CO2对砷酸钙稳定性影响的热力学分析

通过沉淀和溶解两方面的实验数据,应用PHREEQC程序模拟了砷酸钙在不同CO2分压条件下溶解度的变化情况,发现环境中的CO2可使砷酸钙盐在酸度较高(pH大于8.3)的条件下发生不一致溶解,使其溶解度升高;CO2分压越大,砷酸钙盐发生不一致溶解的酸度越低;CO2主要影响3∶2和5∶3的砷酸钙盐,而对4∶2砷酸钙盐的影响较小。这对不同类型砷酸钙盐废物的处置是否应考虑CO2的因素提供了依据。     

Effect of amendments on the leaching behavior of alkaline anions and metal ions in bauxite residue

A column leaching experiment was used to investigate the efficacy of amendments on their ability to remove alkaline anions and metal ions from bauxite residue leachates. Treatments included, simulated acid rain(AR), phosphogypsum + vermicompost(PVC), phosphogypsum +vermicompost + simulated acid rain(PVA), and biosolids + microorganisms(BSM) together with controls(CK). Results indicated that amendment could effectively reduce the leachate pH and EC values, neutralize OH~-, CO_3~(2-), HCO_3~-, and water soluble alkali, and suppress arsenic(As)content. Correlation analysis revealed significant linear correlations with pH and concentrations of OH~-, CO_3~(2-), HCO_3~-, water-soluble alkali, and metal ions. BSM treatment showed optimum results with neutralizing anions(OH~-, CO_3~(2-), and HCO_3~-), water soluble alkali, and removal of metal ions(Al, As, B, Mo, V, and Na), which was attributed to neutralization from the generation of small molecular organic acids and organic matter during microbial metabolism. BSM treatment reduced alkaline anions and metal ions based on neutralization reactions in bauxite residue leachate, which reduced the potential pollution effects from leachates on the soil surrounding bauxite residue disposal areas.     

不同沉淀pH值条件下制备的水合氧化锆对水中磷酸盐的吸附作用

研究了沉淀pH值分别为4.8、8.0和10.6条件下制备的水合氧化锆对水中磷酸盐的吸附作用,结果表明,共存的Na~+仅仅略微促进了沉淀pH值为4.8和8.0时所得水合氧化锆对水中磷酸盐的吸附,却明显促进了沉淀pH值为10.6时所得水合氧化锆对磷酸盐的吸附.共存的Ca~(2+)仅仅略微促进了沉淀pH值为4.8时水合氧化锆对磷酸盐的吸附,却极大地促进了沉淀pH值为8.0和10.6时水合氧化锆对磷酸盐的吸附.共存的HCO_3~-和SO_4~(2-)抑制了水合氧化锆对磷酸盐的吸附,且它们对沉淀pH值为4.8时水合氧化锆吸磷的抑制作用明显大于对沉淀pH值为8.0和10.6时水合氧化锆的抑制作用.不同沉淀pH值条件下制备的水合氧化锆对水中磷酸盐的吸附能力均随着溶液pH值的增加而降低.不同沉淀pH值条件下所得水合氧化锆对水中磷酸盐的吸附平衡数据可以采用Langmuir、Freundlich和Dubinin-Redushckevich(D-R)等温吸附模型加以描述.存在Na+而不存在Ca~(2+)情况下,3种不同沉淀pH值条件下所得水合氧化锆对中性溶液中磷酸盐的最大单层吸附容量差别不大;存在Ca~(2+)情况下,沉淀pH值为8.0和10.6时所得水合氧化锆对中性溶液中磷酸盐的最大单层吸附容量远远高于沉淀pH值为4.8时制备的水合氧化锆.沉淀pH值为4.8和8.0时所得水合氧化锆的吸磷机制主要是表面氯和羟基基团与磷酸盐之间的配位体交换作用,而沉淀pH值为10.6时所得水合氧化锆的吸磷机制主要是表面羟基基团与磷酸盐之间的配位体交换作用.以上研究结果显示,与沉淀pH值为4.8时制备的水合氧化锆相比,沉淀pH值为8.0和10.6时制备的水合氧化锆更加适合作为吸附剂去除废水中的磷酸盐.     

