Geochemical and Pb isotopic evidence for sources and dispersal of metal contamination in stream sediments from the mining and smelting district of Príbram, Czech Republic

Stream sediments from the mining and smelting district of Príbram, Czech Republic, were studied to determine the degree, sources and dispersal of metal contamination using a combination of bulk metal and mineralogical determinations, sequential extractions and Pb isotopic analyses. The highest metal concentrations were found 3-4 km downstream from the main polymetallic mining site (9800 mg Pb kg(-1), 26 039 mg Zn kg(-1), 316.4 mg Cd kg(-1), 256.9 mg Cu kg(-1)). The calculated enrichment factors (EFs) confirmed the extreme degree of contamination by Pb, Zn and Cd (EF>40). Lead, Zn and Cd are bound mainly to Fe oxides and hydroxides. In the most contaminated samples Pb is also present as Pb carbonates and litharge (PbO). Lead isotopic analysis indicates that the predominant source of stream sediment contamination is historic Pb-Ag mining and primary Pb smelting (206Pb/207Pb=1.16), while the role of secondary smelting (car battery processing) is negligible.     

Assessment of metal availability to vegetation (Betula pendula) in Pb-Zn ore concentrate residues with different features

In this work, characterisation of several ore concentrate remains from an abandoned Pb-Zn mining factory was performed determining chemical and physical properties such as pH, organic carbon content, particle size distribution, total heavy metal content (Pb, Zn, Cu, As and Cd) as well as mineralogical composition which showed, in most cases, the oxidization of the parent ore material (mostly galena: PbS and sphalerite: ZnS) to more mobile fractions as anglesite (PbSO(4)) and goslarite (ZnSO(4)). Moreover, two operational defined extraction procedures commonly used in soil and sediment studies (first and second steps of BCR procedure and DTPA extraction protocol) were applied in the different mining wastes in order to study Pb and Zn mobility and likely bioavailability to Betula pendula growing on the same mining spoils, which presents lead and zinc contents in leaves over ten times background values.     

Evaluation of chemical immobilization treatments for reducing heavy metal transport in a smelter-contaminated soil

Three chemical immobilization materials, agricultural limestone (AL), mineral rock phosphate (RP), and diammonium phosphate (DAP), were evaluated using solute transport experiments to determine their ability to reduce subsurface heavy metal transport in a smelter contaminated soil. Percent reductions in metals transported were based on comparison with cumulative totals of metal species eluted through 60 pore volumes from an untreated soil. Reductions of metal eluted from the AL treatment were 55% for Cd, 45.2% for Pb, and 21.9% for Zn. Rock phosphate mixed with soil at 60 and 180 g kg(-1) was generally ineffective for reducing Cd, Pb, and Zn elution with <27% reduction for Cd, Pb, and Zn. Rock phosphate placed under contaminated soil as a reactive barrier (i.e. layered RP) at 180 g kg(-1) reduced Cd 53% and Zn 24%, and was the most efficient treatment for reducing Pb (99.9%) transport. DAP treatments were superior to all other materials for reducing Cd and Zn elution with reduction >77% for Zn and >91% for Cd from the 90 g DAP kg(-1) treatment. Increasing DAP from 10 to 90 g kg(-1) increased total arsenic released from 0.13 to 29.5 mg kg(-1) and total P eluted from 2.31 to 335 mg. DAP at 10 g kg(-1) was the most effective treatment for immobilizing the combination of Cd, Pb, and Zn, with reductions of 94.6, 98.9, and 95.8%, respectively.     

An inter-laboratory study to test the ability of amendments to reduce the availability of Cd, Pb, and Zn in situ

An international inter-laboratory research program investigated the effectiveness of in situ remediation of soils contaminated by cadmium, lead and zinc, measuring changes in soil and soil solution chemistry, plants and soil microbiota. A common soil, from mine wastes in Jasper County MO, was used. The soil was pH 5.9, had low organic matter (1.2 g kg(-1) C) and total Cd, Pb, and Zn concentrations of 92, 5022, and 18 532 mg kg(-1), respectively. Amendments included lime, phosphorus (P), red mud (RM), cyclonic ashes (CA), biosolids (BIO), and water treatment residuals (WTR). Both soil solution and NH4NO3 extractable metals were decreased by all treatments. Phytotoxicity of metals was reduced, with plants grown in P treatments having the highest yields and lowest metal concentration (0.5, 7.2 and 406 mg kg(-1) Cd, Pb, and Zn). Response of soil micro-organisms was similar to plant responses. Phosphorus addition reduced the physiologically based extraction test Pb from 84% of total Pb extracted in the untreated soil to 34.1%.     

