Chiral separation of propranolol by electrokinetic chromatography using nanodiamonds and human serum albumin as a pseudo-stationary phase in river water.

Propranolol is currently considered as an emerging contaminant in water bodies. In this study, R- and S-propranolol were determined in river samples by electrokinetic chromatography (EKC) using nanodiamonds (NDs) and human serum albumin (HSA) as a pseudo-stationary phase in order to achieve enantioseparation. Previously, river samples were preconcentrated using a column filled with Amberlite® IR-120 and Dowex® 50WX8 resins. The setting up of influential factors such as temperature, voltage, pH, and HSA and NDs concentration is accurately described along this manuscript. A multivariate study and optimization was carried out to obtain the enantioseparation of propranolol (Rs = 2.91), which was reached under the following experimental conditions: voltage of 16 kV, temperature of 16°C, phosphate buffer pH 9.5, NDs of 0.20%, and HSA of 15 µmol l-1 . The recoveries of analytes under optimal conditions were higher than 98%. The limits of detection were 0.85 µg l-1 for R- and S-propranolol. The method was applied to real samples, and the obtained results in three different water sources studied were 1.02, 0.59, and 0.30 µg l-1 for the R-enantiomer and 0.99, 0.54, and 0.28 µg l-1 for the S-enantiomer. The accuracy of the proposed methodology (including bias and precision) has allowed us to propose it as a successful tool for the control of water quality.

Coprecipitation-assisted coacervative extraction coupled to high-performance liquid chromatography: An approach for determining organophosphorus pesticides in water samples.

An analytical methodology based on coprecipitation-assisted coacervative extraction coupled to HPLC-UV was developed for determination of five organophosphorus pesticides (OPPs), including fenitrothion, guthion, parathion, methidathion, and chlorpyrifos, in water samples. It involves a green technique leading to an efficient and simple analytical methodology suitable for high-throughput analysis. Relevant physicochemical variables were studied and optimized on the analytical response of each OPP. Under optimized conditions, the resulting methodology was as follows: an aliquot of 9 mL of water sample was placed into a centrifuge tube and 0.5 mL sodium citrate 0.1 M, pH 4; 0.08 mL Al2 (SO4 )3 0.1 M; and 0.7 mL SDS 0.1 M were added and homogenized. After centrifugation the supernatant was discarded. A 700 µL aliquot of the coacervate-rich phase obtained was dissolved with 300 µL of methanol and 20 µL of the resulting solution was analyzed by HPLC-UV. The resulting LODs ranged within 0.7-2.5 ng/mL and the achieved RSD and recovery values were <8% (n = 3) and >81%, respectively. The proposed analytical methodology was successfully applied for the analysis of five OPPs in water samples for human consumption of different locations of Mendoza.

Determination of polybrominated diphenyl ethers in milk samples. Development of green extraction coupled techniques for sample preparation.

Ultrasound-assisted extraction (UAE), cloud point extraction (CPE), and ultrasound back-extraction (UABE) techniques have been coupled for lixiviation, preconcentration, and cleanup of polybrominated diphenyl ethers (PBDEs) from milk samples for determination by gas chromatography-electron capture detection (GC-ECD). Physicochemical parameters that affect the efficiency of the extraction system were investigated using a design of experiments based on multivariate statistical tools, and considering the sample matrix along the development. The coupling of the leaching step, UAE, enhanced ca. 3.5 times the extraction efficiency of the former sample preparation methodology (CPE-UABE) leading to cleaner sample extracts suitable for GC analysis. Under optimum conditions, the proposed methodology exhibits successful performance in terms of linearity and precision, with recoveries in the range of 68-70% and LODs within the range 0.05-0.5 ng/g dry weight (d.w.). The proposed sample preparation methodology coupled three green analytical techniques. It expands the application frontiers of CPE for the analysis of biological samples by GC. The optimized methodology was used for determination of PBDEs in powder milk samples, from both commercial and human sources.

Assessing polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans in air across Latin American countries using polyurethane foam disk passive air samplers.

