F. van Oort

Strategies of heavy metal uptake by three plant species growing near a metal smelter

Some higher plant species have developed heavy metal tolerance strategies which enable them to survive and reproduce in highly metal-contaminated soils. We have investigated such heavy metal uptake and accumulation strategies of two absolute metallophyte species (Armeria maritima ssp. halleri and Cardaminopsis halleri) and one pseudometallophyte (Agrostis tenuis) growing near a former metal smelter. Samples of plant parts and soil were analysed for Zn, Cd, Pb, and Cu. In soil, there were two dominant types of metal concentration gradients with depth. Under the absolute metallophytes, extremely high metal contents were measured in the surficial Ah horizon, followed by a strong decrease in the underlying soil horizons (L(11) and L(12)). Under the pseudometallophyte, metal concentrations in the Ah horizon were much lower and fewer differences were observed in metal concentrations among the Ah, L(11), and L(12) horizons. The concentrations of Zn, Cd, Pb, and Cu in Agrostis tenuis roots were greater than concentrations in leaves, indicating significant metal immobilisation by the roots. For C. halleri, Zn and Cd concentrations in leaves were >20,000 and >100 mg kg(-1), respectively, indicating hyperaccumulation of these elements. Armeria maritima ssp. halleri exhibited root concentrations of Pb and Cu that were 20 and 88 times greater, respectively, than those in green leaves, suggesting an exclusion strategy by metal immobilisation in roots. However, Zn, Cd, Pb, and Cu concentrations in brown leaves of Armeria maritima ssp. halleri were 3-8 times greater than in green leaves, suggesting a second strategy, i.e. detoxification mechanism by leaf fall.

Colloidal facilitated transfer of metals in soils under different land use

In order to assess the importance of colloids in the metal transfer in soils under varying land use (a podzol under a forest, a cultivated luvisol and a luvisol under a metallophyte grassland), gravitational waters were collected in situ by zero-tension lysimeters. Dissolved and colloidal fractions of metals were separated by ultracentrifugation and colloids were studied by transmission electron microscopy (TEM) coupled with energy dispersive X-ray analysis (EDS). The stability of metal complexes in the collected solutions was operationally defined by an ion exchange method. The results show that in the two luvisols about 75% of Pb was always present in colloidal forms and a substantial fraction of Pb in solution was present as stable complexes and labile complexes with slow dissociation kinetics. Zn and Cd were found mostly in dissolved forms and mainly as free ions or labile complexes in solution. In the podzol, all metals were found in dissolved forms and as free ions or labile complexes. The Zn-bearing colloids were organic (biocolloids) or mineral (smectites, Fe-oxyhydroxides, Ca- or Al-rich phosphates) depending on soil type and land use. The results are discussed in terms of metal mobility to explain the different vertical metal distributions observed in the soil profiles.

Mutual effects of soil organic matter dynamics and heavy metals fate in a metallophyte grassland

Abstract Metallophytes, plant species that grow only on soils rich in metals, are used for bioremediation of polluted soils. However, little is known about the functioning of such soil–plant systems. We have investigated soil organic matter (SOM) dynamics and its effects on the fate of heavy metals under a metallophyte grassland highly polluted by industrial dust fallout. Both litter and soil horizons were sampled. Particle-size and density fractionations were carried out to separate particulate organic matter (POM), i.e. the light fraction >50 μm. All samples were analysed for C, N, Zn, Pb, and Cd. Bulk densities were determined for all horizons and stocks of elements per unit area were calculated. Compared to broad uncontaminated temperate grasslands, SOM displayed similar quantities but differed significantly as to its quality and dynamics. The main differences were a lack of incorporation of plant returns in the soil profile and an imbalance of SOM composition towards more POM and less fine humified material. Zn, Pb, and, to a lesser extent, Cd were located mainly in the organic-rich, superficial soil layer. Heavy metal concentrations of POM of different sizes were similar within each horizon. Heavy metal concentrations of total POM increased strongly according to a depth–time scale. Our results suggest a selective decomposition of portions of metallophyte-derived debris with initially low heavy metal concentrations and resistance to biodegradation of those portions with initially high heavy metal concentrations. Such a mechanism may constitute a process of mutual protection, in this soil–plant system, of plant debris towards biodegradation and of heavy metals towards mobility.

