北方典型内陆盆地高砷地下水的水化学特征及处理技术

我国高砷地下水分布广泛,是受砷污染最严重的地区之一,严重危害居民身体健康,开发经济、高效、环境友好的高砷地下水修复治理技术极具必要性。以大同盆地、呼包平原、河套平原和银川平原为代表性研究区域,归纳总结了北方干旱、半干旱地区典型高砷地下水区水化学特征。通常情况下,高砷地下水的pH值较高,共存阴离子(HCO^-3、SO^2-₄和Cl^-)浓度较大,溶解性有机碳含量较高,并且As(Ⅲ)为主要砷形态。开展了针对北方典型高砷地下水特定水化学环境特点(如pH值、共存阴阳离子以及溶解性有机物等)的改性天然菱铁矿除砷性能研究。结果表明,改性天然菱铁矿对溶液pH值具有良好的缓冲能力,其除砷性能基本不受pH值、共存阴离子、Ca/Mg阳离子及以腐殖酸为代表的溶解性有机物等典型高砷地下水水化学特征因素的影响,表明吸附剂对砷具有良好的吸附选择性。另外,改性天然菱铁矿对As(Ⅲ)的去除效果优于对As(V)的去除效果,因此,利用改性天然菱铁矿作为反应介质材料,将其应用于处理主要以As(Ⅲ)形式存在的高砷地下水具备良好的发展前景。     

我国饮用水除砷氟技术研究现状

饮用水砷、氟超标是影响我国农村饮水安全的主要问题之一,近年来我国饮用水除砷、除氟的技术发展迅速,对我国饮用水除砷、氟技术现状进行总结。分别阐述各种技术方法的特点和优劣势。     

碱选择性浸取高岭土制备中孔材料的性能

高岭土煅烧至一定温度,与酸或碱进行反应,可选择性浸出其中的A l2O3或S iO2,制备多孔材料。研究大同煤系高岭土煅烧至1 000℃,用N aOH溶液进行选择性浸取得到多孔材料的性能。X射线衍射、透射电镜及吸附性能研究结果表明:经过选择性浸取后,高岭土中S iO2大部分被浸出,铝硅摩尔比从0.85提高至4.62,以-γA l2O3为主要成分,比表面积达到106.4 m2/g,平均孔径为3.647 nm。这种新材料在石油催化裂化、自律型调湿建材及制备莫来石材料等方面具有广阔的应用前景。     

高岭土/肼插层材料的制备与表征

以高岭土为原料,选取50%水合肼作为插层剂,采用直接液相插层法,并辅以磁力搅拌,成功地将肼分子插入到高岭石结构层间,制得肼插层高岭土材料。利用红外光谱和粒度分析仪对产品进行了表征。IR谱表明, 插层中肼分子中的NH基与高岭石内表面羟基之间产生了N-H-OH作用,形成了新的氢键;插层反应后的样品,其粒径小于5 μm的颗粒占总颗粒数的比例降低了10.55%,平均粒径增大了46.84%。     

高岭土插层材料制备β-Sialon材料

以天然产物—高岭土原土和插层高岭土为原料,尝试在相对较低合成温度和对设备要求更简单的条件下制备β-Sialon粉体。试验结果表明,两种样品在1000℃±经碳热还原、氮化反应合成出了β-Sialon晶须,产物含有莫来石和方石英等杂质;以高岭土为原料合成出的β-Sialon粉体的Z值较低,且生成物中还含有氮化硅。在反应条件相同的情况下,以插层高岭土为原料合成β-Sialon的反应进行得较完全。     

活性氧化铝除氟性能的试验研究

通过静态试验,研究了活性氧化铝对F-的吸附性能,分析了原水氟离子浓度、pH值、活性氧化铝的投加量和吸附时间对吸附性能的影响。研究结果表明：在原水浓度0～50mg／L范围内,活性氧化铝吸附量与原水浓度基本成线性增加的关系;活性氧化铝除氟的最佳pH值为5～7,最佳投加量为10g／L。测定了在25℃时活性氧化铝除氟的吸附等温线,并对吸附等温线进行拟合,证明其符合Langmuir吸附等温式。     

