Fraction Distributions of Lead,Cadmium, Copper,and Zinc in Metal‐Contaminated Soil before and after Extraction with Disodium Ethylenediaminetetraacetic Acid

Abstract: The fraction distributions of heavy metals have attracted more attention because of the relationship between the toxicity and their speciation. Heavy‐metal fraction distributions in soil contaminated with mine tailings (soil A) and in soil irrigated with mine wastewater (soil B), before and after treatment with disodium ethylenediaminetetraacetic acid (EDTA), were analyzed with Tessier's sequential extraction procedures. The total contents of lead (Pb), cadmium (Cd), copper (Cu), and zinc (Zn) exceeded the maximum permissible levels by 5.1, 33.3, 3.1, and 8.0 times in soil A and by 2.6, 12.0, 0.2, and 1.9 times in soil B, respectively. The results showed that both soils had high levels of heavy‐metal pollution. Although the fractions were found in different distribution before extraction, the residual fraction was found to be the predominant fraction of the four heavy metals. There was a small amount of exchangeable fraction of heavy metals in both contaminated soils. Furthermore, in this study, the extraction efficiencies of Pb, Cd, and Cu were higher than those of Zn. After extraction, the concentrations of exchangeable Pb, Cd, Cu, and Zn increased 84.7 mg·kg^?1, 0.3 mg·kg^?1, 4.1 mg·kg^?1, and 39.9 mg·kg^?1 in soil A and 48.7 mg·kg^?1, 0.6 mg·kg^?1, 2.7 mg·kg^?1, and 44.1 mg·kg^?1 in soil B, respectively. The concentrations of carbonate, iron and manganese oxides, organic matter, and residue of heavy metals decreased. This implies that EDTA increased metal mobility and bioavailability and may lead to groundwater contamination.     

Tea Plantation–Induced Activation of Soil Heavy Metals

Abstract

The accumulation of heavy metals in tea leaves is of concern because of its impact on tea quality. This study characterized long‐term changes of soil properties and heavy‐metal fractions in tea gardens and their effect on the uptake of metals from soils by the plants. Soil and tea leaf samples were collected from five plantations with a history of 2–70 years in Jinghua, Zhejiang Province, southeast China. The six chemical fractions (water‐soluble, exchangeable, carbonate‐bound, organic‐matterbound, oxide‐bound, and residual forms) of cadmium (Cd), chromium (Cr), copper (Cu), iron (Fe), nickel (Ni), manganese (Mn), lead (Pb), and zinc (Zn) in the soils were characterized. Dissolved organic‐matter accumulation in the soils and effects of low‐molecular‐weight organic acids on solubility of soil heavy metals were also tested. Long‐term tea plantation use resulted in accumulation of dissolved organic matter, decrease of soil pH, and elevation of water‐soluble and exchangeable metal fractions, thereby increasing metal contents in leaves. The influence was more significant when soil pH was less than 4.4. The results indicated that both acidification and accumulation of dissolved organic matter induced by tea plantations were also important causes of increased accumulation of the metals in the tea leaves. This was particularly true for the soils polluted with low concentration of heavy metals, because availability of the metals in these soils was mainly controlled by pH and dissolved organic matter.     

Bioremediation of Co-contamination of Crude Oil and Heavy Metals in Soil by Phytoremediation Using Chromolaena odorata (L) King & H.E. Robinson

The capability of Chromolaena odorata (L) to grow in the presence of different concentrations of three heavy metals in crude oil-contaminated soil and its capability to remediate the contaminated soil was investigated using pot experiments. C. odorata plants were transplanted into contaminated soil containing 50,000 mg kg^?1 crude oil and between 100 and 2,000 mg kg^?1 of cadmium, nickel, and zinc and watered weekly with water containing 5% NPK fertilizer for 180 days. C. odorata did not show any growth inhibition in 50,000 mg kg^?1 crude oil. Plants in experiments containing 2,000 mg kg^?1 Cd showed little adverse effect compared to those in Zn-treated soil. Plants in 1,000 and 2,000 mg kg^?1 Ni experiments showed more adverse effects. After 180 days, reduction in heavy metals were: 100 mg kg^?1 experiments, Zn (35%), Cd (33%), and Ni (23%); 500 mg kg^?1, Zn (37%), Cd (41%), and Ni (25%); 1,000 mg kg^?1, Zn (65%), Cd (55%), and Ni (44%); and 2,000 mg kg^?1, Zn (63%), Cd (62%), and Ni (47%). The results showed that the plants accumulated more of the Zn than Cd and Ni. Accumulation of Zn and Cd was highest in the 2,000 mg kg^?1 experiments and Ni in the 500 mg kg^?1 experiments. Crude oil was reduced by 82% in the experiments that did not contain heavy metals and by up to 80% in the heavy metal-treated soil. The control experiments showed a reduction of up to 47% in crude oil concentration, which was attributed to microbial action and natural attenuation. These results show that C. odorata (L) has the capability of thriving and phytoaccumulating heavy metals in contaminated soils while facilitating the removal of the contaminant crude oil. It also shows that the plant??s capability to mediate the removal of crude oil in contaminated soil is not significantly affected by the concentrations of metals in the soil.     

