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. The proposed method consists of in-tube extraction dynamic headspace sampling (ITEX-DHS) combined with gas chromatography (GC) and mass spectrometry (MS/MS) determination. RESULTS: Several parameters affecting the ITEX-DHS extraction of 47 additives in plastic samples (including phthalates, bisphenols, adipates, citrates, benzophenones, organophosphorus compounds, among others) were optimised. The use of matrix-matched calibration, together with labelled surrogate standards, minimises matrix effects, resulting in recoveries between 70 and 128%, with good quantitation limits (below 0.1 µg g-1 for most compounds) and precision (<20%). The method proposed can be applied to any type of polymer, but due to the existence of the matrix effect, calibrates with the adequate matrix should be performed for each polymer. SIGNIFICANCE: This method represents an effective improvement compared to previous methods because it is fast, solvent-free, fully automated, and provides reliable quantification of additives in plastic samples.

Source apportionment of PM10 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 PM10 mass concentrations and associated metal(oid)s, δ13C 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 PM10 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). Mean PM10 mass concentration ranged from 37.0 µg m-3 to 45.7 µg m-3 in ITA-2 and MED-2 sites, respectively. Al, Ca, Mg and Na (from 6249 ng m-3 for Mg at MED-1 site to 10,506 ng m-3 for Ca at MED-2 site) were the major elements in PM10 samples, whilst As, Be, Bi, Co, Cs, Li, Ni, Sb, Se, Tl and V were found at trace levels (< 5.4 ng m-3). Benzo[g,h,i] perylene (BghiP), benzo[b + j]fluoranthene (BbjF) and indene(1,2,3-c,d)pyrene (IcdP) were the most profuse PAHs in PM10 samples, with average concentrations of 0.82-0.86, 0.60-0.78 and 0.47-0.58 ng m-3, respectively. Results observed in the four sampling sites showed a similar dispersion pattern of pollutants, with temporal fluctuations which seems to be associated to the meteorology of the valley. A PM source apportionment study were carried out by using the positive matrix factorization (PMF) model, pointing to re-suspended dust, combustion processes, quarry activity and secondary aerosols as PM10 sources in the study area. Among them, combustion was the major PM10 contribution (accounting from 32.1 to 32.9% in ITA-1 and ITA-2, respectively), followed by secondary aerosols (accounting for 13.2% and 23.3% ITA-1 and MED-1, respectively). Finally, a moderate carcinogenic risk was observed for PM10-bound PAHs exposure via inhalation, whereas significant carcinogenic risk was estimated for carcinogenic metal(oid)s exposure in the area during the sampling period.

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. Results show higher adsorption of the selected pollutants for PHB than PA, being PA more affected by the water temperature and the plastic weathering. The highest percentage of adsorption was achieved in most cases at 24 h. In addition, this process was irreversible, as it showed the leaching assays. Besides, this work revealed that plastics mitigate the degradation of α-endosulfan in aquatic media (hydrolysis), showing that plastics can act as inhibitors of degradation of POPs, increasing its persistence in the environment.

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-1 or ng g-1), 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. The ecological risk assessment revealed that in both areas tributyltin, dibutyltin and diethylphthalate pose a significant risk in sediments, whereas in seawater tributyltin in both areas resulted in a high risk.

Inhalation bioaccessibility estimation of polycyclic aromatic hydrocarbons from atmospheric particulate matter (PM10): Influence of PM10 composition and health risk assessment.

Polycyclic aromatic hydrocarbons (PAHs) inhalation bioaccessibility was assessed in 65 atmospheric particulate matter samples (PM10) 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. Accuracy of the bioaccessibility study was assessed by means of a mass balance approaches using a PM10 filter and a certified reference material (ERM-CZ100). High-moderate inhalation bioaccessibilities were found for phenanthrene (Phe), fluoranthene (Ft) and pyrene (Pyr) (average ratios in the 52-65% range); while dibenz (a,h)anthracene (DBahA), indeno (1,2,3-cd)pyrene (IP) and benzo (g,h,i)perylene (BghiP) were observed to be less bioaccessibles (average ratios in the 11-14% range). Relationship between PM10 composition (major ions, trace metals, equivalent black carbon (eBC) and UV-absorbing particulate matter (UVPM)) and PAHs bioaccessibility ratios was also assessed. Principal Component Analysis (PCA) showed that PAHs bioaccessibility percentage is dependent on anthropogenic (eBC, UVPM and Sb concentrations) and marine sources of PM10. Predicted PAHs bioaccessibilities after applying a multiple linear regression model based on marine and anthropogenic source of PM10 could also be established. Health risk assessment of target PM10-associated PAHs via inhalation was assessed considering bioaccessibility concentrations by using hazard index (HI) and BaP equivalent concentration (BaPeq) approaches, suggesting no carcinogenic risk in the area during the sampling campaign.

