Rapid sequential determination of the explosives 2,4,6-trinitrotoluene and cyclotrimethylenetrinitramine in forensic samples employing a graphite sheet sensor and cyclic square-wave stripping voltammetry.

The development of a portable analytical procedure is described for rapid sequential detection and quantification of the explosives 2,4,6-trinitrotoluene (TNT) and cyclotrimethylenetrinitramine (RDX) in forensic samples using a graphite sheet (GS). A single GS platform works as a collector of explosive residues and detector after its assembly into a 3D-printed cell. The detection strategy is based on cyclic square-wave stripping voltammetry. The cathodic scan from + 0.1 to -1.0 V with accumulation at 0.0 V enables the TNT detection (three reduction peaks), and the anodic scan from + 0.2 to + 1.55 V with accumulation at -0.9 V provides the RDX detection (two oxidation processes). Low detection limit values (0.1 µmol L-1 for TNT and 2.4 µmol L-1 for RDX) and wide linear ranges (from 1 to 150 µmol L-1 for TNT and from 20 to 300 µmol L-1 for RDX) were obtained. The sensor did not respond to pentaerythritol tetranitrate (PETN), which was evaluated as a potential interferent, because plastic explosives contain mixtures of TNT, RDX, and PETN. The GS electrode was also evaluated as a collector of TNT and RDX residues spread on different surfaces to simulate forensic scenarios. After swiping over different surfaces (metal, granite, wood, cloths, hands, money bills, and cellphone), the GS electrode was assembled in the 3D-printed cell ready to measure both explosives by the proposed method. In all cases, the presence of TNT and RDX was confirmed, attesting the reliability of the proposed device to act as collector and sensor.

Influence of Sulfurization Time on Sb2S3 Synthesis Using a New Graphite Box Design.

In recent years, antimony sulfide (Sb2S3) has been investigated as a photovoltaic absorber material due to its suitable absorber coefficient, direct band gap, extinction coefficient, earth-abundant, and environmentally friendly constituents. Therefore, this work proposes Sb2S3 film preparation by an effective two-step process using a new graphite box design and sulfur distribution, which has a high repeatability level and can be scalable. First, an Sb thin film was deposited using the RF-Sputtering technique, and after that, the samples were annealed with elemental sulfur into a graphite box, varying the sulfurization time from 20 to 50 min. The structural, optical, morphological, and chemical characteristics of the resulting thin films were analyzed. Results reveal the method's effectivity and the best properties were obtained for the sample sulfurized during 40 min. This Sb2S3 thin film presents an orthorhombic crystalline structure, elongated grains, a band gap of 1.69 eV, a crystallite size of 15.25 Å, and a nearly stoichiometric composition. In addition, the formation of a p-n junction was achieved by depositing silver back contact on the Glass/FTO/CdS/Sb2S3 structure. Therefore, the graphite box design has been demonstrated to be functional to obtain Sb2S3 by a two-step process.

Glycerol Electrolyzer with Graphite Anode and Cathode Produces Carbonyl Compounds and Hydrogen: Background Electrocatalysis of a "Nonparticipating" Current Collector.

This study unveils a novel role of bare graphite as a catalyst in glycerol electrooxidation and hydrogen evolution reactions, challenging the prevailing notion that current collectors employed in electrolyzers are inert. Half-cell experiments elucidate the feasibility of glycerol oxidation and hydrogen production on bulk graphite electrodes at potentials exceeding 1.7 V. The investigation of varying glycerol concentrations (0.05 to 1.5 mol L-1) highlights a concentration-dependent competition between glycerol electrooxidation and oxygen evolution reactions. Employing an H-type glycerol electrolyzer, polarization curves reveal significant activation polarization attributed to the low electroactivity of the anode. Glycerol electrolysis at different concentrations yields diverse product mixtures, including formate, glycolate, glycerate, and lactate at the anode, with concurrent hydrogen generation at the cathode. The anolyte composition changes with glycerol concentration, resulting in less-oxidized compounds at higher concentrations and more oxidized compounds at lower concentrations. The cell voltage also influences the product formation selectivity, with an increased voltage favoring more oxidized compounds. The glycerol concentration also affects hydrogen production, with lower concentrations yielding higher hydrogen amounts, peaking at 3.5 V for 0.05 mol L-1. This model quantitatively illustrates graphite's contribution to current and product generation in glycerol electrolyzers, emphasizing the significance of background current and products originating from current collectors if in contact with the reactants. These results have an impact on the efficiency of the electrolyzer and raise questions regarding possible extra non-noble "nonparticipating" current collectors that could affect overall performance. This research expands our understanding of electrocatalysis on graphite surfaces with potential applications in optimizing electrolyzer configurations for enhanced efficiency and product selectivity.