改性磁铁矿对水体中砷的吸附特性研究

经过酸化改性后的天然磁铁矿,由于比表面积和内部结构发生变化,从而表现出很好的除砷性能,进一步研究其对水体中砷的吸附特征,为实际工程应用提供数据是十分必要的。本文对经0.5 mol/L盐酸浸泡、150℃温度下灼烧10 min的改性磁铁矿吸附砷的特征进行了表征,绘制吸附速率曲线图。吸附影响因素实验结果显示:当初始pH为6~9时,吸附性能强;Cl~-、Ca~(2+)、Mg~(2+)、HCO_3~-、CO_3~(2-)离子与As(Ⅲ)、As(Ⅴ)不会产生竞争吸附,PO_4~(3-)、NO_3~-、SO_4~(2-)离子与As(Ⅲ)产生竞争性吸附,且PO_4~(3-)SO_4~(2-)NO_3~-;PO_4~(3-)、NO_3~-离子与As(Ⅴ)产生竞争性吸附。结合X射线衍射、扫描电镜等研究结果,初步探讨了改性磁铁矿的除砷机理,认为改性后的磁铁矿比表面积明显增大,表面生成物含有Fe(Ⅱ)和Fe(Ⅲ)是其吸附砷能力提高的主要原因。实验结果证实,改性天然磁铁矿是一种值得进一步研究并实际应用的水体除砷材料。     

高砷地下水研究的热点及发展趋势

全球范围内广泛分布的高砷地下水给人们的健康造成了极大的威胁.高砷地下水的形成机理是一项世界性的科学问题.介绍了高砷地下水的分布特点、富集机理,阐明了溶解性有机物、地下水流动特征对高砷地下水形成的影响机制.现今的研究揭示了有机物和微生物协同作用下高砷地下水的形成过程,并且在高砷地下水的空间分布、时间变化特征以及人类活动对高砷地下水形成的影响等方面取得了一些创新性成果.这3方面的研究也逐渐成为近些年高砷地下水研究的热点.这些研究不仅丰富了砷迁移转化的理论成果,而且有助于开辟低砷水源,保障水资源的可持续利用,具有重要的理论和现实意义.     

铁盐改性高岭土吸附结晶紫的研究

研究了高岭土的改性方法及最佳改性土对染料结晶紫的吸附性能,选择焙烧温度200℃,硫酸铁含量为2%,焙烧时间2 h,探讨了振荡时间、吸附剂投加量等因素对吸附的影响。实验结果表明,在30℃下改性高岭土对结晶紫吸附平衡时间为60 min,对150 mg/L结晶紫饱和吸附容量为17.32 mg/g;改性高岭土对结晶紫的吸附等温线与Langmuir型拟合较好,吸附动力学模式符合伪二级动力学方程。     

二氧化锰改性粉煤灰制备及其对地下水中砷的吸附特性

高砷地下水在我国广泛分布,开发绿色高效的除砷材料对于促进地区发展和保障居民饮用水安全具有重要意义.采用共沉淀法结合NaOH水热处理技术制备了二氧化锰改性粉煤灰吸附材料MFA150,并研究其对地下水中As(Ⅲ)和As(Ⅴ)的吸附特性.结果表明,NaOH水热处理破坏了原始粉煤灰的玻璃体结构,且在这一过程中生成沸石相,粉煤灰比表面积由1.30 m²/g增加至40.26 m²/g.在负载MnO₂后,MFA150比表面积达到148.82 m²/g.此外,吸附材料表面-OH的含量显著增加,为As(Ⅲ)和As(Ⅴ)提供了更多的吸附活性位点.MFA150对As(Ⅲ)和As(Ⅴ)的吸附过程符合Elovich模型和Freundlich模型.在中性条件下MFA150对As(Ⅴ)和As(Ⅲ)的吸附量分别达到2.55 mg/g和9.71 mg/g,酸性条件更有利于吸附.溶液中共存的HCO₃^-和PO₄^3-会抑制As(Ⅲ)和As(Ⅴ)的吸附,...     

