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Pendimethalin-based herbicides are used worldwide for pre-emergence selective control of annual grasses and weeds in croplands. The endurance of herbicides residues in the environment has an impact on the soil biodiversity and fertility, also affecting non-target species, including terrestrial invertebrates. Carabid beetles are known as natural pest control agents in the soil food web of agroecosystems, and feed on invertebrates and weed seeds. Here, a mass spectrometry untargeted profiling of haemolymph is used to investigate Pterostichus melas metabolic response after to pendimethalin-based herbicide exposure. Mass spectrometric data are examined with statistical approaches, such as principal component analysis, for possible correlation with biological effects. Those signals with high correlation are submitted to tandem mass spectrometry to identify the associated biomarker. The time course exposure showed many interesting findings, including a significant downregulation of related to immune and defense peptides (M-lycotoxin-Ls4a, Peptide hormone 1, Paralytic peptide 2, and Serine protease inhibitor 2). Overall, the observed peptide deregulations concur with the general mechanism of uptake and elimination of toxicants reported for Arthropods. [ABSTRACT FROM AUTHOR]

The mercury removal efficiency of a novel metal‐organic framework (MOF) derived from the amino acid S‐methyl‐L‐cysteine is presented and the process is characterized by single‐crystal X‐ray crystallography. A feasibility study is further presented on the performance of this MOF—and also that of another MOF derived from the amino acid L‐methionine—when used as the sorbent in mixed matrix membranes (MMMs). These MOF‐based MMMs exhibit high efficiency and selectivity—in both static and dynamic regimes—in the removal of Hg2+ from aqueous environments, due to the high density of thioalkyl groups decorating MOF channels. Both MMMs are capable to reduce different concentration of the pollutant to acceptable limits for drinking water (<2 parts per billion). In addition, a novel device, consisting of the recirculation and adsorption of contaminated solutions through the MOF–MMMs, is designed and successfully explored in the selective capture of Hg2+. Thus, filtration of Hg2+ solutions with multiple passes through the permeation cell shows a gradual decrease of the pollutant concentration. These results suggest that MOF‐based MMMs can be implemented in water remediation, helping to reduce either contaminants from accidental unauthorized or deliberate metal industrial dumping and to ensure access for clean and potable freshwater. [ABSTRACT FROM AUTHOR]

The aim of this work was to analyze the potential of reverse osmosis (RO) membranes in the recovery and concentration of aroma compounds from orange juice evaporator condensate (EC) streams. Concentration experiments were performed by using three RO spiral-wound aromatic polyamide membranes (SG1812C-34D, SC1812C-34D and SE1812) with different NaCl rejections. The effect of transmembrane pressure, axial feed flowrate and volume concentration ratio (VCR) on permeate flux was studied. Rejections of the investigated membranes towards specific aroma compounds (octanol, α-terpineol, terpinen-4-ol, cis-carveol, karvon, linalool) in selected operating conditions were also evaluated. The concentrations of the aroma compounds were determined by gas chromatography coupled with mass spectrometry (GC-MS) using headspace solid-phase microextraction (HS-SPME) as a sample preparation approach. For all selected membranes, the permeate flux increased linearly by increasing the operating pressure from 5 to 25 bar; on the other hand, the feed flowrate did not have any significant effect on the permeate flux. High retention values towards aroma compounds (>80%) were measured for all selected membranes. However, the SC membrane showed the highest rejection values (>96%) and the best correlation between concentration factor of aroma compounds and VCR. [ABSTRACT FROM AUTHOR]

In the following work, a new method for the analysis of the phthalate monoesters in human urine was reported. Phthalate monoesters are metabolites generated as a result of phthalate exposure. In compliance with the dictates of Green Analytical Chemistry, a rapid and simple protocol was developed and optimized for the quantification of phthalate monoesters (i.e., monoethyl phthalate, monoisobutyl phthalate, mono‐n‐butyl phthalate, mono‐(2‐ethylhexyl) phthalate, mono‐n‐octyl phthalate, monocyclohexyl phthalate, mono‐isononyl phthalate) in human urine, which entails preceding derivatization with methyl chloroformate combined with the use of commercial solid phase microextraction and the analysis by gas chromatography‐triple quadrupole mass spectrometry. The affinity of the derivatized analytes toward five commercial coatings was evaluated, and in terms of analyte extraction, the best results were reached with the use of the divinylbenzene/carboxen/polydimethylsiloxane fiber. The multivariate approach of experimental design was used to seek for the best working conditions of the derivatization reaction and the solid phase microextraction, thus obtaining the optimum response values. The proposed method was validated according to the guidelines issued by the Food and Drug Administration achieving satisfactory values in terms of linearity, sensitivity, matrix effect, intra‐ and inter‐day accuracy, and precision. [ABSTRACT FROM AUTHOR]

Particulate matter (PM) is among the most dangerous air pollutants, and there is a growing concern related to the effects of airborne particles on human health. Their harmful effects can be derived are directly linked to the size of particles themselves and the associated pollutants after they have been taken up by inhalation. In this work was developed a new analytical method for the quantification of organophosphorus esters (OPE) bound to airborne PM. The proposed protocol provides for the microwave-assisted extraction (MAE) of the analytes from the PM followed by solid-phase microextraction gas chromatography-tandem mass spectrometry determination (SPME-GC-MS/MS). Unlike to the traditional protocol, which provides for the use of tedious Soxhlet extraction with environmentally damaging organic solvents, the proposed method allows for a reliable quantification by using an eco-friendly hydroalcoholic mixture (water/ethanol; 50:50, v/v). The method was developed using as target compounds ten organophosphate esters, namely tripropyl phosphate (TPP), tri-n-butyl phosphate (TBP), tris(2-chloroethyl) phosphate (TCEP), tris(1-chloro-2-propyl) phosphate (TCPP), tris(1,3-dichloro-2-propyl) phosphate (TDCPP), tributoxyethyl phosphate (TBEP), triphenyl phosphate (TPhP), 2-ethylhexyl-diphenyl phosphate (EHDPP), tris(2-ethylhexyl) phosphate (TEHP) and tricresyl phosphate (TCP). The extraction performance of five SPME fibers was evaluated and the DVB/CAR/PDMS coating demonstrated to be the most suitable for the extraction of the target analytes. Experimental Design was used for the multivariate optimization of the parameters affecting the MAE process as well as the SPME extraction, and the optimal working conditions were determined by using Derringer's desirability function. The developed method was validated in terms of linearity, sensitivity (LLOQ values of 0.5 ng/mL for TDCPP and 0.1 ng/mL for the other analytes), matrix effect (81–117%), intra and inter day accuracy (83–115% and 80–115%, respectively), and precision (repeatability and reproducibility in the range 1.0–12.4% and 2.3–15.2%, respectively). The satisfactory performances reached make the proposed protocol a green and high-throughput alternative for OPE quantification in particulate matter. [ABSTRACT FROM AUTHOR]

