Characterization of PCDD/F and dl-PCB levels in air in Gipuzkoa (Basque Country, Spain).

This research examines the levels and trends of pollutants, specifically 17 congeners of PCDD/Fs and 12 dl-PCBs, in the air measured in the province of Gipuzkoa (Basque Country, Spain). The study used PCDD/Fs, dl-PCB, and the sum of dioxin-like compounds as separate response variables. A total of 113 air samples were collected and analyzed using the method described in the European Standard (EN-1948:2006) from two industrial areas. The results were analyzed using non-parametric test to assess the variability of these pollutants based on different factors (year, season and day of the week) and General Linear Models to assess the weight of each factor. The study found that the toxic equivalents (TEQs) for PCDD/Fs were 12.29 fg TEQm-3 and for dl-PCBs were 1.63 fg TEQm-3, which were in a similar range or lower than those observed in other national and international studies in industrial areas. The results showed temporal variations, with higher levels of PCDD/Fs in autumn-winter than in spring-summer and higher levels of PCDD/Fs and dl-PCBs during weekdays than on weekends. The industrial area where the energy recovery plant (ERP) will be located had higher levels of air pollutants due to the presence of two PCDD/Fs emitting industries nearby, as indicated by the Spanish Registry of Polluting Emission Sources. Both industrial areas showed similar profiles of PCDD/Fs and dl-PCBs, with the PCDD/F profiles dominated by OCDD, 1,2,3,4,6,7,8-HpCDD, and 1,2,3,4,6,7,8-HpCDF in terms of concentrations and 1,2,3,7,8-PeCDD, 2,3,4,7,8-PeCDF, and 2,3,7,8-TCDD in terms of TEQs. The dl-PCB profiles were dominated by PCB 118, PCB 105, and PCB 77 in terms of concentrations and PCB 126 in terms of TEQs. The findings of this study can serve as an indicator of the potential impact of ERP on the health of the resident population and the environment.

Serum levels of PCDDs, PCDFs and dl-PCBs in general population residing far and near from an urban waste treatment plant under construction in Gipuzkoa, Basque Country (Spain).

This research focused on investigating the basal serum concentrations of polychlorinated dibenzo-p-dioxins, dibenzofurans (PCDD/Fs) and dioxin-like polychlorinated biphenyls (dl-PCBs) in the general population residing in two urban-industrial zones near and far from an energy recovery plant under construction in Gipuzkoa, Basque Country (Spain). The study used a cross-sectional design and included 227 participants who were randomly selected from municipal censuses in both areas. The participants were stratified based on age (ranging from 18 to 70 years) and sex. Serum samples were collected from the participants and analysed following the established protocol to measure the concentrations of PCDD/Fs and dl-PCBs. The study used multiple linear regression models to assess the impact of various sociodemographic variables, lifestyle factors, reproductive history, and diet on the variability of the measured compounds in the participants' serum. The median total toxicity equivalent (TEQ) in serum, was 10.58 pg WHO-TEQ2005 g-1 lipid. Serum PCDD levels were lower in the population residing in the "far" zone than the "near" zone. Age was positively associated with both PCDD/F and dl-PCB levels, indicating that older participants had higher concentrations of these compounds in their serum. This finding might be attributed to cumulative exposure over time. In terms of sex differences, women exhibited lower levels of dl-PCBs compared to men. Among lifestyle factors, smokers showed lower levels of dl-PCBs compared to non-smokers. Furthermore, daily alcohol consumption was significantly associated with higher serum levels of these compounds, with daily drinkers showing higher levels than non-drinkers. Consumption of local poultry was associated with significantly higher serum levels and oil consumption with low levels of PCDD/Fs.

Assessment of Micro- and Nanoplastic Composition (Polymers and Additives) in the Gastrointestinal Tracts of Ebro River Fishes.

