Distribution of radiocaesium in an Austrian forest stand

Within an Austrian spruce stand, vertical distribution of radiocaesium in soil as well as 137Cs concentration in different forest ecosystem compartments including spruce and surface water were investigated 10 years after the Chernobyl accident. The total 137Cs inventory in the forest was estimated to be 46 kBq m-2 (ref. date: 86-05-01). From the collected data annual input rates via litterfall of 0.48% per year and output rates through waterflows of only 0.02% per year were derived. The results identify the high importance of forest soils as a sink for radiocaesium. The estimated ecological residence half-times turned out to be highest in the organic soil horizons (1-3 years per cm), whereas in mineral horizons the values decrease significantly. As a consequence, soil inventory represents more than 95% of the total, whereas only approximately 3.3% of the 137Cs inventory is stored in the living biomass of spruce trees and a further 0.5% in the phytomass of understorey vegetation.     

Changes in arsenic speciation through a contaminated soil profile: a XAS based study

An impacted soil located near an industrial waste site in the Massif Central near Auzon, France, where arsenical pesticides were manufactured, has been studied in order to determine the speciation (chemical forms) of arsenic as a function of soil depth. Bulk As concentrations range from 8780 mg kg(-1) in the topsoil horizon to 150 mg kg(-1) at 60 cm depth. As ores (orpiment As2S3, realgar AsS, arsenopyrite FeAsS) and former Pb- and Al-arsenate pesticides have been identified by XRD at the site and are suspected to be the sources of As contamination for this soil. As speciation was found to vary with depth, based on XRD, SEM-EDS, EPMA measurements and selective chemical extractions. Based on oxalate extraction, As is mainly associated with amorphous Fe oxides through the soil profile, except in the topsoil horizons where As is hosted by another phase. SEM-EDS and EPMA analyses led to the identification of arseniosiderite (Ca2Fe3+3(AsVO4)3O2.3H2O), a secondary mineral that forms upon oxidation of primary As-bearing minerals like arsenopyrite, in these topsoil horizons. These mineralogical and chemical results were confirmed by synchrotron-based X-ray absorption spectroscopy. XANES spectra of soil samples indicate that As occurs exclusively as As(V), and EXAFS results yield direct evidence of changes in As speciation with depth. Linear combination fits of EXAFS spectra of soil samples with those of various model compounds indicate that As occurs mainly As-bearing Fe(III)-(hydr)oxides (65%) and arseniosiderite (35%) in the topsoil horizon (0-5 cm depth). Similar analyses also revealed that there is very little arseniosiderite below 15 cm depth and that As(V) is associated primarily with amorphous Fe oxides below this depth. This vertical change of As speciation likely reflects a series of chemical reactions downward in the soil profile. Arseniosiderite, formed most likely by oxidation of arsenopyrite, is progressively dissolved and replaced by less soluble As-bearing poorly ordered Fe oxides, which are the main hosts for As in well aerated soils.     

Acidification of forested podzols in North Belgium during the period 1950-2000

Acidification of forest soils in Europe and North America has been an important concern over the last decades. The last area-covering survey of forest soil acidification in Flanders (North Belgium) goes back to 1985 [Ronse A, De Temmerman L, Guns M, De Borger R. Evolution of acidity, organic matter content, and CEC in uncultivated soils of North Belgium during the past 25 years. Soil Sci; 146, (1988), 453-460] and highlighted a significant acidification of the upper layer (0.3-0.4 m) of forested podzols during the period 1950-1985. The present study aimed to assess (1) to what extent further acidification of forested podzols occurred during the period 1985-2000 at different depths and (2) whether the average annual acidification rate accelerated or slowed down between 1985 and 2000 compared to the period 1950-1985. Average soil pH-KCl values of podzols in northern Belgium dropped during the period 1985-2000. This decline extends to a depth of about 50 cm but was most pronounced and significant in the A horizon. In the A(0), A(1) and A(2) horizons, average pH dropped with 0.2, 0.3 and 0.1 units, and in the B(ir) and C horizons with 0.1 units. No change in average pH value occurred in the B(h) horizon. Average annual acidification rate of the A(1) horizon was significantly higher in the period 1985-2000 than in the period 1950-1985. Changes in pH occurred in the entire soil profile during the period 1950/67-1985 likely because sulphate was the major form of acid deposition before 1985. After 1985, acid sulphur deposition decreased with more than 50% in North Belgium. In contrast, ammonium deposition almost doubled between 1950 and 1980, which may explain why soil acidification between 1985 and 2000 has been restricted to the upper soil horizons.     

