Molybdenum, Mo-Ir and Mo-Ru coatings as permanent chemical modifiers for the determination of cadmium and lead in sediments and soil samples by electrothermal atomic absorption spectrometry

Molybdenum, Ir, Ru, Mo-Ir, Mo-Ru thermally coated on to platforms inserted in pyrolytic graphite tubes as permanent modifiers and Pd + Mg(NO₃)₂ conventional modifier mixture have been employed for the determination of cadmium and lead in dissolved sediments and soil samples by electrothermal atomic absorption spectrometry (ETAAS). Optimum masses and mass ratios of permanent modifiers for the analysis of Cd and Pb in sample solutions have been investigated. The 280 μg of Mo, 200 μg of Ir, 200 μg of Ru, 280 μg of Mo + 200 μg of Ir or 280 μg of Mo + 200 μg of Ru has been found as efficient as 5 μg of Pd + 3 μg of Mg(NO₃)₂ for increasing thermal stabilization of analytes and for decreasing the most serious interferences. Pyrolysis and atomization temperatures, atomization and background signal shapes, characteristic masses and detection limits of analytes in dissolved samples with or without permanent and conventional modifiers have been compared. The detection limits and characteristic masses obtained with Mo-Ir coated platform are 0.01 μg g⁻¹ and 1.1 pg for Cd and 0.09 μg g⁻¹ and 19 pg for Pb, respectively. Long-term stabilities for analytes in samples with Mo, Mo-Ir, Mo-Ru and Pd + Mg(NO₃)₂ have been studied. Cadmium and lead contents have been determined in certified and standard reference materials by using optimum conditions investigated and the results obtained with Mo-Ir or Mo-Ru were in agreement with the values of certified reference materials.     

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.     

Determination of chromium(III) and total chromium using dual channels on glass chip with chemiluminescence detection

A simple, rapid and sensitive method for the determination of chromium(III) and total chromium using the simple dual T channels on glass chip with negative pressure pumping system and chemiluminescence (CL) detection is presented. The CL reaction was based on luminol oxidation by hydrogen peroxide in basic aqueous solution catalyzed by chromium(III). Total chromium in form of chromium(III) was achieved after chromium(VI) was completely reduced by acidic sodium hydrogen sulfite. Total chromium could then be determined with the same strategy as the chromium(III). The CL reagent was composed of 1.0 × 10⁻⁴ mol/L luminol, 1.0 × 10⁻² mol/L hydrogen peroxide and 0.10 mol/L sodium bromide in 0.050 mol/L carbonate buffer (pH 11.00). The 1.0 × 10⁻² mol/L ethylenediaminetetraacetic acid was added into the sample solution in order to improve the selectivity. Chromium(III) could be detected at a notably concentration of 1.6 × 10⁻¹⁶ mol/L and a linear calibration curve was obtained from 1.0 × 10⁻¹⁵ to 1.0 × 10⁻¹³ mol/L. The sample and CL reagent consumption were only 15 and 20 μL, respectively. The analysis time was less than 1 min per sample with the precision (%R.S.D.) was 4.7%. The proposed method has been applied successfully to the analysis of river water, mineral waters, drinking waters and tap water. Its performance was verified by the analysis of certified total chromium-reference materials and by recovery measurement on spiked synthetic seawater sample.     

Simultaneous microwave-assisted extraction of polycyclic aromatic hydrocarbons, polychlorinated biphenyls, phthalate esters and nonylphenols in sediments

A new method was developed for the simultaneous extraction of polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), phthalate esters (PEs), nonylphenols (NPs) and nonylphenol mono- and diethoxylates (NP1EOs and NP2EOs, respectively) in sediment samples by means of a closed microwave system. The extractions were carried out at 21 psi and 80% of microwave power and 15 ml of acetone were used as the common extraction solvent. The filtered extract was further fractionated in two groups using Florisil cartridges: PAHs and PCBs were eluted with n-hexane:toluene (4:1) and the PEs, NPs and ethoxylates were eluted with ethyl acetate. All the compounds were analysed by gas chromatography-mass spectrometry (GC-MS). In case of PAHs and PCBs, the developed method was validated by comparison of the results obtained for the certified reference material NIST 1944 with the certified values. In the absence of a reference material for phthalate esters and nonylphenols, one sediment sample was extracted twice under the optimal conditions in order to check than an exhaustive extraction of the analytes occurred. This method is currently used in the study of the distribution of those organic contaminants in the estuaries of the Bay of Biscay (Spain).     

