Pathways of chemical recovery in acidified,metal-contaminated lakes near Sudbury,Ontario, Canada

This paper describes the recovery pathways of two lakes situated near the Coniston nickel-copper smelter. These lakes were exposed to very intense airborne pollution, including SO₂, H₂SO₄, Ni and Cu, during the 60 year operation of the smelter. After the closure of the Coniston smelter in 1972 and the subsequent improvement in air quality, the water quality in both lakes began to improve. Despite their proximity and exposure to similar inputs, the lakes differed both in the rate and magnitude of recovery. This study demonstrates the capacity of lakes to recover from chemical stresses over a very short period. Changes in Cu and Ni concentration could be predicted, while changes in pH, measured as H⁺, could not. The reasons for this discrepancy as well as the processes and lake parameters that control chemical recovery are discussed.     

Recovery of previously acidified lakes near Coniston,Canada following reductions in atmospheric sulphur and metal emissions

The purpose of the present study was to assess the rate of recovery of acidified lakes located near the town of Coniston following an abrupt reduction in atmospheric SO₂ and metal emissions at the Coniston smelter which closed in 1972. The water chemistry of several lakes was studied over a period of 16 yr (1968–1984). In one extremely acidic lake close to the smelter, the pH increased from 4.05 in 1972 to 5.8 in 1984. Conductivity, as well as concentrations of SO₄, Cu, Ni, Co, Mn, and Zn decreased by 60% to 90% in the lake water during the same period. In another initially less acidic lake nearby, the increase in pH was less dramatic, while the decrease in conductivity, SO₄, and some metals was similar to that of the more acidic lake. Local SO₄ deposition decreased approximately 75 % while Cu and Ni deposition decreased by 90% following closure of the Coniston smelter. These results indicate that even severely acidified lakes can improve within a few years following a substantial reduction in atmospheric S emissions; and that in some regions recovery can occur due to reductions in SO₂ emissions even in the absence of concurrent NO_x control.     

Accumulation of atmospherically deposited metals in Wetland soils of Sudbury,Ontario

Concentrations of Cu, Ni, Fe, and Mg in soil/sediment material from 25 wetlands in the Sudbury, Ontario, region decline logarithmically with increasing distance from several ore smelters. Total Cu and Ni reach concentrations potentially toxic to plant life in soil/sediment material near the smelters. Despite random variation in soil/sediment pH and Eh, NH₄OAc extractable Cu, Ni and Fe, and DTPA extractable Cu Ni and Mg show the same pattern as total Cu, Ni, Fe, and Mg. The failure of DTPA extractable Fe to show the same pattern as total Fe may be due to the inadequacy of the DTPA soil test when testing Fe in acid soils. Soil/sediment organic C content increases with distance from the smelters, but is unrelated to pH or Eh.     

Algal microfossils provide high temporal resolution of environmental trends

Sedimentary chrysophytes and diatoms from Baby Lake (Sudbury, Canada) were analyzed to assess lakewater trends associated with (i) the commencement of metal mining and smelting activity at the Coniston Smelter in 1913, and (ii) the closure of the smelter in 1972. We reconstructed several environmental variables (i.e. pH, total [Al], and [Ni]) by applying weighted-averaging regression and calibration models to our paleolimnological data. As a result of emissions from the Coniston Smelter, the lake started to acidify from a high pH of about 6.5 in 1940 to a low pH of 4.2 in 1975. During this period, inferred lakewater [Al] and [Ni] also increased dramatically. Following the closure of the smelter in 1972, inferred lakewater pH and metal concentrations recovered close to pre-industrial levels. The inferred pH recovery corresponds closely to the known lakewater pH recovery (a difference of about 0.4 and 0.6 of a pH unit was observed between measured pH, and chrysophyte and diatominferred pH, respectively). Our study demonstrates that algal microfossils can provide high resolution inferences of past environmental trends. This approach holds great potential for documenting a lake's response to decreased loadings of sulphate and metals, and in helping to establish and implement emission standards.     

