L. Hinojosa-Reyes

Arsenic accumulation in maize crop (Zea mays): A review

Arsenic (As) is a metalloid that may represent a serious environmental threat, due to its wide abundance and the high toxicity particularly of its inorganic forms. The use of arsenic-contaminated groundwater for irrigation purposes in crop fields elevates the arsenic concentration in topsoil and its phytoavailability for crops. The transfer of arsenic through the crops-soil-water system is one of the more important pathways of human exposure. According to the Food and Agriculture Organization of the United Nations, maize (Zea mays L.) is the most cultivated cereal in the world. This cereal constitutes a staple food for humans in the most of the developing countries in Latin America, Africa, and Asia. Thus, this review summarizes the existing literature concerning the conditions involved in agricultural soil that leads to As influx into maize crops and the uptake mechanisms, metabolism and phytotoxicity of As in corn plants. Additionally, the studies of the As accumulation in raw corn grain and corn food are summarized, and the As biotransfer into the human diet is highlighted. Due to high As levels found in editable plant part for livestock and humans, the As uptake by corn crop through water-soil-maize system may represent an important pathway of As exposure in countries with high maize consumption.

Applicability of multisyringe chromatography coupled to cold-vapor atomic fluorescence spectrometry for mercury speciation analysis

In this paper, a novel automatic approach for the speciation of inorganic mercury (Hg(2+)), methylmercury (MeHg(+)) and ethylmercury (EtHg(+)) using multisyringe chromatography (MSC) coupled to cold-vapor atomic fluorescence spectrometry (CV/AFS) was developed. For the first time, the separation of mercury species was accomplished on a RP C18 monolithic column using a multi-isocratic elution program. The elution protocol involved the use of 0.005% 2-mercapthoethanol in 240 mM ammonium acetate (pH 6)-acetonitrile (99:1, v/v), followed by 0.005% 2-mercapthoethanol in 240 mM ammonium acetate (pH 6)-acetonitrile (90:10, v/v). The eluted mercury species were then oxidized under post-column UV radiation and reduced using tin(II) chloride in an acidic medium. Subsequently, the generated mercury metal were separated from the reaction mixture and further atomized in the flame atomizer and detected by AFS. Under the optimized experimental conditions, the limits of detection (3σ) were found to be 0.03, 0.11 and 0.09 μg L(-1) for MeHg(+), Hg(2+) and EtHg(+), respectively. The relative standard deviation (RSD, n=6) of the peak height for 3, 6 and 3 μg L(-1) of MeHg(+), Hg(2+) and EtHg(+) (as Hg) ranged from 2.4 to 4.0%. Compared with the conventional HPLC-CV/AFS hyphenated systems, the proposed MSC-CV/AFS system permitted a higher sampling frequency and low instrumental and operational costs. The developed method was validated by the determination of a certified reference material DORM-2 (dogfish muscle), and was further applied for the determination of mercury species environmental and biological samples.

Evaluation of the transfer of soil arsenic to maize crops in suburban areas of San Luis Potosi, Mexico.

The presence of arsenic (As) in agricultural food products is a matter of concern because it can cause adverse health effects at low concentrations. Agricultural-product intake constitutes a principal source for As exposure in humans. In this study, the contribution of the chemical-soil parameters in As accumulation and translocation in the maize crop from a mining area of San Luis Potosi was evaluated. The total arsenic concentration and arsenic speciation were determined by HG-AFS and IC-HG-AFS, respectively. The data analysis was conducted by cluster analysis (CA) and principal component analysis (PCA). The soil pH presented a negative correlation with the accumulated As in each maize plant part, and parameters such as iron (Fe) and manganese (Mn) presented a higher correlation with the As translocation in maize. Thus, the metabolic stress in maize may induce organic acid exudation leading a higher As bioavailability. A high As inorganic/organic ratio in edible maize plant tissues suggests a substantial risk of poisoning by this metalloid. Careful attention to the chemical changes in the rhizosphere of the agricultural zones that can affect As transfer through the food chain could reduce the As-intoxication risk of maize consumers.

An evaluation of the migration of antimony from polyethylene terephthalate (PET) plastic used for bottled drinking water.

