Interaction between Cr(VI) and a Fe-rich soil in the presence of oxalic and tartaric acids

This study examined the interaction between Cr(VI) and a Fe-rich soil in the presence of low-molecular-weight organic acids as a function of pH. Oxalic and tartaric acids were chosen since they existed in soils commonly. Batch experiments showed that adsorption of Cr(VI) by the soil within the pH range examined was inhibited in the presence of oxalic acid, which was more pronounced when the initial ratio of [oxalic acid]/[Cr(VI)] was raised from 1:1 to 2:1. With the addition of tartaric acid, concentration of Cr(VI) in equilibrium solutions was far less than that of single adsorbate system across the pH wide (2.5–5.5), which was noticeable especially at low pH. The results were attributed to Cr(VI) adsorption and, particularly, the soil surface catalyzed reduction of Cr(VI) to Cr(III) by tartaric acid. The data reported in this paper suggested that the mobility, the bioavailability, and the toxicity of Cr(VI) in soil environments might be greatly affected by pH, the presence and nature of low-weight-molecular organic acids (oxalic and tartaric acids).     

镍钛改性膨润土对铬的吸附性能研究

以钠基膨润土为原料,制备镍钛交联改性膨润土、镍钛有机复合改性膨润土,并应用于含铬模拟废水的处理。探讨了改性膨润土的用量、pH值、吸附时间等最佳使用条件,比较了原土、交联改性土、有机复合改性土对铬的吸附效果。结果表明改性土的吸附效果明显优于原土,在最佳实验条件下,交联改性土、有机复合改性土对Cr(Ⅵ)的去除率分别达到了87%和96%。两种改性土对铬吸附行为均符合Langmuir吸附等温方程,饱和吸附量和Lang-muir常数分别为3.1827mg/g、8.5543mg/g和3.5007、1.2738。     

自然状态与加热改性的黄铁矿处理含铬(VI)废水的实验研究

最近几年,人们对一些天然矿物在处理重金属污染物过程中所表现出的高效性、经济性和安全性倍加青睐,并逐渐发展成环境矿物材料研究的方向［１,２］。国外对某些矿物吸附机理也有较系统的评述,有关含铬矿物与有机物的作用也有报道［１,３］。１　实验部分（１）试样来源：黄铁矿取自硫铁矿矿山,经鉴定与粉碎,淘洗,烘干,筛分,磁选后获得。（２）含铬（ＶＩ）废水：用分析纯重铬酸钾（Ｋ２Ｃｒ２Ｏ７）和蒸馏水配制。（３）实验仪器：反应体系的酸度用ＰＨＳ３Ｃ型酸度计测定,反应平衡时的吸光度用ＵＶ１６０Ａ分光光度计测定,…     

生物炭负载纳米零价铁对地下水中六价铬的修复效果和影响因素研究

纳米零价铁（nZVI）存在易团聚、钝化和迁移性差等问题,影响对六价铬[Cr(VI)]污染地下水的原位修复效果。为了开发一种低成本、绿色的nZVI改性材料,以球磨生物炭（BC）为载体负载nZVI,构建了nZVI@BC反应体系,再利用羧甲基纤维素（CMC）稳定nZVI@BC,合成了一种新型高效、抗钝化纳米级别的修复材料CMC-nZVI@BC。对改性前后的nZVI进行表征分析,探究了材料添加量、Cr(VI)初始质量浓度、初始pH值、温度及地下水化学组分对CMC-nZVI@BC去除Cr(VI)的影响,并阐明去除Cr(VI)的机理。得出如下结论：（1）铁碳质量比为2∶1时的nZVI@BC对Cr(VI)的去除效果最好, 3 h内0.6 g/L CMC-nZVI@BC对50 mg/L Cr(VI)的去除率达99.9%,表现出较高的去除Cr(VI)的速率和能力;（2）去除Cr(VI)的主要机制是通过还原和沉淀反应;（3）在pH值2～10范围内,pH值对去除Cr(VI)有显著影响,温度影响较小;（4）${\mathrm{SO}}_4^{2-}$的存在促进了Cr(VI)的去除,而${\mathrm{HCO}}_3^{-} $、${\mathrm{NO}}_3^{-} $、Ca2+、Mg2+和腐殖酸对Cr(VI)的去除均有不同程度的抑制作用。这些结果表明,CMC-nZVI@BC可以作为有效去除Cr(VI)的原位修复药剂,为nZVI在地下水原位修复的应用提供了依据。     