Influence of Defects and Charges on the Colloidal Stabilization of Graphene in Water.

Mastering graphene preparation is an essential step to its integration into practical applications. For large-scale purposes, full graphite exfoliation appears as a suitable route for graphene production. However, it requires overpowering attractive van der Waals forces demanding large energy input, with the risk of introducing defects in the material. This difficulty can be overcome by using graphite intercalation compounds (GICs) as starting material. The greater inter-sheet separation in GICs (compared with graphite) allows the gentler exfoliation of soluble graphenide (reduced graphene) flakes. A solvent exchange strategy, accompanied by the oxidation of graphenide to graphene, can be implemented to produce stable aqueous graphene dispersions (Eau de graphene, EdG), which can be readily incorporated into many processes or materials. In this work, we prove that electrostatic forces are responsible for the stability of fully exfoliated graphene in water, and explore the influence of the oxidation and solvent exchange procedures on the quality and stability of EdG. We show that the amount of defects in graphene is limited if graphenide oxidation is carried out before exposing the material to water, and that gas removal of water before the incorporation of pre-oxidized graphene is advantageous for the long-term stability of EdG.

Comprehensive Analysis of Rheological, Mechanical, and Thermal Properties in Poly(lactic acid)/Oxidized Graphite Composites: Exploring the Effect of Heat Treatment on Elastic Modulus.

This study is focused on investigating the rheological and mechanical properties of highly oxidized graphite (GrO) incorporated into a poly (lactic acid) (PLA) matrix composite. Furthermore, the samples were annealed at 110 °C for 30 min to study whether GrO concentration has an effect on the elastic modulus (E') after treatment. The incorporation of GrO into PLA was carried out by employing an internal mixing chamber at 190 °C. Six formulations were prepared with GrO concentrations of 0, 0.1, 0.5, 1, 1.5, and 3 wt%. The thermal stability, thermomechanical behavior, and crystallinity of the composites were evaluated utilizing thermogravimetric analysis (TGA), dynamic mechanical analysis (DMA), and differential scanning calorimetry DSC, respectively. The thermal stability (according to Tmax) of the PLA/GrO composites did not change substantially compared with PLA. According to DSC, the crystallinity increased until the GrO concentration reached 1 wt% and afterward decreased. Regarding the heat treatment of the PLA/GrO composites, the E' increased (by two orders of magnitude) at 80 °C with the maximum value achieved at 1 wt% GrO compared with the non-heat-treated composites.

VIS-active TiO2 films decorated by expanded graphite: impact of the exfoliation time on the photocatalytic behaviour.

TiO2/C nanocomposite films were applied on water treatment. Expanded graphite nanosheets (EG) were obtained by UVC-assisted liquid-phase exfoliation technique, without the addition of acids, surfactants, or aggressive oxidizing agents, which characterizes the process as an eco-friendly method. The carbon nanosheets were synthesized directly from graphite bulk at different times and deposited on TiO2 films surface by airbrush spray coating method, forming a TiO2/C heterojunction. The increase in the exfoliation time promoted a more efficient photocatalytic dye removal under visible light. Morphological modifications, changes in the electronic structure, and wide range of light absorption were observed from the TiO2/C heterojunction formation. The results showed that hybrid TiO2/C supported photocatalyst is a promise alternative for practical photocatalytic applications under sunlight.