Metal uptake in plants from a birch forest area near a copper smelter in Norway

Uptake of Ca, Mg, K, Mn, Fe, Al, Rb, Ph, Cu, Zn, and Cd in vascular plants from a birch forest area near a Cu smelter in northern Norway was investigated. The primary objective was to study metal uptake in plants growing in a strong local acidification gradient. Decreased levels of Mn, Mg, and Ca found in Betula pubescens, Vaccinum myrtillus, and Deschampsia flexuosa near the smelter corresponded to a decrease in base saturation of the soil. This suggests that appreciable soil acidification has taken place. The level of Rb in Vaccinum myrtillus and Sorbus aucuparia increased significantly towards the smelter, probably due to the higher soil acidity. Elevated levels of Cu, Zn, Ph, and Cd in surface soil were found with values up to 2500 mg kg^?1 Cu within 1 km from the smelter. These concentrations decreased significantly with distance, but metal contamination was detectable up to 27 km from the smelter along the prevailing wind direction. A corresponding decrease was detected for Cu in the four plant species analyzed. Elevated levels of Zn, Ph, Fe, and Al were found in some, but not all, species.     

Forms of Cu,Ni, and Zn in soils of sudbury,ontario and the metal concentrations in plants

Forms of Cu, Ni, and Zn in the contaminated soils of the Sudbury mining/smelting district were studied to assess metal mobility and plant availability. Soil, tufted grass (Deschampsia caespitosa (L.) Beauv.), tickle grass (Agrostis scabra Willd.), dwarf birch (Betula pumila L. var. glandulifera Regel) and white birch (Betula paprifera Marsh.) leaf and twig samples were taken from 20 locations around three Cu-Ni smelters. The sampling sites were collected to cover a wide range of soil pH and soil Cu and Ni concentrations. The water-soluble, exchangeable, sodium acetate-soluble, and total concentrations of the metals in the soils were analyzed. The soils were contaminated with Cu and Ni up to 2000 µg g^?1. Zinc concentrations were also elevated in some samples above the normal soil level of 100 µg g^?1. The mobility of Cu and Zn, expressed as the proportion of metals in Fl and F2 forms, increased with soil pH decrease. A strong positive correlation was found between the soil exchangeable (F2) Ni and the soil pH. Concentrations of Cu and Ni in birch twigs showed a good linear relationship with exchangeable forms of the metals in soils. A highly significant correlation was also found between total Ni in soils and the metal content of the twigs. No significant correlation was found between Zn concentrations in the soils and plants. Birch twigs are a good indicator (better than leaves) of Cu and Ni contamination of the Sudbury soils. The mobile forms of Cu and Ni and low pH seem to be the main factors that will control the success of revegetation. Strong variability of the soil metal mobility requires any reclamation effort be site-specific.     

Metals in stocked Lake Trout (Salvelinus namaycush) in lakes near Sudbury,Canada

Muscle tissue from stocked lake trout (Salvelinus namaycush) from lakes near the smelters at Sudbury, Canada was analyzed for Al, Cu, Fe, Hg, Mn, Ni, and Zn. Metals in tissue were not abnormally high compared with fish from lakes farther away from the smelters. Tissue concentrations of Al, Fe, Mn, and Zn declined significantly after stocking. Because metal concentrations were lower in hatchery water than the study lakes, this decline in tissue metal suggests that diet plays a prominent role in the uptake of these metals in lake trout. Only Hg showed evidence of accumulation to levels that might be harmful for human consumption, and then only in a few older, larger trout. In contrast, tissue Mn and Zn were inversely correlated with trout weight. Fluctuations, independent of age, body weight or time of year, were observed in tissue concentrations of Al, Cu, and Zn. Annual cycles, independent of pH and alkalinity were observed in tissue concentrations of Fe, Hg, Mn, and Ni. Bioaccumulation of metal proved to be an unfounded concern for the rehabilitation of fish populations in lakes near Sudbury.     