One of the main routes of fish exposure to micro- and nanoplastics (MNPLs) is their ingestion. MNPLs can act as reservoirs of organic contaminants that are adsorbed onto their surfaces, or that can leach from their complex formulations, with potential impacts on biota and along the aquatic food chain. While MNPLs have been reported in fishes worldwide, complete information on MNPL compositions, polymers and additives continues to be scarce. In this work, the presence of MNPLs in the gastrointestinal tracts (GIT) of fish from the Ebro River (Spain) was investigated using a double suspected screening approach to assess and quantify polymers and additives. The sample-preparation procedure consisted of sequential alkaline and acidic digestions with KOH and HNO3, followed by ultrasonic-assisted extraction (USAE) with toluene. The analysis of polymers was carried out with size-exclusion chromatography followed by high-resolution mass spectrometry using an atmospheric pressure photoionization source, operating in negative and positive ionisation modes (SEC-(±)-APPI-HRMS) using full-scan acquisition (FS). Plastic additives were assessed using high-performance liquid chromatography with a C18 analytical column coupled to HRMS equipped with an electrospray ionisation source operating under positive and negative conditions (LC-(±ESI)-HRMS). The acquisition was performed in parallel with full-scan (FS) and data-dependent scan (ddMS2) modes, working under positive and negative ionisation modes. The polymers most frequently detected and quantified in fish GITs were polysiloxanes, polyethylene (PE), polypropylene (PP) and polystyrene (PS). PE was detected in 84% of the samples, with a concentration range from 0.55 to 3545 µg/g. On the other hand, plasticisers such as phthalates and stabilisers such as benzotriazoles were the most frequently identified plastic additives.

Occurrence of Cerium-, Titanium-, and Silver-Bearing Nanoparticles in the Besòs and Ebro Rivers.

The presence of anthropogenic nanoparticles (NPs) in the aquatic environment has become an emerging concern in terms of environmental and health safety. In the present study, we assessed the presence of Ag-bearing, Ti-bearing, and Ce-bearing NPs in the Barcelona catchment area, including the Besòs River basin and the Barcelona coast, and in the Ebro River Delta, using single particle inductively coupled plasma mass spectrometry (sp-ICP-MS). Ti-NPs and Ce-NPs were ubiquitously detected in surface waters, and their presence was related to a high natural background. Concentrations of Ti-NPs ranged from 23.2 × 106 to 298 × 106 Ti-NPs/L, with high concentrations being detected in areas with little anthropogenic pressure, while the presence of nanosilver (17.9 × 106 to 45.1 × 106 Ag-NPs/L) in the analyzed rivers was limited to certain hotspots close to wastewater treatment plants discharge points. The concentrations of Ce-NPs in the river ranged from 18.1 × 106 to 278 × 106 NPs/L, and they were related to the natural occurrence of the mineral Monazite-(Ce). Overall, the concentrations of these nanomaterials in the Barcelonan coast were significantly attenuated by river-sea environmental dilution. Nevertheless, Ce-NPs were eventually detected in some seawater samples with low levels of lanthanum-NPs, suggesting anthropogenic inputs of nanoCeO2, probably from atmospheric deposition.

Bioconcentration and bioaccumulation of C60 fullerene and C60 epoxide in biofilms and freshwater snails (Radix sp.).

Fullerenes are carbon nanomaterials that have awaken a strong interest due to their adsorption properties and potential applications in many fields. However, there are some gaps of information about their effects and bioconcentration potential in the aquatic biota. In the present work, freshwater biofilms and snails (Radix sp.) were exposed to fullerene C60 aggregates, at concentrations in the low µg/L order, in mesocosms specifically designed to mimic the conditions of a natural stream. The bioconcentration factors of C60 fullerene and its main transformation product, [6,6]C60O epoxide, were studied to the mentioned organisms employing analyses by liquid chromatography coupled to high-resolution mass spectrometry. Our results show that C60 fullerene and its [6,6]C60O present a low bioconcentration factor (BCF) to biofilms: BCFC60 = 1.34 ±â€¯0.95 L/kgdw and BCFC60O = 1.43 ±â€¯0.72 L/kgdw. This suggests that the sorption of these aggregates to biota may be less favoured than it would be suggested by its hydrophobic character. According to our model, the surface of fullerene aggregates is saturated with [6,6]C60O molecules, which exposes the polar epoxide moieties in the surface of the aggregates and decreases their affinity to biofilms. In contrast, freshwater snails showed a moderate capacity to actively retain C60 fullerenes in their organism (BAFC60 = 2670 ±â€¯3070 L/kgdw; BAFC60O = 1330 ±â€¯1680 L/kgdw), probably through ingestion. Our results indicate that the bioaccumulation of these carbon nanomaterials can be hardly estimated using their respective octanol-water partition coefficients, and that their colloidal properties, as well as the feeding strategies of the tested organism, play fundamental roles.

