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This work presents an optimized gas chromatography–electron ionization–high-resolution mass spectrometry (GC-EI-HRMS) screening method. Different method parameters affecting data processing with the Agilent Unknowns Analysis SureMass deconvolution software were optimized in order to achieve the best compromise between false positives and false negatives. To this end, an accurate-mass library of 26 model compounds was created. Then, five replicates of mussel extracts were spiked with a mixture of these 26 compounds at two concentration levels (10 and 100 ng/g dry weight in mussel, 50 and 500 ng/mL in extract) and injected in the GC-EI-HRMS system. The results of these experiments showed that accurate mass tolerance and pure weight factor (combination of reverse-forward library search) are the most critical factors. The validation of the developed method afforded screening detection limits in the 2.5–5 ng range for passive sampler extracts and 1–2 ng/g for mussel sample extracts, and limits of quantification in the 0.6–3.2 ng and 0.1–1.8 ng/g range, for the same type of samples, respectively, for 17 model analytes. Once the method was optimized, an accurate-mass HRMS library, containing retention indexes, with ca. 355 spectra of derivatized and non-derivatized compounds was generated. This library (freely available at https://doi.org/10.5281/zenodo.5647960), together with a modified Agilent Pesticides Library of over 800 compounds, was applied to the screening of passive samplers, both of polydimethylsiloxane and polar chemical integrative samplers (POCIS), and mussel samples collected in Galicia (NW Spain), where a total of 75 chemicals could be identified. [ABSTRACT FROM AUTHOR]

BACKGROUND: Newborns in neonatal intensive care units (NICUs) are in contact with a variety of medical products whose production might include synthetic chemicals with hormonal activity. OBJECTIVES: Our aim was to assess the content of bisphenol A (BPA) and parabens (PBs) and the hormone-like activities of a subset of medical products commonly used in NICUs in prolonged intimate contact with NICU newborns. METHODS: Fifty-two NICU items were analyzed, determining the concentrations of BPA and PBs [methyl- (MeP), ethyl- (EtP), propyl- (PrP), and butylparaben (BuP)] and using the E-Screen and PALM-luciferase assays to measure the in vitro (anti-)estrogenic and (anti-)androgenic activity, respectively, of the extracts. Items found to have elevated BPA/PB content or hormone-like activities were further extracted using leaching methodologies. RESULTS: BPA was found in three-fifths and PBs in four-fifths of tested NICU items, and ~25% and ~10% of extracts evidenced estrogenic and anti-androgenic activity, respectively. The highest BPA content was found in the three-way stopcock (>7.000 ng/g), followed by patterned transparent film dressing, gastro-duodenal feeding tubes, sterile gloves, single-lumen umbilical catheters, and intravenous (IV) infusion extension sets (concentrations ranged from 100 to 700 ng/g BPA). A total PB concentration (?PPBs) >100 ng/g was observed in several items, including light therapy protection glasses, patterned transparent film dressing, winged IV catheters, IV infusion extension sets, and textile tape. The highest estrogenic activity [>450 pM estradiol equivalent (E2eq)] was found in small dummy nipples, three-way stopcocks, and patterned transparent film dressing and the highest anti-androgenic activity [>5 mM procymidone equivalent units per gram (Proceq/g)] in small dummy nipples and three-way stopcocks. DISCUSSION: According to these findings, neonates might be exposed to multiple sources of BPA and PBs in NICUs via inhalation, dermal, oral, and IV/parenteral routes. There is a need to address the future health implications for these extremely vulnerable patients and to adopt precautionary preventive measures as a matter of urgency. [ABSTRACT FROM AUTHOR]

The occurrence of classical and emerging halogenated flame retardants in bird samples collected between 2010–17 from the Castrejón reservoir (central Spain) was studied. Different wetland bird samples were analysed, including unhatched bird eggs and liver of dead nestlings. Polybrominated diphenylethers (PBDEs) were detected in all the samples at high concentration values, with levels up to 5167 ng/g lw. Dechloranes were found in 78% of analysed samples, but at lower concentration levels, between not detected (nd) and 2153 ng/g lw. The time trend evaluation over the sampling period showed an approximately 50% decline in mean concentrations of PBDEs. However, the most recent data for PBDEs (2016–17) still indicate that, in some cases, and based on reported LOECs, wetland birds were exposed to PBDE concentrations that are associated with possible ecological hazards. • PBDEs were detected at high concentrations, with levels up to 5167 ng/g lw. • Dechloranes were found in 78% of samples, at concentrations up to 2153 ng/g lw. • Time trend evaluation for PBDEs along 2010–2017 showed a level decline. • Based on reported LOECs, birds were still exposed to PBDEs associated to ecological hazards. [ABSTRACT FROM AUTHOR]

Little information is available on the content of bisphenol A (BPA) and other endocrine-disrupting chemicals (EDCs) such as parabens in infant textiles and clothes. 1) To determine the concentrations of BPA and parabens in socks for infants and young children purchased in Spain, 2) to assess the (anti-)estrogenicity and (anti-)androgenicity of extracts from the socks, and 3) to estimate dermal exposure doses to these chemicals. Thirty-two pairs of socks for infants and young children (1–48 months) were purchased from 3 stores in Granada (Spain). Textile material was cut from the foot, toe, and leg of each sock (n = 96 samples) for chemical analysis. Hormone-like activities were determined in foot sections (n = 32 samples) by using the E-Screen assay for (anti-)estrogenicity and PALM luciferase assay for (anti-)androgenicity. BPA was present in 90.6% of samples at concentrations ranging from <0.70 to 3736 ng/g. BPA levels were around 25-fold higher in socks from store 1, which had a higher cotton content compared to stores 2 and 3. Ethyl-paraben was found in 100% of samples, followed by methyl-paraben (81.0%), and propyl-paraben (43.7%). No butyl-paraben was detected in any sample. Estrogenic activity was detected in 83.3% of socks from store 1 (range = 48.2–6051 pM E 2 eq/g) but in only three socks from stores 2 and 3. Anti-androgenic activity was detected in six of the 32 socks studied (range = 94.4–2989 μM Proceq/g), all from store 1. Estimated dermal exposure to BPA was higher from socks for children aged 36–48 months (median = 17.6 pg/kg/day), and dermal exposure to parabens was higher from socks for children aged 24–36 months (median = 0.60 pg/kg/day). This is the first report in Europe on the wide presence of BPA and parabens in socks marketed for infants and children. BPA appears to contribute to the hormone-like activity observed in sock extracts. Unlabelled Image • BPA was present in 91% of socks at concentrations ranging from <0.70 to 3736 ng/g. • Ethyl-paraben was found in 100% of socks, followed by methyl- and propyl-paraben. • Around 41% of socks extracts were estrogenic and 19% were anti-androgenic. • Hormone-like activities were higher in socks with higher BPA content. • The median estimated dermal exposure dose to BPA was 19.6 pg/kg/day. [ABSTRACT FROM AUTHOR]

Objective: To examine the association of placental levels of arsenic (As), cadmium (Cd), mercury (Hg), lead (Pb), manganese (Mn), and chromium (Cr) with birth outcomes (birth weight, length, and head circumference, low birth weight [LBW], gestational age, preterm delivery, and small for gestational age [SGA]) in mother-child pairs from the Environment and Childhood (INMA) Project in Spain.Methods: Metal concentrations were measured in placenta tissue samples randomly selected from five INMA cohorts. Data on birth outcomes were obtained from medical records. Associations were assessed in a sub-sample of 327 mother-infant pairs by regression models adjusted for confounding factors and for all metals simultaneously. Effect modification by sex was also evaluated.Results: Elevated placental Cd levels (>5.79 vs. <3.30 ng/g) were associated with reduced birth weight (-111.8 g, 95%CI = -215.6; -8.06, p-trend = 0.01) and length (-0.62 cm, 95%CI = -1.20; -0.04, p-trend = 0.02), while a 10% increase in Cd was associated with 1.21-fold increased odds (95%CI = 1.01; 1.43) of LBW in the global sample but with 14% lower odds (95%CI = 0.78; 0.96) of preterm delivery in males (Pinteraction = 0.10). Detected (vs. undetected) Hg was associated with reduced head circumference (-0.49 cm, 95%CI = -1.00; 0.03) in females (Pinteraction = 0.03). A 10% increase in placental Mn was associated with slight increases in gestational age (0.04 weeks, 95%CI = 0.01; 0.07) in the global sample and in head circumference (0.05 cm, 95%CI = -0.01; 0.10) in females (Pinteraction = 0.03). Elevated Cr levels (>99.6 vs. <56.1 ng/g) were associated with reduced birth length (-0.68 cm, 95%CI = -1.33; -0.04, p-trend = 0.02) and slightly increased gestational age (0.35 weeks, 95%CI = -0.07; 0.77, p-trend = 0.08) in the global sample. As and Pb were detected in few placentas (27% and 13%, respectively) and were not associated with any studied birth outcome.Conclusions: Data suggest that in utero exposure to Cd, Hg, and Cr could adversely affect fetal growth, whereas Mn and Cr appear to have a positive effect on gestational age. Given the relatively small number of subjects, sex-specific associations should be interpreted with caution. [ABSTRACT FROM AUTHOR]

