A Robust Flow-Based System for the Spectrophotometric Determination of Cr(VI) in Recreational Waters.

A flow-based method for the spectrophotometric determination of chromium (VI) in recreational waters with different salinities was developed. Chromium can occur in the environment in different oxidation states with different related physiological properties. With regard to chromium, the speciation is particularly important, as the hexavalent chromium is considered to be carcinogenic. To achieve that purpose, the use of the diphenylcarbazide (DPC) selective colored reaction with the hexavalent chromium was the chosen strategy. The main objective was to develop a direct and simple spectrophotometric method that could cope with the analysis of different types of environmental waters, within different salinity ranges (fresh to marine waters). The potential interference of metal ions, that can usually be present in environmental waters, was assessed and no significant interferences were observed (<10%). For a complete Cr(VI) determination (three replicas) cycle, the corresponding reagents consumption was 75 µg of DPC, 9 mg of ethanol and 54 mg of sulfuric acid. Each cycle takes about 5 min, including the system clean-up. The limit of detection was 6.9 and 12.2 µg L−1 for waters with low and high salt content, respectively. The method was applied for the quantification of chromium (VI) in both fresh and marine water, and the results were in agreement with the reference procedure.

Green Downscaling of Solvent Extractive Determination Employing Coconut Oil as Natural Solvent with Smartphone Colorimetric Detection: Demonstrating the Concept via Cu(II) Assay Using 1,5-Diphenylcarbazide.

Coconut oil as a natural solvent is proposed for green downscaling solvent extractive determination. Determination of Cu(II) using 1,5-Diphenylcarbazide (DPC) was selected as a model for the investigation. Cu(II)-DPC complexes in aqueous solution were transferred into coconut oil phase. The change of the color due to Cu(II)-DPC complexes in coconut oil was followed by using a smartphone and image processing. A single standard concept was used for a series of Cu(II) standard solutions. A downscaling procedure using a 2 mL vial provided a calibration: color intensity = -142 [Cu(II)] + 222, (R2 = 0.98), 10% RSD. Using a well plate, a calibration was: color intensity = 61 [Cu(II)] + 68 (R2 = 0.91), 15% RSD. Both were for the range of 0-1 ppm Cu(II). Application of the developed procedure to water samples was demonstrated. The developed procedures provided a new approach of green chemical analysis.

False-positive result when a diphenylcarbazide spot test is used on trivalent chromium-passivated zinc surfaces.

BACKGROUND: A colorimetric 1,5-diphenylcarbazide (DPC)-based spot test can be used to identify hexavalent chromium on various metallic and leather surfaces. DPC testing on trivalent chromium-passivated zinc surfaces has unexpectedly given positive results in some cases, apparently indicating the presence of hexavalent chromium; however, the presence of hexavalent chromium has never been confirmed with more sensitive and accurate test methods. OBJECTIVES: To examine the presence of hexavalent chromium on trivalent chromium-passivated zinc surfaces with a DPC-based spot test. METHODS: A colorimetric DPC spot test was used for the initial detection of hexavalent chromium on new and 1-year-aged trivalent chromium-passivated zinc surfaces. Then, X-ray photoelectron spectroscopy (XPS) was performed for all samples. RESULTS: The DPC spot test indicated the presence of hexavalent chromium in aged, but not new, trivalent chromium passivation on zinc; however, subsequent analysis by XPS could not confirm the presence of chromium in a hexavalent state. CONCLUSIONS: Unintended oxidation of DPC induced by atmospheric corrosion is suggested as a possible reason for the false-positive reaction of the DPC test on a trivalent chromium-passivated zinc surface. Further validation of the use of the DPC test for chromium-containing metallic surfaces is required.

FIA-coupled spectrophotometric method for determination of Cr (VI) traces in natural waters: application of in-line dissolution of 1,5-diphenylcarbazide after heat treatment and activated alumina as adsorbent for preconcentration.

