Copper Content and Resistance Mechanisms in the Terrestrial Moss Ptychostomum capillare: A Case Study in an Abandoned Copper Mine in Central Spain.

We present a case study on the tissue absorption of copper of a widely distributed moss species, Ptychostomum capillare in the polluted soil of an abandoned copper mine in central Spain. We studied the soil properties in a copper soil pollution gradient and sampled the moss tufts growing on them in four plots with contrasted soil copper levels. We determined the copper content in the soil and in the moss tissues. On these moss samples, we also performed histochemical tests and X-ray dispersive spectrometry coupled with scanning electron microscopy (SEM-EDX), both in untreated shoots and in samples where surface waxes were removed. We checked the behavior of this species using a metallophillous moss, Scopelophila cataractae, for comparative purposes. Copper contents in P. capillare seem to depend more on available, rather than total soil copper contents. Our results indicate that this moss is able to concentrate 12-fold the available soil copper in soil with low available copper content, whereas in the most polluted soil the concentration of Cu in the moss was only half those levels. Both histochemical and SEM-EDX tests show no surface copper in the mosses from the least polluted plot, whereas in samples from the soil with highest copper content, the removal of surface waxes also reduces or removes copper from the moss shoots. Our observations point at a mixed strategy in P. capillare in this copper mine, with metal accumulation behavior in the lowest Cu plot, and an exclusion mechanism involving wax-like substances acting as a barrier in the most polluted plots. These distortions impede the estimation of environmental levels and thus compromise the value of this moss in biomonitoring. We highlight the need of extending these studies to other moss species, especially those used in biomonitoring programs.

Influence of chemical and mineralogical properties of organic amendments on the selection of an adequate analytical procedure for trace elements determination.

Six digestion procedures were tested to improve extraction methods for determination of trace elements in various organic amendments with high inorganic fractions. These procedures were tested in terms of pH, CaCO(3), organic matter, elemental analysis, BCR sequential extraction and X-ray diffraction analysis. Aqua regia extraction (ISO 11466), total digestion HF-HNO(3)-HClO(4) and four microwave-assisted digestions (i.e., HNO(3), HCl-HNO(3), HNO(3)-HF and HCl-HNO(3)-HF) were used. The effect of acid mixtures on microwave-assisted digestion of mineral fractions was assessed by Si and Al analysis and X-ray diffraction in the solid residues obtained. Microwave HF acid mixtures obtained highest trace element recoveries for all tested metals except Al. CaF(2) and CaAlF(5) precipitates were also detected using X-ray diffraction in the residues after microwave digestions with HF acid mixtures of amendments with high calcium content. A decision flowchart was suggested to determine the best acid mixture according to the amendment and the metals to be analyzed.

Phytoextraction of cadmium by four Mediterranean shrub species.

The possibility of remediating contaminated soils though the use of high biomass-generating, native plant species capable of removing heavy metals is receiving increased attention. The cadmium (Cd) accumulation capacities of the native Mediterranean, perennial shrubs Atriplex halimus, Phyllirea angustifolia, Rhamnus alaternus and Rosmarinus officinalis were tested by growing transplanted specimens in a pine bark compost substrate (pH 5.6) contaminated with 100 mg Cd kg(-1). After 70 days, only R. alaternus showed reduced growth. The increase in biomass seen in all the test species enhanced the phytoextraction of Cd. However, the species behaved as metal excluders, except for the halophyte A. halimus, which behaved as an indicator plant. In this species the leaf Cd concentration reached 35 mg Cd kg(-1), with the shoot responsible for some 86% of total Cd accumulation. Atriplex halimus showed the highest bioconcentration factor (BCF) (0.36) and leaf Cd transport index (1.68); consequently, this species showed the highest Cd phytoextraction capacity.

Chemical characterization and evaluation of composts as organic amendments for immobilizing cadmium.

