Physicochemical Properties and Microbiome of Vineyard Soils from DOP Ribeiro (NW Spain) Are Influenced by Agricultural Management.

Agricultural management influences the soil ecosystem by affecting its physicochemical properties, residues of pesticides and microbiome. As vineyards grow crops with the highest incidence of pesticides, the aim of this study was to evaluate the impact of conventional and sustainable management systems of vineyards from DOP Ribeiro on the soil's condition. Samples from soils under three different management systems were collected, and the main soil physicochemical properties were evaluated.

Assessment of the occurrence and interaction between pesticides and plastic litter from vineyard plots.

In this research, aged plastic fragments collected from vineyards were characterized in terms of composition, residues of pesticides, and their potential to exchange these compounds with the aquatic media. To this end, we employed the qualitative and quantitative information provided by complementary analytical techniques, including chromatography, organic and inorganic mass spectrometry, infrared spectroscopy and electronic microscopy. Debris of weathered plastics were identified as polypropylene and polyethylene, containing different types of additives, from organic UV stabilizers to inorganic fillers, such as calcium salts.

Occurrence and risk assessment of pesticides and pharmaceuticals in viticulture impacted watersheds from Northwest Spain.

An automated analytical methodology was developed, validated and applied to monitor 73 organic pollutants (pesticides and pharmaceuticals) in surface and groundwater samples obtained in watersheds from an intensive viticulture, rural region, in the Northwest of Spain. Filtered samples were concentrated using a reusable solid-phase extraction sorbent, on-line combined with liquid chromatography tandem mass spectrometry (LC-MS/MS). The analytical procedure achieved limits of quantification between 1 ng L and 10 ng L, with a throughput of 2 samples hour, providing accurate recoveries for more than 90% of the 73 selected compounds, using calibration solutions prepared in ultrapure water (in presence of methanol and formic acid) as neat solvent.

Comprehensive characterization of volatile and semi-volatile compounds in e-liquids for electronic cigarette using gas chromatography accurate mass spectrometry.

The consumption of electronic cigarettes is a habit with an increasing prevalence, particularly among youths. Knowing the composition of e-liquids used in these devices represents the first step to understand the potential impact of e-smoking in the health of consumers. Herein, a non-target screening methodology was applied to the identification of volatile and semi-volatile compounds in a set of e-liquids from different suppliers, with different flavors, and containing different kinds of additives, such as nicotine or cannabidiol.

Basic micro-pollutants in sludge from municipal wastewater treatment plants in the Northwest Spain: Occurrence and risk assessment of sludge disposal.

Sludge is one of the most problematic residues generated during wastewater treatment. Herein, we validate a single-step, sensitive procedure for the determination of a selection of 46 basic micro-pollutants, either used as pharmaceuticals or pesticides, in sludge from municipal sewage treatment plants (STPs), using liquid chromatography tandem mass spectrometry as determination technique. The proposed method permitted to achieve accurate recoveries (values from 70% to 120%, for samples spiked at different concentration levels) using solvent-based calibration standards.

On Sampling Minimum Energy Path.

Sampling the minimum energy path (MEP) between two minima of a system is often hindered by the presence of an energy barrier separating the two metastable states. As a consequence, direct sampling based on molecular dynamics or Markov Chain Monte Carlo methods becomes inefficient, the crossing of the energy barrier being associated to a rare event. Augmented sampling methods based on the definition of collective variables or reaction coordinates allow us to circumvent this limitation at the price of an arbitrary choice of the dimensionality reduction algorithm.

Chlorhexidine residues in sludge from municipal wastewater treatment plants: analytical determination and toxicity evaluation.

In this work, a procedure for the sensitive and selective determination of chlorhexidine in sludge from municipal sewage treatment plants (STPs) based on matrix solid-phase dispersion (MSPD) and liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS) was optimized and validated. Analysis of sewage sludge samples, obtained from different STPs in Northwest Spain from 2018 to 2021, showed that chlorhexidine was ubiquitous in this environmental compartment with concentrations between 0.3 and 16 µg g.

Supercritical fluid chromatography time-of-flight mass spectrometry enantiomeric determination of basic drugs in sewage samples.