A passive air sampling network has been established to investigate polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) at Global Atmospheric Passive Sampling (GAPS) sites and six additional sites in the Group of Latin American and Caribbean Countries (GRULAC) region. The air sampling network covers background, agricultural, rural, and urban sites. Samples have been collected over four consecutive periods of 6 months, which started in January 2011 [period 1 (January to June 2011), period 2 (July to December 2011), period 3 (January to June 2012), and period 4 (July 2012 to January 2013)]. Results show that (i) the GAPS passive samplers (PUF disk type) and analytical methodology are adequate for measuring PCDD/F burdens in air and (ii) PCDD/F concentrations in air across the GRULAC region are widely variable by almost 2 orders of magnitude. The highest concentrations in air of Σ4-8PCDD/Fs were found at the urban site São Luis (Brazil, UR) (i.e., 2560 fg/m3) followed by the sites in São Paulo (Brazil, UR), Mendoza (Argentina, RU), and Sonora (Mexico, AG) with values of 1690, 1660, and 1610 fg/m3, respectively. Very low concentrations of PCDD/Fs in air were observed at the background site Tapanti (Costa Rica, BA), 10.8 fg/m3. This variability is attributed to differences in site characteristics and potential local/regional sources as well as meteorological influences. The measurements of PCDD/Fs in air agree well with model-predicted concentrations performed using the Global EMEP Multimedia Modeling System (GLEMOS) and emission scenario constructed on the basis of the UNEP Stockholm Convention inventory of dioxin and furan emissions.

Assessment of legacy and alternative halogenated organic pollutants in outdoor dust and soil from e-waste sites in Nigeria: Concentrations, patterns, and implications for human exposure.

E-waste is often processed informally, particularly in developing countries, resulting in the release of harmful chemicals into the environment. This study investigated the co-occurrence of selected persistent organic pollutants (POPs), including legacy and alternative halogenated flame retardants (10 polybrominated diphenyl ethers (PBDEs), decabromodiphenyl ethane (DBDPE), syn and anti-dechlorane plus (DP)), 32 polychlorinated biphenyls (PCBs) and 12 organochlorine pesticides (OCPs), in 20 outdoor dust and 49 soil samples from 7 e-waste sites in Nigeria. This study provides the first report on alternative flame retardants (DBDPE and DP) in Nigeria. The total concentration range of the selected classes of compounds was in the order: ∑10PBDEs (44-12300 ng/g) > DBDPE (4.9-3032 ng/g) > ∑2DP (0.7-278 ng/g) > ∑32PCBs (4.9-148 ng/g) > ∑12OCPs (1.9-25 ng/g) for dust, and DBDPE (4.9-9647 ng/g) > ∑10PBDEs (90.3-7548 ng/g) > ∑32PCBs (6.1-5025 ng/g) > ∑12OCPs (1.9-250 ng/g) > ∑2DP (2.1-142 ng/g) for soil. PBDEs were the major contributors to POP pollution at e-waste dismantling sites, while PCBs were the most significant contributors at e-waste dumpsites. DBDPE was found to be significantly associated with pollution at both e-waste dismantling and dumpsites. Estimated daily intake (EDI) via dust and soil ingestion and dermal adsorption routes ranged from 1.3 to 2.8 ng/kg bw/day and 0.2-2.9 ng/kg bw/day, respectively. In the worst-case scenario, EDI ranged from 2.9 to 10 ng/kg bw/day and 0.8-5.8 ng/kg bw/day for dust and soil, respectively. The obtained intake levels posed no non-carcinogenic risk, but could increase the incidence of cancer at some of the studied e-waste sites, with values exceeding the USEPA cancer risk lower limit (1.0 × 10-6). Overall, our results suggest that e-waste sites act as emission point sources of POPs.

Source identification and human exposure assessment of organophosphate flame retardants and plasticisers in soil and outdoor dust from Nigerian e-waste dismantling and dumpsites.

