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1.
Environ Sci Technol ; 55(9): 6184-6196, 2021 05 04.
Artículo en Inglés | MEDLINE | ID: mdl-33843191

RESUMEN

To date, few studies have examined the role of sea spray aerosols (SSAs) in human exposure to harmful and beneficial marine compounds. Two groups of phycotoxins (brevetoxins and ovatoxins) have been reported to induce respiratory syndromes during harmful algal blooms. The aerosolization and coastal air concentrations of other common marine phycotoxins have, however, never been examined. This study provides the first (experimental) evidence and characterization of the aerosolization of okadaic acid (OA), homoyessotoxin, and dinophysistoxin-1 using seawater spiked with toxic algae combined with the realistic SSA production in a marine aerosol reference tank (MART). The potential for aerosolization of these phycotoxins was highlighted by their 78- to 1769-fold enrichment in SSAs relative to the subsurface water. To obtain and support these results, we first developed an analytical method for the determination of phycotoxin concentrations in SSAs, which showed good linearity (R2 > 0.99), recovery (85.3-101.8%), and precision (RSDs ≤ 17.2%). We also investigated natural phycotoxin air concentrations by means of in situ SSA sampling with concurrent aerosolization experiments using natural seawater in the MART. This approach allowed us to indirectly quantify the (harmless) magnitude of OA concentrations (0.6-51 pg m-3) in Belgium's coastal air. Overall, this study provides new insights into the enriched aerosolization of marine compounds and proposes a framework to assess their airborne exposure and effects on human health.


Asunto(s)
Floraciones de Algas Nocivas , Agua de Mar , Aerosoles , Humanos , Océanos y Mares , Agua
2.
Mar Drugs ; 18(1)2020 Jan 10.
Artículo en Inglés | MEDLINE | ID: mdl-31936833

RESUMEN

Respiratory exposure to marine phycotoxins is of increasing concern. Inhalation of sea spray aerosols (SSAs), during harmful Karenia brevis and Ostreopsis ovata blooms induces respiratory distress among others. The biogenics hypothesis, however, suggests that regular airborne exposure to natural products is health promoting via a downregulation of the mechanistic target of rapamycin (mTOR) pathway. Until now, little scientific evidence supported this hypothesis. The current explorative in vitro study investigated both health-affecting and potential health-promoting mechanisms of airborne phycotoxin exposure, by analyzing cell viability effects via cytotoxicity assays and effects on the mTOR pathway via western blotting. To that end, A549 and BEAS-2B lung cells were exposed to increasing concentrations (ng·L-1 - mg·L-1) of (1) pure phycotoxins and (2) an extract of experimental aerosolized homoyessotoxin (hYTX). The lowest cell viability effect concentrations were found for the examined yessotoxins (YTXs). Contradictory to the other phycotoxins, these YTXs only induced a partial cell viability decrease at the highest test concentrations. Growth inhibition and apoptosis, both linked to mTOR pathway activity, may explain these effects, as both YTXs were shown to downregulate this pathway. This proof-of-principle study supports the biogenics hypothesis, as specific aerosolizable marine products (e.g., YTXs) can downregulate the mTOR pathway.


Asunto(s)
Aerosoles/farmacología , Exposición a Riesgos Ambientales , Pulmón/efectos de los fármacos , Toxinas Marinas/farmacología , Serina-Treonina Quinasas TOR/metabolismo , Células A549 , Aerosoles/toxicidad , Línea Celular , Supervivencia Celular/efectos de los fármacos , Activación Enzimática/efectos de los fármacos , Floraciones de Algas Nocivas , Humanos , Técnicas In Vitro , Toxinas Marinas/toxicidad , Venenos de Moluscos , Oxocinas/farmacología , Transducción de Señal/efectos de los fármacos
3.
Environ Sci Technol ; 53(18): 10803-10812, 2019 Sep 17.
Artículo en Inglés | MEDLINE | ID: mdl-31378062