Migration of radiocesium in two forest soils as obtained from field and column investigations.

Depth profiles of radiocesium were measured in a podsolic parabrown earth of a spruce stand and in a podsol of a pine stand up to 3 years after the Chernobyl accident. At the same sites undisturbed soil columns of 20 cm diameter and 40 cm length were taken, transferred to the laboratory and irrigated intermittently with synthetic rainwater containing initially a known amount of radiocesium. The resulting migration of radiocesium in the columns under unsaturated conditions was determined as a function of time up to 3 years with a scanner technique. The depth profiles of radiocesium observed in the field and in the columns were evaluated with a compartment model to obtain the residence half-times of this radionuclide in the various soil horizons. The field observations yielded a residence half-time in the organic layer of both soils of approximately 4-6 years for Chernobyl-derived cesium, and of 10-15 years for cesium from the global fallout of weapons testing. In the mineral soil (0-5 cm), under spruce the residence time of Chernobyl-derived cesium was 15 years, that of cesium from the global fallout (present in the soil since approximately 30 years) was 50 years. Under pine, the residence time in the mineral soil was 4 years for Chernobyl-derived cesium and 11 years for global fallout cesium. Obviously, in each layer of both soils cesium becomes less available for migration with time. The residence times of radiocesium evaluated from the column experiments were in good agreement with those obtained from the field observations. Due to the comparatively short duration of the column experiments, however, the long-term increase of the residence time of radiocesium in the soil was not yet unambiguously observable.     

Transport of fallout radiocesium in the soil by bioturbation: a random walk model and application to a forest soil with a high abundance of earthworms

It is well known that bioturbation can contribute significantly to the vertical transport of fallout radionuclides in grassland soils. To examine this effect also for a forest soil, activity-depth profiles of Chernobyl-derived 134Cs from a limed plot (soil, hapludalf under spruce) with a high abundance of earthworms (Lumbricus rubellus) in the Olu horizon (thickness=3.5 cm) were evaluated and compared with the corresponding depth profiles from an adjacent control plot. For this purpose, a random-walk based transport model was developed, which considers (i) the presence of an initial activity-depth distribution, (ii) the deposition history of radiocesium at the soil surface, (iii) individual diffusion/dispersion coefficients and convection rates for the different soil horizons, and (iv) mixing by bioturbation within one soil horizon. With this model, the observed 134Cs-depth distribution at the control site (no bioturbation) and at the limed site could be simulated quite satisfactorily. It is shown that the observed, substantial long-term enrichment of 134Cs in the bioturbation horizon can be modeled by an exceptionally effective diffusion process, combined with a partial reflection of the randomly moving particles at the two borders of the bioturbation zone. The present model predicts significantly longer residence times of radiocesium in the organic soil layer of the forest soil than obtained from a first-order compartment model, which does not consider bioturbation explicitly.     

Heavy metal distribution in some French forest soils: evidence for atmospheric contamination

This study is one of very few dealing with the distribution and the origin of heavy metals in French soils from a priori non-polluted forest areas. The abundance of heavy metals measured in these soils decreases as follows: Cr>Zn>Pb>Ni>Cu>Co>Cd. Total concentrations of Pb, Cr and Ni in some soils exceed the European thresholds for non-polluted soils and even the French association of normalization critical values for sludge spreading. The lowest heavy metal contents are observed in acid soils while the highest concentrations are in the calcaric cambisol and in the mollic andosol, which is rather scarce as compared with the other French forest soils. With the exception of the podzol, Cr and Ni concentrations increase with depth in all soil profiles. The distribution pattern of Co, Cu, Zn depends on the soil characteristics. In some acid soils, however, Cu and Zn decrease with depth. Pb and Cd are accumulated in the upper soil horizons. Heavy metals accumulate in deep soil horizons in relation to important clay content in the dystric planosol and stagnic luvisol. The concentration of each heavy metal is always controlled by different parameters (soil pH, iron and aluminum oxide content, clay content, organic matter and cation exchange capacity), which are heavy metal specific. This study highlights the metal-trapping character of andosol and calcaric soil, the weak heavy metal retention in acid soils, the leaching and trapping character in leached clayed soils, and the migration of heavy metals in the podzol. Pb and Cr concentrations indicate a significant enrichment in surface horizons from various soils in areas which receive significant acid atmospheric pollution. Particularly, the highest Pb content is observed in a soil located in the N-NE part of France. Lead isotope ratios measured in the cambic podzol and the calcaric cambisol, exhibit the importance of the anthropogenic sources and particularly the influence of global atmospheric inputs from leaded gasoline compared to regional and local industrial emissions. The anthropogenic Pb contribution is estimated to 83, 30 and 11%, respectively, for surface, intermediate and deep horizons of the cambic podzol located in the northern part of France, and to 68% in surface horizon of the calcaric cambisol located in the Alps.     

