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.     

膨润土负载纳米铁去除地下水中六价铬研究

随着人民生活水平的提高和城市化进程的加快,有机污染物及重金属高强度场地污染对人类健康、生态环境及社会安全构成了严重威胁。地下水中的重金属Cr(Ⅵ)污染逐渐受到重视,纳米零价铁可以有效地将六价铬还原成三价铬,使其沉淀固定下来,从而将污染源区的污染物消减固定,防止其向周围扩散。然而由于纳米铁颗粒微小,易被氧化,极易团聚,自身活性受到限制,因此,纳米铁的分散性、稳定性、良好活性研究至关重要。采用低成本环境友好型粘土矿膨润土作为负载材料制备膨润土负载纳米铁（B-NZVI）,批实验和柱实验研究B NZVI去除模拟地下水中Cr(Ⅵ)。结果表明：(1)自制的膨润土负载纳米铁个体呈球形,呈分散状负载于膨润土;(2)相同铁含量的B-NZVI处理Cr(Ⅵ)的效率远大于纳米铁,还原反应符合伪一级反应动力学模型,表观速率常数K随着B NZVI初始浓度的减小而减小;(3)B NZVI在石英砂柱中基本无迁移,适用于点源污染,Cr(Ⅵ)穿透曲线为B-NZVI的实际应用提供了理论和实验基础。     

A study on the adsorption of chromium on laterite from Guizhou Province,China

The adsorption behaviors of Cr(VI) on laterite from Guizhou Province were studied in this paper, and the adsorption mechanism was discussed as well. Results showed that different mineral compositions in the laterite would cause differences in the capacity of laterite to absorb Cr(VI). Gibbsite, iron oxide minerals and non-crystalloids are the main contributors to enhancing the capacity of laterite to absorb Cr(VI). The pH of the solution is an important factor affecting the adsorption of Cr(VI) on laterite. Acidic environment (pH=2–5) is favorable to the adsorption of Cr(VI). The amount of adsorbed Cr(VI) decreases with increasing pH of the solution. With increasing initial concentrations of Cr(VI), the amount of adsorbed Cr(VI) increases first, and then decreases. The optimal adsorption concentration of Cr(VI) on laterite is 250 μg/mL. The adsorption of Cr(VI) on laterite is a rapid process, about 80% Cr(VI) will be adsorbed within 2 hours. And the adsorption of Cr(VI) on kaolinite is a slow process.     

Cotton Fiber/ZrO2, A New Material for Adsorption of Cr(VI) Ions in Water

The natural cotton fiber was used to synthesize an anion exchange, containing ZrO₂ film on its surface, NCFZC (natural cotton fiber/ZrO₂ composite). This anion exchanger was produced by the reaction of the zirconium oxychloride and hydroxyl groups on surface of the natural cotton fiber. The material was used for Cr(VI) ions adsorption studies. Adsorption equilibrium time and optimum pH for Cr(VI) adsorption were found to be 6 h and 4.0, respectively. The Langmuir and Temkin isotherms were used to models adsorption equilibrium data. The adsorption capacity of NCFZC was found to be 1.33 mmol/g. Kinetic studies showed that the rate of adsorption of Cr(VI) on NCFZC obeyed a pseudo‐second‐order kinetic model.     

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).     

单变量特征选择的苏北地区主要农作物遥感识别

遥感识别多源特征综合和特征优选是提高遥感影像分类精度的关键技术。农作物遥感识别中,识别特征的相对单一和数量过多均会导致作物识别精度不理想。随机森林(random forests)采用分类与回归树(CART)算法来生成分类树,结合了bagging和随机选择特征变量的优点,是一种有效的分类方法。单变量特征选择(univariate feature selection)能够对每一个待分类的特征进行测试,衡量该特征和响应变量之间的关系,根据得分舍弃不好的特征,优选得到的特征用于分类。本文基于随机森林和单变量特征选择,利用多时相光谱信息、植被指数信息、纹理信息及波段差值信息,设计多组分类实验方案,对江苏省泗洪县的高分一号(GF-1)和环境一号(HJ-1A)影像进行分类研究,旨在选择最佳的分类方案对实验区主要农作物进行识别和提取。实验结果表明:(1)多源信息综合的农作物分类精度明显高于单一的原始光谱特征分类,说明不同类型特征的引入能改善分类效果;(2)基于单变量特征选择算法的优选特征分类效果最佳,总体精度97.07%,Kappa系数0.96,表明了特征优选在降低维度的同时,也保证了较高的分类精度。随机森林和单变量特征选择结合的方法可以提高遥感影像的分类精度,为农作物的识别和提取研究提供了有效的方法。     