沈阳某冶炼厂污染土壤中砷的稳定化研究

稳定化是一种相对经济有效的治理重金属污染土壤的方法。文章以沈阳某冶炼厂厂区旧址的重金属复合污染土壤为研究对象,通过向土壤中添加不同药剂,研究了不同碱性化学物质对土壤砷稳定化的效果。结果表明,碳酸钠和硫化钠的加入对土壤pH的贡献均较大,但使砷的浸出毒性增强,对土壤中砷的稳定起负作用;碳酸钙和多硫化钙对土壤中砷的稳定化效果也不明显;氧化钙的效果最好,使得该重污染土壤中砷的浸出毒性降低到危险废弃物毒性浸出标准(GB5085.3-1996)以内。     

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.     

Tannic acid and saponin for removing arsenic from brownfield soils：Mobilization, distribution and speciation

Plant biosurfactants were used for the first time to remove As and co-existing metals from brownfield soils. Tannic acid （TA）, a polyphenol, and saponin （SAP）, a glycoside were tested. The soil washing experiments were performed in batch conditions at constant biosurfactant concentration （3%）. Both biosurfactants differed in natural pH, surface tension, critical micelle concentration and content of functional groups. After a single washing, TA （pH 3.44） more efficiently mobilized As than SAP （pH 5.44）. When both biosurfactants were used at the same pH （SAP adjusted to 3.44）, arsenic mobilization was improved by triple washing. The process efficiency for TA and SAP was similar, and depending on the soil sample, ranged between 50%-64%. Arsenic mobilization by TA and SAP resulted mainly from decomposition of Fe arsenates, followed by Fe3＋ complexation with biosurfactants. Arsenic was efficiently released from reducible and partially from residual fractions. In all soils, As（V） was almost completely removed, whereas content of As（III） was decreased by 37%-73%. SAP and TA might be used potentially to remove As from contaminated soils.     

A new recycling material for removing phosphorus from water

In search of readily available and relatively inexpensive materials for phosphorus removal, waste oyster shell is a waste product from oyster-culturing farm and also presents a major disposal problem in itself. Activated oyster shell produced by pyrolysis at 750 °C exhibits promising performance as a suitable substance for phosphorus removal. The capacity of the activated oyster shell, in terms of equivalents of OH^? per gram of material, is about 80% than that of calcium hydroxide. However, the granular nature of activated oyster shell (AOS) makes it much easier to handle than lime. This would be a very important advantage for treatment facilities that cannot afford specialized powder handling facilities necessary for lime. Another advantage of AOS is its time-release properties, which can allow it to be added to reactors intermittently and still achieve consistent phosphate precipitation. Distribution of phosphate after contact with AOS indicates that adsorption does not play a significant role in phosphate removal with AOS. Rather, it appears that the phosphate is precipitated in the presence of Ca²⁺ and high pH as a key mechanism. Since it is produced from a waste product of mariculture, AOS is a sustainable precipitant for phosphate removal.     

高浓度含砷污泥的药剂稳定化和水泥固化研究

以某铜冶炼厂高浓度含砷污泥为研究对象,分别开展了药剂稳定化和水泥固化小试研究,并对比分析了不同剂量的两种稳定化药剂和矿渣硅酸盐水泥（PSA）单独投加后污泥中砷的浸出毒性。研究发现：该铜冶炼厂污泥中砷含量极高,达到危废级别。对含砷污染土壤具有较好稳定化效果的两种药剂对高浓度含砷污泥的处理效果并不理想,在高剂量投加（15％）条件下仍不能使污泥中砷的浸出浓度低于5mg／L的危废鉴别标准值。相比而言,传统的水泥固化处置方式能有效降低污泥中砷的浸出浓度,使其低于5mg／L,但该处置方式污泥增容显著,会增加后续相关处理费用和难度。本研究对开展含重金属污泥和污染土壤的固化／稳定化修复提供了有重要价值的参考和借鉴。     

Determination of aerosol strong acidity losses due to interactions of collected particles: Results from laboratory and field studies