Tarragona County (Spain) is home to the most important chemical/petrochemical industrial complex in Southern Europe, which raises concerns about the presence and effects of the numerous environmental contaminants. In order to assess the levels and patterns of five classes of semi-volatile organic compounds (SVOCs) - polycyclic aromatic hydrocarbons (PAHs), synthetic musks (SMs), polychlorinated biphenyls (PCBs), brominated flame retardants (BFRs) and one organochlorine pesticide, hexachlorobenzene (HCB), 27 samples of soil and vegetation ( Piptatherum L.) from different areas (petrochemical, chemical, urban/residential, and background) of Tarragona County were analysed. The results show that PAHs levels in soils ranged from 45.12 to 158.00 ng/g and the urban areas presented the highest concentrations, mainly associated with the presence of a nearby highway and several roads with heavy traffic. PAHs levels in vegetation samples ranged from 42.13 to 80.08 ng/g, where the greatest influence came from the urban and petrochemical areas. In the case of SMs, levels in soils and vegetation samples ranged from 5.42 to 10.04 ng/g and from 4.08 to 17.94 ng/g, respectively, and in both cases, background areas (at least 30 km away from the main SVOCs emission sources) showed the highest levels, suggesting an influence of the personal care products derived from beach-related tourism in the coast. PCBs (from 6.62 to 14.07 ng/g in soils; from 0.52 to 4.41 ng/g in vegetation) prevailed in the chemical area in both matrices, probably associated with the presence of two sub-electrical stations located in the vicinities. In general terms, BFRs and HCB values recorded in soil and vegetation samples were quite similar between matrices and sampling areas. [ABSTRACT FROM AUTHOR]

This study aimed to estimate airborne nicotine concentrations and nicotine, cotinine, and tobacco-specific nitrosamines (TSNAs) in settled dust from private cars in Spain and the UK. We measured vapor-phase nicotine concentrations in a convenience sample of 45 private cars from Spain (N = 30) and the UK (N = 15) in 2017–2018. We recruited non-smoking drivers (n = 20), smoking drivers who do not smoke inside the car (n = 15), and smoking drivers who smoke inside (n = 10). Nicotine, cotinine, and three TSNAs (NNK, NNN, NNA) were also measured in settled dust in a random subsample (n = 20). We computed medians and interquartile ranges (IQR) of secondhand smoke (SHS) and thirdhand smoke (THS) compounds according to the drivers' profile. 24-h samples yielded median airborne nicotine concentrations below the limit of quantification (LOQ) (IQR:

The occurrence of furan in commercial baby food samples from the Spanish market was evaluated using an automated headspace solid-phase microextraction method coupled to gas chromatography-mass spectrometry (HS-SPME-GC-MS). A total of 76 baby food samples including infant formula, baby cereals, fruit in cans and/or jars, vegetables, meat, and fish, were surveyed for furan content. The lowest concentration of this compound was found in infant formula (<0.02–0.33 ng ml−1), and cereal-based food (0.15–2.1 ng g−1) while baby food containing fish showed the highest concentrations (19–84 ng g−1). Following recommendation of the European Food Safety Authority (EFSA), the effect on furan content was evaluated of consumer home preparation of foods, heating and handling. Furan concentrations were reduced by up to 35% when samples were heated in a dish using microwave oven and by up to 53% when a hot water bath was used. Finally, we estimated the furan intake from baby food consumption (0.002–1.18 µg kg−1body weight day−1) and we calculated the margin of exposure (MOE) from samples as purchased and also after home preparation of the food. For infant formula and cereal baby foods, the MOEs (26,278–412,776) indicated no infant health concern or priority, while for meat and fish-based baby foods the values pointed to a potential public health risk, even considering the furan losses during preparation at home. [ABSTRACT FROM AUTHOR]

Levels of lead (Pb) were analyzed in tissues of 25 Common shelduck (Tadorna tadorna) from La Albufera Natural Park (NP) in Valencia (Eastern Spain), which were found dead due to a botulism outbreak. The objective was to assess Pb exposure in waterfowl, fourteen years after the implementation of the Real Decreto 581/2001, which banned the use of Pb ammunition for hunting activities in internationally relevant wetlands. For this purpose, this study measured the actual ingestion of lead pellets in Common shelduck from La Albufera de Valencia and provide data on Pb residue concentrations in different tissues of this species breeding in this NP. The Pb distribution pattern in tissues was bone > kidney > liver > brain > muscle, with Pb concentrations of 778.96 ± 998.64, 122.40 ± 89.18, 92.08 ± 57.65, 18.90 ± 16.30 and 15.13 ± 11.85 ng/g (wet weight), respectively. This work presents, as far as we are aware, the first published data on Pb concentrations in Common shelduck. The Pb levels detected were lower than those reported in other studies on Anatid species from Spanish wetlands, which may be explained by this ban. Moreover, lead concentrations found were below those levels for which any observable effect has been described for acute or chronic lead exposure. Image 1 • No Pb pellets were found in gizzards of Common shelduck from La Albufera Natural Park. • The ban of Pb ammunition in the wetland has reduced the Pb exposure in Anatid species. • Pb levels in tissues were lower than those found in other Anatid species in Spain. • Pb levels in Common shelduck were below those related to any observable effect. [ABSTRACT FROM AUTHOR]

Levels and profiles of 10 individual congeners of polychlorinated biphenyls (PCBs) were studied in 3 species of commercial scallops ( Pecten maximus, Chlamys varia, and Chlamys opercularis) from several Rías in Galician littoral (NW, Spain). ΣPCBs levels ranged from 2.21 to 41.0 ng/g wet weight for P. maximus, from 13.9 to 24.9 ng/g wet weight for C. varia, and from 1.58 to 24.3 ng/g wet weight for C. opercularis. The possible influence between biometric parameters (lipid content, condition index, and shell size) and PCBs levels were studied using statistical analysis (ANOVA). No relationship between biometric parameters could be established in the studied samples. Multivariate analysis showed there were differences in bioaccumulation of some PCBs congeners. Principal component analysis classifies clearly the 3 studied Rías (Ría de Ferrol, Ría de Arousa, and Ría de Vigo) taking into account PCBs levels found in the shellfish. Practical Applications: We investigated levels and profiles of 10 congeners of PCBs in 3 commercial scallop species from the Galician littoral zone. The influence of 3 biometric parameters on polychlorinated biphenyls (PCBs) levels was also studied in order to assess results from the monitoring programs of production areas. According to PCBs levels, geographical differences were observed in commercial scallops from the 3 studied estuarine bays (Ría de Ferrol, Ría de Arousa, and Ría de Vigo). [ABSTRACT FROM AUTHOR]

The main objective of this work was to assess and compare the levels, patterns, and sources of contamination of 16 polycyclic aromatic hydrocarbons (PAHs) between Portugal, Spain, and Greece (in the island of Crete). A total of 9 sampling sites were chosen (4 in urban and 5 in non-urban areas) in each country and pine needles from the Pinus pinea L. species were collected. Although the mean total PAH levels was similar in the three countries (279 ± 236 ng g−1 for Portugal, 294 ± 258 ng g−1 for Spain, 301 ± 253 ng g−1 for Greece, all dry weight) and, in general, 3-ring and 4-ring PAHs were predominant (being phenanthrene consistently the most abundant), there were some visible differences in the aromatic ring patterns and possible sources between the three regions. Source apportionment was done using PAH ratios (Phen/Ant and Flt/Pyr crossplots) and reflected mixed petrogenic and pyrogenic sources. Furthermore, Principal Component Analysis (PCA) clearly separated the urban and the non-urban sites and all three countries, which reinforces that the sources of contaminations vary in each case and the suitability of pine needles for trans-boundary biomonitoring of PAHs. [ABSTRACT FROM AUTHOR]