Simple and promising paper-based electrochemical platform for serological detection of American tegumentary leishmaniasis

BACKGROUND American tegumentary leishmaniasis (ATL) is an endemic neglected tropical disease (NTD), its conventional treatment is toxic, slow, and invasive. Rapid diagnosis is crucial for the clinical management of suspected patients, so the development and use of low-cost, miniaturised and portable devices could be the key. OBJECTIVES This work aimed to develop a simple paper-based electrochemical platform for the serological detection of ATL. METHODS Platform was fabricated in Whatman N°1 paper, contains a hydrophobic zone generated by wax printing, two pencil graphite electrodes, and uses specific crude extracts (CA) antigens for ATL immuno-determination. The platform performance was analysed by measuring the relative impedance change for different antigen-antibody combinations. Then, 10 serum human samples previously diagnosed by the gold standard (five positive ATL cases and five non-ATL cases) were evaluated. FINDINGS The platform presented a linear response for the charge transfer resistance (ΔRct) and the interface reactance (ΔXc). Also, optimal working conditions were established (1/60 serum dilution and 180 µg/mL CA concentration). Then, the platform permits to distinguish between ATL and non-ATL (p < 0.05) human serum samples. MAIN CONCLUSIONS Our platform could allow the diagnosis, management, and monitoring of leishmaniasis while being an extremely simple and environmentally friendly technology.

Embedded Graphite and Carbon Nanofibers in a Polyurethane Matrix Used as Anodes in Microbial Fuel Cells for Wastewater Treatment.

Composites of polyurethane and graphite and polyurethane and carbon nanofibers (PU/Graphite 0.5% and PU/CNF 1%) were synthesized and used as anodes in dual-compartment microbial fuel cells (MFCs) for municipal wastewater treatment; electrical energy generation and organic matter removal were assessed. The maximum power density, coulombic efficiency and chemical oxygen demand (COD) removal efficiency in the MFCs packed with the PU/Graphite 0.5% and PU/CNF 1% composites were 232.32 mW/m3 and 90.78 mW/m3, 5.87 and 4.41%, and 51.38 and 68.62%, respectively. In addition, the internal resistance of the MFCs with the best bioelectrochemical performance (PU/Graphite 0.5%) was 1051.11 Ω. The results obtained in this study demonstrate the feasibility of using these types of materials in dual-compartment MFCs for wastewater treatment with electric power generation.

CO2-plasma surface treatment of graphite sheet electrodes for detection of chloramphenicol, ciprofloxacin and sulphanilamide.

Graphite sheet (GS) electrodes are flexible and versatile substrates for sensing electrochemical; however, their use has been limited to incorporate (bio)chemical modifiers. Herein, we demonstrated that a cold (low temperature) CO2 plasma treatment of GS electrodes provides a substantial improvement of the electrochemical activity of these electrodes due to the increased structural defects on the GS surface as revealed by Raman spectroscopy (ID/IG ratio), and scanning electron microscopy images. XPS analyses confirmed the formation of oxygenated functional groups at the GS surface after the plasma treatment that are intrinsically related to the substantial increase in the electron transfer coefficient (K0 values increased from 1.46 × 10-6 to 2.09 × 10-3 cm s-1) and with reduction of the resistance to charge transfer (from 129.8 to 0.251 kΩ). The improved electrochemical activity of CO2-GS electrodes was checked for the detection of emerging contaminant species, such as chloramphenicol (CHL), ciprofloxacin (CIP) and sulphanilamide (SUL) antibiotics, at around + 0.15, + 1.10 and + 0.85 V (versus Ag/AgCl), respectively, by square wave voltammetry. Limit of detection values in the submicromolar range were achieved for CHL (0.08 µmol L-1), CIP (0.01 µmol L-1) and SFL (0.11 µmol L-1), which enabled the sensor to be successfully applied to natural waters and urine samples (recovery values from 85 to 119%). The CO2-GS electrode is highly stable and inexpensive ($0.09 each sensor) and can be easily inserted in portable 3D printed cells for environmental on-site analyses.

Assessment of Graphite, Graphene, and Hydrophilic-Treated Graphene Electrodes to Improve Power Generation and Wastewater Treatment in Microbial Fuel Cells.

