Of the necessity of knowledge of the natural pedo-geochemical background content in the evaluation of the contamination of soils by trace elements

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.     

Differences in Cd and Zn bioaccumulation for the flood-tolerant Salix cinerea rooting in seasonally flooded contaminated sediments

Several authors suggest that a hydrological regime aiming at wetland creation is a potential management option that favours reducing bioavailability for metal-contaminated sites. The hydrological conditions on a site constitute one of the many factors that may affect the availability of potentially toxic trace metals for uptake by plants. Bioavailability of Cd, Mn and Zn on a contaminated dredged sediment landfill (DSL) with variable duration of submersion was evaluated by measuring metal concentrations in the wetland plant species Salix cinerea in field conditions. Longer submersion periods in the field caused lower Cd and Zn concentrations in the leaves in the first weeks of the growing season. Foliar Cd and Zn concentrations at the end of the growing season were highest on the initially flooded plot that emerged early in the growing season. Foliar Zn concentrations were also high at a sandy-textured oxic plot with low soil metal concentrations. Zn uptake in the leaves was markedly slower than Cd uptake for trees growing on soils with prolonged waterlogging during the growing season, pointing at a different availability. Zn availability was lowest when soil was submerged, but metal transfer from stems and twigs to leaves may mask the lower availability of Cd in submerged soils. Especially for Cd, a transfer effect from one growing season to the next season was observed: oxic conditions at the end of the previous growing season seem to determine at least partly the foliar concentrations for S. cinerea through this metal transfer mechanism. Duration of the submersion period is a key factor for bioavailability inasmuch as initially submerged soils emerging only in the second half of the growing season resulted in elevated Cd and Zn foliar concentrations at that time.     

Heavy metal pollution of soils affected by the Guadiamar toxic flood

Total heavy metal concentrations were determined in soil samples of seven selected areas along the Guadiamar river valley affected by the toxic flood, after removal of the deposited sludge. Mean total concentrations of nine elements (As, Au, Bi, Cd, Cu, Pb, Sb, Tl and Zn) out of the 23 (As, Au, Ba, Be, Bi, Cd, Co, Cr, Cu, In, Mn, Mo, Ni, Pb, Sb, Sc, Sn, Th, Tl, U, V, Y and Zn) analysed were higher in sludge-covered soils than in unaffected soils. Mean values of total As, Au, Pb, Sb, Tl and Zn in sludge-affected soils were higher than the upper limits for normal soils world-wide. Mean concentrations of Bi, Cd and Cu were within these ranges, although some individual values exceeded the upper limits. In all sampling areas, severe heavy metal pollution was observed in the superficial layers (0-20 cm) of most of the affected soils, which decreased downward in the soil profile. Generally, in soils with more than 25% of clay, concentration of heavy metals below the 20-cm depth decreased to values close to those of the background level of the Guadiamar valley soils, while in coarser soils, heavy metal pollution penetrated below this depth, being noticeable down to a depth of at least 50-80 cm.     

Environmental contamination and seasonal variation of metals in soils,plants and waters in the paddy fields around a PbZn mine in Korea