Identification of contaminants of emerging concern with potential environmental risk in Spanish continental shelf sediments.

The distribution of per- and polyfluoroalkyl substances (PFAS), alkylphenols, organotin compounds, phthalates, alkylated polycyclic aromatic hydrocarbons, current-use pesticides (CUPs) and personal care products (PCPs) was characterized in 29 surface sediments from two Spanish Iberian continental shelf areas (14 on the Atlantic and 15 on the Mediterranean coasts). Concretely, 115 organic contaminants were determined and a specific methodology was used for each contaminant group, including contaminants of emerging concern (CECs) and traditional ones, such as polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs) and organochlorinated pesticides (OCPs). PAHs, alkylated PAHs, alkylphenols and phthalates were found in all samples, showing mean concentrations per group higher than 20 ng/g (16-4974 ng/g d.w.) in the subregions under consideration (Galician, Cantabrian, Levantine-Balearic and Strait-Alboran). CUPs and PCPs were found in the majority of samples at very low concentrations of ng/g (1.4-46.8 ng/g d.w.), whereas organotins and PFAS were found principally in sediments from the Mediterranean subregions (2.5-3.9 ng/g d.w.). Different distribution patterns were observed for the contaminant groups and subregions under consideration as a consequence of the diverse predominant sources (industrial, urban, transport and agricultural activities) and environmental behavior (mainly hydrophobicity and persistence). Risk assessment confirmed the impact of phthalates, alkylphenols, PAHs and PCBs on Atlantic ecosystems and of alkylphenols, chlorpyrifos, phthalates, TBT, PAHs, OCPs and PCBs on the Mediterranean ones. Furthermore, the presence of CUPs, PCPs and PFAS in sediments from the Spanish continental shelf located between 2 and 31 km from the coast suggested that those contaminants may also provoke adverse effects on coastal marine ecosystems between their sources and their depositional areas. CAPSULE: Alkylphenols, phthalates and organotins may provoke adverse effects on Spanish coastal marine ecosystems from their sources to the sediment depositional areas.

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). For MASE, extraction temperature (30 °C), time (90 min) and effect of an organic modifier were also optimized. The matrix effect was evaluated and compensated using deuterated labelled standards as surrogates for the quantitation of the target compounds. The analytical performance of the method was satisfactory: relative recoveries varied between 78 and 118% and repeatability and intermediate precision were <22% for all compounds. The Method Quantitation Limits (MQL) ranged from 0.9 (TPY) to 75.6 pg m-3 (NAP). Satisfactory results for accuracy and traceability were evidenced by the analysis of a reference material (SRM 1649b) and comparison with previously published methods. The greenness score was estimated and compared with other techniques widely used for the analysis of PAHs in particulate matter, having a lower relative environmental impact.

Polyethylene microplastics do not increase bioaccumulation or toxicity of nonylphenol and 4-MBC to marine zooplankton.

Global production of synthetic polymers, led by polyethylene (PE), rose steadily in the last decades, and marine ecosystems are considered as a global sink. Although PE is not biodegradable, in coastal areas it fragments into microplastics (MP) readily taken up by biota, and have been postulated as vectors of hydrophobic chemicals to marine organisms. We have tested this hypothesis using two organisms representative of the marine plankton, the holoplanktonic copepod Acartia clausi, and the meroplanktonic larva of the Paracentrotus lividus sea-urchin, and two model chemicals with similar hydrophobic properties, the 4-n-Nonylphenol and the 4-Methylbenzylidene-camphor used as plastic additive and UV filter in cosmetics. Both test species actively ingested the MP particles. However, the presence of MP never increased the bioaccumulation of neither model chemicals, nor their toxicity to the exposed organisms. Bioaccumulation was a linear function of waterborne chemical disregarding the level of MP. Toxicity, assessed by the threshold (EC10) and median (EC50) effect levels, was either independent of the level of MP or even in some instances significantly decreased in the presence of MPs. These consistent results challenge the assumption that MP act as vectors of hydrophobic chemicals to planktonic marine organisms.

