Influence of irrigation methods on arsenic speciation in rice grain.

Although the bioaccumulation of arsenic (As) in rice grains is a global health issue, its speciation is not less worrying. Despite the ascertained effectiveness of the intermittent irrigation methods in minimizing the amount of total As in rice, knowledge of its influence on the As speciation has been insufficient so far. Hence, this contribution was aimed to measure the concentrations of As(III), As(V), dimethylarsinic acid (DMA), and monomethylarsonic acid (MMA) in grains from twenty-six different rice genotypes irrigated either with continuous flooding (CF), periodic saturation (SA) or sprinkler irrigation (SP). In CF-irrigated rice, As(III) and DMA prevailed in roughly equal amounts, only As(III) was found in SA-irrigated rice, whereas As(V) was largely predominant on As(III) in SP-irrigated rice. Organoarsenic species were below the limits of detection (LoD) in rice irrigated by intermittent methods. Principal component analysis (PCA) explained the influence of the irrigation method on the total amount of As, its chemical species, and their correlation. Furthermore, PCA showed also significant differences in As speciation as a function of the rice genotype, whereas no differences were found among Indica and Japonica subspecies.

Assessment and validation of ICP-MS and IC-ICP-MS methods for the determination of total, extracted and speciated arsenic. Application to samples from a soil-rice system at varying the irrigation method.

Food is the major route of arsenic (As) intake for humans, and rice is the staple food for more than half of the world's population. Unfortunately, rice bioaccumulates large amounts of As from the paddy field, and the toxicity of this element in the kernel is closely linked to its chemical form. Therefore, it is of the utmost importance to have access to an integrated set of analytical methods, capable of measuring the concentration of As in its various chemical forms in soil and rice. Hence, the principal aim of this study was to assess and validate a group of inductively coupled plasma - mass spectrometry (ICP-MS) and IC-ICP-MS (IC, Ionic Chromatography) methods designed to measure the amount of the total or extracted As and its main chemical species (As(III), As(V), monomethylarsonic acid, MMA, and dimethylarsinic acid, DMA) in flours of rice grain and in soils. Great attention has been given to the assessment and the optimization of extraction methods of As species from these matrices. No appreciable interconversion among As species has been observed using an aqueous solution 1 mol dm-3 of phosphoric acid and 0.5 mol dm-3 of L (+)-ascorbic acid for the extraction from soils, and an aqueous solution 0.2% (w/v) of nitric acid for the extraction from rice flour. Validation has been successfully accomplished in terms of limit of detection, limit of quantification, linearity and accuracy. In addition to many certified reference materials, these methods have been tested on real samples of soils and rice grains of the Aleramo genotype obtained through traditional or intermittent irrigation methods. Data obtained revealed the critical role of the intermittent irrigation methods in determining the nature and the amount of the As chemical species in rice grains as well as in soils. As(V) is the only species found in soil irrigated by sprinkling, while the most toxic As(III) dominates in soil irrigated by continuous flooding. On the other hand, the most abundant species found in continuously flooded Aleramo rice grains are As(III) and - mostly - DMA, whereas As(V), less toxic than As(III), represents 60% of the total inorganic compounds measured in sprinkler-irrigated rice. Lastly, the total amount of As measured in this rice is 3.8% of that measured in rice irrigated by continuous flooding.

Tuning of the Amount of Se in Rice (Oryza sativa) Grain by Varying the Nature of the Irrigation Method: Development of an ICP-MS Analytical Protocol, Validation and Application to 26 Different Rice Genotypes.

The amount of specific trace elements like selenium (Se) may be of health concern for humans if contained in too high (or low) quantities in staple foods like rice. Among the attempts aimed to optimize the Se concentration in rice, only few studies have been focused on the use of irrigation methods other than continuous flooding. Since intermittent irriguous methods, like sprinkler and saturation, have found to be effective in modifying the bioaccumulation of arsenic and cadmium in rice kernels, the main goal of this study is to measure the amount of the total Se contained in grains of 26 rice genotypes cultivated for two consecutive agrarian vintages in the same open field and with the same water, but differently irrigated with continuous flooding, sprinkler or saturation. To do this, an original and validated ICP-MS method has been developed. The validation parameters accounted for a high sensitivity and accuracy. Sprinkler irrigation is able to reduce in the average of 90% the amount of total Se in kernels in comparison to values measured in rice irrigated with continuous flooding. In conclusion, different irrigation techniques and rice genotypes seem to be valuable tools in order to allow in the future the customized modulation of the Se concentration in rice grain according to the needs of the various populations.

Portable NIR Spectroscopy to Simultaneously Trace Honey Botanical and Geographical Origins and Detect Syrup Adulteration.

Fraudulent practices concerning honey are growing fast and involve misrepresentation of origin and adulteration. Simple and feasible methods for honey authentication are needed to ascertain honey compliance and quality. Working on a robust dataset and simultaneously investigating honey traceability and adulterant detection, this study proposed a portable FTNIR fingerprinting approach combined with chemometrics. Multifloral and unifloral honey samples (n = 244) from Spain and Sardinia (Italy) were discriminated by botanical and geographical origin. Qualitative and quantitative methods were developed using linear discriminant analysis (LDA) and partial least squares (PLS) regression to detect adulterated honey with two syrups, consisting of glucose, fructose, and maltose. Botanical and geographical origins were predicted with 90% and 95% accuracy, respectively. LDA models discriminated pure and adulterated honey samples with an accuracy of over 92%, whereas PLS allows for the accurate quantification of over 10% of adulterants in unifloral and 20% in multifloral honey.