Heavy‐Metal Contamination of Soil and Vegetables in Wastewater‐Irrigated Agricultural Soil in a Suburban Area of Hanoi,Vietnam

The To Lich and Kim Nguu Rivers, laden with untreated waste from industrial sources, serve as sources of water for irrigating vegetable farms. The purposes of this study were to identify the impact of wastewater irrigation on the level of heavy metals in the soils and vegetables and to predict their potential mobility and bioavailability. Soil samples were collected from different distances from the canal. The average concentrations of the heavy metals in the soil were in the order zinc (Zn; 204 mg kg^?1) > copper (Cu; 196 mg kg^?1) > chromium (Cr; 175 mg kg^?1) > lead (Pb; 131 mg kg^?1) > nickel (Ni; 60 mg kg^?1) > cadmium (Cd; 4 mg kg^?1). The concentrations of all heavy metals in the study site were much greater than the background level in that area and exceeded the permissible levels of the Vietnamese standards for Cd, Cu, and Pb. The concentrations of Zn, Ni, and Pb in the surface soil decreased with distance from the canal. The results of selective sequential extraction indicated that dominant fractions were oxide, organic, and residual for Ni, Pb, and Zn; organic and oxide for Cr; oxide for Cd; and organic for Cu. Leaching tests for water and acid indicated that the ratio of leached metal concentration to total metal concentration in the soil decreased in the order of Cd > Ni > Cr > Pb > Cu > Zn and in the order of Cd > Ni > Cr > Zn > Cu > Pb for the ethylenediaminetetraaceitc acid (EDTA) treatment. The EDTA treatment gave greater leachability than other treatments for most metal types. By leaching with water and acid, all heavy metals were fully released from the exchangeable fraction, and some heavy metals were fully released from carbonate and oxide fractions. The concentrations of Cd, Cr, Cu, Ni, Pb, and Zn in the vegetables exceeded the Vietnamese standards. The transfer coefficients for the metals were in the order of Zn > Ni > Cu > Cd = Cr > Pb.     

Distribution of Forms of Copper and their Association with Soil Properties and Uptake in Major Soil Orders in Semi-arid Soils of Punjab,India

Profiles of semi-arid-zone soils in Punjab, northwestern India, were investigated for different forms of copper (Cu), including total Cu, diethylenetriaminepentaacetic acid (DTPA)–extractable Cu, soil solution plus exchangeable Cu, Cu adsorbed onto inorganic sites, Cu bound by organic sites, and Cu adsorbed onto oxide surfaces. When all soils were considered, total Cu content ranged from 7 to 37 mg kg^?1, while DTPA-extractable and soil solution plus exchangeable Cu contents ranged from 0.30 to 3.26 mg kg^?1 and from 0.02 to 0.43 mg kg^?1, respectively. Copper adsorbed onto inorganic sites ranged from 0.62 to 2.6 mg kg^?1 and that onto oxide surfaces ranged from 2.0 to 13.2 mg kg^?1. The Cu bound by organic sites ranged from 1.2 to 12.2 mg kg^?1. The magnitudes of different forms of Cu in soils did not exhibit any consistent pattern of distribution. Organic matter and size fractions (clay and silt) had a strong influence on the distribution of different forms of Cu. The content of all forms of Cu was generally greater in the fine-textured Alfisols and Inceptisols than coarse-textured Entisols. Soil solution plus exchangeable Cu, Cu held onto organic sites, and and Cu adsorbed onto inorganic sites (crystalline) had significant positive correlations with organic carbon and silt contents.The DTPA Cu was positively correlated with organic carbon, silt, and clay contents. Total Cu content strongly correlated with silt and clay contents of soils. Among the forms, Cu held on the organic site, water soluble + exchangeable Cu, and Cu adsorbed onto oxide surface were positively correlated with DTPA-extractable Cu. The DTPA-extractable Cu and soil solution plus exchangeable Cu seems to be good indices of Cu availability in soils and can be used for correction of Cu deficiency in the soils of the region. The uptake of Cu was greater in fine-textured Inceptisols and Alfisols than coarse-textured Entisols. Among the different forms only DTPA-extractable Cu was positively correlated with total uptake of Cu.     

