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Acetic acid (HOAc) and diethylenetriaminepentaacetic acid (DTPA) single extraction agents were evaluated as screening methods to estimate the mobility of some trace elements in coastal sediments from Algeciras Bay. Sediments’ total metal concentrations of most heavy metals were found to be high around the areas impacted by anthropogenic activities such a sewage, atmospheric deposition and industrial activities, with notable values for As, Ni, Cr, Pb and Cd. The order of significant extraction efficiencies obtained with DTPA, were as follows: Pb (25.65%), Cu (19.78%), Cd (14.80%) and Zn (11.25%), while those obtained with HOAc were: Mn (33.00%), Tl (24.88%), Pb (18.99%), Cd (13.59%) and Co (11.78%). The comparison between the risk assessment codes (RAC) and the percent metal extractable fractions provided results of serious concern. Very high risk values of Cu, Zn, Cd and Pb extracts in DTPA were observed near the metallurgical industry, with Mn and Tl in HOAc extracts showing high risk values near the same industrial area and harbour activities. Sediments’ total metal concentrations were compared with the Low Alert-Level (LAL) sediment quality guidelines, where Co, Pb, Zn and Ni in both extractants and Cd and Cu in DTPA as well as Tl extracted in HOAc exceeded the LAL values respectively. The Spearman Rank test showed positive correlations between Co, Cu, Ni and Zn in DTPA extracts and their corresponding total metal concentrations, with Co, Cr, Fe, Ni, Tl and Zn in HOAc and total concentrations showing positive correlations. Furthermore, higher positive correlations were found between both extraction methods for Co (ρ = 0.797), Cu (ρ = 0.777), Ni (ρ = 0.789) and Zn (ρ = 0.942), indicating comparable potential extraction efficiencies between these extractants for these metals in the sediment studied. Keywords: Acetic acid, DTPA, Coastal sediment, Single extraction, Trace-element mobility

A global assessment of arsenic (As), nickel (Ni), cobalt (Co) and chromium (Cr) was performed in environmental samples from an important industrial bay. Different fractions of water, sediments and tissues from four species of fish were analysed. Samples were collected from selected sampling sites during four consecutive samplings in spring and autumn seasons, in order to evaluate concentrations and their possible correlations among the aquatic compartments. While a higher availability of Cr and Ni was found in water, Co and As were the most available elements in sediments. In fish, the liver was the tissue with the highest proportion of As and Co, and gills showed the highest concentrations of Ni and Cr. Significance differences were observed among sites showing the pollution sources. In sediments, high correlations were found between total Co content and the most available fractions. Total Ni content highly correlated with the oxidisable fraction, while Cr total content tightly correlated with the least available fractions. Quality guideline values for sediments were frequently exceeded. In sediments and biota, concentrations were slightly higher than in other ecosystems, indicating that maritime, industrial and urban activities are affecting this type of ecosystem with great anthropogenic influence., This research was funded by "Consejeria de Economia, Conocimiento, Empresas y Universidad", Junta de Andalucia (Spain) (PAI-EXCEL-06-FQM-02075) and by "Fomento e Impulso de la Investigacion y de la Transferencia" Programme, Universidad de Cadiz (Spain) (PR2020-013).

