湿法回收砷碱渣中锑的工艺研究

本研究先以水浸实现砷碱渣中的砷锑分离,再对水浸渣进行盐酸浸出,得到了可作为工业原料氯化锑溶液.研究结果表明,在液固比为6∶1,温度40℃,浸出时间40 min的条件下,可使水浸过程中锑的浸出率低于3%,砷的浸出率达到99%;盐酸浸出中,控制酸浓度为1∶1,液固比10∶1,温度60℃,浸出时间30 min,能使锑的浸出率达到88%以上.经过水浸和盐酸浸出,锑的直接回收率为85.36%.     

湿法回收砷碱渣中锑的工艺研究

本研究先以水浸实现砷碱渣中的砷锑分离，再对水浸渣进行盐酸浸出，得到了可作为工业原料氯化锑溶液。研究结果表明，在液固比为6：1，温度40℃，浸出时间40min的条件下，可使水浸过程中锑的浸出率低于3％，砷的浸出率达到99％；盐酸浸出中，控制酸浓度为1：1，液固比10：1，温度60℃，授出时间30min，能使锑的浸出率达到88％以上。经过水浸和盐酸浸出，锑的直接回收率为85．36％。     

响应曲面法优化炼铅高砷烟尘的浸出工艺

考察炼铅高砷烟尘中砷在水中的浸出行为。采用响应曲面法常用的中心复合设计对液固比、温度和时间工艺参数进行优化研究。结果表明,温度对砷浸出率的影响最大,时间次之,液固比最小。通过响应曲面法优化得到的最佳浸出工艺为:液固比=14∶1,温度85℃,时间120 min。该条件下3次验证实验的砷浸出率平均值为89.64%,与预测值89.88%无显著差异,表明所建模型切实可行。烟尘经过二次水浸后砷的总浸出率达到98.1%。     

针对含砷硫酸烧渣酸浸液的铁盐沉淀固砷

为考察含砷硫酸烧渣中酸浸脱砷效果和铁盐沉淀固砷行为,采用常温常压酸浸法脱除硫酸烧渣中的砷,并对进入浸出液中的砷以铁盐沉淀的形式脱除,进而对沉淀渣的浸出毒性进行研究。同时,研究了磨矿细度、酸浓度、固液比、浸出时间对硫酸烧渣中砷脱除效率的影响。结果表明,通过控制浸出参数可以将硫酸烧渣中砷的质量分数降低到0.2%以下,通过调节浸出液的pH和Fe/As摩尔比将其中的砷以沉淀的形式脱除。当Fe/As 2、pH=4～6时,溶液中砷浓度降到了0.5 mg·L~(-1)以下。沉淀砷渣主要是以非晶态的形式存在,提高铁砷比有利于提高砷渣稳定性,从而降低浸出毒性。在Fe/As=3、pH=6.04～6.22的条件下,得到的沉淀渣的浸出毒性为0.711 mg·L~(-1)。因此,通过酸浸脱除硫酸烧渣中的砷,进而采用铁盐沉淀的方法能够实现硫酸烧渣中砷的安全处置。     

矿区含砷尾矿及废渣稳定化研究

通过"硫酸-硝酸法"浸出实验,以砷的浸出浓度为控制指标,选用Fe Cl2为稳定药剂,对矿区砷渣进行药剂稳定化研究。考察Fe/As摩尔比、p H值、粒度、温度及稳定时间对砷浸出浓度的影响,通过研究稳定化前后砷形态的变化,探讨重金属迁移转化规律。结果表明:砷浸出浓度随Fe Cl2投加量增加而降低,当Fe/As摩尔比为1,p H=6.5~7.5时,常温下稳定化1 h后,砷浸出浓度低于2.5 mg/L且基本达到稳定,达到《危险废物填埋污染控制标准》(GB 18598-2001)的入场要求;随反应温度升高,砷浸出浓度略有升高;矿渣稳定化处理后,砷从生物有效性高和毒性大的形态逐渐转化为毒性小、稳定性强的形态,但矿物组成和化学组成不同,砷形态的迁移转化也略有不同。     

