Control of carboxylic acid and ester groups on chromium (VI) binding to functionalized silica/water interfaces studied by second harmonic generation

Resonantly enhanced surface second harmonic generation (SHG) measurements carried out at pH 7 and room temperature were performed to study how surface-bound carboxylic acid and methyl ester functional groups control the interaction of chromate ions with fused silica/water interfaces. These functional groups were chosen because of their high abundance in humic and fulvic acids and related biopolymers commonly found in soils. They were anchored to the silica surface using organosilane chemistry to avoid competing complexation processes in the aqueous solution as well as competitive adsorption of the organic compounds and chromate. The SHG experiments were carried out at room temperature and pH 7 while using environmentally representative chromate concentrations ranging from 1 x10(-6) to 2 x 10(-4) M. Chromate is found to bind to the acid- and ester-functionalized silica/water interfaces in a reversible fashion. In contrast to the plain silica/water interface, chromate binding studies performed on the functionalized silica/water interfaces show S-shaped adsorption isotherms that can be modeled using the Frumkin-Fowler-Guggenheim (FFG) model. This model predicts a coverage-dependent binding constant of K(ads) x exp(gtheta). Values for g are found to be 3.2(2), 2.1(2), and 1.3(2) for the carboxylic acid-, the ester-, and the nonfunctionalized silica/water interfaces, respectively, and are consistent with stabilizing lateral adsorbate-adsorbate interactions among the Cr(VI) species adsorbed to the functionalized surfaces. The FFG model allows for the parametrization of the solid-liquid partition coefficient and chromate retardation factors in silica-rich soil particles whose surfaces contain organic adlayers rich in carboxylic acid and methyl ester groups. The straightforward model presented here predicts that chromate retardation increases by up to 200% when carboxylic acid functional groups are present at the silica/water interface. Increases up to 50% are predicted for methyl ester-containing organic adlayers, and the retardation factor remains effectively near unity for the plain silica/water interface (no siloxanes present).     

Detection of hexavalent chromium using gold/4-(2-mercaptoethyl) pyridinium surface enhanced Raman scattering-active capture matrices

In this communication, the fabrication of SERS-active capture matrices for the detection of hexavalent chromium is described. The amine groups of amine-modified magnetic microparticles were used to immobilize gold colloidal particles. Once immobilized, the gold was reacted with 4-(2-mercaptoethyl) pyridinium (MEP) hydrochloride to form a self-assembled monolayer (SAM). The MEP SAM exhibits great selectivity for hexavalent chromium. It was shown that calibration curves could be generated by ratioing MEP peaks that increased in intensity upon complexation with chromate with a peak that did not change. Flow experiments, using Au/MEP capture matrices held in place by a magnet, showed instantaneous response to changes in chromate concentration.     

Anion chelation by amido acid functionalized fused quartz/water interfaces studied by nonlinear optics

We report resonantly enhanced surface second harmonic generation (SHG) measurements to track the interaction of the EPA priority toxic metal pollutant chromium(VI) with fused quartz/water interfaces containing tailor-made amino acids that serve as model systems for environmental and biological interfaces. chi3 measurements of amido acid functionalized fused quartz/water interfaces are consistent with two acid-base equilibria, suggesting the formation of a laterally hydrogen-bonded environment similar to what is observed for aliphatic carboxylic acids. Chromate adsorption isotherms recorded at pH 7 are suggestive of an intramolecular chelation mechanism that becomes important when four or more hydrogen-bonding moieties are displayed toward the incoming chromate. The strong binding affinities of the amido acid functionalized fused quartz/water interfaces toward chromate are consistent with nearly 50% slower transport rates with respect to free-flowing groundwater, indicating that, in the absence of redox processes, peptide materials in heterogeneous geochemical environments can significantly increase chromate residence times. The strong evidence for synergistic effects dominating the interactions of chromate with surface-bound amido acids indicates that chemical complexity can be systematically addressed using tailor-made organic surfaces and interfaces.     

Contributions to the basic problems of complexometry—XIII Determination of aluminium and tervalent chromium in the presence of chromate

Aluminium can be determined in the presence of tervalent chromium and chromate using 1,2-diaminocyclohexanetetra-acetic acid (DCTA), which forms a complex with aluminium even in the cold. This phenomenon enables a successive determination to be made of aluminium (iron) and tervalent chromium in the presence of hexavalent chromium. This procedure cannot be carried out with the commonly used ethylenediaminetetra-acetic acid (EDTA).     