This work proposes the quantification of Cr (VI) ions in natural waters in trace level, using activated alumina (Al2O3) as preconcentration support, controlled in-line dissolution of the solidified chromophore diphenylcarbazide after heat treatment and spectrophotometric detection. The manifold ensures high sensitivity of analytical response, good repeatability, and stability. In this work, optimization of experimental conditions of a flow injection system was chosen as the parameters for greater sensitivity and better selectivity. The selected optimized conditions were 0.30 mol L-1 for H2SO4 concentration, system flow rate as 0.40 mL min-1, sample injection volume of 192.50 µL, 2 min for preconcentration time, and 0.10 mol L-1 for eluent concentration. The analytical curves obtained for real sample analysis show linear range from 0.192 to 0.961 µM, linear correlation coefficient R = 0.9997 and LOD = 0.024 µM. The preconcentration factor of about four times was obtained through the passage of 800 µL of a standard solution containing 0.961 µM of Cr (VI) through mini-column of preconcentration followed by elution at 192.5 µL of NH4OH 0.1 mol L-1 solution. The solid chromogenic reagent presented high durability (weeks in daily use with mass of 0.0993 g) and good reproducibility in analytical signal. The reactivation of the mini-column of alumina should be executed after ten injections of eluent, using 800 µL of HCl 0.02 mol L-1 solution in flow through the same. Each cycle of injection and elution of the sample takes about 5 min on the proposed terms. Despite the length of each cycle still be high, low concentrations can be detected using a technique of relatively low cost. This is due in part, the association dissolution of the chromogenic reagent directly in the line and the preconcentration step. Another important factor is the economy of reagent chromogenic, low generation of reject contributing to better quality of the environment, and the high potential for applications to work in field.

Chromium(III) and chromium(VI) release from leather during 8 months of simulated use.

BACKGROUND: Chromium (Cr) release from Cr-tanned leather articles is a major cause of Cr contact dermatitis. It has been suggested that Cr(VI) release from leather is not necessarily an intrinsic property of the leather, but is strongly dependent on environmental conditions. OBJECTIVES: To test this hypothesis for long-term (8 months) simulated use. MATERIALS AND METHODS: The release of total Cr and Cr(VI) from Cr-tanned, unfinished leather was analysed in subsequent phosphate buffer (pH 8.0) immersions for a period of 7.5 months. The effect of combined ultraviolet treatment and alkaline solution (pH 12.1) was tested. Dry storage [20% relative humidity (RH)] was maintained between immersions. Atomic absorption spectroscopy, X-ray fluorescence and diphenylcarbazide tests were used. RESULTS: Cr(VI) release was dependent on previous dry storage or alkaline treatment, but not on duration or number of previous immersions. Cr(III) release decreased with time. Fifty-two percent of the total Cr released during the last immersion period was Cr(VI). Cr(VI) release exceeded 9 mg/kg in all immersion periods except in the first 10-day immersion (2.6 mg/kg). CONCLUSIONS: Cr(VI) release is primarily determined by environmental factors (RH prior to immersion, solution pH, and antioxidant content). The RH should be kept low prior to testing Cr(VI) release from leather.

Chromium(VI) release from leather and metals can be detected with a diphenylcarbazide spot test.

BACKGROUND: Along with chromium, nickel and cobalt are the clinically most important metal allergens. However, unlike for nickel and cobalt, there is no validated colorimetric spot test that detects chromium. Such a test could help both clinicians and their patients with chromium dermatitis to identify culprit exposures. OBJECTIVES: To evaluate the use of diphenylcarbazide (DPC) as a spot test reagent for the identification of chromium(VI) release. METHODS: A colorimetric chromium(VI) spot test based on DPC was prepared and used on different items from small market surveys. RESULTS: The DPC spot test was able to identify chromium(VI) release at 0.5 ppm without interference from other pure metals, alloys, or leather. A market survey using the test showed no chromium(VI) release from work tools (0/100). However, chromium(VI) release from metal screws (7/60), one earring (1/50), leather shoes (4/100) and leather gloves (6/11) was observed. We found no false-positive test reactions. Confirmatory testing was performed with X-ray fluorescence (XRF) and spectrophotometrically on extraction fluids. CONCLUSIONS: The use of DPC as a colorimetric spot test reagent appears to be a good and valid test method for detecting the release of chromium(VI) ions from leather and metal articles. The spot test has the potential to become a valuable screening tool.

