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Mushroom consumption has increased in recent years due to their beneficial properties to the proper functioning of the body. Within this framework, the high potential of mushrooms as a source of essential elements has been reported. Therefore, the present study aims to determine the mineral content of seven essential metals, Fe, Mg, Mn, P, K, Ca, and Na, in twenty samples of mushrooms of the genus Lactarius collected from various locations in southern Spain and northern Morocco, by FAAS, UV-Vis spectroscopy, and ICP-OES after acid digestion. Statistics showed that K was the macronutrient found at the highest levels in all mushrooms studied. ANOVA showed that there were statistically significant differences among the species for K, P, and Na. The multivariate study suggested that there were differences between the accumulation of the elements according to the geographic location and species. Furthermore, the intake of 300 g of fresh mushrooms of each sample covers a high percentage of the RDI, but does not meet the recommended daily intake (RDI) for any of the metals studied, except for Fe. Even considering these benefits, the consumption of mushrooms should be moderated due to the presence of toxic metals, which may pose health risks. [ABSTRACT FROM AUTHOR]

This research is concerned with the adsorption and desorption of Cu and As(V) on/from different soils and by-products. Both contaminants may reach soils by the spreading of manure/slurries, wastewater, sewage sludge, or pesticides, and also due to pollution caused by mining and industrial activities. Different crop soils were sampled in A Limia (AL) and Sarria (S) (Galicia, NW Spain). Three low-cost by-products were selected to evaluate their bio-adsorbent potential: pine bark, oak ash, and mussel shell. The adsorption/desorption studies were carried out by means of batch-type experiments, adding increasing and individual concentrations of Cu and As(V). The fit of the adsorption data to the Langmuir, Freundlich, and Temkin models was assessed, with good results in some cases, but with high estimation errors in others. Cu retention was higher in soils with high organic matter and/or pH, reaching almost 100%, while the desorption was less than 15%. The As(V) adsorption percentage clearly decreased for higher As doses, especially in S soils, from 60–100% to 10–40%. The As(V) desorption was closely related to soil acidity, being higher for soils with higher pH values (S soils), in which up to 66% of the As(V) previously adsorbed can be desorbed. The three by-products showed high Cu adsorption, especially oak ash, which adsorbed all the Cu added in a rather irreversible manner. Oak ash also adsorbed a high amount of As(V) (>80%) in a rather non-reversible way, while mussel shell adsorbed between 7 and 33% of the added As(V), and pine bark adsorbed less than 12%, with both by-products reaching 35% desorption. Based on the adsorption and desorption data, oak ash performed as an excellent adsorbent for both Cu and As(V), a fact favored by its high pH and the presence of non-crystalline minerals and different oxides and carbonates. Overall, the results of this research can be relevant when designing strategies to prevent Cu and As(V) pollution affecting soils, waterbodies, and plants, and therefore have repercussions on public health and the environment. [ABSTRACT FROM AUTHOR]

There are many enclaves in the Mediterranean basin with soils contaminated with heavy metal(loid)s, most of these in natural areas of great beauty that have suffered the consequences of industrial and mining activity for years. These soils pose a risk to human and animal health due to the transfer of metal(loid)s condemning these areas to isolation. The rehabilitation by means of phytoremediation is one of the most used techniques, but phytoremediation must be part of a comprehensive strategy of steps that guide owners and administrations in the recovery of ecosystem services. An easily replicable decision-making methodology is defined, considering the initial conditions, the preferences of the decision makers or typologies from among six possibilities and the different models of use, typified in 13 categories. As a result, a landscape is obtained that integrates phytostabilization and areas with recreational and/or educational uses. Two case studies from the southeast of Spain are presented as validation, a deposit of mining sludge residues and the channel of a river contaminated by industrial discharges. Both enclaves are included in the tourist and cultural offer of their area, thus achieving an environmental and socioeconomic benefit and have been visited by more than 1000 people in a two-year period. [ABSTRACT FROM AUTHOR]

In the mining-impacted Rio Tinto, Spain, Fe-cycling microorganisms influence the transport of heavy metals (HMs) into the Atlantic Ocean. However, it remains largely unknown how spatial and temporal hydrogeochemical gradients along the Rio Tinto shape the composition of Fe-cycling microbial communities and how this in turn affects HM mobility. Using a combination of DNA- and RNA-based 16S rRNA (gene) amplicon sequencing and hydrogeochemical analyses, we explored the impact of pH, Fe(III), Fe(II), and Cl2 on Fecycling microorganisms. We showed that the water column at the acidic (pH 2.2) middle course of the river was colonized by Fe(II) oxidizers affiliated with Acidithiobacillus and Leptospirillum. At the upper estuary, daily fluctuations of pH (2.7 to 3.7) and Cl2 (6.9 to 16.6 g/L) contributed to the establishment of a unique microbial community, including Fe(II) oxidizers belonging to Acidihalobacter, Marinobacter, and Mariprofundus, identified at this site. Furthermore, DNA- and RNA-based profiles of the benthic community suggested that acidophilic and neutrophilic Fe(II) oxidizers (e.g., Acidihalobacter, Marinobacter, and Mariprofundus), Fe(III) reducers (e.g., Thermoanaerobaculum), and sulfate-reducing bacteria drive the Fe cycle in the estuarine sediments. RNA-based relative abundances of Leptospirillum at the middle course as well as abundances of Acidihalobacter and Mariprofundus at the upper estuary were higher than DNA-based results, suggesting a potentially higher level of activity of these taxa. Based on our findings, we propose a model of how tidal water affects the composition and activity of the Fe-cycling taxa, playing an important role in the transport of HMs (e.g., As, Cd, Cr, and Pb) along the Rio Tinto. [ABSTRACT FROM AUTHOR]

Plant-based beverages have been positioned as an alternative to cow's milk. Some of the most commonly consumed plant-based beverages are those made from soybeans. Soybean beverages can be an important source of essential elements. However, soybean plants can be exposed to high concentrations of contaminants, such as toxic metals, from the soil and the environment. The objective of this study was to determine the concentrations of potentially toxic elements (PTEs; Fe, Cu, Cr, Co, Mn, Mo, Zn, B, Ba, Ni, Li, Sr, V, Al, Cd, and Pb) to evaluate the human exposure and toxic risk from the consumption of these soybean beverages. Forty samples of various brands of soybean beverages were analyzed by inductively coupled plasma–optical emission spectroscopy. The most abundant PTE was Al (3.93 mg/L), followed by Fe (1.91 mg/L) and Ba (0.69 mg/L). Based on a mean consumption of two servings of soybean beverage per day (250 mL per serving), this consumption results in a daily intake of Al and Pb that is significant but still below of the maximum recommended amount. However, higher consumption could exceed the maximum recommended Al and Pb values, with consequent risks to the human health. Concentrations of PTEs in soybean beverages were determined. Al (3.93 mg/L) was the most notable PTE found in soybean beverages. Estimated consumption of two servings per day resulted in significant Al, Mo, and Ni intake. Higher soybean beverage consumption could pose a risk for consumer health. [ABSTRACT FROM AUTHOR]

This work utilizes a combined biological-electrochemical technique for the in-situ removal of metals from polluted mine tailings. As the main novelty point it is proposed to use electrokinetics (EK) for the in-situ activation of a bioleaching mechanism into the tailings, in order to promote biological dissolution of metal sulphides (Step 1), and for the subsequent removal of leached metals by EK transport out of the tailings (Step 2). Mine tailings were collected from an abandoned Pb/Zn mine located in central-southern Spain. EK-bioleaching experiments were performed under batch mode using a lab scale EK cell. A mixed microbial culture of autochthonous acidophilic bacteria grown from the tailings was used. Direct current with polarity reversal vs alternate current was evaluated in Step 1. In turn, different biological strategies were used: biostimulation, bioaugmentation and the abiotic reference test (EK alone). It was observed that bioleaching activation was very low during Step 1, because it was difficult to maintain acidic pH in the whole soil, but then it worked correctly during Step 2. It was confirmed that microorganisms successfully contributed to the in-situ solubilization of the metal sulphides as final metal removal rates were improved compared to the conventional abiotic EK (best increases of around 40% for Cu, 162% for Pb, 18% for Zn, 13% for Mn, 40% for Ni and 15% for Cr). Alternate current seemed to be the best option. The tailings concentrations of Fe, Al, Cu, Mn, Ni and Pb after treatment comply with regulations, but Pb, Cd and Zn concentrations exceed the maximum values. From the data obtained in this work it has been observed that EK-bioleaching could be feasible, but some upgrades and future work must be done in order to optimize experimental conditions, especially the control of soil pH in acidic values. [Display omitted] • Electrokinetics helps the in-situ biodissolution of metal sulphides in mine tailings • Keeping acidic pH in tailings was detected as the critical parameter to control • Alternate current seems to work better than direct current under polarity reversal • Bioaugmentation option does not improve the biostimulation approach [ABSTRACT FROM AUTHOR]