Soil structure and characteristics of organic matter in two orchards differing in earthworm activity

By consuming plant remains and soil, earthworms incorporate organic matter (OM) into the soil and form biogenic soil structures, which can affect OM dynamics. We carried out a (micro)morphological study of soil structure development and OM distribution in two orchards (45 year) in a Dutch calcareous marine loam: RI − without, and KR + with high earthworm activity, the result of different levels of heavy metal contamination from fungicides. In both soils, sedimentary–stratification was absent to 60 cm depth and equal amounts of biogenic calcite spheroids were counted, suggesting similar earthworm activity in the past. In RI − the current vol.% of worm-worked groundmass in thin sections was 6% in the Ah and 7% in the Bw horizon compared with 51% in the Ah and 16% in the Bw horizon of KR + . Disappearance of earthworms with time in RI − gave rise to a compacted physicogenic soil structure with angular and prismatic aggregates and the absence of earthworm biopores. Due to restricted fragmentation and incorporation of OM fragments in casts, a litter layer formed at the soil surface. OM coatings were present in fissures and root pores of the Ah horizon, indicating the absence of mixing of organic and mineral soil materials. OM fragments were relatively coarse (>50m) and heterogeneously distributed through the Ah groundmass. Stronger decalcification in RI − than in KR + could be ascribed to higher production of organic acids in the litter layer of RI − and the absence of soil homogenisation by earthworms. In KR + earthworm activity was high, which has resulted in a biogenic structure with granular and subangular blocky aggregates and many worm casts and biopores. Particulate OM was relatively fine ( <50m) and encapsulated with clayey material in casts and micro-aggregates. The organic C content was not significantly ( P< 0.05) higher in the Ah horizon of KR + , than in the Ah horizon of RI − (15.7 and 13.7 g kg −1 , respectively). The lower C mineralization rates in KR + below 6 cm depth, however, might be an indication of higher microbial substrate-use efficiency or physical protection of OM against decomposition. The latter explanation would accord with the observed encapsulation of OM in micro-aggregates, and with studies on other management systems that favour biogenic aggregate formation. The quality of the soil macro- and microstructures, degree of soil compaction and decalcification and soil OM dynamics were strongly determined by the occurrence of earthworms in soils.

Metal extraction by Arabidopsis halleri grown on an unpolluted soil amended with various metal-bearing solids: a pot experiment.

Most studies dealing with phytoremediation have considered metal extraction efficiency in relation to metal concentration of bulk soil samples or metal concentration of the soil solution. However, little is known about the effect of various metal-bearing solids on plant growth and metal extraction of hyperaccumulators. In this study, we investigated the ability of Arabidopsis halleri to grow and extract metals from different substrates consisting in an unpolluted soil amended with various metal-bearing solids collected in soils around a Zn smelter complex. The metal-bearing solids used as amendments were: fresh and decomposing organic residues in the soil, a soil clay fraction and two waste slags. Pure mono-metallic salt (ZnSO4) was also used. Two series of substrates were produced, one moderately polluted, and the other highly polluted. An additional substrate was formed by the unamended soil, and used as an unpolluted control. Zn, Cd, Cu, and Pb were measured in the substrates, and in the roots and shoots of A. halleri. The dry matter yield of A. halleri was shown not to depend on the nature of the metal-bearing solid used, except when Cu-toxicity was suspected. On highly-polluted substrates, Zn extraction by A. halleri depended on the nature of metal-bearing solids used, showing the following trend: pure mono-metallic salt > waste slags and soil clay fraction > fresh and decomposing organic matter. We explained these differences by the high solubility of Zn in the mono-metallic salt, whereas in the mineral metal-bearing solids and in both fresh and decomposing organic matter, Zn release required mineral weathering or organic matter mineralization, respectively. This work clearly showed that phytoremediation studies have to consider the nature of metal-bearing solids in contaminated soils to better predict the efficiency of plant extraction.

Anthropogenic lead distribution in soils under arable land and permanent grassland estimated by Pb isotopic compositions

The role of land use on fate of metals in soils is poorly understood. In this work, we studied the incorporation of lead in two neighboring soils with comparable pedogenesis but under long-term different agricultural management. Distributions of anthropogenic Pb were assessed from concentrations and isotopic compositions determined on bulk horizon samples, systematical 5-10 cm increment samples, and on 24-h EDTA extracts. Minor amounts of anthropogenic lead were detected until 1-m depth under permanent grassland, linked to high earthworm activity. In arable land, exogenous Pb predominantly accumulated at depths < 60 cm. Although the proximity between the two sites ensured comparable exposition regarding atmospheric Pb deposition, the isotopic compositions clearly showed the influence of an unidentified component for the cultivated soil. This work highlights the need for exhaustive information on historical human activities in such anthropized agrosystems when fate of metal pollution is considered.

Allophane, imogolite, and gibbsite in coatings in a Costa Rican Andisol

Abstract Neoformation of allophane, imogolite, and gibbsite has been studied extensively in soils in humid climates, but little is known about their micro distribution patterns. such information may provide insight about the conditions at the micro-site scale, responsible for their formation and disappearance. Our study describes amorphous and crystalline coatings in a Melanudand on a 18,000 yr old andesitic lava in Costa Rica. Fine-textured, white to yellow coatings could be observed in the B, C, and R horizon in the field. In thin sections the coatings are translucent and isotropic in plane polarized light (PPL), indicating that they consist of amorphous material. In the B horizon, under crossed polarized light, isotropic coatings show a gradual transition towards crystalline outer margins and spots, while in PPL such transition cannot be observed, suggesting a genetic relationship. Submicroscopical analyses reveal that the amorphous coatings in the R and C horizon consist of allophanic material with a molar Al/Si ratio of 0.9, those in the B horizon consist of allophanic material and imogolite with a molar Al/Si ratio of 1.4. The amorphous coatings resulted from precipitation of Al and Si liberated upon weathering of primary minerals in an initial stage of lava weathering. The crystalline coating parts in the B horizon consist of gibbsite and represent the ultimate stage of mineral neoformation. The different coating composition in the soil horizons is the result of different leaching conditions at a macro and micro scale. Care should be taken to compare results obtained at different sampling scales with different analytical methods.