Modeling transport of arsenic through modified granular natural siderite filters for arsenic removal

Groundwater arsenic(As)contamination is a hot issue,which is severe health concern worldwide.Recently,many Fe-based adsorbents have been used for As removal from solutions.Modified granular natural siderite(MGNS),a special hybrid Fe(II)/Fe(III)system,had higher adsorption capacity for As(III)than As(V),but the feasibility of its application in treating high-As groundwater is still unclear.In combination with transport modeling,laboratory column studies and field pilot tests were performed to reveal both mechanisms and factors controlling As removal by MGNS-filled filters.Results show that weakly acid pH and discontinuous treatment enhanced As(Ⅲ)removal,with a throughput of 8700 bed volumes(BV)of 1.0 mg/L As(Ⅲ)water at breakthrough of 10 μg/L As at pH 6.Influent HCO_3~-inhibited As removal by the filters.Iron mineral species,SEM and XRD patterns of As-loading MGNS show that the important process contributing to high As(Ⅲ)removal was the mineral transformation from siderite to goethite in the filter.The homogeneous surface diffusion modeling(HSDM)shows that competition between As(III)and HCO_3~-with adsorption sites on MGNS was negligible.The inhibition of HCO_3~-on As(Ⅲ)removal was connected to inhibition of siderite dissolution and mineral transformation.Arsenic loadings were lower in field pilot tests than those in the laboratory experiments,showing that high concentrations of coexisting anions(especially HCO_3~-and SiO_4~(4-)),high pH,low EBCT,and low groundwater temperature decreased As removal.It was suggested that acidification and aeration of highAs groundwater and discontinuous treatment would improve the MGNS filter performance of As removal from real high-As groundwater.     

A siderite/limestone reactor to remove arsenic and cadmium from wastewaters

A two-column reactor was designed to remove dissolved As and Cd from contaminated water. The reactor functions by equilibrating the targeted water with CO₂ and directing it via saturated flow through a column of crushed siderite. This results in siderite dissolution and an increase in dissolved Fe(II). The feedwater is then directed into the top of a second, aerated column of crushed limestone, where it passes by unsaturated flow. The Fe²⁺ ion oxidizes quickly to Fe³⁺ and precipitates as Fe(III) oxyhydroxide, which is an effective sorbent of AsO₄³⁻. The aeration that occurs in the second column also removes dissolved CO₂ from the feedwater. This causes precipitation of Ca and Cd carbonates. Together, the two processes reduce As and Cd concentrations from 1 and 3 mg/l, respectively, to below detection (respectively <0.005 and <0.01 mg/l). A time-limited reduction in Cr concentration also occurred. Much of the As was removed in the first column of the reactor, because Fe(III) oxyhydroxides also formed there. This was due to oxidation of Fe(II) by Cr(VI) and other oxidants present in the input wastewater. Although As is removed in the reactor columns by a sorption mechanism, the sorbent responsible, Fe(III) oxyhydroxide, is continuously produced during the operation of the reactor. Thus, unlike attenuation in a system with a fixed amount of sorbent, breakthrough of the As contaminant should never occur.     