Long-term distribution, mobility and plant availability of compost-derived heavy metals in a landfill covering soil

The application of municipal waste compost (MWC) and other organic materials may serve to enhance soil fertility of earthen materials and mine spoils used in land reclamation activities, particularly in the recovery of degraded areas left by exhausted quarries, mines and landfill sites among others. The long-term distribution, mobility and phytoavailability of heavy metals in such anthropogenic soils were studied by collecting soil samples at different depths over a 10 y chronosequence subsequent to amendment of the top layer of a landfill covering soil with a single dose of mechanically-separated MWC. Amendment resulted in a significant enhancement of the metal loadings in the amended topsoils particularly for Cu, Zn and Pb, which were also the predominant metals in the compost utilised. Although metals were predominantly retained in the compost amended soil horizon, with time their vertical distribution resulted in a moderate enrichment of the underlying mineral horizons, not directly influenced by compost amendment. This enrichment generally resulted from the leaching of soluble organo-metal complexes and subsequent adsorption to mineral horizons. However, in the course of the 10-y experimental period, metal concentrations in the underlying horizons generally returned to background concentrations suggesting a potential loss of metals from the soil system. Analysis of the tissues of plants growing spontaneously on the landfill site suggests that metal phytoavailability was limited and generally species-dependent.     

Retention and release of Zn and Cd in spodic horizons as determined by pH(stat) analysis and single extractions

In the northern Campine in Belgium, large areas are contaminated by heavy metals such as Zn and Cd due to the (former) non-ferro metal industry. In the sandy soils, the heavy metal adsorption/attenuation in the spodic horizon represents the main retention mechanism of leached pollutants from the contaminated topsoils. In this study, the pH-dependent behaviour of the elements in these spodic horizons was tested by pH(stat) experiments and compared to sandy loam soils. Extractions with CaCl(2) 0.01 M and EDTA 0.05 M provided a further insight into the binding mechanisms. The results indicate that organic matter is the main factor responsible for the mobility of Cd, Zn and Ca in the spodic horizons. The binding of elements is not very strong, however, and highly dependent on pH. A slight decrease in pH can cause a significant release of metals from the spodic horizons, with up to 60% of Cd and 90% of Zn being released within a 1.5 unit change in pH (starting from the naturally occurring pH). This pH change can happen rapidly in these soils, due to the low buffering capacity, and is realistic given the acidification in Flanders. For the sandy loam soils, a pH decrease of 3 units is needed to release 40% of Cd and 20% of Zn, and the acid neutralization capacity is exhausted more gradually, suggesting that slower buffering mechanisms take place. For the sandy loam soils, Cd retention is mainly governed by organic matter, while for Zn other factors such as the clay minerals also play an important role. Despite the high potential mobility and pH dependence of the heavy metal retention in the spodic horizons, the actual risk for groundwater pollution is limited. For the diffusely contaminated areas, where traditional remediation is not an option, spodic horizons may therefore contribute to a natural attenuation of the soil contamination.     