磷渣-粉煤灰基地聚物材料固化含砷废渣

为了处理有色金属冶炼厂产生的含砷废渣,利用磷渣-粉煤灰基地聚物材料对其进行固化处理。在磷渣∶粉煤灰=60∶40的基础上,通过单因素实验考察了石灰的掺量、化学激发剂水玻璃的模数及掺量、含砷废渣掺量等因素对砷固化体力学性能及砷毒性浸出特性的影响。结果表明:石灰外掺掺量为10%,水玻璃的模数为M=1.2,且其掺量为4%时,砷固化体的抗压强度和As毒性浸出浓度等指标综合效果达到最佳,地聚物材料对含砷废渣的最大固化容量为34%,其固化体抗压强度可达13.6 MPa,砷毒性浸出浓度为2.4 mg·L~(-1),满足危险废弃物堆存国家标准要求。通过XRD、SEM等手段分析可以得出,固化后砷通过化学键合的方式变成难溶盐的形式被地聚物材料牢牢地包裹,结构更加密实。     

污泥与底泥烧结陶粒骨料的中试研究

建立了中试研究生产线,工艺流程包括干燥、粉磨、混合上料、成型、烧结和烟气处理等,在中试生产线上,对污泥(包括工业污泥(ISS)和生活污泥(DSS))与底泥烧结制备陶粒骨料的物料配比、烧结温度、添加剂等相关技术参数进行了系统研究。研究发现,ISS中CaO和磷的化合物含量较高,导致骨料的膨胀性能不佳,添加一定量的生活污水污泥(DSS)可改善骨料的膨胀性能。中试研究确定600～800级的陶粒骨料烧结的适宜工艺条件为:配比SS∶DSS∶RS=1∶4∶5～1∶5∶4或DSS∶RS=3∶7～5∶5,烧结温度1 140℃,烧结时间28 min环境安全性研究表明,在陶粒烧结过程中大部分重金属在烧结过程中被固定在陶粒中,重金属浸出率非常低,在使用过程中不会对环境产生危害。     

锡冶炼含砷烟尘低温陶瓷固化技术

以锡冶炼过程中排放的含砷烟尘为研究对象,对浸出特性和低温陶瓷胶凝材料对其的固化效果进行了研究。结果表明,含砷烟尘As、Cu和Zn毒性浸出浓度分别为6 783、167和224 mg/L,严重超过国家毒性浸出鉴别标准值。其经低温陶瓷胶凝材料固化处理,当含砷烟尘掺量小于40%,自然养护3 d,As、Cu和Zn毒性浸出浓度急剧降低,且低于国家标准值。XRD和SEM分析表明,低温陶瓷胶凝材料在复合化学激发剂作用下,反应生成类沸石水化铝硅酸盐矿物(Al-O-Si);固化体中Ca-Fe-As-O盐是As固化的主要矿物相。Cu2+、Zn2+替换铝硅酸盐聚合物结构中的Na+、K+保持平衡电荷。胶凝材料水化产物填充于材料颗粒间,使其连接成一致密整体,有效降低了有害物质的毒性浸出浓度。     

中温焙烧/钠化氧化法回收电镀污泥中的铬

采用中温焙烧/钠化氧化法从电镀污泥中回收铬.结果表明,影响铬浸出率的最主要因素为焙烧温度.电镀污泥与碳酸钠质量比、焙烧时间、水浸时间对铬浸出率的影响较接近,在水浸水固比为10.0 ; 1.0(质量比)、室温、焙烧温度为650℃、焙烧时间为2.0h、电镀污泥与碳酸钠质量比为1:1、水浸时间为60 min的最佳浸出条件下,铬浸出率为99.3%;去除氢氧化铝、氢氧化锌的最佳反应温度和pH分别为90～95℃和7.5;去除硫酸钠晶体的最佳pH为4.0,在最佳试验条件下,铬回收率为90.57%.     

