Forms of trace metals from inorganic sources in soils and amounts found in spring barley

Barley (Hordeum vulgare L.) was grown on a sandy soil given different doses of cadmium carbonate (salt), copper carbonate (malachite), lead carbonate (cerussite), and zinc carbonate (smithsonite) in a pot experiment conducted in a greenhouse. The element compounds were added to the soil in amounts equivalent to the following levels of the metals: Cd 5, 10, 50 μq ^?1; Cu and Pb 50, 100, 500 μg g^?1; Zn 150, 300, 1500 μg g^?1. Sequential extraction was used for partition these metals into five operationally-defined fractions: exchangeable, bound to carbonates, bound to Fe-Mn oxides, bound to organic matter and residual. The residue was the most abundant fraction in the untreated soil for all the metals studied (43 to 61% of the total contents). The concentration of exchangeable Cd (0.2 μg g^?1), Cu (0.01 μg g^?1), Pb (0.1 μg g^?1), and Zn (1.4 μg g^?1) were relatively low in the untreated soil but increased markedly in the treated soils for Cd (up to 31 μg g^?1) and Zn (up to 83 μg g^?1), whereas only small changes were observed for Cu and Pb. The pot experiment showed a significant increase in the Cd and Zn contents of barley grown on the treated soils, but only small changes in Cu and Pb concentrations.     

Toxicity and binding of copper,zinc, and cadmium by the blue-green alga,Chroococcus paris

The toxic effects and accumulation of the heavy metals, Cd, Cu, and Zn by the sheath forming blue-green alga Chroococcus paris were investigated. All three of the metals were bound rapidly. Approximately 90% of the total amount of the added metal was bound within 1 min. Further significant binding occurred at a slower rate. The maximum metal binding capacity, as determined by filtration studies, was determined to be 53, 120, and 65 mg g^?1 dry algal weight for Cd, Cu, and Zn, respectively. Binding curves for the metals followed the Langmuir adsorption isotherm model. The amount of metal bound increased with increasing pH. Metal binding increased significantly when pH was increased from 4 to 7. Nearly all of the metal was found to be rapidly EDTA extractable. Metals were found to be increasingly toxic to growing cultures in the order, Zn, Cd, and Cu. All of the metals studied exhibited toxic effects at concentrations greater than 1.0 mg L^?1. The lowest concentrations used which showed detectable toxicity were 0.1 mg L^?1 for Cu and >0.4 mg L^?1 for Cd and Zn.     

Effect of elevated concentrations of Cd and Zn in soil on spring wheat yield and the metal contents of the plants

The effect of increasing concentrations of Cd and Zn in a sandy soil on spring wheat (Triticum vulgare L.) yields and the metal contents of the plants was examined in a pot experiment to establish critical levels of these metals in soil. The metals were added (individually and jointly) to the soil as sulfates in the following doses (in μg g^?1, dry wt.): Cd — 2, 3, 5,10, 15, 25, and 50; Zn ?200, 300, 500, 1000, 1500, 2500, and 5000. Cadmium added to soil did not affect yields of wheat. The Zn dose of 1000 μg g^?1 strongly reduced crop yields; at 1500 μg g^? Zn dose wheat did not produce grain. The metal contents of wheat increased with increasing concentrations of Cd and Zn in soil up to 10.3 and 1587 μ g^? of Cd and Zn in straw, respectively. The concentrations of both metals were higher in straw than in grain by factors of 3–7 and 1.5–2 for Zn and Cd, respectively. The relationships between Cd and Zn contents of the plants and soils were best expressed by exponential equations. High concentrations of Zn in soils (1042 and 1542 μg g^?1) enhanced uptake of Cd by plants. The tested threshold concentrations of the metals in soils (3 μg g^?1 for Cd and 200–300 μg g^?1 for Zn) are safe for Zn but are too high for Cd in terms of protecting plants from excessive metal uptake. The critical Cd content of sandy soil should not exceed 1.5 μg g^?.     