单斜与六方磁黄铁矿处理含Cr(VI)废水过程中pH值变化规律

与六方磁黄铁矿相比,单斜磁黄铁矿Fe缺位较普遍。在初始pH值分别为3.40～9.66和3.47～9.66较宽范围内,利用单斜磁黄铁矿和六方磁黄铁矿处理含Cr(VI) 废水,当反应达到充分平衡时,废水的pH值分别变化在3.61～4.47和5.39～6.57范围内。六方磁黄铁矿除Cr(VI)效果明显不及单斜磁黄铁矿,但被氧化的六方磁黄铁矿除Cr(VI)效率有所 提高。电化学分析表明,在酸性介质中处理的反应过程为H+的消耗过程,而在碱性介质中 则为OH 的消耗过程。根据pH值的这一变化规律,可自行调节处理过程中水质的酸性变化 ,能节省传统工艺中需要加碱以中和处理后酸性水的环节,具有一定的实际应用价值。     

天然黄铁矿除Cr（Ⅵ）中Cr2S3物相的发现

利用天然黄铁矿处理含Cr(Ⅵ)废水实验,在反应中与反应后黄铁矿表面和胶体沉淀物中明显出现Cr2p的XPS能谱峰,能拟合出574.7～575.1eV、576.6～576.9eV和578.2～578.7eV3个峰位,分别代表Cr2S3、Cr2O3和CrO3物相。在实验过程中新发现Cr2S3沉淀物相,表明在常温常压下的水溶液介质中也能产生铬的硫化物物相。充分利用这些含铬物相,能使天然黄铁矿包括天然磁黄铁矿在还原Cr(Ⅵ)的同时,无需加碱就可将Cr(Ⅲ)沉淀转移到胶体沉淀物中,处理后的上清液中全Cr含量低于1.5mg/L的国家允许排放标准。天然黄铁矿自身溶解出的重金属含量很低,不影响处理后的出水水质。开发利用Cr2S3等含铬沉淀物相,便于推广应用天然黄铁矿和磁黄铁矿还原Cr(Ⅵ)同时沉淀Cr(Ⅲ)的一步法除铬新工艺。     

焦作地区浅层地下水铬(Ⅵ)污染机理及迁移预测

通过对焦作地区浅层地下水中铬(Ⅵ)污染物分布特征进行调查,分析了研究区浅层地下水中铬(Ⅵ)的污染机理,并运用Visual MODFLOW建立地下水流模型及溶质运移模型,模拟预测了浅层地下水中铬(Ⅵ)的迁移规律。结果表明：研究区浅层地下水铬(Ⅵ)污染严重,污染源是位于老君庙西南方向的焦作某电厂堆灰场,主要原因是露天堆放的粉煤灰中的铬(Ⅵ)污染物在长期淋滤作用下下渗污染含水层。气候条件、包气带岩性、地下水化学环境以及人为因素等也间接使浅层地下水铬(Ⅵ)浓度升高;模拟结果显示在未来的五年时间内,受地形和地下水动力场的影响,浅层地下水中铬(Ⅵ)的迁移方向与地下径流方向一致,沿大沙河水流方向上扩散速度更快,污染区域面积逐渐增大。     

Competition between enzymatic and abiotic reduction of uranium(VI) under iron reducing conditions

Reduction of U(VI) under iron reducing conditions was studied in a model system containing the dissimilatory metal-reducing bacterium Shewanella putrefaciens and colloidal hematite. We focused on the competition between direct enzymatic uranium reduction and abiotic reduction of U(VI) by Fe(II), catalyzed by the hematite surface, at relatively low U(VI) concentrations (< 0.5 μM) compared to the concentrations of ferric iron (> 10 mM). Under these conditions surface catalyzed reduction by Fe(II), which was produced by dissimilatory iron reduction, was the dominant pathway for uranium reduction. Reduction kinetics of U(VI) were identical to those in abiotic controls to which soluble Fe(II) was added. Strong adsorption of U(VI) at the hematite surface apparently favored the abiotic pathway by reducing the availability of U(VI) to the bacteria. In control experiments, lacking either hematite or bacteria, the addition of 45 mM dissolved bicarbonate markedly slowed down U(VI) reduction. The inhibition of enzymatic U(VI) reduction and abiotic, surface catalyzed U(VI) reduction by the bicarbonate amendments is consistent with the formation of aqueous uranyl-carbonate complexes. Surprisingly, however, more U(VI) was reduced when dissolved bicarbonate was added to experimental systems containing both bacteria and hematite. The enhanced U(VI) reduction was attributed to the formation of magnetite, which was observed in experiments. Biogenic magnetite produced as a result of dissimilatory iron reduction may be an important agent of uranium immobilization in natural environments.     

