An improved understanding of soil Cd risk to humans and low cost methods to phytoextract Cd from contaminated soils to prevent soil Cd risks

We believe greater consideration should be given the agronomic and nutritional/bioavailability factors that influence risk from Cd-contaminated soils. We have argued that the ability of rice to accumulate soil Cd in grain while excluding Fe, Zn and Ca (even though the soil contains 100-times more Zn than Cd) was important in adverse effects of soil Cd is farm families in Asia. Further, polished rice grain is deficient in Fe, Zn and Ca for humans, which promotes Cd absorption into duodenal cells. New kinetic studies clarified that dietary Cd is absorbed into duodenum enterocytes; 109Cd from a single meal remained in the duodenum for up to 16 days; part of the turnover pool 109Cd moved to the liver and kidneys by the end of the 64-day 'chase' period. Thus malnutrition induced by subsistence rice diets caused a higher absorption of dietary Cd and much higher potential risk from soil Cd than other crops. Because rice-induced Fe-Zn-Ca-malnutrition is so important in soil Cd risk, it seems evident that providing nutritional supplements to populations of exposed subsistence rice farmers could protect them against soil Cd during a period of soil remediation. In the long term, high Cd rice soils need to be remediated. Remediation by removal and replacement of contaminated soil is very expensive (on the order of $3 million/ha); while phytoextraction using the high Cd accumulating ecotypes of the Zn-Cd hyperaccumulator, Thlaspi caerulescens, should provide low cost soil Cd remediation.     

Cadmium and zinc in plants and soil solutions from contaminated soils

In an experiment using ten heavy metal-contaminated soils from six European countries, soil solution was sampled by water displacement before and after the growth of radish. Concentrations of Cd, Zn and other elements in solution (K, Ca, Mg, Mn) generally decreased during plant growth, probably because of uptake by plants and the subsequent redistribution of ions onto soil exchange sites at lower ionic strength. Speciation analysis by a resin exchange method showed that most Cd and Zn in non-rhizosphere solutions was present as Cd2+ and Zn2+, respectively. The proportion of free ions was slightly lower in rhizosphere solutions, mainly due to an increase in dissolved organic carbon during plant growth. Solution pH increased during plant growth, although the bulk soil pH generally remained constant. Cd concentrations in leaves and tubers were more closely correlated with their total or free ionic concentrations in rhizosphere solutions (adjusted R2 0.90) than with their concentrations in soils (adj. R2 0.79). Cd concentrations in non-rhizosphere solutions were only poorly correlated with Cd concentrations in leaves and tubers. In contrast to Cd, there were no soil parameters that individually predicted Zn concentrations in leaves and tubers closely. However, multiple correlation analysis (including Zn concentrations in rhizosphere solutions and in bulk soils) closely predicted Zn concentrations in leaves and tubers (adj. R2 = 0.85 and 0.70, respectively). This suggests that the great variability among soils in the solubility of Zn affected the rate of release of Zn into solution, and thus Zn uptake. There was no such effect for Cd, for which solubility varied much less. Furthermore, the plants may have partly controlled Zn uptake, as they took up relatively less at high solution concentrations of Zn.Free ionic concentrations in soil solution did not predict concentrations of Cd or Zn in plants better than their total concentrations in solution. This suggests that with these soils, analysis of Cd and Zn speciation is of little practical importance when their bioavailability is assessed.     

Effects of heavy-metal additions on ammonification and nitrification in soils contaminated with cadmium,lead and zinc

Summary The sensitivity of the mineralization of nitrogen by a range of soils contaminated with heavy metals (up to 340 μg Cd g⁻¹, 7500 μg Pb g⁻¹ and 34000 μg Zn g⁻¹) to the addition of heavy metals in solution were studied using pot incubations (ammonification) and a soil perfusion technique (nitrification). The ammonification of peptone showed little correlation between treatments with Cd, Zn (1000 and 5000 μg g⁻¹) and Pb (10000 and 20000 μg g⁻¹) and origin of the soil. Nitrification was considerably more sensitive to heavy metals than ammonification. All the soils had active, often large, populations of ammonifying and nitrifying organisms which showed substantial similarities between the soils. The rate of nitrifying activity (NO₃−N production) was logrithmic in most cases. The presence of tolerant populations of nitrifying organisms in the contaminated soils was demonstrated. Tolerance was also eventually acquired after a longer lag phase, by the non-contaminated soil populations although the rate of activity was often reduced. Metals added in solution were adsorbed by the soil within 4 hours. Differences in toxicity between metal salts (chlorides, sulphates and acetate) were attributed to the amount left in solution. However, in many instances, acetate was found to stimulate all the stages in the mineralisation of nitrogen.     