Polyamines are aliphatic amines with low molecular weight that are widely recognized as one of the most important cancer biomarkers for early diagnosis and treatment. The goal of the work herein presented is the development of a rapid and simple method for the quantification of free polyamines (i.e., putrescine, cadaverine, spermidine, spermine) and N -monoacetylated polyamines (i.e., N 1 -Acetylspermidine, N 8 -Acetylspermidine, and N 1 -Acetylspermine) in human urine. A preliminary derivatization with propyl chloroformate combined with the use of solid phase microextraction (SPME) allowed for an easy and automatable protocol involving minimal sample handling and no consumption of organic solvents. The affinity of the analytes toward five commercial SPME coatings was evaluated in univariate mode, and the best result in terms of analyte extraction was achieved using the divinylbenzene/carboxen/polydimethylsiloxane fiber. The variables affecting the performance of SPME analysis were optimized by the multivariate approach of experimental design and, in particular, using a central composite design (CCD). The optimal working conditions in terms of response values are the following: extraction temperature 40 °C, extraction time of 15 min and no addition of NaCl. Analyses were carried out by gas chromatography-triple quadrupole mass spectrometry (GC-QqQ-MS) in selected reaction monitoring (SRM) acquisition mode. The developed method was validated according to the guidelines issued by the Food and Drug Administration (FDA). The satisfactory performances reached in terms of linearity, sensitivity (LOQs between 0.01 and 0.1 μg/mL), matrix effect (68–121%), accuracy, and precision (inter-day values between −24% and +16% and in the range 3.3–28.4%, respectively) make the proposed protocol suitable to be adopted for quantification of these important biomarkers in urine samples. [ABSTRACT FROM AUTHOR]

In this work, organophosphate ester flame retardant (OPFRs) assay in environmental waters was addressed by using microextraction by packed sorbent (MEPS) and gas chromatography-tandem mass spectrometry (GC-MS/MS). Ten OPFRs with different physicochemical properties were taken into account as target compounds for a comprehensive method evaluation. Five MEPS cartridges (i.e., C2, C8, C18, Silica, and DVB) and seven solvents (i.e., methanol, ethyl acetate, methyl tert-butyl ether, hexane, acetonitrile, dichloromethane, and trichloromethane) were surveyed. The analysis was performed by using a gas chromatograph equipped with a programmed temperature vaporization injector (PTV). Univariate and multivariate approaches were exploited in order to optimize the parameters affecting the MEPS extraction and the PTV injection of the analytes into the gas chromatographic system. The optimal working conditions were achieved using DVB as sorbent material and acetonitrile as elution solvent. Internal standard calibration was carried out using TBP-d27 and TCEP-d12. Satisfactory values of accuracy and precision were generally obtained as well as limit of detection (2.7-99 pg/mL for tap water; 2.9-97 pg/mL for river water; 3-107 pg/mL for wastewater) and limit of quantification (0.01-0.2 ng/mL). The proposed protocol was evaluated on real case scenarios by analyzing tap water, river water and simulated wastewater samples. The developed method is not only eco-friendly due to the low use of organic solvents but also simple and automatable since the MEPS extraction procedure can be implemented in the autosampler routine. [ABSTRACT FROM AUTHOR]

Four class-modeling techniques (soft independent modeling of class analogy (SIMCA), unequal dispersed classes (UNEQ), potential functions (PF), and multivariate range modeling (MRM)) were applied to multielement distribution to build chemometric models able to authenticate chili pepper samples grown in Calabria respect to those grown outside of Calabria. The multivariate techniques were applied by considering both all the variables (32 elements, Al, As, Ba, Ca, Cd, Ce, Co, Cr, Cs, Cu, Dy, Fe, Ga, La, Li, Mg, Mn, Na, Nd, Ni, Pb, Pr, Rb, Sc, Se, Sr, Tl, Tm, V, Y, Yb, Zn) and variables selected by means of stepwise linear discriminant analysis (S-LDA). In the first case, satisfactory and comparable results in terms of CV efficiency are obtained with the use of SIMCA and MRM (82.3 and 83.2% respectively), whereas MRM performs better than SIMCA in terms of forced model efficiency (96.5%). The selection of variables by S-LDA permitted to build models characterized, in general, by a higher efficiency. MRM provided again the best results for CV efficiency (87.7% with an effective balance of sensitivity and specificity) as well as forced model efficiency (96.5%). [ABSTRACT FROM AUTHOR]

Heavy metal contamination is recognized worldwide as a serious threat to human health and wildlife, and reducing their emissions is a priority of international and EU actions. Due to its persistence, high bioaccumulation tendency, and toxicity properties, lead (Pb) is one of the heavy metals of greatest concern. Even at low concentrations, lead induces various clinical and subclinical conditions in both humans and animals, and it has been included in the priority list of hazardous substances. In the present study, we used zebrafish's early stages as a model, given their well-acknowledged predictive value in the risk assessment of chemicals. This study was designed to investigate the morphological and morphometric alterations induced by Pb during zebrafish's early development and disclose the putative effects stage- and/or dose-dependent. We examined injuries induced by two environmentally relevant and extremely low concentrations of Pb (2.5 μg/L and 5 μg/L) during two exposure windows: early (between 1 and 7 dpf) and late (between 2 and 8 dpf). We clearly demonstrated that the incidence and severity of morphological abnormalities increased with increasing Pb dose and exposure time in both early and late-exposed groups. Furthermore, we revealed that malformation severity was significantly higher in the early exposed group than in the late exposure group at all exposure times and for both tested doses, thus highlighting the high sensitivity of zebrafish during the initial stages of development. The information presented in this paper emphasizes the effectiveness of morphological biomarkers in unveiling threatening situations and supports the role of zebrafish embryos and larvae in risk assessment and environmental monitoring. [Display omitted] • Low Pb doses induce morphological alterations in developing zebrafish. • Abnormalities appear after short-term exposure in all experimental groups. • The frequency and severity of injuries increased with increasing dose and time. • The degree of injuries is higher in early-exposed animals. • Specific target organ alterations depend on dose/stage. [ABSTRACT FROM AUTHOR]