In this study, graphite, graphene, and hydrophilic-treated graphene electrodes were evaluated in a dual-chamber microbial fuel cell (DC-MFC). Free-oxygen conditions were promoted in anodic and cathodic chambers. Hydrochloric acid at 0.1 M and pH 1.1 was used as a catholyte, in addition to deionized water in the cathodic chamber. Domestic wastewater was used as a substrate, and a DuPontTM Nafion 117 membrane was used as a proton exchange membrane. The maximum power density of 32.07 mW·m-2 was obtained using hydrophilic-treated graphene electrodes and hydrochloric acid as catholyte. This power density was 1.4-fold and 32-fold greater than that of graphene (22.15 mW·m-2) and graphite (1.02 mW·m-2), respectively, under the same operational conditions. In addition, the maximum organic matter removal efficiencies of 69.8% and 75.5% were obtained using hydrophilic-treated graphene electrodes, for hydrochloric acid catholyte and deionized water, respectively. Therefore, the results suggest that the use of hydrophilic-treated graphene functioning as electrodes in DC-MFCs, and hydrochloric acid as a catholyte, favored power density when domestic wastewater is degraded. This opens up new possibilities for improving DC-MFC performance through the selection of suitable new electrode materials and catholytes.

Development of an inexpensive and rapidly preparable enzymatic pencil graphite biosensor for monitoring of glyphosate in waters.

Glyphosate (GLY) is the most widely used non-selective broad-spectrum herbicide worldwide under well-reported side effects on the environment and human health. That's why it's necessary to control its presence in the environment. This work describes the development of an affordable, simple, and accurate electrochemical biosensor using a pencil graphite electrode as support, a horseradish peroxidase enzyme immobilized on a polysulfone membrane doped with multi-walled carbon nanotubes. The developed electrochemical sensor was used in the determination of GLY in river and drinking water samples. Cyclic voltammetry and amperometry were used as electrochemical detection techniques for the characterization and analytical application of the developed biosensor. The working mechanism of the biosensor is based on the inhibition of the peroxidase enzyme by GLY. Under optimal experimental conditions, the biosensor showed a linear response in the concentration range of 0.1 to 10 mg L-1. The limits of detection and quantification are 0.025 ± 0.002 and 0.084 ± 0.007 mg L-1, respectively, which covers the maximum residual limit established by the EPA for drinking water (0.7 mg L-1). The proposed biosensor demonstrated high reproducibility, excellent analytical performance, repeatability, and accuracy. The sensor proved to be selective against other pesticides, organic acids, and inorganic salts. Application on real samples showed recovery rates ranging between 98.18 ± 0.11 % and 97.32 ± 0.23 %. The analytical features of the proposed biosensor make it an effective and useful tool for the detection of GLY for environmental analysis.

Effect of Process Parameters on the Graphite Expansion Produced by a Green Modification of the Hummers Method.

Adsorption stand out among other standard techniques used for water treatment because of its remarkable simplicity, easy operation, and high removal capability. Expanded graphite has been selected as a promising agent for oil spill adsorption, but its production involves the generation of corrosive remnants and massive amounts of contaminated washing waters. Although the advantageous use of the H2O2-H2SO4 mixture was described in 1978, reported works using this method are scarce. This work deals with the urgent necessity for the development of alternative chemical routes decreasing their environmental impact (based on green chemistry concepts), presenting a process for expanded graphite production using only two intercalation chemicals, reducing the consumption of sulfuric acid to only 10% and avoiding the use of strong oxidant salts (both environmentally detrimental). Three process parameters were evaluated: milling effect, peroxide concentration, and microwave expansion. Some remarkable results were obtained following this route: high specific volumes elevated oil adsorption rate exhibiting a high oil-water selectivity and rapid adsorption. Furthermore, the recycling capability was checked using up to six adsorption cycles. Results showed that milling time reduces the specimen's expansion rate and oil adsorption capacity due to poor intercalant insertion and generation of small particle sizes.

The Electronic Origin of the Zeta Potential is Supported by the Redox Mechanism on an Aqueous Dispersion of Exfoliated Graphite.