The objective of this study is to investigate the extent and degree of heavy metal contamination of paddy fields influenced by metalliferous mining activity. Paddy soils, rice plants and irrigation waters were sampled along six traverse lines in the vicinity of the mine and nearby control site. Soil samples were taken 30, 80 and 150 days after rice transplanting, to study seasonal variation of their chemical properties and heavy metal concentrations. Sampling of rice plants and irrigation waters was also undertaken with seasons. The analysis of the samples were carried out using ICP-AES for 25 elements including Cd, Cu, Pb and Zn. Physical and chemical properties of soils (pH, loss-on-ignition, cation exchange capacity and texture) and waters (pH, Eh and temperature) were also measured. The properties of soils were similar to the average Korean soils, with the exception of some samples taken in the vicinity of the mine. Concentrations of Cd, Cu, Pb and Zn in paddy soils, rice plants and irrigation waters sampled in the immediate vicinity of the mine were relatively high due to the seepage of metals from mining dump sites. Although there was variation between sampling sites, soil pH values under reducing conditions were on average higher than those under oxidising conditions. Relatively low content of organic matter and low cation exchange capacity of soils were found at 80 days after rice transplanting (P < 0.05). No seasonal variations in metal concentrations were found in paddy soils throughout the period of the rice growing, in which soils ranged from flooded reducing conditions through most of the growing season to drained oxidising conditions before and at harvest. Relatively high metal concentrations were found in the rice stalks and leaves under oxidising conditions. The sequential extraction analysis of selected soil samples confirmed that high proportions of exchangeable fractions of the metals were found under oxidising conditions. It was shown that Cd and Zn concentrations in rice leaves and stalks and rice grain increased with increasing metal concentrations in paddy soils to a greater extent than for Cu and Pb. This difference in uptake is in agreement with the greater proportions of Cd and Zn, compared with Cu and Pb, in the exchangeable soil fraction extracted with MgCl₂. Average daily intake from locally grown rice by the residents was estimated to be 121 μg Cd and 126 μg Pb. Thus, long-term metal exposure by regular consumption of the rice poses potential health problems to residents in the vicinity of the mine, although no adverse health effects have as yet been observed.     

Cadmium solubility in paddy soils: effects of soil oxidation, metal sulfides and competitive ions

Cadmium (Cd) is a non-essential element for human nutrition and is an agricultural soil contaminant. Cadmium solubility in paddy soils affects Cd accumulation in the grain of rice. This is a human health risk, exacerbated by the fact that rice grains are deficient in iron (Fe) and zinc (Zn) for human nutrition. To find ways of limiting this potential risk, we investigated factors influencing Cd solubility relative to Fe and Zn during pre-harvest drainage of paddy soils, in which soil oxidation is accompanied by the grain-filling stage of rice growth. This was simulated in temperature-controlled “reaction cell” experiments by first excluding oxygen to incubate soil suspensions anaerobically, then inducing aerobic conditions. In treatments without sulfur addition, the ratios of Cd:Fe and Cd:Zn in solution increased during the aerobic phase while Cd concentrations were unaffected and the Fe and Zn concentrations decreased. However, in treatments with added sulfur (as sulfate), up to 34 % of sulfur (S) was precipitated as sulfide minerals during the anaerobic phase and the Cd:Fe and Cd:Zn ratios in solution during the aerobic phase were lower than for treatments without S addition. When S was added, Cd solubility decreased whereas Fe and Zn were unaffected. When soil was spiked with Zn the Cd:Zn ratio was lower in solution during the aerobic phase, due to higher Zn concentrations. Decreased Cd:Fe and Cd:Zn ratios during the grain filling stage could potentially limit Cd enrichment in paddy rice grain due to competitive ion effects for root uptake.     

Remediation measures and displacement of pollutants in soils affected by the spill of a pyrite mine

The soils affected by the spill of a pyrite mine were analysed in 100 sampling points at three depths (0-10, 10-30, and 30-50 cm) in 1998 (after the tailings were removed), 1999 (after the cleaning of the highly contaminated areas), and 2004 (after the tilling of the upper 20-25 cm). The comparative study reveals that the removal of the tailings left a heterogeneous distribution pattern of the contaminants, with highly polluted spots alternating with less contaminated areas. The cleanup did not substantially lower the concentration in the highly polluted soils, and the spread of the pollutants increased the concentration in As and Pb in the uppermost 10 cm of 60% of the soils, while the Zn and Cd concentrations increased in only 30% of the soils. Given the high concentration of pollutants in the topsoil (especially As), the tilling of the upper 20-25 cm, despite reducing the average concentration of pollutants in the uppermost 10 cm, did not substantially lower the percentage of soils that exceeded the concentration of 40 mg As kg^− 1 dry soil and almost doubled the percentage of soils that surpassed this concentration between 10 and 30 cm. Meanwhile, the displacement of Zn and Cd within the soil supported the reduction in the percentage of soils that in the upper 10 cm exceeded the reference concentrations of these elements (900 mg Zn kg^− 1 dry soil and 2 mg Cd kg^− 1 dry soil), and the percentage of soils exceeding these concentrations between 10 and 50 cm in depth did not increase. Six years after the spill and at the end of all remediation measures, the intervention levels defined by the Environmental Agency of the Regional Government of Andalusia for natural parks were exceeded in the uppermost 10 cm in 35% of the soils.     

