Seasonal and Spatial Comparison of Polycyclic Aromatic Hydrocarbons Among Decapod Shrimp from Coastal Portugal.

Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous global pollutants that are lipophilic, bioaccumulative and can be both endocrine disruptors and carcinogens. In this study, we measured 18 PAHs among decapod shrimp samples (Palaemon spp.) collected during the spring and autumn from multiple locations along the Portuguese coastal, including local markets and aquaculture farms. ΣPAH concentrations in samples ranged from 3.14 to 320.48 ng/g (ww) with the highest value in this range detected in a sample provided from an aquaculture facility. Fifteen of the 18 scanned PAHs were present in shrimp samples. However, detectable concentrations (0.07 ng/g ww) of the carcinogenic benzo-a-pyrene occurred for a single sample only and approached method detection limits. No significant differences in shrimp ΣPAH concentrations were evident between the spring and autumn seasons. Target hazard quotient estimation suggested low probability of adverse health effects to consumers through consumption of shrimp from the study collection locations.

Validation and Evaluation of Selected Organic Pollutants in Shrimp and Seawater Samples from the NW Portuguese Coast.

The development of coastal regions has contributed to the intensification of environmental contamination, which can accumulate in aquatic biota, such as shrimps. These crustaceans, besides being delicious and being a good source of nutrients, can also accumulate environmental pollutants. Amongst others, these include organochlorine pesticides (OCPs), organophosphorus pesticides (OPPs), brominated flame retardants (BFRs), polychlorinated biphenyls (PCBs) and synthetic musks (SMs). These pollutants, classified as endocrine disruptors, are related to adverse effects in humans and since one of the major routes of exposition is ingestion, this is a cause for concern regarding their presence in food. The aim of the present study was to quantify the presence of environmental pollutants in shrimp samples and in the water from their habitat along the northwest Portuguese coast. In seawater samples, only two OCPs (lindane and DDD) and one BFR (BTBPE) were detected, and in shrimp samples, one OCP (DDD) and three SMs (HHCB, AHTN and ketone) were found. Bioaccumulation and the risk assessment of dietary exposure of SMs in shrimp samples were investigated. It was observed that all shrimp samples analyzed significantly presented bioaccumulation of the three SMs found. Concentrations of SMs detected in shrimp samples do not present a health risk for the adult Portuguese population.

Evaluating the impact of polycyclic aromatic hydrocarbon bioaccumulation in adipose tissue of obese women.

Polycyclic aromatic hydrocarbons (PAHs) are widespread across the environment and humans are unavoidably and constantly exposed to them. As lipophilic contaminants, these substances tend to accumulate in fatty tissues as adipose tissue and exposure to these endocrine disruptors has been associated with severe health hazards including prevalence and incidence of obesity. Previous studies have shown significantly higher concentrations of PAHs in adipose tissue compared to other human samples, such as urine and plasma, which are typically used for PAHs assessment. Therefore, conducting biomonitoring studies in adipose tissue is essential, although such studies are currently limited. In this study, the concentrations of 18 PAHs were measured in subcutaneous (scAT) and visceral adipose tissue (vAT) of 188 Portuguese obese females by high performance liquid chromatography (HPLC). The obtained results were then associated with the patient's data namely: 13 clinical, 4 social, and 42 biochemical parameters. Seventeen PAHs were present, at least, in one sample of both scAT and vAT, most of them with detection frequencies higher than 80%. Indeno [1,2,3-cd]pyrene (InP) was the only PAH never detected. Overall higher concentrations of PAHs were observed in scAT. Median concentrations of ∑PAHs were 32.2 ± 10.0 ng/g in scAT and 24.6 ± 10.0 ng/g in vAT. Thirty-six significant associations (7 with social, 18 with clinical, and 11 with biochemical parameters), including 21 Spearman's correlations were identified (12 positive and 9 negative correlations). Indicating the potential effects of PAHs on various parameters such as obesity evolution, body fat, number of adipocytes, total cholesterol, alkaline phosphatase, macrominerals, uric acid, sedimentation velocity, and luteinizing hormone. This study underscores the significance of biomonitoring PAH levels in adipose tissue and their potential effects on metabolic health. Further research is essential to fully comprehend the metabolic implications of PAHs in the human body and to develop strategies for obesity prevention and treatment.