Forms of Cd,Cu, Pb,and Zn in soil and their uptake by cereal crops when applied jointly as carbonates

The cereal crops (barley -Hordeum vulgare L., maize -Zea mays L., wheat -Triticum vulgare L.) were grown in a greenhouse using a sandy soil type treated with various doses of cadmium carbonate (salt), copper carbonate (malachite), lead carbonate (cerussite), and zinc carbonate (smithsonite), added jointly. The following levels of these metals were used: Cd ? 5, 10, 50μg g^?1 soil; Cu and Pb - 50,100, 500 μg g^?1 soil; Zn-150, 300, 1500 μg g-1 soil. Sequential extraction was adopted to partition the metals into five operationally-defined fractions: exchangeable, carbonate, Fe-Mn oxides, organic, and residual. The residual was the most abundant fraction in the untreated (control) soil for all the metals studied (50 to 60% of the total metal content). The concentrations of exchangeable Cd, Cu, Pb, and Zn were relatively low in untreated soil but increased (over the three year period) in treated soils for Cd, Zn, and Cu, whereas only small changes were observed for Ph. This experiment showed a significant increase in Cd, Zn, and Cu in tissue of plants grown on the treated soil, but a non-significant change in plant tissue with respect to Pb concentration.     

Heavy Metals Leachability as Affected by pH of Compost-Amended Growth Medium Used in Container-Grown Rhododendrons

The leaching of heavy metals from plant growth medium, admixed with different amounts of compost (prepared from sewage sludge and yard waste) at pH 5, 6 and 7 was determined over a six-month period. Twelve-week old rhododendron cuttings were planted in 2-L containers and rainfall was supplemented with irrigation to supply two centimeters of water per day. Leachates collected over each two to four week period were analyzed for Cd, Cr, Cu, Ni, Pb and Zn using atomic spectrometry. The concentrations of Cd, Cu, Ni and Zn in the leachates increased with increasing proportions of compost in the medium and decreased with increasing time of leaching. Decreasing media pH dramatically increased the concentrations of Cd, Ni and Zn in the leachates, but had no effect on the Cu concentrations. For example, as the proportion of the compost in the pH 5 medium increased from 0 to 100 percent, the concentrations of metals (μg L^?1) in the leachates collected during the first two weeks increased from 1 to 33 (Cd), 10 to 123 (Cu), 8 to 113 (Ni) and 300 to 24,000 (Zn). Corresponding increases at pH 7 were 0.4 to 0.8 (Cd), 14 to 141 (Cu), 8 to 28 (Ni) and 100 to 400 (Zn) μg L^?1. The concentrations of Cr and Pb in the leachates remained below the detection limits regardless of media pH and amounts of compost.     

Trace metal concentrations in marine organisms from St. Vincent Gulf,South Australia

Trace metal concentrations were measured in the tissues of fish, molluscs, crustaceans and macrophytes from St. Vincent Gulf, South Australia. The concentrations of the measured metals (Cd < 0.025 to 2.1 μg g^?1; Cu 0.51 to 9l μg g^?1 5 Pb 0.02 to 3.6 ?g g^?1; Zn l5 to 110 μg g^?1)are similar to those from unpolluted areas and thus give no indication of pollution.     

Aquatic mosses for the detection and follow-up of accidental discharges in surface waters

Aquatic mosses have been used to study four accidental discharges of the heavy metals Cd, Zn and Hg or the chlorinated hydrocarbons pentachlorophenol (PCP) and lindane in highly contrasting river types. Hg, PCP and lindane moss concentrations reached 880, 4500 and 350 ng g^?1, respectively. In the case of Cd and Zn, water samples and transferred bioindicators were taken simultaneously throughout an accidental discharge. The very high dissolved metal concentrations reached during this accident (9 mg L^?1 Zn, 90 μg L^?1 Cd) induced accumulation by the mosses of up to 28 mg g^?1 for Zn and 225 μg g^?1 for Cd. The increase in concentrations in the mosses was as rapid and substantial as in the water, the time lag due to accumulation kinetics being almost zero. On the other hand, the memory effect enabled mosses to retain marked evidence of Cd, Zn, Hg, PCP and lindane up to 13 days after the accident when difference from background levels can hardly be detected in the water. The four case studies, which killed fish, but not the mosses, show that the previously established scales of quality based on the analysis of aquatic mosses are well suited to estimating the potential damage to the aquatic ecosystem as a whole.     

