Mercury accumulation in soils and plants in the Almadén mining district, Spain: one of the most contaminated sites on Earth

Although mercury (Hg) mining in the Almadén district ceased in May 2002, the consequences of 2000 years of mining in the district has resulted in the dissemination of Hg into the surrounding environment where it poses an evident risk to biota and human health. This risk needs to be properly evaluated. The uptake of Hg has been found to be plant-specific. To establish the different manners in which plants absorb Hg, we carried out a survey of Hg levels in the soils and plants in the most representative habitats of this Mediterranean area and found that the Hg concentrations varied greatly and were dependent on the sample being tested (0.13–2,695 μg g⁻¹ Hg). For example, the root samples had concentrations ranging from 0.06 (Oenanthe crocata, Rumex induratus) to 1095 (Polypogon monspeliensis) μg g⁻¹ Hg, while in the leaf samples, the range was from 0.16 (Cyperus longus) to 1278 (Polypogon monspeliensis) μg g⁻¹ Hg. There are four well-differentiated patterns of Hg uptake: (1) the rate of uptake is constant, independent of Hg concentration in the soil (e.g., Pistacia lentiscus, Quercus rotundifolia); (2) after an initial linear relationship between uptake and soil concentration, no further increase in Hg_plant is observed (e.g., Asparagus acutifolius, Cistus ladanifer); (3) no increase in uptake is recorded until a threshold is surpassed, and thereafter a linear relationship between Hg_plant and Hg_soil is established (e.g., Rumex bucephalophorus, Cistus crispus); (4) there is no relationship between Hg_plant and Hg_soil (e.g., Oenanthe crocata and Cistus monspeliensis). Overall, the Hg concentrations found in plants from the Almadén district clearly reflect the importance of contamination processes throughout the study region.     

Simulation of germination of pioneer species along an experimental drought gradient

The germination of ten plant species from the Iberian Peninsula was assessed along a water deficit gradient between -0. 1652 (moist) and -0.4988 MPa (dry) of osmotic potential, created by addition of increasing concentrations of polyethylene glycol (PEG 6000) to distilled water in which plants were grown hydroponically. The level and rate of germination of Daucus carota and Thapsia villosa significantly decreased with decreasing psi. Seeds of Dactylis glomerata and Dittrichia viscosa had positive germination responses to low osmotic potentials; germination of Epilobium hirsutum was not affected by osmotic potential. Germination of Medicago arabica, Cynosurus cristatus, Cistus ladanifer and Cistus albidus, was no favored by the addition of polyethylene glycol (PEG). Germination of Foeniculum vulgare and Thapsia villosa was inhibited by PEG.     

Binding of Pb(II) in the system humic acid/goethite at acidic pH

The study of Pb(II) binding to the system humic acid/goethite in acidic medium is reported in the present paper. From a macroscopic point of view, we have constructed the experimental sorption isotherms (using atomic absorption spectroscopy) and compared them with the prediction of the additivity rule. It is found that this system presents positive deviations, that is, the amount sorbed is about an order of magnitude higher than predicted. Apart from this, microscopic and structural aspects have also been studied using in situ and ex situ infrared spectroscopy. These results suggest that the presence of Pb(II) increases the amount of humic acid bound to the oxide. It is proposed that proton displacement due to the interaction between humic substances and the oxide, along with the formation of ternary complexes with the Pb(II) cation bridging the oxide and the humic substances (Type A complexes), cause the deviation from additivity.     

Modeling lead bioavailability and bioaccumulation by Lumbriculus variegatus using artificial particles. Potential use in chemical remediation processes

Artificial particles, specifically a diverse selection of chromatographical resins, have been recommended and used as a useful experimental model to predict the bioavailability and bioaccumulation of sediment-bound organic chemicals. In this work the same experimental model was adopted to investigate the bioavailability and bioaccumulation of lead by the freshwater oligochaete Lumbriculus variegatus. Particle-water partition coefficients were also determined. Sand particles and the anionic exchange resin promoted a similar uptake and bioaccumulation of lead. Instead, in the presence of the cationic exchanger the metal was not detected in the animals. For neutral particles, the uptake and accumulation depended on the chemistry of the functional groups at the active sites. In addition, a significant negative correlation was found between bioaccumulation and the particle-water partition coefficients. These studies may help to develop alternative methods for chemical remediation of lead-contaminated aquatic systems.     

Statistical evaluation of chronic toxicity data on aquatic organisms for the hazard identification: the chemicals toxicity distribution approach

Presently, in the Globally Harmonised System of Classification and Labelling of Chemicals the classification of substances for long-term effects to aquatic life is based on acute toxicity in combination with degradation and/or bioaccumulation potential. Recently an OECD Working Group was created to develop the classification scheme to accommodate chronic toxicity data related to aquatic organisms for assigning a chronic hazard category. This study focuses on a new approach for setting chronic toxicity cut-off values based on Chemicals Toxicity Distributions (CTDs). A CTD is obtained through statistical fitting of the data used by regulatory bodies for setting hazard-based classifications. The CTDs were made using the lowest aquatic NOEC value of each chemical. A review of different toxicological sources reporting acute aquatic toxicities was carried out. Initially, the data were arranged according to the specific source and distributions for key taxonomic groups (i.e. fishes, crustaceans and algae) were evaluated separately. In most cases, no significant departures from normality were observed. Thereafter, a compiled database containing >900 values was developed and the CTDs were constructed for each taxonomic group. Significant deviation from normality (P < 0.05) was observed in the fishes and crustaceans' CTDs. However, this deviation was apparently produced by the presence of only seven values with NOECs <1 x 10(-5) mg l(-1), while high correlation between the data and the normal scores (r-values>or= 0.989) indicated that the data were samples from normal distributions. From these observations, potential cut-off values would allow quantitative estimations of the percentage of chemicals falling into each specific category. This approach results in a simple classification hazard scheme where most chemicals are covered in one of the categories, allowing a clear distribution of the chemicals among three categories for chronic toxicity.     

