Arsenic mobilization from soils in the presence of herbicides

Arsenic(As) mobilization in soils is a fundamental step controlling its transport and fate,especially in the presence of the co-existing components. In this study, the effect of two commonly used herbicides, glyphosate(PMG) and dicamba, and two competing ions including phosphate and humic acid, on As desorption and release was investigated using batch and column experiments. The batch kinetics results showed that As desorption in the presence of competing factors conformed to the pseudo-second order kinetics at pH range of 5–9. The impact of phosphate on desorption was greatest, followed by PMG. The competitive effect of dicamba and humic acid was at the same level with electrolyte solution. In situ flow cell ATR-FTIR analysis was performed to explore the mechanism of phosphate and PMG impact on As mobilization. The results showed that PMG promoted As(Ⅲ) desorption by competiting for available adsorption sites with no change in As(Ⅲ)complexing structure. On the other hand, phophate changed As(Ⅲ) surface complexes from bidentate to monodentate structures, exhibiting the most siginficant effect on As(Ⅲ)desorption. As(Ⅴ) surface complexes remained unchanged in the presence of PMG and phosphate, implying that the competitive effect for As(Ⅴ) desorption was primarily determined by the available adsorption sites. Long-term(10 days) soil column experiments suggested that the effect of humic acid on As mobilization became pronounced from 3 days(18 PVs). The insights of this study help us understand the transport and fate of As due to herbicides application.     

Nano-sized Fe2O3/Fe3O4 facilitate anaerobic transformation of hexavalent chromium in soil–water systems

The purpose of this study is to investigate the effects of nano-sized or submicro Fe_2O_3/Fe_3O_4 on the bioreduction of hexavalent chromium(Cr(VI)) and to evaluate the effects of nano-sized Fe_2O_3/Fe_3O_4 on the microbial communities from the anaerobic flooding soil.The results indicated that the net decreases upon Cr(VI) concentration from biotic soil samples amended with nano-sized Fe_2O_3(317.1 ± 2.1 mg/L) and Fe_3O_4(324.0 ± 22.2 mg/L) within21 days,which were approximately 2-fold of Cr(VI) concentration released from blank control assays(117.1 ± 5.6 mg/L).Furthermore,the results of denaturing gradient gel electrophoresis(DGGE) and high-throughput sequencing indicated a greater variety of microbes within the microbial community in amendments with nano-sized Fe_2O_3/Fe_3O_4 than the control assays.Especially,Proteobacteria occupied a predominant status on the phylum level within the indigenous microbial communities from chromium-contaminated soils.Besides,some partial decrease of soluble Cr(VI) in abiotic nano-sized Fe_2O_3/Fe_3O_4 amendments was responsible for the adsorption of nano-sized Fe_2O_3/Fe_3O_4 to soluble Cr(VI).Hence,the presence of nano-sized Fe_2O_3/Fe_3O_4 could largely facilitate the mobilization and biotransformation of Cr(VI) from flooding soils by adsorption and bio-mediated processes.     

Preparation and evaluation of Zr-β-FeOOH for efficient arsenic removal

A Zr-β-FeOOH adsorbent for both As(V) and As(III) removal was prepared by a chemical co-precipitation method.Compared with β-FeOOH,the addition of Zr enhanced the adsorption capacities for As(V) and As(III),especially As(III).The maximum adsorption capacities for As(III) and As(V) were 120 and 60mg/g respectively at pH 7.0,much higher than for many reported adsorbents.The adsorption data accorded with Freundlich isotherms.At neutral pH,for As(V),adsorption equilibrium was approached after 3 hr,while for As(III),adsorption equilibrium was approached after 5 hr.Kinetic data fitted well to the pseudo second-order reaction model.As(V) elimination was favored at acidic pH,whereas the adsorption of As(III) by Zr-β-FeOOH was found to be effective over a wide pH range of 4-10.Competitive anions hindered the adsorption according to the sequence:phosphate > silicate > bicarbonate > sulfate > nitrate,while Ca2+ and Mg2+ increased the removal of As(III) and As(V) slightly.The high adsorption capability and good performance in other aspects make Zr-β-FeOOH a potentially attractive adsorbent for the removal of both As(III) and As(V) from water.     

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.     