Transfer of cadmium, lead, and zinc from industrially contaminated soil to crop plants: a field study

The documeneed adverse health effects of soil Cd and Pb have led to public concern over soil contamination with metals. A 4-year field experiment was conducted to study the transfer of Cd, Pb, and Zn from soil contaminated by smelter flue-dust to crop plants grown in a rotation. The soil was amended with Pb?Zn smelter flue-dust (2-66.8 kg per 10 m(2) plot) to simulate the long-term effect that the smelting of non-ferrous metal ore has on arable soils. The treated soil became strongly contaminated with metals (Cd 3.2-106 mg/kg, Pb 146-3452 mg/kg, Zn 465-11 375 mg/kg). Concentrations of Cd, Pb, and Zn in barley grain, barley straw meadow bluegrass, red clover, and potatoes were generally low. The highest metal concentrations were found in potato tubers (intact), meadow bluegrass, and barley straw. The observed reduction in crop yield was probably the result of possible nutrient imbalances rather than of metal (Zn, Cu) phytotoxicities. Zn and Cd uptake by the plants can be described by the saturation (plateau) model (y = ax(b), b < 1). The relationship between Pb in the soil and plants was linear with an extremely low slope (0.0001-0.0003). No excessive dietary intake of Cd is expected when Cd concentrations in barley grain and potato tubers grown on the contaminated soil are not higher than 0.6 and 1.0 mg/kg, respectively. Based on the risk analysis and taking into account the saturation model of the soil-plant metal relationship, it was concluded that, under the conditions of this experiment (neutral soil pH), soil with Cd concentrations of up to 30 mg/kg is still safe for production of these crop plants.     

Zn, Cd and Pb accumulation and arbuscular mycorrhizal colonisation of pennycress Thlaspi praecox Wulf. (Brassicaceae) from the vicinity of a lead mine and smelter in Slovenia

Significant hyperaccumulation of Zn, Cd and Pb in field samples of Thlaspi praecox Wulf. collected from a heavy metal polluted area in Slovenia was found, with maximal shoot concentrations of 14,590 mg kg(-1) Zn, 5960 mg kg(-1) Cd and 3500 mg kg(-1) Pb. Shoot/root ratios of 9.6 for Zn and 5.6 for Cd show that the metals were preferentially transported to the shoots. Shoot bioaccumulation factors exceeded total soil Cd levels 75-fold and total soil Zn levels 20-fold, further supporting the hyperaccumulation of Cd and Zn. Eighty percent of Pb was retained in roots, thus indicating exclusion as a tolerance strategy for Pb. Low level colonisation with arbuscular mycorrhizal fungi (AMF) of a Paris type was observed at the polluted site, whereas at the non-polluted site Arum type colonisation was more common. To our knowledge this is the first report of Cd hyperaccumulation and AMF colonisation in metal hyperaccumulating T. praecox.     

An engineered plant that accumulates higher levels of heavy metals than Thlaspi caerulescens, with yields of 100 times more biomass in mine soils

Nicotiana glauca transformed with TaPCS1 was tested for its application in phytoremediation. When plantlets were grown in mine soils containing Cu, Zn, and Pb (42, 2600, and 1500 mg kg(-1)) the plant showed high levels of accumulation especially of Zn and Pb. Adult plants growing in mine soils containing different heavy metal concentrations showed a greater accumulation as well as an extension to a wider range of elements, including Cd, Ni and B. The overexpressed gene confers up to 9 and 36 times more Cd and Pb accumulation in the shoots under hydroponic conditions, and a 3- and 6-fold increase in mining soils. When the hyperaccumulator Thlaspi caerulescens was compared, the results were higher values of heavy metal and Boron accumulation, with a yield of 100 times more biomass. Thlaspi was unable to survive in mining soils containing either a level higher than 11000 mg kg(-1) of Pb and 4500 mg kg(-1) of Zn, while engineered plants yielded an average of 0.5 kg per plant.     

