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.     

Metal contamination in the lichen Alectoria sarmentosa near the copper smelter of Murdochville, Québec

Lichens were used to evaluate the metal pollution in a forest ecosystem around the smelter of Murdochville, Canada. As reached values 5.8 times higher in the smelter vicinity than in the 'background' sites. This enrichment was 2 times higher for 3 metals (Cu, Cd and Pb). The highest As, Ba, Cd, Cu, and Pb concentrations in lichens were 4, 112, 1, 23, 50 and 952mg/kg respectively. Contamination declined exponentially with increasing distance from the smelter and was related to elevation and slope exposition to the smelter flux. (206)Pb/(207)Pb and (206)Pb/(204)Pb ratios were low close to the smelter (1.16 and 18), but increased with distance to constant values (1.19 and 18.7) and showed an inverse correlation with lead concentrations. Forest contamination was detectable up to 30km from the smelter.     

Physicochemical and biological characterisation of different dredged sediment deposit sites in France

The aim of this work is to determine sediment properties, metal contents and transfers of Cd and Zn from dredged sediments to plants. To this end 10 deposit sites with different contexts were visited in France. The main agronomic characteristics and metal contents for surface soil layers were measured, the plant species present at the sites, such as Brassicaceae and Fabaceae, were listed, and the distribution of their root systems described. Soil characteristics such as available P (Olsen) varied between sites, with values ranging from 0.01 to 0.49 g kg(-1). Total contents and enrichment factors were studied, highlighting metal contamination in most of the sites. Despite carrying out principal component analyses, it was not possible to group deposits by age or geographical localisation. However, deposits could be distinguished as a function of proximity of industrial facilities, sediment grain size and carbonate content. Associations between metals were also highlighted: (1) Cd, Pb and Zn, and (2) Al, Cr, Cu and Fe. Consequently, we propose classifying them as technogenic anthrosols.     

Heavy metal distribution and bioaccumulation in Chihuahuan Desert Rough Harvester ant (Pogonomyrmex rugosus) populations

Heavy metal contamination can negatively impact arid ecosystems; however a thorough examination of bioaccumulation patterns has not been completed. We analyzed the distribution of As, Cd, Cu, Pb and Zn in soils, seeds and ant (Pogonomyrmex rugosus) populations of the Chihuahuan Desert near El Paso, TX, USA. Concentrations of As, Cd, Cu, and Pb in soils, seeds and ants declined as a function of distance from a now inactive Cu and Pb smelter and all five metals bioaccumulated in the granivorous ants. The average bioaccumulation factors for the metals from seeds to ants ranged from 1.04× (As) to 8.12× (Cd). The findings show bioaccumulation trends in linked trophic levels in an arid ecosystem and further investigation should focus on the impacts of heavy metal contamination at the community level.     

Cadmium availability to wheat in five soil series from the Yonne district, Burgundy, France

Preliminary results from the French ASPITET programme demonstrated that Cd background levels in agricultural soils can vary greatly (0.02-6.9 mg Cd kg(-1)) depending on parent material and pedogenic processes (Baize, 1997). However, the total Cd content in soil is often not significantly related to the Cd concentration in edible plant parts. A field case study was undertaken across the southern part of the Yonne district, Burgundy, France. This area has various soil series with either low or high geochemical Cd content in the topsoil. Cd availability in soils sampled at 16 sites belonging to five soil series was investigated using single extractions. In addition, shoots (at stem elongation) and grains (at harvest) of field-grown wheat were collected at the same sites and analysed for macronutrients and trace elements. Cd concentrations in grain varied from 0.015 to 0.146 mg Cd kg(-1) DM depending on soil characteristics, soil series, and plant mineral composition. Cd grain concentrations did not reflect total Cd content in the surface soil layer; however, they were correlated with Cd extracted by a 0.1 M calcium nitrate unbuffered solution, and to a lesser extent with either soil pH or CEC. These three parameters may be useful guides to predict Cd in wheat grain harvested in the Yonne district. An inverse relationship was found between Cd and Cu contents in grain. The highest Cd concentrations in wheat grain occurred in plants grown on Aubues soils which had marginal Cu and Zn deficiencies in shoots. In order of Cd accumulation in wheat grain, soil series may be ranked as follows: Domérien < Carixien, Terres Noires < Sols Marron < Aubues.     