Cadmium and zinc bioaccumulation by Phytolacca americana from hydroponic media and contaminated soils

Abstract

Hydroponic, greenhouse and field experiments were conducted to explore the potential of pokeweed (Phytolacca americana L.) to accumulate Zn and Cd from nutrient solutions and contaminated soils. The hydroponic results confirmed that this native species is a strong Zn and Cd bioaccumulator that does not experience severe phytotoxicity until quite high root and shoot concentrations, approaching 4000 and 1600?mg?kg^?1 of Zn, and 1500 and 500?mg?kg^?1 of Cd, respectively. These high Zn and Cd concentrations were accompanied by increased sulfur and lower manganese in both shoots and roots. However, in field and greenhouse trials with soils historically contaminated by a number of heavy metals including Zn and Cd, concentrations of Zn and Cd in shoots of P. americana reached concentrations less than 30% and 10%, respectively, of those achieved with hydroponics. The main constraint to phytoremediation of soils by P. americana was the low concentrations of Zn and Cd in soil solution. Pretreatment of the metal-contaminated soil by oxalic acid increased soluble Cd and Zn but failed to increase plant uptake of either metal, a possible result of higher solubility of competing metal ions (Cu, Mn) or low bioavailability of Cd and Zn-oxalate complexes.     

Economic incentive for applying vetiver grass to remediate lead, copper and zinc contaminated soils

The application of vetiver grass (Chrysopogon zizaniodes) for phytoremediation of heavy metal contaminated soils can be promoted by economic return through essential oil production. Four levels of lead (0, 500, 2000, and 8000 mg kg(-1) dry soil), copper (0, 100, 400, and 1600 mg kg(-1) dry soil) and zinc (0, 400, 1600, and 6400 mg kg(-1) dry soil) were used to study their effects on vetiver growth, essential oil composition and yield. This study also investigated the effect of nitrogen concentrations on vetiver oil yield. Vetiver accumulated high concentrations of Pb, Cu and Zn in roots (3246, 754 and 2666 mg kg(-1), respectively) and small amounts of contaminants in shoots (327, 55, and 642 mg kg(-1), respectively). Oil content and yield were not affected at low and moderate concentrations of Cu and Zn. Only the application of Pb had a significant detrimental effect on oil composition. Extraction of vetiver essential oils by hydrodistillation produced heavy metal free products. High level of nitrogen reduced oil yields. Results show that phytoremediation of Cu and Zn contaminated soils by vetiver can generate revenue from the commercialization of oil extracts.     

Inducibility and amounts of metallothionein as influenced by cadmium and zinc in the developing rat

Information on the accumulation and/or depletion of Zn in metallothionein (MT) of rat fetus, rat pup, and maternal rat liver at various ages was obtained with pregnant rats fed a basal casein diet or this diet plus either 100 ppm Zn or 50 ppm Cd. Rats fed each of the respective diets were sacrificed on 12, 16, and 20 d of gestation and 0, 7, 14, and 28 d post-partum. No Cd was detected in the placenta or fetal tissue and the Cd did not affect the accumulation of Zn in the fetal MT, but it did increase the Zn content in liver MT of the dams. Very little Zn in MT was found on day 12 of gestation, but Zn rapidly increased in MT to a maximum at time of birth. The accumulation of Zn in MT was independent of the diet for the fetuses, but the Zn accumulation in the dam and pup tissues was diet dependent. In order to study age-dependent difference in the inducibility of MT, newborn, 5-week-old, or 24-week-old rats were injected with zinc at the levels of 0, 3, 6, or 9 mg/kg and 5 h later injected with³⁵S-cystine. In rats sacrificed 1 h later, the amount of radioactivity in liver MT demonstrated that this protein in older animals was more readily induced by Zn than in younger animals.     