Metal accumulation in wild plants surrounding mining wastes

Four sites were selected for collection of plants growing on polluted soil developed on tailings from Ag, Au, and Zn mines at the Zacatecas state in Mexico. Trace element concentrations varied between sites, the most polluted area was at El Bote mine near to Zacatecas city. The ranges of total concentration in soil were as follows: Cd 11-47, Ni 19-26, Pb 232-695, Mn 1132-2400, Cu 134-186 and Zn 116-827 mg kg(-1) air-dried soil weight. All soil samples had concentrations above typical values for non-polluted soils from the same soil types (Cd 0.6+/-0.3, Ni 52+/-4, Pb 41+/-3mg kg(-1)). However, for the majority of samples the DTPA-extractable element concentrations were less than 10% of the total. Some of the wild plants are potentially metal tolerant, because they were able to grow in highly polluted substrates. Plant metal analysis revealed that most species did not translocate metals to their aerial parts, therefore they behave as excluder plants. Polygonum aviculare accumulated Zn (9236 mg kg(-1)) at concentrations near to the criteria for hyperaccumulator plants. Jatropha dioica also accumulated high Zn (6249 mg kg(-1)) concentrations.     

A 40+ year record of Cd,Hg, Pb,and U deposition in sediments of Patroon Reservoir,Albany County,NY, USA

Sediments of the Patroon Creek watershed (33 km(2)) are known to contain significant concentrations of heavy metals derived from two industrial sites within the watershed. Mercury Refining, Inc (Mereco) has stored and recycled Hg from 1955 to the present day, and National Lead Industries (NLI) manufactured aircraft components containing Cd, Pb, and U from 1958 to 1984. Here we present the first record of heavy metal deposition as preserved in a 3-m long sediment core collected in 1999 from Patroon Reservoir, a small water body (1.3 ha) downstream of the industrial sites. Bulk sediment samples were collected from the core at 0.05-m intervals and analyzed for total Cd, Pb, and U by ICP-MS and total Hg by CVAAS. Total Hg increases from less than 1 mg kg(-1) (dw) below 1.68 m, to a maximum of 6.2 mg kg(-1) at 0.80 m, and then declines to the sediment-water interface. Total Cd, Pb, and U concentrations increase abruptly above 1.68 m to maximum values of 25, 320, and 3600 mg kg(-1) (dw), respectively, and then decline gradually upwards. By correlating metal profiles with industrial history, we conclude that the 1.68 m horizon was deposited no earlier than 1958, the beginning of aircraft component manufacturing at NLI. The average, apparent sedimentation rate within the reservoir has a minimum value of approximately 0.04 m year(-1) for the 41-year period from 1958 to 1999. In the interval 0--1.68 m, average concentrations of Cd, Hg, Pb, and U are 1.69, 1.50, 461, and 13 mg kg(-1), respectively. These levels are comparable with other lake, reservoir and stream sediments that have been moderately to severely impacted by industrial pollution and are above levels expected to be detrimental to aquatic organisms.     

Cadmium availability to wheat grain in soils treated with sewage sludge or metal salts

Grain Cd concentrations were determined in wheat (Triticum aestivum L.) grown in 1999, 2001 and 2003, at six sludge cake field experiments. Three of these sites also had comparisons with Cd availability from metal amended liquid sludge and metal salts. Grain Cd concentrations in all years and at all sites were significantly linearly correlated with NH4NO3 extractable Cd and soil total Cd (P<0.001). Soil extractability was greater in the liquid sludge and metal salt experiments than in the cake experiments, as were grain Cd concentrations. Across all the sites, NH4NO3 extractable soil Cd was no better at predicting grain Cd than soil total Cd. Stepwise multiple linear regression analysis showed that soil total Cd, pH and organic carbon were the only significant (P<0.001) variables influencing wheat grain Cd concentrations, explaining 78% of the variance across all field experiments (1408 plots). This regression predicted that the current UK soil total Cd limit of 3 mg kg(-1) was not sufficiently protective against producing grain above the European Union (EU) grain Cd Maximum Permissible Concentration (MPC) of 0.235 mg Cd kg(-1) dry weight, unless the soil pH was > 6.8. Our predictions show that grain would be below the MPC with > 95% confidence with the proposed new EU draft regulations permitting maximum total Cd concentrations in soils receiving sludge of 0.5 mg kg(-1) for soils of pH 5-6, 1 mg kg(-1) for soils of pH 6-7, and 1.5 mg kg(-1) for soils of pH > or = 7.     