Highlights: [•] A new SPME-GC-QqQ MS approach was developed for the determination of hydrazine in drinking water at trace levels. [•] Multivariate optimization was performed on derivatization reaction, mass spectrometry conditions and SPME parameters. [•] SRM acquisition by GC-QqQ-MS instrument enhances the ability in analyte quantification. [ABSTRACT FROM AUTHOR]

Highlights: [•] Benzothiazoles, benzotriazoles and benzosulfonamides determination in aqueous matrices. [•] New environmental-friendly and high-throughput protocol developed by SPME-GC–QqQMS. [•] Sample preparation strategy completely avoids the use of organic solvents. [•] MRM acquisition by GC–QqQ-MS instrument enhances analytes identification ability. [Copyright &y& Elsevier]

Highlights: [•] A SPME-GC–QqQ MS approach was developed for the quantification of dopamine, serotonin and norepinephrine in human urine. [•] The presence of organic solvents in the final protocol was minimized by the combined use of alkyl chloroformate and SPME. [•] SRM acquisition by GC–QqQ-MS instrument enhances the ability in analytes identification. [Copyright &y& Elsevier]

A new analytical approach, using paper spray tandem mass spectrometry, has been developed for assay of carnitine and acylcarnitines in urine. Paper spray (PS) is a very promising technique, especially in clinical investigations, because of its simplicity, low cost, and rapid sample preparation. A home-made paper spray device was used for assay of urinary acylcarnitines (C2-C18). The performance of solvents with different elution efficiency and paper substrates with different porosity grade and structure were tested by use of spiked synthetic urine. Tandem mass spectrometry in multiple reaction monitoring (MRM) mode was optimized to obtain better specificity and sensitivity. Analyte signals were evaluated for stability and reproducibility. Calibration with [H]propionylcarnitine (C3-d3), [H]octanoylcarnitine (C8-d3), and [H] palmitoylcarnitine (C16-d3) as internal standards was used for quantification. Very good linearity was obtained, with correlation coefficients >0.99 for C0-C12 and C16 acylcarnitines and >0.96 for C14 and C18 acylcarnitines. Accuracy and precision (RSD, %) of the proposed procedure were tested at concentrations of 0.8, 8, and 20 mg L with very satisfactory results: overall mean accuracy was 98.9 % and overall mean relative standard deviation 1 %. Limits of detection (LOD) between 6 and 208 μg L for propionylcarnitine and tetradecanoylcarnitine, respectively, can be regarded as very satisfactory. Application of the method to real urine proved that paper spray tandem mass spectrometry is a simple, rapid, and direct tool (no derivatization is required) for assay of carnitine and C2-C12 acylcarnitines in urine. [ABSTRACT FROM AUTHOR]

Abstract: Homovanillic acid (HVA), vanylmandelic acid (VMA), and 5-hydroxyindoleacetic acid (5-HIAA) are the metabolites of some catecholamines such as epinephrine, nor-epinephrine, dopamine and serotonin and their quantification is used in the diagnosis and management of patients with neurocrine tumors. A novel approach in the assay of these biomarkers in human urine samples by solid phase microextraction (SPME) combined with gas chromatography-triple quadrupole mass spectrometry (GC–QqQ-MS) is presented. A preliminary derivatization with ethyl chloroformate/ethanol was used and the corresponding derivatives were then extracted by SPME in immersion mode. The performance of five SPME fibers and three chloroformates were evaluated in univariate mode and the best results were obtained using the polyacrylate fiber and ethyl chloroformate. The variables affecting the efficiency of SPME analysis were optimized by the multivariate approach of “Experimental design” and, in particular, a central composite design (CCD) was applied. The optimum working conditions in terms of response values were achieved by performing analysis at room temperature with addition of NaCl (9.5%) and with an extraction time of 25.8min. Identification and quantification of analytes were carried out by using a gas chromatography-triple quadrupole mass spectrometry (GC–QqQ MS) system in multiple reaction monitoring (MRM) acquisition. An evaluation of all analytical parameters shows that the proposed method provides satisfactory results. Very good linearities were, in fact, achieved in the tested calibration ranges with correlation coefficient values >0.99 for all the analytes and accuracies and RSDs calculated for between-run and tested at concentrations of 1, 10, and 80mgL−1 were ranging from 91.3% to 106.6%, and from 0.5 to 8.9%, respectively. Moreover, the LOD values obtained can be considered very satisfactory (1.3, 0.046 and 24.3μgL−1 for HVA, VMA and 5-HIAA, respectively). The developed protocol represents, therefore, a simple, rapid and selective tool for assaying these acidic biomarkers in urine samples for neuroendocrine cancer diagnosis. [Copyright &y& Elsevier]

Abstract: A new analytical approach is exploited in the assay of selenium speciation in selenized and not selenium enriched potatoes based on the widely available solid-phase microextraction (SPME) coupled to-GC–triple quadrupole mass spectrometry (SPME-GC–QqQ MS) method. The assay of selenomethionine (SeMet) and selenomethylselenocysteine (SeMeSeCys) in potatoes here reported provides clues to the effectiveness of SPME technique combined with gas chromatography–tandem mass spectrometry, which could be of general use. For the exploitation of the GC method, the selected analytes were converted into their N(O,S)-alkoxycarbonyl alkyl esters derivatives by direct treatment with alkyl chloroformate in aqueous extracts. The performance of five SPME fibers and three chloroformates were tested in univariate mode and the best results were obtained using the divinylbenzene/carboxen/polydimethylsiloxane fiber and propylchloroformate. The variables affecting the efficiency of SPME analysis were optimized by the multivariate approach of design of experiment (DoE) and, in particular, a central composite design (CCD) was applied. Tandem mass spectrometry in selected reaction monitoring (SRM) has allowed the elimination of matrix interferences, providing reconstructed chromatograms with well-resolved peaks and the achievement of very satisfactory detection and quantification limits. Both precision and recovery of the proposed protocol tested at concentration of 8 and 40μgkg−1 (dry matter), offered values ranging from 82.3 to 116.3% and from 8.5 to 13.1% for recovery and precision, respectively. The application of the method to commercial samples of selenized and not selenium enriched potatoes proved that the Se fertilization increases significantly the concentration of these bioavailable selenoamino acids. [Copyright &y& Elsevier]