Phytoextraction of metals and metalloids from contaminated soils

The removal of inorganic contaminants by plants is termed phytoextraction. Recent studies have looked at the feasibility of phytoextraction, and demonstrate that both good biomass yields and metal hyperaccumulation are required to make the process efficient. Adding chelating agents to soil to increase the bioavailability of contaminants can sometimes induce hyperaccumulation in normal plants, but may produce undesirable environmental risks. Thus, it is necessary to investigate the mechanisms responsible for hyperaccumulation, using natural hyperaccumulators as model plant species. Recent advances have been made in understanding the mechanisms responsible for hyperaccumulation of Zn, Cd, Ni and As by plants. Attempts to engineer metal tolerance and accumulation have so far been limited to Hg, As and Cd, and although promising results have been obtained they may be some way from practical application. More fundamental understanding of the traits and mechanisms involved in hyperaccumulation are needed so that phytoextraction can be optimised.     

Effect of heavy metal-solubilizing microorganisms on zinc and cadmium extractions from heavy metal contaminated soil with Tricholoma lobynsis

The macrofungus, Tricholoma lobynsis, was chosen to remedy Zn–Cd–Pb contaminated soil. To enhance its metal-extracting efficiency, two heavy metal resistant microbes M6 and K1 were applied owing to their excellent abilities to solubilize heavy metal salts. The two isolated microbial strains could also produce indole acetic acid (IAA), siderophore and solubilize inorganic phosphate, but neither of them showed 1-aminocyclopropane-1-carboxylate deaminase activity. The strains M6 and K1 were identified as Serratia marcescens and Rhodotorula mucilaginosa based on 16S rDNA and ITS sequence analysis respectively. Pot experiment showed that spraying to T. lobynsis-inoculated soil with M6 and K1 respectively could increase total Cd accumulations of this mushroom by 216 and 61%, and Zn by 153 and 49% compared to the uninoculated control. Pb accumulation however, was too low (<1 mg kg⁻¹) to be determined. The results illustrated that special microbes and macrofungi can work together to remedy polluted soil as plant and plant growth promoting microbes do, probably because of excellent metal-accumulating abilities of macrofungi and IAA-siderophore production, phosphate solubilization abilities of the assisted-microbes. This kind of macrofungi-microbe interaction can be developed into a novel bioremediation strategy.     

Arbuscular mycorrhiza can depress translocation of zinc to shoots of host plants in soils moderately polluted with zinc

There is increasing and widespread interest in the maintenance of soil quality and remediation strategies for management of soils contaminated with organic pollutants and trace metals or metalloids. There is also a growing body of evidence that arbuscular mycorrhizal (AM) fungi can exert protective effects on host plants under conditions of soil metal contamination. Research has focused on the mechanisms involved and has raised the prospect of utilizing the mutualistic association in soil re-vegetation programmes. In this short paper we briefly review this research, summarize some recent work and highlight some new data which indicate that the alleviation of metal phytotoxicity, particularly Zn toxicity, by arbuscular mycorrhiza may occur by both direct and indirect mechanisms. Binding of metals in mycorrhizal structures and immobilization of metals in the mycorrhizosphere may contribute to the direct effects. Indirect effects may include the mycorrhizal contribution to balanced plant mineral nutrition, especially P nutrition, leading to increased plant growth and enhanced metal tolerance. Further research on the potential application of arbuscular mycorrhiza in the bioremediation or management of metal-contaminated soils is also discussed.     