RESUMEN

Hydrophilic divinylbenzene (DVB) (Bakerbond) has surfaced as a promising sorbent for active sampling of analytes from aqueous matrices over a very broad polarity range. Given this, hydrophilic DVB may likewise offer potential for passive sampling, if sorbent/water partitioning coefficients (Ksw) were to be available. In this work, static exposure batch experiments were performed to quantitatively study the equilibrium sorption of 131 environmentally relevant organic contaminants (P values ranging from -1.30 to 9.85) on hydrophilic DVB. The superior affinity of hydrophilic DVB, as compared to Oasis HLB, for compounds with a broad polarity range was confirmed by functional Fourier-transform infrared spectroscopy and Raman characterization, demonstrating the presence of carboxyl moieties. Concentration effects were studied by increasing compound concentrations in mixture experiments and resulted in the steroidal endocrine disrupting compounds in higher Ksw, while lower Ksw were obtained for the (alkyl)phenols, personal care products, pesticides, pharmaceuticals, and phthalates. Nevertheless, Ksw remained constant in the said design for equilibrium water concentrations at environmentally relevant seawater levels. An independent analysis of thermodynamic parameters (change in enthalpy, entropy, and Gibbs free energy) revealed the nature of the main partitioning processes. While polar (log P < 4) compounds were mainly served by physisorption, nonpolar (log P > 4) compounds also exhibited binding by multiple hydrogen bonding. In conclusion, this research facilitates the future application of hydrophilic DVB for active as well as passive sampling in the analysis of organic contaminants for monitoring purposes and for toxicity testing.


Asunto(s)
Plaguicidas , Contaminantes Químicos del Agua , Interacciones Hidrofóbicas e Hidrofílicas , Compuestos de Vinilo
4.
J Chromatogr A ; 1714: 464539, 2024 Jan 11.
Artículo en Inglés | MEDLINE | ID: mdl-38091713

RESUMEN

With the recent development of small particle stationary-phases and dedicated instrumentation, the combination of size-exclusion chromatography (SEC) with ultra-high performance liquid chromatography (UHPLC) technology has been realized. It opened up a new polymer analysis technique called UHP-SEC. Although high resolution and fast analysis can be achieved, the multi-solvent suitability for a given column was limited to either organic or aqueous eluents. In this work, the capability of novel SEC columns (AdvanceBio SEC columns) packed with 1.9 µm particles for the characterization of synthetic polymers in organic solvents as well as the multi-solvent compatibility for organic and aqueous eluents have been demonstrated. About six times faster separation for both polystyrene (PS) and polyethylene glycol (PEG) with good peak shape and repeatability were achieved in comparison with standard SEC columns at comparable resolution. Especially for PEG, in contrast to other SEC columns, this column could provide close-to-accurate determination of molecular weights with tetrahydrofuran (THF) as mobile phase. Good reproducibility was obtained after switching several times from water to THF and vice versa with RSD% in retention times less than 0.5 %. Different samples such as polyols, isocyanates and additives can also be analyzed for molecular weight and distribution or composition determination. Volume overload, especially with injection volumes higher than 10 µL needs to be considered. This new column offers a powerful choice for oligomer and polymer analysis with both aqueous and organic mobile phase. Ultimately, hyphenating SEC columns to various detectors can enable more information regarding chemical composition, molecular weight, concentration, and structure.


Asunto(s)
Polímeros , Agua , Solventes/química , Reproducibilidad de los Resultados , Polímeros/química , Agua/química , Polietilenglicoles , Cromatografía en Gel , Cromatografía Líquida de Alta Presión/métodos
5.
Sci Total Environ ; 777: 146055, 2021 Jul 10.
Artículo en Inglés | MEDLINE | ID: mdl-33684757

