Validation of the analytical methodology used in obtaining the oral bioavailability of organic target pollutants in atmospheric particulate matter (PM) applying an in-vitro method.

In recent years, scientists have started evaluating the portion of PM-bound pollutants that may be liberated (bioaccessible fraction) in human fluids and spread through the digestive system ultimately entering systemic circulation (known as the bioavailable fraction). In the current research, an analytical procedure was validated and applied to characterize the oral bioavailable fraction of PM samples. The approach encompassed the determination of 49 organic contaminants.

Oxidative potential of the inhalation bioaccessible fraction of PM and bioaccessible concentrations of polycyclic aromatic hydrocarbons and metal(oid)s in PM.

Atmospheric particulate matter (PM) has been related to numerous adverse health effects in humans. Nowadays, it is believed that one of the possible mechanisms of toxicity could be the oxidative stress, which involves the development of reactive oxygen species (ROS). Different assays have been proposed to characterize oxidative stress, such as dithiothreitol (DTT) and ascorbic acid (AA) acellular assays (OP and OP), as a metric more relevant than PM mass measurement for PM toxicity.

A green approach for the automatic quantitative analysis of additives in plastic samples using in-tube extraction dynamic headspace sampling technique coupled to GC-MS/MS.

Background: Many of the chemicals frequently used as additives have been recognised as hazardous substances, and therefore their analysis is necessary to evaluate plastic contamination risk. Additives analysis in plastic samples is usually performed by methods involving high volumes of toxic solvents or having high detection limits. In this work, a novel, fast, solventless and reliable green method was developed for the automated analysis of plastic additives from plastic samples.

A reliable method to determine airborne microplastics using quantum cascade laser infrared spectrometry.

The number of studies dealing with airborne microplastics (MPs) is increasing but sampling and sample treatment are not standardized, yet. Here, a fast and reliable method to characterize MPs is presented. It involves the study of two passive sampling devices to collect atmospheric bulk deposition (wet and dry deposition) and three digestion methods (two alkaline-oxidative and an oxidative) to treat the samples.

A multi-residue method for the analysis of organic pollutants released from atmospheric PM in simulated biological fluids: Inhalation bioaccessibility and bioavailability estimation.

Background: In recent decades, there has been a growing interest within the scientific community regarding the study of the fraction that could be released in simulated biological fluids to estimate in vitro bioaccessibility and bioavailability of compounds. Concerning particulate matter (PM), studies were essentially focused on metal (oid)s probably due to more complex methodologies needed for organic compounds, requiring extraction and pre-concentration steps from simulated fluids, followed by chromatographic analysis. Thus, the development of a simple and sensitive methodology for the analysis of multi-class organic compounds released in different inhalation simulated fluids would represent a great contribution to the field.

Organotin compounds in seafood by ultrasonic assisted extraction and gas chromatography-triple quadrupole tandem mass spectrometry.

Although restricting environmental quality values for organotin compounds (OTs) are set by Directive 2013/39/EU of the European Parliament, marine environment remains being affected due to maritime circulation at global scale. Fish and seafood accumulate OTs, making fish and seafood consumption the main source of OTs in humans. Because of the fish and seafood matrices complexity and the required low limits of detection, a robust and fast procedure for the quantification of OTs in fish and seafood, using ultrasound-assisted extraction and gas chromatography-tandem mass spectrometry, was validated and applied.

Source apportionment of PM and health risk assessment related in a narrow tropical valley. Study case: Metropolitan area of Aburrá Valley (Colombia).

This study investigates spatio-temporal variations of PM mass concentrations and associated metal(oid)s, δC carbon isotope ratios, polycyclic aromatic hydrocarbons (PAHs), total organic carbon (TOC) and equivalent black carbon (eBC) concentrations over a half year period (from March 2017 to October 2017) in two residential areas of Medellín (MED-1 and MED-2) and Itagüí municipality (ITA-1 and ITA-2) at a tropical narrow valley (Aburrá Valley, Colombia), where few data are available. A total of 104 samples were analysed by using validated analytical methodologies, providing valuable data for PM chemical characterisation. Metal(oid)s concentrations were measured by inductively coupled plasma mass spectrometry (ICP-MS) after acid digestion, and PAHs concentrations were measured by Gas Chromatography-Mass Spectrometry (GC-MS) after Pressurised Hot Water Extraction (PHWE) and Membrane Assisted Solvent Extraction (MASE).

In-vitro inhalation bioavailability estimation of Metal(oid)s in atmospheric particulate matter (PM) using simulated alveolar lysosomal fluid: A dialyzability approach.

A novel in-vitro method, by using synthetic body fluids, human physiological conditions and a simulated air-blood barrier (by using a dialysis membrane) has been developed and applied to assess in-vitro inhalation bioavailability of metal(oid)s associated to particulate matter (PM) samples collected from an industrial site of the Northwest of Spain. A validated analytical methodology based on inductively coupled plasma mass spectrometry (ICP-MS) was used to analyse metal(oid)s concentrations in bioavailable fractions. This approach would be a more realistic human health risk assessment since considering processes that occur in human body in contrast the overestimation derived from current models (which consider environmental concentrations).

