Comparative study of analytical methods for the determination of chromium in groundwater samples containing iron

Determination of chromium in groundwater samples containing iron may pose analytical problems due to sorption and fixation of chromium species onto Fe(III) hydroxides. Parks et al. (Water Res. 2004, 38, 2827) hypothesized that chromium species trapped inside Fe(III) hydroxides i.e. “fixed chromium” may not be soluble by HNO₃ digestion (APHA method 3030 B). In such cases, hydroxylamine digestion is required to release “fixed chromium”. To verify the hypothesis, we carried out this study on groundwater samples containing chromium and iron, using different methods of APHA and EPA. The results showed the presence of “fixed chromium”, ranged between 0.1 and 19.2 μg L^{− 1}, contributing 0.2 to 14.1% towards true total chromium. Digestion of samples with HNO₃ released Cr(III) bound to organic complexes, but not the “fixed chromium”. The hydroxylamine digestion released “fixed chromium”, but not the Cr(III) bound to organic complexes. Microwave digestion of samples with HNO₃ + HCl was effective for the release of both “fixed” and “Cr(III)-organic complexes”. Cr(III) was only adsorbed onto suspended matter, whereas Cr(VI), and Cr(III)-organic complexes were not adsorbed onto suspended matter due to their solubility. Sample pH, buffering capacity, and matrix have a significant influence on the adsorption and fixation of chromium species onto Fe(III) hydroxides.     

Adsorption of fluoride on synthetic siderite from aqueous solution

The study has investigated the feasibility of using synthetic siderite for F⁻ removal from aqueous solution. Batch experiments were performed to test effects of adsorbent dosage, contact time, initial F⁻ concentration, temperature, solution pH, and coexisting anions on F⁻ removal. Results show that the kinetic rate of F⁻ adsorption was high in the first 2 h, and thereafter significantly decreased. The kinetic data was better fitted to the pseudo-second order kinetic model than the pseudo-first order kinetic model. In comparison with Langmuir isotherm, both Freundlich and Redlich-Peterson isotherms better described the adsorption process, which indicates that the multilayer adsorption should be involved in the process of F⁻ removal. Thermodynamic study manifests that F⁻ adsorption on synthetic siderite was spontaneous and exothermic in nature. The synthetic siderite had high adsorption capacity for F⁻ removal, which was up to 1.775 mg/g in the batch with an adsorbent dosage of 5 g/L and an initial F⁻ concentration of 20 mg/L at 25 °C. The adsorption was relatively independent on solution pH between 4 and 9. The presence of Cl⁻ and NO₃⁻ had less impact on F⁻ adsorption, while PO₄³⁻ significantly affected F⁻ removal from aqueous solution. Results of X-ray diffraction (XRD) and scanning electron microscopy (SEM) suggest that the high adsorption capacity possibly arose from both coprecipitation of ferric hydroxide with F⁻ and adsorption of F⁻ on the fresh goethite.     

Genetic algorithms and cellular automata in aquifer management

A groundwater management problem is presented involving pumping cost minimization with both well discharges and well locations as decision variables. A grid of candidate well locations is set up and optimal arrangements of wells are sought within this discrete space. A genetic algorithm approach is presented with the following particular features: (a) A suitable scaling is applied to the objective function in order to alleviate its regionally flat behavior. (b) No penalty functions are involved in constraint handling. Instead, the feasible region is transformed into a rectangular domain. The transformation introduced is proved to be bijective. (c) A binary representation of well configurations is presented and compared to a combinatorial one. The binary representation necessitates the introduction of specially designed genetic operators. Besides purely genetic algorithms, the concept of cellular automaton is introduced as the basis of an alternative formulation of the optimization problem. The lattice of the cellular automaton provides the discrete set of candidate well positions. The well configuration is represented by a group of agents occupying an equal number of lattice sites. The agents change positions as dictated by the structure of the automaton and, also, by an associated genetic algorithm, which directs the evolution of the whole scheme toward an optimal configuration. An improved performance of this approach is noted and discussed in comparison to the purely genetic algorithm schemes of the present work. A simulated annealing approach is also applied to the same problem for comparison purposes. Finally, a new and more efficient hybrid annealing–genetic approach is introduced and discussed.     

Quantitative determination of toluene,ethylbenzene, and xylene degradation products in contaminated groundwater by solid-phase extraction and in-vial derivatization

Benzylsuccinic acid (BSA) and methylbenzylsuccinic acids (mBSAs) are unambiguous indicators of anaerobic toluene and ethylbenzene/xylene degradation, and so the determination of these compounds in landfill leachates and contaminated groundwater is highly relevant. Samples were diluted to <0.8?mS?cm^?1 in order to reduce their ionic strength, and subsequently extracted through strong anion exchange disks, followed by simultaneous in-vial elution and methylation. A detection limit of 0.1?µg?L^?1 was obtained for 100?mL samples. Using this method, 19.3?µg?L^?1 of BSA was measured in a landfill leachate, and low µg?L^?1 levels of all of the mBSAs were measured in gasoline-contaminated groundwater. The results were compared with the findings of BSAs at 16 other contaminated sites, and BSAs as indicators of biodegradation were evaluated. The estimation of biodegradation rates based on parent hydrocarbons and BSA concentrations or ratios is questionable. However, the degradation products serve as good qualitative in situ indicators for anaerobic biodegradation in contaminated groundwater.     