Bioactive Compounds of Shrimp Shell Waste from Palaemon serratus and Palaemon varians from Portuguese Coast.

The production and consumption of shrimp species create massive amounts of shrimp bio-waste. In this study, shrimp shell waste from Palaemon serratus and Palaemon varians from the Portuguese coast was characterized. Regarding the antioxidant capacity, the obtained values were between 4.7 and 10.4 mg gallic acid equivalents (GAE)/g dry weight (dw) for Total phenolic content (TPC); 3 and 7 mg ascorbic acid equivalents (AAE)/g dw for Ferric reducing antioxidant power assay (FRAP); 0.4 and 1.2 mg Trolox equivalent (TE)/g dw for 2,2-diphenyl-1-picryl-hydrazyl-hydrate free radical scavenging (DPPH•); 4 and 11 mg TE/g dw for 2,2'-azino-bis (3-ethylbenzothiazoline-6-sulfonic acid) radical scavenging activity (ABTS•+); and 72 and 130 mg TE/g dw for Oxygen radical absorbance capacity (ORAC). For the antimicrobial activity, shrimp shell waste from P. varians formed inhibition zones between 14 and 23 mm. Total carotenoid content values were in the range of 28 and 134 µg/g dw, and according to their HPLC-PAD profile, ß-carotene and astaxanthin contents were between 0.3 and 7.6 µg/g dw and 1.1 and 26.1 µg/g dw, respectively. These studies are critical to recognizing the potential added value of shrimp shell waste as possible colorants and preservatives with antioxidant protection capacity to be used in the food industry.

Optimization of a simple, effective, and greener methodology for polycyclic aromatic hydrocarbon extraction from human adipose tissue.

Polycyclic aromatic hydrocarbons (PAHs) are environmentally persistent organic pollutants formed during incomplete combustion and pyrolysis processes. Humans are continuously exposed to PAHs which are linked to severe health effects such as diabetes, cancer, infertility, and poor foetal development, amongst others. PAHs are lipophilic compounds prone to accumulating in adipose tissue. Even though adipose tissue is the ideal matrix to assess over time accumulation of lipophilic pollutants, only a few analytical methods have been developed for this matrix. Aiming to reduce the existent gap, a method for the extraction of PAHs from adipose tissue samples using ultrasound-assisted extraction (UAE) was developed. The behaviour of PAHs (retention, adsorption, and volatilization) over several steps of the analytical procedure was studied. Validation tests were performed on the optimized method. PAHs were quantified using a high performance liquid chromatography (HPLC) system equipped with a photodiode array (PDA) and fluorescence (FLD) detector inline. The method achieved a low matrix effect and presents low method detection (MDL) and quantification (MQL) limits, showing suitability for a selective and sensitive determination of PAHs in adipose tissue. The extraction is performed with 0.4 g of adipose tissue and 6 mL of n-hexane and it does not require clean-up afterwards. Additionally, an Eco-Scale score of 74 and an Analytical GREEnness score of 0.66 were obtained. The method achieved is effective, simpler, greener, and easy to perform, being an alternative to conventional extraction methods. Furthermore, this method can be used as a multi-analyte methodology since it has been previously validated by the authors for the analysis of other lipophilic compounds. Naphthalene (Naph), acenaphthene (Ace), fluorene (Flu), phenanthrene (Phe), anthracene (Ant), fluoranthene (Fln), pyrene (Pyr) and benzo[k]fluoranthene (B[k]Ft) were found in all the tested adipose tissue samples.

Impact of brominated flame retardants on lipid metabolism: An in vitro approach.