Development of an analytical procedure to analyze microplastics in edible macroalgae using an enzymatic-oxidative digestion.

Besides being food and a refuge to marine species, macroalgae are a powerful and renewable economic resource. However, they may introduce microplastics (MPs) in the trophic chain. We developed a reliable analytical method to characterize and quantify MPs in common and edible macroalgae.

Multi-class organic pollutants in atmospheric particulate matter (PM) from a Southwestern Europe industrial area: Levels, sources and human health risk.

The occurrence of 50 multi-class pollutants comprising 18 polycyclic aromatic hydrocarbons (PAHs), 12 phthalate esters (PAEs), 12 organophosphorus flame retardants (OPFRs), 6 synthetic musk compounds (SMCs) and 2 bisphenols was studied in atmospheric particulate matter (PM) samples collected at an industrial area focused on automotive manufacturing located at the Southwestern Atlantic European region (Vigo city, Spain) during 1-year period. Among all quantitated pollutants in PM samples, bisphenol A (BPA) was the most predominant with an average concentration of 6180 pg m, followed by PAHs comprising benzo(b+j)fluoranthene (BbF + BjF) and benzo(g,h,i)perylene (BghiP), accounting for 546 pg m and 413 pg m respectively. In addition, two OPFRs concerning tris(chloropropyl) phosphate (TCPP) and triphenyl phosphine oxide (TPPO) were the next following the concentration order, accounting for 411 pg m and 367 pg m respectively; being butyl benzyl phthalate (BBP) the most profuse PAE (56.

Adsorption of pesticides and personal care products on pristine and weathered microplastics in the marine environment. Comparison between bio-based and conventional plastics.

The hydrophobicity of persistent organic pollutants (POPs) makes them adsorb on microplastics in the marine environment, affecting their distribution, persistence, or their transfer to the trophic chain. Fragrances and non-polar pesticides can be adsorbed by microplastics in the marine environment because of their physico-chemical characteristics. In this work, the adsorption of two pesticides (α-endosulfan and chlorpyrifos) and 6 musk fragrances (musk xylene, musk ketone, musk moskene, galaxolide, tonalide, and celestolide) on polyamide (PA6) (a petroleum based polymer) and on polyhydroxybutyrate (PHB) (biopolymer) in seawater was studied, considering also the effect of water temperature and plastic weathering.

Weathering-independent differentiation of microplastic polymers by reflectance IR spectrometry and pattern recognition.

The presence and effects of microplastics in the environment is being continuously studied, so the need for a reliable approach to ascertain the polymer/s constituting them has increased. To characterize them, infrared (IR) spectrometry is commonly applied, either reflectance or attenuated total reflectance (ATR). A common problem when considering field samples is their weathering and biofouling, which modify their spectra.

Inhalation bioaccessibility of multi-class organic pollutants associated to atmospheric PM: Correlation with PM properties and health risk assessment.

Inhalation exposure to fine particulate matter (PM) represents a global concern due to the adverse effects in human health. In the last years, scientific community has been adopted the assessment of the PM-bound pollutant fraction that could be released (bioaccessible fraction) in simulated lung fluids (SLFs) to achieve a better understanding of PM risk assessment and toxicological studies. Thus, bioaccessibility of 49 organic pollutants, including 18 polycyclic aromatic hydrocarbons (PAHs), 12 phthalate esters (PAEs), 11 organophosphorus flame retardants (OPFRs), 6 synthetic musk compounds (SMCs) and 2 bisphenols in PM samples was evaluated.

A reliable method for the isolation and characterization of microplastics in fish gastrointestinal tracts using an infrared tunable quantum cascade laser system.

Societal and environmental concern due to frequent reports of microplastics in fish stomachs raised as they may accumulate along the trophic chain. The request for analysing microplastics in fish stresses two major analytical issues: sample treatment and final characterization. The, so far, workhorse for chemical characterization is infrared spectroscopy which is time-consuming.

Monitorization of polyamide microplastics weathering using attenuated total reflectance and microreflectance infrared spectrometry.

The EU goal to reduce marine plastic litter by ca. 30% by 2020 stressed the need to deploy analytical methods to ascertain the polymeric nature of a residue. Furthermore, as plastics age under natural conditions and usual databases do not include their weathered spectra, (micro)plastics in environmental samples may be unidentified.

Phthalates, organotin compounds and per-polyfluoroalkyl substances in semiconfined areas of the Spanish coast: Occurrence, sources and risk assessment.

In this work two sensitive areas of the Spanish coast located in the Atlantic (Ria de Vigo) and Mediterranean (Mar Menor lagoon) have been studied regarding their contamination by phthalates, organotin compounds and per-polyfluoroalkyl substances (seawater and sediments) in two different campaigns (spring and autumn in 2015). PFAS and OTCs were detected in seawater and sediments at low concentrations (few ng L or ng g), whereas PAEs were detected at levels two orders of magnitude higher, particularly in Mar Menor lagoon due to its semi-confined characteristics. However, PAEs and OTCs concentration in sediments were higher in Ría de Vigo than in Mar Menor lagoon as a consequence of the influence of the important urban nuclei and port in that area.

