干式还原法处理铬渣的机理及应用

采用干式还原法处理铬渣。在多级还原焙烧炉中于高温条件下,将过量的煤粉和铬渣混合后与O₂反应,经冷却、擦磨、磁分离后可得到铁精砂和处理后铬渣。介绍了干式还原法处理铬渣的机理和工艺参数。以3种铬渣试样进行应用试验,经多级还原焙烧—磁分离后,铬渣中的Cr（Ⅵ）质量浓度为0.05~0.18 mg/L,低于HJ/T301—2007标准中的要求（0.50 mg/L）,可作为建材原料加以利用。磁分离得到的铁精砂产品中铁的质量分数大于50%,铁回收率大于70%。目前设计的多级还原焙烧炉单炉处理铬渣能力为150 kt/a,标煤消耗为35 kg/t,处理成本约为60元/t。     

磁性氧化石墨烯和磁性竹炭对Cr（Ⅵ）的吸附

制备了两种磁性碳基材料——磁性氧化石墨烯（MGO）和磁性竹炭（MBC）,并将其用于模拟含Cr（Ⅵ）废水的吸附。采用SEM,BET,FTIR技术对吸附剂进行了表征。表征结果显示：MBC具有与MGO相似的薄片层结构,且MBC的BET比表面积更大（为32.872 6 m²/g）,可为Cr（Ⅵ）提供大量的吸附位点。实验结果表明：向100 mL废水中加入20.0 mg吸附剂,在废水pH为1.0、吸附温度为30 ℃、初始Cr（Ⅵ）质量浓度为10.0 mg/L的条件下,MGO和MBC的平衡吸附时间分别为50,70 min,平衡吸附量分别为37.7,49.7 mg/g,吸附平衡时的Cr（Ⅵ）去除率分别为75.4%和99.4%;两种磁性材料对Cr（Ⅵ）的吸附均很好地符合Langmuir等温吸附模型;在酸性介质中,MGO和MBC的表面基团与HCr₂O₇^-和Cr₂O₇^2-之间有氢键作用。     

土壤铬（VI）污染及微生物修复研究进展（Progress on Microbial Remediation of Chromium-Contaminated Soil）

在总结国内外相关研究基础上,介绍了土壤环境中铬(Cr)的污染来源、现状及其对生物的危害,阐述了Cr在土壤中的存在形态和转化机理,并重点综述了土壤重金属Cr(VI)污染的微生物修复机理:土壤中的Cr(VI)可以在微生物还原作用、生物吸附、富集等作用下降低其生物可利用性和毒性,从而达到Cr污染土壤修复的目的.此外,针对微生物修复过程中存在的问题,提出了提高微生物修复Cr污染土壤效果的措施,并对土壤Cr污染微生物修复的发展趋势进行了展望.     

水和废水中六价铬测定关键问题研究

结合环境监测工作实际,应用国标经典分析方法——GB7467-1987《二苯碳酰二肼分光光度法》对水和废水中六价铬测定进行系统研究。深入探讨运用该方法进行水和废水中六价铬测定中的一些关键操作技术问题。指出在标准分析方法的基础上,选用最新生产的合格的二苯碳酰二肼试剂,初步了解水样来源,尽量弄清所含成分,准确进行干扰消除,适当改进国标分析方法,能够确保水样六价铬测定的精密度和准确度。     