Removal of arsenic from aqueous solution by natural siderite and hematite

Batch and column experiments were conducted to examine the capability of naturally formed hematite and siderite to remove As from drinking water. Results show that both minerals were able to remove As from aqueous solutions, but with different efficiencies. In general, each material removed arsenate much more efficiently than As–DMA (dimethylarsinic acid), with the lowest adsorption efficiency for arsenite. The best removal efficiency for As species was obtained using a hematite, with a grain size range between 0.25 and 0.50 mm. The adsorption capacity for inorganic As(V) reached 202 μg/g. The pH generally had a great impact on the arsenate removal by the Fe minerals studied, while arsenite removal was slightly dependent on the initial pH of between 3 and 10. The presence of phosphate always had a negative effect on arsenate adsorption, due to competitive adsorption between them. A column packed with hematite in the upper half and siderite in the lower half with a grain size range of 0.25–0.5 mm proved to be an efficient reactive filter for the removal of all As species, causing a decrease in As concentration from 500 μg/L (including 200 μg/L As(V) as arsenate, 200 μg/L As(III) as arsenite and 100 μg/L As(V) as DMA) to less than 10 μg/L after 1055 pore volumes of water were filtered at a flow rate of 0.51 mL/min. After 2340 pore volumes passed through the column filter, the total inorganic As in the effluent was less than 5 μg/L. The total As load in the column filter was estimated to be 0.164 mg/g. Results of μ-synchrotron X-ray fluorescence analysis (μ-XRFA) suggest that coatings of fresh Fe(III) oxides, formed on the surface of the siderite grains after two weeks of operation, greatly increased the adsorption capacity of the filling material towards As.     

Laboratory testing of trace metals removal from mine drainage and arsenic removal from groundwater in the Black Hills of South Dakota

The Gilt Edge Superfund Site is a former heap-leach gold mine that currently is being remediated in the Black Hills of South Dakota. Mine runoff water is treated before release from the site. The field pH, before treatment, is about 3; the water contains arsenic at low levels and some trace metals at elevated levels, in addition to total dissolved solids concentrations of more than 1,900 mg/L. In the Keystone area of the Black Hills, naturally occurring arsenic has been detected at elevated concentrations in groundwater samples from wells. The City of Keystone’s Roy Street Well, which is not used currently, showed arsenic concentrations of 36 parts per billion and total dissolved solids of 320 mg/L. With field samples of water from the Gilt Edge site, a limestone-based method was successful in reducing trace metals concentrations to about 0.001 mg/L or less; at the Keystone site, the limestone method reduced arsenic levels to about 0.006 mg/L. The results are significant because previous research with the limestone-based method mainly had involved samples prepared with distilled water in the laboratory, in which interference of other ions such as sulfate did not occur. The research indicates the potential for broader applications of the limestone-based removal method, including scale-up work at field sites for water treatment.     

Carbon steel slag and stainless steel slag for removal of arsenic from stimulant and real groundwater

Arsenic in groundwater is a serious environmental problem. The contamination of groundwater with arsenic has been of utmost concern worldwide. Steel slag is a solid waste generated from steel production. Although steel slags have been used for arsenic removal from water, this process has not been systematically or integratively researched. In this study, the arsenic removal capacity and mechanism were investigated for carbon steel slag, stainless steel slag and Fe-modified stainless steel slag based on an in-depth study. The study also evaluated the potential utilization of different steel slag for regeneration. The maximum adsorption of arsenic on carbon steel slag, stainless steel slag and Fe-modified stainless steel slag was 12.20, 3.17 and 12.82 mg g^?1 at 25 °C, respectively. The modification of stainless steel slag by FeC1₃ can generate more pore structures and larger surface areas, and 300 °C treatment produces the best regeneration efficiency. The ΔG values were negative for all of the steel slags, indicating the spontaneous nature of the adsorption process. The solution pH was a critical parameter for the removal of arsenic for steel slags. Under highly alkaline solution conditions, the mechanism of arsenic removal by carbon steel slag and stainless steel slag can be attributed to chemisorption, including chemical precipitation and coordination reactions, and under weakly alkaline solution conditions, electrostatic interaction and specific adsorption are the arsenic removal mechanisms by Fe-modified stainless steel slag. Regeneration of the Fe-modified stainless steel slag was better achieved than that of the other steel slags in the application of high-temperature treatment.     