Brominated flame retardants (BFRs) are chemicals employed to lower the flammability of several objects. These endocrine disruptor chemicals are lipophilic and persistent in the environment. Due to these characteristics some have been restricted or banned by the European Union, and replaced by several new chemicals, the novel BFRs (NBFRs). BFRs are widely detected in human samples, such as adipose tissue and some were linked with altered thyroid hormone levels, liver toxicity, diabetes and metabolic syndrome in humans. However, the disturbance in lipid metabolism caused by BFRs with emphases to NBFRs remains poorly understood. In this study, we used a pre-adipocyte (3T3-L1) cell line and a hepatocyte (HepG2) cell line to investigate the possible lipid metabolism disruption caused by four BFRs: hexabromobenzene (HBB), pentabromotoluene (PBT), 2-ethylhexyl-2,3,4,5-tetrabromobenzoate (TBB) and hexabromocyclododecane (HBCD). For that purpose, proliferation and Oil Red O assays, as well as, medium fatty acids profile evaluation using Gas chromatography and RNA extraction for quantitative RT-PCR assays were performed. We detected a significant reduction in the proliferation of preadipocytes and an increased lipid accumulation during differentiation caused by HBB. This BFR also lead to a significant increased expression of IL-1ß and decreased expression of PGC-1α and adiponectin. Nevertheless, PBT, TBB and HBCD show to increase lipid accumulation in hepatocytes. PBT also display a significant increase of PPARγ gene expression. Lipid accumulation in the cells can occur by diverse mechanisms depending on the BFR. These results highlight the importance of endocrine disruptor compounds in obesity etiopathogeny.

Method development for the determination of Synthetic Musks and Organophosphorus Pesticides in Human Adipose Tissue.

Synthetic musks and organophosphorus pesticides represent a potential risk to the human health since exposure can lead to distinct types of carcinogenesis and endocrine disorders. These are lipophilic compounds as such, prone to deposit and persist in fat tissues, mainly in adipose tissue. Very few studies have reported on the occurrence and accumulation profile of these contaminants in human adipose tissue. Analytical methods for the detection and quantification of synthetic musks and organophosphorus pesticides in adipose tissue are lacking. In this study, the efficacy of different extraction with ultrasonic homogenizer and dispersive solid-phase extraction (d-SPE) clean-up methods were evaluated in human adipose tissue. The relative sample clean-up was assessed by measurement of total lipid content. The quantification of four synthetic musks and six organophosphorus pesticides were performed by gas chromatography (GC) mass spectrometry (MS) and flame photometric detection (FPD), respectively. The d-SPE clean-up with 50 mg PSA, 150 mg MgSO4, 100 mg C18EC and 50 mg Z-Sep provided the most effective clean-up, removing the greatest amount of interfering substances including lipids and simultaneously ensuring good chromatographic separation and recoveries. Method detection limits were between 4 to 9 ng/g for synthetic musk and 1 to 7 ng/g for organophosphorus pesticides in adipose tissue. The proposed method was applied to adipose tissue of obese patients and positive samples were confirmed with GC tandem mass spectrometry. Galaxolide was found in all the samples tested with concentrations ranging from 0.08 to 0.5 µg/g of adipose tissue. No other synthetic musk studied was detected. Organophosphorus pesticides were not found in the analysed samples. The developed analytical procedures were successful and can easily be applied to biomonitoring these compounds in human adipose tissue.

Organochlorine pesticides, brominated flame retardants, synthetic musks and polycyclic aromatic hydrocarbons in shrimps. An overview of occurrence and its implication on human exposure.

