Tessier法和BCR法对比磷酸二氢钠处置含铅污染土壤形态分析

应用Tessier与BCR(Bureau Community of Reference)形态分析方法以及固体废物浸出毒性浸出法-醋酸缓冲溶液法(HJ/T300-2007)研究了磷酸二氢钠(MSP)对土壤中铅赋存形态以及浸出浓度的影响。研究表明:Tessier法和BCR法均能证实随着磷酸二氢钠的施加,实验土壤中铅从活泼态向稳定态转化;Tessier法测定的生物活性系数(MF)值较BCR法更为保守;通过线性回归分析发现BCR法测定的MF值相关系数为0.988,优于Tessier法的相关系数0.895;Tessier法与BCR法对污染土壤中铅形态的提取均具有较高的回收率;磷酸二氢钠能有效降低实验土壤中铅的浸出浓度可达98.62%。     

微波法处理含铬废渣的可行性分析

微波辐照解毒铬渣是一项新技术,为考察该技术应用的可行性,本文对铬渣解毒前后性状的变化进行了讨论。结果表明,该技术能较完全地使高价铬转化为低价铬,解毒渣中铬主要以三价形态存在,铬渣毒性得到消除;解毒渣浸出液中Cr6+浓度远低于国家危险废物鉴别标准,解毒渣已不属于危险固体废弃物,其在环境条件下可安全存放。说明该技术具有应用前景。     

铬渣秸秆共热解产物铬稳定性研究

生物质铬渣共热解工艺是新型的铬渣处理工艺,该工艺能有效地将铬渣中的Cr(Ⅵ)还原为Cr(Ⅲ).而由于共热解产物总铬含量较高,因此考察了铬渣与秸秆共热解过程中铬稳定性.通过考察共热解产物成分及形态分析、pH影响实验、淋洗实验及长期稳定性实验,对共热解铬渣的铬环境安全性进行评估.结果表明:(1)共热解温度对铬渣形态有较大影响,可交换态及碳酸盐结合态铬含量随共热解温度升高而逐渐降低,800℃时候可交换态铬降至＜0.1％(质量分数,下同),碳酸盐结合态铬为1.2％;共热解后最稳定的残渣态铬含量随共热解温度升高而逐渐升高.(2)当pH＞7时,两种共热解产物总铬溶出量极低,基本都小于6mg/kg;当pH≤7时,总铬的溶出量显著增加,最高超过500 mg/kg.但由于解毒铬渣的酸中和能力极强,因此铬释放风险较低.(3)共热解产物的总铬累积溶出量极低,根据拟合结果计算出其100年填埋时间的总铬溶出量不超过1.3 mg/kg.长期稳定性实验表明,自然堆置过程中共热解产物的Cr(Ⅵ)含量逐渐降低.     

基于复合球团的以生物质焦油为还原剂的铬渣无害化处理

结合目前铬渣解毒现状,提出生物质焦油热解还原铬渣的新技术,利用生物质气化副产物焦油作为解毒剂,进而提高铬渣解毒和资源化水平,降低能耗。将生物质焦油和铬渣混合制成球团通过热解实现Cr(VI)向Cr(III)的形态转化,对影响焦油热解还原铬渣的主要因素:温度、铬渣粒径、球团尺寸、铬渣与焦油当量比等进行探讨。结果表明:还原铬渣的质量随温度升高而提高,温度超过400℃后无明显变化,减小铬渣粒径与球团尺寸可明显提高还原质量。当热解温度为400℃,还原时间10 min,铬渣与焦油当量比2.29,铬渣粒径0.074 mm,球团粒径2.5 mm时,可得到Cr(VI)还原率98.65%的还原铬产品。     