Herein we have proposed that a redox mechanism can produce surface charges and negative zeta potential on an aqueous graphite dispersion. Graphite was kept in contact with a concentrated ammonia aqueous solution, washed, and exfoliated in water, resulting in a dispersion with lyophobic nature. Ammonia treatment did not provide functional groups or nitrogen doping to graphite. Moreover, this material was washed twice before sonication to remove most hydroxide. Therefore, neither functional groups, nitrogen atoms, nor hydroxide excess is responsible for the zeta potential. Kelvin probe force microscopy has shown that the ammonia-treated and exfoliated graphite has higher Fermi level than the water-treated material, indicating that the contact between ammonia and graphite promotes redox reactions that provide electrons to graphite. These electrons raise the Fermi level of graphite and generate the negative zeta potential, consequently, they account for the colloidal stability.

Magnetic Torus Microreactor as a Novel Device for Sample Treatment via Solid-Phase Microextraction Coupled to Graphite Furnace Atomic Absorption Spectroscopy: A Route for Arsenic Pre-Concentration.

This work studied the feasibility of using a novel microreactor based on torus geometry to carry out a sample pretreatment before its analysis by graphite furnace atomic absorption. The miniaturized retention of total arsenic was performed on the surface of a magnetic sorbent material consisting of 6 mg of magnetite (Fe3O4) confined in a very small space inside (20.1 µL) a polyacrylate device filling an internal lumen (inside space). Using this geometric design, a simulation theoretical study demonstrated a notable improvement in the analyte adsorption process on the solid extractant surface. Compared to single-layer geometries, the torus microreactor geometry brought on flow turbulence within the liquid along the curvatures inside the device channels, improving the efficiency of analyte-extractant contact and therefore leading to a high preconcentration factor. According to this design, the magnetic solid phase was held internally as a surface bed with the use of an 8 mm-diameter cylindric neodymium magnet, allowing the pass of a fixed volume of an arsenic aqueous standard solution. A preconcentration factor of up to 60 was found to reduce the typical "characteristic mass" (as sensitivity parameter) determined by direct measurement from 53.66 pg to 0.88 pg, showing an essential improvement in the arsenic signal sensitivity by absorption atomic spectrometry. This methodology emulates a miniaturized micro-solid-phase extraction system for flow-through water pretreatment samples in chemical analysis before coupling to techniques that employ reduced sample volumes, such as graphite furnace atomic absorption spectroscopy.

Desalination Using the Capacitive Deionization Technology with Graphite/AC Electrodes: Effect of the Flow Rate and Electrode Thickness.

Capacitive deionization (CDI) is an emerging water desalination technology whose principle lies in ion electrosorption at the surface of a pair of electrically charged electrodes. The aim of this study was to obtain the best performance of a CDI cell made of activated carbon as the active material for water desalination. In this work, electrodes of different active layer thicknesses were fabricated from a slurry of activated carbon deposited on graphite sheets. The as-prepared electrodes were characterized by cyclic voltammetry, and their physical properties were also studied using SEM and DRX. A CDI cell was fabricated with nine pairs of electrodes with the highest specific capacitance. The effect of the flow rate on the electrochemical performance of the CDI cell operating in charge-discharge electrochemical cycling was analyzed. We obtained a specific absorption capacity (SAC) of 10.2 mg/g and a specific energetic consumption (SEC) of 217.8 Wh/m3 at a flow rate of 55 mL/min. These results were contrasted with those available in the literature; in addition, other parameters such as Neff and SAR, which are necessary for the characterization and optimal operating conditions of the CDI cell, were analyzed. The findings from this study lay the groundwork for future research and increase the existing knowledge on CDI based on activated carbon electrodes.

Determination of organophosphorus compounds in water and food samples using a non-enzymatic electrochemical sensor based on silver nanoparticles and carbon nanotubes nanocomposite coupled with batch injection analysis.

