Phosphate reactions with natural allophane, ferrihydrite and goethite

The reactions of phosphate with natural samples of allophane, ferrihydrite, hematite and goethite were measured for up to 30 d. The amount of phosphate sorbed on allophane showed the biggest increase with time whereas the amount sorbed on goethite showed the least increase with time. The total amount of phosphate sorbed either at high levels of phosphate addition or after 10 d followed the order hematite < goethite < ferrihydrite < allophane and was probably related to the specific surface. Si was desorbed as phosphate was adsorbed on the minerals.
The reactions of phosphate on allophane involved rapid, strong adsorption, probably at defect sites, followed by weaker adsorption, followed, probably, by disruption of the allophane structure together with precipitation of aluminium phosphates. Previous suggestions either of diffusive penetration of phosphate into surfaces or about the formation of aluminium phosphate coatings, are unlikely to hold for allophane, if all the Al is at the surface and if the structure can be ruptured.
The reactions of phosphate with iron oxides involved a rapid, strong ligand exchange, followed by weaker ligand exchange, and, probably, by a relatively slow penetration at defect sites and pores. Highly crystalline goethite has virtually no slow reaction and therefore solid-state diffusion of phosphate does not readily occur. The extent of phosphate uptake during the slow penetration reactions probably depends on the degree of crystallinity or porosity of iron oxides.
The most reactive adsorbents, such as allophane, ferrihydrite and Al-humus complexes do not have planar surfaces, and this needs to be considered when modelling phosphate reactions.     

The effect of time on the competition between anions for sorption

Solutions of phosphate and of selenite were gently mixed with a soil, both separately and in combination, for periods ranging from 15 min to 30 days. For both anions, the solution concentration continued to decrease throughout the period, but the decrease was more marked for phosphate. Competitive effects were smallest after brief periods of mixing, and increased with time. Phosphate was a more effective competitor for sorption than selenite, and its competitive advantage increased with time. The observed effects were closely described by a mechanistic model. According to the model, competition was largely through changes in the electric potential of the surface rather than through decreases in the number of vacant adsorption sites. This explained why competition effects were initially small. This was especially so for phosphate, which was modelled as having a marked continuing diffusive penetration of the surface. The decrease in electric potential associated with that penetration decreased the surface concentration of selenite and so decreased the rate of penetration of selenite. By the end of the experiment this was the most important aspect of the competitive effect of phosphate on selenite.     

Effects of crystallinity of goethite: II. Rates of sorption and desorption of phosphate

Eight samples of goethite ranging in surface area from 18 to 132 m² g^-1 were mixed with phosphate at a range of pH values for periods which ranged from 0·5 h to 6 weeks. The sample with a surface area of 18 m² g^-1 had been hydrothermally treated to improve its crystallinity. Its rate of reaction with phosphate depended on pH but was complete within a day. Its maximum observed reaction was close to the theoretical maximum for surface adsorption of 2·5 μmol m^?2. For the other samples, phosphate continued to react for up to 3 weeks and exceeded the value of 2·5 μmole m^?2. The duration and extent of the reaction depended on the crystallinity of the goethite. The results were closely described by a model in which the phosphate ions were initially adsorbed on to charged external surfaces. The phosphate ions then diffused into the particles. This was closely described using equations for diffusion into a cylinder. Samples of goethite which had been loaded with phosphate dissolved more slowly in HCl, and had a longer lag phase, than phosphate-free goethite. For the hydrothermally treated goethite, HCl removed much of the phosphate when only a small proportion of the iron had been dissolved. For a poorly crystallized goethite, it was necessary to dissolve much more of the iron to obtain a similar removal of phosphate. Brief treatment with NaOH removed most of the phosphate from the hydrothermally treated goethite but only half the phosphate from a poorly crystallized goethite. These results are consistent with the idea that phosphate ions were not only bound on external surface sites but had also penetrated into meso- and micro-pores between the domains of the goethite crystals and were then adsorbed on internal surface sites. This penetration tied the domains together more firmly thus increasing the lag phase for dissolution. Differences between sites for phosphate adsorption are therefore caused mainly by their location on either external or internal sites. Models that ignore this are incomplete.     