A low-cost biosorbent obtained from the Palomino Fino grape seed, a Sherry wine industry by-product, has been proposed as a way of valorising this material. The biomass was characterised obtaining values of 0.68 +/- 0.05 g mL(-1) for bulk density, 1.02 +/- 0.09 g mL(-1) for apparent density and 33.3% for porosity. The pH(pzc) was 5.2 and the surface negative charge value was 2.4 +/- 0.2 mmol g(-1). The analysis of surface morphology showed differences due to the sorption. The results showed a promising potential for chromium(VI) removal from aqueous solutions. The studies were carried out in batch scale and a 2(3) factorial design was applied for the optimisation of the process. A percentage of 91.7 +/- 0.6% was achieved for the biosorption of Cr(VI) under optimal conditions using pH 5.5, 15 g/L of biosorbent and 8 h of contact time. The biosorption capacity showed a remarkable linearity from 0 to 2 mmol L-1 Cr(VI) and a precision of 0.64% for the removal of 1 mmol L-1 of metal. Langmuir, Freundlich and Temkin isotherm equations and the parameters of six kinetic models were used in the equilibrium modelling and identifying the mechanism of the biosorption. The combination of physical and chemical sorption mechanisms was proposed for the chromium removal with a high maximum sorption capacity (q(max) = 208.3 mg g(-1)). Thermodynamic parameters indicated the spontaneous and endothermic nature of the chromium removal. The successful biosorption was based on the special grape seed components with a relevant content in antioxidant and lignocellulosic compounds., Open Access funding provided thanks to the CRUE-CSIC agreement with Springer Nature. This work has been supported by "Consejeria de Economia, Conocimiento, Empresas y Universidad", Andalusian Government (Spain) (support for RNM-236 Research group) and the Programme of "Fomento e Impulso de la Investigacion y de la Transferencia" from the University of Cadiz (Spain) (Project PR2020-013).

An efficient assisted transport of Fe(III) ions using a bulk liquid membrane containing 2-hydroxybenzaldeyde benzoylhydrazone in toluene has been applied as a separation and preconcentration process for the analysis and speciation of dissolved iron traces in natural and sea waters. A study strategy based on a modified simplex design has been followed to optimise the transport of Fe(III) ions through the liquid membrane. Maximum carrier-mediated transport efficiencies were obtained at following conditions: pH 1.9 for feed aqueous solution; 0.014 mol L− 1 of ligand in toluene as carrier and 2.9 mol L− 1 HNO3 in the stripping solution. Under optimal conditions, the average recovery of Fe(III) ions was 102 ± 2% (n = 7) for 6 h at 35 °C and the preconcentration factor of the method was 18.1. The influence of saline matrix was negligible and experiments at slightly high temperatures led to reduced preconcentration times. The accuracy of the method was verified by using the TMDA-62 certified reference water sample and successfully applied to the analysis of Fe(III) in river and seawater samples from Tangier (Morocco). Due to the proposed liquid membrane system allowed the selective separation and preconcentration of Fe(III) ions but not Fe(II) ions, a scheme for speciation analysis of dissolved iron was proposed. The distribution of total dissolved Fe, non-labile Fe, labile Fe(II) and labile Fe(III) fractions was performed in real seawater samples with successful results in good agreement with those obtained by adsorptive cathodic stripping voltammetry (average relative error of ± 3%).

A comprehensive approach to chemical accumulation and biological effects of short-term Cu exposure in juveniles of European seabass (Dicentrarchus labrax) has been achieved. Fish were exposed to 0.01–10 mg L− 1 nominal Cu concentrations for 24–96 h. Metal concentrations in water and gills, liver, muscle and brain tissues were studied along with oxidative stress biomarkers (superoxide dismutase, catalase, glutathione peroxidase, lipid peroxidation). Induction of oxidative damage was observed in all the organs with differential antioxidant responses; gills appearing as the most sensitive from low environmentally water Cu concentrations as 0.01 mg L− 1. Histopathological alterations were also observed in liver and gills, even without a significant Cu accumulation. The results show that the combination of oxidative stress parameters, particularly lipid peroxidation and glutathione peroxidase activities, and histopathological alterations provide a good model fish and reliable early biomarkers for monitoring Cu pollution in seawater and might call for the protection agencies to revise the Cu environmental standards.

A disposable and miniaturised optical sensor based on colorimetric solid-phase extraction has been designed using poly(styrene-divinylbenzene) membrane disks modified with the colorimetric reagent pyridoxal salicyloylhydrazone to determine the aluminium concentration in aqueous solutions. The extraction of Al(III) ions by the reagent immobilised onto a disk allows the quantification directly on the adsorbent surface by a miniature portable reflectance spectrometer with an optical fibre at 434 nm. The optimisation of the sensing system was carried out by a fractional factorial design 33−1 considering the extraction pH, amount of ligand immobilised onto the disk and time of immobilisation as experimental factors. The linear dynamic range of the sensor response ranged from 0.18 to 2 mg L−1 Al(III) with a detection limit of 0.18 mg L−1 (n = 10), being the precision of 6.3% for 1 mg L−1 Al(III) (n = 10, confidence level of 95%). The proposed method was successfully applied to the analysis of aluminium in leachates from cookware, antacids and hygienic care products, as contribution to the concern about aluminium as a known systemic toxicant at high doses.