Mineralogy and Weathering of Smelter-Derived Spherical Particles in Soils: Implications for the Mobility of Ni and Cu in the Surficial Environment

Spherical particles have been sampled from soils and silica-rich rock coatings close to major smelter centers at Coppercliff, Coniston, and Falconbridge in the Sudbury area, Canada. Detailed analyses employing optical microscopy, scanning electron microscopy, transmission electron microscopy, micro-Raman spectroscopy, and M?ssbauer spectroscopy have been conducted to elucidate their nature, origin and potential alteration. The spherical particles are on the nano- to millimeter-size range and are composed principally of magnetite, hematite, Fe-silicates (olivine, pyroxenes), heazlewoodite, bornite, pyrrhotite, spinels (including trevorite and cuprospinel), delafossite, and cuprite or tenorite. The spinels present have variable Cu and Ni contents, whereas delafossite and cuprite are Ni free. Texturally, the spherical particles are composed of a Fe-oxide?CFe-silicate matrix with sulfide inclusions. The matrix displays growth features of a Fe-rich phase that commonly form during rapid cooling and transformation processes within smelter and converter facilities. Examination of weathered spherical particles indicates that some sulfide inclusions have dissolved prior to the alteration of the Fe-silicates and oxides and that the weathering of Fe-silicates occurs simultaneously with the transformation of magnetite into hematite. A higher proportion of Cu vs. Ni in the clay and organic fraction noted in the Sudbury soils is explained by (1) the formation of stronger adsorption complexes between Cu and the corresponding surface species and (2) the preferential release of Cu vs. Ni by smelter-derived particles. The latter mechanism is based on the observations that (a) cuprospinels have higher dissolution rates than Ni spinels, (b) a larger proportion of Cu occurs in the nanometer-size (and thus more soluble) fraction of the emitted particles, and (c) Ni spinels of relatively low solubility form in the alteration zone of heazlewoodite inclusions.     

Spatiotemporal dynamics of the pollution of Al–Fe-humus podzols in the impact zone of a nonferrous metallurgical plant

The dependence of the level of contamination of the upper horizon of Al–Fe-humus podzols (Podzols Rustic) with heavy metals (Ni, Cu) on the distance from the Severonickel smelter (Monchegorsk, Murmansk oblast) was studied on a number of test plots in the medium-aged pine stands. It was found that metal concentrations in the soils could be reasonably approximated by the negative exponential function. In the buffer zone of the smelter, the concentrations of Ni and Cu exceed background values by 8–17 times; in the impact zone, by 50–100 times. The study of the dynamics of acid-soluble forms of Ni and Cu in the organic horizons of podzols on the key plots showed that the boundaries of polluted territory shift towards background regions despite the recent five–eightfold decrease in the emissions. The concentrations of heavy metals in the litter horizons continued to increase in the buffer zone. In the impact zone, their contamination remained at the very high level. Firm bounding of heavy metals in the organic horizon coupled with their continuing aerial input did not allow the beginning of the soil self-purification process, which might last for decades and centuries. Raster electron microscope and X-ray spectral microanalysis showed that particles (>85%) of the ashed matter of organic horizons from the background region, the buffer zone, and the impact zone is mainly represented by various soil-forming minerals and iron oxides (in particular, magnetite). In the samples from the impact zone, about 5% of the mineral particles had the surface morphology and chemical composition typical of dust particles emitted into the air by metal smelters. Most probably, these spherical particles represented magnetite Fe₃O₄ enriched in heavy metals (Cu, Ni).     

comparison of sulphur and heavy metal contents and their regional distribution in humus and moss samples from the vicinity of Nikel and Zapoljarnij,Kola Peninsula,Russia

Terrestrial moss and humus (the O-horizon) are often used separately for determining and monitoring airborne heavy metal pollution. Here, we directly compare the results of analyses of moss and humus samples taken at a density of one site per 300 km² in a 12 000 km² area (45 samples) around the nickel smelter in Nikel, the nickel ore roasting plant in Zapoljarnij, both in Russia, and the iron ore mine and mill near Kirkenes in Norway. The samples were air dried, digested in conc. HNO₃ and analysed for more than 30 elements by ICP-MS and ICP-AES at the laboratory of the Geological Survey of Finland (GTK). For most elements, observed levels and variations are considerably greater in soil than in moss. The main contaminants, Ni and Cu, reach equally high median levels in the moss and soil, but maximum values are far higher in soil. Both media show comparable regional distribution patterns for the heavy metals, but not for sulphur. Cu and Ni can be used to delineate the limits of contamination in the survey area. Both media show the same picture, with a generally very steep gradient from east to west and background levels being reached 30–50 km from the nickel smelter. When moss is used, Cu/Ni, Cu/S and Ni/S ratios can be used to separate input from the smelting and roasting proccesses in Russia. Both media are well suited to use separately to detect airborne pollution in this heavily contaminated area. The moss data are generally easier to interpret, but moss is not available at the most polluted sites. Levels for many elements other than Cu and Ni are close to the detection levels in moss samples, but not in humus samples. Information gathered from both media thus complement each other in a regional multi-element survey.     