Background: The association of low-level exposure to metals and metal mixtures with cardiovascular incidence in the general population has rarely been studied. We flexibly evaluated the association of urinary metals and metal mixtures concentrations with cardiovascular diseases in a representative sample of a general population from Spain.Methods: Urine antimony (Sb), barium (Ba), cadmium (Cd), chromium (Cr), cobalt (Co), copper (Cu), molybdenum (Mo), vanadium (V) and zinc (Zn) were measured in 1171 adults without clinical cardiovascular diseases, who participated in the Hortega Study. Cox proportional hazard models were used for evaluating the association between single metals and cardiovascular incidence. We used a Probit extension of Bayesian Kernel Machine Regression (BKMR-P) to handle metal mixtures in a survival setting.Results: In single-metal models, the hazard ratios [confidence intervals (CIs)] of cardiovascular incidence, comparing the 80th to the 20th percentiles of metal distributions, were 1.35 (1.06, 1.72) for Cu, 1.43 (1.07, 1.90) for Zn, 1.51 (1.13, 2.03) for Sb, 1.46 (1.13, 1.88) for Cd, 1.64 (1.05, 2.58) for Cr and 1.31 (1.01, 1.71) for V. BKMR-P analysis was confirmatory of these findings, supporting that Cu, Zn, Sb, Cd, Cr and V are related to cardiovascular incidence in the presence of the other metals. Cd and Sb showed the highest posterior inclusion probabilities.Conclusions: Urine Cu, Zn, Sb, Cd, Cr and V were independently associated with increased cardiovascular risk at levels relevant for the general population of Spain. Urine metals in the mixture were also jointly associated with cardiovascular incidence, with Cd and Sb being the most important components of the mixture. [ABSTRACT FROM AUTHOR]

Even relatively low levels of metals exposure may impact health, particularly among vulnerable populations such as infants and young children. However, little is known about the interplay between simultaneous metal exposures, common in real-life scenarios, and their association with specific dietary patterns. In this study, we have evaluated the association between adherence to Mediterranean diet (MD) and urinary metal concentrations individually and as an exposure mixture in 713 children aged 4-5-years from the INMA cohort study. We used a validated food frequency questionnaire to calculate two MD indexes scores: aMED and rMED. These indexes gather information on various food groups within the MD and score differently. To measure urinary concentrations of cobalt, copper, zinc, molybdenum, selenium, lead, and cadmium as exposure biomarkers, we used inductively coupled plasma mass spectrometry (ICP-MS), coupled with an ion chromatography (IC) equipment for arsenic speciation analysis. We applied linear regression and quantile g-computation, adjusted for confounders, to analyse the association between MD adherence and exposure to the metal mixture. High adherence to MD such as the quintile (Q) 5 MD was associated with higher urinary arsenobetaine (AsB) levels than Q1, with β values of 0.55 (confidence interval - CI 95% 0.01; 1.09) for aMED and 0.73 (CI 95% 0.13; 1.33) for rMED. Consumption of fish was associated with increased urinary AsB but reduced inorganic arsenic concentrations. In contrast, the aMED vegetables consumption increased urinary inorganic arsenic content. A moderate level of adherence to MD (Q2 and Q3) was associated with lower copper urinary concentrations than Q1, with β values of −0.42 (CI 95% −0.72; −0.11) for Q2 and -0.33 (CI 95% −0.63; −0.02) for Q3, but only with aMED. Our study, conducted in Spain, revealed that adhering to the MD reduces exposure to certain metals while increasing exposure to others. Specifically, we observed increase in exposure to non-toxic AsB, highlighting the significance of consuming fish/seafood. However, it is crucial to emphasize the necessity for additional efforts in reducing early-life exposure to toxic metals, even when adhering to certain food components of the MD. [Display omitted] • Urinary arsenobetaine and copper increased with the Mediterranean diet. • Metal mixture exposure was primarily led by arsenobetaine, cobalt and cupper. • Eating fish increased urine arsenobetaine, but lowed inorganic arsenic exposure. • Consuming vegetables increased urinary inorganic arsenic. [ABSTRACT FROM AUTHOR]

Abstract The mining activities performed in the Iberian Pyrite Belt (south of Spain) have generated since long-time acid mining drainage (AMD) inputs to the Odiel River and its tributaries. These inputs are continuing nowadays, with origin mostly in the abandoned mines that cover the area, provoking a steady-state situation where the river waters present very low pH and very high concentrations of different heavy metals. In this work, the behavior of several natural radionuclides (210Po, Th- and U-isotopes) in water and sediment samples collected in the Odiel River and its tributaries have been analyzed and their levels determined looking for assessing the radiological environmental impact of the AMD. Highlights • Radioactive NORM impact associated to acid mining drainage (AMD) have been analyzed. • Enhanced U and Th concentrations are present in waters affected by AMD. • Very high 234U/238U activity ratios have been also observed in the affected waters. [ABSTRACT FROM AUTHOR]

Abstract The Río Tinto mining area provides ideal conditions for studying the role of colloidal particles in concentrating. All the elements are present in higher concentrations respect to their content in common natural waters. 234U/238U activity ratio ranges between 2.286 ± 0.149 and 2.531 ± 0.151. Concentration of Fe and Al are in the order of 104–103 mg/L; Co, Zn and Cu values are three times lower than Fe and Al, but still much greater than in natural waters; U reaches values up to 40.73 μg/L. To evaluate the partitioning of these elements into the colloidal fraction, ultrafiltration (UF) experiments were made. A permeation model describing the relationship between concentration of the elements or isotopes in the permeate solution and the concentration factor (CF) was calculated. Experiments were carried out using CF from 1.5 to 25.0. The behaviour of investigated heavy metals and U can be predicted by a permeation model that provides similar permeation coefficient (P c) for all of them (P c = 0.95–0.97 for 50 kDa, P c = 0.86–0.88 for 10 kDa, and P c = 0.80–0.86 for 3 kDa). Retention for all the investigated elements occurs, resulting in up to 23% of the element associated to the 3 kDa colloidal fraction. The increase in U and heavy metals concentrations in the retentate fraction with the increasing CF is due to the retention of the colloidal fraction. The colloidal abundance of related metals increased with decreasing membrane MWCO even though the difference is small between 3 and 10 kDa fraction for some metals Characterization of colloidal material is needed to better understand the state of play in this context. Highlights • Partitioning of U and selected heavy metals in dissolved and colloidal fractions in AMD conditions were examined. • UF with distinct MWCO was used and a permeation model to quantify the behaviour of U and selected metals was applied. • Metal concentrations much higher than those in natural waters were found and high 234U/238U in the water samples were observed. • Little colloidal metals in the size fraction 3–10 kDa are present, likely due to the strong acidic conditions. • Low concentrations of colloidal U in the study area were measured. [ABSTRACT FROM AUTHOR]

Abstract Among the threats to air, soil, and water posed by urbanization, heavy metals appear particularly hazardous. Playgrounds and sport facilities are unique urban places, widely used by children and youth. The aim of this research was to evaluate heavy metal pollution in urban soils, identify relationships among topsoil metal distributions, and assess related health risks in two Polish cities – Warsaw and Bydgoszcz. According to the Regulation of the Polish Minister of the Environment guidelines for total content of Pb, Cu, Zn, Ni, Cd and Co our study sites were classified as uncontaminated. Applied Geoaccumulation Index (I geo ; Müller, 1969) largely confirmed this classification, with only two of the investigated Warsaw areas "moderately polluted" with Pb. Generally, only Pb and Zn concentrations exceeded reference background levels for Polish soils. The highest concentrations of Pb and Zn were found in the city centers, the oldest areas where pollution risk is potentially the highest. Metal mobility and solubility were mainly correlated with total content, indicating potential risk from lead and zinc. At some sites in Warsaw, where mean Pb concentration was 87.25 mg kg−1 and Zn 207.25 mg kg−1, health risks from ingestion and inhalation seemed significant, particularly for children. In Bydgoszcz use of the studied playgrounds and sport facility areas did not pose a risk to human health. Finally, the study (especially in Warsaw) indicates the need for continued monitoring and suggests lowering permissible limits of these metals in soils, especially in recreational areas, may decrease childrens' exposure risk to these pollutants. Highlights • Urban soils of playgrounds and sport facilities are special places in the cities. • The main source of metals was atmospheric deposition. • Concentrations of Pb and Zn indicates potential human health risk. • Metal solubility and mobility were correlated with the total content. • The study indicated the need for lowering the permissible limits of metals. [ABSTRACT FROM AUTHOR]