Studies on the repassivation behavior of aluminum and aluminum alloy exposed to chromate solutions

This study explores the repassivation ability of a scratch in a chromate conversion coating (CCC) on aluminum alloy, AA2024‐T3, and hence evaluates the theory of migration of hexavalent chromium ions from the protected surface of the aluminum alloy to the exposed surface. To confirm that protection was indeed restored by hexavalent chromium ions, the repassivation of a scratch on pure aluminum exposed to a dichromate solution was studied. This forms the simplest subsystem model of the CCC on the alloy in which the CCC is replaced by pure hexavalent chromium and alloy with pure aluminum. Open‐circuit potential measurements, synchrotron infrared microspectroscopy (SIRMS) and secondary ion mass spectroscopy (SIMS) have been used judiciously to evaluate the repassivation behavior. Results indicate that the dichromate ions have high mobility. The slow migration of Cr(VI) ions from the protected surface to the scratch is observed to result in repassivation, as seen from the steady increase in the potential in 0.05 M NaCl solution. The results obtained from SIMS and SIRMS confirm the migration of the oxyanions from the protected region to the metal surface exposed by the scratch. The SIRMS results indicate the formation of an Al(III)–Cr(VI) complex, proposed and shown to be formed in the pits. Copyright © 2003 John Wiley & Sons, Ltd.     

On-line dynamic extraction and automated determination of readily bioavailable hexavalent chromium in solid substrates using micro-sequential injection bead-injection lab-on-valve hyphenated with electrothermal atomic absorption spectrometry

A novel and miniaturized micro-sequential injection bead-injection lab-on-valve (microSI-BI-LOV) fractionation system was developed for on-line microcolumn soil extraction under simulated environmental scenarios and accurate monitoring of the content of easily mobilisable hexavalent chromium in soil environments at the sub-low parts-per-million level. The flow system integrates dynamic leaching of hexavalent chromium using deionized water as recommended by the German Standard DIN 38414-S4 method; on-line pH adjustment of the extract by a 0.01 mol L(-1) Tris-HNO(3) buffer solution; isolation of the chromate leached from the matrix constituents onto a Q Sepharose strong anion-exchanger freshly packed into the microconduits of the microSI-assembly; air-segmented elution of the sorbed species by a 40 microL plug of 0.5 mol L(-1) NH(4)NO(3) (pH 8) eluent; and detection by electrothermal atomic absorption spectrometry (ETAAS). The effect of simulated acidic rain on the accessibility of chromate forms for plant uptake was also investigated. The proposed approach offers several advantages over conventional speciation/fractionation protocols in the batch mode, including immediate separation with concomitant preconcentration of the released chromate, minimization of Cr(vi) to Cr(iii) interconversion risks, enhanced accuracy, and non-existence of re-adsorption/re-distribution problems along with a detailed pattern of the kinetics of the leaching process. The reliability of the proposed method was evaluated via spiking of a moderately polluted agricultural soil material (San Joaquin Soil-Baseline Trace Element Concentrations) with water-soluble Cr(vi) salts at different concentration levels. The potential of the microSI-BI-LOV set-up with renewable surfaces for flame-AAS determination of high levels of readily bioavailable chromate in contaminated soils is also addressed.     

Characterization of the interactions in polymer-filler systems by inverse gas chromatography

Chromium is a primary drinking water contaminant in the USA with hexavalent chromium, Cr(VI), being the most toxic form of the metal. As a required step in developing a revised state drinking water standard for chromium, the California Department of Health Services recently issued a new Public Health Goal (PHG) of 2.5 microg/l for total chromium and 0.2 microg/l for Cr(VI). Hexavalent chromium can be determined (as chromate) by ion chromatography, as described in US Evironmental Protection Agency Method 218.6; however, the method as originally published does not allow sufficient sensitivity for analysis at the California PHG level of 0.2 microg/l. Modification of the conditions described in Method 218.6, including the use of a lower eluent flow-rate, larger reaction coil, and larger injection volume, significantly increases the method sensitivity. The modified method, which uses IonPac NG1 and AS7 guard and analytical columns, an eluent of 250 mM ammonium sulfate-100 mM ammonium hydroxide operated at 1.0 ml/min, a 1000 microl injection volume, and postcolumn reaction with 2 mM diphenylcarbazide-10% methanol-0.5 M sulfuric acid (using a 750 microl reaction coil) followed by UV-Vis detection at 530 nm, permits a method detection limit for chromate of 0.02 microg/l. This results in a quantitation limit of 0.06 microg/l, which is more than sufficient for analysis at the California PHG level. Calibration is linear over the range of 0.1-10 microg/l and quantitative recoveries (>80%) are obtained for chromate spiked at 0.2 microg/l in drinking water. The modified method provides acceptable performance, in terms of chromate peak shape and recovery, in the presence of up to 1000 mg/l chloride or 2000 mg/l sulfate.     