Nitrite interference and elimination in diphenylcarbazide (DPCI) spectrophotometric determination of hexavalent chromium.

Cr(VI) is highly noted as a carcinogenic, mutagenic, and teratogenic pollutant. However, accurate determination of Cr(VI) in aqueous samples is difficult using the conventional diphenylcarbazide (DPCI) spectrophotometric method upon being interfered by co-existed nitrite. This paper illustrates how to eliminate the nitrite influence in a simple but efficient method based on a detailed analysis of interference mechanism. High-performance liquid chromatography analysis revealed that under acidic condition, DPCI was oxidized by nitrite to other substrates, which could not react with Cr(VI). The final oxidation product of DPCI was further purified by thin-layer chromatography and identified as diaryl carbodiazone by Fourier Transform Ion Cyclotron Resonance-Mass Spectrometry (FTICR-MS) and nuclear magnetic resonance. Consequently, an improved method was proposed by simply adding sulfamic acid for eliminating the nitrite interference in Cr(VI) determination. The proposed method was successfully confirmed by the accurate recovery of Cr(VI) from spiked water samples and further proven with inductively coupled plasma-atomic emission spectroscopy, which demonstrated a great potential for determining Cr(VI) concentration in aqueous samples containing nitrite.

Requirement for Asn298 on D1 protein for oxygen evolution: analyses by exhaustive amino acid substitution in the green alga Chlamydomonas reinhardtii.

PSII generates strong oxidants used for water oxidation. The secondary electron donor, Y(Z), is Tyr161 on PSII reaction center D1 protein and mediates electron transfer from the oxygen-evolving Mn(4)CaO(5) cluster to the primary electron donor, P680. The latest PSII crystal structure revealed the presence of a hydrogen bond network around Y(Z), which is anticipated to play important roles in the electron and proton transfer reactions. Y(Z) forms a hydrogen bond with His190 which in turn forms a hydrogen bond with Asn298 on D1 protein. Although functional roles of Y(Z) and His190 have already been characterized, little is known about the functional role of Asn298. Here we have generated 19 mutants from a green alga Chlamydomonas reinhardtii, in which the Asn298 has been substituted by each of the other 19 amino acid residues. All mutants showed significantly impaired or no photosynthetic growth. Seven mutants capable of photosynthetic growth showed oxygen-evolving activity although at a significantly reduced rate. Interestingly the oxygen-evolving activity of these mutants was markedly photosensitive. The 19 mutants accumulated PSII at variable levels and showed a light-induced electron transfer reaction from 1,5-diphenylcarbazide (DPC) to 2,6-dichlorophenolindophenol (DCIP), suggesting that Asn298 is important for the function and photoprotection of the Mn(4)CaO(5) cluster.

Electron transfer between exogenous electron donors and reaction center of photosystem 2.

Transfer of electrons between artificial electron donors diphenylcarbazide (DPC) and hydroxylamine (NH2OH) and reaction center of manganese-depleted photosystem 2 (PS2) complexes was studied using the direct electrometrical method. For the first time it was shown that reduction of redox-active amino acid tyrosine Y(Z)(.) by DPC is coupled with generation of transmembrane electric potential difference (DeltaPsi). The amplitude of this phase comprised ~17% of that of the DeltaPsi phase due to electron transfer between Y(Z) and the primary quinone acceptor Q(A). This phase is associated with vectorial intraprotein electron transfer between the DPC binding site on the protein-water interface and the tyrosine Y(Z)(.). The slowing of DeltaPsi decay in the presence of NH2OH indicates effective electron transfer between the artificial electron donor and reaction center of PS2. It is suggested that NH2OH is able to diffuse through channels with diameter of 2.0-3.0 A visible in PS2 structure and leading from the protein-water interface to the Mn(4)Ca cluster binding site with the concomitant electron donation to Y(Z)(.). Because the dielectrically-weighted distance between the NH2OH binding site and Y(Z)(.) is not determined, the transfer of electrons from NH2OH to Y(Z)(.) could be either electrically silent or contribute negligibly to the observed electrogenicity in comparison with hydrophobic donors.