Existing methods of measuring atmospheric aerosol strong acidity adequately prevent neutralization of fine-particle acidity by removing course alkaline particles and gaseous ammonia from air samples. However, these techniques do not consider particle interactions on the collection medium; therefore, they may still underestimate the actual aerosol acidity. Assessment of acid neutralization due to such interactions is made possible using annular denuder technology in conjuction with a newly designed filter pack. The amount of sulfate-related acidity neutralized by the collected ammonium nitrate (and possibly ammonium chloride and organic acid ammonium salts) is determined. Laboratory data suggest that large fractions of sulfate-related aerosol acidity are neutralized by ammonium nitrate particles during collection on filter media. Field data from the Harvard Acid Aerosol Health Effects Study also suggest that ammonium nitrate and possibly other ammonium salts, such as ammonium chloride, neutralize collected acid aerosols. For low-acid aerosol concentrations, the correction factor is significant; whereas, for high-acid concentrations, correction is negligible.     

锑砷钙渣的应用

有色冶炼产生的锑砷钙渣在玻璃瓶生产中的应用 ,理论和实践证明 :用锑砷钙渣代替白砒是可行的。     

含水层介质对垃圾渗滤液污染缓冲性研究

通过土柱模拟实验研究含水层介质对垃圾渗滤液污染的pH缓冲和氧化还原缓冲性能.结果表明,碳酸钙对pH缓冲起重要作用,随着污染程度的加重,碳酸钙缓冲体系的缓冲容量逐渐增大,从背景值的1.62·pH^-1 mmol/kg增加到41.3·pH^-1 mmol/kg.随着污染程度的加重,含水层介质的氧化容量（OXC）减小,而还原容量（RDC）升高.在未受污染的介质中,Fe³⁺是OXC的主要组成,约占OXC的70.5％;TOC是RDC的主要组成,约占RDC的98.7％.物质的存在形态也与污染程度有关,在污染源附近大部分无定型态和部分晶体态Fe³⁺被还原,而且还原产物主要以FeCO₃和FeS形式沉淀;生成Fe²⁺的沉积使得可离子交换态Fe²⁺含量由未受污染的介质中的0.5％升高至3％.因此,Fe³⁺是含水层介质中主要的氧化还原缓冲剂.     

场地土壤中有效态砷的稳定化处理及机理研究

分别以生石灰和亚铁盐作为辅助剂与稳定剂对2种砷污染的土壤进行稳定化处理,通过化学浸出、形态及结构研究,揭示土壤中有效砷的稳定效率和机理.结果表明,外源铁添加量与土壤砷含量(Fe/As)的物质的量比达到6:1~8:1,CaO投加比例为0.05%~0.1%(w/w)时,土壤中有效态砷的稳定效率超过85%.土壤有效砷的稳定化处理主要是将砷从非专性吸附态和专性吸附态转化为弱结晶的铁铝或铁锰水化氧化物结合态、结晶铁铝或铁锰水化氧化物结合态.稳定处理后2种污染土均有新物相羟砷铜矿(As2Cu5H4O12)生成.     

运用涂铁砂粒进行分散式饮水除砷的效果

采用铁盐处理普通河砂研制成涂铁砂粒(IOCS),通过静态和动态吸附试验观察其分散式饮水除砷效果,并选取地砷病现场进行了验证.结果表明,IOCS性质较为稳定,扫描电镜下可见铁氧化物呈片状分散的覆盖在砂粒表层;IOCS无需活化处理,其对砷的最大吸附发生在30min～60min;pH5～9时,五价砷的去除率随着pH值的升高而下降,三价砷的去除率变化不明显.IOCS对砷的吸附符合朗格缪尔(Langmuir)吸附方程;5次滤柱循环中,75g(50ml)的IOCS分别处理含砷1.0mg·L^-1的水样408～426床(三价砷),390～412床(五价砷),用0.2 mol·L^-1NaOH进行再生处理,砷回收率均在94%以上.充填IOCS 3.0kg的家庭用模拟装置处理含1.0mg·L^-1的五价砷209L和198L,三价砷196L和185L,并在现场实验期间,连续处理含砷0.202～1.733mg·L^-1的水样200L,对水质亦无不良影响.无论是经济上还是技术上,IOCS均是适合于分散式饮水除砷的一种新型除砷剂.     