Abstract: A simple and sensitive method was developed for the quantification of five carbamate pesticides in water samples using solid phase microextraction (SPME) combined with gas chromatography-triple quadrupole mass spectrometry (GC-QqQ-MS). The performance of five SPME fibers was tested in univariate mode whereas the other variables affecting the efficiency of SPME analysis were optimized by the multivariate approach of design of experiment (DoE) and, in particular, a central composite design (CCD) was applied. The optimum working conditions in terms of response values were achieved by performing analysis with polydimethylsiloxane/divinylbenzene (PDMS/DVB) fiber in immersion mode for 45min at room temperature with addition of NaCl (10%). The multivariate chemometric approach was also used to explore the chromatographic behavior of the carbamates and to evaluate the importance of each variable investigated. An overall appraisement of results shows that the factor which gave a statistically significant effect on the response was only the injection temperature. Identification and quantification of carbamates was performed by using a gas chromatography-triple quadrupole mass spectrometry (GC-QqQ-MS) system in multiple reaction monitoring (MRM) acquisition. Since the choice of internal standard represented a crucial step in the development of method to achieve good reproducibility and robustness for the entire analytical protocol, three compounds (2,3,5-trimethacarb, 4-bromo-3,5-dimethylphenyl-n-methylcarbamate (BDMC) and carbaryl-d7) were evaluated as internal standards. Both precision and accuracy of the proposed protocol tested at concentration of 0.08, 5 and 3μgl−1 offered values ranging from 70.8% and 115.7% (except for carbaryl at 3μgl−1) and from 1.0% and 9.0% for accuracy and precision, respectively. Moreover, LOD and LOQ values ranging from 0.04 to 1.7ngl−1 and from 0.64 to 2.9ngl−1, respectively, can be considered very satisfactory. [Copyright &y& Elsevier]

Abstract: The work aims at developing a rapid and sensitive method for the quantification of perfluorocarboxylic acids in aqueous matrices. The proposed analytical approach is based on the use of solid phase microextraction in headspace mode after a fast derivatization of the carboxylate function by propylchloroformate/propanol mixture. Several fibers were evaluated and the optimization of the parameters affecting the SPME process was carried out using a central composite design. The optimum working conditions in terms of response values were achieved by performing analysis with CAR/PDMS fiber at room temperature, without addition of NaCl, with a sample volume of 6ml and an extraction time of 10min. Assay of PFCAs was performed by using a gas chromatography–triple quadrupole mass spectrometry (GC–QqQ MS) system in negative chemical ionization mode with ammonia as reagent gas. An overall evaluation of all analytical parameters shows that the proposed method provides satisfactory results. In particular, the observed accuracies, ranging from 84.4% to 116.8%, and the RSD values in the range 0.4% and 14.5% confirm the effectiveness of the developed protocol in the assay of PFCAs content in aqueous matrices. Moreover, LOD and LOQ values ranging from 0.08 to 6.6ngl−1 and from 0.17 to 14.3ngl−1, respectively, can be considered very satisfactory. None of the compounds were detected in six samples of river collected in Calabria. [Copyright &y& Elsevier]

Sarcosine is an amino acid derivative of N-methylglycine and is involved in the amino acid metabolism and methylation processes that are enriched during prostate cancer progression. It could also serve as a new target to be measured during therapeutic interventions and help in the identification of aggressive tumors for radical treatment. In this study, we present a new urine test that can help early diagnosis of prostate cancer. The method for the quantification of sarcosine in urine consists of a solid-phase microextraction (SPME) step followed by gas chromatography-triple quadrupole mass spectrometry analysis. We used a preliminary derivatization step with ethyl chloroformate/ethanol and the corresponding ester was then extracted by SPME in immersion mode. Several fibers were evaluated and the optimization of the parameters affecting the SPME process was carried out using an experimental design. The optimal values were 20 min extraction time, 10% NaCl, and 270°C using a divinylbenzene/Carboxen/polydimethylsiloxane fiber. The triple quadrupole analyzer acquired data in selected reaction monitoring mode, allowing us to obtain reconstructed chromatograms with well-defined chromatographic peaks. The accuracy and precision of this method were evaluated at concentrations of 70, 250, and 800 ng/ml and were found to be acceptable. Very satisfactory values (0.10 and 0.16 ng/ml, respectively) were also achieved for the limit of detection and the limit of quantification. The proposed protocol represents a rapid, simple, selective, and sensitive tool to quantify sarcosine in urine samples for prostate cancer diagnosis and for a screening test. [ABSTRACT FROM AUTHOR]

The history of the discovery of vitamins is the history of their deficiency disorders. Their discoverer was Casimir Funk, who is considered the 'father of vitamin therapy'. In his experimental research, Funk studied the interrelationships in the human body of those elements that Eijkman had demonstrated in animals, particularly in birds. In his experimental research, Funk identified the dietetic factors whose lack caused the 'deficiency disorders', as he called human beri-beri, scurvy, rickets and pellagra. In 1911, he designated these factors 'vitamins' ('vita' = life, and 'amine' = a nitrogenous substance essential for life); this name was accepted by the scientific community in 1912. Copyright © 2010 S. Karger AG, Basel [ABSTRACT FROM AUTHOR]

Abstract: The transesterification of triglycerides contained in waste oilseed fruits with methanol has been studied in heterogeneous/homogeneous systems using acid and base catalysts. The acid catalysts (strong acid catalysts: USY, BEA, FAU-X, and weak acid catalysts: MCM-41 and ITQ-6 with Si/Al=∞) were prepared by hydrothermal synthesis procedures. In order to obtain acid–base catalysts, potassium was loaded on different materials by ionic exchange (obtaining K-MCM-41, K-ITQ-6,). XRD, ICP-MS, IR after CO and CO2 adsorption, thermal analyses and N2 adsorption/desorption techniques have been used for catalysts characterization. The highest triglycerides conversion and biodiesel yield values were achieved by K-ITQ-6 catalysts, after 24h of reaction at 180°C. Deactivation of this catalyst occurs for potassium leaching, but its regeneration and reuse are feasible and easy to perform. A possible continuous biodiesel production process has been proposed. [Copyright &y& Elsevier]

