L’objectif principal de cette étude est l’évaluation de l’état de contamination en métaux traces de sols cultivés dans la ville d’Abidjan. Pour ce faire, des sols ont été prélevés dans des fosses pédologiques sur les sites maraîchers de Marcory et Cocody et sur la ferme expérimentale de l’Université d’Abobo-Adjamé. L’analyse des échantillons a révélé que sur les 3 sites, la quasi-totalité des horizons sont sableux, acides, riches en Mn et Fe. Les teneurs en Cd à Marcory et à Cocody, la teneur en Cu à Marcory, les teneurs en Pb à Cocody et sur la parcelle expérimentale, les teneurs en Zn sur les 3 sites, et les teneurs en Ni à Marcory et à Cocody, sont supérieures aux teneurs limites recommandées. L’acidité et la forte macroporosité des sols ont favorisé lamigration verticale des métaux traces.Mots clés: métaux traces, sols à maraîchers, Abidjan, migration

Taxonomic categories of the highest level (e.g. the RSG of the World Reference Base for soil resources) are not adequate when dealing with trace element concentrations in soils. This does not however mean that pedology, its basic concepts and knowledge accumulated over more than a century, are of no use in this domain. Examples of the role of soil forming processes on trace element contents in soils will be provided.

The aim of this research was (i) to compare the use of stable (Cd-111) and radioactive (Cd-109) isotopes for assessing the isotopically exchangeable pool of Cd (E-Cd), (ii) to evaluate a simpler alternative method, the extraction by 1 M CaCl2, (iii) to determine E-Cd in a wide range of soil and contamination types and (iv) to assess how E-Cd can be affected by the soil characteristics. Measurement with Cd-111 gave equivalent but more repeatable results than those of Cd-109. Increasing the acidity of the spike solution led to an overestimation of E-Cd. Extraction by 1 M CaCl2 generally gave similar values to isotope dilution. Measured on 29 soil samples, E-Cd was on average 44% of the total Cd (Cd-T). The cultivated soils showed the highest relative cadmium availability (E-Cd/Cd-T=46%on average) and the geochemically enriched soils the lowest (20%). For the whole sample set E-Cd variance was mainly explained by the correlation with CdT (r=0.86). while E-Cd/Cd-T Was negatively correlated with pH (r=-0.73). In the cultivated soils, E-Cd increased with CEC (r=0.94), while E-Cd/Cd-T decreased with increasing iron content (r=-0.91). (C) 2009 Elsevier B.V. All rights reserved.

The long-term redistribution of Zn in a naturally Zn-enriched soil during pedogenesis was quantified based on mass balance calculations. According to their fate, parent limestones comprised three Zn pools: bound to calcite and pyrite-sphalerite grains, bound to phyllosilicates and bound to goethite in the inherited phosphate nodules. Four pedological processes, i.e., carbonate dissolution, two stages of redox processes and eluviation, redistributed Zn during pedogenesis. The carbonate dissolution of limestones released Zn bound to calcite into soil solution. Due to residual enrichment, Zn concentrations in the soil are higher than those in parent limestones. Birnessite, ferrihydrite and goethite dispersed in soil horizon trapped high quantities of Zn during their formation. Afterwards, primary redox conditions induced the release of Zn and Fe into soil solution, and the subsequent individualization of Fe and Mn into Zn-rich concretions. Both processes and subsequent aging of the concretions formed induced significant exportation of Zn through the bottom water table. Secondary redox conditions promoted the weathering of Fe and Mn oxides in cements and concretions. This process caused other losses of Zn through lateral exportation in an upper water table. Concomitantly, eluviation occurred at the top of the solum. The lateral exportation of eluviated minerals through the upper water table limited illuviation. Eluviation was also responsible for Zn loss, but this Zn bound to phyllosilicates was not bioavailable.