氧化氨浸工艺回收硫化砷渣中的铜

对在(NH4)2S2O8-NH3-H2O体系中氧化浸出硫化砷渣(砷渣)中的铜进行热力学分析;讨论了浸出温度、c(NH3)/c(NH+4)、液固比、浸出时间及总氨浓度对铜浸出率的影响,确定了从砷渣中回收铜最佳浸出工艺条件;采用XRD和SEM对浸出渣进行表征。结果表明,氧化氨浸回收铜工艺具有热力学可行性;在浸出温度35℃,c(NH3)/c(NH+4)1∶7,液固比6∶1,浸出时间3 h,总氨浓度4 mol/L的条件下,铜的浸出率为70.74%;大量S0均匀分布在浸出渣中。     

Effects of arsenic on nitrate metabolism in arsenic hyperaccumulating and non-hyperaccumulating ferns

This study investigated the effects of arsenic on the in vitro activities of the enzymes (nitrate reductase and nitrite reductase) involved in nitrate metabolism in the roots, rhizomes, and fronds of four-month old Pteris vittata (arsenic – hyperaccumulator) and Pteris ensiformis (non-arsenic--hyperaccumulator) plants. The arsenic treatments (0, 150, and 300 μM as sodium arsenate) in hydroponics had adverse effects on the root and frond dry weights, and this effect was more evident in P. ensiformis than in P. vittata. Nitrate reductase and nitrite reductase activities of arsenate-treated plants were reduced more in P. ensiformis than in P. vittata. This effect was accompanied by similar decreases in tissue NO₃^? concentrations. Therefore, this decrease is interpreted as being indirect, i.e., the consequence of the reduced NO₃^? uptake and translocation in the plants. The study shows the difference in the tolerance level of the two Pteris species with varying sensitivity to arsenic.     

Phytoremediation of arsenic contaminated paddy soils with Pteris vittata markedly reduces arsenic uptake by rice

Arsenic (As) accumulation in food crops such as rice is of major concern. To investigate whether phytoremediation can reduce As uptake by rice, the As hyperaccumulator Pteris vittata was grown in five contaminated paddy soils in a pot experiment. Over a 9-month period P. vittata removed 3.5-11.4% of the total soil As, and decreased phosphate-extractable As and soil pore water As by 11-38% and 18-77%, respectively. Rice grown following P. vittata had significantly lower As concentrations in straw and grain, being 17-82% and 22-58% of those in the control, respectively. Phytoremediation also resulted in significant changes in As speciation in rice grain by greatly decreasing the concentration of dimethylarsinic acid (DMA). In two soils the concentration of inorganic As in rice grain was decreased by 50-58%. The results demonstrate an effective stripping of bioavailable As from contaminated paddy soils thus reducing As uptake by rice.     

Relation of dietary inorganic arsenic exposure and urinary inorganic arsenic metabolites excretion in Japanese subjects

Inorganic arsenic (InAs) is a ubiquitous metalloid that has been shown to exert multiple adverse health outcomes. Urinary InAs and its metabolite concentration has been used as a biomarker of arsenic (As) exposure in some epidemiological studies, however, quantitative relationship between daily InAs exposure and urinary InAs metabolites concentration has not been well characterized. We collected a set of 24-h duplicated diet and spot urine sample of the next morning of diet sampling from 20 male and 19 female subjects in Japan from August 2011 to October 2012. Concentrations of As species in duplicated diet and urine samples were determined by using liquid chromatography-ICP mass spectrometry with a hydride generation system. Sum of the concentrations of urinary InAs and methylarsonic acid (MMA) was used as a measure of InAs exposure. Daily dietary InAs exposure was estimated to be 0.087 µg kg^?1 day^?1 (Geometric mean, GM), and GM of urinary InAs+MMA concentrations was 3.5 ng mL^?1. Analysis of covariance did not find gender-difference in regression coefficients as significant (P > 0.05). Regression equation Log ₁₀ [urinary InAs+MMA concentration] = 0.570× Log ₁₀ [dietary InAs exposure level per body weight] + 1.15 was obtained for whole data set. This equation would be valuable in converting urinary InAs concentration to daily InAs exposure, which will be important information in risk assessment.     