Lead and zinc in a contaminated pasture at minera,North Wales,and their impact on productivity and organic matter breakdown

Pb and Zn levels were determined in upper and lower soil horizons and vegetation at 14 sites along a 75 m transect in a pasture adjacent to an abandoned Pb/Zn mine spoil in North Wales, and in an uncontaminated control site 500 m from the transect.Water-soluble, 0.1 M calcium chloride, 0.5 M acetic acid, and nitric/perchloric acid extractable levels of soil Zn and Pb were estimated. Depth of accumulated litter and loss on ignition were also measured and estimates of soil humus content were obtained for all transect sites. Dry matter productivity was assessed during Summer 1978 in an exclosure adjacent to the transect.Loosely bound soil Zn and Pb levels increased in upper and lower horizons in soils up to 6 and 8 m respectively from the mine spoil. There was little or no water-extractable lead. Amounts of the more tightly bound forms of both metals declined exponentially from the mine spoil at the transect origin, a pattern of distribution suggesting that erosion by wind is almost exclusively the cause of pollution of adjacent pasture sites.With the exception of water-soluble metals, vegetation Pb and Zn levels were markedly lower than zinc levels. Apart from water-soluble Pb, metal levels in vegetation declined exponentially with distance along the transect.Productivity was very low on the toxic soils adjacent to the spoil but rose to ca. 5000 kg ha^?1 y^?1 10 m from the spoil and remained fairly constant thereafter. Litter was absent on the most and the least toxic soils, reached a peak of 3 cm depth at 6 m and declined steadily thereafter, none being recorded beyond 40 m. Loss on ignition and soil humic matter in upper soil horizons peaked at 387 and 230 mg g^?1 air dried soil 16 m along the transect. Lower soil horizons had maximum values of 224 (loss on ignition) and 100 mg g^?1 air dried soil (soil humic matter) 8 m from the spoil. In both horizons both declined steadily with increasing distance from the spoil, but greater amounts were recorded in all transect soils than in the control site.Sensitivity to metal contamination increased in the sequence; productivity < litter accumulation < soil organic matter breakdown < soil humus decomposition.     

Implications of natural organic matter binding heterogeneity on understanding lead(II) complexation in aquatic systems

Organochlorines (HCH isomers, DDX and individual PCBs) were determined in pine needle litter and upper soil layers of three forest test areas in central Germany. The contents accumulating over a number of years or even decades in the organic surface layer are compared with the levels of new inputs from needle fall as well as with the levels of older inputs in the upper mineral soil layer. Differences in behaviour between the soil horizons are discussed, especially concerning the DDX and HCH groups. With approximately comparable Corg values (approx. 21-24%) the pH value in the range of 4.24-2.90 in the O-horizon of the forest soils exerts a large influence. Hence the A-horizon represents--for p,p'-DDT and gamma-HCH in particular--at pH values of 2.90 a pollutant reservoir which should not be underestimated and which could endanger the rhizosphere and the groundwater. According to PCBs, in the more acidic soils with a pH value <4.0 the lipophilic higher polychlorinated biphenyls were found to be more highly enriched in the humus layer.     

Groundwater derived arsenic in high carbonate wetland soils: sources, sinks, and mobility

Wetlands and organic soils have been recognized as important sinks for arsenic in the environment, yet sources and immobilization mechanisms of As are often unclear. To begin rectifying this deficiency, we investigated As retention and binding mechanisms at a degraded, minerotrophic wetland site in contact with groundwater rich in As and Fe. Arsenic occurred in high dissolved concentrations of up to 467 microg L(-1) in the groundwater, but dropped to values below 10 microg L(-1) towards the surface. The solid phase As content instead was high in the topsoil with up to 3400 mg kg(-1) and decreased with depth to 15 mg kg(-1). A similar pattern was observed with respect to Fe. Amorphous and crystalline iron precipitates were the main sorbents for arsenic in the soil horizons according to results from wet chemical sequential extractions. Arsenic was apparently not associated with inorganic carbon phases, but a substantial portion of up to 31% of As(tot) could be mobilized by dispersion of soil organic matter. Ratios of dissolved As(III)/As(V) decreased from the deeper As(III) dominated groundwater to the As(V) dominated soil porewaters, where As was apparently immobilized in its oxidized form. Concentrations of the organic species DMA and MMA were negligible. According to the results of simple one-dimensional estimates the vertical arsenic transport from the source in the groundwater to the topsoil was slow given an extrapolation of current conditions. These results suggest that As accumulation started before the beginning of drainage in the now degraded peatland soils and the degradation and mass loss of organic matter under oxic conditions caused the very high As concentrations found in the topsoil horizon today.     