Assessment of alternative adsorption models and global sensitivity analysis to characterize hexavalent chromium loss from soil to surface runoff

We investigate our ability to assess transfer of hexavalent chromium, Cr(VI), from the soil to surface runoff by considering the effect of coupling diverse adsorption models with a two‐layer solute transfer model. Our analyses are grounded on a set of two experiments associated with soils characterized by diverse particle size distributions. Our study is motivated by the observation that Cr(VI) is receiving much attention for the assessment of environmental risks due to its high solubility, mobility, and toxicological significance. Adsorption of Cr(VI) is considered to be at equilibrium in the mixing layer under our experimental conditions. Four adsorption models, that is, the Langmuir, Freundlich, Temkin, and linear models, constitute our set of alternative (competing) mathematical formulations. Experimental results reveal that the soil samples characterized by the finest grain sizes are associated with the highest release of Cr(VI) to runoff. We compare the relative abilities of the four models to interpret experimental results through maximum likelihood model calibration and four model identification criteria (i.e., the Akaike information criteria [AIC and AIC_C] and the Bayesian and Kashyap information criteria). Our study results enable us to rank the tested models on the basis of a set of posterior weights assigned to each of them. A classical variance‐based global sensitivity analysis is then performed to assess the relative importance of the uncertain parameters associated with each of the models considered, within subregions of the parameter space. In this context, the modelling strategy resulting from coupling the Langmuir isotherm with a two‐layer solute transfer model is then evaluated as the most skilful for the overall interpretation of both sets of experiments. Our results document that (a) the depth of the mixing layer is the most influential factor for all models tested, with the exception of the Freundlich isotherm, and (b) the total sensitivity of the adsorption parameters varies in time, with a trend to increase as time progresses for all of the models. These results suggest that adsorption has a significant effect on the uncertainty associated with the release of Cr(VI) from the soil to the surface runoff component.     

基于植被信息遥感反演的东亚飞蝗监测研究

植被是东亚飞蝗发生和成灾的重要指示因子。运用遥感技术对植被生长进行监测,对东亚飞蝗的预测和防治具有重要意义。以河北省黄骅市为研究区,利用实地获取的植被冠层孔隙度数据反算的LAI数据以及Landsat-5 TM影像提取的各种VI数据,进行了LAI(LAI-2000改进型算法的反算结果)与TM影像上反演的VI之间的相关分析。结果表明,RDVI最适合反映研究区植被生长状况。分析RDVI与飞蝗发生面积的关系,发现两者呈负线性相关,即随着RDVI减小,飞蝗的发生面积呈线性增大。     

Health risk assessment for typical and abandoned chromium-contaminated sites

Chromium pollution were investigated by sampling the abandoned chromium contaminated sites in Chongqing. Its health risk was assessed following the procedures made by USEPA. The results showed that the most seriously polluted land was found at the former production area （G4） with average Cr（VI） concentration of 3369.2 mg kg-1 on the surface soil. The assessment indicated that there was high risk of non-carcinogens for children. The assessed risk of the first layer of office area （G1） for children, chromium slag transition （G2）, drainage pipeline chromium slag transition （G3） and production area （G4） for both children and adults were not acceptable （〉1.00× 106）. It was strongly suggested that the accessible measures of remediation should be taken for a portion of contaminated sites before the reuse of abandoned lands.     

Chromium(VI) reduction by sulphur(IV) in aqueous solutions

The rates of the reduction of Cr(VI) with S(IV) were measured in deaerated NaCl solution as a function of pH, temperature and ionic strength. The rates of the reaction were found to be first order with respect to Cr(VI) and second order with respect to S(IV), in agreement with previous results obtained at concentrations two order higher than the present study. The reaction also showed a first-order dependence of the rates on the concentration of the proton and a small influence of temperature with an apparent energy of activation ΔH_app of 22.8 ± 3.4 kJ/mol. The rates were independent of ionic strength from 0.01 to 1 M. The rate of Cr(VI) reduction is described by the general expression

−d[Cr(VI)]/dt=k[Cr(VI)][S(IV)]²