• Acidic mine water as a valuable source of valuable metals. • Use of nanofiltration for water (or acid) recovery and metal concentration. • Metal rejections higher than 75% using Desal DK. • Design projection tools for integrating nanofiltration into treatment chains. • 0.52€/m3 for treating Acidic Mine Waters using Nanofiltration. Acid Mine Waters (AMWs) are considered the most challenging environmental problem in the Iberian Pyrite Belt (South of Spain) so far, being characterised by an acidic pH (H 2 SO 4 -based), high content of heavy metals (e.g. Co, Pb, rare earth elements (REEs)) and non-metals (e.g. As). Nowadays, AMWs are being contemplated as a source of valuable metals (e.g. Zn, Cu, REEs), and different recovery routes have been studied (e.g. ion-exchange, membrane technologies). Among them, nanofiltration (NF) provides the possibility of water (or H 2 SO 4) recovery and concentration of metals, which can be recovered in a subsequent stage. This work evaluates the performance of the Desal DK NF membrane to treat AMW from Aznalcóllar open-pit, which presents a low pH (2.6) and high contents of Zn (920 mg/L), Mg (2540 mg/L) and REEs (17 mg/L). The effect of solution pH on membrane performance was evaluated. Results showed that the equilibrium SO 4 2-/HSO 4 - controlled the transport of species. Rejections of sulphate were around 84 % at pH 2.1 (prevalence of HSO 4 -) and increased to 92 % at pH 3.1 (prevalence of SO 4 2-). Metal rejections remained higher than 74 % (except for monovalent species). Additionally, membrane permeances were determined using the Solution-Electro-Diffusion model coupled with reactive transport, and later used to assess the design of the process treatment of the AMW. Results demonstrated the possibility of concentrating metals and recovering H 2 SO 4 as permeate, but also showed that gypsum and anhydrite precipitation can occur. Additionally, CAPEX and OPEX were estimated for a NF plant treating 2 Hm3/year. [ABSTRACT FROM AUTHOR]

The aim of the present study was to determine the concentrations of eight metals (Al, Cd, Co, Cr, Mn, Ni, Pb, Sr) in 33 cigarette brands for sale in Spain. Samples were analysed by Inductively Coupled Plasma Optical Emission Spectrometry (ICP-OES). Mean values obtained were 428 µg Al/g, 0.810 µg Cd/g, 0.558 µg Co/g, 1.442 µg Cr/g, 112.026 µg Mn/g, 2.238 µg Ni/g, 0.602 µg Pb/g and 82.206 µg Sr/g. Statistically significant differences were observed with respect to concentrations of Co (0.004), Cr (0.045), Mn (0.005) and Sr (0.005) between black and blond tobacco and between levels of Mn (0.027) among manufacturers. Considering a Cd inhalation rate of 10% and a Cd absorption rate of 50%, absorption of Cd for smokers of 30 cigarettes/day was estimated at 0.75 µg Cd/day. An inhalation rate of 2–6% and an absorption rate of 86% were considered for Pb, Pb absorption in smokers of 30 cigarettes/day was therefore 0.18–0.54 μg/day. In view of the significant toxic effects of these metals, quantification and control of their concentrations in this drug are of the utmost importance. [ABSTRACT FROM AUTHOR]

• Regional geology seems to be a key factor in the metal(oid) detected in mussels. • Metal(oid) in mussels naturally exceed international environmental criteria. • Cd and Hg risk to mussels seems to be limited to industrialized areas or diminished by mussel protection mechanisms. Several international organisations have recommended the use of bioindicators to improve the evaluation of ecological risk in marine ecosystems. In this context, wild mussels, a recognised bioindicator, were collected from thirty sampling points along the Asturias coastline and studied in order to identify any relationship between metal(oid) concentrations in wild mussel tissues and the geological and environmental conditions of the coastal area via biochemical analyses. Two main concentration trends were observed: Concentrations of As, Cd, Cr, Ni, Pb and Zn slightly decrease from the western to the eastern areas of the region, while the opposite occurred for Fe, Hg and Se whose concentrations increased from the westernmost part of Asturias to the east. Correlations between the elements showed how essential metals for organisms such as Fe, Ni and Cr have good correspondences among them but not with other metal(oid)s. On the other hand, Cd, Hg, Se and Zn were found to be correlated with each other, suggesting the presence of the mussels' natural bio-defence against Cd and Hg. In addition, samples were also grouped by a cluster analysis based on their element concentrations, showing two independent groups. Group 1 was associated with the sampling sites whose concentrations were related to anthropic sources, while mussel concentrations in Group 2 were attributed to natural sources. This last group was divided into two subgroups based on the lithology of the dominant geological materials of each area. Both geological and anthropic sources have caused an increase in the metal loads of mussels which at times surpassed international environmental criteria. [ABSTRACT FROM AUTHOR]

Conservation, rehabilitation and post-valuation of the facilities of old mining districts is considered a valid strategy to revitalize these areas. In this study, the northeastern sector of the Linares-La Carolina mining district was analyzed, integrating geological information with mining to assess its value. The characteristics of the three most emblematic veins (consisting of galena, sphalerite, chalcopyrite, pyrite, quartz, ankerite and calcite) were analyzed, namely El Guindo, Federico and El Sinapismo. In this study, each mining exploitation was evaluated according to their geological context. Currently, old mining operations can only be visited from drainage galleries or from some exploration galleries. However, some of the old mining shafts could be adapted for visitation. On the surface, the remains of the most important extraction shafts and part of the associated facilities are still visible. One can also visit old tailings dumps with a high contents of heavy metals associated with ore concentration plants. The contaminating potential of these wastes is being monitored thanks to control piezometers and sensors installed at different depths within the tailings ponds, which assist in controlling evolution in the latter years. Different localities of special interest from geological, mining and mineralogical points of view are indicated. Therefore, the guided tour described in this work is attractive for tourism and educational purposes. [ABSTRACT FROM AUTHOR]

• Aquatic mosses are good biomonitors for trace elements and other pollutants. • They trap particulate matter (up to 40%) that can bias the concentration estimations. • To avoid bias and excessive variability, the particulate matter must be washed out. • Two washings with distilled water of 30 s with a ratio water:moss greater than 20:1 are needed. • The procedure does not extract significant quantities of elements from the moss. Aquatic macrophytes capture trace elements from water and store them in their tissues, which make them good biomonitors for these substances. But they also capture suspended particulate matter that could bias the concentration measurements in the moss tissues. To avoid this problem, many biomonitoring studies using mosses include a washing step in the sample preparation procedure. However, no data is available on the quantities and variability of the particulate matter trapped by the moss, and the washing procedure has not been standardized between studies (washing time varied between 10 s to 30 min, divided in up to 7 washing steps). To study this, we extracted the particulate matter from samples of the moss Fontinalis antipyretica Hedw. collected in three rivers in NW Spain, washed them for 1, 2 and 5 min and collected the particulate matter extracted in each step. We also measured the contents of Al, As, Ba, Cd, Cr, Cu, Fe, Hg, Mn, Ni, Pb and Zn in the tissues of the washed and unwashed mosses. We made a second experiment washing the samples only for 15 + 45, 30 + 30 and 45 + 15 s to determine if shorter washing times were adequate for cleaning the moss. In a third experiment we estimated the contents of particulate matter in moss samples collected monthly over a two-year period in two rivers in the same area. The results showed that a) particulate matter can be as high as 40\% of the total weight of the sample, and that there were large variations within and between sampling sites, and over time. These results showed the need of washing the samples prior to their analysis; b) that two washings are needed for the removal of most of the particulate matter, but that 30 + 30 ∼ s are long enough to clean the moss, and c) that a 20:1 (or larger) water:moss relation is recommended to avoid saturation of the washing water, which would reduce the efficiency of the procedure. We did not find significant losses of trace elements along the washing process, except for Cr in the three sampling sites, and Al, Fe and Pb in some of them. 1 min total washing time seemed the correct option both from the point of view of reducing the handling time of the samples and to prevent possible element losses. [ABSTRACT FROM AUTHOR]