铬渣污染土壤PM10和PM2.5组分中六价铬的生物可给性及健康风险评估

为获取土壤细颗粒组分中污染物的浓度及其生物可给性,分析了某铬渣污染场地土壤PM_(10)和PM_(2.5)组分中六价铬的浓度分布特征,并采用统一生物可给性测试方法(Unified Bioaccessibility Method,UBM)和呼吸吸入生物可给性测试方法(Inhalation Bioaccessibility Method,IBM) 2种体外模拟法测试了六价铬在胃、肠及肺中的生物可给性。结果显示:(1)六价铬和总铬在PM_(10)和PM_(2.5)组分中的含量大多明显低于PM_(250)组分,PM_(10)组分中六价铬和总铬的累积因子(accumulation factors,AF)分别为0.080#12.297和0.008#0.261,PM_(2.5)组分中六价铬和总铬的AF分别为0.019#5.721和0.005#0.342,相比于总铬而言,六价铬在细颗粒中的累积程度更高。较低的有机质(organic matter,OM)含量可能导致了六价铬AF的明显增加。不同组分中六价铬占总铬的比例分别为2%#17%(<250μm)、21%#98%(<10μm)和22%#82%(<2.5μm),表明在土壤细颗粒中,铬更多地以六价铬的形式存在;(2)通过UBM获取的PM_(250)组分中六价铬在胃提取阶段的生物可给性因子为0.0301%#0.9483%,平均值为0.4821%;肠阶段可给性因子为0.0018%#0.3934%,平均值为0.1578%,约为胃提取阶段的0.33倍;(3)通过IBM获取的PM_(10)组分中六价铬在肺阶段的生物可给性因子为2.52%#41.50%,平均值14.47%; PM_(2.5)组分中六价铬的生物可给性因子为2.40%#88.12%,平均值为48.86%,约为PM_(10)组分的3.38倍;(4)在考虑生物可给性条件下,六价铬产生的人体总致癌风险水平从2 430.04×10~(-6)下降至125.83×10~(-6),而且,六价铬呼吸途径产生的致癌风险水平极高,是经口摄入的5.04#176.38倍(胃)、10.92#10 198.00倍(肠),表明呼吸吸入是六价铬致癌风险最为关键的暴露途径。因此,通过测定土壤细颗粒组分中六价铬的生物可给性,能够显著提高铬渣污染土壤健康风险评估的可靠性。     

酸化-电动强化修复铬渣场地污染土壤

为解决常规电动修复方法对Cr污染土壤Cr(T)(总Cr)去除效率低的问题,提出了酸化预处理-电动强化修复技术. 以国内某化工厂铬渣堆放场地Cr污染土壤为研究对象,通过改变土壤酸化条件,分析乙酸和柠檬酸的酸化时间、酸浓度(以c计)对电动修复Cr污染土壤中Cr去除率的影响,并对土壤中Cr的形态进行分析. 结果表明:①酸化预处理-电动强化修复技术可以显著提高Cr污染土壤中Cr的去除率,其中0.9 mol/L柠檬酸酸化5 d组Cr(T)和Cr(Ⅵ)的去除率由对照组的6.23%、19.01%分别升至26.97%、77.66%. ②土壤酸化可以将部分Cr由碳酸盐结合态向水溶态转化,进而提高Cr去除率;在适宜的酸浓度范围内,酸浓度越高,土壤释放的Cr越多,Cr去除效果就越好. ③与乙酸组相比,柠檬酸组Cr的去除率较高,因为柠檬酸本身也是一种络合剂,在酸化作用释放碳酸盐结合态Cr的基础上,柠檬酸能与Cr发生络合作用,进一步提升了Cr的去除率. 电动修复过程中迁移出土壤的Cr主要以醋酸可提取态、可还原提取态和可氧化提取态为主,残留Cr的生物可利用性降低.      