羧甲基纤维素稳定纳米铁去除水中六价铬的研究

零价纳米铁(NZVI)具有较高活性,近年受到人们关注并将其应用于地下水污染原位修复,但在实际应用中NZVI易发生氧化与团聚,容易失活。因此尝试运用环境友好型材料对NZVI进行表面改性,选择羧甲基纤维素(CMC)对纳米铁进行表面包覆获得CNZVI,研究不同CMC含量包覆NZVI的分散稳定性和CNZVI对水中六价铬的去除效果。结果表明：经过改性后的CNZVI分散稳定性要明显优于商用纳米铁RNIP,包覆CMC的比例越高,CNZVI的稳定性越好,在较高的CMC包覆比例下,纳米铁不易失活并具有良好的反应活性,对溶液中六价铬有很好的去除效果。     

Removal of Cr(VI) and phenol coupled with the reduction of sulfate by sulfate-reducing bacteria sludge

Biological treatment of industrial wastewater containing heavy metal and organic pollutant has attracted extensive attention. In this study, Cr(VI) reduction coupled with phenol degradation was investigated by the sulfate-reducing bacteria (SRB) sludge with addition of zero-valent iron (ZVI). The results showed that the SRB wet sludge (SWS) had a good bioactivity in the reduction of Cr(VI) only when the initial concentration of Cr(VI) was below 60 mg L^?1. The addition of ZVI significantly enhanced the bioactivity and reusability of SWS, and the reduction percentage of Cr(VI) achieved 98% after SWS was successively used for seven cycles. SWS coupled with ZVI showed a high activity in phenol degradation, with more than 94% phenol being degraded in each cycle. However, in the simultaneous removal of Cr(VI) and phenol, phenol degradation was inhibited due to the toxicity of Cr(VI) to phenol degrading microbes in SWS. On the other hand, reduction of sulfate and Cr(VI) was not affected by the presence of phenol, with more than 95% of sulfate and Cr(VI) being removed at the end of the 5th cycle. This study enriches our understanding on the applications of the SRB sludge in the removal of organic and inorganic contaminants in wastewater.     

Chromium speciation and existing natural attenuation conditions in lagoonal and pond sediments in the former chemical plant of Porto-Romano (Albania)

Near the outskirts of the Albanian port of Durres on the Adriatic Coast, at a place called Porto Romano, an old chemical complex has been producing chromate salts for a period of ∼20 years (1972–1993). As a result large quantities of chromite ore processing residue (COPR) waste were released mainly as suspended particles and/or dissolved species in effluents, which settled in a decantation pond area, 200 × 250 m in size, east of the industrial plant. Unfortunately, pollutants were spread out with time. Knowing that chromium mobility and toxicity in natural settings is species dependent, the species characterization has been carried out in different sampling media (pond sediments, lagoonal sediments and water samples). Five pond profiles were sampled within the decantation area up to a depth of ∼1 m, till the underlying Quaternary lagoonal silty-clays were reached. Total Cr content is highly variable with values between 1,130 and 24,409 mg/kg which is clearly higher than the defined local background values for lagoonal silty-clays (198 mg/kg of Cr). Leaching of Cr(VI) especially occurs in the pond sediments, which are low in OC, CEC and clay content, under acidic and neutral pH conditions (e.g. up to ∼2,230 mg/kg Cr(VI) leached from a sample containing a total concentration of Cr 12,200 mg/kg). Moreover, leaching of the Cr(III) occurs only under strictly acidic conditions (maximum 1,144 mg/kg leached from a sample containing a total Cr-concentration of 17,608 mg/kg). In this study also a number of natural attenuation conditions (i.e. reaction with lagoonal clays rich in organic matter and iron as well as isomorphous substitution) have been recognized.     