Abstract: A gas chromatography–tandem mass spectrometry (GC–MS/MS) method for the detection of six phthalates in olive oil was developed. A gel permeation chromatography (GPC) clean-up step with cyclohexane:dichoromethane 7:3 as mobile phase was employed to remove the high-molecular mass species present in oil. Two ionization methodologies, i.e. electron (EI) and isobutane-chemical ionization (CI), were compared, in MS/MS mode, to achieve better analytical performances. An overall evaluation of all analytical parameters shows that the EI-MS/MS approach provides satisfactory results and is to be preferred to CI-MS/MS, at least in the case of the examined analytes. The observed accuracies, ranging from 71.7% to 112.2%, and the RSD values less than 9.7%, confirm the effectiveness of the proposed method in the assay of phthalate content in such a complex matrix as olive oil. The proposed protocol for the identification and assay of phthalates in olive oil might be of interest for the implementation of the QS (quality assurance scheme) for residue monitoring in food safety assessment. [Copyright &y& Elsevier]

Abstract: The multi element profile of milk from 12 cows and 6 water buffaloes was investigated, to establish whether dairy products derived from the two species could be distinguished. Multi-element data were obtained using ICP-MS. Following assessment against the team’s QA/QC criteria, or where the levels were below the LOD for the procedure, 16 elements (P, S, K, Ca, V, Cr, Mn, Fe, Co, Zn, Ga, Rb, Sr, Mo, Cs and Ba) were submitted for statistical analysis. Using linear discriminant analysis (LDA) it was possible to differentiate between milk from the two species, produced under identical environmental and animal husbandry conditions, on one farm. The sources of food and water available for consumption by the animals were also analysed and the results showed that there was no correlation between the elemental composition of the dietary components and the profiles observed in the milk. [Copyright &y& Elsevier]

In the present study, we show how, through time, an ethnic mosaic and a changing social and economic context translated into intrapopulation differentiation and a change in genetic barriers between populations. Surname analysis was applied to a sample drawn from two centuries of marriage records in ten Arbëreshe and nine Italian villages of southern Italy to evaluate the evolution of internal differentiation and changes in genetic relationships between populations. Marital Isonymy and subdivision into subpopulations was higher in the Arbëreshe. Genetic barriers coinciding with ethnic boundaries characterized the 1800s. In the second half of the 1900s, ethnic differentiation disappeared. We hypothesize that socioeconomic changes, such as increased outmigration and regional mobility, were the forces that progressively eliminated the ethnic-related genetic differentiation in the region. This study has important implications for an understanding of the relationship between genetic evolution and the cultural milieu involving enforcement of ethnic differences. [ABSTRACT FROM AUTHOR]

Abstract: The use of catalysts to improve the performances of water treatment technologies is well known; in the last years more scientific attention was given to the treatment of the olive oil mill wastewaters. This problem affects especially the Mediterranean area because this region is the largest world olive oil producer. In this paper, the results of the wet hydrogen peroxide catalytic oxidation on olive oil mill wastewaters using Fenton-like type catalysts (Cu-Silicalite-1 and Cu-pillared clay) are presented. Both the catalysts showed a high conversion in the oxidation of poly-phenols and were able to drastically reduce the chemical oxygen demand, the biochemical oxygen demand and the non-biodegradability of the olive oil mill wastewaters. [Copyright &y& Elsevier]

Abstract: Multi-element analysis of organic virgin olive oils from different Italian regions was carried out by inductively coupled plasma mass spectrometry (ICP-MS) aiming at developing a reliable method in the traceability of the origin of oils. The data were processed by means of the chemiometric approach of linear discriminant analysis (LDA) that allows classifying unknown samples after checking possible differentiation of samples of known origin. An external calibration curve was build for the quantitative analysis. The calibration curves for each element were linear in the range between 0.01 and 100ngmL−1 and 0.2 to 2000ngmL−1, the correlation coefficients were ranging between 0.996 and 0.999. Results from spike and recovery experiments at levels of 30 and 65ngmL−1 were in the range of 91–119%, whereas the quantitation limits, based on 10 times standard deviation of the blank, were also in the range of 0.009–10.2ngg−1, for almost all the elements. [Copyright &y& Elsevier]

Oleuropein (OLP, 1), the active ingredient present (i) in food integrators extracted from olive leaves, (ii) in table olives, and (iii) in extra virgin olive oils is a nutraceutical whose health benefits have been widely documented. A new analytical method for its assay, which is based on the utilization of atmospheric pressure chemical ionization tandem mass spectrometry and on the use of a synthetic labeled analogue, the 4-trideuteriocarboxyoleuropein (2), as an internal standard, is presented. The results obtained with extra virgin olive oils from different cultivars and different Italian regions are discussed. [ABSTRACT FROM AUTHOR]

Examines multiresidue analysis for organophosphates in organic oranges grown in Calabria, Italy, using a pulsed flame photometric detector coupled to a gas chromatograph. Retention times of the phosphorous-containing analytes; Usefulness of the extracted ion chromatograms for the identification of species; Use of the banned pesticide ronnel as an internal standard.

Studies the correlation of the frequencies of low-activity alleles of glucose-6-phosphate dehydrogenase in humans with the prevalence of malaria. Haplotype analysis of 'A-' and 'Med' mutations; Evolution of the mutations; Support for the hypothesis that malaria has a major impact on humans only since the introduction of agriculture.