This work presents, for the first time, a fast and highly sensitive electrochemical method for determination of three organophosphorus compounds (OPs), diazinon (DZN), malathion (MLT), and chlorpyrifos (CLPF), using a modified pyrolytic graphite electrode (PGE) coupled to batch injection analysis system with multiple pulse amperometric detection (BIA-MPA). The PGE was modified by a nanocomposite based on functionalized carbon nanotubes (CNTf) and silver nanoparticles (AgNPs). The OPs samples were directly analyzed on the modified working electrode surface by BIA-MPA system in Britton-Robinson (BR) buffer 0.15 mol L-1 at pH 6.0. The MPA detection of DZN, MLT and CLPF was performed using two potential pulses, which were sequentially applied on modified PGE at -1.3 V (100 ms) and +0.8 V (100 ms) for selective determination of these three OPs and working electrode cleaning, respectively. Under optimized conditions, the sensor presented a linear range of 0.1-20 µmol L-1 for DZN, 1.0-30 µmol L-1 for MLT and from 0.25 to 50 µmol L-1 for CLPF. The limits of detection (LOD) and quantification (LOQ) of 0.35 and 1.18 µmol L-1 for DZN, 0.89 and 2.98 µmol L-1 for MLT, and 0.53 and 1.78 µmol L-1 for CLPF were obtained. The proposed method exhibited high sensitivity of 0.068, 0.030 and 0.043 mA L µmol-1 for DZN, MLT and CLPF detection, respectively. Furthermore, the BIA-MPA system provided an analytical frequency of 71 determinations per hour for direct determination of these OPs in water and food samples. The modified PGE coupled to BIA-MPA system showed a high stability of electrochemical response for OPs detection with relative standard deviation (RSD) of 1.60% (n = 20). The addition-recovery studies of the proposed method were carried out in tap water, orange juice, and apple fruit real samples, which showed suitable recovery values between 77 and 124%. The analytical performance of the developed sensor provides an attractive alternative method for OPs determination with great potential for a fast and sensitive application in contaminated samples with these pesticides.

Microwave-induced self-ignition: An efficient approach for high purity graphite digestion and multitechnique halogen determination.

In this work, high purity graphite, a high chemically stable material, was effectively digested using a single method allowing compatible solutions for the further multitechnique determination of halogens by: ion chromatography (F and Cl), inductively coupled plasma mass spectrometry (Cl, Br and I) and by ion selective electrode (only for F). The recent system using microwave-induced self-ignition (MISI) is based on the strong interaction between microwave radiation and graphite in a closed system pressurized with oxygen (Maxwell-Wagner effect). Carbon-based materials present intense and specific interfacial polarization when exposed to microwave electromagnetic field resulting in a fast heating rate. This effect associated to a pressurized oxygen system, provides a quick self-ignition of carbon-based materials and consequent combustion/digestion of organic matrices. Under optimized conditions, sample masses up to 600 mg were fully digested in a quartz vessel under 20 bar of oxygen pressure and using just a diluted solution (100 mmol L-1 NH4OH) for the quantitative absorption of all the analytes. MISI method was validated, and the accuracy (better than 94%) was evaluated by comparison of results obtained by pyrohydrolysis for two coal certified reference materials as well as with subsequent analytes determination by the three techniques: IC, ICP-MS and ISE. It is important to point out that no filter paper disks, electrical connections or other ignition aids are required as in the case of previous or classical combustion methods. Moreover, just a diluted absorbing solution was used resulting in negligible blanks and relatively low limits of detection. The digestion efficiency was higher than 99%, making the proposed method a suitable and powerful alternative for the quasi complete digestion of graphite and determination of halogens virtually free of interferences.

Amino Acid Complexes of Zirconium in a Carbon Composite for the Efficient Removal of Fluoride Ions from Water.