改性白菜叶渣对重金属Zn~(2+)吸附性能

为了研究白菜叶渣对锌离子的吸附作用,采用静态吸附的方法,以酸碱处理后的废弃白菜渣为原材料,获得加入量(X1)、浓度(X2)、时间(X3)、pH(X4)和温度(X5)各单因素对Zn2+的最佳吸附点,再通过二次回归正交旋转组合设计对白菜渣吸附Zn2+的条件进行优化,并讨论了吸附过程中吸附等温线与动力曲线的相关特征。结果表明,当加入量0.2g、浓度2 mg/L、吸附时间5 h、pH为4以及温度20℃时,吸附达到最大95.08%,验证所测最大吸附率93.89%,与预测值基本相符。对比实验说明白菜渣对Zn2吸附效果要优于活性炭。25℃和35℃时的等温线的拟合结果表明,白菜渣对Zn2+是物理化学共同吸附的复杂过程。     

改性活性炭对废水中铬离子的吸附

改性活性炭被广泛应用于吸附水体中重金属离子,但关于铁改性活性炭吸附性能的研究报道甚少。本研究对活性炭进行铁改性处理,并将之应用于水中的铬离子吸附,考察了吸附时间、溶液p H对改性活性炭吸附Cr(Ⅵ)效果的影响。实验结果表明,在25℃下,p H为3,吸附时间为300 min时,其对Cr(Ⅵ)的去除率为91.4%。铁改性活性炭对铬离子的吸附机理服从准二级动力学方程,该吸附剂吸附等温线服从Langmuir方程,饱和吸附量为28.82 mg/g。     

饮用水源突发性铬污染去除方法的比较研究

通过对水源水中铬污染的不同去除方法的比较实验及验证实验,研究pH值、FeSO_4、NaHSO_3和活性炭的投加量对铬的去除效果的影响。实验结果表明,当原水中铬的含量为0.5 mg/L时,未调节pH值的条件下,亚硫酸氢钠与活性炭对铬的最高去除率为50%左右;硫酸亚铁还原沉淀在FeSO_4·7H_2O:Cr~(6+)投加比=16:1时,滤后出水中Cr~(6+)的去除率达到96.8%,中试出水中未检出Cr~(6+),出水的总Cr、总Fe等指标完全达到《生活饮用水卫生标准》(GB 5749-2006)的要求。     

铬渣冷固结球团的还原实验及其解毒机理

铬渣中六价铬对人体和生态环境都有严重的危害,必须进行处理。在铬渣加入粘结剂、煤粉或铁精矿粉制成冷固结球团,在一定温度下进行还原解毒。实验表明,在1200℃以下用煤气铬渣球团,铬渣基本解毒;在1400℃熔炼还原后的铬渣球团,可使铬全部还原成金属铬或Cr7C3,在铁碳化合物存在的情况下,可形成(Fe·Cr)7C3,铬渣彻底解毒,并能回收铬渣中的Cr、Fe等元素。故可将铬渣制成冷固结球团进行还原解毒,进行高温熔炼后,可达到铬渣无害化、资源化处理。     

锰渣堆肥过程中理化性质及基于Tessier法的重金属行为分析

通过堆肥发酵,研究了电解锰渣、废糖蜜和甘蔗渣在一定配比下添加活性污泥、猪粪水、城市河湖污泥、树林腐土、生物菌剂以及不添加微生物来源物对废渣中重金属化学形态和理化特性的影响。堆肥处理30 d监控其物理特性,采用ICP法分析了6种重金属元素总量,并利用Tessier五步连续浸取法对堆肥前后做重金属的形态分析。结果表明:堆肥过程中系统温度均高于环境温度;6种条件下,堆肥体系的pH值均得到了显著提高;堆肥可以降低电解锰渣态中重金属的生物有效性。堆肥处理有利于降低电解锰渣利用中重金属污染的风险。     

铬渣的高温-快冷-等温转变固化研究

采用高温-快冷-等温转变对铬渣进行固化处理,通过调整配料成分确定最高固化温度,使铬渣的处理量最大且软化温度最低,以利节能和实际工业应用。结果显示,混合物以含铬渣35％～40％、粘土35％～45％、河沙10％、粉煤灰10％时,软化温度最低为1120～1125℃,固化产物经过标准毒性浸出,所测定的浸出液六价铬离子浓度低于0．8mg／L。该固化方法具有操作流程较短、铬渣处理量大等优点,可成功固化其中的六价铬离子。其固化原理是铬渣中铬离子在高温下迁移至相界面,在合理的冷却过程中稳定存在于相界面,而不易被浸出。     