The surface properties of Malan loess and its application to removing Cr（Ⅲ） from contaminated water

Loess has unique compositions and structural characteristics and can be used for environmental protection. Differences between the surface characteristics of the Malan loess from the suburbs of Taiyuan, Shanxi Province before and after reaction with Cr(III) solution were studied by SEM/EDS, IR and XRD. The results showed that the Malan loess has a strong ability to remove Cr(III) from the solution. The surface characteristics of loess include an effect on Cr(III) in solution, as supported by the strong test evidence including the disappearance of Cr peak in the EDS spectrum, the disappearance of carbonate characteristic peaks in the infrared spectrogram, and the positive correlation between Fe and Cr peaks.     

Speciation of Cr and V within BOF steel slag reused in road constructions

Basic Oxygen Furnace (BOF) steel slag is a residue from the basic oxygen converter in steel-making operations, which is partially reused as an aggregate for road constructions. It is essentially composed of calcium, silicon and iron but also contains potential toxic elements present as traces, like chromium (Cr, 2600 mg kg^− 1) and vanadium (V, 690 mg kg^− 1), which can be released. The linked results of chemical analysis, XRD and SEM-EDX enabled to identify the main mineral phases composing BOF slag and EDX micro-analyses indicated that V and Cr were associated to dicalciumferrite. A 47-days static leaching test at a laboratory scale with a controlled pH of 5 (pH_stat leaching test) showed that Cr was little released, while V was significantly released. Finally, X-ray absorption near-edge structure (XANES) spectra of 3 BOF slag samples were recorded (“raw”, leached 47 days at pH 5 and aged 2 years in a lysimeter). XANES spectra showed that Cr is present at octahedral coordination in the trivalent form, the less mobile and less toxic one, and that its speciation does not evolve during natural ageing and leaching at pH 5. They also indicated that V is predominantly present in the + 4 oxidation state and seems to become oxidized to the pentavalent form (the most toxic form) during natural ageing.     

改性膨润土去除水溶液中Cr^6＋的性能研究

文章研究了pH值、改性剂用量和改性时间对聚合氯化铝改性膨润土去除水溶液中Cr^6＋效率的影响。实验结果表明：（1）在不同pH值条件下改性得到的聚合氯化铝改性膨润土对水溶液中Cr^6＋的去除效果明显不同。在80℃反应5 h制得的聚合氯化铝改性膨润土,在pH值=7的中性条件下改性得到的改性膨润土对水溶液中Cr^6＋（取0.5g聚合氯化铝改性膨润土处理5mg/L重铬酸钾溶液100ml）的去除率达到最大值（98.35%）。（2）改性剂用量对聚合氯化铝改性膨润土去除水溶液中Cr^6＋影响很大。当pH值=7,在80℃反应5 h的条件下改性膨润土,改性剂聚合氯化铝选用13mmol/g膨润土为宜。（3）改性时间对聚合氯化铝改性信阳膨润土去除Cr^6＋有一定的影响。当改性剂的用量为15mmol/g,pH值=9,反应温度为80℃条件下,最佳改性反应时间是4 h。     

ANC,BNC and mobilization of Cr from polluted sediments in function of pH changes

During the manufacturing of chromate salts (1972–1992) large quantities of Chromite Ore Processing Residue (COPR) were released into a decantation pond east of the former chemical plant of Porto-Romano (Durres, Albania), giving rise to yellow colored pond sediments. These Cr(VI) bearing sediments were deposited upon Quaternary silty-clay lagoonal sediments rich in iron oxides and organic matter. The pH values in these lagoonal sediments vary around 6.6, while in the pond sediments, it is mainly acidic (due to the presence of the sulfur stock piles in the area and the release of the H₂SO₄ from the activity of the former chemical plant), varying between 1.4 and 3.8. Continuous leaching of the COPR waste resulted in yellow-colored surface water runoff. The prediction of pH changes in the different types of sediments based upon acid/base neutralizing capacity (ANC/BNC) jointly with the quantitative data on release of heavy metals and especially Cr is considered an important advantage of the pH_stat leaching test if compared to conventional leaching procedures. Thus, factors controlling the leaching of Cr(VI), Cr(III), Ca, Al, Fe, Mg from the COPR were investigated by means of pH_stat batch leaching tests and mineralogical analysis. Moreover, mathematical and geochemical modeling complemented the study. The COPR in the area contain very high concentrations of chromium 24,409 mg/kg, which mainly occurs as Cr(III) (75–90%) as well as Cr(VI) (25–10%). The leaching of Cr(VI) occurs in all the range (2–10) of the tested pH values, however, it decreases under acidic conditions. Beside some reduction of Cr(VI) to Cr(III), the Cr(VI) content of the leachtes remains relatively high in the acidic environment, while the limning of Cr(VI) pond sediments will increase the release of the latter specie. The leaching of the Cr(III) occurs strictly under acidic conditions, whereby limning of these sediments will give rise to the lower solubility of Cr(III). The key mineral phases responsible for the fast release of the Cr(VI) are: the chromate salts (i.e. sodium chromate and sodium dichromate), while sparingly soluble chromatite (CaCrO₄) and hashemite (BaCrO₄) release Cr(VI) very slowly. Thus, pH and mineral solubility have been identified as key factors in the retention and the release of the hexavalent CrO₄ ²⁻ and Cr₂O₇ ⁻ from the COPR-rich pond sediments.     