A potentiometric rhodamine-B based membrane sensor for the selective determination of chromium ions in wastewater.

The construction and performance characteristics of a novel chromate ion-selective membrane sensor are described and used for determining chromium(III) and chromium(VI) ions. The sensor is based on the use of a rhodamine-B chromate ion-associate complex as an electroactive material in a poly(vinyl chloride) membrane plasticized with o-nitrophenyloctyl ether as a solvent mediator. In a phosphate buffer solution of pH 6 - 7, the sensor displays a stable, reproducible and linear potential response over the concentration range of 1 x 10(-1) - 5 x 10(-6) mol l(-1) with an anionic Nernstian slope of 30.8 +/- 0.5 mV decade(-1) and a detection limit of 1 x 10(-6) mol l(-1) Cr(VI). High selectivity for Cr(VI) is offered over many common anions (e.g., I-, Br-, Cl-, IO4-, CN-, acetate, oxalate, citrate, sulfate, phosphate, thiosulfate, selenite, nitrate) and cations (e.g., Ag+, Ca2+, Sr2+, Co2+, Ni2+, Cu2+, Mn2+, Fe2+, Zn2+, Cd2+, Al3+, Cr3+). The sensor is used for determining Cr(VI) and/or Cr(III) ions in separate or mixed solutions after the oxidation of Cr(III) into Cr(VI) with H2O2. As low as 0.2 microg ml(-1) of chromium is determined with a precision of +/-1.2%. The chromium contents of some wastewater samples were accurately assessed, and the results agreed fairly well with data obtained by atomic absorption spectrometry.     

Quantification of total chromium and hexavalent chromium in UHT milk by ETAAS

Procedures for the quantification of total chromium and hexavalent chromium in UHT milk samples are presented. Total chromium was determined directly in milk with the addition of a surfactant and a mixture of Pd and Mg as a chemical modifier. For the selective separation of hexavalent chromium, the sample pre-treatment consisted in precipitation of proteins and elution of the supernatant through a Chromabond NH2 column. The metal was eluted with nitric acid. Both total chromium and hexavalent chromium were evaluated by atomic absorption spectrometry with electrothermal atomization using the same instrumental conditions. The detection limits were 0.2 and 0.15 microgram l-1 for total chromium and hexavalent chromium, respectively. The linearity ranges under the optimized conditions were 0.2-20 and 0.15-50 micrograms l-1. For total chromium the precision was 4.9 and 5.7% for the analytical and the over-all procedure, respectively, and for hexavalent chromium 4.3 and 4.9%, respectively. The validation of both procedures was performed by the standard additions method and the recoveries were higher than 93% in all cases. For total chromium, a certified reference material was also used to validate the methodology. The methods were applied to the determination of total chromium and hexavalent chromium in 60 UHT milk samples.     

Determination of hexavalent chromium and accompanying anions in one run using isocratic ion chromatography with column switching

A method for the simultaneous determination of hexavalent chromium and other inorganic anions like chloride, nitrate and sulfate in aqueous solutions was developed using isocratic ion chromatography with suppressed conductometric detection and column switching. Owing to the large differences in distribution coefficient between chromate and the other species, the chromate is separated from the other anions in a first short column, whereas the other anions are led to a longer second column via a column-switching valve, and separated there. Using standard anion separation conditions the length of the columns and the switching procedure were optimized. The time of analysis for eight anions is less than 12 min and the method can be easily automated. Detection limit and precision are not effected by the switching procedure.     

Quaternized wood as sorbent for hexavalent chromium

The potential of quaternized wood (QW) chips in removing hexavalent chromium from synthetic solution and chrome waste under both batch and continuous-flow conditions was investigated. Sorption was found to be dependent on pH, metal concentration, and temperature. QW chips provide higher sorption capacity and wider pH range compared with untreated wood chips. The equilibrium data could be fitted into the Langmuir isotherm model, and maximum sorption capacities were calculated to be 27.03 and 25.77 mg/g in synthetic chromate solution and chrome waste, respectively. The presence of sulfate in high concentration appeared to suppress the uptake of chromium by QW chips. Column studies showed that bed depth influenced the breakthrough time greatly whereas flow rate of influent had little effect on its sorption on the column.     