Pine Needle Chemistry Near a Large Point SO2 Source in Northern Fennoscandia

Air pollution induced changes in pine needle chemistry were observed at sample sites in the surroundings of the Pechenganikel smelter. Close to the smelter, elevated concentrations of Ni, Cu and S were found (Ni: 0.7–1 mmol/kg, Cu: 0.4–0.5, and S 40–60 mmol/kg). Close to the pollution source, needles were enriched in Ni and Cu by needle age. Correlation and principal component analyses show that changes in the element composition of pine needles depended on air pollution and on natural factors as well. The contribution from air pollution increased with needle age. Besides direct input of pollutants from atmosphere, soil contamination and nutritional disturbance contributed significantly to the observed changes.     

Airborne Pollution in Five Drainage Basins in Eastern Finnmark, Norway: an Evaluation of Overbank Sediments as Sampling Medium for Environmental Studies and Geochemical Mapping

To study whether airborne pollution can be detected in overbank sediments, samples collected from five overbank sediment profiles in eastern Finnmark, Norway, at 1 cm depth intervals, were subjected to chemical analysis and ²¹⁰Pb dating. The studied drainage basins constitute parts of an area polluted by emissions from two Ni-Cu smelters in Russia. In the most polluted catchment area, the surface sample showed a 5-fold higher Ni concentration and a 3-fold higher Cu concentration than the pre-industrial sediments at depth. The increases started at the same time as the smelters. Slight Ni increases were also detected in the neighbouring drainage basin, while no significant concentration change was seen in drainage basins previously shown to be only weakly influenced by the smelter emissions. In the most polluted drainage basin, the increase in Ni accumulation rate did not equal the airborne deposition rate. Selective surface erosion of fine grained particles with adhering airborne Ni has probably caused excess Ni accumulation in both overbank and lake sediments. On the contrary, opening of minerogenic point sources may dilute the pollutant concentrations in the drainage sediments. Thus, dating of the sediment profiles is necessary to determine the airborne pollutant accumulation rates. However, dating is not necessary to map the resultant concentration increase, that may show the increased exposure of humans and biota in contact with the sediments.     

Residual heavy metal concentrations in sludge‐amended coastal plain soils ‐ I. Comparison of extractants

Abstract

The purposes for this research were: to examine the long‐term residual effects of farmland applications of municipal sludges from four treatment technologies on the total and extractable Zn, Cu, Mn, Fe, Pb, Ni and Cd concentrations in Coastal Plain soils; to investigate the effects of sludge sources and rates on the effectiveness of soil extractants to remove the various metals; and to determine correlation coefficients for soil extractable versus plant accumulation in tobacco. The extractants evaluated were Mehlich 1 and 3, and DTPA‐pH 7.3. Composite Ap horizon soil samples and tobacco leaf samples were obtained in 1984 from research plots at two sites in Maryland that were established in 1972 and 1976, respectively, using sludge materials from three wastewater treatment facilities in the Washington, D.C. metropolitan region. Similar application rates were used at both sites.