Phytoextraction potential of soils highly polluted with cadmium using the cadmium/zinc hyperaccumulator Sedum plumbizincicola

Abstract

A three-crop repeated phytoextraction experiment was conducted using four soils (S1–S4) highly polluted with cadmium (Cd) and two enhanced phytoextraction pot experiments using the most polluted soil (S4) to investigate the feasibility of Cd removal from highly polluted soils using the Cd/zinc (Zn)-hyperaccumulator Sedum plumbizincicola. Shoot biomass showed no significant difference during the repeated phytoextraction experiment on the four test soils and shoot Cd content showed a decreasing trend with the three consecutive crops in soils S1, S2, and S3 but not in soil S4. The Cd removal rates in soils S1, S2, S3, and S4 were 84.5, 81.6, 45.3, and 32.4%, respectively. Rice straw application increased Cd extraction efficiency by 42.6% but the addition of ethylenediaminedisuccinic acid, biochar or nitrogen had no effect on Cd remediation. Shoot Cd content increased significantly (1.57 and 1.71 times, respectively) at low (S₀-1) and high (S₀-2) sulfur addition rates. Soil extractable-Cd in S₀-1 after the experiment showed no significant difference from the control but was 2.43 times higher in S₀-2 than in the control. These results indicate that S. plumbizincicola shows good prospects for the phytoextraction of Cd from highly polluted soils and that the process can be enhanced by adding straw and/or sulfur to the soil.     

Kinetics of zinc desorption from soils

Summary The kinetics of zinc desorption by DTPA were investigated in several soils. The rate of desorption of soil zinc and adsorbed zinc was rapid initially and gradually declined with time. The desorption reaction can be described by a two constant rate equation, C=At^B. The rate of zinc desorption in soil containing freshly adsorbed zinc was considerably higher than soil zinc, possibly due to the higher solubility and zinc concentration on the surfaces of soil particulate matter. The amount of zinc desorbed by DTPA, however, continued to decrease with increasing aging time. Elevated temperature further enhanced zinc aging and reduced zinc extractability. Recrystallization of adsorbed zinc in soil which subsequently increased the bonding strength of adsorbed zinc, could be responsible for the reduction of zinc desorption by DTPA.Contribution from the Department of Agronomy and Range Science, University of California, Davis, Ca.     

Biosorptive removal of cadmium from contaminated groundwater and industrial effluents

The cadmium removing capacity of a biosorbent Calotropis procera, a perennial wild plant, is reported here. The biomass was found to possess high uptake capacity of Cd(II). Adsorption was pH dependent and the maximum removal was obtained at two different pH i.e. pH 5.0 and 8.0. Maximum biosorption capacity in batch and column mode was found to be 40 and 50.5 mg/g. The adsorption equilibrium (> or =90% removal) was attained within 5 min irrespective of the cadmium ion concentration. Interfering ions viz. Zn(II), As(III), Fe(II), Ni(II) interfered only when their concentration was higher than the equimolar ratio. The Freundlich isotherm best explained the adsorption, yet the monolayer adsorption was also noted at lower concentrations of Cd(II). The FTIR analysis indicates the involvement of hydroxyl (-OH), alkanes (-CH), nitrite (-NO(2)), and carboxyl group (-COO) chelates in metal binding. The complete desorption of the cadmium was achieved by 0.1M H(2)SO(4) and 0.1M HCl. The C. procera based Cd(II) removal technology appears feasible.     

Arsenic accumulation of common plants from contaminated soils

A pot experiment was conducted to investigate the relationship between soluble concentrations of arsenic (As) in soil and its accumulation by maize (Zea mays), English ryegrass (Lolium perenne), rape (Brassica napus) and sunflower (Helianthus annuus) on two different soils: a calcareous Regosol (silty loam) and a non-calcareous Regosol (sandy loam). Arsenic (Na₂HAsO₄·7H₂O) was applied to obtain comparable soluble As concentrations in the two soils. In both soils, soluble As concentrations, extracted with 0.1 M NaNO₃, were found to correlate better with As concentrations in plants after 4 month of growth than total soil concentrations, extracted with 2 M HNO₃. With all four plant species, the relationship between the soluble As concentration in the soil and As that in the plants was non- linear, following Michaelis-Menten kinetics. Similar soluble As concentrations in the two soils did not result in a similar As concentration in the plants. Except for maize, arsenic transport from roots to shoots was significant, resulting in As concentrations in the leaves and grains above the Swiss tolerance limits for fodder and food crops (4 and 0.2 mg As kg^–1, respectively). Based on these results we suggest that beside As solubility, P availability and P demand, which are plant specific, have to be taken into account to predict the uptake of As by crop plants from As contaminated soils and to predict the risk of arsenic entering into the food chain.     