Effect of ionic strength on adsorption of As（Ⅲ） and As（Ⅴ） on variable charge soils

The study was to investigate the adsorption behavior of arsenite (As(Ⅲ)) and arsenate (As(Ⅴ)) on two variable charge soils, i.e., Haplic Acrisol and Rhodic Ferralsol at different ionic strengths and pH with batch methods. Results indicated that the amount of As(Ⅲ) adsorbed by these two soils increased with increasing solution pH, whereas it decreased with increasing ionic strength under the acidic condition. This suggested that As(Ⅲ) was mainly adsorbed on soil positive charge sites through electrostatic attraction under the acidic condition. Moreover, intersects of As(Ⅴ) adsorption-pH curves at different ionic strengths (a characteristic pH) are obtained for both soils. It was noted that above this pH, the adsorption of As(Ⅴ) was increased with increasing ionic strength, whereas below it the reverse trend was true. Precisely the intersect pH was 3.6 for Haplic Acrisol and 4.5 for Rhodic Ferralsol, which was near the values of PZSE (soil point of zero salt effect) of these soils. The effects of ionic strength and pH on arsenate adsorption by these soils were interpreted by the adsorption model. The results of zeta potential suggested that the potential in adsorption plane becomes less negative with increasing ionic strength above soil PZSE and decreases with increasing ionic strength below soil PZSE. These results further supported the hypothesis of the adsorption model that the potential in the adsorption plane changes with ionic strength with an opposite trend to surface charge of the soils. Therefore, the change of the potential in the adsorption plane was mainly responsible for the change of arsenate adsorption induced by ionic strength on variable charge soils.     

Effects of phosphate on the adsorption of glyphosate on three different types of Chinese soils

Glyphosate （GPS） is a non-selective, post-mergence herbicide that is widely used throughout the world. Due to the similar molecular structures of glyphosate and phosphate, adsorption of glyphosate on soil is easily affected by coexisting phosphate, especially when phosphate is applied at a significant rate in farmland. This paper studied the effects of phosphate on the adsorption of glyphosate on three different types of Chinese soils including two variable charge soils and one permanent charge soil. The results indicated that Freundlich equations used to simulate glyphosate adsorption isotherms gave high correlation coefficients（0.990-0.998） with K values of 2751, 2451 and 166 for the zhuanhong soil（ZH soil, Laterite）, red soil（ RS, Udic Ferrisol） and Wushan paddy soil（WS soil, Anthrosol）, respectively. The more the soil iron and aluminum oxides and clay contained, the more glyphosate adsorbed. The presence of phosphate significantly decreased the adsorption of glyphosate to the soils by competing with glyphosate for adsorption sites of soils. Meanwhile, the effects of phosphate on adsorption of glyphosate on the two variable charge soils were more significant than that on the permanent charge soil. When phosphate and glyphosate were added in the soils in different orders, the adsorption quantities of glyphosate on the soils were different, which followed GPS-soil 〉 GPS-P-soil = GPS-Soil-P 〉 P-soil-GPS, meaning a complex interaction occurred among glyphosate, phosphate and the soils.     

Adsorption and recovery of phosphate from water by amine fiber, effects of co-existing ions and column filtration

A weak-base adsorption fiber, acrylic amine fiber (AAF), was prepared for removal and recovery of phosphate from water. The adsorption properties of the AAF for phosphate and effects of co-existing ions were investigated using batch and column filtration experiments, scanning electron microscope, and Fourier transform infrared techniques. Experimental results showed that AAF had a high phosphate adsorption capacity of 119?mg/g at pH?7.0. The effects of calcium, sulfate, carbonate, nitrate, and fluoride showed that sulfate and calcium inhibited phosphate adsorption. However, AAF showed higher binding affinity toward phosphate than sulfate. Column filtration results showed that AAF could filter 1420 bed volumes of tap water containing 1.0?mg-P/L of phosphate. The saturated AAF could be regenerated using 0.5?mol/L hydrochloric acid solution and reused. After desorption, phosphate was recovered through precipitation of hydroxyapatite (Ca₅(PO₄)₃OH). The easy of regeneration, good adsorption performance, and the fiber morphology of AAF make it an attractive alternative for phosphate recovery from multiple water sources.     