The ability of three composted materials to immobilize cadmium (Cd) was examined in order to assess their potential for recovering soils contaminated with this metal. Composted pine bark (PB) pH 5.6, spent mushroom compost (SM) pH 8.0, and composted pruning waste+biosolids (BS) pH 6.9 (containing 81%, 75% and 47% total organic matter, respectively) were characterized. FT-IR and CP-MAS (13)C NMR spectroscopy indicated the BS and SM to have a higher percentage of aliphatic and carboxyl groups than PB. The composts were artificially contaminated with Cd (80 and 200 mg kg(-1)) and, after 4 weeks incubation, subjected to sequential extraction. In column leaching experiments, the total Cd leached from the composts exposed to both Cd treatments was similar, but much less leached from the BS (0.2%) than the PB (4.0%) or SM (0.7%). The greater capacity of BS to immobilize Cd was attributed to the greater humification of its organic matter and higher content of inorganic components, particularly Fe.

Heavy metal speciation and phytotoxic effects of three representative sewage sludges for agricultural uses.

The environmental impact of sewage sludges depends on the availability and phytotoxicity of their heavy metal. The influence of representative sludges (dewatered anaerobic, pelletization, and composted sludge) on the availability of heavy metals, and their effects on seed germination were compared. The total heavy metal concentrations were below the maximum permitted for land-applied waste and the differences among them were small. The DTPA-extracted metal concentrations were rather different. The sequential extraction of the compost showed a slight increase in Cd and Cu availability, and a decrease in the availability of Fe, Mn, Ni and Zn. Pelletization increased the availability of Ni and slightly reduced that of Cr. The dewatering sludge led to greater availability of Cr and Mn but reduced the concentration of Cd. The three different sludges also affected seed germination and root elongation in different ways. The most serious adverse effects were caused by the dewatered sludge extract.

Lead poisoning of horses in the vicinity of a battery recycling plant.

The diagnosis of lead poisoning in horses living on farmland in the vicinity of a battery recycling plant was based on clinical signs as well as on laboratory findings. Chemical analysis of six surface soils (0-15 cm) and herbage samples taken at different distances to the recycling plant showed very high total lead levels in the closest sites to the facility and a clear decrease with distance. Total lead levels in soil samples ranged from 127 to 5657 mg kg(-1), with more than 70% of lead extractable by EDTA in the most polluted soils. Lead levels in the aerial part of herbage samples were in the range of 113-4741 mg kg(-1). A water washing pre-treatment of the vegetal samples considerably diminished the concentration of lead, suggesting that airborne lead particles from the facility emissions were fixed on the shoots. The analysis of samples taken from six dead horses showed lead concentrations, expressed as mg kg(-1) (d.w.), as follows: blood: 0.20-0.89; liver: 2.5-15; kidney: 1.70-6.75. Lead intake levels, estimated according to the ingestion rate of Grammineae forage, illustrates that the apported lead through the ingestion of vegetation growing in the closest sites to the recycling plant was approximately 99.5 mg Pb/kg body weight/day surpassing the fatal dosage for horses of 2.4 mg Pb/kg body weight/day reported by Hammond and Aronson, Ann NY Acad Sci, 1964; 111: 595-611.

Short-term effects of biosolid and municipal solid waste applications on heavy metals distribution in a degraded soil under a semi-arid environment.

Digested biosolid (SS) and municipal solid waste (MSW) were surface-applied to a degraded carbonated soil, under semi-arid environment, at rates of 0 and 80 Mg/ha, to determine the changes in organic matter and in the distribution of heavy metals in the topsoil, 1 year after its application. Waste application slightly increased the organic matter content and improved the composition of humic fractions in the treated soils, mainly in the MSW amended plots. A sequential extraction method (Tessier et al., 1979) was used to determine the distribution of Cd, Cr, Cu, Ni, Pb and Zn in both the waste and the amended.soils. Waste application had little effect on the total concentration of Ni and Cr in the treated soils as a consequence of the low availability of these metals in the wastes. A considerable increase of Cd, Cu, Pb and Zn was observed as a consequence of the high content and/or high availability of these metals in the wastes. The more labile fraction (exchangeable fraction) of all metals studied increased slightly (< 1.5 mg/kg) when SS and MSW were added. However, a remarkable increase in the Fe/Mn oxide fraction of Cd, Cu and Pb and in the organic fraction of Zn were noted in treated plots, this increase being higher in the MSW treated soils.