Effects of plant arsenic uptake and heavy metals on arsenic distribution in an arsenic-contaminated soil

This study examined the effects of heavy metals and plant arsenic uptake on soil arsenic distribution. Chemical fractionation of an arsenic-contaminated soil spiked with 50 or 200mg kg(-1) Ni, Zn, Cd or Pb was performed before and after growing the arsenic hyperaccumulator Pteris vittata L for 8weeks using NH(4)Cl (water-soluble plus exchangeable, WE-As), NH(4)F (Al-As), NaOH (Fe-As), and H(2)SO(4) (Ca-As). Arsenic in the soil was present primarily as the recalcitrant forms with Ca-As being the dominant fraction (45%). Arsenic taken up by P. vittata was from all fractions though Ca-As contributed the most (51-71% reduction). After 8weeks of plant growth, the Al-As and Fe-As fractions were significantly (p<0.01) greater in the metal-spiked soils than the control, with changes in the WE-As fraction being significantly (p=0.007) correlated with plant arsenic removal. The plant's ability to solubilize soil arsenic from recalcitrant fractions may have enhanced its ability to hyperaccumulate arsenic.     

Effect of arsenic on chloroplast ultrastructure and calcium distribution in arsenic hyperaccumulator Pteris vittata L

This study investigated the impacts of arsenic (As) on the chloroplast ultrastructure and calcium (Ca) distribution in Chinese brake (Pteris vittata L.) mainly by histochemical methods, with an emphasis on the possible function of Ca in As detoxification and accumulation in P. vittata. P. vittata was grown in an artificially contaminated soil added with different concentrations of Na(2)HAsO(4) (0, 100, 300 and 800 mg kg(-1) As dry soil) for 24 weeks in a greenhouse. The addition of As did not affect the chloroplast ultrastructure of young pinna, meanwhile most of the membrane systems of chloroplasts in mature pinna were severely damaged under high As condition. Calcium concentration in the fronds of P. vittata was not significantly affected by the addition of As, but Ca concentration in the mature pinna significantly increased by As addition, consistent with the position appearing As toxicity. When no As was added, most of calcium precipitates distributed around the inner membrane of vacuole. But when the pinna appeared plasmolysis, more calcium precipitates resided outside the cell membrane and bigger particles evenly distributed in the cytoplasm. All the results indicated that Ca had a close relation with As toxicity in P. vittata.     

二段铁盐沉淀深度脱除高浓度含砷废水中的砷

探索高浓度含砷废水中砷的深度脱除方法及脱除机理。采用预氧化-二段铁盐沉淀的方法脱除炼铅烟尘浸出液中的砷,研究影响砷脱除效率的控制条件和因素,砷脱除机理。结果表明,用双氧水氧化原料液中的低价铁和砷,加Fe Cl3调节铁砷比=1,在p H=4~5、T=60~70℃反应60 min,砷的脱除率达到99.95%,XRD分析结果表明,沉淀物为非晶态砷酸铁形态;在二段除砷中,控制铁砷比=5、p H=7~8,除砷后液中的砷含量小于0.014 mg/L,远低于允许的排放限值。采用二段铁盐脱砷工艺可以将高砷溶液中的砷深度脱除。     

Enhanced phytoremediation of arsenic contaminated land

In an attempt to clean up arsenic (As) contaminated soil, the effects of phosphorus (P) fertilizer and rhizosphere microbes on arsenic accumulation by the silverback fern, Pityrogramma calomelanos, were investigated in both greenhouse and field experiments. Field experiments were conducted in Ron Phibun District, an As-contaminated area in Thailand. Soil (136-269 microg As g(-1)) was collected there and used in the greenhouse experiment. Rhizosphere microbes (bacteria and fungi) were isolated from roots of P. calomelanos growing in Ron Phibun District. The results showed that P-fertilizer significantly increased plant biomass and As accumulation of the experimental P. calomelanos. Rhizobacteria increased significantly the biomass and As content of the test plants. Thus, P-fertilizer and rhizosphere bacteria enhanced As-phytoextraction. In contrast, rhizofungi reduced significantly As concentration in plants but increased plant biomass. Therefore, rhizosphere fungi exerted their effects on phytostabilization.     