A wide range in soil pH values was found among treatments at each site. Significant (p ≤ 0.05) increases were observed in total Zn, Cu, Fe, Pb, Ni, and Cd for all sludge sources with increased rates; however, values for total soil Mn exhibited high variability in all cases. The rankings among the extractants varied for some elements depending on the sludge sources. For Zn, the rankings were Mehlich 1 > Mechlich 3 > DTPA‐pH 7.3 across all sources and rates. For Cu, Mehlich 3 > Mehlich 1 > DTPA‐pH 7.3 was found for soils amended with Blue Plains digested (BPD) and Piscataway limeddigested (PLD) sludges but Mehlich 1 ≥ DTPA pH 7.3 > Mehlich 3 for Blue Plains limed compost (BPLC) and Annapolis Fe and heat treated (AFH) sludges. Concerning extractable Mn, Mehlich Mehlich 1 > Mechlich 3 > DTPH pH 7.3 was the order for BPLC and AFH sludges but Mehlich 3 > Mehlich 1 > DTPA‐pH 7.3 was observed for BPD and PLD sludges. The rankings among extractants for Fe (Mehlich 3 > Mehlich 1 > DTPA‐pH7.3), Ni (Mehlich 3 ≥ Mehlich 1 > DTPA‐pH 7.3), Pb (Mehlich 3 > DTPA‐pH 7.3 > Mehlich 1) and Cd (Mehlich 1 > Mehlich 3 > DPTA‐pH7.3) were somewhat similar across all sludge sources. Significant correlation coefficients were obtained for all three extractants for soil extractable vs. plant Zn, Cu, Ni, and Cd at both sites; however, Mehlich 3 was not significant for Mn. Also, neither of the extractants produced significant coefficients for Fe and Pb.     

Long-term irrigation with zinc smelter effluent affects important soil properties and heavy metal content in food crops and soil in Rajasthan,India

Use of wastewater for irrigating agricultural crops is on the rise, particularly in the developing countries. The present study was undertaken to assess the long-term effect of irrigation with zinc smelter effluent on important soil properties including heavy metal status. Metal concentration in the edible parts of the crops grown on smelter effluent-irrigated soils was also measured. For this purpose, the agricultural lands which have been receiving the zinc smelter effluent irrigation for about five decades at Debari, Udaipur, India were selected. The adjacent tubewell water-irrigated fields were selected as reference. Long-term irrigation with smelter effluent resulted into significant buildup of ethylenediaminetetraacetic acid extractable Zn (57.7 fold), Cu (4.51 fold), Fe (3.35 fold), Mn (1.77 fold), Ni (1.20 fold), Pb (45.1 fold), and Cd (79.2 fold) in soils over tubewell water-irrigated fields. Total Zn, Cu, Mn, Ni, Pb, and Cd content in effluent-irrigated soils was also increased by 27.0, 1.60, 1.40, 1.30, 26.2, and 167 fold, respectively. Risk assessment indicated a very high to moderate potential ecological risk due to Cd, Pb, and Zn in soils close to the immediate vicinity of the smelter plant. Cadmium and Pb concentrations in edible parts of almost all the crops grown on effluent-irrigated soils were above the safe limit of CODEX commission. On an average, soil pH dropped by 0.31 units due to smelter effluent irrigation. Smelter effluent irrigation resulted into significant increase in soil organic carbon, electrical conductivity, and CaCO₃ content. On an average, there was decrease in available N (21.0%) and P (20.8%) content in effluent-irrigated soils over the tubewell water-irrigated ones. An increase in available K (102%) and S (26.0 fold) was recorded in effluent-irrigated soils. Long-term irrigation with zinc smelter effluent resulted into reduced microbial activities in soil as evidenced from the level of microbial biomass carbon and dehydrogenase activity. In view of the buildup of heavy metals and subsequent imbalance in essential plant nutrients in smelter effluent-irrigated soils, appropriate remediation-cum-fertilization strategy needs to be adopted for better soil health and plant nutrition.     

Lead Accumulation in Quercus Nigra and Q. Velutina near Smelting Facilities in Alabama,U.S.A.

Lead is very toxic and if ingested cancause severe health problems to both animals andhumans. To determine if lead accumulation in treescould provide a direct pathway to enter the foodchain, oaks (Q. nigra or Q. velutina)growing near two lead smelting facilities in Alabama,U.S.A., were analyzed for lead in acorns, leaves and treecores. A relatively pristine site was used as acontrol. Lead was not detected in acorns collected atany site, and was only found in tree cores from thesites near smelters. Significant increases in treecore lead from 1975–1995 were detected at the activesmelter site. Results were different from the inactivesmelter site; lead increased in tree cores until thesmelter ceased operation, then decreased afterclosing. Soil lead decreased linearly with distancefrom both smelters. In addition, a significantpositive relationship was observed between leaf andsoil lead at the site with the active smelter, andmay be the result of both translocation via treeroots, and foliar absorption of deposited lead ionsinto the leaf structure.     