RESUMEN

A promising concept for sampling contaminants of emerging concern (CECs) using a home-made Simple Teabag Equilibrium Passive Sampler (STEPS) containing hydrophilic divinylbenzene (h-DVB) sorbent is presented and evaluated for application in estuarine systems. The uptake of a multi-class mixture of CECs with a broad polarity range (Log P ranging from -0.1 to 9.9) was investigated in static exposure batch experiments. Sampling rates (Rs) and equilibrium partitioning coefficients (Ksw) were determined for up to 74 CECs. Fast uptake (Rs = 0.3-12 L d-1) was noticed and the STEPS attained equilibrium partitioning after 1 to 2 weeks of exposure, with Log Ksw ranging from 4.1 to 6.5 L kg-1. Field application of this novel h-DVB containing STEPS, followed by ultra-high performance liquid chromatography coupled to high-resolution Orbitrap mass spectrometry, revealed the presence of up to 40 steroidal hormones, (alkyl)phenols, phthalates, pharmaceuticals, personal care products, and pesticides in the Belgian Part of the North Sea. The measured trace concentrations (from 0.003 ng L-1 to 1.9 µg L-1) and good precision (average RSD < 30%, n = 3) demonstrate the STEPS as fit-for-purpose for micropollutant analysis in the marine environment.

6.
Anal Chim Acta ; 1108: 79-88, 2020 Apr 29.
Artículo en Inglés | MEDLINE | ID: mdl-32222247

RESUMEN

Faecal metabolomics markedly emerged in clinical as well as analytical chemistry through the unveiling of aberrations in metabolic signatures as reflection of variance in gut (patho)physiology and beyond. Logistic hurdles, however, hinder the analysis of stool samples immediately following collection, inferring the need of biobanking. Yet, the optimum way of storing stool material remains to be determined, in order to conserve an accurate snapshot of the metabolome and circumvent artifacts regarding the disease and parameter(s) under observation. To address this problem, this study scrutinised the impact of freeze-thaw cycling, storage duration, temperature and aerobicity, thereby using ultra-high performance liquid chromatography-high-resolution mass spectrometry (UPLC-HRMS)-based polar metabolomics and lipidomics methodologies for faecal metabolomics. Both targeted (n > 400) and untargeted approaches were implemented to assess storage effects on individual chemical classes of metabolites as well as the faecal fingerprint. In general, recommendations are that intact stool samples should be divided into aliquots, lyophilised and stored at -80 °C for a period no longer than 18 weeks, and avoiding any freeze-thawing. The first preservation week exerted the most decisive impact regarding storage temperature, i.e. 12.1% and 6.4% of the polar metabolome experienced a shift at -20 °C and at -80 °C, respectively, whereas 8.6% and 7.9% was observed to be changed significantly for the lipidome. In addition, aside from the negligible impact of aerobicity, the polar metabolome appeared to be more dependent on the storage conditions applied compared to the lipidome, which emerged as the more stable fraction when assessing the storage duration for 25 weeks. If the interest would greatly align with particular chemical classes, such as branched-chain amino acids or short-chain fatty acids, specific storage duration recommendations are reported. The provided insights on the stability of the faecal metabolome may contribute to a more reasoned design of experiments in biomarker detection or pathway elucidation within the field of faecal metabolomics.


Asunto(s)
Heces/química , Metaboloma , Manejo de Especímenes , Frío , Liofilización , Humanos , Lipidómica/métodos , Espectrometría de Masas , Metabolómica/métodos
7.
Mar Pollut Bull ; 142: 350-360, 2019 May.
Artículo en Inglés | MEDLINE | ID: mdl-31232313

RESUMEN

Knowledge about the occurrence of emerging organic micropollutants in the marine environment is still very limited, especially when focusing on the Belgian Part of the North Sea (BPNS). This study therefore optimized and validated a Speedisk® based SPE and LC-Q-Orbitrap HRMS method to tackle the challenge of measuring the expected ultra-trace concentrations in seawater. This method was applied to 18 samples collected at different locations in the open sea and harbor of the BPNS. Forty-eight compounds, among which several pharmaceuticals, personal care products or pesticides described in the EU Watchlist, were detected - some for the first time in seawater - at concentrations ranging up to 156 ng L-1. Moreover, the untargeted screening potential of the newly developed HRMS method was highlighted by revealing the presence of up to 1300 unknown components in a single sample and by assigning molecular formulae to those components demonstrating high discriminative potential between samples.