Distribution of components of binary nickel—chromium alloys electrodeposited from sulfate—oxalate solutions

The composition and distribution of elements over the thickness of electrodeposited nickel—chromium layers are studied by x-ray photoelectron and Auger electron spectroscopy techniques. During a layer-by-layer etching, the Cr : Ni ratio varies with a period of 2–5 nm. This period and the amplitude of the ratio of concentrations of components increases with the current density. During alloy deposition on a copper cathode, the first to deposit is nickel, which exerts a catalytic effect on the chromium deposition, which in turn exerts a catalytic effect on the oxalate reduction to carbon. Once a deposit thicknesses of ~100 nm is reached, the alloy composition becomes constant. The deposits contain considerable amounts of carbon (in the form of graphitized structures and carbides), which increases from 0.6 to 2 wt % with the current density. The surface of the growing alloy 50–70 nm thick is rich in nickel and chromium hydroxides and organic compounds containing carboxyl groups.Translated from Elektrokhimiya, Vol. 40, No. 12, 2004, pp. 1481–1486.Original Russian Text Copyright © 2004 by Edigaryan, 4, Lubnin, Polukarov.     

Test of the generalized standard addition method and linearization algorithms for the direct,simultaneous, multi-element analysis of solid samples by electrothermal atomic absorption spectrometry

The application of a multi-element electrothermal atomic absorption spectrometry (ETAAS) instrument with line sources and Zeeman-effect background correction to the direct, simultaneous determination of Ag, Cd, Cr and Pb in solid reference materials is described. Due to the occurrence of interference effects, the generalized standard addition method (GSAM) was required for calibration purposes. In order to extend the dynamic range for analytes present at high concentrations, linearization algorithms were tested. The combination of the GSAM and extension of the linear range, when necessary, generally yielded acceptable analytical results for the suite of elements studied, and may provide a useful approach to calibration in the direct analysis of solid samples by multi-element ETAAS. However, while linearization yielded good results for Ag and Cd in solid reference materials, it remains to be demonstrated that acceptable performance can be obtained for other elements in real samples.     

Surface charge and surface chemical characteristics of magnetites substituted with nickel, cobalt and chromium

Magnetite (MAG) and magnetites substituted with nickel, cobalt and chromium (NF, COF and CRF, respectively) have been prepared over the whole range of composition, Me_xFe_3−xO₄ (x=0–3, Me=Ni, Co or Cr) using the coprecipitation technique and have been characterized for their chemical composition, crystallinity and surface area. The types of sorption sites present in them were characterized by analysing the water sorption isotherms ultilizing the D'Arcy and Watt equation. Intrinsic dissociation constants, and point of zero charge, PZC, were evaluated by analysing the pH-titration curves in acid and alkaline media. A similarity in the trend was observed for the crystallinity, surface area, sorption sites and surface charge characteristics as a function of the composition of the substituted MAGs (i.e. x). The overall behaviour of the substituted MAGs could be grouped into two: mixed oxides having composition with x=0–1 and those in the composition region x=1–3. Those in the composition region x=0–1 were crystalline with a lower surface area, less hydrophilic in nature and have surface charge characteristics lower than that of MAG. Those mixed oxides in the composition region x=1–3 nearly had the opposite characteristics, with increasing value of x. The hydrophilicity of the substituted MAGs decreased in the sequence CRF>NFCOF, and the acidic nature decreased in the sequence NF>CRF>COF.     