The leaching of antimony (Sb) from polyethylene terephthalate (PET) bottling material was assessed in twelve brands of bottled water purchased in Mexican supermarkets by atomic fluorescence spectrometry with a hydride generation system (HG-AFS). Dowex® 1X8-100 ion-exchange resin was used to preconcentrate trace amounts of Sb in water samples. Migration experiments from the PET bottle material were performed in water according to the following storage conditions: 1) temperature (25 and 75°C), 2) pH (3 and 7) and 3) exposure time (5 and 15days), using ultrapure water as a simulant for liquid foods. The test conditions were studied by a 2(3) factorial experimental design. The Sb concentration measured in the PET packaging materials varied between 73.0 and 111.3mg/kg. The Sb concentration (0.28-2.30μg/L) in all of the PET bottled drinking water samples examined at the initial stage of the study was below the maximum contaminant level of 5μg/L prescribed by European Union (EU) regulations. The parameters studied (pH, temperature, and storage time) significantly affected the release of Sb, with temperature having the highest positive significant effect within the studied experimental domain. The highest Sb concentration leached from PET containers was in water samples at pH7 stored at 75°C for a period of 5days. The extent of Sb leaching from the PET ingredients for different brands of drinking water can differ by as much as one order of magnitude in experiments conducted under the worst-case conditions. The chronic daily intake (CDI) caused by the release of Sb in one brand exceeded the Environmental Protection Agency (USEPA) regulated CDI value of 400ng/kg/day, with values of 514.3 and 566.2ng/kg/day for adults and children. Thus, the appropriate selection of the polymer used for the production of PET bottles seems to ensure low Sb levels in water samples.

Determination of phthalates in bottled water by automated on-line solid phase extraction coupled to liquid chromatography with uv detection

An on-line solid phase extraction coupled to liquid chromatography with UV detection (SPE/LC-UV) method was automated by the multisyringe flow-injection analysis (MSFIA) system for the determination of three phthalic acid esters (PAEs). The PAEs determined in drinking water stored in polyethylene terephthalate (PET) bottles of ten commercial brands were dimethyl phthalate (DMP), diethyl phthalate (DEP) and dibutyl phthalate (DBP). C18-bonded silica membrane was used for isolation and enrichment of the PAEs in water samples. The calibration range of the SPE/LC-UV method was 2.5-100μgL-1 for DMP and DEP and 10-100μgL-1 for DBP with correlation coefficients (r) ranging from 0.9970 to 0.9975. Limits of detection (LODs) were between 0.7 and 2.4μgL-1. Inter-day reproducibility performed at two concentration levels (10 and 100μgL-1) expressed as relative standard deviation (%RSD) were found in the range of 0.9-4.0%. The solvent volume was reduced to 18mL with a total analysis time of 48min per sample. The major species detected in bottled water samples was DBP reaching concentrations between 20.5 and 82.8μgL-1. The recovery percentages for the three analytes in drinking water were 80-115%. The migration test showed a great variation in the sum of migrated PAEs level (10.2-50.6μgL-1) among the PET bottle brands analyzed indicating that the presence of these contaminants in the plastic containers may depend on raw materials and the conditions used during their production process.

Sensitive determination of chromium (VI) in paint samples using a membrane optode coupled to a multisyringe flow injection system

In this work, the potential of a membrane optode coupled to a multisyringe flow injection system (MSFIA) was assessed for determining the Cr(VI) concentration in paint samples. The detection is based on the color obtained from the reaction of Cr(VI) with 1,5-diphenylcarbazide in the presence of sulfuric acid (H(2)SO(4)). The redox product was immobilized on a poly(styrene-divinylbenzene) (SDB-XC) membrane optode. The analyte in the sample was then directly quantified at the surface of the disk by measuring the intensity of reflected incident light using a bifurcated optical fiber at 540 nm. Experimental parameters (concentration of reagents, sample volume, flow rate of sample solutions, eluent concentration, and effect of diverse ions) were studied in detail. The overall time required for the complete procedure was 4 min and only required 0.2 mL of the sample volume. The dynamic working response of Cr(VI) was found within the concentration range of 2.4-1000 μg L(-1) with a limit of detection (LOD) of 0.7 μg L(-1), while the relative standard deviation (RSD) for 400 μg L(-1) Cr(VI) was lower than 2% (n=6). This developed method was used to determine Cr(VI) concentrations in the paint samples, for which an alkaline extraction procedure was proposed. The extraction procedure was based on the use of a 7.5% Na(2)CO(3)/5% NaOH solution at 90 °C for 30 min. Under optimal conditions, the recoveries ranged from 99% to 101%. The complete method was validated using a certified reference material (ERA-QC540, soil sample) and by comparing the results with those obtained using atomic absorption spectrometry (AAS).

Photocatalytic reduction of Cr(VI) from agricultural soil column leachates using zinc oxide under UV light irradiation

The photocatalytic reduction of Cr(VI) from agricultural soil leachates irrigated with Cr(VI)-containing waste hydroponic solution was evaluated in this work. For this purpose, zinc oxide was used as a catalyst under UV irradiation (λ=365 nm ). The reduction of Cr(VI) was preliminarily evaluated on synthetic solutions with a concentration of 15 mg L −1 to optimize the catalyst loading and the solution pH and to determine the effect of organic matter. Greater removal of Cr(VI) was observed at pH 7, and the optimum catalyst loading was found to be 2 g L −1, which achieved an 84% Cr(VI) reduction in 6 h. The influence of dissolved organic matter on the reduction of Cr(VI) was evaluated through the addition of different concentrations of humic acid (HA) to the chromium solution. The removal of Cr(VI) was continuously enhanced as the HA concentration gradually increased from 0 to 14 mg L −1. The percentage of hexavalent chromium reduction from soil leachates was in the range of 13–99%, and the rate constant was significantly enhanced by the presence of organic compounds in the soil pore water. Thus, a marked synergistic effect between the photocatalytic reduction of Cr(VI) and the organic matter in soil (e.g. humic substances) was observed in real samples and was similar to that observed in the Cr(VI) synthetic solution that contained HA.