Abstract: In 2000 and 2006, we determined the dietary intake of hexachlorobenzene (HCB) by the population of Catalonia, Spain. In order to establish the temporal trend in the levels of HCB in foodstuffs, as well as in the dietary exposure to that environmental pollutant, the concentrations were again analyzed by HRGC/HRMS in 65 composite food samples widely consumed by the Catalan population. Food samples were randomly purchased in November–December 2008 in local markets, small stores, supermarkets, and large grocery stores from 12 representative cities from Catalonia. The daily intake of HCB associated with this consumption was estimated for four age groups of the population of Catalonia: children, teenagers, adults and seniors, which were in turn divided according to sex. The highest mean HCB levels in food were detected in oils and fats (0.297 ng/g fw), dairy products (0.225 ng/g fw), and fish and seafood (0.170 ng/g fw). In the 2000 and 2006 surveys, total dietary intakes of HCB were 166.2 and 71.6 ng/day, respectively (or 2.4 and 1.0 ng/kg of body weight per day). In the current study, it was 37.7 ng/day (or 0.54 ng/kg of body weight per day), which means considerable decreases with respect to the previous intakes. According to recommendations of international regulatory organisms, the current dietary intake of HCB should not mean any significant health risk (carcinogenic and non-carcinogenic) for any of the age/gender groups of population here assessed. [Copyright &y& Elsevier]

Abstract: Occurrence of ochratoxin A (OTA) in ground roasted coffee from different brands and types available in Spain was assessed. Based on these data, exposure of the Catalan population to OTA through coffee consumption was estimated. Coffee samples were purchased in hypermarkets and supermarkets of twelve cities of Catalonia, Spain, and composite samples were prepared for analysis. OTA was extracted, cleaned-up by immunoaffinity columns, and detected by HPLC-fluorescence detection. Mean OTA content (n = 72) was 2.17 ± 0.79 ng/g (range 1.21–4.21 ng/g, 49% occurrence). An additional sampling was done by brands (n = 45), mean OTA contamination being 2.07 ± 0.61 ng/g (range 1.30–5.24 ng/g, 95% occurrence). Coffee consumption data were obtained by means of a food frequency questionnaire. Mean coffee consumption per capita was 11.58 ± 8.73 g/person/day. OTA daily intake (DI) was estimated by means of deterministic and probabilistic methods. In both cases, estimated DI (around 0.22 ng/kg bw/day) was below the latest PTDI value of 17 ng/kg bw/day suggested by EFSA. [ABSTRACT FROM AUTHOR]

Abstract: The contamination of wastewater and sewage sludge has been examined for three phosphodiesterase type V inhibitors sildenafil, vardenafil and tadalafil, active agents of Viagra®, Levitra® and Cialis®, respectively. Sensitive quantification methods based on solid-phase extraction (SPE) and pressurized liquid extraction (PLE) followed by high performance liquid chromatography – tandem mass spectrometry (HPLC–MS/MS) have been developed to analyse these compounds in wastewater and sewage sludge. Effluent water of nine sewage treatment plants (STPs) has been analysed to assess the impact of the phosphodiesterase type V inhibitors on the environment. One municipal STP (Tarragona, Spain) has been thoroughly studied over the year 2008 (i) with respect to the distribution of these compounds among influent and sewage sludge and (ii) the elimination efficiency. The developed methods allowed quantification at trace concentrations. Sildenafil was present in all investigated samples at the low ng/L and ng/g range, respectively. Tadalafil was not detected or below the limit of detection (LOQ) in effluent water taken in Spain but in sewage sludge (12 ng/g –  < LOQ). Vardenafil was present only in one sludge sample and between 5 ng/g and < LOQ in effluent water. The overall removal efficiency of the STP in Tarragona (Spain) is 68%, 69% and 80% for sildenafil, tadalafil and vardenafil, respectively. This study shows for the first time the determination of these compounds in wastewater and sewage sludge. [Copyright &y& Elsevier]

Perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) are globally distributed, persistent, toxic, and are found in human blood and serum. Exposure pathways are not well characterized. To better understand indoor dust ingestion as a potential pathway for human exposure, we determined the concentrations of these compounds in dust collected from 10 houses, 38 apartments, 10 day care centers, 10 offices, and 5 cars. Samples were prepared using a rapid extraction and cleanup method and analyzed using LC-MS/MS. PFOS and PFOA were found in dust samples from all microenvironments and their concentrations were significantly positively correlated to each other. Highest median concentrations were seen in offices (PFOS: 110 ng/g dry weight) and apartments (PFOA: 93 ng/g dw). Adult and toddler dust ingestion exposures were estimated and compared to dietary exposure data from Canada and Spain. Results show that diet is the most important exposure route, but in a worst case scenario, dust ingestion may also be significant. [ABSTRACT FROM AUTHOR]

The concentrations of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), polychlorinated biphenyls (PCBs), and polybrominated diphenyl ethers (PBDEs) were determined in breast milk from women living in the vicinity of a new hazardous waste incinerator (HWI) in Catalonia, Spain. The results were compared with the levels obtained in two previous surveys carried out in 1998 (baseline study) and 2002. The current concentrations of PCDD/Fs in breast milk ranged from 45 to 143 pg/g fat (2.8 to 11.2 pg WHO-TEQ/g fat), while total PCBs ranged from 114 to 617 pg/g fat (2.8 to 17.6 pg WHO-TEQ/g fat). PBDE concentrations (sum 15 congeners) ranged from 0.57 ng/g fat to 5.9 ng/g fat, with a mean value of 2.5 ng/g fat. A general decrease of the concentrations for PCDD/Fs and both planar and total PCBs was observed. Regarding to PBDE concentrations in breast milk, similar levels between the 2002 and the present study were noted. The levels of PCDD/Fs and PCBs in milk of women living in urban areas were higher than those corresponding to the industrial zones (38% and 40%, respectively). However, the current PBDE levels were slightly lower (13%) in the urban than in the industrial zone. For PCDD/Fs and PCBs, the current decreases are in accordance with the reduction in the dietary intake of these pollutants found in recent studies carried out in the same area of study. [Copyright &y& Elsevier]

Mercury (Hg) speciation and partitioning have been investigated in a river-reservoir system impacted by the Almadén mining activities, the world''s largest Hg district. This study is the first to simultaneously investigate Hg dynamics from above the mining district and into the La Serena Reservoir (3219 Hm3), being the third largest reservoir in Europe and the largest in Spain. Water, sediment and biota were sampled at different seasons during a 2-year study from the Valdeazogues River, which flows east–west from the mining District, to La Serena Reservoir. Simultaneously, a comprehensive study was undertaken to determine the influence of some major physico-chemical parameters that potentially influence the fate of Hg within the watershed. Concentrations of dissolved Hg in water were below 0.14 µg/L, whereas particulate Hg ranged from 0.1 to 87 µg/g, with significant seasonal variation. Total Hg concentrations varied from 7 to 74 µg/g in sediment from the Valdeazogues River, while in sediments from La Serena Reservoir were below 2 µg/g. On the other hand, methyl-Hg reached concentrations up to 0.3 ng/L in water and 6 ng/g in sediment from La Serena Reservoir, whereas maximum concentrations in Valdeazogues River were 5 ng/L and 880 ng/g in water and sediment, respectively. The distribution of Hg species in the Valdeazogues River–La Serena Reservoir system indicated a source of Hg from the mine waste distributed along the river. Total Hg in water was strongly correlated with total dissolved solids and chlorophyll a concentrations, whereas organic carbon and Fe concentrations seem to play a role in methylation of inorganic Hg in sediment. Total Hg concentrations were low in fish from Valdeazogues River (0.8–8.6 ng/g, wet weight) and bivalves from La Serena Reservoir (10–110 ng/g, wet weight), but most was present as methyl-Hg. [Copyright &y& Elsevier]

Samples of human breast milk (n = 33) from A Corua (NW of Spain) collected in 2006 and 2007 were analyzed for HBCD diastereoisomers and enantiomers. HBCD was detected in 30 out of 33 human milk samples, at concentration levels ranging between 3 and 188 ng/g lw, with a median value of 27 ng/g lw, showing higher levels than those published for other countries. Diastereoisomeric pattern shows the predominance of the γ-isomer, with low contribution of the α-isomer and the β-isomer being below the limit of quantification. However, in six samples, there is a dominance of the α-isomer versus the γ-isomer. For the first time, HBCD enantiomeric analysis was carried out in human breast milk samples, showing a selective enantiomeric enrichment in human body. As regards α-HBCD, an enrichment of (-)-enantiomer was observed. However, in the case of γ-HBCD, no clear preference for one or the other enantiomer was found. Finally, and based on the calculated HBCD concentrations in human breast milk from Spain, the daily ingestion rate of HBCD was estimated. The nursing infant dietary intake for HBCD was set at 175 ng (kg of body weight)-1 day-1. [ABSTRACT FROM AUTHOR]