SummaryStudies relating macro‐ and microscopic aspects of impacts of long‐term contaminative practices on soils are scarce. We performed such an approach by assessing the fate of metal pollutants in an area close to Paris, where sandy Luvisols were irrigated for 100 years with urban waste water. As a result, these soils display strong accumulation of organic matter, dissolved salts and metal pollutants in surface horizons, but also migration of metals to depth. We examined soil development and metal distribution patterns in two irrigated soils, in comparison with a non‐irrigated reference soil. Soil macromorphological characteristics were studied in the field. Soil micromorphology and micro‐scale metal distributions were both studied in situ in thin sections, the latter by synchrotron X‐ray mapping. Microscopic study focussed on characteristic parts of the Ap and Bt horizons, mainly involved in metal retention. For Ap horizons, both large and diffuse metal concentrations were revealed, mainly associated with organic matter and dissolved components added by irrigation water. For Bt horizons, zinc accumulation was detected on clay‐iron coatings. Our results suggest that with time, a double metal‐filtering capacity has developed in these sandy Luvisols: in the Ap horizon, an anthropogenic filter resulted from input of metal pollutants together with highly reactive organic matter, carbonates and phosphates, thus favouring metal immobilization and limiting migration to depth. In the Bt horizon, the evidence is of a second, natural filter. However, this filtering capacity is endangered by clay destruction due to ferrolysis, as revealed by micromorphology. Ferrolysis, here initiated by intensive irrigation practices, leads to a reduction of the natural filtering potential and an increasing risk of metal transfer towards the groundwater.

A pedo-geochemical survey was carried out in the Nord-Pas de Calais region (France) on soils developed in loess deposits. Total concentrations of Al, Fe and 18 trace elements, as well as common soil characteristics, were determined in samples from 52 surface and 97 deep horizons developed in these loess deposits. The Pb isotopic composition was determined in two sola. The composition of deep horizons, compared with that of the upper continental crust, with that of horizons developed from 21 other sedimentary rocks from the region and with that of loess from various parts of the world, confirms that loess from the Nord-Pas de Calais region derives from multi-recycled and well-mixed ancient sedimentary rocks. Correlation analysis shows that least mobile (i.e. ionic potential (Z/r) is between 3 and 7) geogenic elements (Bi, Co, Cr, Cu, In, Ni, Pb, Sn, Tl, V, Zn) are associated with the fraction < 2 mu m (which we define as 'lutum'). More mobile elements (As, Cd, Hg, Mn, Mo, Sb, Se) are less associated with this fraction. Cadmium is particularly linked to Mn. The distribution of [trace element]/([Al] or [Fe]) in the French loess gives the background content for soils developed from most sedimentary materials in northwestern Europe. Topsoils are enriched with all the trace elements examined, except Co, Cr and Ni. Enrichments with Cd, Cu, Mn and Zn are greater in cultivated soils than in forest soils. Enrichments with Pb and with Cu, Hg, Mo, Sb, Se and Sn are mainly due to human contamination through atmospheric fallout. Organic matter seems to act as a sink for all the exogenous trace elements.