Determination of Lead, Chromium, Manganese and Zinc in Slurries of Botanical and Biological Samples by Electrothermal Atomic Absorption Spectrometry Using Tungsten-Containing Chemical Modifiers

Lead, Cr, Mn and Zn in slurries of botanic and biological samples were determined by electrothermal atomic absorption spectrometry (ETAAS) using W, Ir, NH₄H₂PO₄, W and NH₄H₂PO₄, Ir and NH₄H₂PO₄, W and Ir, and W + Ir + NH₄H₂PO₄ chemical modifiers in an 0.2% (v/v) Triton X-100 plus 0.2% (v/v) nitric acid mixture. Zeeman effect background correction was performed and platforms inserted into graphite tubes were used. Comprehensive comparative studies were carried out with respect to pyrolysis and atomization temperatures, atomization and background absorption profiles, characteristic masses, detection limits and accuracy of the determinations in the presence and absence of modifiers. The mixture of W + Ir + NH₄H₂PO₄ was found to be preferable for the determination of Pb, Cr, Mn and Zn in slurry samples. The pyrolysis temperatures of the analytes were increased up to 1250 °C for Pb, 1000 °C for Zn, 1400 °C for Cr and Mn by using W + Ir + NH₄H₂PO₄ with an 0.2% (v/v) Triton X-100 plus 0.2% (v/v) nitric acid mixture used as diluent solution. The optimum masses of the mixed modifier components were found to be 20 µg W + 4 µg Ir + 50 µg NH₄H₂PO₄. The characteristic masses of Pb, Cr, Mn and Zn obtained are 16.3, 5.6, 0.1 and 1.1 pg, respectively. The detection limits of Pb, Cr, Mn and Zn based on integrated absorbance for 0.5% (m v⁻¹) slurries were found to be 0.14, 0.06, 0.02 and 0.01 µg g⁻¹, respectively. The slurries of botanic and biological certified and standard reference materials were analyzed with and without the modifiers. Depending on the sample type, the percent recoveries increased from 63 up to 104% for analytes when using the proposed modifier mixture.     

Trace analysis of toxic metals,III. Determination of chromium as trivalent chromium by differential pulse polarography

Methods for trace analysis of chromium as Cr³⁺ were investigated, using differential pulse polarography in various media. Determination at the ng/ml-g/ml range can be carried out in KCl/HCl, KCNS/HOAc, and other media. Total concentration of chromium in a solution containing Cr³⁺ and HCrO ₄ ^– can be determined in KCNS/HOAc, and it is found that HCrO ₄ ^– can be converted quantitatively to Cr³⁺. The relative quantity of HCrO ₄ ^– and Cr³⁺ can be determined by the difference between the total chromium concentration and the concentration of HCrO ₄ ^– . The sensitivity (12.5 ng/ml) and accuracy of this method is better than the method that determines total chromium as HCrO ₄ ^– .     

A continuous approach for the determination of Cr(VI) in sediment and soil based on the coupling of microwave-assisted water extraction, preconcentration, derivatization and photometric detection

A dynamic system for the continuous leaching of Cr(VI) from sediment and soil based on both microwave assistance and iterative change of the flow direction of the extractant through the sample cell has been developed. The microwave-assisted extractor has been coupled to a photometric detector through a flow injection interface in order to develop a fully automated method. The Cr(VI) extracted was monitored after derivatization with 1,5-diphenylcarbazide. Two approaches are proposed which differ in the inclusion of a preconcentration minicolumn packed with a strong anion exchange resin. A 0.04 M ammonium buffer solution was used as extractant and 0.2 g of sample—river sediment spiked with 50 and 5 μg g⁻¹ for the method without preconcentration (method A) and with preconcentration (method B)—was subjected to 8-14 min of 300 W microwave-assisted extraction. The within-laboratory reproducibility and repeatability were 2.6 and 1.9 for method A, and 4.0 and 2.6 for method B. The proposed methods have been compared with the reference EPA method 3060/7196.     