Asunto(s)
Monitoreo del Ambiente/métodos , Espectrometría de Masas/métodos , Extracción en Fase Sólida/métodos , Contaminantes Químicos del Agua/análisis , Bélgica , Cromatografía Líquida de Alta Presión/métodos , Cosméticos/análisis , Mar del Norte , Plaguicidas/análisis , Preparaciones Farmacéuticas/análisis , Reproducibilidad de los Resultados , Agua de Mar/química
8.
Environ Toxicol Chem ; 38(6): 1313-1322, 2019 06.
Artículo en Inglés | MEDLINE | ID: mdl-30924961

RESUMEN

To estimate mixture effects caused by the high number of chemicals simultaneously present in the environment, methods for routine effect assessment of environmentally realistic contaminant mixtures are needed. We repeatedly exposed the marine diatom Phaeodactylum tricornutum to SpeediskTM passive sampler extracts and observed statistically significant growth stimulation up to 6 and 7% for samples from inside and outside the harbor of Zeebrugge, respectively. These effects were found at summed contaminant concentrations (159-166 ng L-1 ) that were within a 1.1- to 2.4-fold range of those observed in grab water samples taken during sampler deployment. These stimulatory effects were confirmed in 2 independent tests with extracts stored for <1 or 8 mo that had undergone limited sample handling, whereas no effects were observed for extracts that had been stored for 16 mo that had undergone repeated handling (notably repeated freezing and thawing) before biotest spiking. Targeted analysis by ultra-high performance liquid chromatography was performed to quantify 88 personal care products (n = 8), pesticides (n = 28), and pharmaceuticals (n = 52). Among these compounds, multivariate statistical analysis put forward the ß-blocker atenolol as explaining most of the observed variation in mixture composition between the growth-stimulating and no effect-causing extracts. However, when tested individually over the entire concentration range present in the extracts, atenolol did not have any effect on P. tricornutum, suggesting that nontargeted substances in the extracts may have contributed to the observed stimulatory effects. Nevertheless, the present study shows that exposure to contaminant mixtures at environmentally realistic concentrations can lead to small but significant growth stimulation effects on the marine diatom P. tricornutum. Environ Toxicol Chem 2019;38:1313-1322. © 2019 SETAC.


Asunto(s)
Organismos Acuáticos/crecimiento & desarrollo , Diatomeas/crecimiento & desarrollo , Contaminantes Químicos del Agua/toxicidad , Organismos Acuáticos/efectos de los fármacos , Diatomeas/efectos de los fármacos , Análisis Discriminante , Ecotoxicología , Monitoreo del Ambiente , Análisis de los Mínimos Cuadrados , Análisis Multivariante , Análisis de Componente Principal
9.
Food Chem ; 293: 187-196, 2019 Sep 30.
Artículo en Inglés | MEDLINE | ID: mdl-31151600

RESUMEN

A generic extraction and UHPLC-Q-Orbitrap™-HRMS method was developed for four insect species (mealworm, grasshopper, house cricket and black soldier fly) analyzing a large spectrum of organic chemical contaminants, including pesticides (n = 25), (veterinary) drugs (n = 29), and mycotoxins (n = 23). To prove the method as 'fit-for-purpose', a successful validation was performed, both qualitatively, by determining the screening detection limit (SDL), selectivity and specificity, as well as semi-quantitatively, by assessing the within-day precision (relative standard deviation (RSD)) and recovery. For both the mealworm, grasshopper, house cricket and black soldier fly, 64, 61, 59 and 62 compounds were detected at the respective SDL levels (1-100 µg kg-1), predominantly below existing maximum residue limits for other edible matrices. Mean recoveries ranged between 70% and 120% and RSD-values were in line with European regulations (CD 2002/657/EC; SANCO). Finally, the potential of the screening methodology was demonstrated on real insect samples, revealing minor to no contamination.


Asunto(s)
Cromatografía Líquida de Alta Presión/métodos , Insectos/química , Espectrometría de Masas/métodos , Micotoxinas/análisis , Plaguicidas/análisis , Drogas Veterinarias/análisis , Animales , Inocuidad de los Alimentos , Insectos/metabolismo , Límite de Detección , Micotoxinas/aislamiento & purificación , Plaguicidas/aislamiento & purificación , Extracción en Fase Sólida , Drogas Veterinarias/aislamiento & purificación
10.
Water Res ; 150: 349-357, 2019 03 01.
Artículo en Inglés | MEDLINE | ID: mdl-30530129