Modeling of 137Cs migration in soils using an 80-year soil archive: role of fertilizers and agricultural amendments

An 80-year soil archive, the 42-plot experimental design at the INRA in Versailles (France), is used here to study long-term contamination by 137Cs atmospheric deposition and the fate of this radioisotope when associated with various agricultural practices: fallow land, KCl, NH4(NO3), superphosphate fertilizers, horse manure and lime amendments. The pertinence of a simple box model, where radiocaesium is supposed to move downward by convectional mechanisms, is checked using samples from control plots which had been neither amended, nor cultivated since 1928. This simple model presents the advantage of depending on only two parameters: alpha, a proportional factor allowing the historical atmospheric 137Cs fluxes to be reconstructed locally, and k, an annual loss coefficient from the plow horizon. Another pseudo-unknown is however necessary to run the model: the shape of historical 137Cs deposition, but this function can be easily computed by merging several curves previously established by other surveys. A loss of approximately 1.5% per year from the plow horizon, combined with appropriate fluxes, provides good concordance between simulated and measured values. In the 0-25cm horizon, the residence half time is found to be approximately 18yr (including both migration and radioactive decay). Migration rate constants are also calculated for some plots receiving continuous long-term agricultural treatments. Comparison with the control plots reveals significant influence of amendments on 137Cs mobility in these soils developed from a unique genoform.

Mineral micro- and nano-variability revealed by combined micromorphology and in situ submicroscopy

Abstract A combination of micromorphology and different in situ sub microscopical techniques, performed on thin sections of soil, saprolite, and rock samples, was used to assess possible relationships between micro- and nano-variability and macro- and micro-environmental conditions of mineral transformation during weathering. Four examples, presented in this study illustrate variability in morphology, chemistry and mineralogy of secondary minerals present in pseudomorphs after primary silicate minerals in volcanic soils present in the humid tropics. The study was based on micromorphological characterization of secondary (clay) minerals, with complementary submicroscopical analysis such as scanning electron microscopy with energy dispersive X-ray analysis (SEM–EDXRA), performed on uncovered thin sections, step scan X-ray diffraction (SSXRD) and transmission electron diffraction (TEM–EDS) carried out either on disturbed powder samples or undisturbed microsamples, obtained by micro-drilling in thin sections. These techniques highlight a very complex mineralogy in pseudomorphs after primary minerals, including secondary minerals that generally are assessed to be formed under contrasting physicochemical conditions (gibbsite and 2:1 phyllosilicates in a pseudomorph after plagioclase; halloysite, kaolinite, smectite and aluminum and iron oxi-hydroxides in pseudomorphs after pyroxenes). The study by TEM of undisturbed microfabrics of secondary minerals in a clay pseudomorph after pyroxene revealed typical distribution patterns, with mineralogical compositions varying over some microns. The combination of techniques gave an improved insight on the complexity and variability of the nature composition and distribution of secondary minerals formed during weathering. It indicates the influence of sequential weathering processes on mineral micro- and nano-variability.

Is metal extraction by Arabidopsis halleri related to exchangeable metal rates in soils amended with different metal-bearing solids?

Metals are associated to various constituents in polluted soils, and their availability is closely related to their chemical speciation. Studies on relations between metal extraction efficiency by hyperaccumulators and location of metals with respect to soil constituents are scarce. In this study. we investigate the relationship between metal extraction by Arabidopsis halleri and the exchangeable metals from substrates amended with various metal-bearing solids collected in the vicinity of a Zn smelter complex. These consisted of fresh and decomposing organic matter, the soil clay fraction, and two types of waste slags. ZnSO4 was also used as metal-bearing solid. Each was mixed with an unpolluted soil to produce two types of substrate, one moderately polluted and the other highly polluted. Total Zinc, Cd, Cu, and Pb were measured in substrates and in roots and shoots of A. halleri. Analysis of 0.01 M CaCl2 exchangeable metals in each substrate was performed before and after plant growth. The results showed different concentrations of exchangeable metals after plant growth, depending on the nature of the metal-bearing solids. In the ZnSO4 soil substrate, the proportion of exchangeable Zn decreased after plant growth, whilst it increased significantly on substrates amended with the two waste slags. For the other substrates, exchangeable Zn was not significantly different before and after plant growth. The same trend was observed for Cd. In the case of Cu, exchangeable rates increased in all substrates. The results were discussed according to the characteristics of the metal-bearing solids and to the metal-uptake strategy of A. halleri.