Metabolic Responses of Mytilus galloprovincialis to Fullerenes in Mesocosm Exposure Experiments.

In this study, Mediterranean mussels (Mytilus galloprovincialis) were exposed through the diet to fullerene soot at three concentrations in parallel to a control group. Their metabolomics response was assessed by high-performance liquid chromatography coupled to high-resolution mass spectrometry (HPLC-HRMS). The experiments were conducted in marine mesocosms, during 35 days (7 days of acclimatization, 21 days of exposure, and 7 days of depuration). Real conditions were emulated in terms of physicochemical conditions of the habitat. Results confirmed the bioaccumulation of fullerenes, and the metabolome of the exposed organisms revealed significant differences in the concentrations of seven free amino acids in comparison to the control group. An increase in small nonpolar amino acids (e.g., alanine) and branched chain amino acids (leucine and isoleucine) were observed. Also, glutamine concentrations decreased significantly, suggesting the activation of facultative anaerobic energy metabolism. Branched chain amino acids, such as leucine and isoleucine, followed the opposite trend after the highest level of exposure, which can imply hormesis effects. Other significant differences were observed on lipids content, such as the general increase of free fatty acids, i.e., long-chain fatty acids (lauric, myristic, and palmitic acids) when the concentration of exposure was increased. These results were consistent with hypoxia and oxidative stress.

Changes in serum dioxin and PCB levels in residents around a municipal waste incinerator in Bilbao, Spain.

There is a great concern in the Basque Country regarding emissions from waste incineration, in particular that of organochlorines (OCs), including dioxins, furans and polychlorinated biphenyls (PCBs), and their potential effect on human health. In 2005, a municipal solid waste plant (MSWP) started to operate in Bilbao, representing an opportunity to assess the exposure to the aforementioned pollutants among people living at various distances from the plant. In 2006 and 2008, we carried out two cross-sectional studies to quantify and assess changes in levels of these pollutants. The objective of this study was to describe the levels of OCs in the blood serum in 2013 of 127 adults of this prospective cohort, in four centres of population, near to and further away from the MSWP, and to study trends over time since it started to operate. This study shows the levels of OCs have decreased significantly, from 37.2% to 80.1%. Further, levels of OCs in areas near to the MSWP were not found to be higher than those in areas further afield.

Meeting the European Commission performance criteria for the use of triple quadrupole GC-MS/MS as a confirmatory method for PCDD/Fs and dl-PCBs in food and feed samples.

Until recently, European Union (EU) legislation required the use of high-resolution gas chromatography coupled to high-resolution mass spectrometry (HRGC-HRMS) based on magnetic sector analyzers as a standard approach for confirmatory analysis of dioxins (PCDDs) and furans (PCDFs) in feed and food. However, recent technological advances in MS instruments enabled other alternative analytical techniques to meet the same analytical criteria as those requested for HRGC-HRMS. In this sense, triple quadrupoles (GC-MS/MS) can be a realistic alternative for the analysis of dioxins. In this work, the performance of GC-MS/MS technology was evaluated against the criteria demanded by the EU for confirmatory analysis of dioxins and PCBs in food and feed. Thus, the study comprises a number of parameters including chromatographic separation, limit of quantification, linearity, repeatability, and ion ratio precision. Analyses of solvent standards as well as sample extracts (inter-calibration extracts and certified reference materials) were also considered within the scope of this study. Additionally, direct comparisons of the results obtained by GC-MS/MS with those from GC-HRMS were made. The results of this work suggested that GC-MS/MS was highly sensitive and selective for confirmatory analysis of PCDD/Fs and related compounds in food and feed samples and meets all the criteria requested by the European Commission.