The continuous and extensive application of agrochemicals leads to the accumulation of heavy metals (HMs) and rare earth elements (REEs) in agricultural soils and their transfer in the food web with consequent relevant risks for human and ecosystem health. In this study, HM and REE concentrations were quantified in the soil of wheat crop fields conventionally managed in the agricultural areas of Sila Mountain (Southern Italy) and compared with the concentration in a field of wild herbs, used as control. Statistical analyses and principal component analysis suggested that the use of pesticides, herbicides and fertilizers contributes to the accumulation of HMs and REEs in the soil. Different accumulation patterns were recorded in treated fields as a consequence of the type and amount of agrochemical used and the crop rotation. The exposure risk associated with the transfer through the tropic levels of agroecosystem was carried out measuring the concentration of HMs and REEs in adults of Harpalus (Pseudoophonus) rufipes (De Geer, 1774) collected from each monitored site. Different accumulation patterns found in specimens from the monitored sites highlighted the ability of this generalist predator to regulate metal uptake under field conditions. The values of bioaccumulation factor (BAF) allow to defining the order of accumulation in P. rufipes which was classified as a macroconcentrator of Cd, Cu, Mg and Zn. Our results can supplement the limited information regarding the REE accumulation in soil invertebrates and may provide reference data for assessing potential environmental risks in croplands. Unlabelled Image • Agrochemicals and fertilizers affect levels of HMs and REEs in agricultural soils. • HM and REE transfer along the terrestrial food web leads to exposure risk for human. • Uptake and accumulation of HMs and REEs occurs in beetles acting as generalist predators. • P. rufipes is a suitable tool to monitor Cd, Cu, Mg, and Zn in croplands. [ABSTRACT FROM AUTHOR]

A new and chemoselective method for the cleavage of alkyl and cyclic acetals and ketals at room temperature in wet nitromethane by using catalytic cerium(III) trifluoromethane sulfonate is presented. The high yields, the observed selectivity, the very gentle reaction conditions, and the almost neutral pH make this procedure particularly attractive for multistep synthesis. [ABSTRACT FROM AUTHOR]

The aim of this project was to study the treatment of industrial waste using ETS-10 zeolite. The pollutants that must be removed were metals sourced from zinc ferrite, a processing waste derived from the use of mineral-containing zinc. The first phase of the work involved the characterization of the industrial waste, zinc ferrite, in order to deepen the knowledge regarding its nature and composition. The second phase involved the removal of the metals released by the zinc ferrite in aqueous systems using the ETS-10 phase as an ion exchanger. Different chemical and physical techniques were used: plasma mass spectrometry, X-ray diffraction, scanning electron microscopy, microanalysis, and thermal analyses. A comparison between ETS-10 and commercial zeolite A performance, in the same aqueous systems, was carried out. The results showed that the metal removal efficiency of ETS-10 phase is higher than that obtained by commercial zeolite A, especially towards dangerous heavy metals such as Pb, Zn and Mn. [ABSTRACT FROM AUTHOR]

This work presents a novel method for the analysis of polycyclic aromatic hydrocarbons (PAHs) in saliva samples using solid phase microextraction (SPME) coupled with gas chromatography-triple quadrupole mass spectrometry (GC-QqQ-MS). The protocol utilizes the latest commercially available overcoated fiber (PDMS/DVB/PDMS) for direct immersion extraction of the target analytes, enabling the determination of thirteen PAHs, including low-volatile compounds. The SPME extraction method was optimized using a central composite design (CCD). The evaluation of the fiber coating's robustness over time demonstrated excellent extraction performance with no significant degradation. The validation procedure confirmed good performance for all parameters, with LOQ values (100 ng/L for ten analytes and 500 ng/L for three analytes) comparable to other chromatographic methods. The environmental impact of the protocol was objectively assessed using two recently proposed metrics: the Green Analytical Procedure Index (GAPI) and the Analytical Greenness metric for sample preparation (AGREEprep). Both metrics indicated good overall environmental friendliness, with AGREEprep providing a satisfactory comprehensive score despite the use of highly impactful instrumentation. These characteristics make the developed method suitable for routine analysis in environmental and epidemiological monitoring., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Heavy metal ions are a common source of water pollution. In this study, two novel membranes with biobased metal-organic frameworks (BioMOFs) embedded in a polyacrylonitrile matrix with tailored porosity were prepared via nonsolvent induced phase separation methods and designed to efficiently adsorb heavy metal ions from oligomineral water. Under optimized preparation conditions, stable membranes with high MOF loading up to 50 wt % and a cocontinuous sponge-like morphology and a high water permeability of 50-60 L m -2 h -1 bar -1 were obtained. The tortuous flow path in combination with a low water flow rate guarantees maximum contact time between the fluid and the MOFs, and thus a high heavy metal capture efficiency in a single pass. The performances of these BioMOF@PAN membranes were investigated in the dynamic regime for the simultaneous removal of Pb 2+ , Cd 2+ , and Hg 2+ heavy metals from aqueous environments in the presence of common interfering ions. The new composite adsorbing membranes are capable of reducing the concentration of heavy metal pollutants in a single pass and at much higher efficiency than previously reported membranes. The enhanced performance of the mixed matrix membranes is attributed to the presence of multiple recognition sites which densely decorate the BioMOF channels: (i) the thioether groups, deriving from the S -methyl-l-cysteine and ( S )-methionine amino acid residues, able to recognize and capture Pb 2+ and Hg 2+ ions and (ii) the oxygen atoms of the oxamate moieties, which preferentially interact with Cd 2+ ions, as revealed by single crystal X-ray diffraction. The flexibility of the pore environments allows these sites to work synergically for the simultaneous capture of different metal ions. The stability of the membranes for a potential regeneration process, a key-factor for the effective feasibility of the process in real life applications, was also evaluated and confirmed less than 1% capacity loss in each cycle.

Bio-active ethylcellulose (EC) polymeric films have been obtained by incorporating curcumin (curc) and Ag(I)-based compounds, known for their antioxidant and antimicrobial activity, respectively, within the polymeric matrix. The recently reported Ag(I) coordination polymer, in both its structural forms (α-[(bpy)Ag(OTf)] ∞ and β-{[(bpy)Ag][OTf]} ∞ ), and the [(bpy)Ag(OTf)] ∞ -curc polymeric co-crystal (bpy=2,2'-bipyridine; OTf=trifluoromethanesulfonate) have been selected as Ag(I) species. The hybrid composite films have been prepared through the simple solvent casting method and characterized through Powder X-Ray Diffraction (PXRD), Differential Scanning Calorimetry (DSC) and Fourier Transform Infrared (FTIR) spectroscopy, Scanning Electron Microscope (SEM), UV-vis spectroscopy. The deep investigation of the film samples highlighted the non-inert behaviour of EC towards these specific active ingredients. Antimicrobial tests showed that EC films embedding the Ag(I)-based compounds present good antimicrobial performance, in particular against Staphylococcus aureus, used as a model of Gram-positive bacteria. In addition, Silver migration tests, performed on the Ag(I)-incorporating EC films, evidenced low values of silver release particularly in the case of the EC films incorporating [(bpy)Ag(OTf)] ∞ -curc., (© 2024 Wiley-VCH GmbH.)