Mobile arsenic species in unpolluted and polluted soils

The fate and behaviour of total arsenic (As) and of As species in soils is of concern for the quality of drinking water. To estimate the relevance of organic As species and the mobility of different As species, we evaluated the vertical distribution of organic and inorganic As species in two uncontaminated and two contaminated upland soils. Dimethylarsinic acid (up to 6 ng As g(-1)), trimethylarsine oxide (up to 1.5 ng As g(-1)), 4 unidentified organic As species (up to 3 ng As g(-1)) and arsenobetaine (up to 15 ng As g(-1)), were detected in the forest soils. Arsenobetaine was the dominant organic As species in both unpolluted and polluted forest soils. No organic As species were detected in the contaminated grassland soil. The organic As species may account for up to 30% of the mobile fraction in the unpolluted forest floor, but never exceed 9% in the unpolluted mineral soil. Highest concentrations of organic As species were found in the forest floors. The concentrations of extractable arsenite were highest in the surface horizons of all soils and may represent up to 36% of total extractable As. The concentrations of extractable arsenate were also highest in the Oa layers in the forest soils and decreased steeply in the mineral soil. In conclusion, the investigated forest soils contain a number of organic As species. The organic As species in forest soils seem to result from throughfall and litterfall and are retained mostly in the forest floor. The relative high concentrations of extractable arsenite, one of the most toxic As species, and arsenate in the forest floor point to the risk of their transfer to surface water by superficial flow under heavy rain events.     

137Cs availability for soil to understory transfer in different types of forest ecosystems

A quantitative analysis of 137Cs bioavailability in forest soils in the long term after the Chernobyl NPP accident based on a 3-year (1996-1998) investigation is presented. Five forest sites with different trees, composition and properties of soil were studied to identify factors determining radiocaesium transfer to different understory species. The following parameters were investigated: 137Cs activity concentrations and its speciation in various horizons of forest soil, accumulation of this radionuclide by different species of understory vegetation and distribution of root biomass in the soil profile. It has been shown that one decade after the deposition maximum 137Cs activity in soil of the experimental sites considered is located in different soil layers dependent on moisture regime, characteristics of litter and soil properties. A linear dependence between aggregated transfer factors for different species and groups of species of understory vegetation and exchangeable and available fractions of radiocaesium in soil was found. The vertical distribution of 137Cs activity, percentage of exchangeable radiocaesium in each horizon of litter and soil, as well as distribution of root systems (mycelia) over the soil profile are key factors governing variations in the availability of 137Cs for transfer to all forest understory components.     

Mercury accumulation in upland acid forest ecosystems nearby a coal-fired power-plant in southwest Europe (Galicia, NW Spain)

This study was carried out to determine total Hg concentrations (HgT) in acid soils and main plant species in forest ecosystems located in the river Sor catchment, which is located 20 km to the NE of the biggest coal-fired power-plant in southwestern Europe (Galicia, NW Spain). Mercury enrichment factors and Hg inventories were also determined in the soils, which were regularly sampled between 1992 and 2001. The presence of elemental Hg was estimated by simple thermal desorption at 105 degrees C. The highest HgT concentrations occurred in upper soil layers (O and A horizons) with values up to 300 ng g(-1). HgT decreased with depth, achieving the lowest values in the bottommost horizons (i.e. the soil parent material, <6 ng g(-1)), except in podzolic soils. A similar trend occurred for Hg enrichment factors (HgEF) which showed values from 40 to 76 in topsoils. Upper soil mineral horizons (A or AB) made the largest contribution (>50%) to the HgT inventory despite showing lower concentrations than the organic horizons. The role of vegetation in capturing atmospheric Hg and subsequent deposition to soil agrees with the sequence of HgT in plant material: wood相似文献   

Assessing the fate of antibiotic contaminants in metal contaminated soils four years after cessation of long-term waste water irrigation