Many pharmacologically active compounds are chiral species, and their therapeutic or toxicological effects might differ between isomers. Herein, we develop a fast and sensitive chiral analysis methodology for the determination of eight pharmaceuticals, considered as emerging environmental pollutants and belonging to two different chemical classes, in wastewater and sludge samples. Compounds were separated using supercritical fluid chromatography (SFC) combined with time-of-flight mass spectrometry (TOF-MS) detection.

Solid-phase extraction and fractionation of multiclass pollutants from wastewater followed by liquid chromatography tandem-mass spectrometry analysis.

Herein, we describe a modular solid-phase extraction (SPE) setup, combining three sorbents, for the effective extraction of neutrals, acidic, and basic micropollutants from wastewater, followed by their further elution in three independent extracts. The performance of this approach was demonstrated for a suite of 64 compounds, corresponding to different chemical families, using liquid chromatography tandem-mass spectrometry (LC-MS/MS). Target compounds were effectively extracted from wastewater samples; moreover, 62 out of 64 species were isolated in just one of the three fractions (neutrals, acids, and bases) obtained from the combination of sorbents.

Approaches to liquid chromatography tandem mass spectrometry assessment of glyphosate residues in wine.

The performance of two different analytical methodologies to investigate the presence of glyphosate (GLY) and aminomethylphosphonic acid (AMPA) residues in wine samples was evaluated. Transformation of compounds in their fluorene-9-methyloxycarbonyl derivatives permitted their separation under reversed-phase liquid chromatography with tandem mass spectrometry (LC-MS/MS) determination. Although the wine matrix severely impaired the efficiency of GLY derivatization, this drawback was solved using a molecularly imprinted sorbent for the previous, selective extraction of GLY and AMPA from wine.

Assessment of direct analysis in real time accurate mass spectrometry for the determination of triclosan in complex matrices.

In this work, the applicability of direct analysis in real time coupled to accurate mass spectrometry (DART-MS) to the quantitative determination of triclosan (TCS) in samples with increasing complexity, from personal care products to extracts from sewage, is investigated. In the first term, DART-MS spectra of TCS as free phenol and as derivatized species are characterized; thereafter, the effects of several instrumental variables in the detectability of TCS (i.e.

Supercritical fluid chromatography-mass spectrometric determination of chiral fungicides in viticulture-related samples.

Supercritical fluid chromatography (SFC), combined with mass spectrometry (MS), was employed for the determination of five chiral fungicides, from two different chemical families (acylalanine and triazol) in wine and vineyard soils. The effect of different SFC parameters (stationary phase, chiral selector, mobile phase modifier and additive) in the resolution between enantiomers and in the efficiency of compounds ionization at the electrospray source (ESI) was thorougly described. Under final working conditions, chiral separations of selected fungicides were achieved using two different SFC-MS methods, with an analysis time of 10 min and resolution factors from 1.

Identification and determination of emerging pollutants in sewage sludge driven by UPLC-QTOF-MS data mining.

Sludge from sewage treatment plants (STPs) is recognized as a sink of moderate to high lipophilic compounds resistant to biodegradation. Herein, we investigate the presence of emerging pollutants in sewage sludge combining the information provided by mass spectrometry detection, following ultra-performance liquid chromatography (UPLC), with the use of an accurate spectral database of pesticides and pharmaceuticals. In a first step, the performance of matrix solid-phase dispersion, as sample preparation technique, and two non-target data acquisition strategies (data dependent, DDA, and data independent analysis modes, DIA), used in combination with a UPLC quadrupole time-of-flight system, are assessed using a selection of deuterated compounds added either to freeze-dried sludge samples, or to sludge extracts.

Assessment of UV combined with free chlorine for removal of valsartan acid from water samples.

Valsartan acid (VALA) is a persistent and mobile pollutant, ubiquitously distributed in the aquatic environment. Herein, we assessed the efficiency of UV/free chlorine for the removal of this pollutant. Degradation experiments were performed using different water samples, considering several pH values and concentrations of inorganic anions.

An Innovative Application of a Computer Aided Design and Manufacture Implant for First Metatarsal Phalangeal Joint Arthrodesis: A Case Report.