Amino acid complexes of zirconia represent an entirely new class of materials that were synthesized and studied for the first time for the decontamination of fluoride ion containing aqueous solutions. Glutamic and aspartic acid complexes of zirconia assembled with thin carbon (stacked graphene oxide) platelets deriving from graphite oxide (GO) were synthesized by a two-step method to prepare adsorbents. The characterization of the complexes was carried out using infrared spectroscopy to determine the functional groups and the types of interaction between the composites and fluoride ions. To reveal the mechanisms and extent of adsorption, two types of batch adsorption measurements were performed: (i) varying equilibrium fluoride ion concentrations to construct adsorption isotherms at pH = 7 in the absence of added electrolytes and (ii) using fixed initial fluoride ion concentrations (10 mg/L) with a variation of either the pH or the concentration of a series of salts that potentially interfere with adsorption. The experimental adsorption isotherms were fitted by three different theoretical isotherm equations, and they are described most appropriately by the two-site Langmuir model for both adsorbents. The adsorption capacities of Zr-glutamic acid-graphite oxide and Zr-aspartic acid-graphite oxide are 105.3 and 101.0 mg/g, respectively. We found that two distinct binding modes are combined in the Zr-amino acid complexes: at low solution concentrations, F- ions are preferentially adsorbed by coordinating to the surface Zr species up to a capacity of ca. 10 mg/g. At higher concentrations, however, large amounts of fluoride ions may undergo anion exchange processes and physisorption may occur on the positively charged ammonium moieties of the interfacially bound amino acid molecules. The high adsorption capacity and affinity of the studied dicarboxylate-type amino acids demonstrate that amino acid complexes of zirconia are highly variable materials for the safe and efficient capture of strong Lewis base-type ions such as fluoride.

An Electroanalytical Solution for the Determination of Pb2+ in Progressive Hair Dyes Using the Cork-Graphite Sensor.

Lead is one of the most toxic metals for living organisms: once absorbed by soft tissues, it is capable of triggering various pathologies, subsequently bioaccumulating in the bones. In consideration of this, its detection and quantification in products for human consumption and use is of great interest, especially if the procedure can be carried out in an easy, reproducible and economical way. This work presents the results of the electroanalytical determination of lead in three different commercial products used as progressive hair dyes. Analyses were performed by cyclic voltammetry (CV) and differential pulse stripping voltammetry (DPSV) using a composite cork-graphite sensor in 0.5M H2SO4 solution or 0.1M acetate buffer (pH 4.5), in the presence and absence of hair dye samples. The H2SO4 solution gave better results in terms of analyte sensitivity than the acetate buffer electrolyte. In both cases, well-defined signals for lead were obtained by DPSV analyses, enabling the calibration curve and figures of merit to be determined. The limits of detection (LOD) were found to be approximately 1.06 µM and 1.26 µM in H2SO4 and acetate buffer, respectively. The DPSV standard addition method was successfully applied to quantify the lead in hair dye samples, yielding values below 0.45% in Pb. All three analyzed samples were shown to comply with the limit set by the Brazilian Health Regulatory Agency, i.e., 0.6% lead in this type of product. The comparison of the electroanalytical results with those obtained by the reference method, based on the use of inductively coupled plasma optical emission spectrometry (ICP-OES), confirmed that the electroanalytical detection approach is potentially applicable as a strategy for quality control.

Biofilm formation of Ancylobacter sp. TS-1 on different granular materials and its ability for chemolithoautotrophic As(III)-oxidation at high concentrations.

The oxidation of arsenic (As) is a key step in its removal from water, and biological oxidation may provide a cost-effective and sustainable method. The biofilm-formation ability of Ancylobacter sp. TS-1, a novel chemolithoautotrophic As oxidizer, was studied for four materials: polypropylene, graphite, sand, and zeolite. After seven days under batch mixotrophic conditions, with high concentrations of As(III) (225 mg·L-1), biofilm formation was detected on all materials except for polypropylene. The results demonstrate As(III)-oxidation of TS-1 biofilms and suggest that the number of active cells was similar for graphite, sand, and zeolite. However, the biofilm biomass follows the specific surface area of each material: 7.0, 2.4, and 0.4 mg VSS·cm-3 for zeolite, sand, and graphite, respectively. Therefore, the observed biofilm-biomass differences were probably associated with different amounts of EPS and inert biomass. Lastly, As(III)-oxidation kinetics were assessed for the biofilms formed on graphite and zeolite under chemolithoautotrophic conditions. The normalized oxidation rate for biofilms formed on these materials was 3.6 and 1.0 mg·L-1·h-1·cm-3, resulting among the highest reported values for As(III)-oxidizing biofilms operated at high-As(III) concentrations. Our findings suggest that biofilm reactors based on Ancylobacter sp. TS-1 are highly promising for their utilization in As(III)-oxidation pre-treatment of high-As(III) polluted waters.