Preparation of Fe–Co based MOF-74 and its effective adsorption of arsenic from aqueous solution

To obtain a cost-effective adsorbent for the removal of arsenic in water,a novel nanostructured Fe–Co based metal organic framework(MOF-74)adsorbent was successfully prepared via a simple solvothermal method.The adsorption experiments showed that the optimal molar ratio of Fe/Co in the adsorbent was 2:1.The Fe_2Co_1MOF-74 was characterized by various techniques and the results showed that the nanoparticle diameter ranged from60 to 80 nm and the specific surface area was 147.82 m~2/g.The isotherm and kinetic parameters of arsenic removal on Fe_2Co_1MOF-74 were well-fitted by the Langmuir and pseudo-second-order models.The maximum adsorption capacities toward As(III)and As(V)were 266.52 and 292.29 mg/g,respectively.The presence of sulfate,carbonate and humic acid had no obvious effect on arsenic adsorption.However,coexisting phosphate significantly hindered the removal of arsenic,especially at high concentrations(10 mmol/L).Electrostatic interaction and hydroxyl and metal–oxygen groups played important roles in the adsorption of arsenic.Furthermore,the prepared adsorbent had stable adsorption ability after regeneration and when used in a real-water matrix.The excellent adsorption performance of Fe_2Co_1MOF-74 material makes it a potentially promising adsorbent for the removal of arsenic.     

Enhanced removal of I− on hierarchically structured layered double hydroxides by in suit growth of Cu/Cu2O

To further improve the removal ability of layered double hydroxide(LDH) for iodide(I~-) anions from wastewater, we prepared hierarchically porous Cu_5Mg_(10)Al_5-LDH and used as a matrix for in suit growth of Cu/Cu_2O on its surface, forming Cu/Cu_2O-LDH, which was characterized and applied as an adsorbent.Results displayed high I~-saturation uptake capability(137.8 mg/g) of Cu/Cu_2O-LDH compared with Cu_5Mg_(10)Al_5-LDH(26.4 mg/g) even thermal activated LDH(76.1 mg/g).Thermodynamic analysis showed that the reaction between I~-anions and Cu/Cu_2O-LDH is a spontaneous and exothermic.Uptake kinetics analysis exhibited that adsorption equilibrium can be reached after 265 min.Additionally, the adsorbent showed satisfactory selectivity in the presence of competitive anions(e.g., SO_4~(2-)), and could achieve good adsorption performance in a wide pH range of 3–8.A cooperative adsorption mechanism was proposed on the basis of the following two aspects:(1) ion exchange between iodide and interlayer anions;(2) the adsorption performance of Cu, Cu(Ⅱ) and Cu_2O for I~-.Meanwhile, the difference between the adsorption mechanism of Cu/Cu_2O-LDH, Cu_5Mg_(10)Al_5-LDH and Cu_5Mg_(10)Al_5-CLDH adsorbents was also elaborated and verified.     

Influence of the structure and composition of Fe–Mn binary oxides on rGO on As(Ⅲ) removal from aquifers

Fe–Mn binary oxide(FMBO) possesses high efficiency for As(Ⅲ) abatement based on the good adsorption affinity of iron oxide and the oxidizing capacity of Mn(Ⅳ), and the composition and structure of FMBO play important roles in this process.To compare the removal performance and determine the optimum formula for FMBO, magnetic graphene oxide(MRGO)–FMBO and MRGO–MnO_2 were synthesized with MRGO as a carrier to improve the dispersity of the adsorbents in aquifers and achieve magnetic recycling.Results indicated that MRGO–FMBO had higher As(Ⅲ) removal than that of MRGO–MnO_2,although the ratios of Fe and Mn were similar, because the binary oxide of Fe and Mn facilitated electron transfer from Mn(Ⅳ) to As(Ⅲ), while the separation of Mn and Fe on MRGO–MnO_2 restricted the process.The optimal stoichiometry x for MRGO–FMBO(Mn_xFe_(3-x)O_4) was 0.46, and an extraordinary adsorption capacity of 24.38 mg/g for As(Ⅲ) was achieved.MRGO–FMBO showed stable dispersive properties in aquifers, and exhibited excellent practicability and reusability, with a saturation magnetization of 7.6 emu/g and high conservation of magnetic properties after 5 cycles of regeneration and reuse.In addition, the presence of coexisting ions would not restrict the practical application of MRGO–FMBO in groundwater remediation.The redox reactions of As(Ⅲ) and Mn(Ⅳ) on MRGO–FMBO were also described.The deprotonated aqueous As(Ⅲ) on the surface of MRGO–FMBO transferred electrons to Mn(Ⅳ), and the formed As(Ⅴ) oxyanions were bound to ferric oxide as inner-sphere complexes by coordinating their "–OH" groups with Mn(Ⅳ)oxides at the surface of MRGO–FMBO.This work could provide new insights into highperformance removal of As(Ⅲ) in aquifers.     