Migration of phosphate into aggregated particles of ferrihydrite

The slow reaction of phosphate with aggregated particles of ferrihydrite, after initial rapid phosphate sorption, was investigated by measuring the changes, with time and temperature, in the amount of phosphate sorbed, and the extractability of the sorbed phosphate. The ferrihydrite was, subsequently, recovered and examined by infra–red spectrometry (IR) and electron probe micro–analysis.
Phosphate continued to react with ferrihydrite for at least 90 d at 25°C, but was completely recovered by extraction with 0.1 m NaOH. The IR spectra of sorbed phosphate was insensitive to the temperature and duration of the reaction. Electron probe micro–analysis of the aggregates showed that phosphate migrated to surface sorption sites within the aggregated particles of ferrihydrite.
There was no evidence for the formation of surface coatings of ferric phosphate, for changes in the type of bonding, or for penetration of phosphate into the crystal lattice. The slow reaction was attributed to the migration of phosphate to surface sorption sites of decreasing accessibility within aggregates.     

石灰性土壤与磷酸盐的反应及吸持态磷的同位素交换性

本文研究了种石灰性土壤（Ｌｏｕ土）与磷酸盐的反应动态过程，短期反应的等温吸附研究表明，在低磷浓度下，以吸附反应机制为主，吸持态磷的同位素交换性随着吸持量的增加而增加；在高磷浓度下，以形成磷酸盐的沉淀反应机制为主，吸持态磷的同位素交换性随着反应时间的延长和吸持量磷数量的增加而了降低。认为在低施磷水平下，土壤中铁，铝氧化物对磷的吸持起重要作用。本文还探讨了在长期（２６０天）恒温恒湿培养过程中，土壤可溶     

Influence of soil properties on the response to phosphorus in some tropical soils: I. Initial response to fertilizer

The availability of fertilizer P in six P-deficient tropical soils from Brazil, Kenya, Malaysia and Indonesia was assessed by grass in a pot experiment. Grass dry matter yield (D) and fertilizer P(F) were fitted to a Mitscherlich equation: D= a?b exp(?cF), and P uptake (U) and F to the linear equation: U=α+βF. Fitted parameter β equals the proportion of P recovered in one crop and it varied widely between soils, ranging from 12 to 51%. Quantitative assessments of fertilizer-P availability could also be made using dry-matter data alone if the rates of fertilizer used were well distributed along the response curve, when Mitscherlich parameter c was correlated well with β. Chemical measurements were made on uncropped soil. Phosphate sorption isotherms were measured, using ³²P to assess exchangeable and non-exchangeable phosphate. The availability parameters c and β were correlated best with parameter b_e, the phosphate buffer capacity derived from the fitted Freundlich isotherm for exchangeable phosphate, suggesting that the mobility of exchangeable phosphate is a major influence on P availability. Al and Fe were extracted with acid oxalate, citrate-dithionite and pyrophosphate reagents, and parameters c and β correlated best with Al extracted by acid oxalate. These relationships were inverse, showing that Al in disordered mineral forms lowers the availability of fertilizer P.     

Sorption of isotopically exchangeable and non-exchangeable phosphate by some soils of Colombia and Brazil, and comparisons with soils of southern Nigeria

Fourteen soils from Colombia and Brazil provided a wide range of sorption characteristics. Curves of sorbed phosphate that was exchangeable to ³²P were described by Freundlich's equation, and of non-exchangeable phosphate by Temkin's equation. Exchangeable phosphate was associated with aluminium in poorly-crystalline oxides and in organic complexes. Non-exchangeable phosphate was related to aluminium in organic complexes, and especially to the ratio of AI/C in them. In Nigerian soils similar mechanisms controlled sorption of phosphate but oxides and organic complexes of iron were important. The concentration of phosphate in solution when affinities of soil for exchangeable and non-exchangeable phosphate are equal, and the importance of organic matter, are discussed in relation to soil management and to responses of crops to fertilizer phosphate. The results indicate that sorption curves should not be split into sections.     

Testing a mechanistic model. I. The effects of time and temperature on the reaction of fluoride and molybdate with a soil

A mechanistic model that had been developed to describe the reaction of phosphate with soil was applied to the reactions of fluoride and molybdate with soil. The model assumes that: there is an initial adsorption reaction between ions and charged surfaces; that the surfaces are not uniform in their properties; and that the initial adsorption is followed by diffusive penetration. The model was developed beyond that previously published to permit the rate of the initial adsorption reaction to be included. The model reproduced the effects of solution concentration, and of increasing period and temperature of incubation, on the retention of both fluoride and molybdate. Increasing the temperature of incubation increased the retention, or decreased the solution concentration, and this was reproduced by the effect of temperature on the rate of diffusive penetration. Desorption of fluoride was also reproduced. This supports the argument that slow desorption is mostly due to the need to reverse the diffusive penetration. After incubation at constant temperature, increasing the temperature at which solution concentration of molybdenum was measured, increased the concentration. The direction of this effect of temperature was also reproduced. It arises because of the effect of temperature on the position of the equilibrium between adsorbed molybdate (in the strict sense of the term) and molybdate in solution.     