Potential of gas chromatography-atmospheric pressure chemical ionization-tandem mass spectrometry for screening and quantification of hexabromocyclododecane.

A fast method for the screening and quantification of hexabromocyclododecane (sum of all isomers) by gas chromatography using a triple quadrupole mass spectrometer with atmospheric pressure chemical ionization (GC-APCI-QqQ) is proposed. This novel procedure makes use of the soft atmospheric pressure chemical ionization source, which results in less fragmentation of the analyte than by conventional electron impact (EI) and chemical ionization (CI) sources, favoring the formation of the [M - Br](+) ion and, thus, enhancing sensitivity and selectivity. Detection was based on the consecutive loses of HBr from the [M - Br](+) ion to form the specific [M - H5Br6](+) and [M - H4Br5](+) ions, which were selected as quantitation (Q) and qualification (q) transitions, respectively. Parameters affecting ionization and MS/MS detection were studied. Method performance was also evaluated; calibration curves were found linear from 1 pg/µL to 100 pg/µL for the total HBCD concentration; instrumental detection limit was estimated to be 0.10 pg/µL; repeatability and reproducibility, expressed as relative standard deviation, were better than 7% in both cases. The application to different real samples [polyurethane foam disks (PUFs), food, and marine samples] pointed out a rapid way to identify and allow quantification of this compound together with a number of polybrominated diphenyl ethers (BDE congeners 28, 47, 66, 85, 99, 100, 153, 154, 183, 184, 191, 196, 197, and 209) and two other novel brominated flame retardants [i.e., decabromodiphenyl ethane (DBDPE) and 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE)] because of their presence in the same fraction when performing the usual sample treatment.

Atmospheric-pressure chemical ionization tandem mass spectrometry (APGC/MS/MS) an alternative to high-resolution mass spectrometry (HRGC/HRMS) for the determination of dioxins.

The use of a new atmospheric-pressure chemical ionization source for gas chromatography (APGC) coupled with a tandem quadrupole mass spectrometry (MS/MS) system, as an alternative to high-resolution mass spectrometry (HRMS), for the determination of PCDDs/PCDFs is described. The potential of using atmospheric-pressure chemical ionization (APCI) coupled to a tandem quadrupole analyzer has been validated for the identification and quantification of dioxins and furans in different complex matrices. The main advantage of using the APCI source is the soft ionization at atmospheric pressure, which results in very limited fragmentation. APCI mass spectra are dominated by the molecular ion cluster, in contrast with the high energy ionization process under electron ionization (EI). The use of the molecular ion as the precursor ion in MS/MS enhances selectivity and, consequently, sensitivity by increasing the signal-to-noise ratios (S/N). For standard solutions of 2,3,7,8-TCDD, injections of 10 fg in the splitless mode on 30- or 60-m-length, 0.25 mm inner diameter (id), and 25 µm film thickness low-polarity capillary columns (DB5MS type), signal-to-noise (S/N) ratios of >10:1 were routinely obtained. Linearity was achieved in the region (correlation coefficient of r(2) > 0.998) for calibration curves ranging from 100 fg/µL to 1000 pg/µL. The results from a wide variety of complex samples, including certified and standard reference materials and samples from several QA/QC studies, which were previously analyzed by EI HRGC/HRMS, were compared with the results from the APGC/MS/MS system. Results between instruments showed good agreement both in individual congeners and toxic equivalence factors (TEQs). The data show that the use of APGC in combination with MS/MS for the analysis of dioxins has the same potential, in terms of sensitivity and selectivity, as the traditional HRMS instrumentation used for this analysis. However, the APCI/MS/MS system, as a benchtop system, is much easier to use.

Oceanic Sink and Biogeochemical Controls on the Accumulation of Polychlorinated Dibenzo-p-dioxins, Dibenzofurans, and Biphenyls in Plankton.

Polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs) and dioxin-like polychlorinated biphenyls (dl-PCBs) were measured in plankton samples from the Atlantic, Pacific, and Indian Oceans collected during the Malaspina circumnavigation cruise. The concentrations of PCDD/Fs and dl-PCBs in plankton averaged 14 and 240 pg gdw(-1), respectively, but concentrations were highly variable. The global distribution of PCDD/Fs and dl-PCBs was not driven by proximity to continents but significantly correlated with plankton biomass, with higher plankton phase PCDD/F and dl-PCB concentrations at lower biomass. These trends are consistent with the interactions between atmospheric deposition, biomass dilution, and settling fluxes of organic matter in the water column (biological pump), as key processes driving POPs plankton phase concentrations in the global oceans. The application of a model of the air-water-plankton diffusive exchange reproduces in part the influence of biomass on plankton phase concentrations and suggests future modeling priorities. The estimated oceanic sink (Atlantic, Pacific, and Indian Oceans) due to settling fluxes of organic matter bound PCDD/Fs and dl-PCBs is of 400 and 10,500 kg y(-1), respectively. The atmospheric inputs due to gross diffusive absorption and dry deposition are nearly 3 and 10 times larger for PCDD/Fs and dl-PCBs, respectively, than the oceanic sink. These observations suggest that the coupling of atmospheric deposition with water column cycling supports and drives the accumulation of dl-PCBs and PCDD/Fs in plankton from the global oligotrophic oceans.

Background concentrations of polychlorinated dibenzo-p-dioxins, dibenzofurans, and biphenyls in the global oceanic atmosphere.

The remote oceans are among the most pristine environments in the world, away from sources of anthropogenic persistent organic pollutants (POP), but nevertheless recipients of atmospheric deposition of POPs that have undergone long-range atmospheric transport (LRAT). In this work, the background occurrence of gas and aerosol phase polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and dioxin like polychlorinated biphenyls (dl-PCB) is evaluated for the first time in the atmosphere of the tropical and subtropical Atlantic, Pacific, and Indian oceans. Thirty-nine air samples were collected during the eight-month Malaspina circumnavigation cruise onboard the R/V Hespérides. The background levels of dioxins and dl-PCBs remained very low and in many cases very close to or below the limit of detection. Expectedly, the levels of PCBs were higher than dioxins, PCB#118 being the most abundant compound. In the particular case of dioxins, octachlorodibenzo-p-dioxin (OCDD) was the most abundant PCDD/F congener. Distribution of dl-PCB is dominated by the gas phase, while for PCDD/F the aerosol phase concentrations were higher, particularly for the more hydrophobic congeners. The Atlantic Ocean presented on average the highest PCDD/F and dl-PCB concentrations, being lower in the southern hemisphere. The assessment of air mass back trajectories show a clear influence of continental source regions, and lower concentrations when the air mass has an oceanic origin. In addition, the samples affected by an oceanic air mass are characterized by a lower contribution of the less chlorinated dioxins in comparison with the furans, consistent with the reported higher reaction rate constants of dibenzo-p-dioxins with OH radicals than those of dibenzofurans. The total dry atmospheric deposition of aerosol-bound ∑PCDD/F and ∑dl-PCB to the global oceans was estimated to be 354 and 896 kg/year, respectively.

Preliminary trends over ten years of persistent organic pollutants in air - Comparison of two sets of data in the same countries.

In two series of ambient air measurement campaigns to support the implementation of the global monitoring plan (GMP) component of the Stockholm Convention on Persistent Organic Pollutants (POPs), passive air samplers (PAS) using polyurethane foams were implemented by the United Nations Environment Programme (UNEP). With the same laboratories responsible for the chemical analyses of the different groups of POPs, a total of 423 PUFs were analyzed for organochlorine pesticides (OCPs) including hexachlorobenzene (HCB) and polychlorinated biphenyls (PCB); 242 for dioxin-like POPs. For trend analysis, to compare amounts of POPs in the PUFs during the first phase in 2010/2011 and the second phase from 2017 to 2019, only results were assessed that were generated in the same country and for the same POP in both campaigns. Finally, there were 194 PUFs available for OCPs (GMP1 = 67 and GMP2 = 127), 297 for PCB (GMP1 = 103, GMP2 = 194), 158 for polychlorinated dibenzodioxins and polychlorinated dibenzofurans (PCDD, PCDF) (GMP1 = 39, GMP2 = 119), and 153 for dl-PCB (GMP1 = 34, GMP2 = 119). Indicator PCB and dioxin-like POPs were quantified in all countries at all times; decreases of about 30% based on median values were determined. A 50% increase was found for HCB. By scale, DDT remained with the highest values, although more than 60% decrease was found; mainly due to smaller values in the Pacific Islands region. Our assessment showed that on relative scale - per PUF - trend analysis was achieved and that such approach should be undertaken at regular intervals, not necessarily on an annual basis.