Distribution of total carbohydrates in surface sediments of the Egyptian Mediterranean coast,in relation to some inorganic factors

The interrelation between calcium, magnesium, carbonate, fluoride and total carbohydrates (THCO) distribution was investigated for surface sediments collected from three sectors (A–C) along the Egyptian Mediterranean coast during the summer of 2008. The recent ultrasound-acetic acid technique was used for the simultaneous extraction and hydrolysis of total carbohydrates. Based on the average values, the sandy sediments of sector (C) exhibited the highest THCO levels (163.78 ± 53.28 μg/g). In contrast, the silty sand sediments of sector (A) had the lowest average THCO level (8.56 ± 2.60 μg/g). Linear regression model with one predictor showed that there are significant correlations between total carbohydrates, carbonate and fluoride suggesting the common origin of these components. Neither calcium nor magnesium has correlation with THCO. This study revealed that carbonate is the dominant factor affecting the distribution of carbohydrates in the sediments. The spatial distribution of THCO was not affected by the potential sources of runoff, but varied according to the sediments mineralogy.     

Determination of cadmium, copper and lead in soils, sediments and sea water samples by ETAAS using a Sc + Pd + NH(4)NO(3) chemical modifier

Cadmium, copper and lead in soils, sediments and spiked sea water samples have been determined by electrothermal atomic absorption spectrometry (ETAAS) with Zeeman effect background corrector using NH₄NO₃, Sc, Pd, Sc + NH₄NO₃, Pd + NH₄NO₃, Sc + Pd and Sc + Pd + NH₄NO₃ as chemical modifiers. A comprehensive comparison was made among the modifiers and without modifier in terms of pyrolysis and atomization temperatures, atomization and background absorption profiles, characteristic masses, detection limits and accuracy of the determinations. Sc + Pd + NH₄NO₃ modifier mixture was found to be preferable for the determination of analytes in soil and sediment certified and standard reference materials, and sea water samples because it increased the pyrolysis temperature up to 900 °C for Cd, 1350 °C for Cu and 1300 °C for Pb. Optimum masses of mixed modifier components found are 20 μg Sc + 4 μg Pd + 8 μg NH₄NO₃. Characteristic masses of Cd, Cu and Pb obtained are 0.6, 5.3 and 15.8 pg, respectively. The detection limits of Cd, Cu and Pb were found to be 0.08, 0.57 and 0.83 μg l⁻¹, respectively. Depending on the solid sample type, the percent recoveries were increased up to 103% for Cd, Cu and Pb by using the proposed modifier mixture. The accuracy of the determination of analytes in the sea water samples was also increased.     

Determination of hexavalent chromium in exhaled breath condensate and environmental air among chrome plating workers

Chromium speciation has attracted attention because of the different toxicity of Cr(III), which is considered relatively non-toxic, and Cr(VI), which can cross cell membranes mainly as a chromate anion and has been classified as a class I human carcinogen. The aims of the present study were to measure soluble Cr(VI) levels in environmental samples, to develop a simple method of quantifying Cr(VI) in exhaled breath condensate (EBC), and to follow the kinetics of EBC Cr(VI) in chrome plating workers.Personal air samples were collected from 10 chrome platers; EBC was collected from the same workers immediately after the work shift on Tuesday and before the work shift on the following Wednesday. Environmental and EBC Cr(VI) levels were determined by means of colorimetry and electrothermal absorption atomic spectrometry, respectively.The method of detecting Cr(VI) in environmental air was based on the extraction of the Cr(VI)-diphenylcarbazide (Cr(VI)-DPC) complex in 1-butanol, whereas EBC Cr(VI) was determined using a solvent extraction of Cr(VI) as an ion pair with tetrabutylammonium ion, and subsequent direct determination of the complex (Cr(VI)-DPC) in EBC.Kinetic data showed that airborne Cr(VI) was reduced by 50% in airway lining fluid sampled at the end of exposure and that there was a further 50% reduction after about 15 h. The persistence of Cr(VI) in EBC supports the use of EBC in assessing target tissue levels of Cr(VI).     