Chromium Monitoring in Water by Colorimetry Using Optimised 1,5-Diphenylcarbazide Method.

Chromium contamination of drinking water has become a global problem due to its extensive use in industry. The most commonly used methods for chromium detection in water are laboratory-based methods, such as atomic absorption spectroscopy and mass spectroscopy. Although these methods are highly selective and sensitive, they require expensive maintenance and highly trained staff. Therefore, there is a growing demand for cost effective and portable detection methods that would meet the demand for mass monitoring. Microfluidic detection systems based on optical detection have great potential for onsite monitoring applications. Furthermore, their small size enables rapid sample throughput and minimises both reagent consumption and waste generation. In contrast to standard laboratory methods, there is also no requirement for sample transport and storage. The aim of this study is to optimise a colorimetric method based on 1,5-diphenylcarbazide dye for incorporation into a microfluidic detection system. Rapid colour development was observed after the addition of the dye and samples were measured at 543 nm. Beer's law was obeyed in the range between 0.03-3 mg·L-1. The detection limit and quantitation limit were found to be 0.023 and 0.076 mg·L-1, respectively.

New method for hydrogel synthesis from diphenylcarbazide chitosan for selective copper removal.

In this work, a simple method was developed for hydrogel preparation from 1,5-Diphenylcarbazide (DPC) and chitosan (CS) through Diazotization reaction of CS as a selective adsorbent (DPCCS) for Cu(II) ions. CS was treated with sodium nitrate and subsequent crosslinking reaction with DPC for the preparation of DPCCS. Different techniques were used for characterization of DPCCS. Various parameters such as, temperature, pH, and concentration of Cu(II) were used for adsorption studies. Kinetics of Cu(II) ion on DPCCS follows the Pseudo second order and equilibrium of adsorption occurs in short time. The equilibrium data was best fitted with the Langmuir isotherm and the maximum adsorption capacity of DPCCS was 185.505 mg g-1. Thermodynamic parameters ΔG°, ΔH° and ΔS° suggested that the adsorption of Cu(II) ion on the surfaces of DPCCS was spontaneous, endothermic and randomness of Cu(II) ion in the solution was enhanced respectively. Regeneration of DPCCS and Cu(II) ion recovery were studied up to five cycles without the lost of the adsorption capacity.

Solid phase extraction of chromium(VI) from aqueous solutions by adsorption of its diphenylcarbazide complex on an Amberlite XAD-4 resin column.

A method has been developed for the solid phase extraction of chromium(VI) based on the adsorption of its diphenylcarbazide complex on an Amberlite XAD-4 resin column. The influence of acidity, stability of the column, sample volume, flow rate and interfering ions were studied in detail. The adsorbed complex could be eluted using acetone-sulfuric acid mixture and the concentration of chromium was determined using visible spectrophotometry. A detection limit of 6 microg L(-1) could be achieved. A preconcentration factor of 27 could be obtained for 400 mL sample volume. The validity of the method was checked in spiked water samples and electroplating wastewater.

Solid phase extraction of chromium(VI) from aqueous solutions by adsorption of its diphenylcarbazide complex on a mixed bed adsorbent (acid activated montmorillonite-silica gel) column.