Persistent organic pollutants in air from Asia, Africa, Latin America, and the Pacific.

In support of the United Nations Environment Programme (UNEP) global monitoring plan under the Stockholm Convention concentrations of persistent organic pollutants (POPs) were determined during two years in air from 42 countries in Asia, Africa, Latin America, and the Pacific by using polyurethane foams installed in passive samplers. The compounds included were polychlorinated biphenyls (PCBs), organochlorine pesticides (OCPs), polybrominated diphenylethers (PBDEs), one polybrominated biphenyl and hexabromocyclododecane (HBCD) diastereomers. Total-DDT and PCBs were the highest in concentrations in about 50% of the samples, which shows their high persistency. Total DDT in air from the Solomon Islands ranged from 200 to 600 ng/polyurethane foam disk (PUF). However, at most locations, a decreasing trend is observed for PCBs, DDT and most other OCPs. Patterns varied per country with e.g. elevated dieldrin in air from Barbados and chlordane in air from the Philippines. A number of OCPs, such as heptachlor and its epoxides, some other chlordanes, mirex and toxaphene have decreased down to almost undetectable levels. PBB153 was hardly found and penta and octa--mix related PBDEs were also relatively low at most locations. HBCD and the decabromodiphenylether were more prominent at many locations and may even still increase. To draw more holistic conclusions more colder climate countries should be included in this program.

Dioxin-like POPs in national samples from global monitoring plan projects (2017-2019).

The global monitoring plan (GMP) established under the Stockholm Convention on Persistent Organic Pollutants (POPs) had defined ambient air, human milk or blood, and water as core matrices to be analyzed and assessed for spatial and temporal distribution. Within projects coordinated by the United Nations Environment Programme (UNEP), developing countries were offered to have other matrices analyzed for dioxin-like POPs (dl-POPs) in experienced laboratories. Subsequently, 185 samples from 27 countries located in Africa, Asia, and Latin America were collected during 2018-2019 and analyzed for polychlorinated dibenzodioxins (PCDD), dibenzofurans (PCDF), and biphenyls (PCB). Using the WHO2005 toxic equivalency approach (TEQ), the amounts of dl-POPs found were low (<1 pg TEQ/g); however, singular samples had higher values; e.g., egg from Morocco, fish from Argentina or Tunisia; soil and sediment samples. Results showed that the matrix, abiotic or biota, had more impact on the TEQ pattern than the geographic location. Independent of the location and across all samples, dl-PCB in (shell)fish and beef samples had a contribution of 75% to the total TEQ; milk (63%), chicken (52%), and butter (50.2%) more than 50%. Sediment (57% and 32%) and soil (40% and 36%)) samples were dominated by PCDD and PCDF, respectively; therein, dl-PCB had shares of 11% and 24%. Egg samples (N = 27) did not follow the general biota pattern and had 21% of the TEQ from the PCDD, 45% from PCDF, and 34% from dl-PCB; thus, indicating that abiotic matrices such as soil or other material may have an impact.

Time series data (2008-2023) of polychlorinated dibenzo-p-dioxins, dibenzofurans and polychlorinated biphenyls in bivalves from Shellfish Production Areas of the Basque coast (SE Bay of Biscay).

