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Recently, environment pollution around the globe has increased because of anthropogenic activities. As part of the biota, plants can assimilate the compounds present in air, water and soil and respond to changes in surround conditions, for that, they can be used as bioindicators of global pollution. However, urban plants' ability to monitor organic pollutants in air, soil, and water have not been profoundly studied yet. Anthropogenic contamination produced by five different types of pollutants [polycyclic aromatic hydrocarbons (PAHs), pharmaceuticals and personal care products (PPCPs), perfluoroalkyl substances (PFASs), pesticides and organophosphorus flame retardants (OPFRs)] has been studied in Riyadh and Abha areas (Saudi Arabia). In addition to the points in both cities, a control point located in the Asir National Park (close to Abha), which is little affected by human activity, was used. The 5 groups of contaminants were found with different but high detection frequencies from 85 % to 100 % in wild and ruderal plants. PAHs were detected in all the analyzed samples at the highest average sum of concentrations (ΣPAHs) 1486 ng·g -1 dry weight (d.w.). Statistically significant differences were obtained between Riyadh, Abha and the point located in the national park (p < 0.05). ΣPAHS in Riyadh >> ΣPAHs in Abha > ΣPAHs in the National Park. Values of the average sum of concentrations for the other groups of contaminants ΣPPCPs, ΣPFASs, Σpesticides and ΣOPFRs were 420.5, 171, 48 and 47 ng g -1 d.w., respectively. High values of PPCPs are due to the presence of salicylic acid. Differences in the average sum of each type of contaminant concentrations between cities were not statistically significant. The results of this assessment of wild and ruderal plants as bioindicators for 5 types of organic contaminants suggest that they can be used to monitor anthropogenic contaminants in the terrestrial environment., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 The Author(s). Published by Elsevier B.V. All rights reserved.)

Perfluoralkyl acids (PFAS) have been regarded as global pollutants for at least twenty years, with potentially negative physiological effects on multiple vertebrate species including humans. Here we analyze the effects of the administration of environmentally-relevant levels of PFAS on caged canaries (Serinus canaria) by using a combination of physiological, immunological, and transcriptomic analyses. This constitutes a completely new approach to understand the toxicity pathway of PFAS in birds. While we observed no effects on physiological and immunological parameters (e.g, body weight, fat index, cell-mediated immunity), the transcriptome of the pectoral fatty tissue showed changes compatible with the known effects of PFAS as obesogens in other vertebrates, particularly in mammals. First, transcripts related to the immunological response were affected (mainly enriched), including several key signaling pathways. Second, we found a repression of genes related to the peroxisome response and fatty acid metabolism. We interpret these results as indicative of the potential hazard of environmental concentrations of PFAS on the fat metabolism and the immunological system of birds, while exemplifying the ability of transcriptomic analyses of detecting early physiological responses to toxicants. As the potentially affected functions are essential for the survival of the animals during, for example, migration, our results underline the need for tight control of the exposure of natural populations of birds to these substances., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

Semivolatile organic pollutants have potential for long range atmospheric transport and can thus reach pristine remote lakes by atmospheric deposition. Polycyclic aromatic hydrocarbons (PAHs) are among the most abundant and toxic semivolatile pollutants affecting lakes, however, the main factors controlling their fate are still poorly known. Here we show two contrasting lines of evidence for the importance of microbial degradation on the environmental fate of PAHs in a high altitude deep lake. The first evidence is given by an assessment of the metagenomes from surface and deep waters from Lake Redon (Pyrenees Mountains), which shows the occurrence of the initial ring hydroxylating dioxygenases as well as other PAH degrading genes from the complete metabolic route of PAH degradation. The second line of evidence is by the application of an environmental fate model for PAHs to Lake Redon under two contrasting scenarios considering the inclusion or not of degradation. When degradation is included in the model, PAH concentrations in the sediment are predicted within a factor of two of those measured in Lake Redon. Finally, the extent of the degradation sink is quantified and compared to other cycling PAH fluxes in the lake., (Copyright © 2022. Published by Elsevier Ltd.)

This study aimed to the examination of the levels and effects of organobromine compounds (polybrominated diphenyl ethers: PBDEs and methoxylated brominated diphenyl ethers: MeO-PBDEs), in Sparus aurata native to the Lagoon of Bizerte. For that, different biomarkers of exposure (somatic indices, superoxide dismutase, and catalase activities) and effect (malondialdehyde level, histopathologic alterations, and DNA damage) as well as pollutant levels were measured in specimens collected from this impacted ecosystem and the Mediterranean Sea as a reference site. Bizerte Lagoon PBDE fish levels were higher than the Mediterranean Sea, whereas MeO-PBDEs were higher in the reference site. Fish from Bizerte Lagoon presented a higher hepatosomatic index, lower catalase and superoxide dismutase activity, higher level of malondialdehyde, and higher percentage of DNA tail in comparison to fish from the reference area. The histological study of the liver indicated substantial lesions in fish from the polluted site. The results showed strong positive correlations between the concentrations of the PBDE or MeO-PBDE and the MDA and DNA tail % levels and negative correlations for the activities of enzymes of SOD and CAT. Consequently, these findings could suggest a potential link between exposure to these pollutants and the observed biomarker responses in the Bizerte Lagoon seabream. Taken together, these results highlight the importance of biomarker selection and the selected sentinel fish species as useful tools for biomonitoring of aquatic pollution., (© 2022. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

Coastal seawaters receive thousands of organic pollutants. However, we have little understanding of the response of microbiomes to this pool of anthropogenic dissolved organic carbon (ADOC). In this study, coastal microbial communities were challenged with ADOC at environmentally relevant concentrations. Experiments were performed at two Mediterranean sites with different impact by pollutants and nutrients: off the Barcelona harbor ("BCN"), and at the Blanes Bay ("BL"). ADOC additions stimulated prokaryotic leucine incorporation rates at both sites, indicating the use of ADOC as growth substrate. The percentage of "membrane-compromised" cells increased with increasing ADOC, indicating concurrent toxic effects of ADOC. Metagenomic analysis of the BCN community challenged with ADOC showed a significant growth of Methylophaga and other gammaproteobacterial taxa belonging to the rare biosphere. Gene expression profiles showed a taxon-dependent response, with significantly enrichments of transcripts from SAR11 and Glaciecola spp. in BCN and BL, respectively. Further, the relative abundance of transposon-related genes (in BCN) and transcripts (in BL) correlated with the number of differentially abundant genes (in BCN) and transcripts (in BLA), suggesting that microbial responses to pollution may be related to pre-exposure to pollutants, with transposons playing a role in adaptation to ADOC. Our results point to a taxon-specific response to low concentrations of ADOC that impact the functionality, structure and plasticity of the communities in coastal seawaters. This work contributes to address the influence of pollutants on microbiomes and their perturbation to ecosystem services and ocean health.