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. The use of LTQ-Orbitrap-HRMS in full mode, quantifying the target analytes using the exact mass, provides a very powerful detection in terms of sensitivity and specificity maintaining all the information provided by the full mass spectra, allowing, also, the identification of non-target substances. The use of matrix-matched calibration, together with labelled surrogate standards, minimize matrix effects and compensate potential recovery losses, resulting in recoveries between 95 and 105%, with excellent sensitivity (quantitation limit between 0.7 and 6 ng L-1) and precision (4-10%). The proposed method requires only 35 mL of sample and 100 µL of extracting solvent, is fast and avoids the use of other solvents to obtain the dispersive cloudy solution, simplifying the procedure and improving the existing procedures for the determination of per- and polyfluoroalkyl substances (PFASs) in seawater in terms of green analytical chemistry. The method was successfully validated by participating in a proficiency test assay provided by the National Measurement Institute of the Australian Government for the determination of PFOA, total PFOS and linear PFOS in waters. A revision of the state of the art in the last twelve years of methods for the analysis of PFASs in seawater and other types of water was performed, and a critical comparison between the developed method and the previously published was included. Finally, the method was applied to the analysis of samples from Ría de Vigo, a sensitive and semiconfined coastal area located in the northwest of Spain. PFOS, N-methyl perfluorooctanesulfonamide (n-MeFOSA) and N-ethyl perfluorooctanesulfonamide (n-EtFOSA) were detected in samples at levels lower than the maximum allowable concentration (MAC) established by Directive 2013/39/EU, but above the annual average (AA) levels.

Evergreen or deciduous trees for capturing PAHs from ambient air? A case study.

Tree canopies play a key role in the cycling of polycyclic aromatic hydrocarbons (PAHs) in terrestrial ecosystems, as leaves can capture PAHs from the air. In this study, accumulation of PAHs was compared in an evergreen species, P. pinaster, and in a deciduous species, Q. robur, in relation to some physio-morphological characteristics. For this purpose, pine needles and oak leaves collected from different sites across Galicia (NW Spain) were analysed to determine PAH contents, specific leaf area, stomatal density and conductance. Leaves and needles contained similar total amounts of PAHs. The major contribution of particle-bound PAHs in oak (the concentrations of 4- and 5-ring PAHs were two times higher, and those of 6-ring PAHs five times higher in oak than in pine) may be related to the higher specific leaf area (13 and 4 cm2 g-1 dry mass in respectively oak and pine). However, the major contribution of vapor-phase PAHs in pines may be affected by the stomatal conductance (two times higher in pine than in oak). Moreover, an increase in the diameter at breast height of trees led to an increase in accumulation of PAHs, with pine capturing higher amounts of low and medium molecular weight PAHs. The study findings underline the potential role of trees in improving air quality, taking into account the canopy biomass and life cycle.

Bioaccumulation of PCB-153 and effects on molecular biomarkers acetylcholinesterase, glutathione-S-transferase and glutathione peroxidase in Mytilus galloprovincialis mussels.

In this study, PCB-153 bioaccumulation kinetics and concentration-response experiments were performed employing wild Mytilus galloprovincialis mussels. In addition, the activity of three enzymatic biomarkers: glutathione S-transferase (GST), glutathione peroxidase (GPx) and acetylcholinesterase (AChE), were measured in the mussel gills. The experimental data fitted well to an asymptotic accumulation model with a high bioconcentration factor (BCF) of 9324 L kg(-1) and a very limited depuration capacity, described by a low excretion rate coefficient (Kd = 0.083 d(-1)). This study reports by first time in mussels significant inhibition of GST activity and significant induction of GPx activity as a result of exposure to dissolved PCB-153. In contrast, AChE activity was unaffected at all concentrations and exposure times tested. The effects on both enzymes are time-dependent, which stresses the difficulties inherent to the use of these biomarkers in chemical pollution monitoring programs.

Matrix solid phase dispersion method for determination of polycyclic aromatic hydrocarbons in moss.