Green energy transition has supposed to give a huge boost to the electric vehicle rechargeable battery market. This has generated a compelling demand for raw materials, such as cobalt and nickel, which are key common constituents in lithium-ion batteries (LIBs). However, their existing mining protocols and the concentrated localization of such ores have made cobalt and nickel mineral conundrums, and their supplies experience shortages, which threaten to slow the progress of the renewable energy transition. Aiming to contribute to the sustainable recycling of these valuable metals from LIBs and wastewater, in this work, we explore the use of four mixed matrix membranes (MMMs) embedding different metal-organic frameworks (MOFs), i.e., MIL-53(Al) , MIL-53(Fe) , MIL-101(Fe) , and {Sr II Cu II 6 [( S , S )-serimox] 3 (OH) 2 (H 2 O)}·39H 2 O ( SrCu 6 Ser ) in polyether sulfone (PES), for the recovery of cobalt(II) and nickel(II) metal cations from mixed cobalt-nickel aqueous solutions containing common interfering ions. Whereas the neat PES membrane slightly contributes to the adsorption of metal ions, showing reduced removal efficiency values of 10.2 and 9.5% for Ni(II) and Co(II), respectively, the inclusion of MOFs in the polymeric matrix substantially improves the adsorption performances. The four MOF@PES MMMs efficiently remove these metals from water, with MIL-53(Al)@PES being the one that presents better performance, with a removal efficiency up to 95% of Ni(II) and Co(II). Remarkably, SrCu 6 Ser@PES exhibits outstanding selectivity toward cobalt(II) cations compared to of nickel(II) ones, with removal efficiencies of 63.7 and 15.1% for Co(II) and Ni(II), respectively. Overall, the remarkable efficiencies, versatility, high environmental robustness, and cost-effective synthesis shown by this family of MOF@PES MMMs situate them among the best adsorbents for the extraction of this kind of contaminants., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

The herein presented work aims to the development of an easy method for the quantitative determination of parabens and bisphenols in human salivabased on the use of methyl chloroformate as a derivatizing agent, followed by solid-phase microextraction (SPME) and gas chromatography-triple quadrupole mass spectrometry (GC-QqQ-MS) analysis with selected reaction monitoring (SRM). Using multivariate analysis, two derivatization strategies were compared and optimized, demonstrating that the use of methyl chloroformate led to better sensitivity than the classical derivatization by acetic anhydride. Good performance in the sorption process of the derivatized target analytes was obtained using the most recent commercialized overcoated fiber (PDMS/DVB/PDMS). The validation procedure of the final protocol led to satisfactory results in terms of linearity, limit of quantitation, accuracy, and precision. All parabens were quantified from 10 ng/L using the developed method, except for methylparaben, which was quantified from 100 ng/L along with all bisphenols. Intra- and inter-day accuracy and intra- and inter-day precision can be considered satisfactory for all analytes (values between 73% and 118%), except for the inter-day accuracy of BPF. Quite good results also in terms of matrix effect were obtained for the target compounds (range 71% to 118%, RSD% less than 13.6%), except for BPA at the middle concentration and MeP at the lowest concentration. The greenness of the method was evaluated and the results indicated that our approach is more eco-friendly than previously published methods. Based on its characteristics, the presented method can be considered a suitable approach to determine parabens and bisphenols in routine analysis for biomonitoring purposes., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023. Published by Elsevier B.V.)

This work proposes a new method for the quantification of benzothiazoles (BTs), benzotriazoles (BTRs), and benzenesulfonamides (BSAs) in tap water, river water, and wastewater. The protocol involved the use of microextraction by packed sorbent (MEPS), applied for the first time for the extraction of the target analytes, combined with programmed temperature vaporization-gas chromatography-triple quadrupole mass spectrometry (PTV-GC-QqQ-MS). Considering the synergism between MEPS extraction and PTV injection, the experimental variables affecting their performance were simultaneously optimized by "experimental design", while principal component analysis (PCA) was used to find the overall optimal working conditions. Response surface methodology was used to gain a comprehensive understanding of the effects of working variables on method performance. The developed method achieved very good linearities and satisfactory intra- and inter-day accuracies and precisions. The protocol permitted the detection of the target molecules with limit of detection (LODs) values between 0.005 and 0.85 μg/L. The green character of the procedure was evaluated using three metrics: "Analytical Eco-Scale", "Green Analytical Procedure Index" (GAPI), and "Analytical Greenness metric for sample preparation (AGREEprep). The satisfactory results obtained with real water samples demonstrate the applicability of the method for monitoring campaigns and exposome studies., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper, (Copyright © 2023 Elsevier B.V. All rights reserved.)

The increasing use of agrochemicals, including fertilizers and herbicides, has led to worrying metal contamination of soils and waters and raises serious questions about the effects of their transfer to different levels of the trophic web. Accumulation and biomagnification of essential (K, Na, Mg, Zn, Ca), nonessential (Sr, Hg, Rb, Ba, Se, Cd, Cr, Pb, As), and rare earth elements (REEs) were investigated in newly emerged adults of Tenebrio molitor exposed to field-admitted concentrations of a metribuzin-based herbicide and an NPK blend fertilizer. Chemical analyses were performed using inductively coupled plasma tandem mass spectrometry (ICP-MS/MS) supported by unsupervised pattern recognition techniques. Physiological parameters such as cuticle melanization, cellular (circulating hemocytes), and humoral (phenoloxidase enzyme activity) immune responses and mass loss were tested as exposure markers in both sexes. The results showed that NPK fertilizer application is the main cause of REE accumulation in beetles over time, besides toxic elements (Sr, Hg, Cr, Rb, Ba, Ni, Al, V, U) also present in the herbicide-treated beetles. The biomagnification of Cu and Zn suggested a high potential for food web transfer in agroecosystems. Gender differences in element concentrations suggested that males and females differ in element uptake and excretion. Differences in phenotypic traits show that exposure affects metabolic pathways involving sequestration and detoxification during the transition phase from immature-to-mature beetles, triggering a redistribution of resources between sexual maturation and immune responses. Our findings highlight the importance of setting limits for metals and REEs in herbicides and fertilizers to avoid adverse effects on species that provide ecosystem services and contribute to soil health in agroecosystems.