Studies of finite molecular chains: synthesis, structural, magnetic and inelastic neutron scattering studies of hexa- and heptanuclear chromium horseshoes

We report the synthesis and structural characterisation of a family of finite molecular chains, specifically [{[R(2)NH(2)](3)[Cr(6)F(11)(O(2)CCMe(3))(10)]}(2)] (in which R=nPr 1, Et 2, nBu 3), [{Et(2)NH}(2){[Et(2)NH(2)](3)[Cr(7)F(12)(O(2)CCMe(3))(12)][HO(2)CCMe(3)](2)}(2)] (4), [{[Me(2)NH(2)](3)[Cr(6)F(11)(O(2)CCMe(3))(10)]2.5 H(2)O}(4)] (5) and [{[iPr(2)NH(2)](3)[Cr(7)F(12)(O(2)CCMe(3))(12)]}(2)] (6). The structures all contain horseshoes of chromium centres, with each Cr...Cr contact within the horseshoe bridged by a fluoride and two pivalates. The horseshoes are linked through hydrogen bonds to the secondary ammonium cations in the structure, leading to di- and tetra-horseshoe structures. Through magnetic measurements and inelastic neutron scattering studies we have determined the exchange coupling constants in 1 and 6. In 1 it is possible to distinguish two exchange interactions, J(A)=-1.1 meV and J(B)=-1.4 meV; J(A) is the exchange interactions at the tips of the horseshoe and J(B) is the exchange within the body of the horseshoe (1 meV=8.066 cm(-1)). For 6 only one interaction was needed to model the data: J=-1.18 meV. The single-ion anisotropy parameters for Cr(III) were also derived for the two compounds as: for 1, D(Cr)=-0.028 meV and |E(Cr)|=0.005 meV; for 6, D(Cr)=-0.031 meV. Magnetic-field-dependent inelastic neutron scattering experiments on 1 allowed the Zeeman splitting of the first two excited states and level crossings to be observed. For the tetramer of horseshoes (5), quantum Monte Carlo calculations were used to fit the magnetic susceptibility behaviour, giving two exchange interactions within the horseshoe (-1.32 and -1.65 meV) and a weak inter-horseshoe coupling of +0.12 meV. Multi-frequency variable-temperature EPR studies on 1, 2 and 6 have also been performed, allowing further characterisation of the spin Hamiltonian parameters of these chains.     

Preconcentration and speciation of chromium in drinking water samples by coupling of on-line sorption on activated carbon to ETAAS determination

An on-line flow injection (FI) preconcentration-electrothermal atomic absorption spectrometry (ETAAS) method is developed for trace determination of chromium in drinking water samples by sorption on a conical minicolumn packed with activated carbon (AC) at pH 5.0. The chromium was removed from the minicolumn with 1.0% (v/v) nitric acid. An enrichment factor (EF) of 35-fold for a sample volume of 10 ml was obtained. The detection limit (DL) value for the preconcentration method proposed was 3.0 ng l⁻¹. The precision for 10 replicate determinations at the 0.5 μg l⁻¹ Cr level was 4.0% relative standard deviation (R.S.D.), calculate with the peak heights obtained. The calibration graph using the preconcentration system for chromium was linear with a correlation coefficient of 0.9992 at levels near the detection limits up to at least 50 μg l⁻¹. The method was successfully applied to the determination of Cr(III) and Cr(VI) in drinking water samples.     

Distribution of heavy metal concentrations in surface sediments in Dubai Creeks, United Arab Emirates

Dubai is developing rapidly and many developmental activities are concentrated around its Creek. The present study reports the lateral distribution of heavy metals and compares it with local historical record of heavy metal concentrations. For this purpose surface sediment samples were collected and analyzed for metal contents, total organic carbon content (TOC), mineralogy and grain size. The percentages of the different grain size fraction of the collected sediments were as follow 65% for sand size, 15% for silt size fraction, and the rest accounted for clay size fraction. The microscopic analyses indicate that the sediment composed mainly from carbonate and quartz with traces of rock fragments. Such mineral composition is not believed to be a potential source of heavy metal. The study found that the average recorded heavy metal concentrations in the collected sediment samples were 87, 96, 127, 38.5, and 279 ppm for Cr, Cu, Ni, Pb, and Zn, respectively. Those values were slightly higher than metal concentrations recoded in 2001 with 1.22 (Cr), 2.5 (Cu), 2.87 (Ni), 0.69 (Pb), and 2.1 (Zn) folds. However, in 2001 and 2003 the measured metal contents, along the creek, were lower than those of the average earth crust. Along the Creek most metals recorded the highest concentrations in the upper reach of the Creek. The distribution of the measured heavy metals was not affected significantly with the TOC values. The present study also documented obvious related point sources of pollution.     