Arsenic fractionation in agricultural soil using an automated three-step sequential extraction method coupled to hydride generation-atomic fluorescence spectrometry.

A fully automated modified three-step BCR flow-through sequential extraction method was developed for the fractionation of the arsenic (As) content from agricultural soil based on a multi-syringe flow injection analysis (MSFIA) system coupled to hydride generation-atomic fluorescence spectrometry (HG-AFS). Critical parameters that affect the performance of the automated system were optimized by exploiting a multivariate approach using a Doehlert design. The validation of the flow-based modified-BCR method was carried out by comparison with the conventional BCR method. Thus, the total As content was determined in the following three fractions: fraction 1 (F1), the acid-soluble or interchangeable fraction; fraction 2 (F2), the reducible fraction; and fraction 3 (F3), the oxidizable fraction. The limits of detection (LOD) were 4.0, 3.4, and 23.6 μg L(-1) for F1, F2, and F3, respectively. A wide working concentration range was obtained for the analysis of each fraction, i.e., 0.013-0.800, 0.011-0.900 and 0.079-1.400 mg L(-1) for F1, F2, and F3, respectively. The precision of the automated MSFIA-HG-AFS system, expressed as the relative standard deviation (RSD), was evaluated for a 200 μg L(-1) As standard solution, and RSD values between 5 and 8% were achieved for the three BCR fractions. The new modified three-step BCR flow-based sequential extraction method was satisfactorily applied for arsenic fractionation in real agricultural soil samples from an arsenic-contaminated mining zone to evaluate its extractability. The frequency of analysis of the proposed method was eight times higher than that of the conventional BCR method (6 vs 48 h), and the kinetics of lixiviation were established for each fraction.

An evaluation of the bioaccessibility of arsenic in corn and rice samples based on cloud point extraction and hydride generation coupled to atomic fluorescence spectrometry.

A simple, inexpensive and rapid method was proposed for the determination of bioaccessible arsenic in corn and rice samples using an in vitro bioaccessibility assay. The method was based on the preconcentration of arsenic by cloud point extraction (CPE) using o,o-diethyldithiophosphate (DDTP) complex, which was generated from an in vitro extract using polyethylene glycol tert-octylphenyl ether (Triton X-114) as a surfactant prior to its detection by atomic fluorescence spectrometry with a hydride generation system (HG-AFS). The CPE method was optimized by a multivariate approach (two-level full factorial and Doehlert designs). A photo-oxidation step of the organic species prior to HG-AFS detection was included for the accurate quantification of the total As. The limit of detection was 1.34μgkg(-1) and 1.90μgkg(-1) for rice and corn samples, respectively. The accuracy of the method was confirmed by analyzing certified reference material ERM BC-211 (rice powder). The corn and rice samples that were analyzed showed a high bioaccessible arsenic content (72-88% and 54-96%, respectively), indicating a potential human health risk.

Potential of multisyringe chromatography for the on-line monitoring of the photocatalytic degradation of antituberculosis drugs in aqueous solution.

In this study, a multisyringe chromatography system (MSC) using a C18 monolithic column was proposed for the on-line monitoring of the photocatalytic degradation of isoniazid (INH, 10 mg L(-1)) and pyrazinamide (PYRA, 5mgL(-1)) mixtures in aqueous solution using a small sample volume (200 μL) with an on-line filtration device in a fully automated approach. During the photocatalytic oxidation using TiO2 or ZnO semiconductor materials, total organic carbon (TOC) and the formed intermediates were analyzed off-line using ion chromatography, ion exclusion HPLC, and ESI-MS/MS. The results showed that TiO2 exhibits a better photocatalytic activity than ZnO under UV irradiation (365 nm) for the degradation of INH and PYRA mixtures, generating 97% and 92% degradation, respectively. The optimal oxidation conditions were identified as pH 7 and 1.0 g L(-1) of TiO2 as catalyst. The mineralization of the initial organic compounds was confirmed by the regular decrease in TOC, which indicated 63% mineralization, and the quantitative release of nitrate and nitrite ions, which represent 33% of the nitrogen in these compounds. The major intermediates of INH degradation included isonicotinamide, isonicotinic acid, and pyridine, while the ESI-MS/MS analysis of PYRA aqueous solution after photocatalytic treatment showed the formation of pyrazin-2-ylmethanol, pyrazin-2-ol, and pyrazine. Three low-molecular weight compounds, acetamide, acetic acid and formic acid, were detected during INH and PYRA decomposition. PYRA was more resistant to photocatalytic degradation due to the presence of the pyrazine ring, which provides greater stability against OH attack.