RESUMEN

Ammonia recovery from urine avoids the need for nitrogen removal through nitrification/denitrification and re-synthesis of ammonia (NH3) via the Haber-Bosch process. Previously, we coupled an alkalifying electrochemical cell to a stripping column, and achieved competitive nitrogen removal and energy efficiencies using only electricity as input, compared to other technologies such as conventional column stripping with air. Direct liquid-liquid extraction with a hydrophobic gas membrane could be an alternative to increase nitrogen recovery from urine into the absorbent while minimizing energy requirements, as well as ensuring microbial and micropollutant retention. Here we compared a column with a membrane stripping reactor, each coupled to an electrochemical cell, fed with source-separated urine and operated at 20 A m-2. Both systems achieved similar nitrogen removal rates, 0.34 ±â€¯0.21 and 0.35 ±â€¯0.08 mol N L-1 d-1, and removal efficiencies, 45.1 ±â€¯18.4 and 49.0 ±â€¯9.3%, for the column and membrane reactor, respectively. The membrane reactor improved nitrogen recovery to 0.27 ±â€¯0.09 mol N L-1 d-1 (38.7 ±â€¯13.5%) while lowering the operational (electrochemical and pumping) energy to 6.5 kWhe kg N-1 recovered, compared to the column reactor, which reached 0.15 ±â€¯0.06 mol N L-1 d-1 (17.2 ±â€¯8.1%) at 13.8 kWhe kg N-1. Increased cell concentrations of an autofluorescent E. coli MG1655 + prpsM spiked in the urine influent were observed in the absorbent of the column stripping reactor after 24 h, but not for the membrane stripping reactor. None of six selected micropollutants spiked in the urine were found in the absorbent of both technologies. Overall, the membrane stripping reactor is preferred as it improved nitrogen recovery with less energy input and generated an E. coli- and micropollutant-free product for potential safe reuse. Nitrogen removal rate and efficiency can be further optimized by increasing the NH3 vapor pressure gradient and/or membrane surface area.


Asunto(s)
Amoníaco , Escherichia coli , Reactores Biológicos , Desnitrificación , Nitrificación , Nitrógeno
11.
Anal Chim Acta ; 1049: 141-151, 2019 Feb 21.
Artículo en Inglés | MEDLINE | ID: mdl-30612645

RESUMEN

Plasticizers and other plastics additives have been extensively used as ingredients of plastics and are as a result thereof easily released in the aquatic environment, due to different physical diffusion processes. In this context, a dedicated method was developed for the simultaneous quantification of 27 known and a virtually unlimited number of unknown alkylphenols, Bisphenol A and phthalates in 2 aquatic matrices, i.e. sea- and freshwater. To this extent, a novel instrumental HESI-UHPLC-HRMS (heated electro-spray ionization ultra-high performance liquid chromatographic high resolution mass spectrometric) method was devised for the simultaneous analysis of 7 phenols (i.e. 6 alkylphenols and Bisphenol A) and 20 phthalates within 10 min. Thereafter, a solid-phase extraction protocol was statistically (95% confidence interval, p > 0.05) optimized based on experimental designs. The method was proven fit-for-purpose through a successful validation at environmentally relevant nanomolar concentrations. Analytical precautions were taken for minimizing false-positive results to suppress in-house contamination. The method demonstrated an excellent analytical performance across all known plasticizers and plastics additives for sea- and freshwater, revealing good linearity (R2 > 0.99, n = 39), stable recoveries (98.5-105.8%), satisfactory repeatability (RSD < 8%, n = 54) and reproducibility (RSD < 10%, n = 36). Subsequently, a novel analytical strategy was devised for the tentative identification of unknown plasticizers and plastics additives using specific in-house determined fragments incorporated in a Python code. The applicability of the analytical platform was demonstrated by measuring 24 seawater samples. Interestingly, 16 out of 27 known plasticizers, plastics additives and primary metabolites could be quantified while the untargeted analysis uncovered 1042 compounds, whereof 5% (n = 46) could be assigned a plasticizer-plastics additive chemical identity, providing evidence for the severe plastic contamination status of our marine environment.