The heterogeneous class of what we nowadays call antipsychotics was born almost 70 years ago with the serendipitous discovery of chlorpromazine. Their utilization is constantly growing because they are used to treat a diverse group of diseases and patients across all age groups: schizophrenia, bipolar disease, depression, autism, attention deficit hyperactivity disorder, behavioural and psychological symptoms in dementia, among others. They possess a complex pharmacological profile, acting on multiple receptors: dopaminergic, serotoninergic, histaminergic, adrenergic, and cholinergic, leading scientists to call them "agents with rich pharmacology" or "dirty drugs". Serotonin, dopamine, acetylcholine, noradrenaline, histamine and their respective receptors are evolutionary ancient compounds, and as such, are found in many different living beings in the environment. Antipsychotics do not disappear once excreted by patient's urine or faeces and are transported to wastewater treatment plants. But as these plant's technology is not designed to eliminate drugs and their metabolites, a variable proportion of the administered dose ends up in the environment, where they have been found in almost every matrix: municipal wastewater, hospital sewage, rivers, lakes, sea and even drinking water. We believe that reported concentrations found in the environment might be high enough to exert significant effect to aquatic wildlife. Besides, recent studies suggest antipsychotics, among others, are very likely bioaccumulating through the web food. Crucially, psychotropics may provoke behavioural changes affecting populations' dynamics at lower concentrations. We believe that so far, antipsychotics have not received the attention they deserve with regards to drug pollution, and that their role as environmental pollutants has been underrated., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier B.V. All rights reserved.)

Fifty-five household dust samples collected within six settlements surrounding oil production complexes along the Ecuadorian Amazonia were analysed to evaluate the occurrence and distribution of polycyclic aromatic hydrocarbons (PAHs), phthalates, alkylphenols (APs), bisphenol A (BPA), nicotine, organophosphorus flame retardants (OPFRs), polychlorinated biphenyls (PCBs), legacy organochlorine pesticides (OCs) and organophosphorus pesticides. Studied areas are mainly affected by gas flares emissions and oil spilling coming from extractivist operations and pesticides used in agriculture. Median ΣPAHs values ranged from 739 to 1182 ng g -1 and up to 52% of the PAH dust concentrations were associated to petrogenic activities from crude oil extraction, according to diagnostic ratios. ΣPAHs and toxic equivalents based on benzo[a]pyrene concentration (ΣTEQ BaP , ng g -1 ) suggested similar toxicities among the different areas. Individual lifetime cancer risk (ILCR dust ) was calculated for ingestion and dermal contact exposure routes and a non-acceptable total carcinogenic risk of up to 10 -4 (one case per ten thousand people) was found for newborns from 0 to 3 years-old in Pimampiro area. Plasticisers and OPFRs were present in dust at maximum median concentrations of 332,507 ng g -1 (DEHP), 5,249 ng g -1 (DBP), 1,885 ng g -1 (BPA), 871 ng g -1 (TBOEP) and 122 ng g -1 (TEHP). Some dust samples from Ecuadorian houses had high maximum levels of legacy and modern pesticides such as chlorpyrifos (up to 44,176 ng g -1 ), 4,4'-DDT (12,958 ng g -1 ), malathion (34,748 ng g -1 ) and α+β-endosulfan (10,660 ng g -1 ) attributed to inappropriate use and storage of the pesticides. Finally, nicotine was seldom detected (36 ng g -1 ). The sources and risks of these compounds are discussed based on the activities carried out in the study areas and attending to an additional non-cancer risk assessment which showed high hazard quotients (HQ) and hazard indexes (HI) for DEHP, DBP, 4,4'-DDT, malathion, chlorpyrifos, naphthalene and benzo[a]pyrene in newborns and children up to 16 years-old., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Inc. All rights reserved.)

Activation of peroxymonosulfate (PMS) and persulfate (PS) by Fe 2+ is widely used for oxidizing organic pollutants. However, their application is limited by the slow conversion rate of Fe 3+ to Fe 2+ and the accumulation of Fe 3+ . Here, we introduce commercial molybdenum disulfide (MoS 2 ) to promote the activation of PMS and PS by Fe 2+ , and explore the mechanism of this promotion using experimental and theoretical methods. The Fe 2+ /PMS/MoS 2 and Fe 2+ /PS/MoS 2 systems achieved faster rate of PMS and PS conversion and also higher degradation efficiency toward pollutants. About 94.7% and 87.6% of rhodamine B (RhB) could be degraded in Fe 2+ /PMS/MoS 2 (54 μM Fe 2+ , 1 mM PMS) and Fe 2+ /PS/MoS 2 (54 μM Fe 2+ , 0.25 mM PS) system, respectively. MoS 2 addition simultaneously promoted the Fe 3+ /Fe 2+ cycle, the PMS and PS conversion, and the RhB mineralization. As a co-catalyst, MoS 2 exhibited excellent stability for eight successive cycles of use. The predominant oxidant was identified as SO 4 - in Fe 2+ /PMS/MoS 2 and Fe 2+ systems. Theoretical calculations and a kinetic model were employed to evaluate the catalytic performance of the systems. These novel findings indicate that the combination of a commercially available MoS 2 catalyst with a low dosage of Fe 2 is a promising and effective approach for efficient activation of PMS and PS to produce SO 2+ is a promising and effective approach for efficient activation of PMS and PS to produce SO 4 - and OH., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Inevitable use of pesticides due to modern agricultural practices and the associated worldwide environmental pollution has called the special attention of the researchers to overcome the persistence, recalcitrance, and multi-faceted toxicity of pesticides-based emerging contaminants. Some restricted use pesticides (RUPs) are highly toxic and carcinogenic chemicals that can be easily accumulated into non-target organisms, including humans, aquatic invertebrates, algae, and microbes. With regard to physicochemical strategies, enzymes-mediated bioremediation is a compelling and meaningful strategy for biodegradation and biotransformation of pesticides into harmless chemical species. Oxidoreductases hydrolases and transferases are among the most representative classes of enzymes pursued and engineered for this purpose. Ligninolytic enzymes, particularly laccases, are of exceptional interest due to high efficiency, specificity, eco-sustainability, and wide-ranging substrates. However, the use of native enzymes is often hindered in industrial processes for the effective removal of refractory compounds by their high cost and susceptibility. Many of these drawbacks can be addressed by enzyme immobilization on some suitable support materials. Increase in stability, reusability, reduction of product inhibition, enhanced activity, specificity, and easier product separation are amid the desirable characteristics of immobilization to construct biocatalysts for continuous systems. This review summarizes recent and up-to-date literature on the use of enzymes, explicitly, free as well as immobilized laccases in the degradation of different pesticides. In the first part, source and occurrence of pesticides in the environment, their types, and associated detrimental effects on the ecosystem/human health are comprehensively described. Afterward, we highlighted the use of different enzymes with a particular emphasis on laccase for the degradation and detoxification of an array of pesticides. Finally, the review is closed with concluding remarks, and possible future direction is proposed in this very important research arena. In conclusion, it is envisioned that effective deployment of laccase-assisted biocatalytic systems for the degradation or removal of diverse pesticides and related contaminants will help to better understand the persistence and removal fate of these hazardous pollutants. Moreover, the current research thrust presented in this review will additionally evoke researcher to engineer robust and sustainable processes to remediate pesticides-contaminated environmental matrices effectively., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Exposure to air and dust pollutants can cause several adverse effects on human health. This study proposes the use of nasal lavages as a non-invasive sampling technique to determine in a direct way pollutant intake through inhalation. We evaluate the occurrence of compounds widely used in domestic products and construction materials (organophosphorus flame retardants (OPFR), phthalates, alkylphenols and bisphenol A), applied for pest control in cities (pesticides) and emitted through car exhausts (polycyclic aromatic hydrocarbons, PAHs) or smoking (nicotine). Contaminants were liquid-liquid extracted from nasal lavages and analysed using gas chromatography coupled to tandem mass spectrometry (GC-MS/MS). All 29 individuals inhabiting in Barcelona city had phthalates and bisphenol A at concentrations up to 31,300 ng mL -1 for diethylhexyl phthalate (DEHP) and 118 ng mL -1 for BPA. Individual PAHs, OPFR and alkylphenols had median values below their MQLs except for 2-ethylhexyldiphenyl phosphate (EHDPhP) with a median of 1.47 ng mL -1 . Nicotine was detected at the highest concentrations in all active smokers (median 2.16 ng mL -1 ). Contrarily, pesticides were sporadically detected. Nasal lavages revealed to be an appropriate indicator likely to reflect exposure to dust and air contaminants., (Copyright © 2019 Elsevier Inc. All rights reserved.)

