Characteristics and Relationships between Total Polyphenol and Flavonoid Contents, Antioxidant Capacities, and the Content of Caffeine, Gallic Acid, and Major Catechins in Wild/Ancient and Cultivated Teas in Vietnam.

Vietnam has diverse and long-established tea plantations but scientific data on the characteristics of Vietnamese teas are still limited. Chemical and biological properties including total polyphenol and flavonoid contents (TPCs and TFCs), antioxidant activities (DPPH, ABTS, FRAP, and CUPRAC), as well as the contents of caffeine, gallic acid, and major catechins, were evaluated for 28 Vietnamese teas from North and South Vietnam. Higher values of TPCs and TFCs were found for green (non-oxidised) and raw Pu'erh (low-oxidised) teas from wild/ancient tea trees in North Vietnam and green teas from cultivated trees in South Vietnam, as compared to oolong teas (partly oxidised) from South Vietnam and black teas (fully oxidised) from North Vietnam. The caffeine, gallic acid, and major catechin contents depended on the processing, geographical origin, and the tea variety. Several good Pearson's correlations were found (r2 > 0.9) between TPCs, TFCs, the four antioxidant capacities, and the content of major catechins such as (-)-epicatechin-3-gallate and (-)-epigallocatechin-3-gallate. Results from principal component analysis showed good discriminations with cumulative variances of the first two principal components varying from 85.3% to 93.7% among non-/low-oxidised and partly/fully oxidised teas, and with respect to the tea origin.

Quantification of 397 pesticide residues in different types of commercial teas: Validation of high accuracy methods and quality assessment.

Analytical methods with high sensitivity and accuracy were successfully validated for the quantification of 397 pesticides in different types of tea. For the UPLC-MS/MS method, 191 pesticides of 200 ones in total had "soft" matrix effects and could be quantified by calibration curves in the solvent. For the GC-MS/MS method, matrix-matched calibration curves were established on a mixed blank including white, green, oolong and black organic teas. The method limit of quantifications ranged from 1.0 µg kg-1 to 10 µg kg-1 (UPLC-MS/MS) and 1.0 µg kg-1 to 50 µg kg-1 (GC-MS/MS), with 70-120% of recovery. These methods was subsequently applied to 106 tea samples from several origins, in which 26 samples contained at least one pesticide violation, with a total of 43 pesticide residue violations. The most frequently detected pesticides were neonicotinoids, synthetic pyrethroids, and triazole fungicides. Taiwan had the most pesticide-contaminated samples followed by China, Vietnam, and India.

Synergetic Effect of Dual Functional Monomers in Molecularly Imprinted Polymer Preparation for Selective Solid Phase Extraction of Ciprofloxacin.

BACKGROUND: Ciprofloxacin (CIP), an important broad-spectrum fluoroquinolone antibiotic, was often used as a template molecule for the preparation of imprinted materials. In this study, methacrylic acid and 2-vinylpyridine were employed for the first time as dual functional monomers for synthesizing ciprofloxacin imprinted polymers. METHODS: The chemical and physicochemical properties of synthesized polymers were characterized using Fourier transform-infrared spectroscopy, thermogravimetric analysis-differential scanning calorimetry, scanning electron microscopy, and nitrogen adsorption-desorption isotherm. The adsorption properties of ciprofloxacin onto synthesized polymers were determined by batch experiments. The extraction performances were studied using the solid phase extraction and HPLC-UV method. RESULTS: The molecularly imprinted polymer synthesized with dual functional monomers showed a higher adsorption capacity and selectivity toward the template molecule. The adsorbed amounts of ciprofloxacin onto the imprinted and non-imprinted polymer were 2.40 and 1.45 mg g-1, respectively. Furthermore, the imprinted polymers were employed as a selective adsorbent for the solid phase extraction of ciprofloxacin in aqueous solutions with the recovery of 105% and relative standard deviation of 7.9%. This work provides an alternative approach for designing a new adsorbent with high adsorption capacity and good extraction performance for highly polar template molecules.

Chitosan-Based Nanocomposites for Glyphosate Detection Using Surface Plasmon Resonance Sensor.