High levels of heavy metals in rice (Oryza sativa L.) from a typical E-waste recycling area in southeast China and its potential risk to human health

Very few studies have investigated the heavy metal contents in rice samples from a typical E-waste recycling area. In this study, 10 heavy metals (As, Ba, Cd, Co, Cr, Cu, Hg, Mn, Ni and Pb) in 13 polished rice and relevant hull samples, six relevant paddy soil samples were investigated. The geometric mean concentrations of Cd, Cu and Hg in soil samples were 1.19, 9.98 and 0.32 microg g(-1), respectively, which were 4.0, 2.0 and 1.1-folds of the maximum allowable concentration (MAC) (0.30, 50.00, 0.30 microg g(-1), respectively) for Chinese agricultural soils. The analyzed metal concentrations were significantly different between rice and relevant hull except for As, Cd and Hg (p<0.05). All metal concentrations, except for Co, in rice hull were higher than those in polished rice. The geometric mean of Pb in polished rice reached 0.69 microg g(-1), which was 3.5-folds higher than the MAC (0.20 microg g(-1)) by the safety criteria for milled rice. Cd contents in 31% of the rice samples exceeded the national MAC (0.20 microg g(-1)), and the arithmetic mean also slightly exceeded national MAC. In addition, Cd and Pb contents in local rice were much higher than commercial rice samples examined in this work and previous studies. Comparing the tolerable daily intakes given by FAO/WHO with the mean estimated daily intakes; Pb daily intake through rice consumption in this area was 3.7 microg day(-1)kg(-1) body weight (bw), which already exceeded the FAO tolerable daily intake, and the Cd daily intake (0.7 microg day(-1)kg(-1) bw) through rice had already taken up 70% of the total tolerable daily intake (1 microg day(-1)kg(-1) bw). The daily intake of Hg and As through rice was much lower than the tolerable daily intakes, but bioaccumulation of Hg through the food chain and intake of As from other food stuff should also be of concern.     

Heavy metal contamination from mining sites in South Morocco: 1. Use of a biotest to assess metal toxicity of tailings and soils

Our work was conducted to investigate the heavy metal toxicity of tailings and soils collected from five metal mines located in the south of Morocco. We used the MetPAD biotest Kit which detects the toxicity specifically due to the heavy metals in environmental samples. This biotest initially developed to assess the toxicity of aquatic samples was adapted to the heterogeneous physico-chemical conditions of anthropogenic soils. Contrasted industrial soils were collected from four abandoned mines (A, B, C and E) and one mine (D) still active. The toxicity test was run concurrently with chemical analyses on the aqueous extracts of tailings materials and soils in order to assess the potential availability of heavy metals. Soil pH was variable, ranging from very acidic (pH 2.6) to alkaline values (pH 8.0-8.8). The tailings from polymetallic mines (B and D) contained very high concentrations of Zn (38,000-108,000 mg kg(-1)), Pb (20,412-30,100 mg kg(-1)), Cu (2,019-8,635 mg kg(-1)) and Cd (148-228 mg kg(-1)). Water-extractable metal concentrations (i.e., soil extracts) were much lower but were highly toxic as shown by the MetPAD test, except for soils from mines A, E and site C3 from mine C. The soil extracts from mine D were the most toxic amongst all the soils tested. On this site, the toxicity of soil water extracts was mainly due to high concentrations of Zn (785-1,753 mg l(-1)), Cu (1.8-82 mg l(-1)) and Cd (2.0-2.7 mg l(-1)). The general trend observed was an increase in metal toxicity measured by the biotest with increasing available metal contents in tailings materials and soils. Therefore, the MetPAD test can be used as a rapid and sensitive predictive tool to assess the heavy metal availability in soils highly contaminated by mining activities.     

The two-phase leaching of Pb, Zn and Cd contaminated soil using EDTA and electrochemical treatment of the washing solution