Lead exposure in waterfowl was studied using noninvasive fecal sampling in the Guadalquivir Marshes in Spain, an area affected by the 1998 Aznalcóllar mine disaster. Feces of greylag geese (Anser anser, n = 191) and purple gallinule (Porphyrio porphyrio, n = 91) were collected from three different impacted sites (Entremuros, Caracoles and Cerro de los Ánsares) during the winters of 2004 to 2008. Lead and aluminium (an indicator of sediment ingestion) and Pb isotope signatures (to discriminate between sources of Pb exposure) were analyzed in freeze-dried, acid digested samples. The concentrations of fecal porphyrins and biliverdin were determined as noninvasive biomarkers to study Pb exposure effects. Results showed a decrease in Pb exposure over time in wintering greylag geese. In contrast, for purple gallinule resident in the Entremuros a clear trend was not evident. For both species, sediment ingestion appeared to be the main source of exposure to Pb. In the Entremuros, some samples from purple gallinule were detected with higher Pb levels than expected for simple soil ingestion, and these had Pb isotopic profiles compatible with mining sludge or Pb shot. Whilst fecal Pb isotopic profiles were effective in differentiating between samples from sites with different levels and sources of pollution, the combined use of element ratios (such as Pb/Al) and other non-traditional stable isotope signatures may also prove worthwhile. Overall, the fecal Pb levels detected were below those described in feces for waterfowl from other uncontaminated areas(<10 µg/g d.w.). Despite this, for both species fecal Pb levels were positively correlated with porphyrin excretion, and for purple gallinule, with the coproporphyrin III/I ratio, suggesting some subtle effects on heme synthesis in birds. Ten years after the mine spill, Pb contamination in birds by this pollution source was still detectable and subtlethal effects may persist. [ABSTRACT FROM AUTHOR]

The long-term influence of a mine spill in soil was studied 12 years after the Aznalcóllar accident. Soils where the pyritic sludge was not removed, a fenced plot established for research purposes (2000 m2) and soils where the process of remediation was accomplished successfully were sampled and studied in detail. Soils were characterized at different depths, down to 100 cm depth, determining chemical parameters and total concentrations of major and trace elements. Moreover plants colonizing remediated (RE) and non remediated (NRE) soils were also analysed attending their potential risk for herbivores. Strong acidification was observed in the NRE soil except in surface (0–10 cm). The progressive colonization of natural vegetation, more than 90% of the fenced plot covered by plants, could facilitate this increased pH values in the top soil (pH 6). In the NRE soil, the successive oxidation and hydrolysis of sulphide in the deposited sludge on the surface after the accident resulted in a re-dissolution of the most mobile element (Cd, Cu and Zn) and a penetration to deeper layers. Trace element concentrations in plants growing in the NRE soil showed normal contents for higher plants and tolerable for livestock. Nitrogen and mineral nutrients were of the same order in both soils, and also normal for high plants and adequate for animal nutrition. Despite of the natural remediation of the NRE soil, results demonstrate that the remediation tasks carried out in all the area, the Guadiamar Green Corridor at present, were necessary to avoid the leaching of the most mobile elements and minimize the risk of contamination of groundwater sources, many of them close to the Doñana National Park. [Copyright &y& Elsevier]

Tinto River (Huelva, Spain) is a natural acidic rock drainage (ARD) environment produced by the bio-oxidation of metallic sulfides from the Iberian Pyritic Belt. This study quantified the abundance of diverse microbial populations inhabiting ARD-related sediments from two physicochemically contrasting sampling sites (SN and JL dams). Depth profiles of total cell numbers differed greatly between the two sites yet were consistent in decreasing sharply at greater depths. Although catalyzed reporter deposition fluorescence in situ hybridization with domain-specific probes showed that Bacteria (>98%) dominated over Archaea (<2%) at both sites, important differences were detected at the class and genus levels, reflecting differences in pH, redox potential, and heavy metal concentrations. At SN, where the pH and redox potential are similar to that of the water column (pH 2.5 and +400 mV), the most abundant organisms were identified as iron-reducing bacteria: Acidithiobacillus spp. and Acidiphilium spp., probably related to the higher iron solubility at low pH. At the JL dam, characterized by a banded sediment with higher pH (4.2 to 6.2), more reducing redox potential (--210 mV to 50 mV), and a lower solubility of iron, members of sulfate-reducing genera Syntrophobacter, Desulfosporosinus, and Desulfurella were dominant. The latter was quantified with a newly designed CARD-FISH probe. In layers where sulfate-reducing bacteria were abundant, pH was higher and redox potential and levels of dissolved metals and iron were lower. These results suggest that the attenuation of ARD characteristics is biologically driven by sulfate reducers and the consequent precipitation of metals and iron as sulfides. [ABSTRACT FROM AUTHOR]

Cork oak (Quercus suber L.) is an autochthonous tree species that is being used for reforestation in heavy-metal-contaminated areas in Spain. A hydroponics experiment was carried out to characterize the effects of Cd on several morphological and physiological parameters in this species, including shoot length, nutrient concentrations and allocation in different organs, leaf pigment concentrations, photosynthetic efficiency, root ferric chelate reductase (FCR) activity and organic acid concentrations in xylem sap. Four different Cd treatments were applied, adding Cd chelated with EDTA or as chloride salt at two different concentrations (10 and 50 µM Cd). After 1 month of Cd treatment, plant growth was significantly inhibited in all treatments. Results indicate that Cd accumulates in all organs 7- to 500-fold when compared with control plants. The highest Cd concentration was found in the 50 µM CdCl2 treatment, which led to concentrations of ∼30, 123 and 1153 µg Cd g−1 dry weight in leaves, stems and roots, respectively. In the strongest Cd treatments the concentrations of P and Ca decreased in some plant parts, whereas the Mn leaf concentrations decreased with three of the four Cd treatments applied. The concentrations of chlorophyll and carotenoids on an area basis decreased, whereas the (zeaxanthin plus antheraxanthin)/(total violaxanthin cycle carotenoids) ratio and the non-photochemical quenching increased significantly in all Cd treatments. Cadmium treatments caused significant increases in the activity of the enzyme FCR in roots and in the concentrations of organic acids in xylem sap. Some of the physiological changes found support the fact that Cd induces a deficiency of Fe in cork oak, although the plant Fe concentrations were not reduced significantly. At higher concentrations the effects of Cd were more pronounced, and were more marked when Cd was in the free ion form than when present in the form of Cd-EDTA. [ABSTRACT FROM PUBLISHER]

Abstract: This work documents for the first time the levels and composition of atmospheric particulate matter in the historic mining district of Rio Tinto (Spain) to estimate the contribution and impact of resuspended particles from hazardous mine waste on air quality. The resuspended mine waste dust contributes notably (32%) to the total concentrations of toxic trace metals (Bi, As, Cu, Pb, Cd, Zn and Sb) into the atmosphere, with the consequent impact on public health. [Copyright &y& Elsevier]

Non-amended soils affected by pyritic sludge residues were monitored for 7 years to assess the long-term natural attenuation ability of these soils. The decrease in both the total concentration of elements (particularly As) and (NH4)2SO4-extractable fractions of Mn, and Zn, below the maximum permissible levels indicate a successful natural ability to attenuate soil pollution. Soil acidification by pyrite oxidation and rainfall-enhanced leaching were the largest contributors to the reduction of metals of high (Mn, Cu, Zn and Cd) and low (Fe, Al, and As) availability. Periodic use of correlation and spatial distribution analysis was useful in monitoring elemental dispersion and soil property/element relationships. [Copyright &y& Elsevier]