Chemiluminescence determination of chromium(III) and total chromium in water samples using the periodate-lucigenin reaction

A new chemiluminescence (CL) method combined with flow injection technique is described for the determination of Cr(III) and total Cr. It is found that a strong CL signal is generated from the reaction of Cr(III), lucigenin and KIO₄ in alkaline condition. The determination of total Cr is performed by pre-reduction of Cr(VI) to Cr(III) by using H₂SO₃. The CL intensity is linearly related to the concentration of Cr in the range 4.0 × 10⁻¹⁰–1.0 × 10⁻⁶ g mL⁻¹. The detection limit (3s _b) is 1 × 10⁻¹⁰ g mL⁻¹ Cr and the relative standard deviation is 1.9% (5.0 × 10⁻⁸ g mL⁻¹ of Cr(III) solution, n = 11). The method was applied to the determination of Cr(III) and total Cr in water samples and compared satisfactorily with the official method.     

Differential-pulse polarographic determination of chromium and nickel in zircaloys using microsamples

Three methods were developed for the analysis of the alloying elements chromium and nickel in Zircaloy-2 and Zircaloy-4, alloys of zirconium used extensively in the nuclear industry as nuclear fuel sheathing. Zircaloy was dissolved in hydrofluoric acid followed by oxidation of Cr(III) to Cr(VI) by perchloric acid. The polarographic peak of CrO ₄ ^2– in alkaline medium was used to determine Cr. Nickel was determined, after HF dissolution, using the polarographic peak of the nickel-ammonia complex, Ni (NH₃) ₆ ²⁺ . In an alternative method for Ni, the sample was dissolved in HF and the polarographic peak of the nickel-fluoride complex, NiF ₄ ^2– , was used. Careful control of fluoride ion concentration and the pH eliminated the harmful effect of fluoride on the capillary behaviour of the dropping mercury electrode. The detection limits for chromium, nickel-ammonia and nickel-fluoride in Zircaloys were 0.0016, 0.0033, and 0.0041%, respectively.     

Comparative assessment of two sequential chemical extraction schemes for the fractionation of cadmium, chromium, lead and zinc in surface coastal sediments

Two existing sequential chemical extraction schemes, involving respectively five and six leaching steps with solutions of increasing dissolving power, were compared. The methods have been applied to surface sediment samples collected in a marine estuary zone potentially exposed to contamination arising from nearby industrial activities. A certified reference material (MURST-ISS-A1) consisting of an Antarctic bottom sediment for which no information regarding phase dependent concentration is available, was also analyzed. In order to evaluate the partition of metals among different geochemical forms, the concentrations of cadmium, chromium, lead and zinc were measured in the liquid extracts by Zeeman-corrected flame atomic absorption and by inductively coupled plasma-atomic emission spectrometry. The total metal concentrations were determined after strong acid attack, and the adequacy of this total digestion/dissolution technique was verified by its application to the reference material. Comparison of total metal concentrations with the sum of concentrations associated with the individual phases was employed to assess possible analyte losses or contaminations. Precisions for both sequential procedures were comparable, but some inconsistencies in mass balances were found in one of the samples for the distribution of Zn in the soluble/exchangeable fractions and for Cd in the bound to carbonates form. In addition, the six steps procedure produced lower concentration values in the case of elements associated to the residual fraction. For the five steps method mass balances showed acceptable agreement, with average recoveries in the 87 to 106% range. On the whole, differences in metal distributions were observed, being more marked for the bottom sediment. Significant proportions of the studied elements, with the exception of Cr, were found as easily extractable forms. X-ray diffraction and petrographic observation of the surface sediments allowed qualitative correlation between the leaching results obtained and the presence of defined geochemical phases.     

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.