铜渣与含砷污酸反应行为及除砷机理

分析铜渣组成结构和形貌特性的基础上,研究了铜渣与含砷污酸反应行为及脱砷规律,阐明了反应动力学过程,揭示了铜渣除砷机理.结果表明：在铜渣用量为0.2g/mL,反应温度为23℃,反应时间为24h的最优条件下,铜渣的最大去除容量达到25.89mg/g,除砷率达到99.56%,并且除砷后铜渣的砷浸出浓度低于5mg/L的危险废弃物界定限值,属于一般固体废弃物.铜渣除砷过程符合拟二级动力学模型,该过程受铁离子释放速度限制,离子交换吸附和化学沉淀方式同步进行实现了砷的脱除,两种方式的结合有利于砷的稳定化.铜渣与污酸反应释放大量的铁离子,通过离子交换吸附与砷酸根离子发生沉淀反应,形成较为稳定的砷酸盐及其衍生化合物,进而达到除砷目的.铜渣表现出优越的除砷性能,为重有色冶炼污酸处置提供了一种高效和低成本的方法.     

磁性壳聚糖微球吸附水中As(Ⅲ)的实验研究

文章主要考察实验室制得的乙二胺改性磁性壳聚糖微球对毒性高,迁移能力强的A(sⅢ)去除效果。通过单因素实验研究了pH值、吸附时间、A(sⅢ)溶液初始浓度和吸附剂投加量对磁性壳聚糖微球吸附除A(sⅢ)效果的影响。实验结果表明在pH值为2,吸附时间为90 min,磁性壳聚糖微球投加量为0.4 g时,对初始浓度为10 mg/L,体积为100 mL的A(sⅢ)溶液去除率达到96.96%,吸附后溶液中A(sⅢ)浓度仅为0.304 mg/L,低于我国污水综合排放标准中砷含量标准值。磁性壳聚糖微球的解吸实验表明,吸附剂解吸4次后,对A(sⅢ)的去除率仍达到95%以上,吸附性能稳定,具有较好的可重复利用性。因此,磁性壳聚糖微球是一种去除低浓度含砷废水非常有效的材料。     

在污染大气环境中NaCl对镁合金的协同作用

研究了沉积NaC l的AZ91D镁合金在含有SO2和CO2的模拟污染大气环境中初期腐蚀行为。研究了在SO2和CO2协同作用下,表面沉积NaC l的AZ91D镁合金大气初期腐蚀规律。采用扫描电子显微镜(SEM)观察表面腐蚀形貌,XRD进行腐蚀产物分析。结果表明,由于NaC l的沉积加速了AZ91D镁合金的初期大气腐蚀,SO2、CO2和NaC l多种因素协同作用对AZ91D镁合金的初期大气腐蚀的影响远大于单一SO2、CO2和NaC l因素。     

凭祥金矿风化剖面中砷的地球化学研究

利用连续提取法结合电子探针分析对龙塘金矿风化剖面中砷的赋存状态及其地球化学行为进行了研究。结果表明金矿区表层土壤中砷含量达588mg/kg,是土壤质量标准的十几至几十倍，该土壤已受到砷的严重污染。风化母岩中砷主要赋存于含砷黄铁矿与毒砂之中，而风化样品中砷主要赋存于晶质氧化铁中，其次为非晶质氧化铁之中，其他三个结合态相对较少。风化初期，含砷黄铁矿与毒砂风化溶解，其中大部分砷被风化溶液淋失，其他砷被氧化铁吸附。非晶质氧化铁结合态砷在风化过程中显示先升后降的趋势，而晶质氧化铁结合态砷则逐渐升高。雨水对表层土壤的冲刷、风化母岩中硫化物的风化溶解、风化产物中氧化铁在饱和条件下的溶解等都会使剖面中的砷释放出来，对周围环境造成潜在的威胁。     