Phosphate sorption by calcareous Vertisols and Inceptisols as evaluated from extended P-sorption curves

The plant availability of phosphate applied to calcareous soils is affected by precipitation and adsorption reactions, the relative significance of which is not well known. We used extended P-sorption curves obtained at phosphate addition rates up to 340 mmol P kg^?1 soil to examine the relative contribution of precipitation and adsorption by 24 calcareous Spanish Vertisols and Inceptisols. Adsorption was dominant at 1 day and at small rates of addition (10–35 mmol P kg^?1). With increasing clay and Fe and Al oxides contents of the soil, more phosphate was sorbed before the sorption curve bent upwards, as a result of Ca phosphate precipitation. Sorption curves showed a nearly vertical intermediate region, the length of which increased with time, suggesting that a Ca phosphate buffered the concentration of P in solution. The buffering concentration decreased with time, suggesting a progressive transformation of more to less soluble forms of Ca phosphate. A phase less soluble than octacalcium phosphate seemed to control the concentration of P in solution at 180 days in most soils. The apparent solubility of this phase decreased with increasing carbonate content in the soil. Precipitation of poorly soluble Ca phosphates apparently predominated up to a P addition dose ranging from about 30 mmol P kg^?1 in some soils to more than 340 mmol P kg^?1 in others. At larger doses, the way additional P was bound to the solid phase was different; phosphate was probably adsorbed, at least in part, to low-affinity sites on silicate clays and oxides. The proportion of sorbed phosphate that was isotopically exchangeable decreased with time, soil carbonate content and P addition dose for doses <100 mmol P kg^?1. This is consistent with the idea that P in Ca phosphates is less isotopically exchangeable than P adsorbed on mineral surfaces. At larger additions of P, isotopic exchangeability was unrelated to the soil properties measured, probably because there was a variety of sorbed P forms influenced in turn by different soil components.     

ON THE POSSIBILITY OF CHARACTERIZING CALCIUM PHOSPHATES IN CALCAREOUS SOILS BY ISOTOPIC EXCHANGE

Characterization of calcium phosphates depended upon the nature and the amount of phosphate used to react with reagent-grade CaCO₃. Formation of octa-calcium phosphate (OCP) was inferred from the solubility equilibria after reacting CaCO₃ with KH₂PO₄ solutions. Isotopic exchange measurements confirmed the presence of OCP, when the amount of P retained exceeded 44 μrnoles/g CaCO₃. The determined surface-Ca to surface-P molar ratios were close to the theoretical Ca/P ratio of 1.33 in OCP. As P retained on CaCO₃ decreased the surface Ca/P ratio markedly increased because of interference from surface Ca of the CaCO₃. When CaCO₃ was reacted with monocalcium phosphate (MCP), solubility equilibria indicated the formation of dicalcium phosphate dihydrate (DCPD). Isotopic exchange measurements, however, showed an average Ca/P ratio of only 0.375. This value corresponds to the composition of the metastable triple point solution (MTPS) formed on MCP dissolution rather than to the Ca/P ratio in DCPD. MCP application decreased the measured surface-Ca (exchangeable Ca) either for soil or Ca-resin, because of blocking of the exchange sites by the MCP reaction products and, consequently, a lower rate of isotopic exchange. Surface phosphorus of the two investigated calcareous soils proved to be proportional to the lowering in pH initiated by MCP application. Characterization of MCP reaction products in calcareous soils may thus prove infeasible, in view of the unexpected reduction in surface-Ca and the pH dependency of surface P.     