The accumulation of contaminants in aquatic organisms is of concern to human health due to the potential for exposure through the consumption of seafood. This dataset presents the levels of 17 polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), and 12 dioxin-like polychlorinated biphenyls (DL-PCBs) (PCB-81, PCB-77, PCB-126, PCB-169, PCB-123, PCB-118, PCB-114, PCB-105, PCB-167, PCB-156, PCB-157 and PCB-189) in bivalves collected annually between 2008 and 2023 from the four Shellfish Production Areas of the Basque coast (southeastern Bay of Biscay). Additionally, data on 6 non-dioxin like polychlorinated biphenyls (NDL-PCBs) (PCB-28, PCB-52, PCB-101, PCB-153, PCB-138 and PCB-180) is provided for the 2012-2023 time period. Depending on the availability of bivalves at each Shellfish Production Area, different species, such as mussels (Mytilus galloprovincialis) and oysters (Magallana gigas and Ostrea edulis) were used for the evaluation. Bivalve samples were analyzed at the accredited Laboratory of Dioxins of the Institute of Environmental Assessment and Water Research - CSIC in Spain, following standardized methodologies according to the specific requirements established at the corresponding EU Regulation. Concentrations and the World Health Organization-Toxic Equivalents (WHO-TEQ) were calculated. Considering the data from the four Shellfish Production Areas and the study period, WHO-TEQ values ranged from 0.12 to 0.64 pg g-1 wet weight for PCDD/Fs and from 0.45 to 2.23 pg g-1 wet weight for DL-PCBs, whereas concentrations ranged from 7.45 to 51.10 ng g-1 wet weight for NDL-PCBs. This database is useful for (i) assessing the spatial and temporal trends of PCDD/Fs and various PCBs in bivalves from the Basque coast, (ii) determining the relative contribution of different congeners, (iii) comparison with levels for human consumption and environmental quality standards, as well as with levels of other biogeographical areas, and (iv) the management of Shellfish Production Areas on the Basque coast.

Exposure to micro(nano)plastics polymers in water stored in single-use plastic bottles.

Human exposure to micro (nano)plastics (MNPLs) has become a significant concern as a potential health threat. Exposure routes include ingestion, inhalation, and dermal contact, being food and drinking water the primary sources of oral exposure. Here we present the quantification of polymers of MNPLs particles from 700 nm to 20 µm in bottled water commercialised in Spain, including an estimation of the potential risk for daily consumers. We evaluated samples from 20 popular brands in 0.5 and 1.5 L plastic bottles. A double-suspect screening approach developed and validated in our research group for drinking water was adapted for bottled water samples. The identification and quantification of MNPLs-polymers in mass units and the tentative identification of plastic additives (PA) until the second level of confidence was carried out based on high-performance liquid chromatography coupled to high-resolution mass spectrometry (HPLC-HRMS). The results showed the presence of polypropylene (PP), polyethylene (PE) and polypropylene terephthalate (PET) in the samples. Among them, PE was the most frequently detected and quantified polymer (55% of samples) followed by PET which was detected in 33% of the samples and showing the highest concentration (4700 ng L-1). The median value of the sum of polymer concentrations was 359 ng L-1. In addition, 28 plastic additives were detected, where at least one of them was present in 100% of the samples. Stabilizers and plasticisers were the most frequently identified. A prioritisation study was performed using a multi-QSAR modelling software, where bis(2-ethylhexyl) adipate and bis(2-ethylhexyl) phthalate were estimated as the most potentially harmful compounds for human health. Overall, findings suggest that bottled water is a non-negligible route to exposure to MNPLs.

Micro(nano)plastics in the atmosphere of the Atlantic Ocean.