Electronic waste (e-waste) dismantling and dumpsite processes are major sources of organophosphate flame retardant and plasticiser emissions and may pose potentially adverse effects on environment and human health. In 20 outdoor dust and 49 soil samples collected from four e-waste dismantling and three e-waste dumpsites in two States of Nigeria (Lagos and Ogun), we identified 13 alternative plasticisers (APs), 7 legacy phthalate plasticisers (LPs), and 17 organophosphorus flame retardants (OPFRs) for the first time in African e-waste streams. In the samples from dismantling sites, the range (median) concentrations of ∑13APs, ∑7LPs, and ∑17OPFRs were 11-2747 µg/g (144 µg/g), 11-396 µg/g (125 µg/g), and 0.2-68 µg/g (5.5 µg), in dust respectively and 1.8-297 µg/g (55 µg/g), 1.3-274 µg/g (48.5 µg/g), and 1.6-62 µg/g (1.6 µg/g), in soil respectively. Results for soil samples from e-waste dumpsites were (6.6-195 µg/g (23.7 µg/g), 6.0-295 µg/g (54.8), and 0.4-42.3 µg/g (9.0 µg/g) for ∑13APs, ∑7LPs, and ∑17OPFRs respectively. Overall, concentrations of APs were significantly higher at the dismantling sites (p = 0.005) compared to dumpsites, levels of LPs were higher at dismantling sites but not significant, while OPFR concentrations were significantly higher in dumpsite samples (p = 0.005). Plasticisers were found to be major contributors to pollution at e-waste dismantling sites, while OPFRs were associated with both automobile dismantling and e-waste dumpsite processes. Following particle size fractionation of selected soil samples, higher concentrations of targeted compounds were observed in the smaller mesh (180 µm) soil sieve fraction. For dust, the total median estimated daily intake via ingestion and dermal adsorption (EDIing and EDIderm) ranged from 43 to 74 ng/kg bw/day and 0.4-0.7 ng/kg bw/day, respectively. Correspondingly, 4.6-45 ng/kg bw/day and 0.015-0.57 ng/kg bw/day were the values found for soil, respectively. According to these results, the targeted chemicals do not appear to pose a non-carcinogenic risk to e-waste workers through ingestion or dermal contact of bio-accessible fractions of the chemicals. Human biomonitoring campaigns are recommended in the Nigerian e-waste environment considering the elevated concentration levels found for the majority of targeted compounds and that risk parameters required for exposure assessment were only available for a limited number of compounds.

Pesticides and PPCPs in aquatic ecosystems of the andean central region: Occurrence and ecological risk assessment in the Uco valley.

Uco valley (Mendoza, Argentina) suffers the concomitant effect of climate change, anthropic pressure and water scarcity. Moreover chemical pollution to aquatic ecosystems could be another pressuring factor, but it was not studied enough to the present. In this sense, the aim of this study was to assess the occurrence of pesticides, pharmaceuticals and personal care products (PPCPs) in aquatic ecosystems of the Uco Valley and to perform an ecological risk assessment (ERA). The presence of several insecticides (mainly neonicotinoids), herbicides (atrazine, diuron, metolachlor, terbutryn) and fungicides (strobilurins, triazolic and benzimidazolic compounds) in water samples in two seasons, related to crops like vineyards, garlic or fruit trees was associated to medium and high-risk probabilities for aquatic biota. Moreover, PPCPs of the group of non-steroidal anti-inflammatory drugs, parabens and bisphenol A were detected in all the samples and their calculated risk quotients also indicated a high risk. This is the first record of pesticides and PPCPs with an ERA in this growing agricultural oasis. Despite the importance of these findings in Uco Valley for decision makers in the region, this multilevel approach could bring a wide variety of tools for similar regions in with similar productive and environmental conditions, in order to afford actions to reach Sustainable Development Goals. SYNOPSIS: Aquatic ecosystems in arid mountain regions are threatened worldwide. This study reports relevant data about chemical pollution in Central Andes, which could be a useful tool to enhance SDGs' accomplishment.

Organic matter degradation determines the concentrations of polybrominated diphenyl ethers in sediments. Multivariate learning on environmental and experimental models.