A novel polymer inclusion membrane (PIM), doped with pyridine-2-acetaldehyde benzoylhydrazone (2-APBH) as extractant, was synthesized and applied for the simultaneous extraction and preconcentration of Cu(II), Ni(II) and Cd(II) ions from natural waters of different salinities. Poly(vinyl chloride) (PVC) and tributyl phosphate (TBP) were used to prepare the polymeric membrane. The carrier-mediated extraction of Cu(II), Ni(II) and Cd(II) ions by PIM was based on the reaction of 2-APBH as a polydentate ligand, forming uncharged chelates at pH 8. After a back-extraction step from the membrane to an acid solution (0.3 mol L-1 nitric acid), these ions were quantitative determined by flame atomic absorption spectroscopy. The optimum values of different analytical variables were determined by using the modified simplex method. The results showed limits of detection of 0.33 µg L-1 for Cu(II), 0.75 µg L-1 for Ni(II) and 0.48 µg L-1 for Cd(II). The accuracy was successfully assessed by analyzing a certified reference river water (LGC 6019). The applicability of the proposed PIM on real samples was also demonstrated on estuarine and seawater samples, with high salinities.

A single-use optical sensor was designed for Zn(II) determination based on the immobilisation of the colorimetric reagent 2-acetylpyridine benzoylhydrazone (2-APBH) in a polymer inclusion membrane (PIM) adhered on the surface of an inert rectangular strip of polyester (Mylar). Different components for the membrane preparation were tested and those resulting in membrane with good appearance, proper physical and optical properties and ease of preparation were selected. Factorial design 23 with three replicates of the central point was applied for the optimisation of the membrane composition. The optimal composition consisted of 2.5 g of poly(vinyl chloride) (PVC), 4 mL of tributyl phosphate (TBP) and 0.04 g of 2-APBH. The optode showed a linear dynamic range from 0.03 (detection limit) to 1 mg L−1 of Zn(II) ions with a response time of 30 min in aqueous solution at pH 6 and a relative standard deviation of 3.90% for 0.4 mg L−1 of Zn(II). The sensor exhibited good selectivity to Zn(II) over other commonly ions. It was successfully applied to the determination of Zn(II) in a water certified reference material, spiked tap water, vitamin-mineral drink, food supplement and foot health care products, as contribution to the concern about this heavy metal due to its significant role in many biological and physiological processes although toxicant at high doses.

A tandem system based on the coupling of a bulk liquid membrane and a flow injection analysis for the separation, preconcentration and spectrophotometric determination of copper in saline water is presented. The ligand pyridine-2-acetaldehyde benzoylhydrazone has been used as a carrier in the liquid membrane as well as a spectrophotometric reagent for UV–VIS detection. Simultaneous and sequential experimental designs were used to optimise the chosen variables of each technique, respectively. The metal was separated and preconcentrated from the sample with an efficiency of 100.5 ± 0.9% and a metal preconcentration factor of 16.1. The on-line FIA determination was accomplished after metal complexation by the reagent at pH 3. A linear response was obtained in a range from 6.9 to 984.5 µg L–1 Cu(II), providing a detection limit of 1.8 µg L–1. Saline matrix and other metal ions were not cause of interferences with relative errors below 4.6% for 50 µg L−1 of Cu(II) determination. The proposed tandem system was successfully tested using a TMDA-62 certified reference material providing a relative error of + 1.9%; it was also applied to the Cu(II) determination in coastal seawater samples with low relative errors ranging from − 3.8% to 0.0% (using DPASV as reference method).