Increased thyroid volume and frequency of thyroid disorders signs in schoolchildren from nitrate polluted area

Thyroid volume (ThV) and echogenicity by ultrasound were estimated in 324 schoolchildren (aged between 10 and 13-years) from high nitrate area (HNA) located in agricultural lowland with high nitrate drinking water supply (51-274 mg/l) from shallow wells. The data were compared to children of the same age from low nitrate area (LNA) consisting of 168 children from the neighboring area with very low nitrate (< 2 mg/l) drinking water and of 596 children from the city of Kosice located in a vicinity of LNA and also supplied by low nitrate water. Blood samples were obtained from 315 willing children from HNA and 109 children from LNA and the levels of thyrotropin (TSH), total thyroxine (TT4), free triiodothyronine (FT3) and thyroperoxidase antibodies (anti-TPO) in serum were determined. ThV (mean +/- SE) in 10-year (5.10 +/- 0.14 ml) and 13-year (5.97 +/- 0.11 ml) old children from HNA was significantly higher than that in two groups of respective age from LNA, 4.58 +/- 0.17 (p < 0.02) and 5.23 +/- 0.15 ml (p < 0.05), and from the city of Kosice, 4.77 +/- 0.10 ml (p < 0.05) and 4.87 +/- 0.1 0ml (p < 0.0001). The frequency of hypoechogenicity in HNA was also significantly higher than that in pooled LNA plus Kosice, 13.7% vs. 4.7% (p < 0.01) in 10-year and 10.6% vs. 5.7% (p < 0.03) in 13-year, respectively. The frequency of TSH level in the range of subclinical hypothyroidism (> 4.0 mU/l) in pooled age groups from HNA was 13/324 (4.0%) and that of positive anti-TPO was 8/324 (2.5%), while no case of either increased TSH or positive anti-TPO was found in 109 children from LNA. Finally, no differences in the levels of TT4 and FT3 were found between HNA and LNA. It was concluded that long-term exposure to high nitrate intake by drinking water and home made meals from local products results in increased thyroid volume and increased frequency of signs of subclinical thyroid disorders (thyroid hypoechogenicity by ultrasound, increased TSH level and positive anti-TPO).     

The composition and relationships between trace element levels in inhalable atmospheric particles (PM10) and in leaves of Nerium oleander L. and Lantana camara L

In order to evaluate the composition of inhalable atmospheric particles and to study the relationship between trace element levels in PM10 and in leaves of two plant species, the amount of Ba, Cu, Fe, Mn, Pb, Ti and V were analysed in PM10 and in Nerium oleander L. and Lantana camara L. leaves from two sites in the city of Seville and one remote control site. In PM10, the Cu and Fe content was significantly lower (p<0.05) in the control site than in the other sites. No correlations between leaf content and air content were found for the elements in L. camara. On the contrary, positive and significant correlations (p<0.05) were found between leaf content of N. oleander and PM10 content for Cu and Fe. The data suggest that N. oleander can be used in atmospheric biomonitoring studies, because it is especially useful for Cu and Fe, N. oleander being a better indicator than L. camara.     

Decolourization of synthetic dyes by Trametes hirsuta in expanded-bed reactors

The present paper studies the decolourization of different synthetic dyes (Indigo Carmine, Bromophenol Blue, Methyl Orange and Poly R-478) by the white-rot fungus Trametes hirsuta at bioreactor scale under solid-state conditions, operating with ground orange peelings as a support-substrate. Dye decolourization was performed in both batch and continuous mode. Batch cultivation led to high decolourization percentages in a short time (100% for Indigo Carmine in 3h and 85% for Bromophenol Blue in 7 h). As for continuous cultivation, different hydraulic retention times (HRT) were studied (0.8, 1, 1.5 and 3d). The highest decolourization percentages were obtained operating at a HRT of 3d, especially for the dyes Methyl Orange and Poly R-478 (81.4% and 46.9%, respectively). This is a very interesting result, since there are few studies dealing with the continuous decolourization of dyes at bioreactor scale by fungal laccases.     

Enantiomeric fractions and congener specific determination of polychlorinated biphenyls in eggs of predatory birds from Doñana National Park (Spain)

The content of 30 polychlorinated biphenyls (PCBs) and the enantiomeric fractions of 10 chiral PCBs were determined in 17 infertile eggs from three different predatory bird species collected in Do?ana National Park (DNP, Spain) in the period 1999-2000. The highest PCB concentration was found in eggs from red kites (0.52-110 microg/g on a fresh weight basis, f.w.) followed by buzzard (0.08-13 microg/g f.w.) and booted eagle (0.10-1.5 microg/g f.w.). Seventy-five percent of the red kite eggs had PCB levels above 4.7 microg/g f.w., which is associated in the literature with reproductive failure. This could be related to the fact that red kite populations have decreased by more than 50% in the last five years in DNP. PCBs # 138, 153, and 180 were the most abundant in all cases. This is the first time that atropisomers of 10 chiral PCBs (PCBs # 45, 84, 91, 95, 132, 135, 136, 149, 174, and 176) in predatory bird eggs have been performed. The enantiomeric fractions (EFs) for most PCBs investigated were non-racemic (EF not = 0.5), ranging from 0.05 to 0.95. The results suggested that predatory birds, mainly red kite species, are highly polluted by PCBs, and PCBs # 95, 132, 135, 136, and 174 strongly deviate from the racemic-mixture values.