pH对土壤吸持磷酸根的影响及其原因

本文选择了浙江、江苏15个性质变化范围较大的土壤样品,研究在两种支持电解质、不同pH条件下对磷酸根的吸持反应。结果表明,加碱提高强酸性土壤的pH值,导致交换性铝的水解和羟基铝聚合物的生成,增加对磷的吸持。磷酸根同酸性土壤的反应,可促进交换性铝的水解,释放出H⁺,降低体系的pH。在CaCl₂介质中,当pH>6时,可能有磷酸钙类盐形成,使溶液中磷浓度显著降低。有机质对土壤吸持磷有重要影响。在低pH下有机质通过与Al³⁺形成络合物,阻碍溶液中A1³⁺的水解,并与磷酸根竞争羟基铝化合物表面的反应点位,从而降低酸性土壤对磷酸根的吸附量。     

The reaction between phosphate and dry soil. I. The effect of time, temperature and dryness

Phosphate (P) was added to soil in solution. The soil was air-dried or freeze-dried and then incubated at a range of temperatures for periods of up to 110 d. The rate of the continuing reaction between the P and soil was measured using the null-point method, and by measuring the amount of desorption induced by filter paper impregnated with iron oxide (Pi test). The reaction between soil and P continued in both air-dried and freeze-dried soil, albeit more slowly than in moist soil. Freezing the soil, whether moist or dry, virtually stopped the reaction. These results are consistent with the hypothesis that the continuing reaction between P and soil involves a solid-state diffusive penetration of the soil particles by the sorbed P ions. They also indicate that the common practice of storing soil air-dry, even for short periods at low temperature, will not preserve the P status of the soil as at sampling. It was estimated that for a sample of soil which remained moist at 25°C for 100d after the addition of 335 μg P g⁻¹ soil, before being sampled and stored air-dry at 4°C for 16 years, the measured P_i test value would be about 15 μg P g⁻¹. This compares with 46 μg P g⁻¹ which is the estimated Pⁱ test value measured on the same day as sampling. When samples cannot be analysed for P status immediately following sampling, they should be stored at the lowest convenient temperature, preferably below 0°C.     

THE HIGH- AND LOW-ENERGY PHOSPHATE ADSORBING SURFACES IN CALCAREOUS SOILS

The two-surface Langmuir equation was used to study P adsorption by 24 calcareous soils (pH 7.2-7.6; 0.8-24.2 per cent CaCO₃) from the Sherborne soil series, which are derived from Jurassic limestone. High-energy P adsorption capacities (x″_m) ranged from 140–345 μg P/g and were most closely correlated with dithionite-soluble Fe. Hydrous oxides therefore appear to provide the principal sites, even in calcareous soils, on which P is strongly adsorbed (x″_m 6–51 ml/μg P). The low-energy adsorption capacities (x″_m) ranged from 400–663 μg P/g and were correlated with organic matter contents and the total surface areas of CaCO₃ but not with per cent CaCO₃, pH, or dithionite-soluble Fe. Total surface areas of CaCO₃ in the soils ranged from 4.0 to 8.5 m²/g soil. Low-energy P adsorption capacities agree reasonably with values (100 pg P/m²) for the sorption of phosphate on Jurassic limestones but phosphate was bonded much less strongly by soil carbonates (k″= 0.08–0.45 ml/μg P) than by limestones (k～10.0 ml/μg P). Low-energy P adsorption in these soils is tentatively ascribed to adsorption on sites already occupied by organic anions (and probably also by bicarbonate and silicate ions) which lessen the bonding energy of co-adsorbed P.     

THE MEASUREMENT AND MECHANISM OF ION DIFFUSION IN SOILS

The counter-diffusion of phosphate against chloride was measured in a moisture-saturated block of soil by following the efflux of phosphate into a limited volume of well-stirred CaCl₂ solution, of the same ionic composition as the soil-pore solution except for a lower initial phosphate concentration. By varying this phosphate concentration effective diffusion coefficients over a wide range of depletion were measured. The fraction of labile phosphate desorbed, and the relation between phosphate desorbed and concentration of phosphate in the equilibrium solution were measured in the same experiments. Effective diffusion coefficients varied from 0.43 to 1.50 × 10^-4cm² sec^-1, tending to decrease as depletion increased. Depletions ranged from about 0.3 to 25 per cent of the ³²P exchangeable phosphate, which corresponded to a lowering of the solution concentration by about 30 to 65 per cent of the initial concentrations. Diffusive movement of phosphate in this soil can be accounted for by diffusion through the liquid pathway only. The effective diffusion coefficient can be predicted from phosphate desorbed in response to a change in the concentration of the equilibrium solution, and an impedance factor.     