The feasibility of a novel two-phase method for remediation of Pb (1374 mg kg(-1)), Zn (1007 mg kg(-1)), and Cd (9.1 mg kg(-1)) contaminated soil was evaluated. In the first phase we used EDTA for leaching heavy metals from the soil. In the second phase we used an electrochemical advanced oxidation process (EAOP) for the treatment and reuse of washing solution for soil rinsing (removal of the soil-retained, chelant-mobilized metallic species). In EAOP, a boron-doped diamond anode was used for the generation of hydroxyl radicals and oxidative decomposition of EDTA-metal complexes at a constant current density (15 mA cm(-2)). The released metals were removed from the solution by filtration as insoluble participate and by electro-deposition on the cathode. Four consecutive additions of 5.0 mm ol kg(-1) EDTA (total 20 mmol kg(-1)) removed 44% Pb, 14% Zn and 35% Cd from the soil. The mobility of the Pb, Zn and Cd (Toxicity Characteristic Leaching Procedure) left in the soil after remediation was reduced by 1.6, 3.4 and 1.5 times, respectively. The Pb oral availability (Physiologically Based Extraction Test) in the simulated stomach phase was reduced by 2.4 and in the intestinal phase by 1.7 times. The discharge solution was clear, almost colorless, with pH 7.73 and 0.47 mg L(-1) Pb, 1.03 mg L(-1) Zn, bellow the limits of quantification of Cd and 0.023 mM EDTA. The novel method enables soil leaching with small water requirements and no wastewater generation or other emissions into the environment.     

The EDTA effect on phytoextraction of single and combined metals-contaminated soils using rainbow pink (Dianthus chinensis)

Rainbow pink (Dianthus chinensis), a potential phytoextraction plant, can accumulate high concentrations of Cd from metal-contaminated soils. The soils used in this study were artificially added with different metals including (1) CK: original soil, (2) Cd-treated soil: 10 mg Cd kg(-1), (3) Zn-treated soil: 100 mg Zn kg(-1), (4) Pb-treated soil: 1000 mg Pb kg(-1), (5) Cd-Zn-treated soil: 10 mg Cd kg(-1) and 100 mg Zn kg(-1), (6) Cd-Pb-treated soil: 10 mg Cd kg(-1) and 1000 mg Pb kg(-1), (7) Zn-Pb-treated soil: 100 mg Zn kg(-1) and 1000 mg Pb kg(-1), and (8) Cd-Zn-Pb-treated soil: 10 mg Cd kg(-1), 100 mg Zn kg(-1), and 1000 mg Pb kg(-1). Three concentrations of 2Na-EDTA solutions (0 (control), 2, and 5 mmol kg(-1) soil) were added to the different metals-treated soils to study the influence of applied EDTA on single and combined metals-contaminated soils phytoextraction using rainbow pink. The results showed that the Cd, Zn, Pb, Fe, or Mn concentrations in different metals-treated soil solutions significantly increased after applying 5 mmol EDTA kg(-1) (p<0.05). The metal concentrations in different metals-treated soils extracted by deionized water also significantly increased after applying 5 mmol EDTA kg(-1) (p<0.05). Because of the high extraction capacity of both 0.005 M DTPA (pH 5.3) and 0.05 M EDTA (pH 7.0), applying EDTA did not significantly increase the Cd, Zn, or Pb concentration in both extracts for most of the treatments. Applying EDTA solutions can significantly increase the Cd and Pb concentrations in the shoots of rainbow pink (p<0.05). However, this was not statistically significant for Zn because of the low Zn concentration added into the contaminated soils. The results from this study indicate that applying 5 mmol EDTA kg(-1) can significantly increase the Cd, Zn, or Pb concentrations both in the soil solution or extracted using deionized water in single or combined metals-contaminated soils, thus increasing the accumulated metals concentrations in rainbow pink shoots. The proposed method worked especially well for Pb (p<0.05). The application of 2 mmol EDTA kg(-1) might too low to enhance the phytoextraction effect when used in silty clay soils.     

Earthworms as biological monitors of cadmium, copper, lead and zinc in metalliferous soils

Earthworms (Lumbricus rebellus and Dendrodrilus rubidus) were sampled from one uncontaminated and fifteen metal-contaminated sites. Significant positive correlations were found between the earthworm and 'total' (conc. nitric acid-extractable) soil Cd, Cu, Pb and Zn concentrations (data log1) transformed). The relationships were linear, and the accumulation patterns for both species were similar when a single metal was considered, even though there were species difference in mean metal concentrations. Generally, the earthworm Cd concentration exceeded that of the soil; by contrast, the worm Pb concentration was lower than the soil Pb concentration in all but one (acidic, low soil Ca) site. Our observations suggest that Cu and Zn accumulation may be physiologically regulated by both species. Total-soil Cd explained 82-86% of the variability (V2) in earthworm Cd concentration; 52-58% of worm Pb and worm Zn concentrations were explained by the total-soil concentrations of the respective metals. Total-soil Cu explained only 11-32% of the worm Cu concentration. The effect of soil pH, total Ca concentration, cation-exchange capacity (CEC) and organic carbon on metal accumulation by L. rubellus and D. rubidus was investigated by multiple regression analysis. Soil pH (coupled with CEC) and soil Ca had a major influence on Pb accumulation (V2 of worm Pb increased to 77-83%), and there was some evidence that Cd accumulation may be suppressed in extremely organic soils. The edaphic factors investigated had no effect on Cu or Zn accumulation by earthworms. In the context of biomonitoring, it is proposed that earthworms have a potential in a dual role: (1) as 'quantitative' monitors of total-soil metal concentrations (as shown for Cd); and (2) as estimators of 'ecologically significant' soil metal, integrating the effects of edaphic factors (as shown for Pb).     