A novel approach has been developed for the solid phase extraction of chromium(VI) based on the adsorption of its diphenylcarbazide complex on a mixture of acid activated montmorillonite (AAM)-silica gel column. The effect of various parameters such as acidity, stability of the column, sample volume, interfering ions, etc., were studied in detail. The adsorbed complex could be easily eluted using polyethylene glycol-sulfuric acid mixture and the concentration of chromium has been determined using visible spectrophotometry. The calibration graph was linear in the range 0-1microgmL(-1) chromium(VI) with a detection limit of 6microgL(-1). A highest preconcentration factor of 25 could be obtained for 250mL sample volume using glass wool as support for the mixed bed adsorbent. Chromium(VI) could be effectively separated from other ions such as nickel, copper, zinc, chloride, sulfate, nitrate, etc., and the method has been successfully applied to study the recovery of chromium in electroplating waste water and spiked water samples.

[Investigation of concentration levels of chromium(VI) in bottled mineral and spring waters by high performance ion chromatography technique with application of postcolumn reaction with 1,5-diphenylcarbazide and VIS detection]. / Badanie poziomów stezen chromu(VI) w butelkowanych wodach mineralnych i zródlanych technika wysokosprawnej chromatografii jonowej z wykorzystaniem reakcji postkolumnowej z 1,5-difenylokarbazydem i detekcji VIS.

The aim of this work was optimization and validation of the method of determination of Cr(VI) existing in the form of chromate(VI) in mineral and spring waters by High Performance Ion Chromatography (HPIC) technique with application of postcolumn reaction with 1,5-diphenylcarbazide and VIS detection. Optimization of the method performed with the use of initial apparatus parameters and chromatographic conditions from the Method 218.6 allowed to lowering detection limit for Cr(VI) from 400 ng/l to 2 ng/l. Thanks to very low detection limit achieved it was possible to determine of Cr(VI) concentrations in 25 mineral and spring waters presented at Polish market. In the cases of four mineral and spring waters analyzed, determined Cr(VI) concentrations were below of quantification limit (< 4 ng/l) but simultaneously in another mineral and spring waters the concentrations of chromium(VI) were determined in the range of 5.6 - 1281 ng/l. The fact of existence of different Cr(VI) concentrations in investigated waters could be connected with secondary contamination of mineral and spring waters by chromium coming from metal installations and fittings. One should be underlined that even the highest determined concentration level of chromium(VI) was below of the maximum admissible concentration of total chromium presented in Polish Decree of Minister of Health from April 29th 2004. Therefore after taking into account determined in this work concentration of Cr(VI), the consumption of all waters analyzed in this study does not lead to essential human health risk.

Comparative performance of novel magnetic ion-imprinted adsorbents employed for Cd2+, Cu2+ and Ni2+ removal from aqueous solutions.

Novel magnetic ion-imprinted polymer was prepared by use of SBA-15 as functional monomer, ethylene glycol dimethacrylate as cross linker, diphenylcarbazide as ligand, and Cd2+, Cu2+, and Ni2+ as the template of ion source. The adsorption capacity of the synthesized adsorbent was 111, 95, and 87 mg g-1, respectively for cadmium, copper, and nickel. The selectivity of the adsorbents examined in the presence of different cations including Na+, K+, Ca2+, Mg2+, Zn2+, Co2+, Fe2+, Mn2+, Hg2+, and Pb2+ indicated that the synthesized ion-imprinted adsorbents were highly selective for the appropriate cations. Kinetic studies indicated that the adsorption process was very fast and the equilibrium was established within 5 min and followed the pseudo-second-order kinetic model. The used ion-imprinted adsorbent was readily regenerated by elution with 2 M HNO3, and the regenerated adsorbent retained most of its initial capacity. The calculated thermodynamic parameters indicated that the adsorption process was spontaneous and endothermic.

Cr(VI) and Cr(VI)-diphenylcarbazide removal from aqueous solutions using an iron rotating disc electrode.

