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.

Polycyclic aromatic hydrocarbons bioaccessibility in seafood: Culinary practices effects on dietary exposure.

This work aimed to determine the effect of culinary practices on the contamination level and bioaccessibility of polycyclic aromatic hydrocarbons (PAHs) in seafood. The selected farmed seafood species (marine shrimp, clams and seaweed) were commercially available in Portugal. The mean concentrations of PAHs varied between 0.23 and 51.8 µg kg-1, with the lowest value being observed in raw shrimp and the highest in dried seaweed. The number of compounds detected in seaweed and clams (naphthalene, acenaphthene, fluorene, phenanthrene, benzo(b)fluoranthene and benzo(j)fluoranthene) were higher than in shrimp (fluorene and pyrene). Among the PAHs measured, fluorene was the predominant one. There was a significant interaction effect between species and culinary treatment (p < 0.05), thus boiled and dried seaweed samples presented the lowest and the highest levels of fluorene (0.13 and 1.8 µg kg-1), respectively. The daily intake of PAHs decreased with bioaccessibility, varying from 22% for benzo(k)fluoranthene (in raw clam) to 84% for phenanthrene (in steamed clam). According to the potency equivalent concentrations, screening values and bioaccessibility of PAHs, the consumption of marine shrimp, clam and seaweed is considered as safe for consumers.

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.

Moringa oleifera Lam. Commercial Beverages: A Multifaceted Investigation of Consumer Perceptions, Sensory Analysis, and Bioactive Properties.

This study employs a multidisciplinary approach to evaluate consumers' perceptions and acceptance of Moringa oleifera Lam. beverages, examining sensory attributes, chemical composition, and bioactivities. High-performance liquid chromatography with diode array detection (HPLC-DAD) analyses revealed significant chemovariation in phenolic compositions among commercial moringa beverages. A soluble moringa powder drink exhibited the greatest concentrations of phenolic and flavonoid compounds, along with powerful antioxidant capacity powers assessed with ABTS•+, DPPH•, FRAP assays, •NO, and H2O2 scavenging activities. However, this sample was the least preferred and presented high Cd levels, exceeding WHO-acceptable values of 0.3 mg/kg. Sensory testing indicated that sweet and floral flavors contributed to beverages being liked, while green, grass, herbal flavors, sour, bitter, and precipitate presence were considered unfavorable sensory attributes. Health claims positively influenced acceptance, particularly among women. Consumers associated feelings of health, wellness, relaxation, and leisure with moringa beverages. During purchase, the most observed information included the ingredient list, health benefits, and type/flavor. These findings emphasize the importance of consumer awareness in reading labels, verifying product origins, and ensuring the absence of contaminants. By understanding consumer preferences and the impact of health claims, producers can better tailor M. oleifera beverages to meet consumer expectations while maintaining safety and quality standards.

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.

Assessment of the Antioxidant Capacity of Commercial Coffee Using Conventional Optical and Chromatographic Methods and an Innovative Electrochemical DNA-Based Biosensor.

As one of the most popular beverages in the world, coffee is a rich source of non-enzymatic bioactive compounds with antioxidant capacity. In this study, twelve commercial coffee beverages found in local Portuguese markets were assessed to determine their total phenolic and flavonoid contents, as well as their antioxidant capacity, by conventional optical procedures, namely, ferric reducing antioxidant power and DPPH-radical scavenging assay, and non-conventional procedures such as a homemade DNA-based biosensor against two reactive radicals: HO• and H2O2. The innovative DNA-based biosensor comprised an adenine-rich oligonucleotide adsorbed onto a carbon paste electrode. This method detects the different peak intensities generated by square-wave voltammetry based on the partial damage to the adenine layer adsorbed on the electrode surface by the free radicals in the presence/absence of antioxidants. The DNA-based biosensor against H2O2 presented a higher DNA layer protection compared with HO• in the presence of the reference gallic acid. Additionally, the phenolic profiles of the twelve coffee samples were assessed by HPLC-DAD, and the main contributors to the exhibited antioxidant capacity properties were caffeine, and chlorogenic, protocatechuic, neochlorogenic and gallic acids. The DNA-based sensor used provides reliable and fast measurements of antioxidant capacity, and is also cheap and easy to construct.