Differential pulse cathodic stripping voltammetric determination of nanomolar levels of dissolved sulfide applicable to field analysis of groundwater

Conventional batch mode analysis of dissolved sulfide by cathodic stripping voltammetry (CSV) is known to suffer from loss of sulfide in the cell to the waste mercury pool, compromising quantification of sulfide. Here we report a simple alternative approach to batch-mode differential pulse CSV (DPCSV). A fresh aliquot of sample is used for each voltammetric scan to minimize loss of sulfide through reaction with the mercury by limiting the time for sulfide-mercury contact, which is found to be more important in suppressing the sulfide signal than the amount of free mercury in the cell. Our improved batch-mode method exhibited a limit of detection of 1.3 nM, a relative standard deviation of 2.5% in NaOH supporting electrolyte and a linear response to as high a concentration as 1600 nM in a supporting electrolyte composed of Na₂CO₃/NaHCO₃ (pH 8.3) mixed with an equal volume of oxic groundwater. A relative standard deviation of 4.5% was obtained for a groundwater sample in Na₂CO₃/NaHCO₃ (pH 8.3) supporting electrolyte. These values are comparable to previously published results. Compared to other sensitive sulfide analytical techniques such as gas chromatography or high performance liquid chromatography (HPLC), DPCSV is preferred for sulfide analysis in the field due to its simple and portable instrumentation, lack of complex sample preparation, and short analysis time. The method was applied on site to analyze Fe-rich, reducing groundwater samples collected at a landfill site in Winthrop, Maine. Sulfide concentrations ranged from undetectable (<4 nM) to 7340 nM, generally increasing as the oxidation/reduction potential (ORP) of the water became more negative. We also demonstrate, for the first time, that the onset of sulfate reduction as indicated by the presence of small amounts of sulfide (tens to hundreds of nM) occurs in groundwater systems when the ORP value reaches −130 mV.     

Reductive immobilization and long-term remobilization of radioactive pertechnetate using bio-macromolecules stabilized zero valent iron nanoparticles

Carboxymethyl cellulose-and starch-stabilized nZVI nanoparticles were prepared and showed high efficiency for reductive immobilization of ⁹⁹TcO₄^- in simulated groundwater.     

杭州市郊来龙山滑坡的治理与监测

滑坡是一种重大的地质灾害,本文结合杭州市郊来龙山的滑坡工程,具体分析了滑坡的成因、稳定计算和最终采取的治理措施,通过监测的具体内容和结果进行分析,表明治理效果比较好,为以后该地区的滑坡治理与加固提供相关参照。     

云母石英片岩斜坡弯曲倾倒变形的理论分析

片岩斜坡中弯曲倾倒变形是通过密集的片理上逐层剪切位移实现的。文中给出了瞬时变形终止时σ1与片理面法线夹角γ的理论公式。瞬时变形结束后, 由于片理面上剪应力作用, 将继续发生剪切蠕变。本文给出了γ随着时间t变化的公式。最后本文讨论了地下水压力在倾倒变形中的作用, 并在理论公式中考虑了这一因素。     

Trace-level analysis of organic contaminants in drinking waters and groundwaters

We expect drinking water and groundwater samples to be contaminated very little, so they are subject to trace-level analysis. Due to the very low levels of contamination, this sort of analysis requires not only powerful analytical technologies to reach limits around the ng/L level, but also quality-control parameters (e.g., blank and spike samples) to monitor potential contamination or losses during sample treatment. Based on a literature review and laboratory experience, we discuss the problems linked to the difficulties of calculating limits of detection, distinguishing instrumental from methodological limits and preventing false-positive results in cases of sample contamination, or false-negative results in cases of compound losses. When possible, we suggest solutions to compensate for, or to prevent, these problems.     

Determination of benzotrifluoride derivative compounds in groundwater

Two simple analytical methods for the simultaneous determination and quantification of benzotrifluoride and eight chlorinated, amino and nitro benzotrifluoride derivatives in groundwater are proposed. Benzotrifluoride, 4-chlorobenzotrifluoride, 2,4-dichlorobenzotrifluoride and 3,4-dichlorobenzotrifluoride, were extracted by Purge-and-Trap on the basis of their volatile properties, while 3-aminobenzotrifluoride, 4-nitrobenzotrifluoride, 3-amino-4-chlorobenzotrifluoride, 3-nitro-4-chlorobenzotrifluoride and 4-chloro-3,5-dinitrobenzotrifluoride extractions were done with an automated SPE system. The analytical separations and detections were performed with two different GC systems, both equipped with single quadrupole mass spectrometer as detector. The LOD ranges for the two methods were 0.002–0.005 μg L⁻¹ and 0.01–0.07 μg L⁻¹, respectively. Both extraction methods were developed using spiked Milli-Q water and were then demonstrated with groundwater samples collected during autumn 2008. The areas of groundwater collection were polluted due to an episode of improper industrial soil disposal and consequent leakage of aliphatic and aromatic, fluorinated chemicals into the groundwater. This work eventually revealed the presence of several benzotrifluoride compounds most of them, like dichloro- and amino-derivatives, never been reported as environmental contaminants.