Concentration and health risk evaluation of heavy metals in market-sold vegetables and fishes based on questionnaires in Beijing,China

Concentrations of heavy metals (As, Cd, Pb, Cu, Ni, Fe, Mn, and Zn) in market vegetables and fishes in Beijing, China, are investigated, and their health risk to local consumers is evaluated by calculating the target hazard quotient (THQ). The heavy metal concentrations in vegetables and fishes ranged from not detectable (ND) to 0.21 mg/kg fresh weight (f.w.) (As), ND to 0.10 mg/kg f.w. (Cd), and n.d to 0.57 mg/kg f.w. (Pb), with average concentrations of 0.17, 0.04, and 0.24 mg/kg f.w., respectively. The measured concentrations of As, Cd, Pb, Cu, Ni, Fe, Mn, and Zn are generally lower than the safety limits given by the Chinese regulation safety and quality standards of agriculture products (GB2762-2012). As, Cd, and Pb contaminations are found in vegetables and fishes. The exceeding standard rates are 19 % for As, 3 % for Cd, and 25 % for Pb. Pb contaminations are found quite focused on the fish samples from traditional agri-product markets. The paper further analyzed the health risk of heavy metals in vegetables and fishes respectively from supermarkets and traditional agri-product markets; the results showed that the fishes of traditional agri-product markets have higher health risk, while the supermarkets have vegetables of higher heavy metal risk, and the supervision should be strengthened in the fish supply channels in traditional agri-product markets.     

Concentrations and composition of PCB congeners in the air around stored used capacitors containing PCB insulator oil in a suburb of Bangkok, Thailand

Accumulation of Zn, Cu, Pb and Cd was studied in snails fed for 120 days on diets contaminated with each metal separately and with all metals mixed together. The concentrations of Zn in food were in the range 39 to 12 200 mg kg(-1), Cu 9-1640 mg kg(-1), Pb 0.4-12 700 mg kg(-1), and Cd 0.16-146 mg kg(-1) on a dry weight basis. At the highest concentrations of all metals the consumption rates decreased significantly. For the remaining concentrations, Zn and Cu were accumulated in soft tissue in proportion to their concentrations in food. The lowest treatments of Pb and Cd did not cause any increase in soft tissue concentrations of these metals but at average treatments, a clear increase was observed. Copper was accumulated especially efficiently, exceeding concentrations in food throughout the whole range of treatments. Except for the lower end of experimental treatments, Zn was accumulated approximately in direct proportion to its concentration in the diet. Lead was the most efficiently regulated metal, with soft tissue concentrations always substantially lower than in food. Approximately 60% of Zn, 90% of Cu, 43% of Pb and 68% of Cd on average was assimilated from food. The assimilation efficiency of food alone was ca 74%. The concentrations of metals in shells increased significantly with exposure, but (with one exception) the concentrations in shells did not exceed 5% of those found in soft tissue. We argue that snails are more important as agents of food-chain transport of Cu and Cd, than of Zn or Pb. Our results indicate also that snails are not able to deposit significant quantities of metals in their shells, at least during the time scale of our laboratory experiment.     