Effect of competing solutes on arsenic(V) adsorption using iron and aluminum oxides

The study focused on the effect of several typical competing solutes on removal of arsenic with Fe2O3 and Al2O3. The test results indicate that chloride, nitrate and sulfate did not have detectable effects, and that selenium(IV) (Se(IV)) and vanadium(V) (V(V)) show slight effects on the adsorption of As(V) with Fe2O3. The results also showed that adsorption of As(V) on Al2O3 was not affected by chloride and nitrate anions, but slightly by Se(IV) and V(V) ions. Unlike the adsorption of As(V) with Fe2O3, that with Fe2O3 was affected by the presence of sulfate in water solutions. Both phosphate and silica have significant adverse effects on the adsorption of As(V) adsorption with Fe2O3 and Al2O3. Compared to the other tested anions, phosphate anion was found to be the most prominent solute affecting the As(V) adsorption with Fe2O3 and Al2O3. In general, Fe2O3 has a better performance than Al2O3 in removal of As(V) within a water environment where multi competing solutes are present.     

Removal of trace arsenic（V） and phosphate from water by a highly selective ligand exchange adsorbent

The ligand exchange adsorbent could be used to remove the toxic arsenic(V) and phosphate efficiently from water even in the presence of foreign anions and possible to apply in chemical industry.     

磁性吸附材料CuFe2O4吸附砷的性能

根据Cu(Ⅱ)和Fe(Ⅲ)都对砷有较强的亲和性,制备了同时含有Cu(Ⅱ)和Fe(Ⅲ)的、可用磁分离方法进行分离回收的磁性吸附材料CuFe₂O₄,并对其进行了表征及吸附砷的性能研究.结果表明,该吸附剂对砷的吸附能力与溶液pH有关,在弱酸性及中性条件下,吸附砷的能力最强,而对As(V)的吸附能力比对As(Ⅲ)更强些,在平衡浓度为10μg/L时,其吸附容量可达10mg/g左右,可以很容易地将水中浓度为1～20mg/L的As(V)降到10μg/L以下.实验考察了几种无机阴离子对吸附砷的影响,表明较高浓度(砷浓度的20倍)的硫酸盐对As(Ⅲ)和As(V)的吸附均有一定影响,盐酸盐及磷酸盐则影响不明显;负载的As(V)可较容易地用0.1mol/L NaOH洗脱下来,使吸附剂再生,而As(Ⅲ)则难以洗脱,这与2种价态砷的吸附机理不同有关.     

铝改性粉煤灰漂珠吸附水溶液中砷的性能研究

采用湿法与干法相结合的方法合成铝改性粉煤灰漂珠环境材料,借助静态吸附实验研究吸附剂量、pH值、离子强度、共存离子、反应时间和温度对其吸附水溶液中砷性能的影响,并进行吸附等温线和动力学拟合.结果表明:铝改性粉煤灰漂珠吸附水中As(V)的最佳pH值范围为中性偏酸;混合离子和H2PO4-对As(V)的吸附影响较大,CO32-次之;离子强度对As(V)吸附的影响不明显;在温度298K、吸附剂量2.5g/L和反应时间24h的条件下,最大吸附容量约5000μg/g;吸附等温线符合Langmuir单层吸附模型;动力学过程符合准二级动力学模型.     

A laboratory scale study on arsenic（Ⅴ） removal from aqueous medium using calcined bauxite ore

The present work deals with the As（Ⅴ） removal from an aqueous medium by calcined refractory grade bauxite （CRB） as a function of solution pH, time, As（Ⅴ） concentration and temperature. The residual As（Ⅴ） was lowered from 2 mg/L to below 0.01 mg/L in the optimum pH range 4.0-7.0 using a 5 g/L CRB within 3 h contact time. The adsorption data fits well with Langmuir isotherm and yielded Langmuir monolayer capacity of 1.78 mg As（Ⅴ）/g of CRB at pH 7.0. Presence of anions such as silicate and phosphate decreased As（Ⅴ） adsorption efficiency. An increase temperature resulted a decrease in the amount of As（Ⅴ） adsorbed by 6%. The continuous fixed bed column study showed that at the adsorbent bed depth of 30 cm and residence time of 168 min, the CRB was capable of treating 340 bed volumes of As（V） spiked water （C0 = 2 mg/L） before breakthrough （Ce = 0.01 mg/L）. This solid adsorbent, although not reusable, can be considered for design of adsorption columns as an efficiency arsenic adsorption media.     