12.
Anal Chim Acta ; 1033: 108-118, 2018 Nov 29.
Artículo en Inglés | MEDLINE | ID: mdl-30172316

RESUMEN

In recent years, metabolomics has surfaced as an innovative research strategy in human metabolism, whereby selection of the biological matrix and its inherent metabolome is of crucial importance. However, focusing on a single matrix may imply that relevant molecules of complementary physiological pathways, covered by other matrices, are missed. To address this problem, this study presents a unique multi-matrix platform for polar metabolic fingerprinting of feces, plasma and urine, applying ultra-high performance liquid-chromatography coupled to hybrid quadrupole-Orbitrap high-resolution mass spectrometry, that is able to achieve a significantly higher coverage of the system's metabolome and reveal more significant results and interesting correlations in comparison with single-matrix analyses. All three fingerprinting approaches were proven 'fit-for-purpose' through extensive validation in which a number of endogenous metabolites were measured in representative quality control samples. For targeted and untargeted validation of all three matrices, excellent linearity (coefficients of determination R2 ≥ 0.99 or 0.90 respectively), recovery and precision (coefficients of variance ≤ 15% or 30% respectively) were observed. The potential of the platform was demonstrated by subjecting fecal, urine and plasma samples (collected within one day) from ten healthy volunteers to metabolic fingerprinting, yielding respectively 9 672, 9 647, and 6122 components. Orthogonal partial least-squares discriminant analysis provided similar results for feces and plasma to discriminate according to gender (p-value, R2(X), R2(Y) and Q2(Y)), suggesting feces as an excellent alternative biofluid to plasma. Moreover, combining the different matrices improved the model's predictivity, indicating the superiority of multi-matrix platforms for research purposes in biomarker detection or pathway elucidation and in the selection of the most optimal matrix for future clinical purposes.


Asunto(s)
Heces/química , Metabolómica , Cromatografía Líquida de Alta Presión , Análisis Discriminante , Voluntarios Sanos , Humanos , Espectrometría de Masas
13.
Anal Chim Acta ; 984: 140-150, 2017 Sep 01.
Artículo en Inglés | MEDLINE | ID: mdl-28843557

RESUMEN

The lack of adequate strategies for monitoring endocrine disrupting compounds (EDCs) in the aquatic environment is emphasized in the European Water Framework Directive. In this context, a new UHPLC-HR-Q-Orbirtrap-MS multi-residue method was developed for the simultaneous measurement of 70 steroidal EDCs in two aquatic matrices, i.e. sea and fresh water. First, an instrumental APCI-UHPLC-HR-Q-Orbitrap-MS was devised for separating and detecting the EDC isomers and mass analogues, within 12.5 min per run. Next, an appropriate extraction was statistically optimised using a three-strep workflow (95% confidence interval, p > 0.05); including fractional factorial resolution IV, simplex lattice, and response surface methodological designs. The fitness-for-purpose of the method was demonstrated through successful validation at relevant environmental concentrations, i.e. the low nano- and picogram range. Method quantification limits ranged for the androgens (n = 33), oestrogens (n = 14), progestins (n = 12), and corticosteroids (n = 11) between, respectively, 0.13 and 5.00 ng L-1, 0.25 and 5.00 ng L-1, 0.13 and 2.50 ng L-1, and 0.50 and 5.00 ng L-1. Good linearity (R2 ≥ 0.99) and no lack of fit was observed (95% confidence interval, p > 0.05) for the 70 steroidal EDCs. In addition, good recovery (95-109%) and satisfactory repeatability (RSD < 8.5%, n = 18) and reproducibility (RSD < 10.5%, n = 12) were obtained. Finally, the applicability of the multi-residue method was demonstrated by measuring steroidal EDC in 28 sea water samples collected from four different locations during fall 2016 and winter 2017. Regarding the sea water samples, all the classes were ubiquitously present and included different metabolites, transformation product and or degradation products from the parent EDCs (n = 43).


Asunto(s)
Cromatografía Líquida de Alta Presión , Disruptores Endocrinos/análisis , Monitoreo del Ambiente , Espectrometría de Masas , Contaminantes Químicos del Agua/análisis , Reproducibilidad de los Resultados
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