This paper presents the results of the investigation on the removal of Cr(VI) and the complex Cr(VI)-diphenylcarbazide from aqueous solutions using an electrochemical reactor, with iron electrodes. A maximum value of 99% Cr(VI) removal from aqueous solutions is observed for both Cr(VI) and Cr(VI)-diphenylcarbazide, at initial concentrations from 150 to 800 mg l(-1). Cyclic voltammetry experiments of water show the presence of electroactive species in the oxidation and reduction zones previous to the treatment and how this presence diminishes as the electrochemical treatment is applied to the wastewater. UV-Vis analyses corroborate the improvement on the quality of aqueous solutions treated. Finally, scanning electron microscopy and energy dispersion spectra show that Cr and Fe are present as constituents of the sludge formed during the electrochemical treatment. It was demonstrated that the use of electrochemical methods for the treatment of Cr(VI) and Cr(VI)-diphenylcarbazide aqueous solutions is an effective and economical method.

Cloud point extraction and diffuse reflectance-Fourier transform infrared spectroscopic determination of chromium(VI): A probe to adulteration in food stuffs.

A new cloud point extraction (CPE) method for the determination of hexavalent chromium i.e. Cr(VI) in food samples is established with subsequent diffuse reflectance-Fourier transform infrared (DRS-FTIR) analysis. The method demonstrates enrichment of Cr(VI) after its complexation with 1,5-diphenylcarbazide. The reddish-violet complex formed showed λmax at 540nm. Micellar phase separation at cloud point temperature of non-ionic surfactant, Triton X-100 occurred and complex was entrapped in surfactant and analyzed using DRS-FTIR. Under optimized conditions, the limit of detection (LOD) and quantification (LOQ) were 1.22 and 4.02µgmL-1, respectively. Excellent linearity with correlation coefficient value of 0.94 was found for the concentration range of 1-100µgmL-1. At 10µgmL-1 the standard deviation for 7 replicate measurements was found to be 0.11µgmL-1. The method was successfully applied to commercially marketed food stuffs, and good recoveries (81-112%) were obtained by spiking the real samples.

Evidence for PSII donor-side damage and photoinhibition induced by cadmium treatment on rice (Oryza sativa L.).

The effects of cadmium (from 7.5 to 75 microM) on chloroplasts of rice were studied at the structural and biochemical level. Loss of pigments, reduction of thylakoids and decrease in oxygen evolution and Fv/Fm ratio occur in leaves following cadmium treatment. However, the amount of photosystem II reaction center proteins and that of its light harvesting complex is not affected, indicating that cadmium does not adversely influence the structural organization of this photosystem. In thylakoids isolated from cadmium-treated plants a loss in the capability to reduce 2,6-dichlorophenolindophenol is observed, which is partially restored if diphenylcarbazide is used as an electron donor, indicating that cadmium affects water splitting activity. In thylakoids isolated from control plants and treated with cadmium, diphenylcarbazide preserves most of the photosystem II activity lost after incubation with cadmium; most of the S(2) multiline electron paramagnetic resonance signal from the manganese cluster is lost, whereas the TyrD(+) and other signals are retained. Light-induced photosystem II damage, in vitro, is promoted by Cd-treatment as deduced from the mobility shift of the D1 protein observed by immunoblot.

Multiple-flash activation of the water-photolysis system in wheat leaves as observed by delayed emission.

The chloroplasts from wheat leaves greened under intermittent illuminations (1 ms in duration) at long intervals (5 min) are capable of photoreducing DCIP (2,6-dichlorophenolindophenol) with diphenylcarbazide as an electron donor but are incapable of photoreducing DCIP with water as the donor. On exposure of such intermittently illuminated leaves to flashes spaced at intervals of less than 10s, the delayed light emission from the leaves was greatly enhanced in parallel with the generation of Hill activity. The mechanism of this photoactivation was studied by following the changes of the delayed emission from intermittently illuminated leaves exposed to short-interval flashes programmed in various ways. Analysis of the kinetic data indicated that the photoactivation involves three consecutive photoreactions with a rate-limiting dark reaction between them; P-light leads to A0-light leads to A1-dark leads to A2-light leads to A3 in which P is a precursor convertible to A0, the first intermediate with a longer lifetime of t 1/2 approximately 100s and A3 is the final activated compound or state converted by short-interval flashes from A0 through A1 and A2, two other intermediates with shorter lifetimes of t 1/2 approximately 0.4s and 5s, respectively.