Sediment organic matter (SOM) plays an important role in capturing polybrominated diphenyl ethers (PBDEs) due to its affinity to hydrophobic and lipophilic compounds. Previous publications about correlations between PBDE concentrations and SOM content showed discrepancies among the results, reporting either significant positive correlations or no correlations at all. This work aimed to provide a deeper insight into SOM characteristics that might determine the concentrations of PBDEs in sediments. Sediment samples from Mendoza province, Argentina, were analyzed to contrast two models, environmental and experimental, using multivariate learning methods. Mendoza has been going through increasing events of drought and water scarcity, hence the occurrence, transport, and fate of contaminants as PBDEs in aquatic environments is of superlative importance. Principal component analysis (PCA) and partial least squares regression (PLS) were used to evaluate the correlations between physicochemical properties of sediments, semi-quantitative Fourier transform infrared (FTIR) area ratios obtained from SOM spectra, and PBDE concentrations in sediments. Moreover, a linear model was proposed to determine SOM density using FTIR area ratios and it was used as an additional variable in multivariate analyses. The results obtained from PCA and PLS were consistent and revealed that PBDE concentrations in sediments were correlated with a more degraded SOM, characterized by shorter and more branched hydrocarbon chains. PBDE concentrations were also correlated with higher SOM density values, which in turn were correlated with SOM degradation. These findings extend previous understanding and emphasize that not only is the organic matter content a factor in determining PBDE concentrations in sediments, but also and more significantly, its degree of degradation.

Characterization of Purple Carrot Germplasm for Antioxidant Capacity and Root Concentration of Anthocyanins, Phenolics, and Carotenoids.

The present study characterized a genetically and phenotypically diverse collection of 27 purple and two non-purple (one orange and one yellow) carrot accessions for concentration of root anthocyanins, phenolics, and carotenoids, and antioxidant capacity estimated by four different methods (ORAC, DPPH, ABTS, FRAP), in a partially replicated experimental design comprising data from two growing seasons (2018 and 2019). Broad and significant (p < 0.0001) variation was found among the accessions for all the traits. Acylated anthocyanins (AA) predominated over non-acylated anthocyanins (NAA) in all the accessions and years analyzed, with AA accounting for 55.5-100% of the total anthocyanin content (TAC). Anthocyanins acylated with ferulic acid and coumaric acid were the most abundant carrot anthocyanins. In general, black or solid purple carrots had the greatest TAC and total phenolic content (TPC), and the strongest antioxidant capacities, measured by all methods. Antioxidant capacity, estimated by all methods, was significantly, positively, and moderately-to-strongly correlated with the content of all individual anthocyanins pigments, TAC, and TPC, in both years (r = 0.59-0.90, p < 0.0001), but not with the carotenoid pigments lutein and ß-carotene; suggesting that anthocyanins and other phenolics, but not carotenoids, are major contributors of the antioxidant capacity in purple carrots. We identified accessions with high concentration of chemically stable AA, with potential value for the production of food dyes, and accessions with relatively high content of bioavailable NAA that can be selected for increased nutraceutical value (e.g., for fresh consumption).

Impact of dietary lipid level on esterase enzyme activities in the non-target freshwater shrimp Macrobrachium borellii exposed to chlorpyrifos.

This study increases our understanding of how diet-driven phenotypic plasticity can help non-target aquatic invertebrates deal with chlorpyrifos (CPO) exposure. A bioassay was performed over 6 days with the freshwater shrimp Macrobrachium borellii. Experimental treatments included CPO-treated shrimps (10 µg L-1) were fed with (i) a lipid-rich diet, (ii) a lipid-medium diet, or (iii) a lipid-poor diet. Control shrimps (no CPO exposure) received the same diets as detailed above. Cholinesterases and carboxylesterases were determined as an indicator of CPO exposure. Results showed that diets with a medium-to-high lipid content were important inducers of esterase activity, while shrimps exposed to CPO under a lipid-poor diet showed a significant enzymatic inhibition. This diet-dependent esterase induction suggests that the intake of fatty dietary items mitigates the esterase enzyme inhibition caused by CPO exposure.

Monitoring of SARS-CoV-2 RNA in wastewater as an epidemiological surveillance tool in Mendoza, Argentina.

Wastewater-based epidemiology (WBE) is an emerging tool that gives temporal and spatial information on a population's health status. Here, we report the epidemiological dynamics of a population of ~1.2 million residents in the metropolitan region of Mendoza province, Argentina, within the period July 2020 to January 2021. We combined the use of WBE of two wastewater treatment plants with epidemiological surveillance of the corresponding populations. We applied two viral concentration methods (polyethylene glycol precipitation and aluminum-based adsorption-flocculation) and RNA isolation methods in each wastewater sample to increase the possibility of detection and quantification of nucleocapsid markers (N1 and N2) of SARS-CoV-2 by RT-qPCR. Overall, our results allowed us to trace the rise, exponential growth, plateau, and fall of SARS-CoV-2 infections for 26 weeks. Individual analysis for each wastewater treatment plant showed a positive correlation between the viral load of SARS-CoV-2 genetic markers and COVID-19 cases that were diagnosed per week. Our findings indicate that WBE is a useful epidemiological indicator to anticipate the increase in COVID-19 cases and monitor the advance of the pandemic and different waves of infections.