Testing a mechanistic model. II. The effects of time and temperature on the reaction of zinc with a soil

Samples of a soil were mixed with zinc nitrate solutions and incubated from 1 to 30 days at temperatures from 4 to 60°C. The solution concentration of zinc, which would not have changed on brief mixing with the soil at 25°C, was measured. Background electrolytes for this measurement of null-point concentration were both calcium and sodium nitrate. The effect of the temperature at which null-point concentration was measured was also investigated. After incubation with zinc nitrate, desorption of zinc, and sorption of further zinc, were measured. Null-point concentration of zinc decreased with increasing period of incubation, with the rate of decrease greatest at high temperatures of incubation. The effects of both temperature and time were closely described by a model which postulated an initial rapid adsorption of ZnOH⁺ ions onto heterogenous charged surfaces, followed by a diffusive penetration. Increasing the temperature of incubation increased the rate of diffusive penetration and led to low solution concentrations. In contrast, increasing the temperature at which null-points were measured increased the concentration of ZnOH⁺ ions. This was shown to be consistent with a change in position of the equilibrium of the initial, rapid, adsorption reaction. Curves for desorption of zinc were continuous with curves for sorption of further zinc, but neither desorption nor further sorption coincided with the position of the curves relating retention of previously added zinc to concentration. This result was consistent with the model and occurred because desorption must reverse diffusive penetration. However, the model under-predicted the magnitude of both desorption and sorption of further zinc. Desorption in calcium solutions was greater than in sodium solutions, even when the solution concentration of zinc approached zero. This was consistent with exchange diffusion of calcium ions for some of the penetrated zinc.     

The self-diffusion of strongly adsorbed anions in soil: a two-path model to simulate restricted access to exchange sites

The consequences of slow diffusion of strongly adsorbed solutes into soil aggregates are not fully understood. The distribution of ³²P after diffusing down a soil column cannot be explained from a consideration of liquid-phase impedance factor and isotopic exchange alone, as can that of ³⁶CI. A model was developed that considers the soil to provide linked parallel intra-aggregate and inter-aggregate pathways. With this geometry, simulations agreed fairly well with experimental data when the intra-aggregate impedance factor was 0.001, using other model parameters that had been determined in independent equilibration studies. With this intra-aggregate impedance factor, the model yielded straight-line plots for chloride and the overall impedance factor derived agreed closely with the experimental one. The intra-aggregate impedance factor for ³²P also agreed with the rate of reaction of the rapidly-exchanging P fraction previously determined. The slowly-exchanging P fraction has little influence on the P concentration profiles up to 10 d, but the small exchanged amount does have an effect at run times of 57 d. The slow intra-aggregate diffusion of strongly adsorbed solutes decreases the amount adsorbed from a surface source of supply, and it also decreases the amount that is taken up by a surface sink. However, the interaggregate solution concentration remote from a source of supply is considerably increased, which may be important if the solute is a pollutant or a nutrient.     

Phosphorus fractions and dynamics as affected by land-use changes in the Central Mexican highlands

Land-use change from forest to agriculture in the volcanic ash-derived soils of Mexico has increased over recent decades. It is likely that land uses and management practices, particularly fertilizer use have affected phosphorus (P) distribution and availability. The objective of this study was to evaluate the effects of land-use types (native forest and maize mono-cropping), and the related P addition, on the forms and distribution of soil P and their isotopic exchangeability. An Andisol, sampled from a cropping site, along with the contiguous area under native forest was treated with ³²P-labelled potassium phosphate (KH₂³²PO₄). The soil samples were extracted after incubation times of 7, 21, 35 and 49 days. Phosphorus content and ³²P recovery in fractions sequentially extracted were assessed for each incubation time. Total soil P was dominated by inorganic fractions (79 to 86%) in both land-use types. Resin-Pi, bicarbonate extractable inorganic P (Bic-Pi) and sodium hydroxide extractable inorganic P (NaOH_0.1-Pi) were all raised with P addition. However, the proportion of organic P fraction was reduced under cropped soil. The recovery of ³²P in soils with P addition indicates that resin-Pi, Bic-Pi and NaOH_0.1-Pi comprised nearly all the exchangeable P. In native soils with no P addition, more than 19% of the ³²P was recovered in Bic-Po and NaOH_0.1-Po forms. This finding indicates that organic P cycling is crucial when soil Pi reserves are presented in an inadequate amount. Ecologically based management has to be designed for replenishment and succeeding maintenance of soil organic P compounds to increase sustainable agricultural production.     