土壤中无机钠盐对不同形态Cu含量的影响

采用TESSIER连续提取法研究了不同种类、不同加入量的无机钠盐对土壤中不同形态Cu含量的影响。结果表明,对于可交换态Cu,3种无机钠盐的加入均使其含量减少,其中NaCl的影响最大,4、8g/kg的NaCl分别使其减少了28.13%(质量分数,下同)和50.59%;对于碳酸盐结合态Cu,3种无机钠盐的加入均使其含量增加,其中Na2CO3(8g/kg)对其影响最大;对于铁锰氧化态Cu,Na2SO4和Na2CO3的加入使其含量先升高后降低,NaCl则使其含量降低;有机结合态Cu受Na2SO4和Na2CO3的影响较大,在它们的影响下含量均增加;残渣态Cu在3种无机钠盐的影响下变化幅度均很大,其中4、8g/kg的Na2SO4分别使其含量减少了47.47%和62.21%。     

Phytoavailability and geospeciation of cadmium in contaminated soil remediated by Rhodobacter sphaeroides

A microorganism was isolated from oil field injection water and identified as Rhodobacter sphaeroides. It was used for the remediation of simulated cadmium-contaminated soil. The phytoavailability of Cd was investigated through wheat seedling method to determine the efficiency of remediation. It was found that after remediation, the accumulation of Cd in wheat roots and leaves decreased by 67% and 53%, respectively. The Cd speciation in soil was determined with Tessier extraction procedure. It was found that the total Cd content in soil did not change during the experiments, but the geo-speciation of Cd changed remarkably. Among the five fractions, the concentration of exchangeable phases decreased by 27-46% and that of the phases bound to Fe-Mn oxides increased by 22-44%. The decrease of Cd accumulation in wheat showed significant positive correlation with the decrease of exchangeable phases. It could be concluded that the remediation of R. sphaeroides was carried out through the conversion of Cd to more stable forms. The decrease of sulfate concentration in supernatant indicated that the R. sphaeroides consumed sulfate.     

Speciation of scandium and gallium in soil

A method for the speciation of scandium and gallium in soil has been developed. The sequential extraction scheme of Tessier et al. for heavy metals was examined for the scandium and gallium separation. The regents proposed by Tessier were used for the extraction, and only for the residual fraction the HClO(4) was replaced with H(2)SO(4). The optimum conditions for leaching scandium and gallium from the soil were chosen for each fraction. Very sensitive, spectrophotometric methods based on the mixed complexes of Sc(III) and Ga(III) with Chrome Azurol S and benzyldodecyldimethylammonium bromide were applied for the scandium and gallium determination after their separation by solvent extraction. 100% mesityl oxide and a 0.5M solution of 2-thenoyltrifluoroacetone in xylene were chosen for the extraction of scandium and butyl acetate was selected for gallium. Soil samples from two different regions of Poland were the object of this research. The content of scandium and gallium found in the individual fractions of Upper Silesia soil (industrial region) was [in mugg(-1)] Sc: I, 1.52; II, 0.53; III, 7.78; IV, 1.79; V, 0.20; Ga: I, 24.7; III, 29.2; IV, 35.4; V, 6.9. In Podlasie soil (agricultural region), the content of both elements was clearly lower. The total content of scandium and gallium in the five soil fractions was in good correlation with the total content of these elements in the soils found after HF-H(2)SO(4) digestion. Analysis using the ICP-OES method gave comparable results.     

Speciation of chromium in 12 agricultural soils from Turkey

The objective of the study was to speciate and to evaluate various soil Cr species in relation to soil properties. Surface soil samples were taken from outskirts of the Cr factory and applied a sequential extraction procedure. Extracts analyzed in atomic absorption spectrophotometry (AAS). Chromium was partitioned into exchangeable Cr, Cr bound to carbonate, Fe-Mn oxide, and organic matter, and residual Cr. The most common form of chromium was in the residual form, followed by the organic form. Very low concentrations of Cr were found in the exchangeable and carbonate forms. Mean values of the extractable forms of Cr, expressed in percentages of total soil contents were: 0.94% exchangeable, 0.80% carbonates, 2.13% oxides, 7.08% organics and 89.81% residual. Multiple regression analysis of analytical data revealed that soil pH, contents of organic matter and calcium carbonate were the most important factor controlling the distribution of Cr forms determined.     