Spreading of urban wastewater on agricultural land may lead to concomitant input of organic and inorganic pollutants. Such multiple pollution sites offer unique opportunities to study the fate of both heavy metals and pharmaceuticals. We examined the occurrence and fate of selected antibiotics in sandy-textured soils, sampled four years after cessation of 100 years irrigation with urban wastewater from the Paris agglomeration. Previous studies on heavy metal contamination of these soils guided our sampling strategy. Six antibiotics were studied, including quinolones, with a strong affinity for organic and mineral soil components, and sulfonamides, a group of more mobile molecules. Bulk samples were collected from surface horizons in different irrigation fields, but also in subsurface horizons in two selected profiles. In surface horizons, three quinolones (oxolinic acid, nalidixic acid, and flumequine) were present in eight samples out of nine. Their contents varied spatially, but were well-correlated one to another. Their distributions showed great similarities regarding spatial distribution of total organic carbon and heavy metal contents, consistent with a common origin by wastewater irrigation. Highest concentrations were observed for sampling sites close to irrigation water outlets, reaching 22 μg kg⁻¹ for nalidixic acid. Within soil profiles, the two antibiotic groups demonstrated an opposite behavior: quinolones, found only in surface horizons; sulfamethoxazole, detected in clay-rich subsurface horizons, concomitant with Zn accumulation. Such distribution patterns are consistent with chemical adsorption properties of the two antibiotic groups: immobilization of quinolones in the surface horizons ascribed to strong affinity for organic matter (OM), migration of sulfamethoxazole due to a lower affinity for OM and its interception and retention in electronegative charged clay-rich horizons. Our work suggests that antibiotics may represent a durable contamination of soils, and risks for groundwater contamination, depending on the physicochemical characteristics both of the organic molecules and of soil constituents.     

A snapshot of soil water composition as an indicator of contrasted redox environments in a hedged farmland plot

While soil water composition has long been recognised as being related to soil type (characteristics of the horizons), the influence of structures resulting from agricultural activities (hedges, ditches, wheel ruts, etc) is still under discussion. This work was undertaken to show that a snapshot of spatial variability of the geochemical characteristics of soil water at the scale of a plot can improve our understanding of soil geochemistry in a farmland setting. We selected a 3 hectare hedged plot located on a hillside, limited by a stream and used as pasture where soils have developed in weathered gneiss. The water depth, electrical conductivity, major ions, temperature, pH, dissolved organic carbon (DOC) content, dissolved oxygen content, fluorescence, alkalinity, Fe²⁺, Mn²⁺, NO₂⁻, Fe(III) and F⁻ contents were measured in 62 auger holes randomly drilled on the site. Four sectors were identified in order to describe the distribution of the main geochemical parameters. Electrical conductivity and some major ions, especially sulphate, had larger concentrations near hedges where oxic conditions prevailed. These features were attributed to the impact of the linear anthropogenic network on the circulation of subsurface soil waters and evapo-transpiration and represent sector I. Dissolved Mn was an indicator of well channelled runoff subsurfaces facilitating the circulation of more highly reducing water (sector III), while DOC probably marked areas drained less well, with a prolonged contact time between soil solutions and organic topsoil horizons (sector II). The presence of dissolved Mn and Fe(II) indicates bottomland anoxic conditions (sector IV). It is concluded that a survey of the chemical composition of soil water may be a direct approach to show the influence of permanent structures on current soil properties and dynamics.     

Upward mobilization of 137Cs in surface soils of Chamaecyparis obtusa Sieb. et Zucc. (hinoki) plantation in Japan

The use of 137Cs has recently been adopted to estimate erosion in hinoki plantations in Japan. However, there have been several reports of the upward mobilization of 137Cs in forest humus layers. In this study, the vertical distribution of 137Cs within the soil profile was measured in a hinoki plantation. In order to confirm the upward migration of 137Cs from mineral soil to fresh surface litter and to identify mechanisms of the transfer, changes in 137Cs specific activity in the contents of litterbags were examined in a hinoki plantation. A controlled laboratory experiment was also conducted to assess the effect of microbial activity on the upward migration of 137Cs. As a result, the higher 137Cs activities in the surface organic layer of a hinoki plantation than in fresh litter and the increasing 137Cs total content of litterbags with time demonstrated the upward mobilization of 137Cs from mineral soil to the surface organic layer. Physical movement of soil particles by raindrop splash was considered an important process in 137Cs upward migration. The results of our laboratory experiment indicate an influence from soil microbial activity on the upward mobilization of 137Cs. Thus, upward migration of 137Cs and constant litter removal by runoff may induce 137Cs loss from steep forested catchments and underestimation of the 137Cs inventory leading to the overestimation of soil redistribution rates.     