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.     

Environmental levels of cadmium and lead in the vicinity of a major refuse incinerator

This study examines whether the atmospheric release of Cd and Pb from a refuse incinerator in London has caused contamination of the local environment. Sampling networks were established for street dusts, surface soils, vegetation and total deposit gauges in areas up to 5 km downwind and upwind from the incinerator. Measurements of Cd and Pb indicate there is neither a marked nor an extensive contamination by these metals in the downwind area. However, dust Cd values decreased with distance from the incinerator in this area and Cd deposition rates were higher than in the upwind area. Nevertheless, most Cd values obtained in the downwind area were similar to those previously reported for other parts of London while Pb values were often lower. It is considered that the 100 m stack of the incinerator minimizes the deposition of particulate emissions in the vicinity of this source. Appreciable Cd contamination was found within the grounds of the incinerator, the values being about 4–50-fold higher than in either the upwind or downwind areas. The extent of Pb contamination in this small area was more limited, with values being about twice those found in the two study areas. The source of this contamination is ascribed to fugitive releases arising from the storage and transport of the ashes produced by the incinerator.     

Multi-element composition of historical lichen collections and bark samples,indicators of changing atmospheric conditions

Thirty six element signatures were compared in historical Parmelia sulcata samples from the Natural History Museum herbarium collected over the period 1797–1967 with those recorded in the same species and tree bark sampled in 2000 from Burnham Beeches, lying 40 km west of London. Nineteen elements reached highest concentrations in herbarium samples, consistent with a pollution legacy and dust contamination in the herbarium. Healthy Parmelia sampled east and down-wind of London at a farm during peak SO₂ emissions in 1967 contained highest V, Ni, Zn, Cd, Se, Ge contents, supporting derivation from fuel combustion; the same sample was previously determined as having a low δ34S and high S and N contents. Lowest V, Co, Ni, Cu, Zn, Sn, Ba, Pb, Mo, Sb, Li, B, Cs, U, Th, Ga contents were recorded in a sample with a high δ34S and low S content collected in 1887 from a remote region from Ross-shire, Scotland. Se and Cd enrichment, never-the-less suggest a transboundary pollution influence. Lichen Pb concentrations from Burnham Beeches were amongst the lowest recorded in spite of lichens being collected close to roads. Herbarium samples help interpret changes in element deposition where few data exist, in spite of dust contamination.     

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.     

Potentially toxic metal contamination of urban soils and roadside dust in Shanghai, China

A detailed investigation was conducted to understand the contamination characteristics of a selected set of potentially toxic metals in Shanghai. The amount of Pb, Zn, Cu, Cr, Cd and Ni were determined from 273 soil/dust samples collected within urban area. The results indicated that concentration of all metals except Ni in soils was significant, and metal pollution was even severer in roadside dust. A series of metal spatial distribution maps were created through geostatistical analysis, and the pollution hotspots tended to associate with city core area, major road junctions, and the regions close to industrial zones. In attempt of identifying the source of metals through geostatistical and multivariate statistical analyses, it was concluded as follows: Pb, Zn and Cu mainly originated from traffic contaminants; soil Ni was associated with natural concentration; Cd largely came from point-sourced industrial pollution; and Cr, Ni in dust were mainly related to atmospheric deposition.     