Abstract: Heavy metals have become one of the most serious anthropogenic stressors for plants and other living organisms. Having efficient and feasible bioassays available to assess the ecotoxicological risks deriving from soil pollution is necessary. This work determines pollution by Cd, Co, Cr, Cu, Ni, Pb, V and Zn in two soils used for growing rice from the Albufera Natural Park in Valencia (Spain). Both were submitted to a different degree of anthropic activity, and their ecotoxicological risk was assessed by four ecotoxicity tests to compare their effectiveness: Microtox® test, Zucconi test, pot bioassay (PB) and soil plate bioassay (SPB). The sensitivity of three plant species (barley, cress and lettuce) was also assessed. The results reveal a different degree of effectiveness and level of inhibition in the target organisms’ growth depending on the test applied, to such an extent that the one-way analysis of variance showed significant differences only for the plate bioassay results, with considerable inhibition of root and shoot elongation in seedlings. Of the three plant species selected, lettuce was the most sensitive species to toxic effects, followed by cress and barley. Finally, the results also indicate that the SPB is an efficient, simple and economic alternative to other ecotoxicological assays to assess toxicity risks deriving from soil pollution. [Copyright &y& Elsevier]

Abstract: Medina lagoon in Andalusia has one of the highest densities of spent lead (Pb) shot in Europe. Blood samples from waterbirds were collected in 2006–2008 to measure Pb concentration (PbB), δ-aminolevulinic acid dehydratase (ALAD), oxidative stress biomarkers and plasma biochemistry. PbB above background levels (>20μg/dl) was observed in 19% (n=59) of mallards (Anas platyrhynchos) and in all common pochards (Aythya ferina) (n=4), but common coots (Fulica atra) (n=37) and moorhens (Gallinula chloropus) (n=12) were all <20μg/dl. ALAD ratio in mallards and coots decreased with PbB levels >6μg/dl. In mallards, an inhibition of glutathione peroxidase (GPx) and an increased level of oxidized glutathione (oxGSH) in red blood cells (RBC) were associated with PbB levels >20μg/dl. In coots, PbB levels were negatively related to vitamin A and carotenoid levels in plasma, and total glutathione in RBCs; and positively related with higher superoxide dismutase and GPx activities and % oxGSH in RBCs. Overall, the results indicate that previously assumed background levels of PbB for birds need to be revised. [Copyright &y& Elsevier]

Abstract: Since 2008, sewage sludge is being used as alternative fuel in a cement plant placed in Vallcarca (Catalonia, Spain). To evaluate the temporal trend of the environmental levels of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and a number of metals (As, Cd, Co, Cr, Cu, Hg, Mn, Ni, Pb, Sn, Tl, V, and Zn), as well as the potentially associated human health risks, samples of soil, herbage, and air were collected around the facility, after approximately one year of the permanent partial substitution of fuel. The temporal evolution of the pollutant levels was assessed by comparing the measured concentrations (2009) with those from samples collected in previous surveys (2003 and 2006) at the same sampling sites. The concentrations of PCDD/Fs in herbage and soil were 0.10 and 1.11ng I-TEQ·kg−1 dw, respectively, values very similar to those found in our previous surveys. For metals, although a clear tendency could not be observed, there were fluctuations through time. In this study, the levels of metals, which had not been analyzed in previous campaigns, were also determined in air, additionally to soil and vegetation. Airborne metal concentrations were similar to those found in other industrial areas worldwide. The human health risks for the population living around the cement plant were comparable to those obtained in previous studies, when petroleum coke was exclusively used as combustible, being in both cases tolerable according to the international standards. [ABSTRACT FROM AUTHOR]

Abstract: For 20 years ending in the 1990s the city of Barcelona discharged the products from a large primary sewage treatment plant directly into the Mediterranean Sea via underwater conduits. About ca. 3 million m3 of relict sewage sludge, rich in organic matter and heavy metals, has spread over an elongated area offshore, due to successive ruptures of the conduits. The use of the discharge pipes ceased, but the sludge deposit remains in place for the time being. To understand the history and present state of the sludge deposit in advance of future remediation, a program of geophysical mapping, sampling, and analytical work was undertaken. Rock Eval pyrolysis, although created for use in petroleum prospecting, can also be applied to environmental contamination studies. It offers a simple means to effectively delineate the sludge deposit, with the S 2 parameter and the hydrogen and oxygen indices particularly useful. On the molecular level, the sludge flash pyrolysis products notably include relatively abundant C27 and C29 sterenes and steranes, likely produced from the pyrolysis of fecal and other steroids, including coprostanol, in the sewage sludge. Linear alkylbenzenes and trialkylamines, derived from surfactant residues in the sludge, are also detected. The indoles detected are likely the pyrolysis products of proteins, while the alkylnitriles and alkylamides in the pyrolyzate likely derive from bacterial biomass. Principal components analysis aided the interpretation of the large geochemical dataset and a geographic information system enabled the three-dimensional visualization of the results in their geospatial context. The distinctive pyrolysis products and the trace elements would be geochemical markers useful in planning and assessing a future remediation program. The recognition of a distinctive sewage pyrolysis–GC/MS signature in this deposit would facilitate the use of this method in the detection of sewage-contaminated sediments in urban waterways worldwide. [Copyright &y& Elsevier]

Abstract: The Ria of Huelva (south-west Spain) is a highly polluted estuary as a consequence of long-term mining and industrial activities. Between 2003 and 2004, we conducted a biomonitoring study of exposure to arsenic and some heavy metals (cadmium, chromium, copper and nickel) in urine samples of a representative sample (n =227) of children and adolescents residing in this area, and of a reference group of 196 children and adolescents living in other less industrialised areas of Andalusia (south Spain). We also assessed the determinants of the variability in urinary metals within the population of the Ria of Huelva. There were no significant differences in the concentration of metal compounds between the two groups with the exception of Cd levels, which were significantly higher in the reference group. Levels of the five metal ions in both groups were generally within the range of values reported by other biomonitoring studies for general children population, although mean Cd levels tended to be higher as compared to other European studies. Among the population of the Ria of Huelva, the main determinants of the interindividual variation in urinary metals were age, sex, area of residence, and frequency of intake of certain food items (mainly fish and shellfish). Overall, results suggest that living in the Ria of Huelva is not increasing current levels of exposure to certain metals among children and adolescents above those found in other urban areas of Andalusia. [Copyright &y& Elsevier]

Abstract: The main objective of the present study was to evaluate the concentration of trace metals in eight species of Caprella from sites of different degree of pollution along Southern Spain, and compare them with nine additional species of peracaridean crustaceans (5 gammarids, 3 isopods and 1 tanaid) and three molluscs. This is the first comprehensive study of trace metals in caprellids and other peracaridean crustaceans as a baseline work for future research. For most of the metals, values are higher in caprellids than in the rest of peracarideans and molluscs, as Mytilus or Patella, traditionally used as biomonitor in previous studies. Caprellids showed a significant higher range for Cr, Hg and Zn, while molluscs were better biomonitors for Pb; non-caprellid peracarids showed lower range of Fe and Ni than caprellids and molluscs. Besides the wider ranges shown by caprellids for trace metals in comparison with other invertebrates, Caprella spp. is especially abundant in intertidal and shallow waters ecosystems worldwide; this genus includes species characterised by a short generation time, and a sedentary way of life as a consequence of direct development and low capacity of swimming. Consequently, the use of Caprella spp. could be an interesting tool in monitoring programmes of heavy metal pollution. [Copyright &y& Elsevier]

Abstract: Sea turtles are of increasing interest as potential bioindicators of the heavy metal pollution in marine ecosystems. In the present work, concentrations of heavy metals and essential elements (As, Cd, Hg, Pb, Se, Zn) in different organs and tissues (liver, kidney, muscle, bone, blood, central nervous system and skin) of loggerhead sea turtles (Caretta caretta) were determined from stranded animals found along the Spanish Mediterranean coastlines of Murcia. Relatively high average levels of As (skin: 52.13μgg−1 dry weight; muscle: 40.95μgg−1 dry weight), and especially high individual levels of Zn in muscle tissue (1002.4μgg−1 dry weight) were detected. Furthermore, a significant degree of organotrophism of Cd was observed in kidney tissue. The concentrations detected, the distribution among the tissues and the differences observed between juvenile and adult specimens are generally compatible with chronic exposure to the elements studied, whilst levels produced by acute exposure were ruled out. [Copyright &y& Elsevier]