Extraction of arsenic in a synthetic arsenic-contaminated soil using phosphate

An environment-friendly and cost-effective extraction method has been studied for the removal of arsenic from contaminated soil. A yellow-brown forest soil was contaminated with arsenic(V) and used as a model soil. Among various potassium and sodium salts, potassium phosphate was most effective in extracting arsenic, attaining more than 40% extraction in the pH range of 6–8 with minimum damage to the soil properties. Exchange mechanism is proposed for the extraction of arsenic from soil by phosphate. Sequential extraction shows that phosphate is effective in extracting arsenic of Al- and Fe-bound forms. Arsenic of residual form was not extracted. Arsenic was efficiently extracted by phosphate solution of pH 6.0 at 300 mM phosphate concentration and at 40°C.     

聚环氧琥珀酸萃取锰泥残渣中铬的研究

聚环氧琥珀酸(PESA)是一种具有无磷及非氮结构、环境友好型水溶性聚合物,且具有螯合多价金属阳离子的性能和可生物降解性的特征,选取其作为锰泥残渣中铬的螯合萃取剂,研究了不同pH、螯合萃取剂剂量、搅拌时间下PESA对铬的萃取率。结果表明:(1)最佳萃取条件为pH=4、PESA剂量30mg/g、搅拌时间60min;在最佳萃取条件下,铬的萃取率可达95%。(2)从结构上看,PESA是由醚基和羧基基团组成的高分子聚合物,羧基基团是与金属离子作用的主要官能团,它对Ca2+、Mg2+、Zn2+、Cr(Ⅲ)、Cr(Ⅵ)和Pb2+等有较强的螯合能力;从溶液的配位角度看,PESA与金属有较强的结合能力。因此,PESA对锰泥残渣中的铬有萃取作用。     

Forms of cadmium in sandy soils after amendment with soils of higher fixing capacity

Most of the Cd applied through phosphatic fertilizers in sandy soils tends to stay in mobile forms (soluble or exchangeable) and hence the risk of it leaching to underground water or its uptake by plants is higher. A sequential extraction procedure was used to assess the efficacy of amending materials (soils containing inorganic or organic adsorption components) on the re-distribution of forms of Cd in a sandy soil. Amendment of the sandy soil with each of the three soils (yellow earth, lateritic podzolic and peaty sand) was generally effective in altering the more mobile or available forms of Cd to immobile or unavailable forms. The extent of alteration varied with the type of component present in the amendment soil, pH and the rate of Cd addition. The yellow earth was more effective at pH 7, whereas the peaty sand was equally effective at both pH 4 and 7 in altering the mobile to immobile forms. The lateritic podzolic soil was the least effective of the soils used at any of the pH values.     

Potentially toxic element fractionation in technosoils using two sequential extraction schemes

This study reports the chemical fractionation of several potentially toxic elements (Zn, Pb, Cd, As, and Sb) in contaminated technosoils of two former smelting and mining areas using two sequential extraction schemes. The extraction schemes used in this study were the Tessier’s scheme and a modified BCR scheme. The fractions were rearranged into four equivalent fractions defined as acid soluble, reducible, oxidizable, and residual to compare the results obtained from two sequential extraction schemes. Surface soils were samples from a waste landfill contaminated with Zn, Pb, and Cd located at Mortagne-du-Nord (MDN; North France) and from a settling basin contaminated with PTE such as As, Pb, and Sb located at La Petite Faye (LPF; Limoges, France). The study of the Zn, Pb, Cd, As, and Sb partitioning in the acid soluble, reducible, oxidizable, and residual fractions of the technosoils revealed that Zn, Cd, and Pb were mainly associated with the acid soluble and reducible fractions for MDN site, while As, Sb, and Pb were associated with residual fraction for LPF site. Fractionation results indicate that the percentages of Zn, Pb, Cd, As, and Sb extracted in Fe–Mn oxide bound fraction of Tessier’s scheme were always higher than those extracted by modified BCR scheme. This may be attributed to the stronger Tessier’s scheme conditions used to extract this fraction. In contrast the percentages of Zn, Pb, Cd, As, and Sb extracted in the organic fraction of the modified BCR scheme were always higher than those of the Tessier’s scheme. The order of mobility of PTE was as follows: Cd?>?Zn?>?Pb in MDN site and As?>?Sb?>?Pb in LPF site. PTE were distributed in all soil fractions, with the most relevant enrichments in extractable and residual fractions. A significant amount of Cd, Pb, and Zn were rather mobile, which suggests that these elements can be readily available to plants and soil organisms.     