Bioavailability,fractionation of pb and Zn in the rhizosphere of sunflower in chelators-amended contaminated soil

Assisted phytoremediation procedures have been widely employed as soil removal instrument of heavy metals from contaminated soils. Rhizosphere processes have a major impact on pb and Zn availability and its fractions in soils. The present study evaluates the effects of EDTA, citric acid (CA) and poultry manure extract (PME) on bioavailability and fractionation of pb, Zn in both the rhizosphere of sunflower (Helianthus annuus L.) and bulk soil. EDTA and CA were added to soils at the rates of 0, 0.5 and 1 mmol kg^?1 soil and PME at 0, 0.5 and 1 g kg^?1 soil as factorial in a completely randomized pattern with three replicates in greenhouse condition. Results showed that chelator application had a significant impact (p < 0.05) on pb, Zn extraction by different extractants and its fractions in soils. The order of concentrations of pb, Zn present in different fractions in soil treated by chelators was: oxides-bounded fraction > residual fraction > OM-bounded fraction > carbonate-bounded fraction > exchangeable fraction. Biochemical soil characteristics in the sunflower rhizosphere change resulting from its roots contributing to pb, Zn decline in mobile soil fractions, and change in soil pb, Zn fractions that are generally regarded as more stable.     

Forms and Uptake of Manganese in Relation to Soil Taxonomic Orders in Alluvial Soils of Punjab,India

Different forms of manganese (Mn) were investigated, including total, diethylenetriamine penta-acetic acid (DTPA) extractable, soil solution plus exchangeable (Mn), Mn adsorbed onto inorganic sites, Mn bound by organic sites, and Mn adsorbed onto oxide surfaces, from four soil taxonomic orders in northwestern India. The total Mn content was 200–950 mg kg^?1, DTPA-extractable Mn content was 0.60–5.80 mg kg^?1, soil solution plus exchangeable Mn content was 0.02–0.80 mg kg^?1, Mn adsorbed onto inorganic sites was 2.46–90 mg kg^?1, and Mc adsorbed onto oxide surfaces was 6.0–225.0 mg kg^?1. Irrespective of the different fractions of Mn their content was generally greater in the fine-textured Alfisols and Inceptisols than in coarse-textured Entisols and Aridisols. The proportion of the Mn fractions extracted from the soil was in the order as follows: Adsorbed onto oxide surfaces > adsorbed onto inorganic site > organically bound > DTPA > soil solution + exchangeable. Based on coefficient of correlation, the soil solution plus exchangeable Mn, held onto organic site and oxide surface (amorphous) and DTPA-extractable Mn, increased with increase in organic carbon of the soil. The two forms, adsorbed onto inorganic site (crystalline) and DTPA extractable, along with organic carbon, increased with increase in clay content of the soil. DTPA-Mn and Mn adsorbed onto oxide surfaces and held on organic site decreased with increased with an increase in calcium carbonate and pH. Total Mn was strongly correlated with organic carbon and clay content of soil. Among the forms, Mn held on the organic site, water soluble + exchangeable and adsorbed onto oxide surface were positively correlated with DTPA-extractable Mn. DTPA-extractable Mn seems to be a good index of Mn availability in soils and this form is helpful for correction of Mn deficiency in the soils of the region. The uptake of Mn was greater in fine-textured Inceptisols and Alfisols than in coarse-textured Entisols and Aridisols. Among the different forms only DTPA-extractable Mn was positively correlated with total uptake of Mn. Among soil properties Mn uptake was only significantly affected by pH of the soil.     

Chemical Fractionation of Trace Elements in Biosolid‐Amended Soils and Correlation with Trace Elements in Crop Tissue