Metal Enrichment in Zlatna, a Romanian Copper Smelting Town

A preliminary survey of metal concentrations in soil and vegetable samples was undertaken in the town of Zlatna, in western Romania that is dominated by a large copper smelter. One data set (town survey) consisted of soil samples taken from sites both in the centre of the town (near smelter and school grounds) and the outskirts and included those from roadside verges and wooded areas. The second data set consisted of soil samples taken from vegetable garden plots together with an associated sample of spring onion (Allium fistulosum). The aim of this study was to measure levels of the elements Cu, Zn, Pb, Cd and As in soil samples from Zlatna in general, and to assess their uptake into home grown vegetables and thus into the food chain. Concentrations of the elements of interest in soils and vegetables peaked southwest of the smelter and also in soils near the school in the town centre. Concentrations of elements in soils from the town, including those near the school, had the following ranges: Cu, 41–12,000, geometric mean 863 μg/g; Zn, 89–15,600, geometric mean 920 μg/g; Pb, 32–7860, geometric mean 740 μg/g; Cd, BDL–329.5, geometric mean 3.35 μg/g; As, 15–1440 geometric mean 223 μg/g; Thus, the residents of Zlatna are potentially exposed to levels of these elements that are higher than the recommended guideline values. Mean concentrations of the toxic elements in spring onions were: Cu, 10.2; Zn, 95; Pb, 11; Cd, 0.8; As 2.6 μg/g dry weight.     

Fluoride deposition via litterfall in a coastal-plain pine plantation in South Carolina

The concentration of fluoride in needles, its effects on tree defoliation and on decomposition of needles (litter), and its subsequent accumulation in the upper soil horizons were observed in pine plantations near and far from a new aluminum smelter. Pinus taeda and Pinus palustris stands within 0.8 km of the smelter had significantly higher levels of foliar F than a P. taeda stand 1.8 km from the source. Neither temporal patterns nor amounts of needlefall were altered by airborne F from the smelter. In addition, elevated levels of foliar F did not affect the rate of decomposition of pine needles over a period of 6 mo. Soluble F in soil samples increased significantly in the upper 10 cm of the soils at the sites nearest the F source over a period of 7 yr since the start of F emissions.     

Soil decomposer animal community in heavy-metal contaminated coniferous forest with and without liming

Responses of decomposer animals to heavy-metal contamination were studied near a Cu–Ni smelter in Finland. Samples were taken 0.5, 2 and 8 km from the smelter. In addition, plots fertilised with lime were sampled. Decomposer community in coniferous forest soil appeared to be quite resistant to heavy-metals. Only in the vicinity (0.5 km) of the smelter, were numbers of soil animals clearly decreased and their community structure strongly altered as compared to the control site (8 km). At the 2-km site, the community structure was only slightly changed. Most of the collembolan species were still found at the 0.5-km site. High metal sorption capacity of the humus, and heterogeneous distribution of the metals obviously mitigated the effects of metals. Thus, a more diverse and more abundant decomposer community is able to exist in contaminated forest soil than can be expected. Liming affected the decomposer animal community only at the control site where its impact on soil pH was the highest.     