Various approaches have been used to estimate metal pollutant element (TE) contents at unsampled locations in a 15-ha contaminated site located in the plain of Pierrelaye-Bessancourt (about 24 km Northwest of Paris). 87 samples of soil plough layer were randomly sampled at each mesh of a regular square grid over the whole study area and the total contents of Cd, Cr, Cu, Ni, Pb, and Zn were measured. A first set of 50 measurements, randomly selected from the 87 samples, was used for the prediction and another set of 37 measurements was kept for the validation. Topsoil organic carbon contents (SOC) were measured at 75 sites with 50 measurements sharing the same locations as TE. An aerial photography of the study area showing bare soils was selected for relating brightness intensities and SOC. Mapping procedures used were ordinary kriging (OK), cokriging (COK), collocated cokriging (CC), and kriging with external drift (KED). SOC maps used as exhaustively sampled information in KED and CC of TE were obtained by KED and CC procedures, respectively, accounting for 75 SOC measurements and the brightness intensities of numerical counts provided by the visible bands of the aerial photograph bare soils. Consequently, for each TE, four maps were generated: two maps resulting from KED and CC procedures (K-ED-SOC75P, CC-SOC75P), another one provided by standard cokriging (COK-TE50SOC75) accounting for TE prediction set plus 75 SOC measurements, and the last one corresponding to that estimated by ordinary kriging from only prediction set measurements (OK50). Three indices: (1) the mean prediction error (ME) and the mean absolute prediction error (vertical bar ME vertical bar); (2) the root mean square error (RMSE); and (3) the relative improvement (RI) of accuracy, as well as residuals analysis, were computed from the validation set (observed data) and predicted values. On the 37 test data, the results showed that the more accurate predictions were systematically those obtained by kriging accounting for SOC map predicted by KED from 75 SOC measurements and brightness values of the aerial photo (K-ED-SOC75P) followed closely by CC-SOC75P procedure, except for Cu and Zn where CC-SOC75P appeared to be slightly more accurate than KED-SOC75P. In regard to the RI of accuracy between prediction methods, the results confirmed once for all the benefit of accounting for SOC data set plus the exhaustively sampled information provided by the aerial photography regardless of the considered TE. Nevertheless, for Cd, Pb, and Zn, the RI of accuracy was less than 20% between the two most accurate methods (KED-SOC75P and CC-SOC75P) and standard colcriging in which the information provided by the aerial photography is ignored when mapping.The sensitivity of KED-SOC75P and CC-SOC75P approaches to the sampling density of the target variables (TE) was assessed using 10 random subsets of different sizes (25 and 33 observations) drawn from a prediction set that includes 50 data. Results have shown that the TE estimates by KED-SOC75P and CC-SOC75P approaches using only 25 TE samples were much more accurate than the estimates performed by OK50 and COK-TE50SOC75 approaches that use the whole samples of the prediction set. Moreover, the RI of accuracy was reduced by less than 15% if the original sampling density was reduced by a third. (c) 2005 Elsevier B.V. All rights reserved.

SummarySoils irrigated with raw wastewater for many years accumulate trace metals, especially in the surface horizon. We do not know, however, to what extent the metals migrate down the profile and whether they accumulate in deeper horizons. We assessed the migration of trace metals in the suburbs of Paris where market gardens had been irrigated with wastewater for more than 100 years. Within a soil series, we compared metals in the polluted soils with those of a reference soil of the same kind. We sampled by horizons three representative Luvisol profiles in the irrigated area and a fourth profile selected as a reference just outside the irrigated area. Large quantities of Zn, Pb, Cd and Cu appeared to have accumulated in the topsoil, at the base of which concentrations diminished markedly. There appeared to be appreciable migration into the subsoil only at the most intensely irrigated site. By relating the total trace metal contents to the total iron contents we could detect anomalous values and identify migration into the subsurface horizons more sensitively. This approach was tested first with the endogenous metal Cr, then with metal pollutants. We showed that Zn, Pb, Cd and Cu migrated downwards in all three irrigated soils.

Total concentrations of 18 trace and 2 major elements (Al, Fe) as well as physico-chemical characteristics (texture, organic C, pH, CaCO3, CEC) were measured in cultivated soil samples (fraction <2 mm) from 23 surface and 38 deeper horizons developed in recent marine deposits. Correlations between trace element contents and other soil parameters were compared in order to reveal those soil factors affecting the trace element distributions. Whatever the horizon type, Co, Cr, In, Ni and V are almost exclusively associated with the fine (<20 μm) mineral fraction and do not show a direct association with organic matter. Bismuth, Sn, Tl and Zn also show a close association with the fine mineral fraction of the deep horizons, but seem to be partly associated with organic matter in the ploughed horizons. In the deep horizons, the association of Cd, Cu and Pb with the fine mineral fraction is clearly less close, while these elements appear to be associated with organic matter in the ploughed horizons. The Mn content increases with that of the fine mineral fraction up to a certain point. Arsenic, Mo and Sb contents are poorly correlated with the fine solid phase of the deep horizons. The distribution of Hg does not appear to be associated with any specific soil component. The ploughed horizons are highly enriched with Pb, Cu, Cd, Hg and Se (+84% to +225%) and moderately enriched with Tl, Mn, Sb, Bi, Sn and Zn (+7% to +48%). There is no surface enrichment of As, Co, Cr, In, Mo, Ni and V. It is possible to model most of the trace element distributions with pedotransfer functions of the physico-chemical characteristics.