Development of a fast and efficient method to analyze microplastics in planktonic samples.

Microplastics (MPs) affect plankton (a basis of the trophic chain) and planktivorous fish can ingest them through food confusion or by trophic transmission. Consensus to determine MPs in plankton is lacking and, so, three digestion treatments were evaluated: Alkaline (potassium hydroxide) and enzymatic (protease plus lipase) digestions, both combined with a hydrogen peroxide stage; and an oxidative method using a surfactant (sodium dodecyl sulfate) plus hydrogen peroxide. The alkaline method using potassium hydroxide was found to damage polystyrene.

The occurrence and distribution of polycyclic aromatic hydrocarbons, bisphenol A and organophosphate flame retardants in indoor dust and soils from public open spaces: Implications for human exposure.

Global concern exists regarding human exposure to organic pollutants derived from public open spaces and indoor dust. This study has evaluated the occurrence of 18 polycyclic aromatic hydrocarbons (PAHs), 11 organophosphorus flame retardants (OPFRs) and bisphenol A (BPA). To achieve this, a new simple, efficient and fast multi-residue analytical method based on a fully automated pressurised liquid extraction (PLE) and subsequent quantification by gas chromatography coupled to electron ionization-mass spectrometry (GC-EI-MS) in selected ion monitoring (SIM) mode was developed.

Inhalation bioaccessibility estimation of polycyclic aromatic hydrocarbons from atmospheric particulate matter (PM): Influence of PM composition and health risk assessment.

Polycyclic aromatic hydrocarbons (PAHs) inhalation bioaccessibility was assessed in 65 atmospheric particulate matter samples (PM) collected at an Atlantic coastal European urban site. The proposed method consists on a physiologically based extraction (PBET) by using Gamble's solution followed by a vortex assisted liquid-liquid micro-extraction (VALLME) and quantification by high performance liquid chromatography with fluorescence detection (HPLC-FLD). The use of a micro-extraction technique combined with FLD detection, provides a simple, fast, sensitive, accurate and low-cost methodology to PAHs quantification in bioaccessible fractions.

Rapid evaluation of ammonium in different rain events minimizing needed volume by a cost-effective and sustainable PDMS supported solid sensor.

The presence of ammonium ion in rainwater is due to atmospheric processes which involve its scavenging from gas phase and particulate matter. The fractionated samplings of rainwater can provide information about these processes and their potential sources. However, only a low sample volume may be available, which constrained the analysis in general and more particularly in situ mode.

Standardization of the minimum information for publication of infrared-related data when microplastics are characterized.

Infrared spectrometry (IR) became a workhorse to characterize microplastics (MPs) worldwide. However, reports on the experimental conditions to measure them decreased alarmingly. As complete, relevant information on the instrumental setup determining IR spectra is crucial for scientific reproducibility, ca.

Determination of atmospheric particle-bound polycyclic aromatic hydrocarbons using subcritical water extraction coupled with membrane microextraction.

A green analytical methodology for the determination of 16 priority polycyclic aromatic hydrocarbons (PAHs) and 8 related compounds in air particulate matter was developed and validated. The method was based on pressurized hot water extraction (PHWE) followed by miniaturized membrane-assisted solvent extraction (MASE) and programmed temperature vaporization-gas chromatography-ion trap tandem mass spectrometry detection (PTV-GC-MS/MS). The parameters studied for PHWE were percentage of organic modifier (25% MeOH), temperature (200 °C) and static extraction time (5 min).

Selenium species determination in foods harvested in Seleniferous soils by HPLC-ICP-MS after enzymatic hydrolysis assisted by pressurization and microwave energy.

Fast, green, automated, highly efficient and accurate methodology for extracting selenium species in foods samples (Brazil nut, golden berries and heart of palm) harvested in seleniferous soils by using pressurized-assisted enzymatic hydrolysis (PAEH) and microwave-assisted enzymatic hydrolysis (MAEH) were optimized. After foods defatting or drying, selenium species were released using protease XIV and enzyme activator in 7 and 12 min for PAEH and MAEHmethods, respectively. Inductively coupled plasma - mass spectrometry (ICP-MS) and high performance liquid chromatography (HPLC) coupled with ICP-MS detection were used to assess total selenium and selenium species contents in the enzymatic extracts.

Fast and sensitive determination of per- and polyfluoroalkyl substances in seawater.

In this work, a novel, fast, and sensitive method was developed for perfluorooctanoic acid (PFOA), perfluorooctane sulfonic acid (PFOS) and PFOS precursor's determination in seawater. The proposed method consists in a vortex-assisted liquid-liquid microextraction (VALLME) combined with liquid chromatography (LC) and LTQ-Orbitrap high resolution mass spectrometry (LTQ-Orbitrap HRMS) determination. Several parameters affecting both the HPLC-LTQ Orbitrap HRMS determination and the VALLME were studied, with special attention to blank contamination problem.