Uptake and bioaccumulation of heavy elements by two earthworm species from a smelter contaminated area in northern Kosovo

As, Cd, Cu, Pb, Sb and Zn concentrations were determined in two earthworm species (Allolobophora rosea and Nicodrilus caliginosus) from a mining and industrial area in northern Kosovo and compared with their contents in the bulk soil and the main soil fractions. Earthworm specimens were collected at fifteen sites located at different distances from a Pb–Zn smelter along a gradient of decreasing contamination. Individuals of A. rosea and N. caliginosus showed similar tissue levels of As, Cd, Cu, Pb, Sb and Zn, suggesting that earthworm species belonging to the same eco-physiological group have a similar propensity to uptake and bioaccumulate heavy elements. Cd, Pb, Sb and Zn concentrations in both earthworm species were positively correlated with the respective total soil contents and generally decreased with distance from the smelter. The bioaccumulation factor (BAF) revealed that Cd and Zn were the only elements bioaccumulated by earthworms. The rank order of BAF values for both species was as follows: Cd > > Zn > > Cu > As = Pb = Sb. The absorption of Cd, Pb, Sb and Zn by earthworms mostly depended on the extractable, reducible and oxidable soil fractions, suggesting that the intestine is likely the most important uptake route. The extractable soil fraction constantly influenced the uptake of these heavy elements, whereas the reducible fraction was important mainly for Pb and Zn. The water soluble fraction had an important role especially for the most mobile heavy elements such as Cd and Zn, suggesting that dermal uptake is not negligible. As a whole, the analytical data indicate that soil fractionation patterns influence the uptake of heavy elements by earthworms, and the extractable fraction is a good predictor of heavy element bioavailability to these invertebrates in soil.     

After effects of metals derived from a highly metal-polluted sludge on maize (Zea mays L.)

High Cd and Ni concentrations in sandy soils were built up in a field experiment, receiving an unusually metal-polluted sewage sludge between 1976 and 1980, at Bordeaux, France. The study evaluates the availability of metals and their after effects on maize at one point in time, the 8th year following termination of sludge application (1988). Plant parts (leaves, stalks, roots, grains) and soil samples were collected from plots which received 0 (Control), 50 (S1) and 300 Mg sludge DW ha^?1 (S2) as cumulative inputs. Dry-matter yield, plant metal concentrations, total, and extractable metals in soils were determined. Metal inputs resulted in a marked increase in total and extractable metals in soils, except for extractable Mn and Cu with either 0.1 N Ca(NO₃)₂ or 0.1 N CaCl₂. Total metal contents in the metal-loaded topsoils (0–20 cm depth) were very often lower, especially for Cd, Zn, and Ni, than the expected values. Explanation was partly given by the increases of metal contents below the plow layer, particularly for Cd at the low metal loading rate, and for Cd, Ni, and Cu at the high one (Gomez et al., 1992). In a control plot beside a highly metal- polluted plot, Cd, Zn, and Ni concentration in soil increased whereas the concentration of other metals was unchanged; lateral movement, especially with soil water, is plausible. Yield of leaves for plants from the S2 plot was reduced by 27%, but no toxicity symptoms developed on shoots. Yields of stalks for plants in both sludge-treated plots numerically were less than the controls but the decrease was not statistically significant. Cd and Ni concentrations increased in all plant parts with metal loading rate while Mn concentrations decreased. Leaf Cd concentration in plants from sludge-treated plots (i.e. 44 and 69 mg Cd kg^?1 DM for S1 and S2) was above its upper critical level (i.e. dry matter yield reduced by 10%: 25μg Cd g^?1 DM in corn leaves, Macnicol and Beckett, 1985). Yield reduction at the high metal-loading rate was probably due to 3 main factors: Mn deficiency in leaves, the accumulation of Ni especially in roots, and the increase of Cd in leaves. The amount of metal taken up by plants from the control plot ranked in the following order (mole ha^?1): Fe(22)? Mn(7)>Zn (5.6)?Cu (0.7), Ni (0.6), Cd (0.4). For sludge-treated plots, the order was (values for S1 and S2 in mole ha ^?1): Fe (16, 15)>Zn (7.9, 7.7)>Ni (4.3, 4.7)>Cd (1.9, 2.1)>Cu (1.0,1.2), Mn (1.5, 1.1). Zn and Cd had the greatest offtake percent from the soil to the above ground plant parts. Cd or Ni uptake by maize were correlated with extractable metals by unbuffered salts (i.e. 0.1 N Ca(NO₃)₂ and 0.1 N CaCl₂). It is concluded that part of the sludge-borne Cd and Ni can remain bioavailable in this sandy soil for a long period of time (e.g. 8 yr) after the termination of metal-polluted sludge application.