Abstract: Erica australis L. is a widely distributed shrub able to grow in a variety of environments. In the Iberian Pyritic Belt (SW Spain and Portugal), E. australis can be observed growing successfully in very acidic and highly metal-enriched soils. However, no data about the metal tolerance of this plant in wild populations have been reported so far. In this study, we have analysed metal contents in the leaves of E. australis from three wild populations growing in soils affected by metals in different ways (mine wastes, the terrace of a river affected by acid mine drainage and soils not affected by mining activities but enriched in metals due the geology of the area) and, taking into account that metals may generate reactive oxygen species, we also assayed the oxidative damages and the antioxidative defences. All plants contained high levels of Fe and Mn in the leaves, but plants exposed to mining activities also accumulate different levels of As, Ni, Mo, Pb, and Zn depending on the population considered. Our data show that E. australis responds to metal-catalysed production of reactive radicals by oxidising ascorbic acid, which is present at concentrations much higher than described in other plant species, but it is highly oxidised, close to 40%. Ascorbic acid may counteract reactive oxygen species, and no cell damage was produced, as shown by the low levels of H2O2 and lipid peroxidation found compared with other plant species and no damage reflected in pigment levels. [Copyright &y& Elsevier]

Abstract: Most fly ashes produced in municipal waste incinerators of Catalonia (Spain) are deposited in a hazardous waste landfill (HWL) placed in Castellolí (Barcelona). This facility means a concern for the population living nearby. In response to this, we performed a probabilistic study focused on assessing human health risks derived from environmental exposure to heavy metals and polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) around the HWL. Concentrations of various metals and PCDD/Fs were determined in soil and air samples collected at the HWL, and in 4 locations around it. Health risks were evaluated according to the distance from the sampling locations to the HWL (near and far-sites). In general terms, metal and PCCD/F levels were relatively low in air and soil samples. However, concentrations of PCDD/Fs, as well as those of some metals, were found to be relatively higher in the HWL and Castellolí (the nearest village) samples than in those collected far away, resulting in a slight increase of exposure to those pollutants. Anyhow, the current concentrations of metals and PCDD/Fs suggest that it is highly unlikely that there are any additional non-carcinogenic and carcinogenic risks for the population living near the HWL. [Copyright &y& Elsevier]

Abstract: The aims of this study are to explore metal contamination in food with respect to variations in: i) the levels found over a period of eleven months and/or ii) by food types; and iii) to report patterns in reporting between countries. The frequencies of reported cases of metal ion contamination were ≤25% of total food alerts with notable increases between June and October. The alerted food products were dominated by seafood, where the majority were due to Mercury contamination and were made by EU member states with Italy making 57 of the 102 reports. The contaminated seafoods originate in thirty two countries with only Spain producing over 10 contaminated seafood products with a total of 47. In conclusion, this analysis highlights the main detector and transgressor nations along with the seafood and metal types that lead to alerts owing to high levels of contamination. [Copyright &y& Elsevier]

Abstract: The Proserpina dam was built in Roman times to provide drinking water to Emerita Augusta (today''s Mérida in SW Spain). During maintenance work, a sediment core was extracted, offering an excellent opportunity to analyze the historical environmental impacts of the dam and its reservoir over the 2000 years since Roman times. In order to establish an accurate chronology, 14C ages were determined by accelerator mass spectrometry (AMS). Core samples were assayed for their content in uranium and thorium series isotopes, 40K, and the anthropogenic radionuclides 137Cs, 90Sr, and 239+240Pu. Potassium-40 presented the highest activity level and was not constant with depth. The uranium and thorium series were generally in equilibrium, suggesting there had been no additional input of natural radionuclides. The presence of 137Cs was only found in relation with the global fallout in the early 1960s. Multi-element assays were performed using the PIXE and PIGE techniques. Some variations in the multi-element concentrations were observed with depth, but the sediment core could be considered as clean, and no presumptive anthropogenic pollutants were found. Nevertheless, an unusually high Zn content was detected at depths corresponding to pre-Roman times, due to geological anomalies in the area. [Copyright &y& Elsevier]

Abstract: The aim of this paper is to explore the applicability of Target Hazard Quotient (THQ) estimations to inform on seafood hazards through metal contamination. The food recall data set was collated by the Laboratory of the Government Chemist (LGC, UK) over the period from January to November 2007. Pearson chi-square goodness of fit test, nonparametric correlation (Kendall tau) and Kruskal–Wallis test were used. Descriptive statistics and statistical analyses were computed by using Excel and SPSS 15.0. The vast majority of food alerts/recalls owing to metal contamination occur in seafood and during the summer months. Only swordfish and shark containing produce received over 10 recalls which were mainly for mercury contamination. Seafood produce originating from only 3 countries had over 10 recalls owing to metal contamination (Spain 50; France 11 and Indonesia 11). Based upon the food alert/recall system, the application of THQ estimations of risk in cases of metal contamination of seafood is questionable as THQ implies frequent if not daily exposure over a lifetime. Infrequent recalls owing to metal contamination and the absence of patterns make it highly unlikely that an individual would be subject to multiple exposures to significant levels of metal ions in seafood. [Copyright &y& Elsevier]

Abstract: Soil pollution by lead, zinc, cadmium and copper was characterized in the mine tailings and surrounding soils (arable and pasture lands) of an old Spanish Pb–Zn mine. Sixty soil samples were analyzed, determining the total metal concentration by acid digestion and the chemical fractionation of Pb and Zn by the modified BCR sequential extraction method. Samples belonging to mine waste areas showed the highest values, with mean concentrations of 28,453.50mgkg−1 for Pb, 7000.44mgkg−1 for Zn, 20.57mgkg−1 for Cd and 308.48mgkg−1 for Cu. High concentrations of Pb, Zn and Cd were found in many of the samples taken from surrounding arable and pasture lands, indicating a certain extent of spreading of heavy metal pollution. Acidic drainage and wind transport of dust were proposed as the main effects causing the dispersion of pollution. Sequential extraction showed that most of the Pb was associated with non-residual fractions, mainly in reducible form, in all the collected samples. Zn appeared mainly associated with the acid-extractable form in mine tailing samples, while the residual form was the predominant one in samples belonging to surrounding areas. Comparison of our results with several criteria reported in the literature for risk assessment in soils polluted by heavy metals showed the need to treat the mine tailings dumped in the mine area. [Copyright &y& Elsevier]

A biomonitoring survey using the moss species Hypnum cupressiforme Hedw. was performed in the North of Navarra (Spain) in 2006. The levels of V, Cr, Mn, Ni, Cu, Zn, As, Zr, Cd, Hg and Pb, and the total nitrogen content were determined in the samples by means of ICP-MS, CV-AA, and the Kjeldahl method. PCA analysis showed a differentiation between lithogenic (V, Cr, Mn, Ni, As and Zr) and anthropogenic elements (Mn, Cu, Zn, Cd, Hg and Pb). Spatial distribution maps were drawn using the kriging method, in order to identify the most affected areas and the main pollution sources. A similar spatial distribution was observed for the elements belonging to each group separated by the PCA, showing an important contribution from metal industries located in the Basque Country, as well as influence of long-range transboundary pollution processes. Background levels were also determined for the study area, along with the contamination factor for the different elements analysed. Mosses seemed to be good biomonitors of N deposition in areas of accumulation. [ABSTRACT FROM AUTHOR]

Settleable particulate matter (SPM) was collected at two sampling points within an urban area highly affected by nearby industrial activities. Total deposition values up to 386 mg ·m−2·d−1 were registered, the majority of samples exceeding the limit value established in the legislation in force in Spain until 2002 (300 mg·m−2·d−1). Dry deposition values showed high variability (8.6–830.3 mg·m−2·d−1). Forty-one metals and metalloids were analysed in the dry fraction of SPM, the main being Fe and Ca (maximums: 304.4 and 68.6 mg·m−2·d−1, respectively), followed by Al, Mg, Na, K, Mn, Ti, P and Zn. Trace elements like As and Pb reached up to 7.3 and 76.3 μg· m−2·d−1, respectively. Strong correlations (r > 0.90, p-value < 0.05) between Fe and other elements (Ca, Mn and Pb) were found at both sampling sites. Scanning electron microscopy confirmed the presence of these particles rich in Fe and Ca, in addition to other components, whose morphologies pointed out to anthropogenic sources. These results combined with meteorology data suggest a common industrial source contributing to the levels of these metals. Furthermore, a human health risk study was carried out to assess the potential carcinogenic and non-carcinogenic risks of exposure to thirteen elements in these particles (Al, As, Cd, Co, Cu, Mn, Mo, Ni, Pb, Sb, Sr, V and Zn). The highest levels of risk seemed to be associated with the presence of As, Pb and Sb. [Display omitted] • Settleable particulate matter was determined in a city affected by heavy industries. • Highly variable daily levels of dry deposition were recorded depending on the winds. • Fe and Ca, Al, Mg, Na, K and Mn were the main metals found in dry deposition samples. • The high total deposition values registered may cause discomfort to the population. • As, Pb and Sb in settleable matter may potentially posed a health risk to residents. [ABSTRACT FROM AUTHOR]