Huge amounts of waste containing flame retardants reach landfills annually, which can result in environmental contamination if this type of solid residues is not properly managed. This study presents data concerning the occurrence of organophosphorus flame retardants (OPFRs), polybrominated diphenyl ethers (PBDEs) and new brominated flame retardants (NBFRs) in soil, dust, leachate and well water samples from a landfill in Brazil. Samples were collected in different points of the landfill site, including offices, concierge, electronic waste storage area, bulk waste storage area, a place where a recycling cooperative operates, leachate pound and wells. Most of the flame retardants (FRs) were quantified in soil samples (up to 2500 ng g -1 ). The tris(2-chloroisopropyl) phosphate (TCIPP) and tris(1,3-dichloroisopropyl) phosphate (TDCIPP) were present at the highest levels in the site where bulk waste was disposed in the open air. The most abundant brominated FRs in soil samples were BDE-99, BDE-209, decabromodiphenyl ethane (DBDPE) and 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE), and the highest levels were observed in the samples collected from the electronic waste storage area. Concerning dust samples, the highest levels of brominated FRs were observed in the electronic waste storage area, while the highest levels of OPFRs were observed in the landfill office. TCIPP, TDCIPP and tris(2-choroethyl) phosphate (TCEP) were quantified in the well water sample collected downstream the bulk waste area. Finally, six OPFRs were quantified in leachate at concentrations ranging from 14 to 965 ng L -1 . In conclusion, this study demonstrates that an improper management of wastes containing FRs in landfills can potentially contaminate the surrounding environment and groundwater., (Copyright © 2018 Elsevier Inc. All rights reserved.)

Persistent organic pollutants (POPs) have the potential to impair the endocrine regulation of organisms and alter their ability to respond to environmental changes. We studied whether polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) affected the endocrine regulation of free-living and captive red kites (Milvus milvus) through studying the dynamics of corticosterone (CORT) and dehydroepiandrosterone (DHEA). We sampled migratory free-living kites coming from northern Europe and captive kites born in a rehabilitation center in Spain. We used body feathers from the interscapular region as a minimally-invasive and integrative matrix. The most abundant compound detected in free-living kites was 4,4'-dichlorodiphenyldichloroethylene (4,4'-DDE; 6.10 ± 1.56 ng g -1 dw feather) followed by CB-153 (3.10 ± 0.63 ng g -1 dw feather) and CB-180 (2.43 ± 1.08 ng g -1 dw feather). In captive kites, the most abundant compounds were 4,4'-dichlorodyphenyltrichloroethane (4,4'-DDT; 2.38 ± 1.30 ng g -1 dw feather), CB-153 (2.15 ± 0.47 ng g -1 dw feather) and hexachlorobenzene (HCB; 2.03 ± 0.45 ng g -1 dw feather) at similar concentrations. Free-living kites showed higher levels of 4,4'-DDE and CB-180 in comparison to captive kites. Age influenced HCB and CB-101 levels, whereas body mass was inversely related to CB-180 and 4,4'-DDT. Interestingly, captive kites showed a ratio DDT/DDE higher than 1 suggesting a relatively recent exposure of DDT, in contrast to free-living kites. Regarding hormonal levels, free-living kites showed higher levels of CORT (3.30 ± 0.22 pg mm -1 feather) than captive (2.40 ± 0.16 pg mm -1 feather), reflecting higher allostatic load. In addition, a positive association between PCBs and DDTs and adrenal hormones was found in free-living kites, suggesting an increase of CORT as a response of the endocrine system to cope with stressors and a subsequent elevation of DHEA to ameliorate the potential negative effects that high CORT levels could cause to the organism., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

The aim of the present work was to comparatively assess the occurrence and impact of persistent organic pollutants (POPs) in nine natural and national parks from Spain and Portugal using gull eggs (Larus michahellis and L. audouinii) as bioindicators of environmental contamination. Sampling was performed during the breeding season of 2016. Compounds studied include polychlorinated biphenyls (PCBs), organochlorinated pesticides (OC pesticides), perfluorooctane sulfonic acid (PFOS) and polybrominated diphenyl ethers (PBDEs), and were analyzed using mass spectrometric based techniques. The results showed a high contamination by PCBs in all colonies, with total levels ranging from 59 to 1278ng/g wet weight (ww), despite their use is not currently authorized. OC pesticides were also present in all colonies, with a high incidence of 4,4'-DDE in gull eggs at levels up to 218±50ng/g ww in L. michahellis and 760±412ng/g ww in L. audouinii from the Ebro Delta natural park. PBDEs and PFOS were also detected at levels up to 91.7±21.3ng/g ww, which can be attributed to a more recent use. Except for PBDEs, the POP levels in eggs from L. audouinii were higher than in L. michahellis, presumably associated to the fish-based diet of the former. Finally, the effect of POP levels on eggshell parameters (volume, eggshell thickness and desiccation index) were investigated for each colony and gull species in order to evaluate the egg viability and, therefore, the reproduction success., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Discarded vehicle tires have become an increasing concern worldwide due to the enormous amount of wastes generated and the increasing evidence of health problems associated to their disposal and accidental combustion. Previous studies conducted involving either simulated or open uncontrolled tire fires have identified aromatics belonging to two main classes, volatile organic compounds and polycyclic aromatic compounds (PAHs), as the most relevant chemicals generated in these burning processes. As a consequence, and due to their recognized toxicity, most studies reported up to now have mainly focused on these two categories of compounds being information concerning the possible occurrence of other aromatic classes rather limited. In this study, the enhanced separation power and structural confirmation capabilities provided by comprehensive two-dimensional gas chromatography-time-of-flight mass spectrometry (GC×GC-ToF MS) has been used, for the first time, for the non-targeted analysis of soils impacted by a tire fire and an ash collected at the scene of the fire. In total, 118 volatile and semi-volatile aromatic compounds have been differentiated. Among them, 104 compounds have been either positively or tentatively identified. PAHs with 3-5 rings and their alkyl-derivatives were the most numerous and relevant classes in the investigated samples. A significant number of sulfur, oxygen- and nitrogen-containing PAHs were also detected in the samples. The application of a script function to the raw GC×GC-ToF MS data allowed the fast filtering and automatic recognition of compounds containing halogens in their structure. This part of the study evidenced that only a limited number of regulated persistent organic pollutants were present in the investigated samples. However, it also revealed the presence of emerging organophosphorous flame retardants, whose levels in tire fire impacted soils are reported for the first time., (Copyright © 2017 Elsevier B.V. All rights reserved.)