Uranium removal from groundwater using hydroxyapatite

The present work shows that U can be effectively removed from groundwater using permeable reactive barriers with hydroxyapatite (HAP) as reactive material. The main factor influencing the removal processes is the composition of the groundwater, namely the concentration of Ca and carbonate. Sorption of U onto the HAP surface seems to be the dominant removal process with the possibility of remobilisation. Newly formed U-phosphate minerals were detected by ESEM/EDX and XRD in samples with high U content indicating either a dissolution-precipitation mechanism or sorption onto the apatite surface followed by alteration of the structure. The formed U-phosphate minerals are stable under common groundwater conditions and can be remobilised only at high pH-values and high carbonate concentrations.     

Application of zeolitic volcanic rocks for arsenic removal from water

Natural zeolitic rocks consisting mainly of chabazite-phillipsite, clinoptilolite, and volcanic glass have been evaluated by means of batch methods to remove arsenic from waters with different mineralization degree (from deionized water to natural water with a specific conductivity of 1,600 μS cm^− 1). Arsenic was previously spiked in the studied waters at concentrations of about 100 µg l^− 1 to simulate actual cases. The compositional range of natural waters is representative of large hydrogeochemical regions around the world. The experiments were focussed on the application of natural common zeolitic rocks to water treatment for human consumption. The removal efficiency observed rises, in the better cases, 60–80% for chabazite-phillipsite raw materials whereas is 40–60% for clinoptilolite-bearing ones. The arsenic removal tends to increase with water mineralization degree, independently of the zeolitic rock type. A large zeolitic content in the chabazite-phillipsite raw materials increase the removal. Instead, the inverse situation is observed in the clinoptilolite-bearing rocks. The relevance of the quantitative mineralogical analysis, determining also the content of volcanic glass, as well as the use of natural waters in the removal tests has been demonstrated.     

Comparative study of the kinetics of the thermal decomposition of synthetic and natural siderite samples

The mechanism of the thermal decomposition of two siderites (a pure synthetic and a natural Mg-containing sample) has been determined from comparison of the results obtained from linear heating rate (TG) and constant rate thermal analysis (CRTA) experiments in high vacuum. The thermal decomposition of the synthetic siderite takes place approximately 200 K below the decomposition temperature of the natural sample. The mechanism and the product of the thermal decomposition are different for the siderite samples. In fact, an A₂ kinetic model describes the thermal decomposition of the synthetic siderite, whereas the thermal decomposition of the natural sample obeys an F₁ kinetic law. Decomposition products of the synthetic siderite are iron and magnetite, those of the natural siderite are wüstite and minor magnetite. Received: 22 July 1999 / Accepted: 12 February 2000     

Mobilization of natural arsenic in groundwater: targeting low arsenic aquifers in high arsenic occurrence areas

研究表明饮用水中微小数量的砷会对人类健康产生不利影响.世界上居住在贫穷地区的人数超过了100万,目前他们正直接饮用来自含水层中砷离子含量(>10μg/L)非安全标准的地下水.砷有时称为毒中之王,在水环境中常常以五价氧化物形式出现.自2000年以来,许多国家开始执行更为严格的10μg/L(WHO认可的居民安全饮水标准)饮用水标准,可以确定地说,在世界范围内的饮用水中检测到砷的情况越来越多.亚洲地区砷中毒的人数比世界其他地区总和还多.最受影响的地区位于南亚和东南亚富砷带,环绕恒河一雅鲁藏布江-梅克纳河三角洲及恒河平原上游的冲洪积扇含水层、红河三角洲、湄公河和伊洛瓦底江;在中国境内包括内蒙黄河冲积盆地,山西大同盆地、新疆准噶尔盆地,其中的地下水富含砷和氟化物而引发砷中毒和氟中毒.尽管还未完全掌握其中的水文地质及生物地球化学作用的详细过程,但对大多数沉积介质含水层,在还原条件下砷离子容易从沉积介质转移到地下水中.孟加拉研究实例表明地质时期尺度的冲刷降低了沉积介质中的As和有机物含量从而形成低砷地下水.这一认识为孟加拉国的降砷策略提供了科学指导,是未来水文学,矿物学,地质学和生物地球化学方面很有意义的研究方向,并有利于地砷病区低砷地下水的可持续利用.