In this work a matrix solid-phase dispersion extraction method, followed by programmed temperature vaporization-gas chromatography-tandem mass spectrometry determination is proposed for the analysis of polycyclic aromatic hydrocarbons (PAHs) in moss samples. A devitalized, cultivated Sphagnum palustre L. moss clone obtained from the "Mossclone" EU-FP7 Project was used for the optimization and validation of the proposed method. Good trueness (84-116%), precision (intermediate precision lower than 11%) and sensitivity (quantitation limits lower than 1.7ngg(-1)) were obtained. The proposed method was compared with other procedures applied for this complex matrix, achieving a considerable reduction of sample amount, solvent volume and time consumption. The procedure was successfully tested for the analysis of PAHs in exposed moss clone samples for the monitoring of air pollution. Finally, the method was also tested for its suitability in the analysis of PAHs in other moss species as well as a lichen species.

Proposal of a procedure for the analysis of atmospheric polycyclic aromatic hydrocarbons in mosses.

A useful analytical procedure for the analysis of 19 polycyclic aromatic hydrocarbons (PAHs) in moss samples using microwave assisted extraction and programmed temperature vaporization-gas chromatography-tandem mass spectrometry (PTV-GC-MS/MS) determination is proposed. The state of art in PAHs analysis in mosses was reviewed. All the steps of the analysis were optimized regarding not only to the analytical parameters, but also the cost, the total time of analysis and the labour. The method was validated for one moss species used as moss monitor in ambient air, obtaining high recoveries (between 83-108%), low quantitation limits (lower than 2 ng g(-1)), good intermediate precision (relative standard deviation lower than 10%), uncertainties lower than 20%. Finally, the method was checked for other species, demonstrating its suitability for the analysis of different moss species. For this reason the proposed method can be helpful in air biomonitoring studies.

Emerging pollutants in sewage, surface and drinking water in Galicia (NW Spain).

A monitoring programme was carried out on wastewater, surface and drinking water on the NW area of Spain during the four seasons of a year period (November 2007-September 2008). This study covered a series of emerging pollutants of different classes, including pharmaceuticals, neutral and acidic organophosphorus flame retardant/plasticizers (OPs), triclosan, phenoxy-herbicides, insect repellents and UV filters. From the total set of 53 compounds, 19 were found in raw wastewater with median concentrations higher than 0.1 µg L(-1). Among them, salicylic acid, ibuprofen and the UV filter benzophenone-4 (BP-4) were the most concentrated, exceeding the 1 µg L(-1) median value. Subsequently, 11 of these contaminants are not efficiently enough removed in the small WWTPs tested and their median concentrations in effluents still surpassed the 0.1 µg L(-1), so that they can spread through surface water. These chemicals are the pharmaceuticals naproxen, diclofenac and atenolol; the OPs tri(2-chloroethyl) phosphate (TCEP), tri(chloropropyl) phosphate (TCPP), tri-n-butyl phosphate (TnBP), diphenyl phosphate (DPhP) and diethylhexyl phosphate (DEHP); and the sulphonate UV filters BP-4 and 2-phenylbenzimidazole-5-sulphonic acid (PBSA). These OPs were then the dominant emerging pollutants occurring in surface and drinking water, where they are detected in the 20-200 ng L(-1) range. Pharmaceuticals and UV filters are typically below the 10 ng L(-1) level. Finally, herbicides were only detected in the last sampling campaign under the 100 ng L(-1) drinking water European Union limit.

A matrix solid-phase dispersion-gel permeation chromatography-programmed temperature vaporisation-GC-MS procedure for the analysis of polycyclic aromatic hydrocarbons in mussel samples.

A simultaneous matrix solid-phase dispersion extraction-gel permeation chromatography cleanup with programmed temperature vaporisation GC-MS determination is proposed for the analysis of parent and alkylated polycyclic aromatic hydrocarbons (PAHs) in mussel samples. The parameters affecting the extraction and elution efficiency were studied. Final conditions were: 0.5 g of mussel sample, 0.5 g diatomaceous earth as dispersant; and 4 g of Bio-Beads S-X3 for the gel permeation chromatography. Ethyl acetate/hexane (1:1, v/v) was selected for the elimination of the lipid fraction and the elution of PAHs. The detection and quantification limits achieved with this procedure were between 0.01 µg/kg and 0.67 µg/kg and 0.02 µg/kg and 1.93 µg/kg, respectively. The linearity of the method ranged between 5 µg/kg and 1000 µg/kg for most of the studied PAHs. The method was validated by the analysis of mussel tissue reference material (SRM 2977). The repeatability, intermediate precision and accuracy of the method obtained are in excellent agreement with the certified values. The proposed method is simple, precise and robust; no special instruments or costly equipment are required, and a reduction in the total time of analysis, sample handling and solvent consumption is achieved in comparison with classic procedures.