Marine pollution has been increasing as a consequence of anthropogenic activities. The preservation of marine ecosystems, as well as the safety of harvested seafood, are nowadays a global concern. Here, we report for the first time the contamination levels of a large set of 99 emerging and persistent organic contaminants (butyltins (BTs), polycyclic aromatic hydrocarbons (PAHs), pesticides including pyrethroids, pharmaceuticals and personal care products (PCPs) and flame retardants) in roe/gonads of sea urchin Paracentrotus lividus. Sea urchins are a highly prized worldwide delicacy, and the harvesting of this seafood has increased over the last decades, particularly in South West Atlantic coast, where this organism is harvested mainly for exportation. Sampling was performed in three harvesting sites of the NW Portuguese coast subjected to distinct anthropogenic pressures: Carreço, Praia Norte and Vila Chã, with sea urchins being collected in the north and south areas of each site. Butyltins and pharmaceuticals were not found at measurable levels. Several PAHs, four pyrethroids insecticides, four PCPs and eleven flame retardants were found in roe/gonads of sea urchins, though in general at low levels. Differences among harvesting sites and between areas within each site were found, the lowest levels of contaminants being registered in Carreço. The accumulation of contaminants in sea urchins' roe/gonads seemed to reflect the low anthropogenic pressure felt in the sampling sites. Nevertheless, taking into account the low accumulated levels of chemicals, results indicate that sea urchins collected in South West Atlantic coast are safe for human consumption., (Copyright © 2017 Elsevier Inc. All rights reserved.)

Incorporation of chemometric tools in behavioural data management workflows allows for the early identification of most relevant endpoints complementarily to statistical confirmatory approaches. In this work, the effects of two model neurotoxicants, chlorpyrifos (CPF) and nicotine, exposures on behavioural profiles of adult zebrafish at three different times (2, 6 and 24h) were evaluated using open field test (OFT) paradigm experiments. Two chemometric methods like Principal Component Analysis (PCA) and Analysis of Variance-Simultaneous Component Analysis (ASCA) have been used to interpret the changes observed in the obtained behavioural data. A decreased of the locomotor activity, an anxiolytic effect and an altered exploratory behaviour were the most affected behavioural endpoints in the CPF exposures. However, an increase of the locomotor activity and an anxiogenic effect were observed in the nicotine exposures. Finally, an excellent correlation between the ASCA results and the results obtained using traditional statistical procedures for both compounds were encountered., (Copyright © 2017 Elsevier Inc. All rights reserved.)

Occurrence and effects of contaminants of emerging concern pose a special challenge to environmental scientists. The investigation of these effects requires reliable, valid, and comparable analytical data. To this effect, two critical aspects are raised herein, concerning the limitations of the produced analytical data. The first relates to the inherent difficulty that exists in the analysis of environmental samples, which is related to the lack of knowledge (information), in many cases, of the form(s) of the contaminant in which is present in the sample. Thus, the produced analytical data can only refer to the amount of the free contaminant ignoring the amount in which it may be present in other forms; e.g., as in chelated and conjugated form. The other important aspect refers to the way with which the spiking procedure is generally performed to determine the recovery of the analytical method. Spiking environmental samples, in particular solid samples, with standard solution followed by immediate extraction, as is the common practice, can lead to an overestimation of the recovery. This is so, because no time is given to the system to establish possible equilibria between the solid matter-inorganic and/or organic-and the contaminant. Therefore, the spiking procedure need to be reconsidered by including a study of the extractable amount of the contaminant versus the time elapsed between spiking and the extraction of the sample. This study can become an element of the validation package of the method.

The impact of pollution caused by severe anthropogenic pressure in the Mediterranean Sea, an important biodiversity hotspot, requires continuous research efforts. Sources of highly toxic chemicals such as Persistent Organic Pollutants (POPs) are misunderstood in representative Mediterranean species, which limits our capability to establish proper conservation strategies. In the present study, eggs of Audouin's and yellow-legged gulls (Larus audouinii and L. michahellis) were used to investigate the trophic sources, as measured by δ(13)C, δ(15)N, and δ(34)S, of legacy POPs, in particular, polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs) and non-ortho polychlorinated biphenyls (no-PCBs), as well as recently-regulated POPs, e.g., polybrominated diphenyl ethers (PBDEs). Special attention was paid to the usefulness of rarely-explored δ(34)S ratios in explaining POP exposure in wildlife, and δ(34)S was the isotopic ratio that best explained POP variations among gulls in most cases, thus demonstrating its usefulness for understanding POP exposure in wildlife. Significant relationships between stable isotope signatures and POP concentrations revealed increasing levels of no-PCBs and low halogenated PCDD/Fs and PBDEs in Mediterranean gulls as the consumption of marine resources increases. In contrast, highly chlorinated and brominated congeners appeared to preferentially accumulate in gulls feeding primarily on refuse from dump sites and terrestrial food webs. The use of suitable dietary tracers in the study of POPs in yellow-legged gulls revealed the importance of dump sites as a source of POPs in Mediterranean seabirds, which has not previously been reported. In contrast, the preferential accumulation through marine food webs of low chlorinated PCCD/Fs and no-PCBs, which show the highest toxic equivalents factors (TEFs), led to a significantly greater toxicological concern in Audouin's as compared to yellow-legged gulls. Audouin's gull exposure to POPs appears primarily related to the pelagic food webs commonly exploited by fisheries, highlighting the need for further research given the potential impact on human consumption., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

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 223pg/g lipid weight (lw) and ∑dl-PCB concentrations varied from 146 to 911ng/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., (Copyright © 2015 Elsevier B.V. All rights reserved.)