Retention of Cd, Cu, Pb and Zn by Wood Ash, Lime and Fume Dust

Heavy metals are of interest due to their deleterious impacts on both human and ecosystem health. This study investigated the effectiveness of wood ash in immobilizing the heavy metals Pb, Cd, Cu and Zn from aqueous solutions. The effects of initial metal concentrations, solution pH, ash dose and reaction time on metal sorption, as well as the metal sorption mechanisms were studied. To investigate the effect of initial metal concentrations, solutions containing Cd, Zn (25, 50, 75, 100 or 125 mg L^?1), Cu (25, 50, 75, 100, 125, 150 or 175 mg L^?1) or Pb (250, 500, 750, 1000, 1250, or 1500 mg L^?1) were reacted with 10 g L^?1 ash for two hours. For the effect of pH, solutions containing 100 mg L^?1 of Cd, Cu or Zn or 1500 mg L^?1 of Pb were reacted with 15 g L^?1 ash over a pH range of 4 to 7. The wood ash was effective in immobilizing the four metals with a sorption range of 41–100 %. The amounts of metals retained by the ash followed the order of Pb > Cu > Cd > Zn. As expected, absolute metal retention increased with increasing initial metal concentrations, solution pH and ash dose. Metal retention by the ash exhibited a two-phase step: an initial rapid uptake of the metal followed by a period of relatively slow removal of metal from solution. Metal retention by the ash could be described by the Langmuir and Freundlich isotherms, with the latter providing a better fit for the data. Dissolution of calcite /gypsum minerals and precipitation of metal carbonate/sulfate like minerals were probably responsible for metal immobilization by the ash in addition to adsorption.     

Limited downward migration of pollutant metals (Cu,Zn, Ni,and Pb) in acidic virgin peat soils near a smelter

The distribution of pollutant heavy metals (Cu, Zn, Ni, Cd, and Pb) was determined in 11 acidic virgin peat profiles located along two transects moving away from a smelter plant in the Noranda region of Quebec. The levels of all five metals were found highest in the 0 to 15 cm layer at site near the smelter, and decreased progressively with the distance from the smelter, up to 42 km. Copper had the highest concentrations (5525 μg g^?1) followed by Pb and Zn. The maximum levels of total metals built up in the peat surface near the smelter were high, approximately reaching the threshold limits for phytotoxicity in peat soils. The amounts of heavy metals moving down and accumulating in the anaerobic zone of the peat profiles were limited. The distribution and enrichment ratios in the profiles showed that Cu, Zn, and Cd would have relatively higher mobility than Pb.     

Anomalous contents of heavy metals in soils and vegetation of a mine area in S.W. Sardinia,Italy

Samples of soils and vegetation from the mining area of South-West Sardinia (Italy) were analyzed for Pb, Zn, Cd, and Cu content. The area (more than 100 km²) is inhabited by many thousands of people; land utilization includes mainly grapes on some small plains and permanent sheep pasture on the hills. The levels of Pb, Zn, and Cd were found to be exceptionally high in most samples. Lead concentration was up to 71000 μg g^?1 in the soils and 4000 jig g^?1 in vegetation; Cd concentration was found up to 665 μg g^?1 in soils and 26.5 μg g^?1 in vegetation. The heavy metal content of some soil samples was highly variable. Data show that Pb is easily absorbed by plant roots and translocated to foliage. In spite of the high heavy metal level, no signs of toxicity were apparent in vegetation.     

Hg, Cu, Pb, Cd, and Zn Accumulation in Macrophytes Growing in Tropical Wetlands

The concentrations of Hg, Cu, Pb, Cd, and Zn accumulated by regional macrophytes were investigated in three tropical wetlands in Colombia. The studied wetlands presented different degrees of metal contamination. Cu and Zn presented the highest concentrations in sediment. Metal accumulation by plants differed among species, sites, and tissues. Metals accumulated in macrophytes were mostly accumulated in root tissues, suggesting an exclusion strategy for metal tolerance. An exception was Hg, which was accumulated mainly in leaves. The ranges of mean metal concentrations were 0.035?C0.953 mg g^?1 Hg, 6.5?C250.3 mg g^?1 Cu, 0.059?C0.245 mg g^?1 Pb, 0.004?C0.066 mg g^?1 Cd, and 31.8?363.1 mg g^?1 Zn in roots and 0.033?C0.888 mg g^?1 Hg, 2.2?C70.7 mg g^?1 Cu, 0.005?C0.086 mg g^?1 Pb, 0.001?C0.03 mg g^?1 Cd, and 12.6?C140.4 mg g^?1 Zn in leaves. The scarce correlations registered between metal concentration in sediment and plant tissues indicate that metal concentrations in plants depend on several factors rather than on sediment concentration only. However, when Cu and Zn sediment concentrations increased, these metal concentrations in tissues also increased in Eichhornia crassipes, Ludwigia helminthorriza, and Polygonum punctatum. These species could be proposed as Cu and Zn phytoremediators. Even though macrophytes are important metal accumulators in wetlands, sediment is the main metal compartment due to the fact that its total mass is greater than the corresponding plant biomass in a given area.     