Chemical partitioning of iron,cadmium, nickel and chromium in contaminated soils of south-eastern Nigeria

Abstract

Selected heavy metals Fe, Cd, Ni and Cr were studied in contaminated soil samples collected from south-eastern Nigeria. Geochemical differentiation into different chemical fractions, using Ma and Rao six-step sequential chemical extraction procedure, was carried out to assess the potential mobility and bioavailability of the heavy metals in the soil profiles. The residual fraction was the most important phase for the four heavy metals with the following average percentage values 74.43 for Fe, 37.69 for Cd, 70.11 for Ni and 62.47 for Cr. The carbonate fraction contained an appreciable proportion of Fe, Cd and Ni with the average percentage values of 16.29, 14.86 and 10.47 respectively, while organic fraction was of next importance for Cr with an average percentage value of 27.14. The Fe-Mn oxide fraction also contained 15.86% of Cd. Relatively low amounts of the metals were associated with water soluble and exchangeable fractions. The mobility factors for the metals in all the sites ranged from 8.55 to 40.04 for Fe, 8.66 to 56.58 for Cd, 12.74 to 30.19 for Ni and 0.82 to 7.22 for Cr. The generally low values of mobility factors coupled with significantly high levels of association of the metals with the residual fraction, indicate that the metals do not pose any environmental risk nor hazard.     

Rhizosphere concentrations of zinc and cadmium in a metal contaminated soil after repeated phytoextraction by Sedum plumbizincicola

A growth chamber pot experiment and a field plot experiment were conducted with the installation of rhizobags to study the effects of repeated phytoextraction by Sedum plumbizincicola on the bioavailability of Cd and Zn in the rhizosphere and bulk soil Repeated phytoextraction gave significantly lower Cd and Zn concentrations in both rhizosphere and bulk soil solutions compared with soil without repeated phytoextraction. The depletion rates of NH40Ac-extractable Zn in rhizosphere soil in each treatment (L-PS, L-NPS, H-PS, and H-NPS) were 59.7, 18.0, 16.3, and 18.6%, respectively. For NH40Ac-extractable Cd, the depletion rates in treatments L-PS, L-NPS, H-PS, and H-NPS were 6.67, 29.4, 40.3, and 41.4%, respectively. Plant shoot biomass decreased in the order H-PS > H-NPS > L-PS > L-NPS, with dry weights of 0.56, 0.42, 1.43, and 1.21 g pot(-1), respectively. Plant Cd uptake increased with increasing aqua-regia extractable metal concentrations. The NH4OAc extraction procedure was satisfactory to predict the bioavailability of Cd and Zn in rhizosphere soil in terms of shoot uptake by S. plumbizincicola with positive correlation coefficients of 0.545 (p < 0.05) and 0.452 (p < 0.05), respectively. The field study results show a slight decrease in water soluble and NH4OAc-extractable metals, a trend similar to that found in the pot experiment.     

Binding of zinc and cadmium to human serum albumin

1. The interaction of zinc and cadmium ion with human serum albumin (HSA) is evaluated and compared by potentiometric titration method and computer simulation of complex equilibria. 2. Zinc binds to histidine and free amino groups, cadmium in addition to basic functional groups of the protein. 3. Whereas zinc binds stronger in 1:1 complexes, chelate binding favours cadmium ions. 4. Within biological pH-conditions, high amounts Zn(II) and even more of Cd(II) will be bound to HSA.     

Cadmium and zinc content of fish from an industrially contaminated lake

Eleven species of fish from an industrially-contaminated lake were analysed for whole body cadmium and zinc content by atomic absorption spectrophotometry. Cadmium and zinc content of fish were species related, and most species accumulated these trace metals to levels significantly higher than background. Maximum concentrations detected were 13.60 μg Cd g⁻¹ (dry wt) in a bluegill and 820 μg Zn g⁻¹ in a redear sunfish. Cadmium content was much more variable than zinc content. Distributions of concentrations of both cadmium and zinc in fish were lognormal, and concentrations of both metals tended to decrease in higher trophic levels. Zinc concentrations significantly decreased as total length increased in three species.