Heavy metal accumulation in wheat plant grown in soil amended with industrial sludge

The concentrations of different forms of Zn, Cu, Mn, Ni, Cd, Cr, Pb and Fe metals were determined for the roadside sludge collected from pickling-rolling and electroplating industrial area. In sludge the relative abundance of total heavy metals were Fe>Mn>Cr>Ni>Cu>Pb>Zn>Cd and DTPA-extractable metals were in the order--Fe>Ni>Mn>Cr>Cu>Zn>Pb>Cd. Pot-culture experiment was conducted in soils amended with sludge (0%, 10%, 20%, 30%), pretreated with lime (0%, 0.5% and 1%). The soils were alkaline in nature (pH>8.3) with organic carbon contents were 0.34% and 0.72%. The most abundant total and bio-available metal was Fe. Two wheat seedlings were grown in each pot containing 3kg sludge-amended or control soil and the experiment was conducted till harvesting. Application of sludge increased both total and bio-available forms of metals in the soils, while lime application decreased the bioavailability of heavy metals in sludge-amended soils. The content of organic carbon showed positive correlation with all metals except Zn, Cr and Pb. CEC also showed a strong positive correlation (R2>0.7) with Fe, Mn, Cu, Ni and Cd. Though wheat plants are not accumulators, the translocation efficiency was appreciably high. The translocation factor from shoot to grain was found smaller than that of root to shoot of wheat plants. This makes an implication that the heavy metal accumulation was proportionally lesser in grain than in shoot. In, 10% sludge with 0.5% lime-amended soils; each of these toxic heavy metals was found to be within permissible range (USEPA). Hence, on the basis of present study, the best possible treatment may be recommended.     

Contamination of wild-grown edible mushrooms by heavy metals in a former mercury-mining area

The aim of this study was to evaluate the contamination of six edible wild species of mushrooms (Boletus pulverulentus, Cantharellus cibarius, Lactarius quietus, Macrolepiota procera, Russula xerampelina and Suillus grevillei) by heavy metals (Hg, Cd, Pb, Zn, Cu, Ni, Cr, Co, Mn and Fe). Mushroom samples were collected from sites contaminated by emissions from mining and processing of polymetallic ores in operation during the period 1969–1993 in Rudňany, southeast Slovakia. The four study sites spanned up to a 5-km distance from the emission source. The collected mushroom samples were analyzed using Flame Atomic Absorption Spectrophotometry and/or Flame Atomic Absorption Spectrophotometry with graphite furnace. Mercury, Cd and, in some samples, also Pb present the highest risks in terms of contamination of the food chain following subsequent consumption. The content of two metals in the dry matter (dm) of the mushrooms exceeded the limits set by the European Union (EU; Cd: 0.5 mg/kg dm, Pb: 1.0 mg/kg dm). The highest mean contents of the eight metals recorded for S. grevillei were 52.2, 2.15, 107, 104, 2.27, 2.49, 81.6 and 434 mg/kg dm for Hg, Pb, Zn, Cu, Ni, Cr, Mn and Fe, respectively. The highest content of Cd was recorded in M. procera (3.05 mg/kg dm) and that of Co in L. quietus (0.90 mg/kg dm). The calculated weekly intake for Hg, Pb and Cd shows that regular consumption of mushrooms from the studied area poses risks to human health.     

Metal fractionation in a contaminated soil after reforestation: Temporal changes versus spatial variability

In a lysimeter experiment, topsoils were polluted with filter dust from a non-ferrous metal smelter and then planted with trees. Sequential extractions were used to follow the changes in metal fractionation of Cu, Zn, Cd, and Pb over 42 months. Plant-free and uncontaminated soils served as reference. In the contaminated and planted soils, the largest changes in speciation occurred within the first 6 months. The relative amounts of certain metal fractions were linearly related to each other, indicating systematic redistribution between fractions. The results indicate that under natural conditions with high heterogeneity in total metal contents spatial differences are more important than temporal variations in determining the fractionation and solubility of metals in contaminated soils. In the absence of plants soils exhibited a completely different fractionation 30 months after pollution, with much higher proportions in the more refractory phases. This suggests that plant activity kept the metals in a more soluble form.     