This study was carried out to determine total Hg concentrations (HgT) in acid soils and main plant species in forest ecosystems located in the river Sor catchment, which is located 20 km to the NE of the biggest coal-fired power-plant in southwestern Europe (Galicia, NW Spain). Mercury enrichment factors and Hg inventories were also determined in the soils, which were regularly sampled between 1992 and 2001. The presence of elemental Hg was estimated by simple thermal desorption at 105 °C. The highest HgT concentrations occurred in upper soil layers (O and A horizons) with values up to 300 ng g−1. HgT decreased with depth, achieving the lowest values in the bottommost horizons (i.e. the soil parent material, <6 ng g−1), except in podzolic soils. A similar trend occurred for Hg enrichment factors (HgEF) which showed values from 40 to 76 in topsoils. Upper soil mineral horizons (A or AB) made the largest contribution (>50%) to the HgT inventory despite showing lower concentrations than the organic horizons. The role of vegetation in capturing atmospheric Hg and subsequent deposition to soil agrees with the sequence of HgT in plant material: woodT concentrations, suggesting that organic matter (total amount and the presence of metal–humus compounds) plays a key role in Hg accumulation in the studied acid soils. [Copyright &y& Elsevier]

Abstract: The concentrations of hexachlorobenzene (HCB) were analyzed by HRGC/HRMS in 42 composite samples of the 14 most consumed marine species (sardine, tuna, anchovy, mackerel, swordfish, salmon, hake, red mullet, sole, cuttlefish, squid, clam, mussel, and shrimp) in Catalonia, Spain. The daily intake of HCB associated with this consumption was also estimated for four age groups of the population of Catalonia: children, adolescents, adults and seniors, which were in turn divided according to sex. The highest HCB levels were found in salmon and mackerel: 1.68 and 0.80 ng/g of wet weight, respectively, whereas the lowest HCB levels were found in cuttlefish, mussel, and shrimp (0.02, 0.03, and 0.04 ng/g of wet weight, respectively). In general terms, these results are within the range of data reported in recent years by a number of authors. The highest and lowest HCB intake (ng/day) corresponded to female adults (13.3) and girls (4.0), respectively. For most age/sex groups, salmon and sole were the species showing the highest contribution to HCB intake. When HCB intake was calculated according to the average body weight of the individuals in each group, the highest and lowest values corresponded to boys (0.32 ng/kg/day) and female adolescents (0.14 ng/kg/day). For all groups, HCB intake from fish and seafood consumption was considerably lower than the WHO tolerable daily intake (TDI), for non-cancer effects and for neoplastic effects in humans. [Copyright &y& Elsevier]

Sixty samples of corn from both conventional and organic farms were tested for internal fungal contamination. Molds were identified to genus, and those belonging to the genus Fusarium were identified to species. Twenty isolates of Fusarium verticillioides were tested with a high-performance liquid chromatography-naphthalene dicarboxaldehyde-fluorescence method for their ability to produce fumonisins B1 and B2. The internal fungal infection in organic maize (63.20%) was significantly higher than that in conventional maize (40.27%) (P < 0.05). However, the distribution of fungal genera indicated a significantly higher prevalence of Fusarium in conventional (34.93%) than in organic (18.15%) maize, making Fusarium the predominant fungus in conventional maize. This difference in mold distribution between organic and conventional maize was attributed to the difference in cultivation system. The dominant Fusarium species in both conventional and organic samples was F. verticillioides. There were no significant differences in the ability of 20 selected isolates of F. verticillioides to produce fumonisins on conventional or organic corn. Up to 13.3% of the conventional corn samples contained fumonisins B1 and B2 at mean concentrations of 43 and 22 ng/g, respectively. Organic corn samples had somewhat lower levels of contamination: 35 ng/g fumonisin B1 and 19 ng/g fumonisin B2 (P > 0.05). The organic farming system, with well-balanced crop rotation, tillage, and compost fertilization, produced corn that was less likely to be contaminated with Fusarium species, although no significant difference in fumonisin concentrations was found between the two types of contaminated corn. [ABSTRACT FROM AUTHOR]

Abstract: We present data from an early reconnaissance survey (stream sediments, soil, and water Hg chemistry; plants and water crustaceans Hg intake) of the Almadén district (central Spain), that was carried out to establish the potential environmental hazards derived from the anomalous mercury concentrations measured in this realm. The Almadén mercury district (∼300 km2) can be regarded as the largest geochemical anomaly of mercury on Earth. The district includes a series of mercury mineral deposits, having in common a simple mineralogy (dominant cinnabar: HgS, and minor pyrite: FeS2). The ore deposits have been mined for more than 2000 years, and the main mine of the district (Almadén), has been active from Roman times to present day with almost no interruptions. The mercury distribution in soils of the district reveals the existence of high, and extremely high mercury values (up to 8889 μg g−1), whereas concentrations in stream sediments and waters reach exceptional values of up to 16,000 μg g−1 and 11,200 ng l−1 respectively. On the other hand, very high concentrations of methylmercury (MeHg) have been detected in calcines (up to 3100 ng g−1), sediments (0.32–82 ng g−1), and waters (0.040–30 ng l−1). Mercury gets incorporated to edible river crustaceans and plants. The red swamp crayfish Procambarus clarkii, has Hg concentrations of up to 9060 ng g−1 (muscle) and 26,150 ng g−1 (hepatopancreas). Regarding plants, the local wild asparagus (Asparagus acutifolius) yields values of up to 298 μg g−1 Hg. Mercury also escapes to the atmosphere, and mineral deposits, together with metallurgical activities, generate strong anomalies of atmospheric Hg. The most important concentrations relate to the emissions from the Almadén metallurgical roaster, in the order of 14,000 ng Hg m−3. Additionally, large open pit operations also contribute to the district atmospheric pool of mercury, with high concentrations above 1000 ng Hg m−3. Thus, no system (rocks, soils, sediments, waters, atmosphere, biota) in the Almadén district is free from strong Hg contamination. [Copyright &y& Elsevier]

Fish and sediments from four places along the Spanish River Cinca were analyzed for polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecane (HBCD). The samples were collected up- and downstream from MonzOn, a heavily industrialized town draining to the river. PBDEs and HBCD were found in sediments at levels ranging from 2 to 42 ng/g dry weight and from not detected (nd) to 514 ng/g dry weight respectively. Twenty-three fish samples (Barbus graellsi) collected at the same places were also analyzed, showing levels from rid to 446 ng/g wet weight for PBDEs and from nd to 1172 ng/g wet weight for HBCD. The lowest values for both sediment and fish samples were found upstream of the industry. Of 40 congeners (from mono- to deca-BDEs) included in the analytical work, 8 PBDE congeners were detected in river sediments, whereas 17 different PBDEs were found in fish samples. Large fish-to- sediment ratios for these brominated compounds indicate that they are highly bioavailable, with the exception of deca- BOE which was only detected in sediment samples. Concentrations of PBDEs and HBCD were slightly higher in muscle tissues than in liver samples obtained from the same specimen of fish. Moreover, PBDE and HBCD concentrations are correlated with fish length indicating the bioaccumulation of these contaminants. [ABSTRACT FROM AUTHOR]

Mussels (Mytilus galloprovincialis) were sampled in March 1996 from five stations along the Western Mediterranean coast (Barcelona, Ebro Delta, Alboraya, Cullera, Denia) corresponding to urban, industrial and agricultural areas. Different biochemical and cellular markers were determined in the mussels in order to assess the effects and/or exposure to pollutants. The cytochrome P450 system, acetylcholinesterase and metallothioneins were among the biochemical markers selected for the study. Histochemical analysis of ß-glucuronidase and catalase activity were performed as marker enzymes for lysosomes and peroxisomes. Chemical analyses indicated that mussels from Barcelona and Denia as highly exposed to polycyclic aromatic hydrocarbons (PAHs)(1.8-2.7 µg g[sup -1] w.w. against 0.02-0.10 µg g[sup -1] w.w.), and polychlorinated biphenyls (PCBs)(132-260 ng g[sup -1] w.w. against 8-24 ng g[sup -1] w.w.). This was in agreement with changes in lysosome structure and higher number of peroxisomes in those organisms. High levels of metals (particularly Cr and Cu) were recorded in the digestive gland of Alboraya mussels, which also had elevated metallothionein content (28 nmol g[sup -1] w.w.) in comparison with the other stations (15-20 nmol g[sup -1] w.w.). Benzo(a)pyrene hydroxylase (BPH) activity indicated Cullera and Barcelona as possibly polluted sites. The results support the usefulness of the biomarker approach to assess and diagnose environmental pollution. The use of a battery of biomarkers at different levels of biological organization coupled with chemical analysis is highlighted. [ABSTRACT FROM AUTHOR]