This article describes an optical method based on the association of surface plasmon resonance (SPR) with chitosan (CS) film and its nanocomposites, including zinc oxide (ZnO) or graphene oxide (GO) for glyphosate detection. CS and CS/ZnO or CS/GO thin films were deposited on an Au chip using the spin coating technique. The characterization, morphology, and composition of these films were performed by Fourier-transform infrared spectroscopy (FTIR), atomic force microscopy (AFM), and contact angle technique. Sensor preparation conditions including the cross-linking and mobile phase (pH and salinity) were investigated and thoroughly optimized. Results showed that the CS/ZnO thin-film composite provides the highest sensitivity for glyphosate sensing with a low detection limit of 8 nM and with high reproducibility. From the Langmuir-type adsorption model and the effect of ionic strength, the adsorption mechanisms of glyphosate could be controlled by electrostatic and steric interaction with possible formation of 1:1 outer-sphere surface complexes. The selectivity of the optical method was investigated with respect to the sorption of glyphosate metabolite (aminomethylphosphonic acid) (AMPA), glufosinate, and one of the glufonisate metabolites (3-methyl-phosphinico-propionic acid) (MPPA). Results showed that the SPR sensor offers a very good selectivity for glyphosate, but the competition of other molecules could still occur in aqueous systems.

Determination of 400 pesticide residues in green tea leaves by UPLC-MS/MS and GC-MS/MS combined with QuEChERS extraction and mixed-mode SPE clean-up method.

Maximum residue limits (MRLs) for pesticides have been established in teas for quality control and protection of consumer health in many countries and regions, including Europe. It is, however, challenging to quantify multi-pesticide residues at low concentrations in complex matrices, such as tea. In this study, highly sensitive, efficient, and rugged analytical methods were adapted for simultaneous determination of 400 pesticide residues in green tea products using ultra performance liquid and gas chromatography coupled to tandem mass spectroscopy (UPLC-MS/MS and GC-MS/MS). Matrix effects were minimized by combining QuEChERS (quick, easy, cheap, effective, rugged, and safe) extraction and mixed-mode SPE clean-up with different sorbents in sample preparation. A C18 SPE cartridge paired with SPE GCB/PSA proved to be the most effective clean-up method and enabled 225 pesticide residues to be quantified, based on solvent calibration curves (154 residues using UPLC-MS/MS and 71 residues using GC-MS/MS). The analytical methods were validated fully in accordance with the SANTE/11945/2015. LOQs for most pesticides (386/400 or 96.5%) were below 10 µg/kg, i.e., less than the EU MRL (5-70 mg/kg). Thus, these approaches can be applied for routine analysis of multi-pesticide residues in green tea.

Bioaccumulation of some trace elements in tropical mangrove plants and snails (Can Gio, Vietnam).

Mangrove sediments can store high amount of pollutants that can be more or less bioavailable depending on environmental conditions. When in available forms, these elements can be subject to an uptake by mangrove biota, and can thus become a problem for human health. The main objective of this study was to assess the distribution of some trace elements (Fe, Mn, Co, Ni, Cr, As, and Cu) in tissues of different plants and snails in a tropical mangrove (Can Gio mangrove Biosphere Reserve) developing downstream a megacity (Ho Chi Minh City, Vietnam). In addition, we were interested in the relationships between mangrove habitats, sediment quality and bioaccumulation in the different tissues studied. Roots and leaves of main mangrove trees (Avicennia alba and Rhizophora apiculata) were collected, as well as different snail species: Chicoreus capucinus, Littoraria melanostoma, Cerithidea obtusa, Nerita articulata. Trace elements concentrations in the different tissues were determined by ICP-MS after digestion with concentrated HNO3 and H2O2. Concentrations differed between stands and tissues, showing the influence of sediment geochemistry, species specific requirements, and eventually adaptation abilities. Regarding plants tissues, the formation of iron plaque on roots may play a key role in preventing Fe and As translocation to the aerial parts of the mangrove trees. Mn presented higher concentrations in the leaves than in the roots, possibly because of physiological requirements. Non-essential elements (Ni, Cr and Co) showed low bioconcentration factors (BCF) in both roots and leaves, probably resulting from their low bioavailability in sediments. Regarding snails, essential elements (Fe, Mn, and Cu) were the dominant ones in their tissues. Most of snails were "macroconcentrators" for Cu, with BCF values reaching up to 42.8 for Cerithidea obtusa. We suggest that high quantity of As in all snails may result from its high bioavailability and from their ability to metabolize As.