Accumulation of PBDEs and MeO-PBDEs in notothenioid fish from the South Shetland Islands, Antarctica: An interspecies comparative study.

Concentrations of polybrominated diphenyl ethers (PBDEs) and methoxylated polybrominated diphenyl ethers (MeO-PBDEs); are reported in specimens of fish notothenioids Chaenocephalus aceratus (SSI), Trematomus bernacchii (ERN), and Nototheniops nudifrons (NOD) from the South Shetland Islands, Antarctica. Significant differences in the accumulation of 2'-MeO-BDE-68 and 6-MeO-BDE-47 were detected among the analysed species. MeO-BDEs were significantly higher in SSI (11.7, 8.6, and 14.1 ng g-1 lw) than in NOD (1.63, 1.63, and 3.0 ng g-1 lw) in muscle, liver, and gill, respectively. Feeding ecology traits explain the accumulation patterns of MeO-PBDEs. SSI has a higher feeding activity with a broader diet, followed by ERN, whereas NOD is a benthic/sedentary fish with a narrower diet. The accumulation of PBDEs was neither species-, nor tissue-specific. The current study expands the knowledge concerning the accumulation of PBDEs and MeO-PBDEs in Antarctic marine fish and supports the importance of species-specificity in the accumulation of MeO-PBDEs.

Identifying patterns and sources of anthropogenic trace metals in the Argentine Central Andes by using snow samples and an atmospheric dispersion model.

This study presents the first local measurements of metals in snow from the Argentine Central Andes. Cu, Pb and Zn were selected as specific tracers of anthropogenic local emission sources in the study area. Snow samples were collected during winter (2014, 2015 and 2016) at two sites with different characteristics: Punta de Vacas and Vallecitos. The samples were analyzed by ICP-MS, and the average concentrations found were 1.4 µg L-1 (Cu), 2.2 µg L-1 (Pb) and 14.2 µg L-1 (Zn) in the snow samples from Vallecitos, and 5.3 µg L-1 (Cu), 2.6 µg L-1 (Pb) and 24.0 µg L-1 (Zn) in the snow samples from Punta de Vacas. These data and the snowfall amount in each sampling site were statistically analyzed. Results suggested that the levels of metals in the snow are influenced not only by the atmospheric concentrations, but also by the amount of precipitated snow. Additionally, an atmospheric dispersion model, CALPUFF, was applied in the study area to determine the origin of the studied metals and to understand the spatial distribution pattern of the concentrations found. Results showed that the metal atmospheric loads in the study area originated from local sources, especially vehicular traffic and mining. This work represents an important contribution to the knowledge and preservation of the local Andean cryosphere, and it could be used as an input to develop protection policies in the area through the combination of different and complementary tools for the evaluation of air quality.

Simple approach based on ultrasound-assisted emulsification-microextraction for determination of polibrominated flame retardants in water samples by gas chromatography-mass spectrometry.