The presence of deoxynivalenol (DON) has been repeatedly detected in cereal-based products collected from Spanish markets over the last years. Hence, the aim of this study was to conduct a systematic review and meta-analysis of the concentration and prevalence of DON in cereals and cereal-based products from Spanish markets intended for human consumption, in order to integrate the available data. Then, an exposure assessment was performed based on national consumption data. Results revealed a strong impact of DON in breakfast cereals (pooled concentration = 105.34 ng/g; pooled prevalence = 58%) and bread and derived products (pooled concentration = 95.17 ng/g; pooled prevalence = 67%). Meta-regression showed a decrease in DON prevalence (p -value = 0.761) and concentration (p -value = 0.027) over the last 15 years. Exposure assessment outlined a high exposure to DON, especially in infants and children below 3 years old that showed a 175% and 119% of the tolerable daily intake (TDI). Bread and derived products were the main contributor to DON throughout age groups, with %TDI values ranging from 12% to 34%. Therefore, the here-presented results provide more evidence about the non-negligible impact of DON in Spain as result of cereal-based products consumption. • First meta-analysis of DON contamination in cereal products from Spain. • Significant decrease of DON concentration in cereal products over time. • Non-significant decrease of DON prevalence in cereal products over time. • Bread and derived products were the main contributors to DON exposure. • Exposure to DON in population below 3 years old exceeded the TDI. [ABSTRACT FROM AUTHOR]

Sludge is one of the most problematic residues generated during wastewater treatment. Herein, we validate a single-step, sensitive procedure for the determination of a selection of 46 basic micro-pollutants, either used as pharmaceuticals or pesticides, in sludge from municipal sewage treatment plants (STPs), using liquid chromatography tandem mass spectrometry as determination technique. The proposed method permitted to achieve accurate recoveries (values from 70% to 120%, for samples spiked at different concentration levels) using solvent-based calibration standards. This feature, combined with limits of quantification lower than 5 ng g−1 (dry weight), allowed the rapid and sensitive quantification of target compounds in freeze-dried sludge samples. Out of 46 investigated pollutants, 33 species showed detection frequencies above 85% in a group of 48 sludge samples, obtained from 45 STPs located in the Northwest of Spain. The assessment of eco-toxicological risks associated to sludge disposal as fertilizer in agriculture and/or forestry, considering average concentrations found in sludge samples, highlighted eight pollutants (sertraline, venlafaxine, N-desethyl amiodarone, amiodarone, norsertraline, trazodone, amitriptyline and ketoconazole) representing an environmental hazard based on ratios between predicted soil levels and non-effect concentrations estimated using the equilibrium partition method. [Display omitted] • Single-step, effective extraction of basic micro-pollutants from sludge. • Accurate recoveries using solvent-based calibration standards. • Detection frequencies above 85% for 33 compounds in sludge from 45 STPs. • Eight species highlighted as hazardous based on their RQs for sludge-amended soil. [ABSTRACT FROM AUTHOR]

Organochlorinated pesticides (OCPs) were measured in a representative sample of Spanish adults within the Bioambient.es project, a nationwide human biomonitoring program promoted by Spanish Ministry of Agriculture, Food and Environment. The objective of Bioambient.es is to establish reference levels of environmental pollutants in the general population. Participants were recruited in 2009-2010 during their annual medical examination at work. Serum levels of thirteen OCPs were investigated: Aldrin, endrin, dieldrin, heptachlor, heptachlor-epoxide, dichlorodiphenyldichloroethylenes (DDEs), hexachlorobenzene (HCB), dichlorodiphenyltrichloroethanes (DDTs) and hexachlorocyclohexanes (HCHs) The highest concentrations were observed for DDE, HCB and β-HCH. The 95th percentile, in ng/g lipids, were: 717.7 for 4,4-DDE, 160.4 for HCB and 107.2 for β-HCH, while concentrations of aldrin, endrin, heptachlor, α-HCH, 2,4-DDT, 4,4-DDT and 2,4-DDE were markedly lower and detected in less than 10% of the samples. Significant differences (p<0.05) were found for DDE and HCB and seasonality, gender and age. Analyzing the geographical distribution, participants from the north of Spain had highest levels of HCB while those from the center of Spain had highest levels of 4,4-DDE. Comparing to earlier studies, the results indicated a sharp decline in the OCP concentrations in the Spanish population over time, and today values are in the same range or lower than those reported in similar studies worldwide, except for HCHs and HCB that presented higher levels than in other European countries and much higher than those observed in US and Canada. This study represents the first nationwide survey of exposure to OCPs in Spain and provides a background reference range for exposure to OCPs in the Spanish adult occupied population. These results will allow establishing reference values, observing temporal trends and identifying high exposure groups. [ABSTRACT FROM AUTHOR]

Coastal ecosystems are particularly vulnerable to terrestrial inputs from human-impacted areas. The prevalence of wastewater treatment plants, unable to remove contaminants such as pharmaceuticals (PhACs), leads to their continuous input into the marine environment. In this paper, the seasonal occurrence of PhACs in a semi-confined coastal lagoon (the Mar Menor, south-eastern Spain) was studied during 2018 and 2019 by evaluating their presence in seawater and sediments, and their bioaccumulation in aquatic organisms. Temporal variation in the contamination levels was evaluated by comparison to a previous study carried out between 2010 and 2011 before the cessation of permanent discharges of treated wastewater into the lagoon. The impact of a flash flood event (September 2019) on PhACs pollution was also assessed. A total of seven compounds (out of 69 PhACs analysed) were found in seawater during 2018–2019, with a limited detection frequency (<33%) and concentrations (up to 11 ng/L of clarithromycin). Only carbamazepine was found in sediments (ND–1.2 ng/g dw), suggesting an improved environmental quality in comparison to 2010–2011 (when 24 and 13 compounds were detected in seawater and sediments, respectively). However, the biomonitoring of fish and molluscs showed a still remarkable accumulation of analgesic/anti-inflammatory drugs, lipid regulators, psychiatric drugs and β-blocking agents, albeit not higher than in 2010. The flash flood event from 2019 increased the prevalence of PhACs in the lagoon, compared to the 2018–2019 sampling campaigns, especially in the upper water layer. After the flash flood the antibiotics clarithromycin and sulfapyridine yielded the highest concentrations ever reported in the lagoon (297 and 145 ng/L, respectively), alongside azithromycin in 2011 (155 ng/L). Flash flood events associated with sewer overflows and soil mobilisation, which are expected to increase under climate change scenarios, should be considered when assessing the risks posed by pharmaceuticals to vulnerable aquatic ecosystems in the coastal areas. [Display omitted] • Lower pharmaceutical concentrations were found in Mar Menor lagoon (SE Spain) in 2018–2019 than in 2010–2011. • Reuse of WWTP effluents (since 2015) has likely contributed to the observed decrease in pharmaceutical levels. • A flash flood episode in 2019 increased the presence of pharmaceuticals in the upper seawater layer. • Biomonitoring more informative than grab water regarding pharmaceutical presence in the lagoon. [ABSTRACT FROM AUTHOR]