Abstract

A previous study indicated that agricultural biosolid applications increased the concentration of EPA₃₀₅₀‐digestible trace elements in soils on Pennsylvania production farms but could not indicate potential trace‐element environmental availability. This study was conducted to determine if biosolid application had altered the distribution of trace‐elements among operationally defined soil fractions and the relationship of trace element concentrations in soil and crop tissues. Biosolid‐amended and unamended soils from production farms in Pennsylvania were extracted using a modified Bureau Communautaire de Référence (BCR) sequential fractionation technique and analyzed for chromium (Cr), copper (Cu), nickel (Ni), lead (Pb), and zinc (Zn). Trace‐element concentrations in crop tissues (soybean silage, sudangrass, corn grain, alfalfa hay, and orchardgrass hay) from the same farms were also determined. Fractionation results indicated that the proportion of Cr, Cu, Ni, Pb, and Zn that is potentially bioavailable is quite small in unamended soils. Biosolid applications significantly (P≤0.1) increased concentrations of Cu in all soil fractions (average increase over unamended soil=1.14, 8.27, 6.04, and 5.84 mg kg^?1 for the exchangeable, reducible, oxidizable, and residual fractions, respectively), Ni (0.41, 1.65 mg kg^?1 for the reducible and residual fractions, respectively), Pb (5.12 and 1.49 mg kg^?1 for the reducible and residual fractions, respectively), and Zn (8.28, 7.12, 4.44, and 8.98 mg kg^?1 for the exchangeable, reducible, oxidizable, and residual fractions, respectively) but did not significantly increase Cr in any soil fraction. Concentrations of Cu in all soil fractions were significantly (P≤0.01) correlated with concentrations of Cu in orchardgrass tissue (r=0.70, 0.66, 0.76, and 0.69 for the exchangeable, reducible, oxidizable, and residual soil fractions, respectively). Concentrations of exchangeable and reducible Zn were significantly correlated with Zn in sudangrass tissue (r=0.81 and 0.67), and reducible Zn was significantly correlated with Zn concentrations in orchardgrass tissue (r=0.65). Application of biosolids had little effect on bioavailability of Cr, Ni, or Pb, whereas higher loadings of Cu and Zn led to a shift toward the more labile soil fractions. Loadings of Cu and Zn were much smaller than cumulative loadings permitted under U.S. Environmental Protection Agency (USEPA) Part 503 regulations. Chemical soil fractionation was able to detect increases in labile soil Cu and Zn that relate to increased phytoavailability.     

Arsenic and heavy metal accumulation by Athyrium yokoscense from contaminated soils

Abstract

Athyrium yokoscense, a type of fern that grows vigorously in mining areas in Japan, is well known as a Cd hyperaccumulator as well as a Cu, Pb and Zn tolerant plant. However, no information is available on As accumulation of A. yokoscense, although it often grows on soils containing high levels of both heavy metals and As. In this study, young ferns collected from a mine area were grown in media containing As-spiked soils or mine soil in a greenhouse for 21 weeks. Athyrium yokosense was highly tolerant to arsenate and survived in soils containing up to 500 mg As (V) kg^?1. The addition of 100 mg As (V) kg^?1 resulted in the highest fern biomass (1.95 g plant^?1) among As-spiked soils. Although the As concentration of the fern was lower than other As hyperaccumulators, such as Pteris vittata, A. yokoscense could hyperaccumulate As in mature and old fronds. Arsenic was accumulated most efficiently in old fronds (922 mg kg^?1) in the media containing 5 mg As (III) kg^?1. Moreover, higher As accumulation was found in the roots of the ferns, with a range from 506 to 2,192 mg kg^?1. In addition, in the mine soil with elevated concentrations of As and heavy metals, A. yokoscense not only hyperaccumulated As (242 mg As kg^?1 in old fronds), but also accumulated Cd, Pb, Cu and Zn at concentrations much higher than those reported for other terrestrial plants. Athyrium yokoscense accumulated Cd mostly in fronds in high concentrations, up to 1095 mg kg^?1, while it accumulated Cu, Zn and Pb mainly in the roots and the concentrations were 375, 2040 and 1165 mg kg^?1, respectively.     

Accumulation of lead and arsenic in Malabar spinach (Basella alba L.) and sweet potato (Ipomoea batatas L.) leaves grown on urban and orchard soils

Ethnic vegetable crops are increasingly being grown in the United States and may accumulate heavy metals when grown on urban soils. This study evaluated accumulation of lead (Pb) and arsenic (As) in tissues of Malabar spinach (Basella alba L.) and sweet potato (Ipomoea batatas L.) grown on an urban and an orchard soil with Pb concentrations of 1,120 and 272 mg kg^?1, respectively, and As concentrations of 6.92 and 90 mg kg^?1, respectively. Tissue Pb was higher in both crops grown on both contaminated soils compared with an uncontaminated soil, while tissue As was higher on the orchard soil only. Malabar spinach did not accumulate Pb or As in its shoot, but concentrations of both metals were higher in sweet potato stems compared to leaves or tubers. Consumption of sweet potato stems should be avoided when sweet potato leaves are grown as a vegetable on soils with elevated levels of Pb and As.     