The variability of Cr content is studied along a toposequence of soils developed on amphibolite and gneiss. Amphibolites are Ca-rich, gneiss are K- and Cr-rich. A mineralogical study shows that biotite is the main bearer of Cr, and explains the relationship between K and Cr in the alterites. This relation still exists in pedological horizons. The nature of the parent material and the erosion are the main factors explaining the variability of Cr along the toposequence. (C) 2001 Academic des sciences / Editions scientifiques et medicales Elsevier SAS.

In order to evaluate the contamination of the Dornach (Switzerland) site within the framework of the CEEM-Soil project, each participating team was allowed to take a maximum of 15 samples. The French team's sampling was organized in such a way as to answer the following questions: (i) what is the natural concentration of the soils at this site (local pedo-geochemical background content)?; (ii) what are the levels of Cd, Cu, Pb and Zn contamination of the soil?; (iii) what is the depth reached by the surface contamination that is derived from atmospheric fallout?; (iv) how is the contamination spread along the longest axis of the area under study? The relationships between total Fe and the trace metals have allowed local variations in the natural pedo-geochemical background content to be detected and thus permitted the anthropogenic contamination to be estimated. There would appear to be a low level of Pb contamination over all the site investigated (an increase of the order of 5-10 mg kg(-1) on the background level), limited to the surface humus-bearing layers. There is also a significant contamination by Cu over all of the site (an increase of the order of 30-40 mg kg(-1)). This contamination has remained in the surface horizons (0-20 cm). Very high Zn and Cd concentrations have been found in the four surface (0-4 cm) and deep horizons (15-70 cm) taken under the forest and very much lower values in the samples taken from cultivated soils. The most likely explanation is an unequal inheritance between the upper part of the site (wooded with thinner very clayey soils) and the lower cultivated part of the site (with thicker less clayey soils developed in a loamy material). For various reasons, it seems unlikely that a contamination of the wooded part should be so much higher than the cultivated part due to the interception of atmospheric dust by the trees. The local pedo-geochemical background Cd and Zn content of the upper wooded part proved to be clearly higher than that which would be encountered in most soils of Switzerland and France. Given this evaluation of the background content, it seems that only the surface horizons have been affected by Zn contamination (an addition of approx. 60-100 mg kg(-1)). In the case of Cd, the increase in concentrations is only 0.5-1 mg kg(-1) for the ploughed horizons, as well as the for the A horizons.

Preliminary results from the French ASPITET programme demonstrated that Cd background levels in agricultural soils can vary greatly (0.02–6.9 mg Cd kg−1) depending on parent material and pedogenic processes (Baize, 1997). However, the total Cd content in soil is often not significantly related to the Cd concentration in edible plant parts. A field case study was undertaken across the southern part of the Yonne district, Burgundy, France. This area has various soil series with either low or high geochemical Cd content in the topsoil. Cd availability in soils sampled at 16 sites belonging to five soil series was investigated using single extractions. In addition, shoots (at stem elongation) and grains (at harvest) of field-grown wheat were collected at the same sites and analysed for macronutrients and trace elements. Cd concentrations in grain varied from 0.015 to 0.146 mg Cd kg−1 DM depending on soil characteristics, soil series, and plant mineral composition. Cd grain concentrations did not reflect total Cd content in the surface soil layer; however, they were correlated with Cd extracted by a 0.1 M calcium nitrate unbuffered solution, and to a lesser extent with either soil pH or CEC. These three parameters may be useful guides to predict Cd in wheat grain harvested in the Yonne district. An inverse relationship was found between Cd and Cu contents in grain. The highest Cd concentrations in wheat grain occurred in plants grown on Aubues soils which had marginal Cu and Zn deficiencies in shoots. In order of Cd accumulation in wheat grain, soil series may be ranked as follows: Domérien < Carixien, Terres Noires < Sols Marron < Aubues.