A simple, efficient, innovative and environmentally friendly analytical technique was successfully applied for the first time for the extraction and preconcentration of polybrominated diphenyl ethers (PBDEs) from water samples. The PBDEs selected for this work were those most commonly found in the literature in natural water samples: 2,2',4,4'-tetraBDE (BDE-47), 2,2',4,4,5-pentaBDE (BDE-99), 2,2',4,4,6-pentaBDE (BDE-100) and 2,2,4,4',5,5'-hexaBDE (BDE-153). The extracted PBDEs were separated and determined by gas chromatography-mass spectrometry (GC-MS). The extraction/preconcentration technique is based on ultrasound-assisted emulsification-microextraction (USAEME) of a water-immiscible solvent in an aqueous medium. Several variables including, solvent type, extraction time, extraction temperature and matrix modifiers were studied and optimized over the relative response the target analytes. Chloroform was used as extraction solvent in the USAEME technique. Under optimum conditions, the target analytes were quantitatively extracted achieving enrichment factors (EF) higher than 319. The detection limits (LODs) of the analytes for the preconcentration of 10 mL sample volume were within the range 1-2 pg mL(-1). The relative standard deviations (RSD) for five replicates at 10 pg mL(-1) concentration level were <10.3%. The calibration graphs were linear within the concentration range of 5-5000 pg mL(-1) for BDE-47 and BDE-100; and 5-10,000 pg mL(-1) for BDE-99 and BDE-153, respectively. The coefficients of estimation were > or = 0.9985. Validation of the methodology was performed by standard addition method at two concentration levels (10 and 50 pg mL(-1)). Recovery values were > or = 96%, which showed a successful robustness of the analytical methodology for determination of picogram per milliliter of PBDEs in water samples. Significant quantities of PBDEs were not found in the analyzed samples.

Occurrence of organochlorine compounds in fish from freshwater environments of the central Andes, Argentina.

The Central Andes region is considered an area of high environmental relevance in South America and it is rich in glaciers, which are the main fresh water sources and reservoirs of the region. The presence of organochlorine compounds (OCs) is an environmental threat due to their persistence and adverse effects on wildlife and humans. The levels of OCs, such as chlordane compounds (CHLs), dichlorodiphenyltrichloroethane and metabolites (DDTs), hexachlorobenzene (HCB), hexachlorocyclohexanes (HCHs), and polychlorinated biphenyls (PCBs), were determined in muscle and liver tissues of fish and in sediments collected from different sites of the central Andes: the Mendoza River and the Yaucha River (rainbow trout: Oncorhynchus mykiss) and Carrizal Dam (silverside: Odontesthes bonariensis). Regardless of studied site and fish tissue, the general OC trend was: DDTs > PCBs > HCHs > CHLs > HCB. The results showed clear geographic distribution patterns for DDTs. Among the sampling sites, silverside fish showed the highest average load of DDTs (614 and 867 ng g-1 lw in muscle and liver tissues, respectively). Based on the biota-sediment bioaccumulation factor (BSAF), both rainbow trout and silverside fish showed comparable capability to accumulate p,p'-DDT in their tissues. Intraspecific correlational analysis showed that CB-138 in muscle and p,p'-DDT in liver were clearly correlated with the lipid content in silverside specimens, which highlights the relevance of taking into account the fat content and the type of target tissues.

Modeling and separation-detection methods to evaluate the speciation of metals for toxicity assessment.

There is an increasing appreciation for the importance of speciation in the assessment of metal toxicity. In this review, two approaches to speciation are discussed, with an emphasis on their application to biological samples. One approach is the direct separation and detection of metal species of toxicological interest. Various "hyphenated" techniques, consisting of a chromatographic system coupled to inductively coupled plasma-mass spectrometry (ICP-MS), are discussed. The chromatographic strategies employed for separation emphasize liquid chromatography (LC), but the increasing use of gas chromatography (GC) and capillary electrophoresis (CE) in speciation analysis is discussed. The second approach to speciation is the use of computer models to calculate the speciation of a metal ion within a complex mixture of ligands. This approach is applicable to systems in which the metal cation exchanges ligands rapidly, so that the sample represents an equilibrium mixture of metal complexes. These computational models are based on the equilibrium constants for the metal complexes and a series of mass balance equations and give the distribution of metal complexes in the original sample. This approach is illustrated using the speciation of Al(III) in serum as an example.

State of the art of environmentally friendly sample preparation approaches for determination of PBDEs and metabolites in environmental and biological samples: A critical review.