粘土对地下水中U（VI）的吸附作用及其污染控制研究

进行了U（VI）在粘土上吸附的批实验，其中，粘土样采自我国南方某大型铀尾矿库库底。实验结果表明U（VI）在粘土上的吸附与浸泡液的pH值呈强烈的非线性关系，在pH值近中性时，U（VI）在粘土上的吸附达到了一个最大值，而在偏酸性或偏碱性条件下，U（VI）在粘土上的吸附迅速减少；运用表面络合理论建立了U（VI）在粘土上吸附的表面络合模型（DLM），该模型很好地拟合了实验数据。模型检验表明，它可以精确预测U（VI）在不同热力学条件下的吸附行为；此外，模拟结果表明，U（VI）的粘土上吸附在酸性条件下受固液比（M／V）影响明显，而在碱性条件下主要受浸泡液中HCO3^-和CO3^2-的控制。     

黄铁矿处理含Cr(Ⅵ)废水的进一步实验研究

利用加热与超细粉碎方法对天然黄铁矿进行改性 ,探讨其去除 Cr( )的效果。将黄铁矿加热到 4 50℃时 ,试样除 Cr( )的效率大幅度增高 ,适宜的 p H范围从小于 2 .5增加到 3.0 6～1 1 .2 0 ,且加热改性的试样用量不到天然试样用量的 1 0 %。2 0 0目至 4 0 0目的天然黄铁矿去除 Cr( )的效率远较 2 0 0目以上的天然黄铁矿去除 Cr( )的效率高。试样久置不影响对 Cr( )的去除效果 ,去除率可达 99.2 %以上 ,反应后的 p H值都接近 4 .0 ,与磁黄铁矿处理 Cr( )废水过程中 p H值的变化规律一致。不同产地的黄铁矿样品除 Cr( )的效果稍有差异。     

Role of Iron(III) and Aluminum Hydroxides in Concentration/reduction of Au(III) Complexes

Abstract: The adsorption of gold on iron(III) and aluminum hydroxides from solutions containing Au(III) complexes has been studied as a function of pH and chloride concentration at 30C. Iron(III) hydroxide was more effective in adsorbing gold from solution than aluminum hydroxide. However, both hydroxides controlled the behavior of Au(III) complex with very similar manner. The most effective gold adsorption occurred in aqueous solution with near neutral pH and low Cl concentration. In this solution condition, Au(III) complexes were mainly dissolved as AuCl₂(OH)₂^- and AuCl(OH)₃^-, and the surface charge for both hydroxides was positive. In addition, the adsorbed Au(III) complexes were spontaneously reduced to elemental gold in spite of the absence of a specific reducing agent.
The results of this study suggest that adsorption and spontaneous reduction of gold complexes on the surface of hydrous metal oxides with positive charge play an important role in gold precipitation in subsurface environment.     

山柞镇旬地区盆地体制与金属成矿关系

山柞镇旬地区现今构造格架是在后泥盆纪秦岭造山过程中奠定的,秦岭北鄂尔多斯板块左行旋转,扬子地块向北挤压及左行旋转,使秦岭微板块沿商丹和勉略两条长寿深大断裂发生大规模的左行走滑,主要形成EW向的柞(水)-山(阳)断裂,镇(安)-板(岩镇)大断裂;伴随佛坪地块的隆滑而产生的NW-NWW向公(馆)-白(河)断裂、旬河断裂,形成和控制了山柞、旬阳热水盆地和镇安-青山隆起以及沿旬河的裂陷,控制了柞山镇旬地区金属成矿带的分布和最终矿床的形成.