Bioactive Lipids of Seaweeds from the Portuguese North Coast: Health Benefits versus Potential Contamination.

The total lipid content and lipidic profile of seaweeds harvested in the North Coast and purchased in Portugal were determined in this paper. The amount of total lipids in the different species of seaweeds varied between 0.7 ± 0.1% (Chondrus crispus) and 3.8 ± 0.6% (Ulva spp.). Regarding the fatty acid content, polyunsaturated fatty acids (PUFA) ranged between 0-35%, with Ulva spp. presenting the highest amount; monounsaturated fatty acids (MUFA) varied between 19 and 67%; and saturated fatty acids (SFA) were predominant in C. crispus (45-78%) and Gracilaria spp. (36-79%). Concerning the nutritional indices, the atherogenicity index (AI) was between 0.4-3.2, the thrombogenicity index (TI) ranged from 0.04 to 1.95, except for Gracilaria spp., which had a TI of 7.6, and the hypocholesterolemic/hypercholesterolemic ratio (HH) values ranged between 0.88-4.21, except for Gracilaria spp., which exhibited values between 0.22-9.26. The n6/n3 ratio was below 1 for most of the species evaluated, except for Ascophyllum nodosum, which presented a higher value, although below 2. Considering the PUFA/SFA ratio, seaweeds presented values between 0.11-1.02. The polycyclic aromatic hydrocarbons (PAHs) and aliphatic hydrocarbons (AHCs) contamination of seaweeds under study was also quantified, the values found being much lower than the maximum levels recommended for foodstuff.

Polycyclic aromatic hydrocarbons in wild and farmed whitemouth croaker and meagre from different Atlantic Ocean fishing areas: Concentrations and human health risk assessment.

This work assessed the concentrations of 18 polycyclic aromatic hydrocarbons (PAHs) in edible tissues of whitemouth croaker (Micropogonias furnieri) and meagre (Argyrosomus regius) captured in different Atlantic Ocean fishing areas and available to Brazilian and Portuguese consumers. Total PAH (∑PAHs) levels ranged from 1.32 to 5.41 µg/kg ww in wild-caught croaker and 2.66 (wild)-18.0 (farmed) µg/kg ww in meagre. Compounds with 2- and 3-rings represented 54-86% of ∑PAHs in the muscle tissues of wild-caught species (croaker and meagre) being naphthalene, fluorene, and phenanthrene the predominant compounds. ∑PAHs in farmed meagre were 4-7 times higher than in wild-caught meagre, with 2-, 3-, 4-, 5-, and 6-ring compounds representing 15, 18, 44, 22, and 1% of ∑PAHs, respectively. Benzo(a)pyrene levels in farmed meagre varied between 0.06 and 0.34 µg/kg ww. Crude oil refining and combustion sources were identified as the major sources of PAHs in FAO 27, 34 and 41 Atlantic Ocean fishing areas. The biometric characteristics (length, weight, moisture, and fat content) and ∑PAHs allowed to discriminate between wild-caught and farmed meagre samples and between meagre and croaker. Assessment of carcinogenic risks suggested that a diet exclusive on farmed meagre may pose additional risks for the health of European top consumers fish.

Analysis of polycyclic aromatic hydrocarbons in fish: evaluation of a quick, easy, cheap, effective, rugged, and safe extraction method.