Distribution of Zinc Fractions in Some Major Soils of India and the Impact on Nutrition of Rice

Abstract

Speciation study of microelements in soils is useful to assess their retention and release by the soil to the plant. Laboratory and greenhouse investigations were conducted for five soils of different agro‐ecological zones (viz., Bhuna, Delhi, Cooch‐Behar, Gurgaon, and Pabra) with diverse physicochemical properties to study the distribution of zinc (Zn) among the soil fractions with respect to the availability of Zn species for uptake by rice plant. A sequential extraction procedure was used that fractionated total soil Zn into water‐soluble (WS), exchangeable (EX), specifically adsorbed (SA), acid‐soluble (AS), manganese (Mn)‐oxide‐occluded (Mn‐OX), organic‐matter‐occluded (OM), amorphous iron (Fe)‐oxide‐bound (AFe‐OX), crystalline Fe‐oxide‐bound (CFe‐OX), and residual (RES) forms. There was a wide variation in the magnitude of these fractions among the soils. The studies revealed that more than 90% of the total Zn content occurred in the relatively inactive clay lattice and other mineral‐bound form (RES) and that only a small fraction occurred in the forms of WS, EX, OM, AFe‐OX, and CFe‐OX. Rice (Oryza sativa L.) cultivars differ widely in their sensitivity to Zn deficiency. Results suggested that Zn in water‐soluble, organic complexes, exchange positions, and amorphous sesquioxides were the fractions (pools) that played a key role in the uptake of Zn by the rice varieties (viz., Pusa‐933‐87‐1‐11‐88‐1‐2‐1, Pusa‐44, Pusa‐834, Jaya, and Pusa‐677). Isotopic ally exchangeable Zn (labile Zn) was recorded higher in Typic Ustrochrept of Pabra soil, and uptake of Zn by rice cultivars was also higher in this soil. The kinetic parameters such as maximum influx at high concentrations (I_max) and nutrient concentration in solution where influx is one half of I_max (K_m) behaved differentially with respect to varieties. The highest I_max value recorded was 9.2×10^?7 µmol cm^?2 s^?1 at the 5 mg kg^?1 Zn rate for Pusa‐933‐87‐1‐11‐88‐1‐2‐1, and the same was lowest for Pusa‐44, being 4.6×10^?7 µmol cm^?2 s^?1 at the 5 mg kg^?1 Zn rate. The K_m value was highest for Pusa‐44 (2.1×10^?4µmol cm^?2 s^?1) and lowest for Pusa‐933‐87‐1‐11‐88‐1‐2‐1 (1.20×10^?4µmol cm^?2 s^?1). The availability of Zn to rice cultivars in Typic Ustrochrepts of Bhuna and Delhi soils, which are characterized by higher activation energy and entropy factor, was accompanied by breakage of bonds or by significant structural changes.     

Copper/Zinc Bioaccumulation and the Effect of Phytotoxicity on the Growth of Lettuce (<Emphasis Type="Italic">Lactuca sativa</Emphasis> L.) in Non-contaminated,Metal-Contaminated and Swine Manure-Enriched Soils

Copper/zinc bioaccumulation and the effect of phytotoxicity on the growth of lettuce (Lactuca sativa L.) were studied in plastic vessels containing (i) non-contaminated soil, (ii) copper-contaminated soils at concentrations of 75.0 and 125.0 mg kg^?1, (iii) zinc-contaminated soils at concentrations of 1200 and 2400 mg kg^?1, and (iv) soil enriched with swine manure. Copper and zinc concentrations in lettuce leaves were determined by flame atomic absorption spectrometry during 42 days of growth. Copper concentrations from 0.92 to 13.06 mg kg^?1 were found in lettuce leaves grown in copper-contaminated soils and zinc concentrations from 58.13 to 177.85 mg kg^?1 were found in lettuce leaves grown in zinc-contaminated soils. Copper and zinc concentrations in lettuce leaves grown in swine manure-enriched soils ranged from 0.82 to 8.33 and 0.68 to 13.27 mg kg^?1, respectively. Copper and zinc bioaccumulation caused a decrease in lettuce growth in metal-contaminated soils and an increase in phytotoxicity effects when compared to growth in non-contaminated and manure-enriched soils. These findings were confirmed by measuring leaf areas and biomasses. Copper was less toxic to lettuce than zinc due to the different concentrations in the soil. Lettuce growth and development was better in the swine manure-enriched soil than non-contaminated soil, which indicates that swine manure is a safe agricultural biofertilizer when used in appropriate amounts to avoid metal bioaccumulation in soil and plants.     

Different Fractions of Soil Potassium,Olsen Phosphorus,and Available Sulfur Status of Intensively Cultivated Berpura Soil Series of India and Nutrient Indexing of Rice Crop