The aim of this study was to assess thallium (Tl) uptake into the aerial parts of selected crop species grown on French soils with high Tl content of pedogeochemical origin (0.3-40 mg Tl kg(-1) on a dry wt (DW) basis). Husked wheat and maize grains contained less than 4 microg Tl kg(-1) DW, but rape shoots accumulated Tl with a shoot-soil partition coefficient (PC) > 1, and rape seeds had PC > 3. Tl content of rape seed reached 33 mg Tl kg(-1) DW and higher concentrations in soil corresponded to increased concentrations in rape seeds. It is argued that parent material of the soil and pedogenesis have a considerable effect on Tl accumulation in rape seeds. These results show enhanced phytoavailability of Tl of pedogeochemical origin and prompt questions on the potential for food chain contamination by Tl in rape cattle cakes.

The thallium (Tl) content of the upper horizons of 244 French soils was determined as the first step towards the creation of a reference data bank for total Tl content of arable soils. Forty soil samples were collected in the vicinity of potential anthropogenic sources of Tl, but the remainder came from rural areas. The distribution of Tl concentrations in soils was characterized by a median value of 0.29 mg Tl kg−1 and a 90th percentile value of 1.54 mg Tl kg−1. Very high pedogeochemical contents were found (up to 55 mg Tl kg−1) but none could be attributed to obvious anthropogenic pollution. Areas of very high Tl concentration belong to an epihercynian transgression zone with a contact between a sedimentary basin and a crystalline massif. This contact is associated with stratified mineralizations (Zn, Pb, F, Sb, Ba, Tl and pyrites). High Tl concentrations were common in limestone, marl or granite derived soils, and the Tl in limestones or marls is probably concentrated in the sulfides contained in these rocks because Tl has a high affinity to S. In granites, Tl may be in the micas and feldspars because Tl+ can replace K+ in these minerals. Silty or clay-silty soils showed the highest concentrations. These granulometric fractions contain the majority of the minerals, which are supposed to be the major hosts of Tl in soils, i.e. clay minerals, oxides and micas. Tl in the soils was positively correlated with Ba, V, Pb, Fe, Ni, Cd, Zn, Co, As and especially Mn. A significant proportion of Tl may be in the Mn oxides: in oxidizing conditions, Tl(III) could enter the Mn oxides by sorption, or Tl(I) could replace K(I) in the oxide.

Regression equations successfully allowed the calculation of water retained at -0.3 x 10(5) Pa and -15 x 10(5) Pa matric potentials from single soil characteristics, such as bulk volume or clay content, in clayey horizons derived in similar ways from a single parent material. It is possible to use these regression equations on other soils with similar clay fabrics. The fabric is expressed numerically using the pore volume associated with clay particles.

In 1986 the ''Association Francaise pour l'Etude du Sol (A.F.E.S.)'' started a project to replace the former soil classification introduced in 1967 by the ''Commission de Pedologie et de Cartographie des Sols (C.P.C.S.)''.The new system owes much to advances made in the past twenty years and is the collective work of more than sixty scientists with additional material derived from various other sources. It conforms to the usually accepted morphogenetic approach, nevertheless two major innovations have been introduced: (i) the real objects under investigation are ''Soil Mantles''; (ii) the system is not hierarchical but typological.The ''Referentiel Pedologique'' (abbreviated as R.P.) is yet to be fully developed and a fourth version will be published in 1992. Nevertheless, his general principles are well defined and are explained below.The R.P. is based on four basic notions: ''Soil Mantles'', ''Solums'', ''Reference Horizons'' and ''References'' (fig. 1).