Monitoring metals in the vicinity of a municipal waste incinerator: temporal variation in soils and vegetation

The aim of this study was to determine the temporal variation in the concentrations of arsenic (As), beryllium (Be), cadmium (Cd), chromium (Cr), manganese (Mn), mercury (Hg), nickel (Ni), lead (Pb), tin (Sn), thallium (Tl), vanadium (V) and zinc (Zn) in soil and vegetation near an old municipal solid waste incinerator (MSWI). In October 1997, 24 soil and 24 herbage samples were collected at the same sampling points in which samples were also taken in October 1996. With the exception of an increase in the levels of Be and Ni, no significant differences in soils between both surveys were found; only Cr and V (decreases) and Hg (increase) showed significant variations in herbage samples during the last year. The concentrations of most elements in soil and vegetation samples collected near the MSWI are within the ranges previously reported for soil and vegetation in the vicinity of MSWIs.     

Metal contamination of soils and crops affected by the Chenzhou lead/zinc mine spill (Hunan, China)

In 1985, the collapse of the tailing dam in Chenzhou lead/zinc mine (Hunan, southern China) led to the spread of mining waste spills on the farmland along the Dong River. After the accident, an urgent soil cleaning up was carried out in some places. Seventeen years later, cereal (rice, maize, and sorghum), pulses (soybean, Adzuki bean, mung bean and peanut), vegetables (ipomoea, capsicum, taro and string bean) and the rooted soils were sampled at four sites: (1) the mining area (SZY), (2) the area still covered with the mining tailing spills (GYB), (3) the cleaned area from mining tailing spills (JTC), and (4) a background site (REF). Metal concentrations in the crops and soils were analyzed to evaluate the long-term effects of the spilled waste on the soil and the potential human exposure through food chains. The results showed that the physical-chemical properties of the soils obviously changed due to the different farming styles used by each individual farmer. Leaching effects and plant extraction of metals from some soils were quite weak. Certain soils were still heavily polluted with As, Cd, Zn, Pb and Cu. The contamination levels were in the order of GYB>SZY>JTC showing that the clean-up treatment was effective. The maximum allowable concentration (MAC) levels for Chinese agricultural soils were still highly exceeded, particularly for As and Cd (followed by Zn, Pb and Cu), with mean concentrations of 709 and 7.6 mg kg(-1), respectively. These concentrations exceed the MAC levels by 24 times for As and 13 times for Cd at GYB. Generally, the edible leaves or stems of crops were more heavily contaminated than seeds or fruits. Ipomoea was the most severely contaminated crop. The concentrations of Cd and Pb were 3.30 and 76.9 mg kg(-1) in ipomoea leaves at GYB, which exceeded the maximum permit levels (0.5 mg kg(-1) for Cd and 9 mg kg(-1) for Pb) by 6.6 and 8.5 times, respectively. Taro (+skin) could accumulate high concentrations of Zn and Cd in the edible stem, and rice and capsicum had high Cd concentration in the edible parts. However, the toxic element concentrations in maize, sorghum, Adzuki bean, soybean and mung bean remained lower than the threshold levels. The bio-accumulation factors (BAFs) of crops were in the order: Cd>Zn>Cu>Pb>As. BAF was typically lower in the edible seeds or fruits than in stems and leaves. The accumulation effect strongly depends on the crop's physiological properties, the mobility, of the metals, and the availability of metals in soils but not entirely on the total element concentrations in the soils. Even so, the estimated daily intake amount of Cu, Zn, Cd, and Pb from the crops grown in the affected three sites and arsenic at SZY and GYB exceeded the RDA (Recommended dietary allowance) levels. Subsequently, the crops grown in Chenzhou Pb/Zn mine waste affected area might have a hazardous effect on the consumer's health. This area still needs effective measures to cure the As, Cd, Pb, Zn and Cu contamination.     