Effects of heavy metals on growth and arsenic accumulation in the arsenic hyperaccumulator Pteris vittata L

The effects of Cd, Ni, Pb, and Zn on arsenic accumulation by the arsenic hyperaccumulator Pteris vittata were investigated in a greenhouse study. P. vittata was grown for 8 weeks in an arsenic-contaminated soil (131 mg As kg(-1)), which was spiked with 50 or 200 mg kg(-1) Cd, Ni, Pb, or Zn (as nitrates). P. vittata was effective in taking up arsenic (up to 4100 mg kg(-1)) and transporting it to the fronds, but little of the metals. Arsenic bioconcentration factors ranged from 14 to 36 and transfer factors ranged from 16 to 56 in the presence of the metals, both of which were reduced with increasing metal concentration. Fern biomass increased as much as 12 times compared to the original dry weight after 8 weeks of growth (up to 19 g per plant). Greater concentrations of Cd, Ni, and Pb resulted in greater catalase activity in the plant. Most of the arsenic in the plant was present as arsenite, the reduced form, indicating little impact of the metals on plant arsenic reduction. This research demonstrates the capability of P. vittata in hyperaccumulating arsenic from soils in the presence of heavy metals.     

Sulfate and glutathione enhanced arsenic accumulation by arsenic hyperaccumulator Pteris vittata L.

This experiment examined the effects of sulfate (S) and reduced glutathione (GSH) on arsenic uptake by arsenic hyperaccumulator Pteris vittata after exposing to arsenate (0, 15 or 30 mg As L⁻¹) with sulfate (6.4, 12.8 or 25.6 mg S L⁻¹) or GSH (0, 0.4 or 0.8 mM) for 2-wk. Total arsenic, S and GSH concentrations in plant biomass and arsenic speciation in the growth media and plant biomass were determined. While both S (18-85%) and GSH (77-89%) significantly increased arsenic uptake in P. vittata, GSH also increased arsenic translocation by 61-85% at 0.4 mM (p < 0.05). Sulfate and GSH did not impact plant biomass or arsenic speciation in the media and biomass. The S-induced arsenic accumulation by P. vittata was partially attributed to increased plant GSH (21-31%), an important non-enzymatic antioxidant countering oxidative stress. This experiment demonstrated that S and GSH can effectively enhance arsenic uptake and translocation by P. vittata.     

Studies on arsenic transforming groundwater bacteria and their role in arsenic release from subsurface sediment

Ten different Gram-negative arsenic (As)-resistant and As-transforming bacteria isolated from As-rich groundwater of West Bengal were characterized to assess their role in As mobilization. 16S rRNA gene analysis confirmed the affiliation of these bacteria to genera Achromobacter, Brevundimonas, Rhizobium, Ochrobactrum, and Pseudoxanthomonas. Along with superior As-resistance and As-transformation abilities, the isolates showed broad metabolic capacity in terms of utilizing a variety of electron donors and acceptors (including As) under aerobic and anaerobic conditions, respectively. Arsenic transformation studies performed under various conditions indicated highly efficient As³⁺ oxidation or As⁵⁺ reduction kinetics. Genes encoding As³⁺ oxidase (aioA), cytosolic As⁵⁺ reductase (arsC), and As³⁺ efflux pump (arsB and acr3) were detected within the test isolates. Sequence analyses suggested that As homeostasis genes (particularly arsC, arsB, and acr3) were acquired by most of the bacteria through horizontal gene transfer. A strong correlation between As resistance phenotype and the presence of As³⁺ transporter genes was observed. Microcosm study showed that bacterial strain having cytosolic As⁵⁺ reductase property could play important role in mobilizing As (as As³⁺) from subsurface sediment.