Residual metal concentrations in soils and leaf accumulations in tobacco a decade following farmland application of municipal sludge

The objectives of this investigation were to examine the long-term residual effects of metal loading through sewage sludge applications on the total vs. diethylene triamine pentacetic acid (DTPA) extractable metal concentrations in soil and leaf accumulations in tobacco. Maryland tobacco (Nicotiana tabacum L.), cv. 'MD 609', was grown in 1983 and 1984 at two sites in Maryland that had been amended in 1972 with dewatered, digested sewage sludge from washington, DC, at rates equal to 0, 56, 112 and 224 mg ha(-1). The metal concentrations in the sludge, in mg kg(-1) dry weight, were: 1300 Zn, 570 Cu, 280 Pb, 45 Ni and 13 Cd. Soil samples collected from the surface horizon and composite leaf samples of cured tobacco were analyzed for total Zn, Cu, Mn, Fe, Pb, Ni and Cd concentrations. The soil samples were also examined for soil pH and DTPA extractable metals. Equations were generated using polynomic and stepwise regression analyses which described the relationships between total vs. DTPA extractable soil metals, and between DTPA soil and soil pH vs. plant metal concentrations, respectively. Significant increases were observed for both total and DTPA extractable metal concentrations for all metals, with all but total Mn and Ni being significant for linear and quadratic effects regarding sludge rates. However, linear relationships were found between DTPA extractable vs. total soil concentrations for all elements except Pb and Ni which were quadratic. Significant increases in plant Zn, Cu, Mn, Ni and Cd and decreases in Fe were observed with increased sludge rates. Plant Pb levels were unaffected by sludge applied Pb. Linear relationships were observed between plant Zn and Cd and DTPA soil metal levels: however, Mn and Cu levels were described by quadratic and cubic relationship, respectively. Relationships between plant Fe and Pb and DTPA extractable concentrations were nonsignificant. Additional safeguards to protect crop contamination from heavy metals such as Cd were discussed.     

Cadmium in soil solutions from a transect of soils away from a fertiliser bin

The effects of high inputs of phosphate fertiliser on Cd concentrations were studied in soil solutions extracted from topsoils. Soils were sampled along a transect at distances of 1-100 m away from a fertiliser bin. The transect was sampled four times during 1 year. Soil solutions were analysed for Cd, pH, major cations and anions, and other heavy metals (As, Cr, Cu, Pb). For one of the transect samplings, soil total Cd, Cr, Cu, Pb and P were also measured. Cd speciation in the soil solutions was calculated by the GEO-CHEM-PC computer program. Chemical composition varied substantially along the transect, and also between samplings, indicative of seasonal effects and the influence of a fresh application of superphosphate fertiliser during the year. Application of fertiliser decreased soil solution pH and increased the levels of heavy metals in soil solution. Generally, soil total Cd, Cr, Cu, Pb, and P decreased with increasing distance from the fertiliser bin. Correlations between P and the four heavy metals were: P and Cd (R2 = 0.978), P and Cr (R2 = 0.712), P and Pb (R2 = 0.538), P and Cu (R2 = 0.267). Less than 1% of the total Cd in the soil samples was found in the soil solution. The free metal ion Cd2+ accounted for 55-90% of solution Cd. Of the complexed species of Cd, the chloride and sulphate complexes were usually the most important, even when nitrate and phosphate concentrations were relatively high. The presence of As, Cr, Cu and Pb had no effect on Cd speciation.     

Heap leaching of Pb and Zn contaminated soil using ozone/UV treatment of EDTA extractants

The feasibility of a novel EDTA-based soil heap leaching method with treatment and reuse of extractants in a closed process loop was evaluated on a laboratory scale. Ozone and UV irradiation were used for oxidative decomposition of EDTA-metal complexes in extractants from Pb (1243 mg kg(-1)) and Zn (1190 mg kg(-1)) contaminated soil. Released metals were absorbed in a commercial metal absorbent Slovakite. Six-consecutive additions of 2.5 mmol kg(-1) EDTA (total 15 mmol kg(-1) EDTA) removed 49.6 +/- 0.6% and 19.7 +/- 1.7% of initial total Pb and Zn from soil (4.6 kg) packed in 22 cm high columns. The efficiency of extraction was similar to small-scale simulations of heap leaching (15 0 g of soil), where EDTA used in the same manner removed 49.7 +/- 1.0% and 13.7 +/- 0.4% of Pb and Zn. The new heap leaching method produced discharge extractant with fairly low final concentrations of Pb, Zn and EDTA (1.98 +/- 2.17 mg l(-1), 4.55 +/- 2.36 mg l(-1), and 0.05 +/- 0.04 mM, respectively), which could presumably be reduced even further with continuation of treatment. The results of our study indicate that for soils contaminated primarily with Pb, treating the EDTA extractants with ozone/UV and reuse of extractants enables efficient soil heap leaching with very little or no wastewater generation, easy control over emissions, and lowers the requirements for process water.