This study aimed to determine the accumulation and maternal transfer of perfluorooctane sulphonic acid (PFOS) in yellow-legged gulls (YLG, Larus michahellis) and the protected species Audouin's gull (AG, Larus audouinii), which cohabit in the Ebro Delta Natural Park (Catalonia, Spain). The Estimated Daily Intake (EDI) through diet (fish and crayfish), depuration rates and transfer capacity from blood to first eggs was studied for a set of 44 pairs. For AG, mean (±SD) EDI was of 128 ± 36 ng/d in males and 119 ± 32 ng/d in females, and for YLG, 170 ± 48 ng/d in males and 159 ± 42 ng/d in females. PFOS levels in blood were higher in males than females (60.6 ± 21 and 61.1 ± 2 7ng/g ww in AG and YLG males versus 25.2 ± 12 and 27.3 ± 14 ng/g ww in AG and YLG females), with little differences among species. The lower levels in females were attributed to the annual release of PFOS to eggs during the laying period, which was estimated of 5544 ± 1571 ng/egg for AG females and 6716 ± 2689 ng/egg for YLG. The overall mass balance of PFOS calculated for both species clearly demonstrates that uptake is higher than elimination rates, considering depuration rates and transfer of PFOS to eggs, and this explains that PFOS is accumulated in gulls in a yearly basis., (Copyright © 2015 Elsevier Inc. All rights reserved.)

The aim of this study is to evaluate the presence of perfluoroalkyl substances (PFASs) in the blood of 46 residents from Barcelona and to study the factors that affect exposure. Compounds analysed included perfluorooctane sulfonate (PFOS), perfluorohexane sulfonate (PFHxS), perfluorobutane sulfonate (PFBS), perfluorooctanoate acid (PFOA) and perfluorononanoate acid (PFNA). Blood was liquid-liquid extracted and PFASs were determined by liquid chromatography coupled to tandem mass spectrometry. Good recoveries (between 97 ± 14 and 105 ± 13 %) were obtained and method detection limits were from 0.03 to 0.07 ng mL(-1). ΣPFASs ranged from 0.11 to 4.37 ng mL(-1). PFOS was the main compound detected at 0.09-3.35 ng mL(-1), followed by PFOA and PFHxS. PFBS and PFNA were seldom detected. Working conditions, smoking and gender did not cause any significant differences among ΣPFASs levels in the blood while age and parity produced decreased concentrations. On the other hand, laboratory working conditions produced significant higher PFOA levels compared to the general population. Compared to other studies, the PFASs levels in blood from Barcelona residents is low (mean ΣPFASs of 1.67 ± 0.88 ng mL(-1)) and with little variation among the studied population.

The aim of the present study was to determine the distribution of per- and polyfluoroalkyl substances (PFASs) in three-egg clutches of Audouin's gull (Larus audouinii) breeding in Ebro Delta's colony according to the laying order (a, b and c eggs). Five PFASs were analyzed in 30 eggs (yolk and albumen separately), corresponding to 10 three-egg clutches. Carbon and nitrogen stable isotopes were measured as dietary tracers. PFASs were not detected in albumen. In egg yolks, perfluorooctane sulfonate (PFOS) was the main compound detected followed by perfluorononanoic acid (PFNA), perfluorohexane sulfonate (PFHS) and perfluorooctanoic acid (PFOA). Perfluorooctane sulfonate (PFBS) was not detected. Mean ΣPFASs for a-eggs was of 236±57 ng g(-1) yolk wet weight (ww), for b-eggs was of 140±56 ng g(-1) yolk ww and for c-eggs, 133±54 ng g(-1) yolk ww. PFOS concentration decreased according to the laying order of the eggs, showing significant differences between consecutive eggs. In addition, significant correlation (rs2=0.7-0.9) was observed for PFOS concentration within the eggs from the same clutch. No relationship was found between PFOS levels and stable isotopes signatures. Capsule: In Audouin gull's eggs, PFOS was the main PFASs detected and its concentration decreased according to the laying sequence., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

A novel fully automated method based on dual column switching using turbulent flow chromatography followed by liquid chromatography coupled to tandem mass spectrometry (TFC-LC-MS/MS) was applied for the determination of endocrine disruptors (EDCs) and related compounds in sediment and sewage sludge samples. This method allows the unequivocal identification and quantification of the most relevant environmental EDCs such as natural and synthetic estrogens and their conjugates, antimicrobials, parabens, bisphenol A (BPA), alkylphenolic compounds, benzotriazoles, and organophosphorus flame retardants, minimizing time of analysis and alleviating matrix effects. Applying this technique, after the extraction of the target compounds by pressurized liquid extraction (PLE), sediment and sewage sludge extracts were directly injected to the chromatographic system and the analytes were concentrated into the clean-up loading column. Using six-port switching system, the analytes were transferred to the analytical column for subsequent detection by MS-MS (QqQ). In order to optimize this multiplexing system, a comparative study employing six types of TurboFlow™ columns, with different chemical modifications, was performed to achieve the maximum retention of analytes and best elimination of matrix components. Using the optimized protocol low limits of quantification (LOQs) were obtained ranging from 0.0083 to 1.6 ng/g for sediment samples and from 0.10 to 125 ng/g for sewage sludge samples (except for alkylphenol monoethoxylate). The method was used to evaluate the presence and fate of target EDCs in the Ebro River which is the most important river in Spain with intensive agricultural and industrial activities in the basin that contribute to deteriorating soil and water quality., (Copyright © 2014 Elsevier B.V. All rights reserved.)

Recently, hydroxylated polybrominated diphenyl ethers (OH-PBDEs) have emerged as environmentally relevant pollutants due to recent reports of their natural production and metabolism. Recent mechanistic studies in human and rats have shown that some OH-PBDEs are more potent than parent compounds (PBDEs) and may contribute substantially to neurodevelopmental disorders by direct neurotoxicity, or indirectly through altered thyroid disruption. However, analytical methodologies for determination of OH-PBDEs are currently limited. In this study a robust liquid chromatography-electrospray tandem triple quadrupole-linear ion trap mass spectrometer (LC-ESI-QqLIT-MS-MS) in negative mode method was developed for the determination of eleven OH-tri- to OH-hexa-PBDEs. Two different columns were tested and compared for chromatographic separation: a C18 BetaBasic and a Purospher STAR RP 18, working at pH 8 and 10, respectively. Mobile phase (acetonitrile:water) was optimized by changing the pH of the aqueous phase and the concentration of the organic modifier (methanol). The MS-MS parameters (declustering potential (DP), collision energy (CE) and cell exit potential (CXP)) were optimized. Selected reaction monitoring (SRM) was used in order to increase sensitivity. Two SRM transitions ([M-H](-)>[Br](-)) were selected for each OH-PBDE, one for quantification and the second one for confirmation. Under the optimized conditions, the instrumental limits of detection were between 0.17 and 0.72injectedpg. The method provided good linearity (r>0.99 for a concentration range of 0.30-100ng/mL), accuracy and precision (%Dev and %RSD≤20% for intra- and inter-assays)., (Copyright © 2013 Elsevier B.V. All rights reserved.)