Cu, Pb, and As, which are among the most abundant metals in the aquatic environment, are also among the most health-threatened by causing diverse cellular injuries. The aim of this study was to assess and compare the potential early induction of genotoxic effects after waterborne Cu, Pb, and As exposure in European seabass, Dicentrarchus labrax, a commercial widely cultured fish, using the micronucleus (MN) assay in peripheral blood erythrocytes. Fish were exposed under laboratory conditions to nominal solutions ranging 0–10 mg/L for 24 and 96 h. Furthermore, actual metal ion concentrations were measured by inductively coupled plasma atomic emission spectroscopy (ICP-AES) or differential pulse anodic stripping voltammetry (DPASV) in water and four fish tissues differentially related to environmental exposition and metal accumulation, i.e. the gills, liver, muscle, and brain. Dose-dependent increases of micronuclei (MNi) frequency were observed after these very short exposures; based on measured metal concentrations in water, the genotoxic effect ordered as Cu > As > Pb. Significant genotoxic effect at 0.009 mg/L Cu, 0.57 mg/L Pb, and 0.01 mg/L As was seen. For Cu and Pb these are only slightly higher, but for As it is notably lower than the USEPA criteria of maximum concentration to prevent acute toxicity in aquatic organisms. Furthermore, genotoxicity was differentially related to metal accumulation. MNi frequency correlated positively with the content of Pb in all the organs, with the content of As in liver and gills and only with the content of Cu in the brain. In conclusion, our findings raised environmental concerns because these depicted a genotoxic potential of Cu, Pb, and As after a very short exposure to low but environmentally relevant concentrations, too close to regulatory thresholds. In addition, the MN test in D. labrax could be considered an early biomarker of genotoxicity induced by these metals in fish.

A study to determine total and mobile heavy metals concentrations in sediments from Algeciras Bay was performed and pollution hotspots were identified. The effects on aquatic organisms were established using sediment quality guidelines (SQGs). Ni and Cr exceeded the effect range medium and low levels, respectively, around industrial area. Potential toxicity of metals was determined by diethylenetriaminepenta-acetic acid (DTPA) extractions and low alert levels of Co, Cu, Zn, Cd, Ni and Pb were exceeded at most sampling sites. Three pollution indicators were used showing significant values for As, Ni, Cr, Pb and Cd. Sediment speciation using the sequential extraction BCR procedure was carried out, being Cd, Zn, Pb and As the most available metals. Principal component, cluster and ANOVA analyses were performed in order to assess the sources of metals and the influence of seasonality and anthropogenic activities on the sediment quality. Two principal component analysis (PCA) factors were obtained identifying the sampling sites affected by anthropogenic activities; Ni–Cr and Zn–Cu–V clusters were also obtained associated with stainless steel and petrochemical industrial activities. ANOVA showed the outstanding sites because of total metal concentration and significant differences among sampling sites by the acid extractable and reducible fractions for all metals except for Ba and V.

Environmental context Metal contamination of seawater can present severe environmental problems owing to the high toxicity of metals and their persistence in the environment. This study explores the possibility of analysing lead in seawater media using two recently developed electrochemical methods. The methods are shown to be very useful tools to monitor the behaviour and fate of lead and other metals in seawater. Abstract The speciation of PbII in synthetic and real seawater is studied by absence of gradients and Nernstian equilibrium stripping (AGNES) and stripping chronopotentiometry at scanned deposition potential (SSCP). The usefulness of the combination of both techniques in the same electrochemical cell for trace metal speciation analysis is assessed at different pH values (2.7, 5.0, 6.0, 7.0 and 8.6). The AGNES (free metal ion concentrations) and SSCP (stability constants) results for synthetic seawater agree reasonably with each other and with the theoretical predictions of the software Visual MINTEQ 3.0. This is also true for real seawater media below pH 7.0. Because of the influence of natural organic matter (2.01mgL–1 total organic carbon) in the real seawater at pH 7.0 and 8.6 the SSCP signal showed that the PbII complexes became less labile and were formed by chemically heterogeneous ligands. At these pH values, free metal concentrations determined by AGNES agreed with concentrations predicted by Visual MINTEQ using a generic fulvic acid concentration.