2005年中国燃煤大气砷排放清单

燃煤排放的砷是引起大气环境污染和经济损失的重要痕量元素之一.对燃煤大气砷排放进行估算可以为砷排放法规政策的制定和选择适宜的燃煤砷污染控制技术提供依据.采用基于燃料消耗的排放因子法,按照经济部门、燃烧方式和除尘设施将燃煤排放源进行分类,根据各省区不同排放类型的煤炭消耗量和燃煤平均砷含量,建立了2005年中国燃煤大气砷排放清单. 2005年中国燃煤生产和消耗量分别为2 119.8和2 099.8 Mt.燃煤导致的大气砷排放总量估算约为1 564.4 t,其中排放量最大的省区是山东（144.4 t）,其次是湖南（141.1 t）、河北（108.5 t）、河南（77.7 t）、江苏（77.0 t）等,燃煤大气砷排放主要集中在中东部省区;绝大部分燃煤大气砷排放来自工业（818.8 t）和电力部门（303.4 t）,分别占燃煤大气砷排放总量的52.3%和19.4%;2005年中国燃煤排放的砷大约有375.5 t是以气态形式排放到大气中,占排放总量的24%.总体上,在全国范围内燃煤大气砷污染排放控制的重点是电力和工业部门;而对于新疆、甘肃、青海、贵州等地区,还应关注生活消费燃煤引起的砷中毒事件.     

Effect of wastewater composition on the calcium carbonate precipitation in upflow anaerobic sludge blanket reactors

Calcium carbonate often precipitates in anaerobic reactors treating wastewater with high calcium content. The aim of this paper is to study the effect of wastewater composition on calcium carbonate precipitation in upflow anaerobic sludge blanket (UASB) reactors. Two laboratory-scale UASB reactors were operated with calcium-containing influents using acetate and carbohydrate as substrate, respectively. There was an obvious accumulation of inorganic precipitate observed in the biogranules. Observations via scanning electron microscope (SEM) and energy dispersive spectroscopy (EDS) showed that the acclimated biogranules in the two reactors differed in microstructure. Calcium carbonate was found to have precipitated on the surface of acetate-degrading biogranules, but precipitated at the core of the carbohydrate-degrading biogranules. The results indicated that substrates had significant influence on the location of calcium carbonate precipitation in anaerobic granular sludge, which was expected due to the different methanogens distribution and pH gradient within the granular sludge degrading various substrates. Moreover, the location of calcium carbonate precipitation substantially affected the specific methanogenic activity (SMA) of the granular sludge. The SMA of the acetate-degrading biogranules dropped from $ 1.96 gCOD_{CH_4 } \cdot gVSS^{ - 1} \cdot d^{ - 1} $ 1.96 gCOD_{CH_4 } \cdot gVSS^{ - 1} \cdot d^{ - 1} to $ 0.61 gCOD_{CH_4 } \cdot gVSS^{ - 1} \cdot d^{ - 1} $ 0.61 gCOD_{CH_4 } \cdot gVSS^{ - 1} \cdot d^{ - 1} after 180-d of operation in the reactor. However, the SMA of the carbohydrate-degrading biogranules was not adversely affected by calcium carbonate precipitation.     

砷酸钙化合物的溶解度及其稳定性随pH值的变化

通过混合沉淀和溶解实验详细研究了pH值和Ca/As摩尔比对石灰沉淀法处理高浓度含砷废水的影响.沉淀后溶液中的As浓度随pH值的变化趋势与混合液的Ca/As摩尔比有关,在Ca/As=1·50和1·67时,沉淀后溶液中的As浓度在pH=7附近达到最低,然后随pH值的升高而呈现出增大的趋势;在Ca/As=2·00和4·00时,沉淀后溶液中的As浓度随pH值的升高而降低,且2种Ca/As摩尔比条件下的实验结果基本一致.混合沉淀过程中生成的砷酸钙化合物的组成与结构取决于溶液的Ca/As摩尔比和pH值.在低pH值和低Ca/As摩尔比条件下形成的沉淀物要比在高pH值和高Ca/As摩尔比条件下形成的沉淀物的颗粒要大,而且结晶程度要好.在Ca/As摩尔比为1·0~4·0和不同pH值条件下,主要生成Ca_3(AsO_4)_2·3H_2O、Ca_3(AsO_4)_2·2·25H_2O、Ca_5(AsO-4)_3OH和Ca_4(OH)-2(AsO_4)2·4H_2O,溶度积分别等于10~(-21·14)、10~(-21·40)、10~(-40·12)和10~(-27·49).