The presence of fungicide and insecticide residues in wine has been largely investigated. However, few studies have addressed the persistence of these compounds in vineyard soils. In this research, we investigate the residues of a relevant number of fungicides and insecticides in vineyard soils, obtained in the Northwest of Spain, at the beginning of each agriculture campaign. Moreover, the dissipation of species showing high concentrations were monitored during the non-vegetative period of vines, in order to understand their soil evolution between application campaigns. To this end, a multiresidue analytical procedure based on pressurized liquid extraction (PLE) followed by liquid chromatography tandem mass spectrometry (LC-MS/MS) determination was first optimized. Under final working conditions, absolute recoveries in the range from 70 to 130% were achieved for 44 out of 51 selected compounds. The method LOQs remained at the low ng g−1 level (0.2–13 ng g−1) with a linear response range up to 500 ng g−1. Analysis of vineyard soils, collected during a 2-year period, from a geographic area with a high incidence of fungal diseases, demonstrated the presence of relevant concentrations of several fungicides and the insecticide imidacloprid (IMI) in this compartment. Most compounds detected at the end of the application season remained in soil at the beginning of the next year campaign. Among them, six fungicides (dimethomorph, boscalid, myclobutanil, penconazole, pyraclostrobin and pyrimethanil) and IMI showed average dissipation efficiencies below 50%, so they pose a potential to accumulate in this kind of soils. Image 1 • Multiresidue method optimization for pesticides analysis in vineyard soils. • Significant residue levels remain in soil at the beginning of each campaign. • Several fungicides are poorly removed during the resting cycle of vines. • Soil residues of persistent fungicides increase during autumn. [ABSTRACT FROM AUTHOR]

The aim of this study was to evaluate the presence and distribution of polychlorinated dibenzo- p -dioxins, dibenzofurans (PCDD/Fs) and biphenyls (PCBs), concretely those so-called as dioxin-like PCBs, in yellow-legged gull eggs ( Larus michahellis ) collected from five Natural Parks (some of them National Parks) in Spain during the period 2010–2013. PCDD/Fs and dl-PCBs were detected in all the samples. Due to the proximity to important urban and industrial areas higher concentrations were determined in colonies located in the Northern Mediterranean coast than those found in the Southern Mediterranean or Atlantic colonies where a softer anthropogenic impact occurs. Mean ∑ PCDD/F concentrations ranged from 49 to 223 pg/g lipid weight (lw) and ∑ dl-PCB concentrations varied from 146 to 911 ng/g lw. In the Natural Park of the Ebro Delta (Northern Mediterranean coast) two gull species share habitat: yellow-legged and Audouin gull ( Larus audouinii ). Eggs from both species were collected and PCDD/F and dl-PCB levels compared. The species that feeds exclusively on pelagic fish ( L. audouinii ) had significantly higher PCDD/F and dl-PCB levels than the scavenger L. michahellis , pointing out the diet-dependent differences in the accumulation of persistent organic pollutants between similar cohabitant breeding species. Finally, mean TEQ values were in general below those considered as critical for toxicological effects in birds. [ABSTRACT FROM AUTHOR]

PCBs were analyzed in raft mussels cultured in several polygons from Galician Rías (Rías of Ares-Betanzos, Muros-Noia, Arousa, Pontevedra and Vigo) during the period 1998–2013. The main aim of this work is study the quality of culture marine environment in relation to PCBs compounds. We report the results of a monitoring. The mean levels of ΣPCBs (ten congeners) ranged from 7.41 to 59.50 ng g − 1 dw. The isomer concentrations in the Mytilus galloprovincialis cultured in raft were in the order hexachlorobiphenyls > pentachlorobiphenyls > tetrachlorbiphenyls > trichlorobiphenyls. Some biological parameters of mussel were also investigated (shell length, lipid content and condition index) in order to know their influence on ability of PCBs accumulation. ANOVA analysis confirms that levels of most of congeners had a significant relation (p < 0.05) with shell length. The geographical patterns and temporal variations of PCBs were also investigated. Principal Component Analysis (PCA) showed differences between geographic areas (Rías) in the distribution of PCBs levels. Samples coming from Rías of Vigo and Ares-Betanzos presented the highest levels of PCBs and samples from Rías of Arousa and Muros-Noia had the lowest levels of these compounds. Time trends (linear regressions) showed a decline of levels of PCB congeners along the period 1998–2013. [ABSTRACT FROM AUTHOR]

• OP levels in the house dust were two orders of magnitude higher than BFRs. • TCEP and TCIPP increased with the percentage of the floor covered by textiles. • EHDP presented higher levels in homes located in industrial neighborhoods. • Calculated EDI levels were below available RfD values for all analytes. 52 pollutants including organophosphate flame retardants and plasticizers (OPs), polybrominated diphenyl ethers (PBDEs) and novel brominated flame retardants (NBFRs) were evaluated in household dust from Belgium, Italy and Spain. Pollutant pattern was dominated by ∑OPs (12.8 μg/g; median) followed in decreasing order by ∑PBDEs (229 ng/g), decabromodiphenyl ethane (DBDPE, 130 ng/g), 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE, 1.35 ng/g), hexabromobenzene (HBB, 0.28 ng/g) and finally pentabromoethylbenzene (PBEB, 0.03 ng/g). Country differences and substitution of regulated chemicals by unregulated ones were explored. Results clearly reflected a decrease in c-penta and c-octaBDE commercial mixtures, which are mainly substituted by OPs, BTBPE and PBEB. On the other hand, c-decaBDE concentrations increased in Spanish case. However, positive correlations with its proposed substitute (DBDPE) and recent restricted policies make it possible to assume that this trend will change in the coming years. On the basis of the relationship between pollutants, house characteristics and inhabitant habits, potential sources were studied. Finally, data obtained were used to determine estimated daily intakes (EDI) via house dust ingestion and dermal absorption for toddlers and adults at central and upper percentiles. Calculated EDI levels even at worst case scenario were below available reference dose (RfD) values in all cases. [ABSTRACT FROM AUTHOR]

• Optimization of FUSE-SPE-SBSE-TD-GC-MS/MS for booster biocides in marine sediment. • The use of SBSE for the pre-concentration of booster biocides in marine sediment. • The use of FUSE for the extraction of booster biocides in marine sediment. • Validation of FUSE-SPE-SBSE-TD-GC-MS/MS for booster biocides in marine sediment. Booster biocides present in natural waters may be captured by the sediments. Highly sensitive, robust, selective and reliable analytical methods are required to evaluate their presence in the sediments. A focused ultrasound assisted extraction method for the simultaneous determination of five organic booster biocides (Chlorothalonil, Dichlofluanid, Sea-Nine 211, Irgarol 1051 and TCMTB) in marine sediments is proposed. The isolation of the target compounds from 0.5 g of sediment was efficient using 2.5 mL of methanol as solvent, an output amplitude of 50 W, 100% duty cycle and an extraction time of 300 s. The extraction procedure was followed by solid-phase clean-up on non-polar sorbents (Oasis HLB). The compounds were sampled using stir bars (20 mm length, 0.5 mm film thickness) coated with polydimethylsiloxane (PDMS). The stir bars were stirred at 900 rpm for 3 h at room temperature. Desorption was carried out by thermal desorption (TD), and the analytes were separated in the gas chromatography (GC). They were detected by triple quadrupole mass spectrometry (MS/MS) using the multiple reaction monitor (MRM) mode. The detection limits (DLs) of booster biocides were in the range of 0.02 to 2.2 ng g −1 dry weight. The regression coefficients were higher than 0.999. The average recovery was higher than 86% (R.S.D.: 7–11%). The analytical procedure was applied to determination of the booster biocides in port sediment samples from the southwestern Spain. Sea-Nine 211 was found in one sediment at a level of 2.1 ng g−1. Irgarol was present in all the sediments at concentrations between 2 and 9 ng g−1. Image, graphical abstract [ABSTRACT FROM AUTHOR]

For the first time, this work described pyrethroid bioaccumulation in edible river fish samples. We analyzed 42 whole fish samples collected in 4 different Iberian rivers. All samples were positive to these insecticides. Levels of concentration ranged from 12 to 4938 ng g − 1 lipid weight (lw). Moreover, isomeric characterization was carried out. Our results remarked a general preference of cis isomers in bioaccumulation. Finally, the enantiomeric evaluation showed that there was an enantioselective bioaccumulation of some pyrethroids, depending on the studied species. Pyrethroid concentrations were compared with levels obtained for other common pollutants, such as flame retardants, personal care products, hormones and pharmaceuticals. The highest values corresponded to pyrethroid insecticides, even though, pyrethroid levels are safe for human consumption taken into account the current regulations. [ABSTRACT FROM AUTHOR]