A soil sampling strategy for mapping trace element concentrations in a test area

A sampling strategy, based on previous knowledge of a test area, was compared with a Reference Sampling in the frame of the EU-funded CEEM project. The aim was a comparison of sampling strategies for the drafting of concentration maps for a set of trace elements (Cd, Pb, Cu and Zn), with three-dimension information that can be used for risk assessment. The main constraint was that only 15 soil samples were to be analysed. The test area (in Dornach, Switzerland) included different soil types and land uses (forest, arable land and permanent grasslands). The sampling strategy proposed defined strata on the basis of land use, then applying a systematic regular sampling within each stratum. A composite sample was formed from each individual sample. In forests, H and Ah horizons were taken separately. In arable lands, a depth within the ploughed layer (0-15 cm) was analysed. In grasslands, samples were taken at two depths (0-10 and 10-20 cm) to provide information on the vertical variability. The comparison of the results obtained with those derived from the Reference Sampling allowed us to estimate if the information obtained from the proposed sampling strategy was sufficiently representative for an assessment of the level of elements considered. It was concluded that recommendations on sampling strategy depend on the interaction pattern of the element. In this case, for mobile trace elements, such as Cd, the information derived from sampling of two soil layers was not as important as that for the rest of metals studied that accumulated in the upper layer. If the H horizons in forests was not considered this led to unreliable predictions of the concentration levels, since the concentrations in H and Ah horizons differed irrespective of whether they were expressed in mg kg(-1) (the H horizon was enriched in those trace elements, except for Cd) and in mg m(-2) (the low bulk density of the H horizon led to a lower trace element level than in Ah horizon). Finally, in undisturbed systems such as grasslands, sampling 0-10 cm instead of 0-20 cm is recommended to prevent dilution of the concentration of trace elements.     

Assessment of nutritional status and trace element contamination of holm oak woodlands through analyses of leaves and surrounding soils

The nutritional status and trace element contamination of holm oak woodlands in Vesuvius National Park were assessed by analyses of Quercus ilex L. leaves and surrounding soils. The concentrations of Cd, Cr, Cu, Fe, K, Mg, Mn, Na, Ni, Pb, V and Zn were measured in 1-year-old leaves, and in the soils at 0-5 and 15-20 cm depths. The potentially available concentrations were also measured for the soils. The leaf element concentrations were similar to the Q. ilex chemical fingerprint, thus indicating a good nutritional status and the absence of short-term trace element depositions. Total K and V were more abundant in the deep soil layers than in the surface ones, whereas Cd and Pb showed higher values in the surface soils. This suggests that long-term soil accumulations of Cd and Pb are due to atmospheric input. The soil availabilities of Cd, Pb and Zn were high, and Cr availability was very low. A correlation between the available concentrations in the deep soil layers and leaf concentrations was found only for Zn.     

Reproducibility of the BCR sequential extraction procedure in a long-term study of the association of heavy metals with soil components in an upland catchment in Scotland

Humic iron podzol soils from three different plots at the Glensaugh Research Station, Aberdeenshire have been sampled on an annual basis since 1990 and analysed using both total digestion and the original BCR sequential extraction procedure. Particular care was required during the oxidation of these organic soils to prevent loss of material. The residue from the sequential extraction was analysed so that the values for total concentration derived from the total digestion and from the sum of the concentrations in the fractions of the extraction procedure could be compared. The comparison was good for all three soils indicating that not only did the sequential extraction give good recovery but that this was reproducible over a period of several years. The proportion of metals extractable at each step remained relatively constant thereby demonstrating the reproducibility of the procedure and the stability of the metals in the soils over the time scale of the sampling used. Whereas the total concentrations of Cr, Cu and Ni were highest in the soil from a roadside plot, this was not the case for Cd, Pb and Zn. In the case of Pb, concentrations in soils (0-25-cm depth) well away from the road were over 100 mg/kg and well above the expected background level. The distribution of metals between each of the extracted fractions varied not only between each metal but also between each of the three soils indicating that both metal and soil influenced the measured distribution. The distribution of Pb in the roadside soil was different from those in the other two soils and over 10% was extracted in the first, acetic acid soluble, fraction.     