In the present study the occurrence of emerging hydrophobic organic pollutants in sediment samples from South America (Chile and Colombia) was investigated for the first time. Nineteen Chilean and thirteen Colombian sediment samples were analyzed in order to determine their content of brominated flame retardants (BFRs) (including PBDEs and emerging BFRs) as well as UV filters (UV-F). Samples were collected from neighboring aquatic ecosystems highly urbanized and industrialized in Colombia (Magdalena River area) and Chile (Biobio region). Different analytical procedures were applied depending on the selected analytes, based on chromatographic and mass spectrometric methodologies (GC-MS and LC-MS-MS). In general, concentration levels of both BFRs (up to 2.43 and 143ngg(-1) dw of PBDEs in Chile and Colombia, respectively) and UV-F (nd-2.96 and nd-54.4ngg(-1) dw in Chile and Colombia, respectively) were in the low range of published data, and the contribution of BFRs was higher than that of UV-F for almost all the sampled sediments., (Copyright © 2013 Elsevier Ltd. All rights reserved.)

After decades of primary emissions, reservoirs of persistent organic pollutants (POPs) have accumulated in soils and snow/ice in polar regions. These reservoirs can be remobilized due to decreasing primary emissions or due to climate change-driven warmer conditions. Results from a sampling campaign carried out at Livingston Island (Antarctica) focusing on field measurements of air-soil exchange of POPs show that there is a close coupling of the polychlorinated biphenyls (PCBs) in the atmosphere and snow/ice and soils with a status close to air-surface equilibrium to a net volatilization from Antarctic reservoirs. This remobilization of PCBs is driven by changes in temperature and soil organic matter (SOM) content, and it provides strong evidence that the current and future remobilization and sinks of POPs are a strong function of the close coupling of climate change and carbon cycling in the Antarctic region and this is not only due to warming. Whereas an increase of 1 °C in ambient temperature due to climate change would increase current Antarctic atmospheric inventories of PCBs by 21-45%, a concurrent increase of 0.5% SOM would counteract the influence of warming by reducing the POP fugacity in soil. A 1 °C increase in Antarctic temperatures will induce an increase of the soil-vegetation organic carbon and associated POPs pools by 25%, becoming a net sink of POPs, and trapping up to 70 times more POPs than the amount remobilized to the atmosphere. Therefore, changes in soil biogeochemistry driven by perturbations of climate may increase to a larger degree the soil fugacity capacity than the decrease in air and soil fugacity capacity due to higher temperatures. Future research should focus on quantifying these remobilization fluxes and sinks for the Antarctic region.

Dechlorane Plus, dechlorane 602, dechlorane 603 and dechlorane 604 are flame retardants that have been used for a long time as a substitute for mirex, but they have not been noticed as environmental contaminants until recently (2006). Regardless of their large molecular size and very high lipophilicity (log K(OW) > 9), Dechlorane Plus and related compounds have been detected in different aquatic and terrestrial species, supporting their bioaccumulation and biomagnification. Moreover, some studies showed different behaviour of the syn-Dechlorane Plus and anti-Dechlorane Plus isomers in the environment and different biomagnification factors in biota. This review describes the different analytical approaches applied to the determination of Dechlorane Plus and related compounds. Moreover, a summary of their levels in aquatic and terrestrial biota, as well as in humans, is presented, showing also current research results on their bioaccumulation and biomagnification potential. Finally, isomer-specific bioaccumulation of Dechlorane Plus is also discussed.

The aim of this study was to determine the impact of priority and emerging Persistent Organic Pollutants (POPs) in gull eggs from two species, the scavenger Larus michahellis and the protected species, Larus audouinii. These two species share habitat in the Natural Park of the Ebro delta (Catalonia, Spain). Compounds studied are included or under consideration in the Stockholm Convention and comprise polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs), polybrominated diphenyl ethers (PBDEs), polychlorinated biphenyls (PCBs), organochlorinated compounds (OCs), perfluorinated compounds (PFCs) and short chain chlorinated paraffins (SCCPs). Four methods based in selective extraction and gas or liquid chromatography coupled to mass spectrometry were used and quality parameters are provided. OC pesticides and marker PCBs were the most abundant chemical families detected in eggs from the two species, followed by PFCs, PBDEs (especially BDE 209) and SCCPs. Dioxin-like PCBs and PCDD/Fs were also detected in all samples. The overall widespread presence of POPs is discussed in terms of feeding habits, bird ecology and anthropogenic pressures in the protected Ebro delta breeding area., (Copyright © 2012 Elsevier Ltd. All rights reserved.)

Comparisons of brominated flame retardants (BFRs) in the eggs of peregrine falcons (Falco peregrinus) recently collected (2003-2007), are made between Canada (N=12) and Spain (N=13). Overall, concentrations of sum (Σ) polybrominated diphenyl ethers (PBDEs; 16 di-deca-BDE congeners) exceeded Σhexabromocyclododecane (HBCD) and were an order of magnitude higher than 2,2'4,4',5,5'-hexabromobiphenyl (BB-153)>hexachlorocyclopentenyl-dibromocyclooctane (HCBDCO)>1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE)>decabromodiphenylethane (DBDPE)>octabromotrimethylphenyllindane (OBIND)>hexabromobenzene (HBB)>bis(2-ethyl-1hexyl)tetrabromophthalate (BEHTBP). This is the first report of detectable HBCDCO and BEHTBP concentrations in biota, and the highest in ovo concentration of ∑HBCD (14,617 ng/glw; Montreal, Canada) to date. There were significantly greater egg concentrations of BB-153, ΣHBCD, and ΣPBDE including BDE-153, -99, -100 and -183, in Canadian than Spanish peregrines with a terrestrial diet. HBB, BTBPE, and OBIND were detected in eggs from both countries, but only Canadian peregrine eggs had detectable levels of HCDBCO (25%) and DBDPE (N=1). The in ovo PBDE congener profile was dominated by BDE-153>BDE-99>BDE-47>BDE-183>BDE-100>BDE-209, with the isomeric HBCD pattern being α-HBCD>γ-HBCD (β-HBCD undetected). The Canadian peregrine eggs had lower enantiomeric HBCD values consistent with their higher fractions of (-) α-HBCD, suggesting selective enantiomeric enrichment or that the (+) α-isomer is more readily metabolized and so deposited in the egg through maternal transfer. Continental differences in egg burdens of peregrines are discussed relative to BFR usage patterns and exposure of peregrines on their breeding grounds., (Crown Copyright © 2011. Published by Elsevier Ltd. All rights reserved.)