Through an extensive sampling in the Llobregat River basin, the presence of 50 currently used pesticides in water, sediment, and biota was assessed. Pesticides were detected primarily in water (up to 56% of the analytes), whereas their presence in sediments was more intermittent, and in biota was scarce. Those at high concentrations in water were the benzimidazoles (carbendazim in 22% of the samples up to 697 ng L − 1 ), the organophosphorus (malathion in 54% of the samples up to 320 ng L − 1 ), and the ureas (diuron in 54% of the samples up to 159 ng L − 1 ). However, this pattern differed in sediments and biota, which were contaminated primarily with organophosphorus (higher K ow ) (chlorpyrifos 93% of sediments up to 131 ng g − 1 ). According to the results of this study, pesticide residues in the Llobregat River basin do not seem to represent a high risk to biota, even though some algae and fish can be affected. Nevertheless, the monitoring program can be very useful to control the contamination of the river basin, as the availability of historical data on the basin confirmed background contamination in the last 20 years. [ABSTRACT FROM AUTHOR]

There is an increasing trend in the incidence of cancer worldwide, and it has been accepted that environmental factors account for an important proportion of the global burden. The present paper reports preliminary findings on the influence of the historical exposure to a group of persistent organic pollutants on total cancer risk, at year 9 in the follow-up of a cohort from Southern Spain. A cohort of 368 participants (median age 51 years) was recruited in 2003. Their historical exposure was estimated by analyzing residues of persistent organic pollutants in adipose tissue. Estimation of cancer incidence was based on data from a population-based cancer registry. Statistical analyses were performed using multivariable Cox-regression models. In males, PCB 153 concentrations were positively associated with total cancer risk, with an adjusted hazard ratio (95% confidence interval) of 1.20 (1.01–1.41) for an increment of 100 ng/g lipid. Our preliminary findings suggest a potential relationship between the historical exposure to persistent organic pollutants and the risk of cancer in men. However, these results should be interpreted with caution and require verification during the future follow-up of this cohort. [ABSTRACT FROM AUTHOR]

BACKGROUND: There is increasing interest in the potential effects of polybrominated diphenyl ethers (PBDEs) on children's neuropsychological development, but only a few small studies have evaluated such effects. OBJECTIVES: Our goal was to examine the association between PBDE concentrations in colostrum and infant neuropsychological development and to assess the influence of other persistent organic pollutants (POPs) on such association. METHODS: We measured concentrations of PBDEs and other POPs in colostrum samples of 290 women recruited in a Spanish birth cohort. We tested children for mental and psychomotor development with the Bayley Scales of Infant Development at 12-18 months of age. We analyzed the sum of the seven most common PBDE congeners (BDEs 47, 99, 100, 153, 154, 183, 209) and each congener separately. RESULTS: Increasing Σ[sub 7]PBDEs concentrations showed an association of borderline statistical significance with decreasing mental development scores (Βper log ng/g lipid = -- 2.25; 95% CI: -4.75, 0.26). BDE-209, the congener present in highest concentrations, appeared to be the main congener responsible for this association (Β= -- 2.40, 95% CI: -4.79, -- 0.01). There was little evidence for an association with psychomotor development. After adjustment for other POPs, the BDE-209 association with mental development score became slightly weaker (Β= -- 2.10, 95% CI: -4.66, 0.46). CONCLUSIONS: Our findings suggest an association between increasing PBDE concentrations in colostrum and a worse infant mental development, particularly for BDE-209, but require confirmation in larger studies. The association, if causal, may be due to unmeasured BDE-209 metabolites, including OH-PBDEs (hydroxylated PBDEs), which are more toxic, more stable, and more likely to cross the placenta and to easily reach the brain than BDE-209. [ABSTRACT FROM AUTHOR]

Abstract: Contamination of barley by moulds and mycotoxins results in quality and nutritional losses and represents a significant hazard to the food chain. The presence of aflatoxin B1 (AFB1), B2 (AFB2), G1 (AFG1) and G2 (AFG2) and ochratoxin A (OTA) in stored barley in Spain has been studied. Species-specific PCR assays were used for detection of Aspergillus flavus, A. parasiticus, A. ochraceus, A. steynii, A. westerdijkiae, A. carbonarius and A. niger aggregate in mycotoxin-positive barley samples at different incubation times (0, 1 and 2days). Classical enumeration techniques (CFU/g) in different culture media for evaluation of Aspergillus in sections Flavi, Circumdati and Nigri were also used. One hundred and five barley kernel samples were collected in Spanish grain stores from 2008 to 2010, and analyzed using a previously optimized method involving accelerated solvent extraction, cleanup by immunoaffinity column, liquid chromatographic separation, post-column derivatization with iodine and fluorescence detection. Twenty-nine samples were contaminated with at least one of the studied mycotoxins. AFB1, AFB2, AFG1, AFG2, and OTA were detected in 12.4%, 2.9%, 4.8%, 2.9%, and 20% of the samples, respectively. Aflatoxins and OTA co-occurred in 4.8% of the samples. Maximum mycotoxin levels (ng/g) were 0.61 (AFB1), 0.06 (AFB2), 0.26 (AFG1), 0.05 (AFG2), and 2.0 (OTA). The results of PCR assays indicated the presence of all the studied species, except A. westerdijkiae. The PCR assays showed high levels of natural contamination of barley with the studied species of Aspergillus which do not correspond to the expected number of CFU/g in the cultures. These results suggest that a high number of non-viable spores or hyphae may exist in the samples. This is the first study carried out on the levels of aflatoxins and OTA in barley grain in Spain. Likewise, this is the first report on the presence of aflatoxigenic and ochratoxigenic Aspergillus spp. in barley grain naturally contaminated with those mycotoxins using a species-specific PCR approach. [Copyright &y& Elsevier]

As a part of a project aiming to assess the potential toxicological effects of contaminants in aquatic ecosystems, the objective of this work was to determine the occurrence of several selected endocrine-disrupting compounds in water and sediment and to estimate the estrogenicity of the water. The study consisted of four sampling campaigns at seven sampling points in the lower Llobregat catchment area (NE Spain). Water and sediment samples underwent chemical target analysis for 19 steroid estrogens and alkylphenols, which are known to be endocrine-disrupting compounds. In this study, the only estrogens detected in the water samples were estrone and estrone-sulfate, which were found at low levels (2–5 ng l−1). The alkylphenolic compound showing the highest concentrations was nonylphenol di-ether carboxylate (NP2EC), which was found at levels up to 30.62 µg l−1 in water samples and 535 ng g−1 in sediment samples. Kd was determined for several alkylphenolic compounds and showed the expected trend of decreasing Kd with increasing polarity. The concentrations of nonylphenol and octylphenol only exceeded the annual average of the European Union’s environmental quality standards (EQS) in one sampling point. However, the calculated estrogenic potential surpassed the expected effect concentration in several sampling points, indicating a potential risk. Therefore, we recommend that future EQS include short-chain alkylphenol ethoxylates and carboxylates. [ABSTRACT FROM AUTHOR]

Abstract: The aim of this study was to measure of serum levels of p,p′-dichlorodiphenyl trichloroethane (p,p′-DDT), p,p′-dichlorodiphenyl dichlorethylene (p,p′-DDE), β-hexachlorocyclohexane (β-HCH), and hexachlorobenzene (HCB) in healthy adults in Spain. Furthermore, we also analyzed these levels according to dietary, other lifestyle factors and anthropometric characteristics. We measured the concentrations of such organochlorine pesticides (OCPs) in serum samples collected during 1992–1996 from 953 subjects aged 35–64years, they were residents of five Spanish regions, they were randomly selected from the European Prospective Investigation into Cancer and Nutrition (EPIC) cohort. OCPs were determined by means of gas chromatography with electron-capture detection (GC-ECD). The most frequent compound found in serum was p,p′-DDE, present in 98% of the samples, followed by HCB and β-HCH, found in 89% and 77% of samples, respectively, while p,p′-DDT could be measured only in 26% of subjects. The geometric means of serum concentrations (ng/g lipid) were 822 for p,p′-DDE, 167 for β-HCH, and 379 for HCB. The concentrations of all OCPs were positively associated with age and body mass index, and decreased along the period of blood collection. No association was found between OCPs levels and dietary factors. The concentrations of p,p′-DDE and β-HCB were higher in Murcia, one of southern regions, most likely associated with intensive past use of pesticides related to agricultural practices, while higher levels of HCB were found in Navarra, located in the north, maybe due to industrial use rather than agricultural application. [Copyright &y& Elsevier]