Berpura alluvial soil series of the Indo‐Gangetic Plains is situated in the Ambala District of the Haryana State of India. Soils of this series had medium concentrations of both potassium (K) and phosphorus (P) and large concentrations of sulfur (S) before 1970. To study different fractions of K, Olsen P, and 0.15% calcium chloride (CaCl₂)–extractable (available) S of soils of the Berpura series and to create nutrient indexing of rice crops growing on this series, surface soil samples were collected from 100 farmers' fields after the harvest of the wheat crop in 2005. During kharif season of same year, samples of upper two leaves at anthesis growth stage of rice crop were also collected from the same 100 farmers' fields that had earlier been sampled for soil analysis. Analysis of soil samples showed more K depletion in soils of this series, of which 86% of farmers' fields were deficient in ammonium acetate (NH₄OAc) K (available K). Thirty and 62% of leaf samples of the rice crop growing on the 100 fields of this series were extremely and moderately deficient in K, respectively. The mean values of water‐soluble, exchangeable, nonexchangeable, lattice, and total K were 10.6, 30.3, 390.0, 8204, and 8635 mg kg^?1, respectively. In soils of this series, 0.123, 0.351, 4.517, and 95.009% of total K were found in water‐soluble, exchangeable, nonexchangeable, and lattice K forms, respectively. On the other hand, long‐term farmers' practice of more application of P fertilizer in wheat crop has resulted in P buildup in the soils of the Berpura series. Olsen P in soils of farmers' fields of this series ranged from 9.0 to 153.0 mg kg^?1, with the mean value of 41.8 mg kg^?1. Eighty‐two percent of leaf samples of rice crops grown on this series without application of P fertilizer were sufficient in P. The analysis of soil and rice crops for P and K proved the suitability of 0.5 M sodium bicarbonate (NaHCO₃) and 1 N NH₄OAc for extracting available P and K, respectively, in alluvial soils of the Indo‐Gangetic Plains. The 0.15% CaCl₂–extractable S in this soil ranged from 9.6 to 307 mg kg^?1 with a mean value of 34.6 mg kg^?1. Four and 26% of soil samples had low and medium, respectively, in 0.15% CaCl₂–extractable S. S deficiency was recorded in rice crops, as 29% of the leaf samples were extremely deficient in S and 58% were moderately deficient in S. This indicated the unsuitability of the 0.15% CaCl₂ to extract available S from the Udic ustochrept utilized for cultivation of rice crops.     

Heavy metal distribution in different soil aggregate size classes from restored brackish marsh,oil exploitation zone,and tidal mud flat of the Yellow River Delta

Purpose

Heavy metal distribution in soils is affected by soil aggregate fractionation. This study aimed to demons trate the aggregate-associated heavy metal concentrations and fractionations in “sandy,” “normal,” and “mud” soils from the restored brackish tidal marsh, oil exploitation zone, and tidal mudflat of the Yellow River Delta (YRD), China.

Materials and methods

Soil samples were sieved into the aggregates of >2, 0.25–2, 0.053–0.25, and <0.053 mm to determine the concentrations of exchangeable (F1), carbonate-bound (F2), reducible (F3), organic-bound (F4), and residual fraction (F5) of Cd, Cr, Cu, Ni, Pb, and Zn.

Results and discussion

The 0.25–2 mm aggregates presented the highest concentrations but the lowest mass loadings (4.23–12.18 %) for most metal fractions due to low percentages of 0.25–2 mm aggregates (1.85–3.12 %) in soils. Aggregates <0.053 mm took majority mass loadings of metals in sandy and normal soils (62.04–86.95 %). Most soil aggregates had residual Cr, Cu, Ni, Zn, and reducible Cd, Pb dominated in the total Cd, Cr, Cu, Ni, Pb, and Zn concentrations. Sandy soil contained relatively high F4, especially of Cu (F4) in 0.25–2 mm aggregates (10.22 mg kg^?1), which may relate to significantly high organic carbon contents (23.92 g kg^?1, P?<?0.05). Normal soil had the highest total concentrations of metals, especially of Cu, Ni, and Pb, which was attributed to the high F3 and F5 in the <0.053 mm aggregates. Although mud soil showed low total concentrations of heavy metals, the relatively high concentrations of bioavailable Cd and Cu resulted from the relatively high Cd (F2) and Cu (F2) in the >2 mm aggregates indicated contribution of carbonates to soil aggregation and metal adsorption in tidal mud flat.

Conclusions

Soil type and aggregate distribution were important factors controlling heavy metal concentration and fractionation in YRD wetland soil. Compared with mud soil, normal soil contained increased concentrations of F5 and F3 of metals in the 0.053–0.25 mm aggregate, and sandy soil contained increased concentrations of bioavailable and total Cr, Ni, and Zn with great contribution of mass loadings in the <0.053 mm aggregate. The results of this study suggested that oil exploitation and wetland restoration activities may influence the retention characteristics of heavy metals in tidal soils through variation of soil type and aggregate fractions.