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

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

Heavy metals exposure of children from stairway and sidewalk dust in the smelting district,northeast of China

The aim of this work was to study metals accumulation in stairway (inside the residential building) and sidewalk (outside the residential building) dust, and health risk of children due to dust exposure. The investigation included the: (a) spatial distributions of Hg, Pb, Cd, Zn and Cu in stairway and sidewalk dust, (b) source analysis of metals in stairway and sidewalk dust, and (c) assessment of the children health risks due to metals exposure from stairway and sidewalk dust. In the smelting district of Huludao, the maximum Hg, Pb, Cd, Zn and Cu contents in stairway dust were 5.324, 4594, 936.8, 48 253, 1377 mg kg^?1, respectively, and were 144, 213, 8674, 760 and 69.5 times as high, respectively, as the background values in soil. A strong positive relationship was shown between the stairway and sidewalk dust for each metal (p < 0.01). The trends for Hg, Pb, Cd, Zn and Cu in the stairway and sidewalk dust were similar and with higher concentrations trending Huludao Zinc Plant (HZP). Atmospheric deposition due to metal smelting from HZP was the common source of heavy metals in the sidewalk and stairway dust. Vehicular traffic affected the metal accumulation in dust, but their contribution was slight comparing with atmospheric emission from HZP. Almost all hazard indexes (HIs) for metals due to stairway dust exposure in this study were lower than 1. The health risk for children was low if they would not play in the stairway. However, children were also experiencing the potential health risk from Cd and Pb exposure from sidewalk dust outside residential building, especially near HZP.     

Food chain transfer of cadmium and lead to cattle in a lead–zinc smelter in Guizhou, China

Cadmium (Cd) and Lead (Pb) are environmental pollutants. Environmental samples and bovine tissues were collected from the areas around a lead–zinc smelter in Guizhou, China for Cd, Pb, zinc (Zn) and copper (Cu) analysis. Cd in soil (10 mg/kg) and feed (6.6 mg/kg) from the polluted areas was 10 times higher than the Chinese Standards, resulting in higher Cd in bovine kidney (38 mg/kg) and liver (2.5 mg/kg). Pb in feed (132 mg/kg) from the polluted area was much higher than unpolluted areas, causing higher Pb levels in bovine tissues. Environmental Zn was elevated, but bovine tissue Zn was normal. Cu in bovine liver decreased with increased Cd and Pb. Metals in drinking water and in bovine muscle were within the Standard range. Thus, in the areas of this lead–zinc smelter, the environment has been contaminated with Cd and Pb, which has been transferred to cattle through the food chain.     

Factors affecting the concentrations of lead in British wheat and barley grain

The entry of Pb into the food chain is of concern as it can cause chronic health problems. The concentration of Pb was determined in cereal grain samples collected representatively from British Cereal Quality Surveys in 1982 and 1998 (n = 176, 250 and 233 for wheat collected in 1982 and 1998, and barley in 1998, respectively). In addition, paired soil and grain samples were collected from 377 sites harvested across Britain in 1998-2000. Wheat grain Pb ranged from below the analytical detection limit (0.02 mg kg(-1) dry weight, DW) to 1.63 mg kg(-1) DW, and barley grain Pb from <0.02 to 0.48 mg kg(-1) DW. The vast majority of samples (>99% for both wheat and barley, excluding Scottish barley samples collected in 2000) were well below the newly introduced EU limit for the maximum permissible concentration of Pb in cereals (0.2 mg kg(-1) fresh weight, equivalent to 0.235 mg kg(-1) DW). There was a significant reduction in wheat grain Pb in the 1998 survey compared with the 1982 survey. However, 40 barley samples collected from Scotland in 2000 in the paired soil and crop survey showed anomalously high concentrations of Pb, with 10 samples exceeding the EU limit. Washing experiments demonstrated that surface contamination, introduced during grain harvest and/or storage, was the main reason for the high concentrations in these samples. In the paired soil and crop surveys, there were no significant correlations between grain Pb concentrations with total soil Pb and other soil properties, indicating low bioavailability of Pb in the soils and limited uptake and transport of Pb to grain. The Pb in cereal grain is likely to originate mainly from atmospheric deposition and other routes of surface contamination during harvest and storage.     