Benzothiazoles (BTHs), benzotriazoles (BTRs), and benzenesulfonamides (BSAs) are chemicals used in several industrial and household applications. Despite these compounds are emerging pollutants, there is still a lack of information about their presence in outdoor air samples. In this paper, we developed a new method for the quantification of BTHs, BTRs, and BSAs in airborne particulate matter (PM 10 ). The extraction of fourteen analytes from PM 10 was accomplished by microwave-assisted extraction (MAE) using an environmentally friendly mixture of water and ethanol. SPME was used to analyze the target compounds from the MAE extract by gas chromatography-tandem mass spectrometry (SPME-GC-MS/MS), eliminating additional sample clean-up steps. The best working conditions for MAE and SPME were examined multivariately by experimental design techniques. The target compounds were quantified in selected reaction monitoring acquisition mode. The proposed method was carefully validated, and the achieved results were satisfactory in terms of linearity, lower limit of quantification (picograms per cubic meter), intra- and inter-day accuracy (81-118% and 82-114%, respectively), and precision (repeatability and reproducibility in the range 2.3-17% and 7.4-19%, respectively). The application in a real monitoring campaign showed that the developed protocol is a valuable and eco-friendly alternative to the methods proposed so far., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

The present pilot study was undertaken to investigate the impaired acquired color vision on Calabrian male sample showing this parameter as a biological marker in type 2 diabetes. All patients and controls underwent three pseudo-isochromatic clinical test batteries: Ishihara test, Farnsworth test, and City University test. The results show a specific loss of short-wavelength (blue sensitivity) and typical tritan responses in diabetic patients. Generally, in later stages of the disease, the red-green mechanisms are involved. By the impaired color vision study in diabetic patients, we can confirm the impaired retina-brain cortex pathway. We believe that the above not invasive test analysis can support the other instrumental and imaging analysis to study the impaired retina-brain cortex pathway. Moreover, we think that the present clinical method can be useful in terms of preventive medicine.

Objective: To assess the type and degree of both red-green and blue-yellow color vision deficiencies of Calabrian males affected by multiple sclerosis., Material: Eighty Calabrian male patients were enrolled (age range 18-70 years; mean age 40.6 ± 12.4 years) showing a disease duration mean of 10.6 ± 8.2 years (range = 0.5-46 years) coming from the Institute of Neurology, Magna Graecia University, Catanzaro. Optic neuritis present in the medical histories of the 21 patients does not influence color vision. Excluding seven colorblind subjects and one affected by a bilateral maculopathy, the analyzed sample group was 72. Seventy controls were matched for age and sex., Method: An ophthalmologist examined all patients and controls in order to rule out diabetic retinopathy, cataracts, senile maculopathy, or ocular fundus' anomalies. The Ishihara test identified the colorblind patients. The City University Test screened for people with abnormal color vision by grading the severity of color vision deficiency. The second part of the City University Test as well as the Farnsworth Test confirmed both the color vision deficiency type and degree., Results: Fifty-one percentage (37/72) of the patients showing a color vision deficiency were subdivided into two subgroups: subgroup one showed red-green deficiency (57%, 21/37); subgroup two showed a coupled red-green and blue-yellow deficiency (43%, 16/37). Furthermore, we found two distinct curves showing a groove within the first 10 years of the disease. Both monocular and binocular analyses allowed us to identify the patients showing the monocular color vision deficiency, but they were well compensated by binocular vision., Conclusion: We think that the majority of the patients with the red-green deficiency will develop the coupled red-green and blue-yellow deficiency in the latter years of multiple sclerosis.

We report two new highly crystalline metal-organic frameworks (MOFs), derived from the natural amino acids serine (1) and threonine (2), featuring hexagonal channels densely decorated with hydroxyl groups belonging to the amino acid residues. Both 1 and 2 are capable of discriminating, via solid-phase extraction, a mixture of selected chloride salts of lanthanides on the basis of their size, chemical affinity, and/or the flexibility of the network. In addition, this discrimination follows a completely different trend for 1 and 2 because of the different locations of the hydroxyl groups in each compound, which is evocative of steric complementarity between the substrate and receptor. Last but not least, the crystal structures of selected adsorbates could be resolved, offering unprecedented snapshots on the capture process and enabling structural correlations with the separation mechanism.

European people believed that epilepsy was both a sacred and demoniac disease in the pre- and post-Hippocratic Age, and this belief continued into the Christian era. Epilepsy was wrapped in mystery. The present work shows an epileptic treatment using elk (Alces alces) hoof, which was better known among Northern European people, and explains its historical and popular origins that lead to its importance and success within the Official Medicine in the sixteenth and seventeenth centuries until its gradual decline as a specific treatment in the subsequent centuries. We study authors from both Antiquity and the Modern Age. The present work concludes by highlighting the relationship between epilepsy and its magic-religious inheritance. It could be considered a valid example showing how a popular treatment can earn honors in the Official Pharmacopoeia, but later be excluded.

The analysis of characteristic urinary acidic markers such as glutaric, 3-hydroxyglutaric, 2-hydroxyglutaric, adipic, suberic, sebacic, ethylmalonic, 3-hydroxyisovaleric and isobutyric acid constitutes the recommended follow-up testing procedure for glutaric acidemia type 1 (GA-1) and type 2 (GA-2). The goal of the work herein presented is the development of a fast and simple method for the quantification of these biomarkers in human urine. The proposed analytical approach is based on the use of solid phase microextraction (SPME) combined with gas chromatography-triple quadrupole mass spectrometry (GC-QqQ-MS) afterward a rapid derivatization of acidic moieties by propyl chloroformate, propanol and pyridine. Trueness and precision of the proposed protocol, tested at 5, 30 and 80mgl -1 , provided satisfactory values: recoveries were in the range between 72% and 116% and the relative standard deviations (RSD%) were between 0.9% and 18% (except for isobutyric acid at 5mgl -1 ). The LOD values achieved by the proposed method ranged between 1.0 and 473μgl -1 ., (Copyright © 2014 Elsevier B.V. All rights reserved.)