     

Relationships of Heavy Metals in Natural Lake Waters with Physico-chemical Characteristics of Waters and Different Chemical Fractions of Metals in Sediments

The relationships between heavy metal concentrations and physico-chemical properties of natural lake waters and also with chemical fractions of these metals in lake sediments were investigated in seven natural lakes of Kumaun region of Uttarakhand Province of India during 2003–2004 and 2004–2005. The concentrations of Cr, Mn, Fe, Ni, Cu, Zn, Cd and Pb in waters of different lakes ranged from 0.29–2.39, 10.3–38.3, 431–1407, 1.0–6.6, 5.3–12.1, 12.6–166.3, 0.7–2.7 and 3.9–27.1 μg l^?1 and in sediments 14.3–21.5, 90.1–197.5, 5,265–6,428, 17.7–45.9, 13.4–32.0, 40.0–149.2, 11.1–14.6 and 88.9–167.4 μg g^?1, respectively. The concentrations of all metals except Fe in waters were found well below the notified toxic limits. The concentrations of Cr, Mn, Ni, Cu, Zn, Cd and Pb were positively correlated with pH, electrical conductivity, biological oxygen demand, chemical oxygen demand and alkalinity of waters, but negatively correlated with dissolved oxygen. The concentrations of Cr, Ni, Zn, Cd and Pb in waters were positively correlated with water soluble + exchangeable fraction of these metals in lake sediments. The concentrations of Zn, Cd and Pb in waters were positively correlated with carbonate bound fraction of these metals in lake sediments. Except for Ni, Zn and Cd, the concentrations of rest of the heavy metals in waters were positively correlated with organically bound fraction of these metals in lake sediments. The concentrations of Cr, Mn, Ni, Cu and Zn in waters were positively correlated with reducible fraction of these metals in lake sediments. Except for Cd, the concentrations of rest of the metals in waters were positively correlated with residual fraction and total content of these heavy metals in lake sediments.     

Release Kinetics of Nonexchangeable Potassium by Different Extractants from Soils of Varying Mineralogy and Depth

Abstract

Nonexchangeable potassium (K) release kinetics of six major benchmark soil series of India as affected by mineralogy of clay and silt fractions, soil depth and extraction media was investigated. The cumulative release of nonexchangeable K was greater in smectitic soils (353 mg K kg^?1 at 0‐ to 15‐cm depth and 296 mg K kg^?1 at 15‐ to 30‐cm depth, averaged for 2 soils and 3 extractants) than in illitic (151 mg K kg^?1 at 0‐ to 15‐cm depth and 112 mg K kg^?1 at 15‐ to 30‐cm depth) and kaolinitic (194 mg K kg^?1 at 0‐ to 15‐cm depth and 167 mg K kg^?1 at 15‐ to 30‐cm depth) soils. Surface soils exhibited larger cumulative K release in smectitic and illitic soils, whereas subsurface soils had larger K release in kaolinitic soils. Among the extractants, 0.01 M citric acid extracted a larger amount of nonexchangeable K followed by 0.01 M CaCl₂ and 0.01 M HCl. The efficiency of citric acid extractant was greater in illitic soils than in smectitic and kaolinitic soils. Release kinetics of nonexchangeable K conformed fairly well to parabolic and first‐order kinetic models. The curve pattern of parabolic diffusion model suggested diffusion controlled kinetics in all the soils, with a characteristic initial fast rate up to 7 h followed by a slower rate. Greater nonexchangeable K release rates in smectitic soils, calculated from the first‐order equation (b=91.13×10^?4 h^?1), suggested that the layer edge and wedge zones and swelling nature of clay facilitated the easier exchange. In contrast to smectitic soils, higher release rate constants obtained from parabolic diffusion equation (b=39.23×10^?3 h^?1) in illitic soils revealed that the low amount of exchangeable K on clay surface and larger amount of interlayer K allowed greater diffusion gradients, thus justifying the better fit of first‐order kinetic equation in smectitic soils and parabolic diffusion equation in illitic soils.     

Chemical characterization of heavy-metal contaminated soil in southeast Kansas

A tri-state mining region, including parts of Missouri, Oklahoma, and Kansas, was the site of intense lead and zinc mining and smelting activity until the 1950's. A study was initiated to characterize the heavy-metal contamination of soils in this area. Water-soluble, an index of plantavailable, total, and sequentially extractable metals; organic, and total carbon; and saturated paste pH were determined for mine tailings and soil samples. Mine tailings contained 81 to 89 mg kg^?1 total Cd, 1 150 to 1 370 mg kg^?1 total Pb, and 11 400 to 13 700 mg kg^?1 total Zn. Total concentrations in soil samples were 15 to 86 mg kg^?1 Cd, 35 to 1 620 mg kg^?1 Pb, and 99 to 18 500 mg kg^?1 Zn; and, DTPA extractable concentrations ranged from 0.6 to 10 mg kg^?1 Cd, 7.8 to 68 mg kg^?1 Pb, and 33 to 715 mg kg^?1 Zn. Samples were sequentially extracted to approximate the proportions of the metals in the sulfide, carbonate, organic, sorbed, and exchangeable fractions. For Zn and Cd, concentrations were greatest in the sulfide fraction followed by carbonate, organic, sorbed, and exchangeable. Lead followed the same pattern, except higher concentrations were observed in the sorbed than the organic fractions.     