The flux of Cd,Cu, Pb and Zn in mining polluted soils

The monitoring of heavy metal deposition onto soils surrounding old Pb-Zn mines in two locations in the UK has shown that relatively large amounts of Cd, Pb, Zn and, in one case, Cu are entering the soil annually. Small particles of ore minerals in windblown mine tailings were found to be contributing up to 1.46 g m^?2 yr^?1 of Pb, 1.41 g m^?2 yr^?1 of Zn and 0.027 g m^?2 yr^?1 of Cd. However, when these inputs from bulk deposition are compared with the concentrations of the same metals within the soil profiles it is apparent that relatively little long-term accumulation is occurring. Metals are being lost from the soil profiles, probably through leaching. A calculated relative retention parameter gave values that ranged from 0.01 to 0.17 for Cd, 0.11 to 0.19 for Zn, 0.32 to 0.63 for Cu and over 1 for Pb. These relative retention values were found to follow the order of electronegativity of the elements concerned: Pb>Cu>Zn>Cd. Distribution coefficient (Kd) values quantifying the adsorptive capacity of the mine soils for Cd and Pb showed marked differences for the two metals (12 to 69 cm³ g^?1 for Cd and 14 to 126 cm³ g^?1 for Pb) and may, in part, account for the two to one hundred-fold variation in the relative retention parameter for the different metals within these soils.     

Trace Metals in the Water Columns of the Red Sea and the Gulf of Aqaba,Egypt

Seawater samples were collected from the northern Red Sea and the Gulf of Aqaba at different depths during February 1999 and analyzed for iron, zinc, manganese, nickel, copper, cadmium, cobalt and lead to determine the existing concentration of these metals, their distribution patterns and where contamination has occurred. The concentrations of Fe, Zn, Mn, Ni, Cu, Cd, Co, Pb were scatteredin the ranges: (0.56–4.44; mean 1.67±0.9 μg L^-1), (0.13–1.17; mean 0.24±0.12 μg L^-1), (0.06–0.21; mean 0.13±0.03 μg L^-1), (0.05–0.52; mean 0.16±0.06 μg L^-1), (0.07–0.29; mean 0.14±0.06 μg L^-1), (0.02–0.78; mean 0.49±0.14 μg L^-1), (0.06–0.29; mean 0.15±0.04 μg L^-1), and (0.02–0.68; mean 0.31±0.13 μg L^-1), respectively. The results revealed a small range of variation and regional irregularities. It also indicated significant higher concentrations for Fe, Cd and Pb compared to other metals. Compared to the northern Red Sea, significant higher concentrations for Ni and Cd are measured at the Gulf of Aqaba. Other metals, i.e. Fe, Zn, Mn, Cu, Co, and Pb are not significantly different in both areas indicating no distinct concentration gradients. Except for Pb, the distribution patterns indicated significantly lower concentrations at surface layer in both regions, then increasing to their maximum values at the sub-surface layers which followed by a decrease in deep water. The study indicated also that the mean concentrations of trace metals examined here are much lower than those reported for the Mediterranean Sea and typical of open ocean water.     

Effects of heavy metals in soil on microbial processes and populations (a review)

The effects of Cd, Cu, Zn, and Pb on soil microorganisms and microbially mediated soil processes are reviewed. The emphasis is placed on temperate forest soils. The sensitivity of different measurements is discussed, and data compiled to compare relative toxicity of different metals. On the whole the relative toxicity of the metals (on a μg g^?1 soil basis) decreased in the order Cd > Cu > Zn > Pb, but differences between different investigations were found. The influence of abiotic factors on metal toxicity is briefly discussed and especially examplified by different soil organic matter content. Evidence of tolerance and adaptation in the soil environment and the time scale involved in the evolution of a metal-tolerant microbial community after metal exposure are also considered.     