Determination of dissolved hexavalent chromium in industrial wastewater effluents by ion chromatography and post-column derivatization with diphenylcarbazide

A proposed EPA method for the determination of dissolved hexavalent chromium in drinking water, groundwater and industrial wastewater effluents was developed using existing ion chromatographic techniques. Two solid waste matrices were briefly investigated. Aqueous samples were passed through a 0.45-micron filter and the filtrate was either (1) left unadjusted, (2) adjusted to pH 8 or (3) adjusted to pH 10 prior to analysis by ion chromatography. The method detection limits were 0.3-0.4 micrograms/l. When analyzed within 24 h, the two pH levels and the unadjusted sample yielded ca. 100% recovery of spikes. No oxidation of trivalent chromium to hexavalent chromium was observed at pH 7, 8 or 10 when aqueous samples were spiked with 50 mg/l Cr(III).     

Non-destructive rapid analysis discriminating between chromium(VI) and chromium(III) oxides in electrical and electronic equipment using Raman spectroscopy.

The European Union has banned chromium(VI) compounds in electrical and electronic equipment (EEE), such as chromate conversion coating films. Chromium(III) compounds are not banned. Using Raman spectroscopy without any preparation, we distinguished chromium(VI) oxide from chromium(III) oxide and chromium(III) hydroxide in chromate conversion coating films. Raman bands of chromium(VI) oxide were detected in films at around 1000 and 500 cm(-1), while chromium(III) compounds generated no bands in the region between 2000 and 200 cm(-1). The analysis took about 1 min, whereas the usual diphenylcarbazide-colorimetric method for analyzing chromium(VI) compounds takes about 10 h.     

Surface Microstructure and Component Changes of Chromium-resistant Enterobacter Cloacae CYS-25 Strain

Enterobacter cloacae CYS-25 strain was isolated from a chromate plant. This bacterium was capable of resisting high hexavalent chromium concentration and reducing Cr（VI） under aerobic condition. CrO4^2- stimulated the increase of bacterial size and production of compact convex paths containing chromium on the bacterial surface. The increase of bacterial size was caused by integrative growth but not extracellular polymeric substance hyperplasia. IR and SDS-PAGE analyses showed the extracellular polymeric substance （EPS） components were mainly proteins and had no obvious changes whether the strains were induced by Cr（VI） or not. The EPS was amorphous and contained trivalent chromium. Under CrO4^2- growth condition, the extracellular substance of Enterobacter cloacae CYS-25 strains and Cr（VI） had redox reaction. The products were Cr^3＊-protein complexes which formed a piece of compact convex paths on the surface of bacteria and prevented Cr（VI） from entering into cells.     

Simultaneous determination of hexavalent and total chromium in water and plating baths by spectrophotometry

A new spectrophotometric determination method of hexavalent chromium in waste water and plating baths is described based on the oxidation of beryllon III by chromium(VI) in 0.02M sulphuric acid medium. The decrease in the absorbance of beryllon III was measured at 482 nm with an apparent molar absorptivity of 5.15 x 10(4)1.mole(-1).cm(-1). Beer's law was obeyed for chromium(VI) over the range 0-25 mug/25 ml. After the oxidation of Cr(III) to Cr(VI) by ammonium persulphate, total chromium can be determined. Therefore, chromium(III) can be calculated by subtracting chromium(VI) from total chromium. The detection limit is 0.015 and 0.020 mug/25 ml for chromium(VI) and total chromium, respectively. A sensitive spectrophotometric method for trace Cr(III) and Cr(VI) in waste water and plating baths was developed with good precision and accuracy. The reaction is also discussed.     

超痕量六价铬分析仪检测制革场地中六价铬

为解决制革等污染场地中Cr(III)-有机络合物会干扰六价铬测定的问题,通过优化仪器色谱条件、在现有行标基础上改进前处理方式,使用超痕量六价铬分析仪检测六价铬,并通过在土壤中投加低、中、高浓度的三价铬、六价铬以及Cr(III)-有机络合物考察三价铬、色度和Cr(III)-有机络合物对六价铬测定的影响。结果表明仪器的最佳色谱条件为：流动相浓度为0.1 mol/L、流动相pH为9、浓硫酸用量为5 mL、流动相流速为1.2 mL/min,衍生试剂流速为0.7 mL/min。样品预处理方式由抽滤提取改进为离心提取,上机前样品pH无需调节,可提高检测效率;该方法与现行行标相比操作简便、耗时短且不受三价铬、样品色度及Cr(III)-有机络合物的干扰。方法精密度和正确度均显著提高,相对标准偏差为1.7%~5.2%,回收率均在94.6%~103%之间。通过与液相色谱-电感耦合等离子体质谱仪对实际样品测定结果的统计学检验发现,结果无显著性差异。该方法适用于制革、电镀等富含Cr(III)-有机络合物场地中六价铬的测定。     