Accumulations of Cadmium,Zinc, and Copper by Rice Plants Grown on Soils Amended with Composted Pig Manure

A pot experiment, in which composted pig manure was applied to soils at rates of 0%, 0.5%, 1.5%, 3.0%, and 5.0% (W/W) to simulate additions of different amounts of cadmium (Cd), copper (Cu), and zinc (Zn) to soil, was conducted to assess accumulation of metals by rice (Oryza sativa L.) plants from soils treated with manure. Results indicated that Cd concentrations in rice grains were more than the limit of 0.2 mg kg^?1 when 0.14 mg kg^?1 or more Cd was loaded to Ferralsols by manure application, but it was not more than the limit in Calcaric Cambisols. Zinc contents in polished rice grains did not exceed the permissible limit of 50 mg kg^?1 in two soils. Copper concentrations in rice grain were slightly more than the limit of 10 mg kg^?1 in Ferralsols but not in Calcaric Cambisols. Results suggested greater risk of heavy‐metal contamination from manure to paddy rice in Ferralsols than in Calcaric Cambisols.     

Nutrient Element Contents and Cation Exchange Capacity in Fine Fractions of Southeastern Nigerian Soils in Relation to Their Stability

Abstract

Soils collected from 15 locations from SE Nigeria at the 0‐ to 20‐cm depth were studied for the nutrient elements of fine fractions and their role in the stability of the soils. The objective was to understand the role of these elements in the stability of the aggregates. The fine fractions were clay and silt, and elements measured in the fine fractions were exchangeable sodium (Na⁺), potassium (K⁺), calcium (Ca²⁺), magnesium (Mg²⁺), exchangeable acidity (EA), cation exchange capacity (CEC), and available phosphorus (P). The aggregate stability was measured at the microlevel with clay dispersible indices and water‐stable aggregate (WSA) <0.25 mm, and at macrolevel with other WSA indices and mean‐weight diameter (MWD). Soils varied from loamy sand to sandy clay. There were more exchangeable cations, CEC, EA, and available P in clay than in the silt fraction. Whereas EA values ranged from 2.8 to 10.4 cmol kg^?1, they were between 1.6 and 9.2 cmol kg^?1 in silt. The CEC in the clay fraction was from 7.4 to 70 cmol kg^?1 and between 4.0 and 32.8 cmol kg^?1 in the silt fraction. The WDC were from 50 to 310 g kg^?1 while the average dispersion ratio (DR) was generally higher than the corresponding clay‐dispersion ratio (CDR), and the MWD ranged from 0.45 to 2.68 mm. Soils with WSA skewed mostly to higher WSA (>2–1.00 mm) had a higher MWD. Exchangeable Ca²⁺ in clay correlated significantly with CDR and WSA sizes 1.0–0.5 mm and 0.5–0.25 mm (r=0.45,* 0.51,* and 0.60*), respectively, but negatively correlated with clay flocculation index (CFI) (r=?0.45*). Also, available P in clay correlated respectively with CDR and CFI (r=0.45*, ?0.45*), whereas K⁺ in silt correlated significantly with WDSi (r=0.64*), CFI (r=0.62*), and CDR (r=?0.65*). Principal component analysis revealed that elemental contents in the silt fraction can play very significant roles in the microaggregate stability.     

DISTRIBUTION AND SEQUENTIAL EXTRACTION OF SOME HEAVY METALS FROM SOILS IRRIGATED WITH WASTEWATER FROM MEXICO CITY

A sequential extraction procedure was used to fractionate Cu, Cd, Pb and Zn in 4 soil profiles into the designated forms of water soluble + exchangeable, organically bound, carbonate and Mn oxides bound. Soil profiles were obtained from the Rural Development District 063, State of Hidalgo, which have been irrigated with wastewater coming out of the basin of Mexico. The total heavy metal contents range as follows: Cu, 8.9 to 86.5 mg kg^-1 Cd, 0.86 to 5.07 mg kg^-1 Pb, 18.1 to 131.7 mg kg^-1 and Zn, 101 to 235.5 mg kg^-1. The highest concentrations of total heavy metals were found in the surface layers at all soil profiles. Sequential chemical fractionation indicated that the four metals were predominantly associated with the organic fraction at most soil samples. The contents in all fractions of the four metals showed a decrease with depth which has been explained by the variations in the organic matter and CaCO₃ contents in the different layers of soils. These soil properties were also the most important variables in the biological availability of the metals in these soils.