QuEChERS method was evaluated for extraction of 16 PAHs from fish samples. For a selective measurement of the compounds, extracts were analysed by LC with fluorescence detection. The overall analytical procedure was validated by systematic recovery experiments at three levels and by using the standard reference material SRM 2977 (mussel tissue). The targeted contaminants, except naphthalene and acenaphthene, were successfully extracted from SRM 2977 with recoveries ranging from 63.5-110.0% with variation coefficients not exceeding 8%. The optimum QuEChERS conditions were the following: 5 g of homogenised fish sample, 10 mL of ACN, agitation performed by vortex during 3 min. Quantification limits ranging from 0.12-1.90 ng/g wet weight (0.30-4.70 microg/L) were obtained. The optimized methodology was applied to assess the safety concerning PAHs contents of horse mackerel (Trachurus trachurus), chub mackerel (Scomber japonicus), sardine (Sardina pilchardus) and farmed seabass (Dicentrarchus labrax). Although benzo(a)pyrene, the marker used for evaluating the carcinogenic risk of PAHs in food, was not detected in the analysed samples (89 individuals corresponding to 27 homogenized samples), the overall mean concentration ranged from 2.52 +/- 1.20 ng/g in horse mackerel to 14.6 +/- 2.8 ng/g in farmed seabass. Significant differences were found between the mean PAHs concentrations of the four groups.

Commercial octopus species from different geographical origins: Levels of polycyclic aromatic hydrocarbons and potential health risks for consumers.

Polycyclic aromatic hydrocarbons (PAHs) are persistent pollutants that have been raising global concern due to their carcinogenic and mutagenic properties. A total of 18 PAHs (16 USEPA priority compounds, benzo(j)fluoranthene and dibenzo(a,l)pyrene) were assessed in the edible tissues of raw octopus (Octopus vulgaris, Octopus maya, and Eledone cirrhosa) from six geographical origins available to Portuguese consumers. Inter- and intra-species comparison was statistically performed. The concentrations of total PAHs (∑PAHs) ranged between 8.59 and 12.8 µg/kg w.w. Octopus vulgaris caught in northwest Atlantic Ocean presented ΣPAHs significantly higher than those captured in Pacific Ocean and Mediterranean Sea, as well as than the other characterized species from western central and northeast Atlantic Ocean. PAHs with 2-3 rings were the predominant compounds (86-92% of ∑PAHs) but diagnostic ratios indicated the existence of pyrogenic sources in addition to petrogenic sources. Known and possible/probable carcinogenic compounds represented 11-21% of ΣPAHs. World and Portuguese per capita ingestion of ∑PAHs due to cephalopods consumption varied between 1.62-2.55 × 10-4 and 7.09-11.2 × 10-4 µg/kg body weight per day, respectively. Potential risks estimated for low and high consumers according to USEPA methodology suggested that a regular consumption of raw octopus does not pose public health risks.

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.

Development of a modified acetonitrile-based extraction procedure followed by ultra-high performance liquid chromatography-tandem mass spectrometry for the analysis of psychiatric drugs in sediments.

An analytical method based on a modified Quick, Easy, Cheap, Effective, Rugged and Safe (QuEChERS) extraction procedure followed by ultra-high performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) was developed for the analysis of psychiatric drugs in sediments. An optimized approach was applied in sample preparation by using basic acetonitrile as extraction solvent. Extraction was followed by a clean-up using dispersive solid phase extraction (dSPE) to remove matrix interfering compounds. The analytical method was validated in terms of sensitivity, linearity, recovery, intra- and inter-day precisions and method detection and quantification limits. Under optimized conditions, limits of detection ranged from 0.01ngg(-1) to 2.08ngg(-1); and recoveries between 47 and 110% with relative standard deviation (RSD) below 5%. The developed methodology was applied to sediments of two Portuguese rivers (Douro and Lima rivers) and nine out of eleven psychiatric drugs were detected in sediments at concentrations up to 26.4ngg(-1) (dry weight). To the best of our knowledge, it was the first time that the human metabolites norfluoxetine and norsertraline were detected in river sediments at levels of few nanograms per gram.

Sertraline accumulation and effects in the estuarine decapod Carcinus maenas: importance of the history of exposure to chemical stress.