The present study involved intercalibration of the concentrations of Al, As, Be, Cd, Co, Cr, Cu, Fe, Hg, Mn, Ni, Pb, Se, V, and Zn in two species of terrestrial mosses, Pseudoscleropodium purum and Hypnum cupressiforme, collected in Galicia (NW Spain). The moss samples were collected from highly contaminated areas as well as areas with intermediate levels of contamination. Intercalibration was performed by type II regressions, and differences in the bioconcentration capacity of the two species were analyzed by ANCOVA. The slopes and elevations of the regression lines were well characterized and the lines obtained enabled intercalibration of a wide range of concentrations. The high values of the coefficients of determination for Cd, Cr, Fe, Hg, Mn, Pb, V, and Zn, allowed practical application of intercalibration because noise was reduced in the final data set. The high values of the slopes of the regression lines for some elements suggest that data corresponding to these species should not be used simultaneously without it first being transformed by the corresponding intercalibration line. In general terms, H. cupressiforme has a higher bioconcentration capacity than P. purum; this cannot be explained by differences in the concentration of uronic acids in the cell wall, the level of desesterification of these acids, the cationic exchange capacity of the species. However, the differences between species may be explained by morphological differences or differences in specific surface area. [Copyright &y& Elsevier]

The extraction of metallic minerals and the mineral dressing operations in concentrators produced a high impact in soils and sediments. Heavy metals in soils constitute a high risk of pollution, not only for mining areas, but also for agriculture and villages placed in subsidiary areas. This research has been focused on the assessment of the real environmental and health hazards of Zn in relation to geochemistry and metal mobility in surface soils from a mining area in SE Spain, under semiarid weather conditions. Mineralogy of the studied soils revealed major presence of quartz, but also of other silicates, sulfates, carbonates, and sulfides. Regarding Zn minerals, the presence of sphalerite as the main Zn sulfide, and of goslarite as Zn sulfate, and of smithsonite as Zn carbonate should be highlighted. Soil pH ranged between 4.4 and 4.9 and the electrical conductivity between 55 and 85μS/cm. By using the sequential extraction procedure, the achieved results show that zinc is not only mainly associated to primary but also to secondary sulfides. Total concentration of the non-available fractions rises up to 98.45% of total Zn in the studied soils. On the other hand, available Zn fraction did not exceed more than 1.55% in percentage and less than 2000ppm in absolute terms, and when referred to more easily available fraction (water-soluble and exchangeable fractions), these values are not more than 0.44% and then 800ppm. Therefore, although there is a significant pollution level in this area, immediate hazard for the environment can be assessed as moderate. Finally it should be highlighted that these surface soils have undergone concentration processes of sphalerite, whose mechanisms should be related to the ascending flow of capillary water and the dragging of sphalerite crystals and Zn salts by electrokinetic and colloidal processes These processes seem to occur based on environmental pollution by wind and water erosion, and therefore directly associated to environmental pollution and risks by free metals. [Copyright &y& Elsevier]

This study characterized and mapped the spatial variability patterns of seven topsoil heavy metals (Cr, Ni, Pb, Cu, Zn, Hg and Cd) within the Ebro river basin (9.3 million ha) by Multivariate Factorial Kriging. The variograms and cross-variograms of heavy metal concentrations showed the presence of multiscale variation that was modeled using three variogram models with ranges of 20km (short-range), 100km (medium-range) and 225km (long-range). Our results indicate that the heavy metal concentration is influenced by bedrock composition and dynamics at all the spatial scales, while human activities have a notorious effect only at the short- and medium-range scale of variation. Sources of Cu, Pb and Zn (and secondary Cd) are associated with agricultural practices (at the short-range scale of variation), whereas Hg variation at the short- and medium-range scale of variation is related to atmospheric deposition. [Copyright &y& Elsevier]

To evaluate both the natural and anthropogenic influences on surface waters of Guadalquivir River (SW-Spain), concentrations of dissolved trace metals (Mn, Co, Ni, Cu, Cd, Zn, and Pb), inorganic nutrients (, , , and ) and other variables as conductivity, pH, dissolved oxygen (DO) and suspended solids (SS) were measured during a three-years period (2001–2003). Samples were taken at 26 stations twice a year, during rain and dry periods. The analysis of variance (ANOVA) suggested that temporal variations within the period of study were statistically negligible. Spatial distributions identified three different zones, mainly influenced by sewage (Eastern Zone), agriculture runoffs (Central Zone), and estuarine processes (Western Zone), respectively. Principal Component and Cluster Analysis allowed to identify the variables controlling the water quality of each zone as: , , Mn, and Co, (Eastern Zone), SS, and (Central Zone), and Cd, pH and conductivity (Western Zone). Other variables such as Ni, Cu, Zn or , influenced two different zones, while Pb presented a singular behavior. [Copyright &y& Elsevier]

Here we quantified the bioaccumulation of metals (lead, mercury, cadmium, iron, magnesium, zinc, copper, manganese, molybdenum, and chromium) and assessed several morphological (RI, relative weights) and genotoxic parameters as biomarkers of pollution from the landfill of Garraf (Barcelona, NE Spain). Specimens of Crocidura russula (Insectivora, Mammalia) from the landfill site showed increased Pb, Cd, Mg, Zn, Cu, and Cr concentrations in their tissues. Levels of mercury were below detection limits. Concentrations of Cd, Pb, and Cr varied significantly with age and no differences were found between males and females. While no differences were found in morphological parameters between shrews from the two sites, those from the polluted one showed more micronuclei in blood than those from reference site (1. 786±0. 272 vs. 0. 088±0. 045‰; U =46. 000, p <0. 001). The considerable amounts of potentially toxic metals (Pb till 59. 71 and Cd till 56. 57μgg−1 DW in kidneys) and the genotoxic effects indicate the harmful effect on biota. We consider necessary biomonitoring this landfill sited in a partially protected area. [Copyright &y& Elsevier]

This work presents the concentrations of twenty PCB congeners, p,p′-DDT, and its two main metabolites, p,p′-DDE, p,p′-TDE, As, Cd, Cu, Pb, and Zn found in common chameleon eggs from nine different nests located in Southwest Spain. Of the heavy metals and arsenic, Zn and Cu exhibited the highest concentrations in egg contents (ranging from 10100 to 12950 and from 567 to 706ngg−1 wet weight basis [w. W. ], respectively) and eggshells (ranging from 5605 to 13290ngg−1 w. W. For Zn and from 1487 to 4361ngg−1 w. W. For Cu). Total PCB concentrations in egg contents ranged from 32 to 52ngg−1 w. W. And were higher than total dichlorodiphenylethanes concentrations (ranging from 0. 67 to 1. 9ngg−1 w. W. , calculated as the sum of p,p′-DDT plus p,p′-DDE and p,p′-TDE). Comparison of the data from the present study with the data from a study conducted in 1997 revealed a large decrease in Pb concentration and a twofold increase in PCB concentrations. Taking into account all the pollutants investigated, the contamination level found in common chameleon eggs from Southwest Spain was generally lower than has been reported in the literature for eggs of different reptile species. However, it should be borne in mind that most of the data found in the literature refer to highly polluted areas. [Copyright &y& Elsevier]

The accumulation rates, the geochronology of metals and PAH contamination, and the Microtox® toxicity are studied in five sediment cores (50 cm length) covering different areas of the Santander Bay, Northern Spain. Chronology given by 210Pb and 137Cs reveals significant differences in accumulation rates between sites (0.2–1.1 cm/year), as well as a variable degree of anthropogenic enrichment factors for Fe, Mn, Cu, Pb, Zn, Ni (from 1 to 15) and concentrations of ∑16PAHs (from 0.01 to 23.84 mg/kg dw) in sediments over the last 90 years. The results indicate the increasing contamination pressure from industrial and urban activities along the Bay. No toxic results from the Microtox® test are obtained either with pore water or with normalised sediment aqueous extracts (European Norm EN 12457), suggesting low water solubility and low availability of contaminants in the studied sediments. However, the EC50 values from the Microtox® Basic Solid Phase Test (BSPT) ranged from 0.03% to 2.35%, showing vertical toxicity profiles in accordance with metal and PAHs behaviour. The correlation degrees of Microtox® BSPT toxicity to chemical concentration in sediment profiles are widely variable showing a high site-dependent toxicity. The oligochaete Limnodrilus hoffmeisteri has been used as a chronic bioassay over surface sediments of two of the studied sites, showing results coherent with the Microtox® BSPT acute test results. Global results of the present work provide regional geochemical baselines for metals and PAHs and toxicological data now make it possible to obtain a preliminary quality assessment of the Santander Bay sediment profiles. [Copyright &y& Elsevier]