Electroanalytical Detection of Cr(VI) and Cr(III) Ions Using a Novel Microbial Sensor

A microbial sensor, namely carbon paste electrode (CPE) modified with Citrobacter freundii (Cf–CPE) has been developed for the detection of hexavalent (Cr(VI)) and trivalent (Cr(III)) chromium present in aqueous samples using voltammetry, an electroanalytical technique. The biosensor developed, demonstrated about a twofold higher performance as compared to the bare CPE for the chosen ions. Using cyclic voltammetry and by employing the fabricated Cf–CPE, the lowest limit of detection (LLOD) of 1x10⁻⁴ M and 5x10⁻⁴ M for Cr(VI) and Cr(III) ions respectively could be achieved. By adopting the Differential Pulse Cathodic Stripping Voltammetric technique, the LLOD could be further improved to 1x10⁻⁹ M and 1x10⁻⁷ M for Cr(VI) and Cr(III) ions respectively using the biomodified electrodes. The reactions occurring at the electrode surface‐chromium solution interface and the mechanisms of biosorption of chromium species onto the biosensor are discussed. The stability and utility of the developed biosensor for the analysis of Cr(VI) and Cr(III) ions in chromite mine water samples has been evaluated.     

Analytical speciation of chromium in in-vitro cultures of chromate-resistant filamentous fungi

In this work, different analytical speciation schemes have been used to study the reduction of Cr(VI) by a chromate-resistant strain of filamentous fungi Ed8 (Aspergillus sp), indigenous to contaminated industrial wastes. As demonstrated previously, this strain has the capability to reduce chromate present in the growth medium without its accumulation in the biomass, yet the reduced chromium end-products have not been characterized. Liquid growth medium, initially containing 50 mg L(-1) Cr(VI), was analyzed for Cr(III)/Cr(VI) and for total Cr at different time intervals (0-24 h) after inoculation with fungi. Three hyphenated procedures, based on the Cr(III)-EDTA formation and species separation by anion-exchange or ion-pairing reversed-phase chromatography with ICP-MS or DAD detection were used. The results obtained for Cr(VI) in each case were consistent, demonstrating efficient reduction of chromate during 24 h of Ed8 growth. However, pre-column complexation with EDTA did not ensure complete recovery of the reduced forms of chromium in the above procedures. An alternative speciation scheme, based on extraction of Cr(VI)-benzyltributylammonium bromide (BTAB) ion pairs into chloroform and subsequent determination of residual chromium by ICP-MS has provided evidence on the effective conversion of chromate into reduced chromium species in the growth medium. The results indicate the feasibility of using Ed8 strain for chromate bioremediation purposes. Analytically it can be concluded that speciation of chromium in biological systems should not be limited to its two most common oxidation states, because the actual reduced chromium species are not converted quantitatively to Cr(III)-EDTA.     

Removal of chromate from water by a new CTAB-silica gelatin composite

A novel composite able to remove hexavalent chromium Cr(VI) from aqueous solutions was obtained by adding the silica precursor tetraethoxysilane (TEOS) to the hexadecyltrimethylammonium bromide (CTAB) microemulsion-based gel. A physical characterization of the new matrix revealed high stability of the silica gelatin composite in water at high temperatures and at neutral pH. Good efficiency in removing chromate from neutral solutions was also demonstrated by the adsorption kinetics. In particular, the adsorption data of chromate obtained with the CTAB-silica gelatin composite at 25 degrees C and pH 7.5 are described by the Freundlich isotherm model. The specific role of CTAB in the silica gelatin composite was also evaluated by comparing the kinetics of the anionic AOT-silica gelatin composite to the CTAB one. The data collected clearly showed that the positively charged surfactant was necessary to efficiently adsorb Cr(VI) from aqueous solutions. SEM and pulsed gradient spin-echo NMR analysis of the composite demonstrated that the silicon is well assembled in the gelatin network, in which water molecules maintain a high mobility. The diffusion coefficient of water in this system was shown to remain close to the value of pure water. Finally, X-ray analyses of the elemental content in the CTAB-silica gelatin composite indicated no difference in terms of percentage of silica distributions in different areas of the matrix and suggested that chromium adsorption could take place in internal areas.