Patterns of trace metal concentration and acidity in montane forest soils of the northeastern United States

Forest floor and mineral soil samples were collected from subalpine spruce-fir forests at 1000 m above mean sea level on 19 mountains in the northeastern United States to assess patterns in trace metal concentrations, acidity, and organic matter content. The regional average concentrations of Pb, Cu, and Zn in the forest floor were 72.3 (2.9 s.e.) μg g^?1, 8.5 (0.7) μg g^?1, and 46.9 (2.0) μg g^?1, respectively. The regional average concentrations of Pb, Cu, and Zn in the mineral soil were 13.4 (0.8) μg g^?1, and 18.2 (1.2) μg g^?1, respectively. The regional average pH values of the forest floor and mineral soil were 3.99 (0.03), and 4.35 (0.03), respectively. The Green Mountains had the highest concentrations of Pb (105.7 μg g^?1), and Cu (22.7 μg g^?1), in the forest floor. They also had the highest concentrations of Cu (18.0 μg g^?1), in the mineral soil. Site aspect did not significantly influence any of the values. Concentrations of Pb were lower than concentrations reported earlier in this decade at similar sites while concentrations of Cu and Zn remained the same. We believe that these lower Pb concentrations reflect real changes in forest Pb levels that have occurred in recent years.     

Wet Deposition of Trace Metals in Singapore

The concentrations of 12 trace metals (Al, Cd, Cr, Cu, Co, Fe,Mn, Ni, Pb, Zn, V, and Ti) in wet depositions are reported. Eighty four rainwater samples were collected using an automated wet-only sampler in Singapore for one year (2000) and subjected to chemical analysis using ICP-MS. Based on the volume-weighted meanconcentrations measured, the trace metals were classified into three groups: Al and Fe with an average concentration of largerthan 15 μg L^-1, Cr, Cu, Mn, Ni, Pb, Zn, V, and Ti withconcentrations between 1 and 10 μg L^-1, and finally Co and Cd with concentrations lower than 1 μg L^-1. Elementenrichment factors were calculated to distinguish between naturaland anthropogenic sources. The calculation of crustal enrichmentfactors with Al as the reference element indicated that while Ti,Fe and Mn originated from crustal sources, the remaining trace metals (Cd, Cr, Co, Cu, Ni, Pb, Zn and V) were mainly derived from anthropogenic sources. The removal of the trace metals from the atmosphere by precipitation was influenced by the rainfall amount as well as pH. The magnitude of the measured average annual wet deposition fluxes of Al, Fe, and combustion-generatedelements such as V, Ni, and Cu is higher than that reportedfor other sites outside Singapore, owing to abundant rainfallthroughout the year in this region.     

Zusammensetzung und Speziierung der Bodenlösung eines mit Schwermetallen belasteten kalkreichen Bodens

Composition and Speciation of Soil Solution collected in a Heavy Metal polluted calcareous Soil Close to a brass foundry, which had emitted heavy metal containing dusts for over 80 years, soil water was collected in the topsoil (18 cm) and in the subsoil (40 cm) of a severely polluted Calcic Fluvisol by means of polyethylen suction cups over a period of 2 years. The total metal content of the topsoil (extracted with 2M HNO₃ at 100 °C for 2 hours) was 38 nmol g^?1, 24 μmol g^?1, and 25 μmol g^?1 for Cd, Cu, and Zn, respectively. The mean heavy metal concentrations of the soil solution were 0.5 mol L^?1, 300 nmol L^?1, and 200 nmol L^?1 in the topsoil and 0.6 nmol L^?1, 90 nmol L^?1, and 30 nmol L^?1 in the subsoil for Cd, Cu, and Zn, respectively. Solubility calculations showed that the soil solutions were undersaturated with respect to heavy metal carbonates as well as to hydroxides. It seems that the heavy metal concentration is determined by sorption processes rather than by precipitation. The composition of the soil solution has been shown to be governed by the presence, of calcite, by the soil temperature and by the partial pressure of CO₂ in the soil air. The pCO₂ in the soil air (in both depths) has been estimated at 2 mbar during the winter term and at 20 mbar during the summer term. A corresponding increase of the concentration of macroelements (Ca, Mg, Na) as well as of total dissolved carbonate and of dissolved organic matter (DOC) has been measured in the summer half year. No significant seasonal variations of the heavy metal concentrations were detected and no correlations with concentrations of other components could be found.     