Simulation of surface water chemistry change resulting from soil acidification: a strontium isotope approach

Soil monoliths were treated with artificial acid rain (pH 3.71). The acidity load was 40 times higher than the present acidity load. Surface water chemistry was modelled on the basis of atmospheric deposition and organic and mineral soil horizon contributions to drainage water. Contributions were calculated using ⁸⁷Sr/⁸⁶Sr ratios measured in Sr sources and drainage water. In the early stages of acidification the contribution of organic horizons to surface water chemistry increased by up to 70%. This increase was accompanied by increases in Ca²⁺, Mg²⁺, K⁺, Na⁺, and dissolved organic carbon (DOC) concentrations. The amount of DOC washed out from mineral horizons was higher than from organic horizons, in contrast to base cations. In the range of acidity loads from 1.4 to 2.1 keq/ha, organic anions were predominant in solution. Further acidification resulted in a reduction of all solute concentrations and an increase in the contributions by deposition and mineral horizons.     

The cumulative effect of three decades of phosphogypsum amendments in reclaimed marsh soils from SW Spain: (226)Ra, (238)U and Cd contents in soils and tomato fruit

Phosphogypsum (PG), a by-product of the phosphate fertiliser industries, has been applied as soil amendment to reduce Na saturation in soils, as in the reclaimed marsh area from SW Spain, where available PG has a typical fingerprint of 710+/-40 Bq kg(-1) of (226)Ra, 165+/-15 Bq kg(-1) of (238)U and 2.8+/-0.4 mg kg(-1) of Cd. This work was focussed on the cumulative effects of PG amendments on the enrichment of these pollutants in cultivated soils and plants (Lycopersicum esculentum Mill L.) from the area studied, where PG has been applied since 1978 at recommended rates of 20-25 Mg ha(-1) every 2-3 years. A field experiment was conducted over three years to compare activity concentrations of (226)Ra ((214)Pb) and (238)U ((234)Th) in non-reclaimed soils, reclaimed soils with no additional PG application, and reclaimed soils with two additional PG applications. A non-significant effect of two PG amendments (in three years) was observed when compared with non-amended reclaimed plots. Nevertheless, a significant (p<0.05) enrichment of (226)Ra was observed in the surface horizon (0-30 cm) of reclaimed plots relative to deeper horizons and also when compared with the surface horizon of non-reclaimed soil (p<0.05), thereby revealing the cumulative effect of three decades of PG applications. Furthermore, the effect of a continuous application of PG was studied by analysing soils and tomato fruits from six commercial farms with different cumulative rates of PG applied. Cadmium concentrations in tomatoes, which were one order of magnitude higher than those found in tomatoes from other areas in South Spain, were positively correlated (r = 0.917) with (226)Ra-concentration in soils, which can be considered an accurate index of the cumulative PG rate of each farm.     

Groundwater contamination by azinphos methyl in the northern Patagonic Region (Argentina)

Approximately 30 groundwater monitoring wells, under a fruit production field, in the Valley of the Neuquen River (Northern Patagonic, Argentina), to which different pesticides have been applied, were sampled eleven times between October 1995 and March 1997. Azinphos methyl was the main pesticide applied and it was detected with the highest frequency in groundwater wells during the period of intensive pesticide application in the Southern Hemisphere. Dimethoate, methidathion, fosmet, cipermethrin, carbaryl, propoxur, carbofuran, benomyl and carbendazim were also detected with lower frequency. The characteristic of the area under study was alkaline soil, with an organic matter content below 2.5% and texture sandy clay loam. The half life of azinphos methyl in soils was 166.2 days in the sun light for horizon A and 194.15 in the dark for horizon B. Leaching of azinphos methyl through the different soil horizons was minimum. On the basis of our lysimeter laboratory data, in which most of the pesticide was adsorbed into the soil column and only small quantities leachate, we inferred that the impact of azinphos methyl on groundwater would be minimal. However, field data indicates that there is a persistence of azinphos methyl in groundwater during the application season.