Rollover cyclometalation with 2-(2'-pyridyl)quinoline.

Rollover cyclometalation of 2-(2'-pyridyl)quinoline, L, allowed the synthesis of the family of complexes [Pt(L-H)(X)(L')] and [Pt(L*)(X)(L')][BF4] (X = Me, Cl; L' = neutral ligand), the former being the first examples of Pt(II) rollover complexes derived from the ligand L. The ligand L* is a C,N cyclometalated, N-protonated isomer of L, and can also be described as an abnormal-remote pyridylene. The corresponding [Pt(L-H)(Me)(L')]/[Pt(L*)(Me)(L')](+) complexes constitute an uncommon Brønsted-Lowry acid-base conjugated couple. The species obtained were investigated in depth through NMR and UV-vis spectroscopy, cyclic voltammetry, and density functional theory (DFT) methods to correlate different chemico-physical properties with the nature of the cyclometalated ligand (e.g., L vs bipy or L* vs L) and of the neutral ligand (DMSO, CO, PPh3). The crystal structures of [Pt(L-H)(Me)(PPh3)], [Pt(L-H)(Me)(CO)] and [Pt(L*)(Me)(CO)][BF4] were determined by X-ray powder diffraction methods, the latter being the first structure of a Pt(II)-based, protonated, rollover complex to be unraveled. The isomerization of [Pt(L*)(Me)(PPh3)](+) in solution proceeds through a retro-rollover process to give the corresponding adduct [Pt(L)(Me)(PPh3)](+), where L acts as a classical N,N chelating ligand. Notably, the retro-rollover reaction is the first process, among the plethora of Pt-C bond protonolysis reactions reported in the literature, where a Pt-C(heteroaryl) bond is cleaved rather than a Pt-C(alkyl) one.

Differential pulse voltammetry and chronoamperometry as analytical tools for epinephrine detection using a tyrosinase-based electrochemical biosensor.

The main goal of the presented study was to design a biosensor-based system for epinephrine (EP) detection using a poly-thiophene derivative and tyrosinase as a biorecognition element. We compared two different electroanalytical techniques to select the most prominent technique for analyzing the neurotransmitter. The prepared biosensor system exhibited good parameters; the differential pulse (DPV) technique presented a wide linear range (1-20 µM and 30-200 µM), with a low detection limit (0.18 nM and 1.03 nM). In the case of chronoamperometry (CA), a high signal-to-noise ratio and lower reproducibility were observed, causing a less broad linear range (10-200 µM) and a higher detection limit (125 nM). Therefore, the DPV technique was used for the calculation of sensitivity (0.0011 µA mM-1 cm-2), stability (49 days), and total surface coverage (4.18 × 10-12 mol cm-2). The biosensor also showed very high selectivity in the presence of common interfering species (i.e. ascorbic acid, uric acid, norepinephrine, dopamine) and was successfully applied for EP determination in a pharmaceutical sample.

Chemometric treatment of simple physical and chemical data for the discrimination of unifloral honeys.

In this work, nonspecific physico-chemical parameters were determined in 160 honey samples belonging to the four main botanical categories present in Sardinia Island, Italy (strawberry tree, thistle, asphodel and eucalyptus) in order to develop a discriminant method for determining the botanical origin of honey. All the possible combinations of the seven physico-chemical parameters (pH, free acidity, electrical conductivity, color, total phenolic compounds, FRAP activity, and DPPH activity) measured in the honey samples were evaluated by Linear Discriminant Analysis (LDA). LDA models led to the prediction of each botanical origin with a very low level of misclassification (typically less than 5%). Since very high levels of correct prediction in cross validation (98.3%) and external validation (100%) were obtained considering only four parameters (i.e. pH, acidity, conductivity and DPPH), these results might allow a fast and easy control of the botanical origin of honeys.

Nature, distribution and origin of polycyclic aromatic hydrocarbons (PAHs) in the sediments of Olbia harbor (Northern Sardinia, Italy).

The nature, origin and distribution of US EPA polycyclic aromatic hydrocarbons (PAHs) in the sediments of Olbia harbor (North Sardinia, Italy) were investigated by gas-chromatography/mass spectrometry (GCMS). PAH concentrations in the sediments (SigmaPAHs) ranged from 0.16 to 0.77 microg g(-1), indicating a homogeneously low level of pollution. A rather exceptional prevalence of low molecular weight PAHs was substantiated: nearly 80% of SigmaPAHs include naphthalene (15.19%) and phenanthrene (64.47%). Carcinogenic compounds were present in very low (BaP, BkF, BaA and DBA) or negligible (BbF and Inp) concentrations. As indicated by the Phen/Ant molar ratio, the main source of PAHs is petrogenic, probably due to oil spills from shipping. The low/high molecular weight ratio (ranging between 1.2 and 26) distinguishes the sediments of the tourist harbor from those of the commercial/industrial harbor. Moreover, a slight but meaningful pyrolytic contribution to pollution was found in the tourist harbor, which has the most polluted sediments in the whole harbor. Finally, good linear correlations were found between a selected PAH (Phen and Naph) and selected sums of PAHs (i.e. the total amount of the other 15 US EPA and the sum of low molecular weight PAHs).