Inputs of trace elements in agricultural soils via phosphate fertilizers in European countries

Mineral fertilizers are sources of diffuse metal enrichment of agricultural soils. A survey of phosphate fertilizers (blends or raw) sold on the European market was undertaken to quantify metal input via fertilizers in European agricultural soils. A total of 196 phosphate fertilizer samples from 12 European countries were analyzed for trace metals. Analytical quality was controlled with a certified rock phosphate sample. The average metal concentrations (mg kg(-1)) in the fertilizers were 14.8 (Ni), 7.4 (Cd), 166 (Zn), 2.9 (Pb), 7.6 (As), and 89.5 (Cr). The trace metal concentrations were positively correlated with the P concentrations confirming that the rock phosphate was the major source of these elements. Lowest metal concentrations were generally found in samples from Scandinavian countries. At average P use, the trace metal input via fertilizers was similar to or even larger than the metal input via atmospheric deposition in European agricultural soils for Cd, As, and Cr, whereas the reverse was true for Zn, Ni, and Pb. The input of Cd in European agricultural soils has decreased from previously estimated values and the soil Cd mass balance was close to steady state on an average basis.     

Evaluation of metal concentrations in edible vegetables grown in compost amended soil

Agricultural uses of compost usually have a positive effect on the yield of vegetable crops for human consumption. However, compost that contains heavy metals can transfer these components to soils and plants. To evaluate the contamination levels of metals in soil, compost, and edible vegetables, the Mn, Zn, Pb, Cd, Cu, and Ni total contents were measured. Metal availability in soils, as well as other variables – the pH, CEC (cation exchange capacity), total nitrogen, organic carbon, particle size distribution and mineralogy of the clay fraction – were examined in the soil samples. The analysed compost samples were produced from urban solid waste, cattle manure, and edible vegetable and tree pruning residues. The values of pH, CEC, total nitrogen, organic matter, exchangeable hydrogen and carboxylic groups were measured in the compost samples. Of the six metals examined in the soils, in general, Mn and Zn attained the highest concentrations, followed by Cu. Relatively high Mn, Zn, Cu, Cd and Pb concentrations were found in the soils. Metal concentrations extracted with DTPA were below the critical levels in soils, i.e. the levels above which toxicity is likely. In general, Zn, Pb, Cd, Cu and Ni concentrations in compost were lower than those reported by other workers, while Mn levels were within the range for this metal in compost. The results showed that there was an effect of the vegetable type (p < 0.01) for all the parameters examined. High Pb concentrations were found in lettuce and chive as compared with the tolerance limit for this metal in fresh vegetables in Brazil. Cadmium concentrations were also enhanced in the fresh vegetables compared with the typical concentrations of metals in plants. Zinc, Cu, Cd, and Ni concentrations were lower than the tolerance limits established for foods by the Brazilian legislation.     

Heavy metals in wheat grain: assessment of potential health risk for inhabitants in Kunshan, China