Metals geochemistry and ecological risk assessment in a tropical mangrove (Can Gio, Vietnam).

Mangrove sediments act as natural biogeochemical reactors, modifying metals partitioning after their deposition. The objectives of the present study were: to determine distribution and partitioning of metals (Fe, Mn, Ni, Cr, Cu, Co and As) in sediments and pore-waters of Can Gio Mangrove; and to assess their ecological risks based on Risk Assessment Code. Three cores were collected within a mudflat, beneath Avicennia alba and Rhizophora apiculata stands. We suggest that most metals had a natural origin, being deposited in the mangrove mainly as oxyhydroxides derived from the upstream lateritic soils. This hypothesis could be supported by the high proportion of metals in the residual fraction (mean values (%): 71.9, 30.7, 80.7, 80.9, 67.9, 53.4 and 66.5 for Fe, Mn, Ni, Cr, Cu, Co, and As respectively, in the mudflat). The enrichment of mangrove-derived organic matter from the mudflat to the Rhizophora stand (i.e. up to 4.6% of TOC) played a key role in controlling metals partitioning. We suggest that dissolution of Fe and Mn oxyhydroxides in reducing condition during decomposition of organic matter may be a major source of dissolved metals in pore-waters. Only Mn exhibited a potential high risk to the ecosystem. Most metals stocks in the sediments were higher in the Avicennia stand than the Rhizophora stand, possibly because of enhanced dissolution of metal bearing phases beneath later one. In a context of enhanced mangrove forests destruction, this study provides insights on the effects of perturbation and oxidation of sediments on metal release to the environment.

Trace metals partitioning between particulate and dissolved phases along a tropical mangrove estuary (Can Gio, Vietnam).

Mangroves can be considered as biogeochemical reactors along (sub)tropical coastlines, acting both as sinks or sources for trace metals depending on environmental factors. In this study, we characterized the role of a mangrove estuary, developing downstream a densely populated megacity (Ho Chi Minh City, Vietnam), on the fate and partitioning of trace metals. Surface water and suspended particulate matter were collected at four sites along the estuarine salinity gradient during 24 h cycling in dry and rainy seasons. Salinity, pH, DO, TSS, POC, DOC, dissolved and particulate Fe, Mn, Cr, As, Cu, Ni, Co and Pb were measured. TSS was the main trace metals carrier during their transit in the estuary. However, TSS variations did not explain the whole variability of metals distribution. Mn, Cr and As were highly reactive metals while the other metals (Fe, Ni, Cu, Co and Pb) presented stable log KD values along the estuary. Organic matter dynamic appeared to play a key role in metals fractioning. Its decomposition during water transit in the estuary induced metal desorption, especially for Cr and As. Conversely, dissolved Mn concentrations decreased along the estuary, which was suggested to result from Mn oxidative precipitation onto solid phase due to oxidation and pH changes. Extra sources as pore-water release, runoff from adjacent soils, or aquaculture effluents were suggested to be involved in trace metal dynamic in this estuary. In addition, the monsoon increased metal loads, notably dissolved and particulate Fe, Cr, Ni and Pb.

Evaluation of Titanium Dioxide as a Binding Phase for the Passive Sampling of Glyphosate and Aminomethyl Phosphonic Acid in an Aquatic Environment.