The occurrence, long-range atmospheric transport and deposition of micro and nano plastics (MNPLs) remains un-quantified for the oceanic atmosphereopen ocean. Here we show the characterisation of MNPLs and the aerosol composition (PM10) in a north-south Atlantic transect from Vigo (Spain) to Punta Arenas (Chile). The analytical procedure to assess the composition of MNPLs consisted of a double suspect screening approach of the polymers and additives, the two constituents of plastics. Polymers were analysed by size exclusion chromatography coupled with high-resolution mass spectrometry using an atmospheric pressure photoionization source operated in positive and negative conditions (HPLC(SEC)-APPI(+/-)-HRMS). Plastic additives were screened with high-performance liquid chromatography coupled to high-resolution mass spectrometry using an electrospray ionisation source (HPLC-ESI(+/-)-HRMS). The most common polymers were polyethylene (PE), polypropylene (PP), polyisoprene (PI), and polystyrene (PS), with the highest polymer concentration being 51.7 ng·m-3 of PI. The air mass back trajectories showed the variable influence of oceanic and terrestrial air masses. These differences were reflected in the aerosol composition with different contributions of Saharan dust, sea spray aerosol, organic/elemental carbon, and MNPLs. Results showed that samples largely influenced by sea-spray and air masses originating from coastal South America and the north Atlantic subtropical gyre were more contaminated by MNPLs. Moreover, this information was complemented by the characterisation of the largest particles using scanning electron microscopy (SEM) and µ-Fourier Transform Infrared Spectroscopy (µ-FTIR). This work provides the first field evidence of the long-range transport of MNPLs in most of the Atlantic Ocean, as the result of dynamic coupling between the lower atmosphere and the surface ocean. Sea-spray formation arises as a key driver for the aerosolisation of MNPLs, and atmospheric transport followed by dry deposition may modulate the occurrence of MNPLs in large oceanic regions, issues that will require future research efforts.

NbThermo: a new thermostability database for nanobodies.

We present NbThermo-a first-in-class database that collects melting temperatures (Tm), amino acid sequences and several other categories of useful data for hundreds of nanobodies (Nbs), compiled from an extensive literature search. This so-far unique database currently contains up-to-date, manually curated data for 564 Nbs. It represents a contribution to efforts aimed at developing new algorithms for reliable Tm prediction to assist Nb engineering for a wide range of applications of these unique biomolecules. Nbs from the two most common source organisms-llama and camel-show similar distributions of melting temperatures. A first exploratory research that takes advantage of this large data collection evidences that understanding the structural bases of Nb thermostability is a complex task, since there are no apparent differences in sequence patterns between the frameworks of Nbs with lower and higher melting temperatures, indicating that the highly variable loops play a relevant role in defining Nb thermostability. Database URL https://valdes-tresanco-ms.github.io/NbThermo.

A randomized, double-blind study on the efficacy of oral domperidone versus placebo for reducing SARS-CoV-2 viral load in mild-to-moderate COVID-19 patients in primary health care.

INTRODUCTION: The clinical effect of domperidone against COVID-19 has been investigated in a double-blind phase III clinical trial (EudraCT number 2021-001228-17). Domperidone has shown in vitro antiviral activity against severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) and potential immudolatory properties through the stimulation of prolactin secretion. PATIENTS AND METHODS: The efficacy of oral domperidone plus standard of care (SOC; n = 87) versus placebo plus SOC (n = 86) was evaluated in a 28-day randomized double-blind multicentre study in primary health care centres. A total of 173 outpatients with mild-to-moderate COVID-19 were included. Three daily doses of 10 mg (30 mg/day) of domperidone or placebo were administered for 7 days. Reduction of viral load on day 4 was the primary efficay endpoint. It was estimated in saliva samples by reverse transcription-quantitative polymerase chain reaction (RT-qPCR), as the cycle thresholds detected ORF1ab, N Protein and S Protein genes. RESULTS: A significant reduction in the viral load was observed (p < 0.001) from baseline to days 4, 7 and 14 of the three genes studied with non-significant differences between domperidone and placebo groups. Twenty-three patients (13.3%) experienced adverse events, 14 patients in the domperidone group (16.1%) and 9 patients in the placebo group (10.5%). No patients needed to be hospitalized. CONCLUSION: Results do not prove the use of domperidone as antiviral in patients with COVID-19.

A 28-day double-blind clinical trial was performed to investigate the antiviral effect of domperidone, 30 mg/day for 7 days (n = 87) versus placebo (n = 86) in outpatients with mild-to-moderate COVID-19.The primary efficacy endpoint was the reduction of viral load on day 4 as compared with baseline, estimated as the cycle thresholds to detect ORF1ab, N Protein and S Protein genes by RT-qPCR in saliva samples.The study findings do not prove the use of domperidone as antiviral in patients with COVID-19.