size formed by AlCl3, PAC, and HPAC were 196.0, 188.0, and 203.6 µm, respectively, and the halfway time of reactions were 31.23, 17.08, and 9.55 min, respectively. The HPAC showed the strongest floc formation ability and the fastest floc growth rate in the flocculation process, which might be caused by the stronger adsorption and bridging functions of Alb and Alc contained in HPAC.

Influence of coagulation mechanisms on the residual aluminum--the roles of coagulant species and MW of organic matter.

Aluminum (Al) based coagulants are widely used in coagulation process to enhance the removal of turbidity and dissolved substances in the drinking water treatment. However, it raised more concerns due to the increase of residual aluminum in treated water, which can cause even more issues. In this study, the effects of organic matter molecular weight and coagulants species on the concentration and aluminum distribution in residual aluminum were investigated. The residual aluminum concentration decreases as the organic matter (OM) molecular weight (MW) rises. Charge neutralization mechanism was found to be the most important factor that determines the residual aluminum concentration directly. Basically, higher Ala percentage leads to lower residual Al concentration at acidic conditions, and Alb/Alc plays an important role in controlling the residual Al concentration at neutral and alkaline condition. The flocs structures formed by charge neutralization mechanism will be more compact for the mid and high MW OM, and fractal dimension (Df) was important to reflect the dissolved residual aluminum rather than the flocs size. The total dissolved residual aluminum concentration of Al13 and Al30 was mainly contributed by the fractions with low and/or high MW, especially by the fraction with MW range of 0-1 kDa.

Mechanisms of nC60 removal by the alum coagulation-flocculation-sedimentation process.

This study explored the mechanisms for nC60 removal in pure water and filtered saline wastewater by the alum coagulation-flocculation-sedimentation process through analyzing the hydrolyzed aluminum species and exploring the complexation of nC60 with aluminum hydroxide precipitates. Sweep flocculation (enmeshment and adsorption) with Alc is the most dominant mechanism contributing to the nC60 removal in pure water. In filtered saline wastewater, hetero-precipitation of Alb with nC60, colloids, and dissolved solids also contributes to the nC60 removal. Alkalinity affected the nC60 removal by changing the hydrolyzed aluminum species distributions. XPS, FTIR, and SEM evidences suggest that the enmeshment and adsorption of nC60 onto the aluminum hydroxide precipitates can be described as the inner-sphere complexation. Based on the above observations, conceptual models for nC60 removal by the alum coagulation-flocculation-sedimentation process in the different water matrices are proposed.

Caracterização da solução de solos do Bioma Cerrado sob pastagens / Characterization of the soil solution of brazilian Cerrado soils under pasture

O objetivo deste trabalho foi caracterizar a solução de solos e avaliar a especiação do Al em solos sob pastagens no Bioma Cerrado. Para a coleta das soluções dos solos utilizou-se tubo de PVC com a extremidade inferior acoplada a uma ponta porosa de cerâmica especial. Para quantificar as formas iônicas do alumínio, foram comparadas duas metodologias: método químico do “aluminon” e o método WHAM (modelo geoquímico de especiação). Os solos utilizados no presente estudo foram coletados às margens das rodovias GO – 060 e BR – 154, no trecho entre os municípios de Goiânia, GO e Barra do Garças, MT. Os resultados permitiram concluir que as espécies iônicas de alumínio predominantes variaram em função do tipo de solo, pH e concentração de NO3 - na solução do solo. Verificou-se também que as espécies iônicas mais abundantes foram: Al-M.O., Al3+ e Al(OH)4.

The aim of the present work was to characterize the soils solution and to examine Al's speciation in soilsunder pasture in Brazilian Cerrado region. The soils used in this study were collected in the spacebetween the towns of Goiânia, GO and Barra do Garças, MT, to the margins of GO ­ 060 and BR ­ 154highways. For the collection of soil solutions it was used a special equipment built with a PVC tubewhose inferior extremity was coupled to a porous tip of special ceramic. To quantify the aluminum ionicspecies, two methods were used: chemical method of " aluminon " and the method WHAM (geochemicalspeciation model). The results allowed to conclude that the predominant aluminum ionic species variedin function of soil type, pH and concentration of NO3- in the soil solution. More abundant Al's speciesin the soils were Al-M.O., Al3+ and Al(OH)4- , in this order.