Thallium is a scarce, highly toxic element. There are several investigations that report Tl accumulation in plants of the family Brassicaceae. These plants could pose a risk in areas where Tl is present at higher concentrations than normal soils. The present study reports analyses of two wild Brassicaceae, Hirschfeldia incana and Diplotaxis catholica, growing spontaneously at five sampling sites moderately polluted with Tl and other trace elements in the Green Corridor of the Guadiamar river, Seville, S. Spain. In general, trace element content was unremarkable in all part plants, despite the concentrations present in soil. Thallium was the only element whose concentration in both plant species was above normal for plants (maximum values of 5.00mgkg−1 in H. incana flowers). There were significant positive correlations between total Tl in soil and Tl in both plant species. Transfer Coefficients (TC) for all elements were, in general, <1 for both species, except for Tl in flowers and fruits at some sites. The highest Enrichment Factor (EF) was found for Tl in H. incana fruits (EF=607) and D. catholica flowers (EF=321). H. incana was studied in a previous growing season (2004) in the same area, although the rainfall was 3 times more than in the year of the present study (2005), giving a maximum Tl content of 46.5mgkg−1 in H. incana flowers. The data presented here show that Tl content of plants growing in semi-arid conditions can be significantly influenced by precipitation. In dry years, plant Tl accumulation may be significantly reduced. [Copyright &y& Elsevier]

The big oil tanker Prestige wrecked at 130 miles from the coast of Galicia, on the Northwest of Spain, in November 19, 2002. During the accident over 40,000 tons of oil were spilled, and along the next weeks 22,000 more reached the shore in the way of three black tides. A great number of people participated in the cleaning tasks. The objective of this study was to initially evaluate the damage caused by Prestige oil in exposed individuals both from the cytogenetic and the endocrine points of view. Exposure level was determined by analysing volatile organic compounds in the environment and heavy metals in blood. Cytogenetic damage was determined by sister chromatid exchanges (SCE), and plasmatic prolactin and cortisol levels were used as biomarkers of endocrine toxicity. Finally we have determined the possible influence of GST genetic polymorphisms (GSTM1 and GSTT1 deletion polymorphisms, GSTP1 Ala105Val) on the evaluated effects. The exposed population was classified according to the performed cleaning tasks in three groups: volunteers that collaborated for 1 week (N =25), hired manual workers (N =20) and hired high-pressure cleaner workers (N =23). The control population consisted of 42 individuals. Exposure to Prestige oil caused cytogenetic damage in exposed individuals, being its effect influenced by age, sex, tobacco consumption and GSTM1 polymorphism. With regard to endocrine toxicity, our results showed that xenobiotics present in Prestige oil induced alterations in hormonal status, and thus it may be considered as an endocrine disruptor. Therefore, the selected parameters have shown to be good indicators of toxicity related to exposure to Prestige oil. In addition, data obtained point to the importance of using protective devices in preventing the effects related to the exposure. [Copyright &y& Elsevier]

In the Iberian Pyrite Belt (IPB), acid rock drainage gives rise to aquatic habitats with low pH and high concentrations of heavy metals, a situation that causes important environmental problems. We investigated the occurrence and diversity of yeasts in two localities of the IPB: São Domingos (Portugal) and Rio Tinto (Spain). Yeast isolation was performed on conventional culture media (MYP), acidified (pH 3) media (MYP3), and on media prepared with water from the study sites (MYPw). The main goal of the study was to determine the structure of the yeast community; a combination of molecular methods was used for accurate species identifications. Our results showed that the largest fraction of the yeast community was recovered on MYPw rather than on MYP and MYP3. Twenty-seven yeast species were detected, 48% of which might represent undescribed taxa. Among these, an undescribed species of the genus Cryptococcus required low pH for growth, a property that has not been observed before in yeasts. The communities of S. Domingos and R. Tinto showed a considerable resemblance, and eight yeast species were simultaneously found in both localities. Taking into consideration the physicochemical parameters studied, we propose a hierarchic organization of the yeast community in terms of high-, intermediate-, or low-stress conditions of the environment. According to this ranking, the acidophile yeast Cryptococcus sp. 5 is considered the most tolerant species, followed by Cryptococcus sp. 3 and Lecytophora sp. Species occurring in situations of intermediate environmental stress were Candida fluviatilis, Rhodosporidium toruloides, Williopsis californica, and three unidentified yeasts belonging to Rhodotorula and Cryptococcus. [ABSTRACT FROM AUTHOR]

The correlation between water physicochemical parameters and eukaryotic benthic composition was examined in Rio Tinto. Principal component analysis showed a high inverse relationship between pH and most of the heavy metals analyzed as well as Dunaliella sp., while Chlamydomonas sp. abundance was positively related. Zn, Cu, and Ni clustered together and showed a strong inverse correlation with the diversity coefficient and most of the species analyzed. These eukaryotic communities seem to be more influenced by the presence of heavy metals than by the pH. [ABSTRACT FROM AUTHOR]

Eighty-three samples of atmospheric particles were collected at a representative traffic site in the Mediterranean city of Seville during a period of one year. Urban particles were collected on quartz filters with a high-volume sampler coupled with a cascade impactor which separates particles into six size ranges: >10, 10–4.9, 4.9–2.7, 2.7–1.3, 1.3–0.6, and <0.6 μm. The total metal content, its distribution by size (physical speciation), and the concentrations of different chemical forms (chemical speciation) in particles less than 0.6 μm were determined. The chemical speciation scheme furnished four fractions: soluble and exchangeable metals; carbonates, oxides, and reducible metals; oxidisable and sulfidic metals bound to organic matter; and residual metals. The samples were analysed by ICP–OES for Pb, Ni, Cd, S, Fe, Zn, Cu, Ba, Mn, and V. Gaseous pollutants, traffic intensities, and primary meteorological data provided by the atmospheric and traffic networks were statistically related to the analytical data. Analytical and statistical results from physical and chemical speciation singled out Ba as a valid tracer of vehicular traffic, instead of Pb, in cities with high traffic density. Another important relationship was found between Pb and Cu. Physical speciation of lead showed that the major risk for health was from fine particles less than 2.7 μm, because particles between 2.7 and 0.6 μm were the size fractions of the total suspended particles with the major mass abundance of lead (mainly particles between 2.7 and 1.3 μm) and because particles less than 0.6 μm were the fraction of airborne particles most abundant in the urban air. Chemical speciation results showed that special attention must be taken with Ni and Cd concentrations, because of their high potential bioavailability, mainly a result of the high solubility of the chemical forms of Ni in the finest particles. [ABSTRACT FROM AUTHOR]

The latest version (1999) of the BCR-sequential extraction technique was used to determine the distribution of metals (Cu, Zn, Cd, Pb, Fe, Ni, Cr, and Mn) with major sedimentary phases (acid-soluble, reducible, oxidisable and residual) in samples from the southwest coast of Spain. The total metal content was also determined. The results showed that an extensive area along the coast (35 km long), near the joint mouth of the Tinto and Odiel Rivers, contains sediments with high concentrations of metals, with maximums of 649 mg/kg of Zn, 336 mg/kg of Cu, 197 mg/kg of Pb and 2.5 mg/kg of Cd. The values found for Cr, Ni and Mn are comparable to those in unpolluted areas. Based on the chemical distribution of metals, we found that Zn is the most mobile (i.e., it can pass easily into the water under changing environmental conditions). This metal showed the highest percentages in the acid-soluble fraction (the most labile), especially in the central coastal area, where the samples contained over 50% of this element associated with this fraction. This area close to the Tinto and Odiel river mouths also shows a significant increase in the mobility of Cd and Cu. In both cases the amount present in the residual fraction is lower, and the acid-soluble fraction is increased for Cd and the oxidisable fraction for Cu. However, the highest percentages of Fe, Cr and Ni are found in the residual fraction (84%, 89% and 75%, respectively), which implies that these metals are strongly bound to the sediments. [Copyright &y& Elsevier]