纳米结构Fe3O4/Y2O3磁性颗粒的制备、表征及磷吸附行为研究

采用共沉淀法制备了一种新型铁钇氧化物(Fe3O4/Y2O3)磁性吸附剂,并对其表面特性及磷吸附行为进行了初步研究.扫描电镜(SEM)与X-射线衍射仪(XRD)表征结果表明,此吸附剂具有纳米结构,初级粒子平均粒径为15.2nm.振动样品磁强计(VSM)测得比饱和磁化强度为38.7emu·g-1,磁性较强,可方便地实现固液分离.吸附剂的等电点为6.8.磷吸附实验表明,25℃时,Langmuir吸附等温线可较好地拟合Fe3O4/Y2O3对溶液中磷的吸附(R2=0.989),最大吸附量(pH=5.0)为60.6mg·g-1(以P计);吸附速率较快,在120min内可完成吸附容量的80%以上,符合准二级动力学模型(R2=0.997);溶液pH对Fe3O4/Y2O3吸附磷的影响较为明显,离子强度则影响不大;共存阴离子对吸附影响的大小顺序为Cl-相似文献   

Arsenic and chromate removal from water by iron chips-Effects of anions

The purpose of this study is to estimate the removal efficiency of As and Cr (VI) by one kind of industrial waste — iron chips, as well as to estimate the effects of typical inorganic anions (sulfate, phosphate, and nitrate), and typical organic anions (citrate, oxalate, and humate) on As or Cr (VI) removal. The results showed that 98% of As (V) and 92% of As (III) could be removed from aqueous phase by the iron chips within 60 min. Compared with As species, Cr (VI) was removed much more rapidly and efficiently with 97% of Cr (VI) being removed within 25 min. The removal efficiency for arsenic was in the order: As (III) (sulfate), As (III) (nitrate) or As (III), As (III) (humate), As (III) (oxalate), As (III) (citrate), As (III) (phosphate), and for chromate was in the order: Cr (VI) (sulfate), Cr (VI) (phosphate) or Cr (VI) (nitrate) or Cr (VI) (oxalate), Cr (VI), Cr (VI) (citrate), Cr (VI) (humate). In all the treatments, pH level increased with time except for As (III), the removal of which was either without anions or in the presence of humate or nitrate.     

磷酸盐对土壤吸附一硫代砷的影响

通过设计批实验和表征分析,探究不同浓度的磷酸盐影响下,一硫代砷酸盐（MTA）在土壤上的吸附特征和机理.结果发现,Elovich动力学模型和Langmuir等温吸附模型可较好地拟合MTA在土壤中的吸附过程,相关系数R²分别为0.983和0.994,表明土壤吸附MTA发生在局部位置,吸附过程主要以非均相扩散为主,拟合所得最大单层吸附量为254.214mg/kg.MTA与磷酸盐共存时,随着溶液中磷酸盐初始浓度的增大,土壤对MTA的平衡吸附量逐渐下降,对磷酸盐的吸附量逐渐增大;SEM-EDS结果表明无论是否添加磷酸盐,反应后的土壤表面都能检测到少量As,但添加磷酸盐条件下土壤表面的As含量则相对较低,证实磷酸盐的存在降低了土壤对MTA的吸附;XRD结果表明MTA能与土壤中的铁铝矿物发生络合反应生成内球络合物－[2Al （H₂AsO₄）₃]、≡Al₂O₂AsO （SH）和－[2Fe （H₂AsO₄）₃],而磷酸盐会与土壤表面的羟基形成内球络合物,导致土壤对MTA的吸附能力减弱.     

铁锰复合氧化物吸附去除五价锑性能研究

对比研究了铁锰复合氧化物(FMBO)、羟基氧化铁(FeOOH)和二氧化锰(MnO₂)吸附去除五价锑(Sb(V))的性能.结果表明FMBO对Sb(V)具有很好的吸附性能,在pH=5.0的条件下,最大吸附容量达到1.05 mmol·g^-1,略高于FeOOH (0.82 mmol·g^-1)及远高于MnO₂ (0.43 mmol·g^-1);采用Freundlich模型可以很好地描述Sb(V)在FMBO的吸附行为(R² = 0.98).就吸附动力学而言,假二级动力学可很好地描述Sb(V)在FMBO (R² = 0.93)和MnO₂表面的吸附过程(R² = 0.96),而Sb(V)在FeOOH表面的吸附过程可用Elovich模型拟合 (R² = 0.94).Sb(V)的吸附量随着pH值的升高而降低;磷酸盐显著抑制了Sb(V)的吸附,而硫酸盐和碳酸盐影响不大.提高体系离子强度可促进Sb(V)在FMBO表面的吸附,推断Sb(V)在FMBO表面形成内层络合物后被吸附去除.