Shrimps are widely distributed in coastal areas, estuaries and rivers. Although this shellfish is a good source of nutrients, it can also accumulate environmental contaminants, such as organochlorine pesticides (OCPs), brominated flame retardants (BFRs), synthetic musks (SMs) and polycyclic aromatic hydrocarbons (PAHs). Due to their bioaccumulative properties, these pollutants are endocrine disruptors. In this review, an overview of the world's shrimp market, pollutants legislation and values found in shrimp samples will be discussed. Shrimps analysed from all continents showed the presence of contaminants, Asia being the continent with the highest values reported. The concentration values reached a maximum of 26100 ng/g wet weight (ww) for OCPs, of 226.45 ng/g ww for BFRs, of 12.1 ng/g ww for SMs and of 50650 ng/g ww for PAHs. Exposure data and risk, taken from different studies, are very variable and indicate that shrimp's consumption may represent a risk especially in certain geographic areas.

Magnetic dispersive micro solid-phase extraction and gas chromatography determination of organophosphorus pesticides in strawberries.

Magnetic nanoparticles (MNPs) with different sizes and characteristics were synthesized to be used as a QuEChERS sorbents for the determination of seven organophosphorus pesticides (OPPs) in strawberries by gas chromatography analysis with flame photometric and mass spectrometry detection. To achieve the optimum conditions of modified QuEChERS procedure several parameters affecting the cleanup efficiency including the amount of the sorbents and cleanup time were investigated. The results were compared with classical QuEChERS methodologies and the modified QuEChERS procedure using MNPs showed the better performance. Under the optimum conditions of the new methodology, three spiking levels (25, 50 and 100 µg kg-1) were evaluated in a strawberry sample. The results showed that the average recovery was 93% and the relative standard deviation was less than 12%. The enrichment factor ranged from 111 to 145%. The good linearity with coefficients of determination of 0.9904-0.9991 was obtained over the range of 25-250 µg kg-1 for 7 OPPs. It was determined that the MNPs have an excellent function as sorbent when purified even using less amount of sorbents and the magnetic properties allowed non-use of the centrifugation in cleanup step. The new methodology was applied in strawberry samples from conventional and organic farming. The new sorbents were successfully applied for extraction and determination of OPPs in strawberries.

Seaweeds from the Portuguese coast as a source of proteinaceous material: Total and free amino acid composition profile.

The total protein content and the (total and free) amino acid composition of nine edible species of red, brown and green seaweeds collected in the Portuguese North-Central coast were quantified to assess their potential contribution to the recommended dietary intake. Whenever possible, the protein and amino acid composition was compared with that of commercial European seaweeds. The protein content was the highest (P < 0.05) in red species (19.1-28.2 g/100 g dw), followed by the green seaweed Ulva spp. (20.5-23.3 g/100 g dw), with the lowest content found in brown seaweeds (6.90-19.5 g/100 g dw). Brown seaweeds presented the lowest mean contents of essential amino acids (EAAs) (41.0% protein) but significantly (P < 0.05) higher concentrations of non-essential amino acids (36.1% protein) and free amino acids (6.47-24.0% protein). Tryptophan, methionine and leucine were the limiting EAAs in all species. In contrast, lysine was found in high concentrations, especially in red (2.71-3.85% protein) and green (2.84-4.24% protein) seaweeds.

Remediation of soils combining soil vapor extraction and bioremediation: benzene.

This work reports the study of the combination of soil vapor extraction (SVE) with bioremediation (BR) to remediate soils contaminated with benzene. Soils contaminated with benzene with different water and natural organic matter contents were studied. The main goals were: (i) evaluate the performance of SVE regarding the remediation time and the process efficiency; (ii) study the combination of both technologies in order to identify the best option capable to achieve the legal clean up goals; and (iii) evaluate the influence of soil water content (SWC) and natural organic matter (NOM) on SVE and BR. The remediation experiments performed in soils contaminated with benzene allowed concluding that: (i) SVE presented (a) efficiencies above 92% for sandy soils and above 78% for humic soils; (b) and remediation times from 2 to 45 h, depending on the soil; (ii) BR showed to be an efficient technology to complement SVE; (iii) (a) SWC showed minimum impact on SVE when high airflow rates were used and led to higher remediation times for lower flow rates; (b) NOM as source of microorganisms and nutrients enhanced BR but hindered the SVE due the limitation on the mass transfer of benzene from the soil to the gas phase.