Green chemistry principles for developing methodologies have gained attention in analytical chemistry in recent decades. A growing number of analytical techniques have been proposed for determination of organic persistent pollutants in environmental and biological samples. In this light, the current review aims to present state-of-the-art sample preparation approaches based on green analytical principles proposed for the determination of polybrominated diphenyl ethers (PBDEs) and metabolites (OH-PBDEs and MeO-PBDEs) in environmental and biological samples. Approaches to lower the solvent consumption and accelerate the extraction, such as pressurized liquid extraction, microwave-assisted extraction, and ultrasound-assisted extraction, are discussed in this review. Special attention is paid to miniaturized sample preparation methodologies and strategies proposed to reduce organic solvent consumption. Additionally, extraction techniques based on alternative solvents (surfactants, supercritical fluids, or ionic liquids) are also commented in this work, even though these are scarcely used for determination of PBDEs. In addition to liquid-based extraction techniques, solid-based analytical techniques are also addressed. The development of greener, faster and simpler sample preparation approaches has increased in recent years (2003-2013). Among green extraction techniques, those based on the liquid phase predominate over those based on the solid phase (71% vs. 29%, respectively). For solid samples, solvent assisted extraction techniques are preferred for leaching of PBDEs, and liquid phase microextraction techniques are mostly used for liquid samples. Likewise, green characteristics of the instrumental analysis used after the extraction and clean-up steps are briefly discussed.

Investigation of pyrrolizidine alkaloids and their N-oxides in commercial comfrey-containing products and botanical materials by liquid chromatography electrospray ionization mass spectrometry.

Pyrrolizidine alkaloids (PAs) and their N-oxides are found in several plant families throughout the world. PAs are potentially toxic to the liver and/or lungs in humans and may cause acute liver failure, cirrhosis, pneumonitis, or pulmonary hypertension. PAs are also carcinogenic to animals, and they have been linked to the development of hepatocellular and skin squamous cell carcinomas as well as liver angiosarcomas. According to experimental studies, the quantity of PAs in some herbal teas and dietary supplements is sufficient to be carcinogenic in exposed individuals. A method for the extraction and identification of PAs and their N-oxides in botanical materials and commercial comfrey-containing products has been developed using liquid chromatography electrospray ionization mass spectrometry. Following optimization of the extraction procedure and the chromatographic conditions, the method was applied to the analysis of 10 herbal remedies. All of the products that were labeled to contain comfrey were found to contain measurable quantities of PAs.

Stability of iron-quercetin complexes in synthetic wine under in vitro digestion conditions.

UNLABELLED: Wine is a dietary source of polyphenolic compounds with reported health benefits when moderately consumed. Several of these compounds can associate with metals forming complexes. Therefore, this work was conducted to reach a better understanding of the nature and chemical stability of wine-derived Fe(3+)-quercetin complexes in a digestion model. The stability of the complexes in a synthetic (simulated) wine was studied before and after in vitro gastric and intestinal digestions by high-performance liquid chromatography (HPLC) with UV-Vis detection. Metal determination was performed by atomic absorption spectrometry (ETAAS) to evaluate possible dissociation of complexes. During HPLC analysis all peaks eluted from the chromatographic column were collected, acidified, and analyzed by ETAAS. The results showed that complexes remain substantially stable after gastric digestion conditions, with recoveries of 84% to 90%. Although metal complexes were partially degraded during intestinal digestion, 41% to 45% of the Fe(3+)-quercetin complexes was recovered. PRACTICAL APPLICATION: This work reveals the chemical stability of Fe3+­quercetin complexes in synthetic wines after an in vitro gastrointestinal digestion. The knowledge of this process would be useful to understand the bioavailability of these compounds.

Solid phase microextraction coupled to liquid chromatography. Analysis of organosulphur compounds avoiding artifacts formation.

This work proposes the novel application of a microextraction technique, solid phase microextraction (SPME), coupled to liquid chromatography with UV detection (HPLC-UV) for the analysis of organosulfur compounds (OSCs) in garlic samples. Additionally, a comparative study of OSCs profiles obtained by SPME coupled to HPLC-UV and gas chromatography with flame photometric detector (GC-FPD), respectively; was carried out. This study provided complementary evidence about OSCs's lability and "artifacts" formation during the analytical process. Raw, cooked and distilled garlic samples were considered. The target analytes were diallyl disulphide (DADS), diallyl sulphide (DAS), diallyl trisulphide (DATS), allicin, 3-vinyl-4H-1,3-dithiin (3-VD), 2-vinyl-4H-1,2-dithiin (2-VD) and (E)- and (Z)-ajoene, which are the most important OSCs with biological activities present in raw and processed garlic. The coupling of SPME and HPLC showed to be reliable, fast, sensible and selective methodology for OSCs analysis.