Metal content in street dust as a reflection of atmospheric dust emissions from coal power plants, metal smelters, and traffic

Resuspended street dust is a source of inhalable particles in urban environments. Despite contaminated street dust being a possible health risk factor for local population, little is known about the contribution of atmospheric dust emissions and other factors to the content of toxic metals in street dust. The impact of smelting, traffic, and power plants on metal contaminates in street dust is the focus of street dust sampling at 46 locations in the Witbank area (Republic of South Africa). This area is characterized by numerous open-pit coal mines in the Karoo coal basin, which provides a cheap source of energy to numerous metallurgical smelters and ironworks and supplies coal to the coal-fired power plants located nearby. Street dust was collected on asphalt or concrete surfaces with hard plastic brushes, avoiding collecting of possible sand, soil, or plant particles. Chemical analysis was done on the <0.125 mm fraction using inductively coupled plasma mass spectrometry subsequent to total digestion. Exceptionally high concentrations of metals were detected with concentrations of Fe reaching 17.7 %, Cr 4.3 %, Mn 2 %, Ni 366 mg/kg, and V 4,410 mg/kg. Factor analysis indicates three sources for the pollution. Road traffic which contributes to the high concentrations of Cu, Pb, Sb, and Sn, with the highest impacts detected in the town of Witbank. The second source is associated with the metal smelting industry, contributing to Fe, Co, Mn, and V emissions. The highest factor scores were observed around four metallurgical smelter operations, located in the Ferrobank, Highveld, and Clewer industrial areas. Impact of vanadium smelter to street dust composition could still be detected some 20 km away from the sources. Exceptionally high concentrations of Cr were observed in four samples collected next to the Ferrobank industrial area, despite Cr not being loaded in factor 2. The last source of the pollution is most probably fly ash associated with the coal-fired power plants and fly ash dumps. Elements which are associated with this source are Al, Sr, and Li. This factor is abundant in the coal mining part of the study area.     

Metal contents of fish from cultureponds near scrap metal reclamation facilities

Milkfish (Chanos chanos) from four fish-culture ponds adjacent to different metal recovery facilities along the Er-Jen River area, Tainan, Taiwan, were sampled to determine their metal contents. Chemical analysis showed that fish tissue contained different concentrations of Cu: 0.71-6.37 micrograms/g, Pb: ND (not detectable) approximately 41.04 micrograms/g, Cd: ND approximately 0.41 microgram/g, Al: 6.75-64.11 micrograms/g, Ni: 0.062-0.504 microgram/g and Zn: 16.11-41.86 micrograms/g. The average concentrations of Cu, Al, Zn, Cd and Pb in fish samples from some of the ponds were significantly higher than those from the reference pond. In addition, there were variations in metal concentrations of fish collected from different ponds. Pond D had the highest mean values of Cu, Cd and Zn, and Pond B of Al and Pb. Further investigations are needed to determine the source of metal contamination in the fish.     

Isotopic characterisation of lead in contaminated soils from the vicinity of a non-ferrous metal smelter near Plovdiv, Bulgaria

Soil samples from the vicinity of a non-ferrous metal smelter near Plovdiv, Bulgaria contained very high concentrations of cadmium, lead and zinc (up to 140, 4900 and 5900 mg kg(-1), respectively). A roadside soil in a relatively uncontaminated area also contained high concentrations of the same metals (24, 1550 and 1870 mg kg(-1), respectively) indicating that the transport of ores could be a source of contamination. Even though the lead isotope ratios in all the samples fell within a very narrow range (for example, 1.186-1.195 for (206)Pb/(207)Pb), the samples could be differentiated into three distinct groups: ores ((206)Pb/(207)Pb and (208)Pb/(207)Pb ratios of 1.1874-1.1884 and 2.4755-2.4807, respectively), current deposition (1.1864 and 2.4704-2.4711, respectively) and local background (1.1927-1.1951 and 2.4772-2.4809, respectively). Although most of the current deposition has its origin in the ores used at the smelter, up to 12% could be from other sources such as petrol lead.