In this study, the presence of 18 perfluorinated compounds was investigated in biota and environmental samples from the Antarctica and Tierra de Fuego, which were collected during a sampling campaign carried out along February and March 2010. 61 samples were analysed including fish, superficial soils, guano, algae, dung and tissues of Papua penguin by liquid chromatography coupled to tandem mass spectrometry. The concentrations of PFCs were ranging from 0.10 to 240 ng/g for most of the samples except for penguin dung, which presented levels between 95 and 603 ng/g for perfluorooctane sulfonate, and guano samples from Ushuaia, with concentration levels of 1190-2480 ng/g of perfluorohexanoic acid. PFCs acids presented, in general, the highest levels of concentration and perfluorooctanesulfonate was the most frequently found compound. The present study provides a significant amount of results, which globally supports the previous studies, related to the transport, deposition, biodegradation and bioaccumulation patterns of PFCs., (Copyright © 2011 Elsevier Ltd. All rights reserved.)

Banned pesticides such as HCB and p,p'-DDE, and other legacy and ongoing pollutants such as PCBs and PAHs, were measured in different vegetation types and soil samples collected at selected areas from Antarctic Peninsula (Deception and Livingstone Islands, Southern Shetlands). Two Antarctic expeditions (in 2005 and 2009) were carried out to assess POPs levels at remote areas, and close to current and abandoned Antarctic research settlements, to assess potential sources of pollutants. Overall, the patterns in lichens, mosses, and grass were dominated by low molecular PCB congeners and PAHs and the presence of HCB and p,p'-DDE rather than heavier compounds, suggesting the importance of long-range atmospheric transport of POPs as the main vector for the introduction of these chemicals to Antarctica. Statistically significant correlations (p-level < 0.05) between concentrations in vegetation of PCBs, p,p'-DDE, and the more volatile PAHs with lipid content were found with r(2) of 0.22-0.52 for PCBs, 0.42 for p,p'-DDE, and 0.44-0.72 for the more volatile PAHs. Thus, lipid content is an important factor controlling POPs in Antarctic lichens, mosses, and grass. A strong significant dependence of HCB (r(2) = 0.83), p,p'-DDE (r(2) = 0.60), and PCBs (r(2) = 0.36-0.47) concentrations in soil on its organic carbon content was also observed, indicating the important role of soil organic matter (SOM) in the retention of PCBs and OCPs in Polar Regions, where SOM content is low. Penguin colonies enhance the SOM content in some areas which is reflected in higher concentrations of all POPs, especially of persistent compounds such as p,p'-DDE. Higher concentrations of PCBs and PAHs found at the currently active Byers Camp (in an Antarctic Specially Protected Area) were explained by higher SOM content, thus indicating that Antarctic regulations are being successfully fulfilled in this small research area. On the other hand, PAHs in soils proximate to current Juan Carlos I research station show that even small human settlements are an important source of PAHs to the local environment. Therefore, even though the concentrations in Antarctica are low, there is evidence of local hotspots of contamination.

Perfluorinated compounds (PFCs) are widely used in everyday life and one of the main recipients of these compounds is waste water treatment plants (WWTPs). Due to the structure and physicochemical properties of PFCs, these compounds could be redistributed from influent water to sludge. This work reports a new validated protocol for the analysis of 13 perfluorinated acids, 4 perfluorosulfonates and the perfluorooctanesulfonamide. The present work has been focused to develop a sensitive and robust method for the analysis of 18 PFCs in sewage sludge, based on pressurized solvent extraction (PSE) followed by solid phase extraction (SPE) clean-up, analytes separation by liquid chromatography and analysis in a hybrid quadrupole-linear ion trap mass spectrometer (LC-QLiT-MS/MS) working in single reaction monitoring (SRM) mode. The final methodology was validated using a blank sewage sludge fortified at different concentration levels. The method limits of detection were ranging in general from 15 to 79 ng/kg. These values were comparable to the decision limit (CCα) and the detection capability (CCβ), which were 17-1134 ng/kg and 18-1347 ng/kg, respectively. The percentage of recovery was from 79 to 111% in the most cases at different spiked levels. Finally, the repeatability of the method was in the range 4% (PFOS and PFOA) to 25% (RSD %). In order to evaluate the applicability of the method, 5 sludge samples were analyzed. The results showed that the 18 PFCs were present in all samples. However, the concentrations for most of them were below the limits of quantification. The compound present at higher concentrations was perfluorooctanesulfonate (PFOS), which was in concentrations from 53.0 to 121.1 μg/kg. The other PFCs were at concentrations between 0.3 and 30.3 μg/kg., (Copyright © 2011 Elsevier B.V. All rights reserved.)

Concentrations of Mirex, Dechlorane (Dec) Plus (DP), Dec 602, Dec 603, and Dec 604 were significantly higher in peregrine falcon (Falco peregrinus) eggs from Canada than Spain, with the former having the only measurable concentrations of the dechlorinated DP products, decachloropentacyclooctadecadiene (aCl10DP) and undecachloropentacyclooctadecadiene (aCl11DP). Large variations also occurred in the in ovo concentrations of the DP monoadduct, DPMA. This is the first study to report the accumulation and metabolism of DP by peregrines, both DP and dechloranes in European biota, as well as dechloranes in a terrestrial organism and one at the top of the food web. The geographical differences in the measured in ovo concentrations reflect local exposure of the adult peregrines on their breeding grounds, likely differences in diet of the adults, the production of DP on the Niagara River, and the greater use of Mirex and dechloranes as flame retardants in North America than Europe.

Governments throughout the world are intensifying their efforts to improve food safety. These efforts come as a response to an increasing number of food-safety problems and increasing consumer concerns. In addition, the variety of toxic residues in food is continuously increasing as a consequence of industrial development, new agricultural practices, environmental pollution, and climate change. This paper reviews a selection of emerging contaminants in food, including the industrial organic pollutants perfluorinated compounds (PFCs), polybrominated diphenyl ethers (PBDEs), and nanomaterials; the pharmaceutical residues antibiotics and coccidiostats; and emerging groups of marine biotoxins. The main analytical approaches for their detection and quantification in food will be presented and discussed with special emphasis on biological techniques, when these are feasible. In the last section, a summary of recent publications reporting the concentrations of these compounds in food will be presented and discussed.