Glyphosate is the most widely used herbicide on a world scale for the last 40 years, for both urban and agricultural uses. Here we describe the first passive sampling method for estimating the concentration of glyphosate and AMPA (aminomethyl phosphonic acid, one of its major degradation products) in surface water. The sampling method is based on a newly developed configuration of the diffusive gradient in thin-film (DGT) technique, which includes a TiO2 binding phase, already in use for a wide range of anions. Glyphosate and AMPA were retained well on a TiO2 binding phase, and elution in a 1 mL of 1 M NaOH led to recoveries greater than 65%. We found no influence of pH or flow velocity on the diffusion coefficients through 0.8 mm polyacrylamide gels, although they did increase with temperature. TiO2 binding gels were able to accumulate up to 1167 ng of P for both glyphosate and AMPA, and linear accumulation was expected over several weeks, depending on environmental conditions. DGT sampling rates were close to 10 mL day(-1) in ultrapure water, while they were less than 1 mL day(-1) in the presence of naturally occurring ions (e.g., copper, iron, calcium, magnesium). These last results highlighted (i) the ability of DGT to measure only the freely dissolved fraction of glyphosate and AMPA in water and (ii) the needs to determine which fraction (total, particulate, dissolved, freely dissolved) is indeed bioactive.

Authenticity control of essential oils containing citronellal and citral by chiral and stable-isotope gas-chromatographic analysis.

Enantioselective capillary GC on a Supelco beta-DEX 225 column (heptakis(2,3-di-O-acetyl-6-O-tert-butyldimethylsilyl)-beta-cyclodextrin SPB 20poly--20% diphenyl, 80% dimethylsiloxane) and isotope-ratio mass spectrometry, coupled online with capillary GC on an HP5 column have been used for origin-specific analysis and authenticity control of essential oils, for example lemon (Citrus limon), lemongrass (Cymbopogon citratus and Cymbopogon flexuosus), citronella (Cymbopogon nardus L.--Ceylon type and Cymbopogon winterianus--Java type), Litsea cubeba, Lippia citriodora, lemon myrtle (Backhousia citriodora), lemon gum (Eucalyptus citriodora), and, especially, precious lemon balm oil (Melissa officinalis L.). Isotope data (delta13C(PDB) and delta2H(V-SMOW)) for citral (neral + geranial) and citronellal from on-line GC-C/Py-IRMS and chiral data for citronellal in these essential oils are reported. The possibility of using these data to determine the origin of these essential oils and to detect adulteration is discussed. Principal-components analysis (PCA) of specific compounds in two essential oils of lemongrass and Litsea cubeba was performed as a practical statistical method for distinguishing between these two types of oil.

Deuterium/hydrogen ratio analysis of thymol, carvacrol, gamma-terpinene and p-cymene in thyme, savory and oregano essential oils by gas chromatography-pyrolysis-isotope ratio mass spectrometry.

Isotope ratio mass spectrometry online coupled with capillary gas chromatography (GC-Py-IRMS) on column INNOWAX is used in the origin specific analysis and the authenticity control of the phenolic essential oils (EOs). Isotopic data delta(2)H(V-SMOW) of thymol and carvacrol in natural essential oils were evidently more depleted than synthetic products (from -49 to 7 per thousand for thymol and -61 per thousand for carvacrol). delta(2)H(V-SMOW) values of p-cymene, gamma-terpinene and thymol in authentic thyme oils (Thymus vulgaris L. and Thymus zygis L.) were found from -300 to -270 per thousand, from -285 to -248 per thousand and from -259 to -234 per thousand, respectively. delta(2)H(V-SMOW) values of carvacrol and p-cymene in authentic oregano oils (Origanum heracleoticum L., Coridothymus capitatus L. and Origanum compactum L.) varied from -223 to -193 per thousand and from -284 to -259 per thousand, respectively. For authentic Satureja montana subsp. montana essential oils, the mean delta(2)H(V-SMOW) value for aromatic compounds were found to be the following: gamma-terpinene -273 per thousand (SD=4.6 per thousand) and p-cymene -283 per thousand (SD=3.0 per thousand), thymol -245 per thousand (SD=1.8 per thousand) and carvacrol -226 per thousand (SD=1.7 per thousand). In addition, p-cymene was previously found as a precursor of the biosynthesis of thymol and carvacrol in thyme oil, thus, we considered p-cymene as an endogenous reference compound (ERC) for D/H ratio analysis. The isotopic fractionation factors alpha(thymol/p-cymene)=1.05 and alpha(carvacrol/p-cymene)=1.08 were obtained and also used to control the authenticity of the phenolic EOs.