Sertraline is widely prescribed worldwide and frequently detected in aquatic systems. There is, however, a remarkable gap of information on its potential impact on estuarine and coastal invertebrates. This study investigated sertraline accumulation and effects in Carcinus maenas. Crabs from a moderately contaminated (Lima) and a low-impacted (Minho) estuary were exposed to environmental and high levels of sertraline (0.05, 5, 500 µg L(-1)). A battery of biomarkers related to sertraline mode of action was employed to assess neurotransmission, energy metabolism, biotransformation and oxidative stress pathways. After a seven-day exposure, sertraline accumulation in crabs' soft tissues was found in Lima (5 µg L(-1): 15.3 ng L(-1) ww; 500 µg L(-1): 1010 ng L(-1) ww) and Minho (500 µg L(-1): 605 ng L(-1) ww) animals. Lima crabs were also more sensitive to sertraline than those from Minho, exhibiting decreased acetylcholinesterase activity, indicative of ventilatory and locomotory dysfunction, inhibition of anti-oxidant enzymes and increased oxidative damage at ≥ 0.05 µg L(-1). The Integrated Biomarker Response (IBR) index indicated their low health status. In addition, Minho crabs showed non-monotonic responses of acetylcholinesterase suggestive of hormesis. The results pointed an influence of the exposure history on differential sensitivity to sertraline and the need to perform evaluations with site-specific ecological receptors to increase relevance of risk estimations when extrapolating from laboratory to field conditions.

Polycyclic aromatic hydrocarbons in commercial squids from different geographical origins: levels and risks for human consumption.

The concentrations of 18 polycyclic aromatic hydrocarbons (PAHs) were determined in five commercially valuable squid species from different geographical origins (Atlantic, Indic and Pacific Oceans). Out of the 18 quantified PAHs (the 16 PAHs considered by US EPA as priority pollutants, dibenzo(a,l)pyrene and benzo(j)fluoranthene) only dibenz(a,h)anthracene was not detected. The total concentrations of PAHs varied by a factor of more than 100-fold, from 0.22 (Loligo gahi) to 60.9 µg/kg ww (Loligo reynaudii). Intra- and inter-specific variability of PAH levels was statistically assessed. Nine carcinogenic (probable/possible) PAHs accounted for 1% (L. reynaudii) to 26% (Loligo opalescens) of the total PAHs content being the main contributors naphthalene (in Loligo duvaucelii, L. reynaudii and Loligo vulgaris species), chrysene (in L. opalescens) and indeno(1,2,3-cd)pyrene (in L. gahi). PAHs source analysis indicated that four of the five zones of capture of the different squid species are significantly affected by both petrogenic and pyrolytic sources. Assessment of the target carcinogenic risks, established by the US EPA, suggested that L. gahi (Atlantic Ocean) and L. opalescens (from Pacific Ocean) may pose additional risks for consumers, if not eaten in moderation, derived from benzo(a)pyrene ingestion.

Polycyclic aromatic hydrocarbon levels in three pelagic fish species from Atlantic Ocean: inter-specific and inter-season comparisons and assessment of potential public health risks.

The concentrations of 18 polycyclic aromatic hydrocarbons (PAHs) were determined in three commercially valuable fish species (sardine, Sardina pilchardus; chub mackerel, Scomber japonicus; and horse mackerel, Trachurus trachurus) from the Atlantic Ocean. Specimens were collected seasonally during 2007-2009. Only low molecular weight PAHs were detected, namely, naphthalene, acenaphthene, fluorene and phenanthrene. Chub mackerel (1.80-19.90µg/kgww) revealed to be significantly more contaminated than horse mackerel (2.73-10.0µg/kgww) and sardine (2.29-14.18µg/kgww). Inter-specific and inter-season comparisons of PAHs bioaccumulation were statistically assessed. The more relevant statistical correlations were observed between PAH amounts and total fat content (significant positive relationships, p⩽0.05), and season (sardine displayed higher amounts in autumn-winter while the mackerel species showed globally the inverse behavior). The health risks by consumption of these species were assessed and shown to present no threat to public health concerning PAH intakes.