Distribution and Fractionation of Copper in Soils of Apple Orchards (5 pp)

Background Frequent application of Bordeaux mixture, which includes copper, as a fungicide in fruit and grape orchards may lead to copper accumulation in the soil, especially when orchard age and application times increase. The objectives of this study were: (i) to investigate the copper content and its spatial distribution in orchard soils; (ii) to identify the copper fractionation in soil and its relationship with plant uptake; (iii) to understand the characteristics of copper contamination in orchard soils. Materials and Methods Soil profile samples were taken in apple orchards with ages of 0, 5, 10, 20, 30 years and pot experiments were also carried out to study the effects of external copper input on copper fractionation. All soil samples were air-dried, ground and extracted with 0.43 mol L–1 HNO3 for the total absorbed copper. Fractionation determination was conducted following Tessier and Shuman sequential extraction methods, and copper was measured with AAS. Plant samples were first dry ashed, dissolved with 6 mol L–1 HCl and then copper and other elements were measured with ICP-MS.Results and Discussion Soil total Cu was higher in the apple orchards than that in non-orchard fields and was seen to have increased with orchard age. Soil Cu increased substantially with the average annual copper increase, ranging from 2.5 to 9 mg Cu kg–1. The distribution of copper in the soil profile was uneven, decreasing from surface to deeper layers, and the differences were significant, but the contents in every layer were also significantly correlated with those in the next layers. For all copper fractions, the organically bound, crystalline Mn oxide bound, and amorphous Fe bound fractions extracted with the Shuman method were much higher than the exchangeable and residual fractions. Using the Tessier method, organically bound, carbonate bound and Fe-Mn oxide bound fractions were much higher. With an increase in external copper input, the organically bound, crystalline Mn oxide bound and amorphous Fe bound fractions in the Shuman method and organically bound, carbonate bound and Fe-Mn oxide bound fractions in the Tessier method all increased significantly, while the changes in other fractions were not significant. Soil total copper and copper fractions were found to have good correlations with apple tree uptake. Copper in fruit flesh had significant correlations with soil total content in the 0–10 cm layer, all the copper fractions in the 0–5 cm layer, and some fractions in the deeper layers. Conclusion Copper content in orchard soils increased significantly with intensive application of Bordeaux mixtures and orchard age. Copper content decreased sharply from the topsoil to deeper soil layers. The copper contents in different layers also significantly correlated with those in the next layers. Dominant fractions of the copper in soil were mainly associated with organic matter, iron and manganese oxides and carbonates. A close relationship was found between the copper content in soils and in apple tree organs (which contained 8.9 to 66mg kg–1 Cu). Recommendation and Perspective Though most copper in the soil was specifically adsorbed or immobilized, and copper was mainly distributed in topsoil, which was essentially devoid of roots, the copper concentration of fruit still had significantly positive correlations with soil copper and most copper fractions. Therefore, measures must be taken to control copper accumulation in orchard soils and to make the apple fruit production sustainable.     

纳滤处理含Cr(VI)废水的试验研究

采用纳滤对含Cr(Ⅵ)废水进行试验研究,讨论了初始浓度、pH、浓差极化、共存离子对处理效果的影响.试验结果表明,NF90膜对含Cr(Ⅵ)废水有良好的处理效果,去除率超过了98%,出水Cr(Ⅵ)浓度低于0.5 mg/L,可以达标排放或回用于镀件漂洗.