Heavy metals (HMs) may cause deleterious effects on human health due to the ingestion of food grain grown in contaminated soils. Concentrations of HMs (Hg, As, Cr, Cu, Ni, Pb, Zn and Cd) in wheat grains were investigated in different areas of a developed industry city in Southeast China (Kunshan city), and their potential risk to health of inhabitants was estimated. The results showed that concentrations of HMs in the top soil (0-15 cm) were in this order: Zn>Cr>Ni>Pb>Cu>As>Hg>Cd. The Zn, Cr, Ni Cd and Hg concentrations of several soil samples exceeded the permissible limits of China standard. In addition, concentrations of HMs in wheat grain decreased in the order of Zn>Cu>Pb>Cr>Ni>Cd>As>Hg. There were 1, 6 and 10 wheat samples whose Zn, Pb and Cd concentrations were above the permissible limits of China standard, respectively. In relation to non-carcinogenic risks, Hazard Quotient (HQ) of individual metal presented values inside the safe interval. However, health risk due to the added effects of eight HMs was significant for rural children and rural adults, but not for urban adults and urban children. HQ (individual risk) and HI (Hazard Index of aggregate risk) to different inhabitants due to HMs followed the same sequence of: country children>country adults>urban children>urban adults. Amongst the HMs, potential health hazards due to As, Cu, Cd and Pb were great, and that due to Cr was the minimum. It was suggested to pay more attention on the potential added threat of HMs to the health of country inhabitants (both children and adults) through consumption of wheat in Kunshan.     

重金属污染场地原位固化稳定化修复试验研究

以甘肃省某铅锌冶炼厂高浓度铅(Pb)、锌(Zn)和镉(Cd)复合污染场地为对象,开展新型固化剂SPC原位固化稳定化(S/S)技术修复现场试验研究。进行含水率、p H值、浸出毒性和重金属形态分布和动力锥贯入试验,以考察修复前后污染土理化、浸出及强度特性变化,评价SPC原位S/S技术的修复效果,并初步探讨相关机制。试验结果表明SPC原位S/S技术能显著降低污染土含水率,提高其p H值;修复后Pb,Zn和Cd浸出浓度值显著降低,且均能满足相应限值要求;SPC修复能够有效降低土中重金属弱酸提取态含量,并将其转化为残渣态,同时显著提高土层贯入阻力值。提高SPC掺量可进一步增强其对污染土的修复效果。     

Distribution of Cd, Zn, Cu and Fe among selected tissues of the earthworm (Allolobophora caliginosa) and Eurasian woodcock (Scolopax rusticola)

We have measured the concentrations of heavy metals in soils, earthworms and tissues of woodcocks in Quaderna Valley, northern Italy. The soil concentration of metals analysed in this research is consistent with data reported by other authors for uncontaminated or slightly contaminated soils. In earthworms, metals were mostly accumulated in the encapsulating chloragogenous tissue; the positive correlation between Cu concentration in the soil and in earthworms is noteworthy. Heavy metal distribution in the tissues of woodcock showed that Cd accumulation in the kidney was linked to the diet. Cu and Fe were preferentially concentrated in the liver and Zn in the testis. Kidney Cd and Zn concentrations were higher in adults than in juveniles. In addition, a main kidney metallothionein isoform, containing Cd and Zn, was isolated. In the kidney, Cd levels were linearly correlated with the concentration of metallothionein. Of the investigated metals, Cd raises the greatest concern, due to the increasing soil contamination by human activities.     

Cadmium and zinc in soil solution extracts following the application of phosphate fertilizers

This study investigated the solubility of cadmium and zinc in soils after the application of phosphate fertilizers containing those two metals. The solubility of cadmium and zinc was assessed by measuring their concentration in soil water extracts. Three monoammonium phosphate fertilizers containing various amounts of metals were applied on cultivated fields for 3 years at three different rates. In order to investigate the effects of long-term applications of fertilizers on the solubility of Cd and Zn, a similar design was used to apply contaminated fertilizers to soils in a laboratory experiment using a single fertilizer addition equivalent to 15 years of application. Phosphate fertilizers increased the concentration of Cd in soil extracts compared to control in 87% and 80% of the treatments in field and laboratory experiments respectively. Both increasing the rate of application and using fertilizer containing more Cd lead to higher Cd concentrations in extracts for the field and the laboratory experiments. The addition of the equivalent of 15 years of fertilizer application in the laboratory results in higher Cd concentration in extracts compared to the field experiment. For Zn, the fertilizer treatments enhanced the metal solution concentration in 83% of field treatments, but no significant correlations could be found between Zn inputs and its concentration in solution. In the laboratory, fertilizer additions increase the Zn concentrations in 53% of the treatments and decrease it in most of the other treatments. The decrease in Zn concentrations in the laboratory trial is attributed to the higher phosphate concentrations in the soil solution; which is presumed to have contributed to the precipitation of Zn-phosphates. For both trials, the metal concentrations in soil extracts cannot be related to the Zn concentration in the fertilizer or the rate of application. The high Zn to Cd ratio is presumably responsible for the Cd increase in the soil extracts due to competitive displacement by Zn. Finally, the observed acidification of soils with fertilizer application will also contribute to metal solubilisation.     