The definitive treatment to correct the deformity of hallux abducto valgus involves surgical fixation. This pathological condition focuses on combined abnormalities of the first metatarsal phalangeal joint (MPJ), medial progression of the first metatarsal, and lateral deviation of the hallux. In most known literature described to date, a computer aided design/manufacture implant has not yet been reported as a viable salvage tool used as an inter-positional structural implant for a first MPJ arthrodesis.

Multiresidue procedure to assess the occurrence and dissipation of fungicides and insecticides in vineyard soils from Northwest Spain.

The presence of fungicide and insecticide residues in wine has been largely investigated. However, few studies have addressed the persistence of these compounds in vineyard soils. In this research, we investigate the residues of a relevant number of fungicides and insecticides in vineyard soils, obtained in the Northwest of Spain, at the beginning of each agriculture campaign.

A new hexenoic acid glycoside with cytotoxic activity from the leaves of .

A new hexenoic acid glycoside () together with known compounds, flavonol glycosides (-), iridoid glycoside (), megastigmane glycoside (), and amino acid () were isolated from the leaves of . by resin column chromatography and preparative HPLC. Their structures were determined based on spectroscopic analysis, including HRFABMS and NMR (H and C, H-H COSY, HMQC, and HMBC) data.

Residues of anilinopyrimidine fungicides and suspected metabolites in wine samples.

The coexistence of the anilinopyrimidine fungicides pyrimethanil (PYR) and cyprodinil (CYP), and suspected metabolites in wine samples was investigated by liquid chromatography (LC) with tandem mass spectrometry (MS/MS), based on triple quadrupole (QqQ) and quadrupole time-of-flight (QTOF) MS instruments. For the first time, quantitative data obtained after solid-phase extraction (SPE) of wine samples have demonstrated the systematic presence of 4-hydroxyanilino derivatives of PYR and CYP in wines containing residues of parent fungicides, at concentrations from 0.2 to 58 ng mL.

Portable dehumidifiers condensed water: A novel matrix for the screening of semi-volatile compounds in indoor air.

The comprehensive identification of organic species existing in indoor environments is a key issue to understand their impact in human health. This study proposes the analysis of condensed water samples, collected with portable dehumidifiers, to characterize semi-volatile compounds in the gas phase of confined areas. Water samples are concentrated by solid-phase extraction (SPE).

Evaluation of supercritical fluid chromatography accurate mass spectrometry for neonicotinoid compounds determination in wine samples.

The suitability of supercritical fluid chromatography, coupled to accurate mass spectrometry (SFC-MS), for the determination of seven commercial neonicotinoid pesticides and one transformation product in wine samples has been investigated. Thorough optimization of the different parameters (column, modifier, back-flush pressure, make up, etc.) affecting the SFC-MS selectivity and sensitivity was carried out.

Direct analysis in real time accurate mass spectrometry determination of bisphenol A in thermal printing paper.

Contact with thermal printing paper is a relevant source of dermal exposure to unbonded bisphenol A (BPA). In order to limit this exposure route, the European Union has introduced a drastic reduction in the maximum allowed concentration of BPA in thermal paper produced after beginning of year 2020. This study investigates the suitability of direct analysis in real time (DART), combined with accurate mass spectrometry, as a faster alternative to chromatography-based methods for the quantitative determination of BPA, and three analogues species, in receipts and tickets usually printed on thermal paper.

Assessment of gas chromatography time-of-flight mass spectrometry for the screening of semi-volatile compounds in indoor dust.

Indoor dust contains a complex mixture of anthropogenic and synthetic compounds closely related to dermal and respiratory diseases. Target methods have been developed for the quantification of distinct groups of substances in dust samples; however, the comprehensive characterization of the different species existing in this matrix remains a challenging issue. Herein, we assess the performance of gas chromatography (GC) time-of-flight mass spectrometry (TOF-MS), using electron ionization (EI), for the screening of compounds present in indoor dust.

Schwannoma of the plantarmedial aspect of the foot: A case report.

Schwannomas of the common medial plantar nerve branch are rare solitary nerve sheath tumors. Fewer than a dozen cases have since been described in the literature, most of which were initially misdiagnosed as ganglion cysts. The case of a 56-year-old male who developed a painful mass on the plantar medial hallux, misdiagnosed as a ganglion cyst, is presented.