Ecological Status of Algeciras Bay, in a Highly Anthropised Area in South-West Europe, through Metal Assessment-Part I: Abiotic Samples.

The ecological status of Algeciras Bay (South-west Europe), highly influenced by anthropogenic activities, was assessed by monitoring Zn, Cd, Pb, and Cu in water and sediment samples. Total contents and metal fractions with different availabilities and their spatial-seasonal distribution were determined. The trend in water and sediment contents were Zn > Pb ≈ Cu > Cd, without significant seasonal variations. Sites 3 and 4, closest to industrial activities, had the highest metal concentrations, mainly in sediments. Cd showed low partition coefficient in water, indicating higher bioavailability. Total metal content in sediments exceeded the threshold effect level for Cu and were close to Pb. The BCR procedure revealed the highest availabilities for Cd and Pb, due to its higher content in exchangeable and reducible fractions. Higher Pb levels (21.4 ± 5.1 mg/kg) were found in sediments of this bay compared with other ecosystems. Pollution indexes for sediment quality revealed that site 3 was the most polluted (CF = 7.12 and Igeo = 2.25). For an integrative study of the ecological status of this significant bay, these results have been complemented with the metal evaluation in benthic and benthopelagic fish tissues in Ecological status of Algeciras Bay, in a highly anthropised area in south-west Europe, through metal assessment-Part II: Biotic samples.

Ecological Status of Algeciras Bay, in a Highly Anthropised Area in South-West Europe, through Metal Assessment-Part II: Biotic Samples.

Biotic samples from Algeciras Bay (South-west Europe) were studied to assess its ecological status, complementing the previous abiotic monitoring of trace metals in water and sediments. This bay is a densely populated area with intense port traffic and is highly industrialised with metal inputs. To study the impact of this, Zn, Cd, Pb, and Cu contents were determined in tissues of benthic (Solea senegalensis) and benthopelagic species (Scorpaena porcus, Trigloporus lastoviza, and Diplodus sargus sargus). Notable levels of Zn and Cu were found in the liver and gills of all fish species. Compared to international muscle guidelines, Pb sometimes exceeded the most restrictive values, outstanding S. porcus with 27% of samples above the permissible value. Metal pollution indexes revealed that the liver and gills of benthic species were more affected by metal pollution than benthopelagic species, especially in most industrialised sites. Particularly, S. senegalensis presented a higher accumulation factor from sediment of Cd and Cu in the liver (30.1 and 345.1), probably due to the close interaction as benthic species. Among the species studied, S. senegalensis and D. sargus sargus proved to be the best representative and useful bioindicators of metal-polluted environments as this bay. The results were consistent with the findings from the abiotic samples.

Induction of Oxidative Stress by Waterborne Copper and Arsenic in Larvae of European Seabass (Dicentrarchus labrax L.): A Comparison with Their Effects as Nanoparticles.