The concentrations of hexachlorobenzene (HCB) were measured in samples of foodstuffs widely consumed by the population of Catalonia, Spain. Food samples were randomly acquired in 12 cities of Catalonia between March and June of 2006. HCB levels were determined by high-resolution gas chromatography-high-resolution mass spectrometry. The dietary intake of HCB was subsequently estimated for the population of Catalonia, and the results were compared with those of a survey performed in 2000. The highest HCB concentrations were found in oils and fats, fish and seafood, and dairy products, with mean levels of 0.481, 0.330, and 0.284 ng/g of fresh weight, respectively. HCB intake was estimated for four population groups: children, adolescents, adults, and seniors (aged >65 years). The highest and lowest HCB intake corresponded to children and seniors, respectively. Similar results were found in our 2000 survey. For a standard male adult of 70-kg body weight, in the 2000 study, total dietary intake of HCB was 166.2 ng/day (2.4 ng/kg of body weight per day), whereas in the current survey the intake was 71.6 ng/day (1.0 ng/kg of body weight per day). On a body-weight basis, it means a decrease of 57%, which was mainly due to the important reductions in the contribution of dairy products (mainly cheese), as well as those of meat and meat products and fish and seafood. All the intakes are considerably lower than the World Health Organization tolerable daily intake, which is 0.17 µg/kg/day for noncancer effects and 0.16 µg/kg/day for neoplastic effects in humans. [ABSTRACT FROM AUTHOR]

[Display omitted] • UHPLC-MS/MS for the analysis of UV filters in Mediterranean mussel samples. • Lyophilization, UAE and clean-up with C18 are proposed for sample treatment. • The highest levels of UV filters are associated with areas with higher recreational pressure. • BP-3 was the predominant UV filter at all locations, being at levels up to > 200 ng g−1. • The method has been validated and the analytical quality parameters described. Ultraviolet (UV) filters are a family of organic compounds widely used in sunscreens and personal care products (PCPs) as well as other materials such as plastics, toys and outdoor furniture, for their effectiveness in absorbing UVA and UVB radiation. These compounds directly enter the marine environment because of inefficient wastewater treatments and anthropogenic activities, posing a risk to the marine biota. The present study develops and validates a method to determine some of the most used UV filters (BP-1, BP-2, BP-3, BP-6, BP-8, 4-OH-BP and 4-MBC), in wild Mytilus galloprovincialis mussels using ultra-high performance liquid chromatography tandem mass spectrometry (UHPLC-MS/MS). The sample treatment is based on an ultrasound-assisted extraction followed by a clean-up step using C18 as sorbent. The methodology was satisfactorily validated, obtaining good features, and it was applied for the evaluation of the occurrence of the target analytes in mussels collected in five areas along the tourist coast of Granada (Spain) just after summer holydays period. The results showed a higher bioaccumulation in specimens sampled in recreational areas and with a closed geomorphology, being BP-3 the most predominant in all locations. BP-1 and BP-3 were quantified in all samples and the rest of UV filters were detected in most of them, except for BP-2. The data raises concern about the undesirable effects that UV filter pollution can cause in the area and highlights the need to establish practices that help preserve and sustain the marine ecosystem. [ABSTRACT FROM AUTHOR]

Spain is a relevant producer of oats (Avena sativa), but to date there has been no study on the occurrence/co-occurrence of mycotoxins in oats marketed in Spain. The present study is addressed to overcome this lack of knowledge. One hundred oat kernel samples were acquired across different Spanish geographic regions during the years 2015–2019 and analyzed for mycotoxin content using an ultra-high performance liquid chromatography electrospray ionization tandem mass spectrometry (UPLC–ESI–MS/MS) method and matrix-matched calibration. The focus was on the regulated mycotoxins although other relevant mycotoxins were considered. The percentage of incidence (levels ≥ limit of detection), mean and range (ng/g) of mycotoxins were as follows: zearalenone (66%, mean 39.1, range 28.1–153), HT-2 toxin (47%, mean 37.1, range 4.98–439), deoxynivalenol, (34%, mean 81.4, range 19.1–736), fumonisin B1 (29%, mean 157.5, range 63.2–217.4), and T-2 toxin, (24%, mean 49.9, range 12.3–321). Fumonisin B2, 3-acetyldeoxynivalenol, aflatoxins B1, B2, and G2, and ochratoxin A were also detected at low levels, but aflatoxin G1 was not. The maximum limits established by the European Commission for unprocessed oats were not exceeded, except for zearalenone (in one sample), and the sum of aflatoxins (in two samples). Mycotoxin co-occurrence at quantifiable levels in the same sample (two to five combinations) was found in 31% of samples. The most common mixtures were those of HT-2 + T-2 toxins alone or together with deoxynivalenol and/or zearalenone. [ABSTRACT FROM AUTHOR]

In this work, the performance of the atmospheric pressure chemical ionization (APCI) and photoionization (APPI) was assessed to develop a new selective and sensitive gas chromatography-high resolution mass spectrometry (GC-HRMS) method for the determination of polychlorinated naphthalenes (PCNs) in sediment samples. The capability of both APCI and APPI sources for the ionization of PCNs was investigated, showing the formation of the molecular ion and the [M‒Cl+O]‒ ion in positive and negative ion modes, respectively. Positive ion APCI provided high responses using high corona ion current, while the use of high vapour pressure dopant-solvents, such as toluene in positive mode and diethyl ether in the negative mode, was required to achieve high ionization efficiencies in APPI. The performance of the two API sources in the PCN determination by GC-HRMS were compared and the best results were achieved using the GC-APPI(+)-HRMS (Orbitrap) system. The GC-APPI(+)-HRMS (Orbitrap) method was applied to the characterization of Halowax mixtures and the analysis of marine sediments collected near to the coastal area of Barcelona (NE, Spain), demonstrating a great detection capability with low method limits of detection (0.2–1.6 pg g−1 dry weight), good precision (RSD <15%) and trueness (relative error <13%). Total PCN concentrations ranged from 0.35 to 5.0 ng g−1 dry weight and the presence of related compounds, such as polychlorinated biphenyls (PCBs), was also detected by combining positive and negative ion modes, providing complementary information to better monitor of all PCN congener groups. The results presented here show the feasibility of the GC-APPI-HRMS method for the suitable determination of PCNs. Image 1 • GC-APCI-HRMS and GC-APPI-HRMS were applied for the first time to determine PCNs. • GC-APPI provided the best ionization efficiency using high vapour pressure dopants. • GC-APPI-Orbitrap allowed the determination of PCN homologues and specific-isomers. • Positive ion GC-APPI-Orbitrap allowed the characterization of Halowax mixtures. • The GC-APPI-HRMS was successfully applied to the analysis of marine sediments. [ABSTRACT FROM AUTHOR]

One of the major challenges currently faced is to develop systematic ways of addressing chemical mixtures in environmental assessment. With this purpose, a simple, rapid, and sensitive method for the detection and quantification of a mixture of relevant contaminants in molluscs has been developed. The method is based on QuEChERS (Quick, Easy, Cheap, Effective, Rugged and Safe) and Ultra-High Performance Liquid Chromatography-High Resolution Mass Spectrometry (UHPLC-HRMS). It includes a mixture of 23 compounds formed by pesticides, endocrine disruptors and pharmaceuticals (metolachlor, simazine, desethylatrazine, atrazine, thiabendazole, diazinon, malathion, bentazone, MCPA, propanil, acetamiprid, imidacloprid, caffeine, bisphenol A, triclosan, triclocarban, methylparaben, ethylparaben, propylparaben, 1H-benzotriazole, sulfamethoxazole, venlafaxine and carbamazepine). The method was developed and validated in 4 different types of shellfish of high commercial interest such as mussel (Mytilus galloprovincialis), oyster (Crassostrea gigas), cockle (Cerastoderma edule) and razor shell (Solen marginatus). The mean percentage of recoveries obtained for all the compounds in each mollusc type (intra-specie) ranged from 96% to 107% showing the good performance of the method developed. The relative standard deviation was under 10% for the intra-day and 17% inter-day analyses. Method detection limits and method quantification limits were below 10 ng/g dry weight for all the species and compounds targeted. Finally, the method was applied to aquaculture samples, oysters and cockles, from Ebro Delta (Spain), after some episodes of mortality occurred in 2017. A high level of bisphenol A was detected in C. edule which may explain the mortality suffered by this organism. C. gigas presented low levels of metolachlor, bentazone, acetamiprid, and methylparaben. Image 1 • Simultaneous determination of a mixture of relevant contaminants in molluscs. • The method includes pesticides, endocrine disruptors and pharmaceuticals. • Simple, rapid and sensitive. • Developed and validated in 4 different types of shellfish of high commercial interest. • Applied to aquaculture samples from Ebro Delta, Spain. [ABSTRACT FROM AUTHOR]