In this study, an analytical method to determine six perfluorinated compounds (PFCs) based on alkaline digestion and solid phase extraction (SPE) followed by liquid chromatography-quadrupole-linear ion trap mass spectrometry (LC-QqLIT-MS) was validated for the analysis of human breast milk, milk infant formulas and cereals baby food. The average recoveries of the different matrices were in general higher than 70% with a relative standard deviation (RSD) lower than 21% and method limits of detection (MLOD) ranging from 1.2 to 362 ng/L for the different compounds and matrices. The method was applied to investigate the occurrence of PFCs in 20 samples of human breast milk, and 5 samples of infant formulas and cereal baby food (3 brands of commercial milk infant formulas and 2 brands of cereals baby food). Breast milk samples were collected in 2008 from donors living in Barcelona city (Spain) on the 40 days postpartum. Perfluorooctanesulfonate (PFOS) and perfluoro-7-methyloctanoic acid (i,p-PFNA) were predominant being present in the 95% of breast milk samples. Perfluorooctanoic acid (PFOA) was quantified in 8 of the 20 breast milk samples at concentrations in the range of 21-907 ng/L. Commercial formulas and food were purchased also in 2009 from a retail store. The six PFCs were detected in all brands of milk infant formulas and cereals baby food analyzed, being perfluorodecanoic acid (PFDA), PFOS, PFOA and i,p-PFNA the compounds detected in higher concentrations (up to 1289 ng/kg). PFCs presence can be associated to possible migration from packaging and containers during production processes. Finally, based on estimated body weight and newborn intake, PFOS and PFOA daily intakes and risk indexes (RI) were estimated for the firsts 6 month of life. We found that ingestion rates of PFOS and PFOA, with exception of one breast milk sample did not exceed the tolerable daily intake (TDI) recommended by the EFSA. However, more research is needed in order to assess possible risk associated to PFCs contamination during early stages of life., (Copyright 2010 Elsevier Ltd. All rights reserved.)

Blood biomarkers and levels of major pollutants in eggs and feathers were used to determine pollution effects in nestlings of the Purple Heron Ardea purpurea and the Little Egret Egretta garzetta, sampled on three Ebro River (NE Spain) areas: a reference site, a site affected by the effluents of a chlor-alkali industry and the river Delta. The two impacted heron populations showed mutually different pollutant and response patterns, suggesting different sources of contamination. In the population nesting near the chlor-alkali plant, elevated levels of hexachlorobenzene (HCB) and polychlorobiphenyls (PCBs) in eggs, and mercury in feathers in A. purpurea chicks were related with reduced blood antioxidant defenses and increased levels of micronuclei. In Ebro Delta, high levels of plasmatic lactate dehydrogenase in A. purpurea chicks and high frequency of micronuclei in blood of both species were tentatively associated with intensive agricultural activities taking place in the area. These results provide the first evidence of a biological response in heron chicks to the release of pollutants at a chlor-alkali plant., (Copyright (c) 2009 Elsevier Ltd. All rights reserved.)

We report here an efficient and comprehensive analytical methodology based on gas chromatography with high resolution mass spectrometry (GC-HRMS) to simultaneously determine PBDEs from mono to deca brominated and hydroxy (OH-) and methoxy (MeO-) PBDE metabolites in environmental samples, particularly, sediment, fish tissue and milk. Among a number of extraction and clean-up methods tested, pressurized liquid extraction followed by gel permeation chromatography and florisil clean-up proved to be simple, robust and optimized so that all target analytes (parent compounds and metabolites) were collected in a single fraction. Extracts were analyzed by GC-HRMS to identify PBDEs. Following, the same extracts were derivatized and re-analyzed by GC-HRMS to determine 11 target and 35 non-target OH- and MeO-PBDEs. Monitoring of the M(+) for MeO-PBDEs and the [M-CH(2)CO](+) ions for derivatized OH-PBDEs at 10,000 resolution permitted unequivocal identification of the PBDE metabolites in the environmental matrices examined. The method was validated in terms of accuracy, precision, detection limits and long-term stability. The analytical precision obtained with this method was between 0.3 and 17%, and the limits of quantification were lower than 3.28 pg/g dry weight, 20.5 and 41.4 pg/g lipid weight in sediment, milk and fish, respectively. The method was applied to determine PBDEs and target and non-target metabolites in all three matrices., (2009 Elsevier B.V. All rights reserved.)

Organic pollutants include a very wide variety of chemical compounds with different structures, properties, functions and origins, which may produce diverse damages to the ecosystem and the human beings. This review presents the recent progress on the use of chemometrics to evaluate the occurrence of these substances in the environment. The main topics addressed are: (a) the problems related to the interpretation of the analytical measurements used in the determination of organic pollutants (quantitative analytical determinations section), (b) the profiling of the related environmental pollution sources through their compositional, geographical and temporal distribution patterns (environmental exploratory studies section) and (c) the prediction of the toxicological activity of these substances through models based on the use of structural or physical/chemical descriptors (toxicity studies section). Each section includes selected works related to pesticides, polycyclic aromatic hydrocarbons and other organic pollutants.

This study presents the optimization and application of an analytical method based on the use of stir bar sorptive extraction (SBSE) gas chromatography coupled to mass spectrometry (GC-MS) for the ultra-trace analysis of POPs (Persistent Organic Pollutants) in Arctic ice. In a first step, the mass-spectrometry conditions were optimized to quantify 48 compounds (polycyclic aromatic hydrocarbons, brominated diphenyl ethers, chlorinated biphenyls, and organochlorinated pesticides) at the low pg/L level. In a second step, the performance of this analytical method was evaluated to determine POPs in Arctic cores collected during an oceanographic campaign. Using a calibration range from 1 to 1800 pg/L and by adjusting acquisition parameters, limits of detection at the 0.1-99 and 102-891 pg/L for organohalogenated compounds and polycyclic aromatic hydrocarbons, respectively, were obtained by extracting 200 mL of unfiltered ice water. alpha-hexachlorocyclohexane, DDTs, chlorinated biphenyl congeners 28, 101 and 118 and brominated diphenyl ethers congeners 47 and 99 were detected in ice cores at levels between 0.5 to 258 pg/L. We emphasise the advantages and disadvantages of in situ SBSE in comparison with traditional extraction techniques used to analyze POPs in ice.

A new multiresidue method for the determination of 13 emerging and priority pollutants in lettuce, including pesticides, pharmaceuticals, personal care products, polycyclic aromatic hydrocarbons (PAHs), and phenolic estrogens, has been developed using matrix solid-phase dispersion combined to pressurized fluid extraction (PFE) followed by gas chromatography coupled to mass spectrometry determination. A sequential optimization strategy based on solvent optimization first, followed by experimental design, was performed in order to maximize target analyte extraction with the aid of response surface methodology. Firstly, a full factorial design was applied to choose the significant variables in PFE; extraction time and temperature were found to have the biggest overall effect on response for most of analytes. They were later optimized performing a central composite design and the variable response of these factors was modeled for all analytes. It was found that marked differences in physicochemical nature exerted a strong influence on extraction conditions and yield. Therefore, the effect of parameters on the response was rather different for some compounds. To overcome this conflicting behavior, a multiple response simultaneous optimization was applied using the desirability function to achieve global optimal operating conditions. The optimal conditions were attained at 13.5 min (two extraction cycles) and 104 degrees C in the PFE by using hexane acetone mixture (1:1). Limit of detection and limit of quantitation values were found to be between 6.6 and 58 and 7.6 and 61.7 microg kg(-1), respectively.