Effect of alkaline pH and associated Zn on the concentration and total uptake of Cd by lettuce: comparison with predictions from the CLEA model

An eight-fold underestimate of the potential Cd exposure to humans via ingestion of lettuce grown in moderately alkaline soil has been measured experimentally. Current models of Cd uptake by leafy vegetables, which are used in risk assessment (e.g. CLEA in UK) predict higher concentration factors in acid than in alkaline soils. Experimental evidence shows that Cd uptake, although it decreases with increasing pH from acid to neutral soils, increases again in alkaline soils, confirming recent finding from other workers. The concentration of Zn in the soil also significantly affects the uptake of Cd, although this is not included in the current prediction models either. The effect of Zn on the uptake of Cd by plants is greater in slightly alkaline soils (pH 7.7) than in slightly acidic or neutral soils. High concentrations of Zn in soil (1000 mg/kg), which are often associated with elevated Cd levels, further increase the Cd concentration factor to values 12 times higher than that predicted by the CLEA model. This is due in part to the effect of the high soil Zn on reducing the above-ground biomass of the plants.     

Use of sorption and extraction tests to predict the dynamics of the interaction of trace elements in agricultural soils contaminated by a mine tailing accident

Over 2000 ha of agricultural soils were contaminated by a pyritic sludge and acidic waste waters coming from a spill from a mining exploitation. The affected soils were acidic with sandy-loam texture (SL), loamy with neutral pH (L), and calcareous, saline, with clay texture (Cs). The Cs soils were contaminated only with acidic waste waters. Sorption and extraction tests were applied to examine the medium-term dynamics of the interaction of trace elements (As, Cd, Cu, Pb and Zn) in the soils. The solid-soil solution distribution coefficient (KD) was determined in soil samples taken 3 months (initial stage, 3M samples) and then nearly 2 years (final stage, 21M samples) after the accident. Distribution coefficient values ranged from the lowest values in the SL samples (from 0.2 l kg(-1) for Cd and Zn to 25 l kg(-1) for As) to higher values in the L and Cs soils. Lead and As had the highest KD in all soils (over 10(5) l kg(-1) in the L soils). No clear dynamics pattern could be derived from these data because of the low heavy metal concentrations in the soil solution. As a complementary approach, four single extractions (0.01 and 1 mol l(-1) CaCl2; 0.05 mol l(-1) EDTA; 0.43 mol l(-1) CH3COOH) were applied to soil and sludge samples. Samples derived from submitting field 3M samples to drying-wetting (DW) cycles were included to define a complete laboratory approach to predict field dynamics. Results from extraction tests indicated that changes of the trace element interaction over time depended on the soil pH and on the source of contamination. For those soils affected only by the acidic waste waters, where an increase in fixation occurred, natural processes such as diffusion controlled dynamics. For those soils contaminated by a mixed source, the dynamics of the interaction was the resultant process of the combination of the natural attenuation and the oxidation of the pyritic sludge. This latter process led to an increase in the remobilization for those elements associated with soluble secondary minerals (Cd and Zn) and to an increase in the fixation for those elements coprecipitating with insoluble secondary minerals (Pb and As). Drying-wetting cycles were useful to predict the dynamics in the field at month-year scale. The CH3COOH was recommended as the best test among those studied here to derive conclusions about dynamics pattern because it provided significant desorption yields in most scenarios. Acidic soils with sludge contamination represented the scenarios with the highest risk, while calcareous soils better attenuated contamination. In a longer time scale, the depletion of calcareous components needs to be controlled.