The aim of this work was to compare the potential induction of oxidative stress and the antioxidant enzymatic response after a short-term waterborne exposure to copper (Cu) and arsenic (As) with that of the nanoparticles (NPs) of these elements (Cu-NPs and As-NPs) in fish larvae of the species Dicentrarchus labrax. Larvae were grouped in several tanks and exposed to different concentrations of contaminants (0 to 10 mg/L) for 24 or 96 h under laboratory conditions. Copper and arsenic concentrations were analysed in larval tissues using ICP-MS. A set of oxidative stress biomarkers, including the levels of hydroperoxides (HPs), and superoxide dismutase (SOD) and catalase (CAT) activities were assessed. The trace element concentrations (mg/kg d.w.) in larvae ranged as follows: 3.28-6.67 (Cu at 24 h) and 2.76-3.42 (Cu at 96 h); 3.03-8.31 (Cu-NPs at 24 h) and 2.50-4.86 (Cu-NPs at 96 h); 1.92-3.45 (As at 24 h) and 2.22-4.71 (As at 96 h); and 2.19-8.56 (As-NPs at 24 h) and 1.75-9.90 (As-NPs at 96 h). In Cu tests, the oxidative damage (ROOH levels) was induced from 0.1 mg/L at both exposure times, while for Cu-NPs, this damage was not observed until 1 mg/L, which was paralleled by concomitant increases in SOD activity. The CAT activity was also increased but at lower metal concentrations (0.01 mg/L and 0.1 mg/L for both chemical forms). No oxidative damage was observed for As or As-NPs after 24 h, but it was observed for As after 96 h of treatment with 0.01 mg/L. A decrease in SOD activity was observed for As after 24 h, but it turned out to be increased after 96 h. However, As-NPs did not alter SOD activity. The CAT activity was stimulated only at 96 h by As and at 24 h by As-NPs. Therefore, the two chemical forms of Cu exhibited a higher bioaccumulation and toxicity potential as compared to those of As. Importantly, the association of both Cu and As in NPs reduced the respective trace metal bioaccumulation, resulting also in a reduction in the toxic effects (mortality and biochemical). Furthermore, the assessment of oxidative stress-related biomarkers in seabass larvae appears to be a useful tool for biomonitoring environmental-occurring trace elements.

A Novel Polymer Inclusion Membrane-Based Green Optical Sensor for Selective Determination of Iron: Design, Characterization, and Analytical Applications.

The design, characterization, and analytical application of a green optical sensor for the selective determination of Fe(II) ions is proposed. The sensor is based on the immobilization of the chromogenic reagent picolinaldehyde salicyloylhydrazone (SHPA) within a polymer inclusion membrane. To reduce solvent usage, the reagent was synthesized using a green mechanochemical procedure. The components for sensor preparation were optimized with a sequential simplex method and the optimal composition was found to be 0.59 g cellulose triacetate (base polymer), 0.04 g SHPA (chemosensor reagent), 4.9 mL dibutyl phthalate (plasticizer), and 38 mL dichloromethane (solvent). The conditions of iron analysis were also optimized resulting in pH 6 for aqueous solution, 90 min exposure time and 10 min short-term stability. The optical sensor showed a linear range from the limit of detection (0.48 µmol L-1) to 54 µmol L-1 Fe(II). The precision of the method was found to be 1.44% and 1.19% for 17.9 and 45 µmol L-1 Fe(II), respectively. The characteristics of the sensor allowed the design of a Fe(II)/Fe(III) speciation scheme. The methodology was successfully applied to the determination of iron in food preservatives, food additives, and dietary supplement. Additionally, the Fe speciation scheme was successfully applied to an agricultural fertilizer.

Sensing Cd(II) Using a Disposable Optical Sensor Based on a Schiff Base Immobilisation on a Polymer-Inclusion Membrane. Applications in Water and Art Paint Samples.

A disposable colour-changeable optical sensor based on an interesting polymer inclusion-membrane (PIM) was designed to determine Cd(II) ions in aqueous medium. The Schiff base 2-acetylpyridine benzoylhydrazone (2-APBH) immobilised on the polymer membrane was used as a sensing molecule. The amounts of the PIM components were optimised by a 32 fractional factorial design with two central points and two blocks. The best optical sensor composition consisted of 2.5 g of poly(vinylchloride) (PVC) as a base polymer, 3 mL of tributyl phosphate (TBP) as a plasticiser, and 0.02 g of 2-APBH as a reagent. The sensor showed a good linear response in the range from 0.02 mg L-1 (limit of detection) to 1 mg L-1 of Cd(II) under the following experimental conditions: pH 9.5 (adjusted using ammonium chloride buffer solution at 0.337 mol L-1), 60 min of exposure time plus 2 min of sonication (pulses at 2 s intervals), and 10 min of short-term stability. The relative standard deviation of the method was determined to be 4.04% for 0.4 mg L-1 of Cd(II). The optical sensor was successfully applied to the determination of Cd(II) in natural-water and art-paint samples.