Concentrations and Pools of Heavy Metals in Urban Soils in Stockholm,Sweden

The concentrations of heavy metals (Cd, Cr, Cu, Hg, Ni, Pb andZn) and arsenic (As) were surveyed and the metal pools estimatedin soils in Stockholm Municipality. The sampling sites were distributed all over the entire municipality with a higher sampling density in the city centre. Soils were sampled to a maximum depth of 25 to 60 cm. Soil texture, total-C content, electrical conductivity and pH were analysed. Heavy metal concentrations were determined after wet digestion with boiling7 M HNO₃.The results showed a wide range in heavy metal concentrations, as well as in other soil properties. The city centre soils constituted a rather homogeneous group whereas outside this areano geographical zones could be distinguished. These soils were grouped based on present land use, i.e. undisturbed soils, public parks, wasteland (mainly former industrial areas), and roadside soils. The city centre and wasteland soils generally hadenhanced heavy metal concentrations to at least 30 cm depth compared to park soils outside the city centre and rural (arable)soils in the region, which were used to estimate background levels. For example, the mean Hg concentration was 0.9 (max 3.3)mg kg^-1 soil at 0–5 cm and 1.0 (max 2.9) at 30 cm depth in the city centre soils, while the background level was 0,04 mg kg^-1. Corresponding values for Pb were 104 (max 444) and135 (max 339) mg kg^-1, at 0–5 and 30 cm, respectively, while the background level was 17 mg kg^-1.The average soil pools (0–30 cm depth) of Cu, Pb and Zn were 21,38 and 58 g m^-2 respectively, which for Pb was 3–4 timeshigher and for Cu and Zn 1.5–2 times higher than the backgroundlevel. The total amount of accumulated metals (down to 30 cm)in the city centre soils (4.5^*10 ⁶ m² public gardens and green areas) was estimated at 80, 1.1, 120 and 40 t for Cu, Hg, Pb and Zn, respectively. The study showed (1) thatfrom a metal contamination point of view, more homogeneous soilgroups were obtained based on present land use than on geographicdistance to the city centre, (2) the importance of establishing a background level in order to quantify the degree of contamination, and (3) soil samples has to be taken below the surface layer (and deeper than 30 cm) in order to quantify theaccumulated metal pools in urban soils.     

用鼓风炉渣消除铬渣毒性的研究

针对含铬废渣对环境污染大及治理难的特点,提出了以废渣治理废渣的技术,利用鼓风炉渣的还原性以及刚排出时的高温,将铬渣按一定比例与之混合,进行铬渣的解毒处理,并对铬渣的解毒机理进行了理论分析。从实验结果可以看出,当铬渣加入量低于10%时,该技术能够较彻底的将铬渣中的Cr6+进行解毒。     

模拟酸雨对红壤中铬释放的影响研究

采用室内模拟酸雨淋溶土柱的方法,研究了酸雨淋溶下4种红壤铬的释放特征与规律.结果表明:经过相当于9 150和10 650 mm降水量的淋溶后,与对照(pH为5.6)相比,pH为4.5的酸雨使红壤铬的累积释放量提高4.03%～88.54%,pH为3.5的酸雨使其提高6.75%～308.42%;不同红壤铬的释放量随淋溶量的变化规律较为相似,总体上表现为释放量随淋溶量的增加而缓慢上升.酸雨对红壤铬释放的促进作用一方面是由于酸雨提高了Cr(OH)₃的溶解度;另一方面是由于H+对Cr3+的竞争吸附作用、酸雨所导致的土壤溶液中离子强度增加及酸雨对土壤胶体(主要是铝和铁的氧化物及氢氧化物)的溶蚀作用而降低了Cr(Ⅲ)的吸附量.      

Optimization of the removal of chromium and lead by Penicillium chrysogenum using 2k factorial experiments

This study aims to prepare a low-cost, environmentally friendly, and alternative, biosorbent to remove chromium Cr (III) and lead Pb (II) from polluted water and to find out the highest removal efficiencies using 2^k factorial experiments. The Cr (III) and Pb (II) tolerant fungal strain identified as Penicillium chrysogenum was isolated from ceramic industrial sludge. The impact of process variables on biosorption of Cr (III) and Pb (II) by P. chrysogenum was first evaluated with the Taguchi screening design. Factors and levels were determined to optimize Cr (III) and Pb (II) removal efficiency. According to this, five factors; initial concentration, pH, biosorbent dose, temperature, and inactivation methods were determined for both metals, each factor defined as a fixed factor with two levels. Optimization of the parameters affecting the removal process was determined by the Taguchi method and the signal-to-noise (S/N) ratios are calculated. The maximum removal efficiency (99.92%) was observed at pH 7, biosorbent 1 mg L^–1, inactivation with autoclaving, and at 20°C with an initial metal concentration of 50 mg L^–1 Cr (III). On the other hand, the maximum removal efficiency (98.99%) was observed at pH 4, biosorbent 5 mg L^–1, inactivation with autoclaving, and at 20°C with an initial metal concentration of 50 mg L^–1 Pb (II). Furthermore, metal ions removal by P. chrysogenum was also confirmed by scanning electron microscopy (SEM) combined with an energy dispersive X-ray spectrometer (EDS). The presence of functional groups on fungal cells of metal binding was investigated by Fourier transform infrared (FT-IR).