Chemical Characteristics and Acid Buffering Capacity of Surface Soils in Japanese Forests

To determine the geological distribution of acid buffering capacity and exchangeable Al of forest soils in Japan, surface soils under forest vegetation were collected nationwide from a total of 1,034 sites. Generally, surface soils in Japanese forests are mostly acidic and low in both exchangeable cation content and exchangeable Al. The median of soil pH(H₂O), total exchangeable cations, and exchangeable Al are 5.1, 76 mmol₍₊₎Kg^?1, and 19.6 mmol₍₊₎kg^?1, respectively. Acid buffering capacities of selected soils were determined using a soil column, which was comparable to the capacity that resulted from cation exchanges with protons. Soils with high buffering capacity and low exchangeable Al are widely distributed in Japan, and overlap with the areas of Andisol distribution. Volcanogenic materials seem to mask soil characteristics derived from underlying geology even though they are not Andisols. However, central to western Honshu Island, Shikoku Island, and northern Kyushu Island showed weak acid buffering capacities with high exchangeable Al potential in surface soils.     

Behaviour of arbuscular-mycorrhizal fungi on Vigna luteola growth and its effect on the exchangeable (32P) phosphorus of soil

 The effect of the inoculation of Glomus mosseae and Scutellospora fulgida, singly or in mixed inocula, was tested on the growth and mycorrhizal characteristics of Vigna luteola. Soil depletion by mycorrhizal inoculation was determined as exchangeable ³²PO₄. Five treatments were performed: non-inoculated control (C); inoculated with a suspension of microorganisms free of mycorrhizae (M); inoculated with S. fulgida plus microorganisms (Sf+M); inoculated with G. mosseae plus microorganisms (Gm+M) and a treatment inoculated with both S. fulgida and G. mosseae plus microorganisms (Sf+Gm+M). G. mosseae was the most efficient fungus in promoting growth of V. luteola. This fungus produced higher shoot dry weight, P uptake in shoots (P_shoot) and P_shoot/arbuscules ratio than the S. fulgida inoculum, even though percent arbuscular-mycorrhizal (AM) colonization was similar for the two single AM-inoculated treatments. The highest value of isotopically exchangeable P was recorded for treatment M (P<0.05). In comparison with M, Gm+M treatment reduced the different P pools more than Sf+M treatment. C_p values were reduced to half by Gm+M and Sf+M treatments and were minimum for the combined treatment. Pools A (exchangeable phosphate between 1 min and 1 day) and B (exchangeable phosphate between 1 day and 3 months) were reduced by Gm+M treatment in contrast to Sf+M, which left them unchanged. The depression of isotopically exchangeable P for all pools obtained for the Sf+Gm+M treatment suggested that specific characteristics of fungi caused differences in P absorption, which in addition was altered by the possible interactions among them, when multiple inocula were used in a soil low in native P. Received: 29 January 1999     

Distribution of the Metals Lead,Cadmium, Copper,and Zinc in the Top Soil of Cartagena,Spain

This article presents the results of the analysis of the metals lead, cadmium, copper, zinc and aluminum, conducted on a total of 112 soil samples arising from 57 sampling points, distributedthroughout the Cartagena area in southeastern Spain. Both, totalmetal content and soluble fraction (1 M nitric acid medium, exchangeable fraction) were analyzed. Soil samples were taken on the surface of the terrain and at a depth of 35 cm from eachsampling point. For the purposes of this study, sampling points were classified in three groups based on the results of previous research on air pollution in the region: clean areas,contaminated areas and vacant industrial areas. The statisticalanalyses of the results show no significant differences betweenthe surface samples and the 35 cm deep samples from all three areas. Lead, zinc and copper (soluble and total fractions) aresignificantly higher, and pH significantly lower, in the samples coming from the contaminated and vacant industrial areasthan in samples coming from the clean area. Total lead and cadmium are significantly higher in the vacant industrial areas(150 g kg^-1 Pb and 9.3 g kg^-1 Cd) than in the contaminated areas (5.2 g kg^-1 Pb and 2.1 g kg^-1 Cd).Iso-concentration maps have been prepared in order to correlatethe presence of metals with the industrial and mining activities in the region under study. These maps show a clear relationship between human activities and metal concentrationgradients, with peaks corresponding to both active and abandoned industrial and mining facilities.