Enhanced Heavy Metal Phytoextraction from Marine Dredged Sediments Comparing Conventional Chelating Agents (Citric Acid and EDTA) with Humic Substances

Metal (Cu, Mn, Ni, Zn, Fe) concentrations in marine sediment and zooplankton were investigated in Izmir Bay of the Eastern Aegean Sea, Turkey. The study aimed to assess the levels of metal in different environmental compartments of the Izmir Bay. Metal concentrations in the sediment (dry weight) ranged between 4.26–70.8 μg g^?1 for Cu, 233–923 μg g^?1 for Mn, 14.9–127 μg g^?1 for Ni, 25.6–295 μg g^?1 for Zn, 12,404–76,899 μg g^?1 for Fe and 38,226–91,532 μg g^?1 for Al in the Izmir Bay. Maximum metal concentrations in zooplankton were observed during summer season in the inner bay. Significant relationships existed between the concentrations of certain metals (Al, Fe, Mn and Ni) in sediment, suggesting similar sources and/or similar geochemical processes controlling such metals. Higher concentrations of Cu, Zn and percent organic matter contents were found in the middle-inner bays sediments. Based on the correlation matrix obtained for metal data, organic matter was found to be the dominant factor controlling Cu and Zn distributions in the sediment. In general, mean Cu and Zn levels in the bay were above background concentrations in Mediterranean sediments. Zooplankton metal concentrations were similar to sediment distributions.     

Metal concentrations in the ground water of the Ouachita Mountains,Arkansas, U.S.A.

Ninety-one ground water samples (predominantly from springs) in two mineralized areas of the Ouachita Mountains in west-central Arkansas, were analyzed for Fe, Mn, Zn, Cu, Co, Ni, Pb, Hg, Sb, Sr, Ba, Ca, and Li. These areas contain Mn, barite, strontianite, cinnabar, stibnite and scattered Pb-Zn mineralization, Cumulative frequency curves were used to determine the threshold and anomalous concentrations for each element in the two areas. These values were, in general, higher in the ground water from the more mineralized area for several of the base metals, but most notably for Mn and Fe, the principal metals in the Mn oxide minerals. The United States Environmental Protection Agency (EPA, 1976) criteria for Fe (300 μg L ^?1) and Mn (50 μg L^?1) in drinking water were exceeded, respectively, in 34% and 30% of the springs in Area I, and 13% and 23% in Area II. One spring exceeded the EPA Hg criterion (2 μg L^?1) and 3 springs exceeded the 50 μg L^?1 criterion for Pb. In spite of the large number of anomalous Ba concentrations, the highest concentration of Ba was 930 μg L^?1 (EPA criterion 1000 μg L ^?1).     

Single and Combined Effects of Cadmium and Zinc on Carrots: Uptake and Bioaccumulation

ABSTRACT

The present study was conducted to evaluate the effects of different concentrations of cadmium (Cd) and zinc (Zn), singly and in combination, on uptake and bioaccumulation of Cd and Zn in Daucus carota L. (carrot) grown under natural field conditions. Carrot plants were treated with two Cd concentrations (10 and 100 μg mL^?1), two Zn concentrations (100 and 300 μg mL^?1), and two combined concentrations of Cd and Zn (10 + 100 and 100 + 300 μg mL^?1) 15 d after seed germination. Treatments were repeated at 10 d intervals up to 90 d of plant age. A control was also kept without a Cd or Zn treatment. Uptake, total accumulation rate (TAR), bioconcentration factor (BCF), primary transport index (PTI), secondary transport index (STI), and accumulation of Cd and Zn in root, stem, and leaf were quantified. The results show that uptake, TAR, and accumulation of Cd and Zn are concentration-dependent phenomena. Highest accumulation of Cd and Zn was found in the root, followed by the stem and then leaves. The results also showed that bioaccumulation of Cd in root, stem, and leaf was greater at the low metal-application rates of Cd and Zn in combination than at the higher rate. This study further showed that interactions of Zn and Cd are dependent on the concentrations of those metals in the soil.