Radio-labile cadmium and zinc in soils as affected by pH and source of contamination

The determination of radio‐labile metals in soil has gained renewed interest for predicting metal availability. There is little information on to what extent the fraction of labile metal is affected by the soil properties and the source of metal contamination. The radio‐labile content (E value) of Cd and Zn was measured in field‐collected soils with Cd and Zn originating from different sources. The E values were erratic and sometimes even exceeded total metal content when the concentration in the soil extract was less than 8 μg Zn l^?1 or less than 3 μg Cd l^?1. Addition of EDTA (0.1 mm ) to the radio‐labelled soil suspension resulted in larger concentrations of Cd and Zn in solution and smaller E values for these soils. The E values were, however, unaffected by the presence of EDTA (0.1 mm ) in soils with larger concentrations of Cd and Zn in solution. The %E values (E value relative to metal soluble in aqua regia) ranged from 9% to 92% (mean 61%) for Cd and from 3% to 72% (mean 33%) for Zn. No correlation between soil properties and %E was observed for Cd, and the %E of Zn was negatively correlated with soil pH (r = ?0.65). There was a strong negative correlation between pH and %E in soils enriched with metals in soluble form (e.g. metal salts, corrosion of galvanized structures). In soils where Cd or Zn were added in a less soluble form, no such correlation was found, and %E values were generally less than in soils spiked with metal salts, suggesting that the source of the contamination controls mainly the labile fractions of Cd and Zn.     

Soil solution concentration of Cd and Zn canbe predicted with a CaCl2 soil extract

Risk assessment of heavy metals in soil requires an estimate of the concentrations in the soil solution. In spite of the numerous studies on the distribution of Cd and Zn in soil, few measurements of the distribution coefficient in situ, K_d, have been reported. We determined the K_d of soils contaminated with Cd and Zn by measuring metal concentrations in the soil and in the soil solution and attempted to predict them from other soil variables by regression. Soil pH explained most of the variation in logK_d (R² = 0.55 for Cd and 0.70 for Zn). Introducing organic carbon content or cation exchange capacity (CEC) as second explanatory variable improved the prediction (R² = 0.67 for Cd and 0.72 for Zn), but these regression models, however, left more than a factor of 10 of uncertainty in the predicted K_d. This large degree of uncertainty may partly be due to the variable degree of metal fixation in contaminated soils. The labile metal content was measured by isotopic dilution (E value). The E value ranged from 18 to 92% of the total metal content for Cd and from 5 to 68% for Zn. The prediction of K_d improved when metals in solution were assumed to be in equilibrium with the labile metal pool instead of the total metal pool. It seems necessary therefore to discriminate between ‘labile’ and ‘fixed’ pools to predict K_d for Cd and Zn in field contaminated soils accurately. Dilute salt extracts (e.g. 0.01 m CaCl₂) can mimic soil solution and are unlikely to extract metals from the fixed pool. Concentrations of Cd and Zn in the soil solution were predicted from the concentrations of Cd and Zn in a 0.01 m CaCl₂ extract. These predictions were better correlated with the observations for field contaminated soils than the predictions based on the regression equations relating logK_d to soil properties (pH, CEC and organic C).     

Composition,biomass and activity of microflora,and leaf yields and foliar elemental concentrations of lettuce,after in situ stabilization of an arsenic-contaminated soil

Beringite (B) and zerovalent iron grit (Z), singly and in combination (BZ), were added to a loamy sand soil contaminated by trace elements (Reppel, Belgium), mainly by arsenic (As), to reduce As labile fractions and phytoavailability. An uncontaminated sandy soil was studied for comparison. Soils were placed in large lysimeters cultivated with maize and vegetables for 6 years. pH, organic C and total N content increased in amended soils. The Z and BZ treatments reduced the Ca(NO₃)₂⁻ extractable soil As and As uptake by lettuce. The BZ lettuces had also the lowest foliar Pb, Cd, Zn, and Mn concentrations. All amendments had positive effects on the soil microbial biomass and reduced the qCO₂. Glucose mineralization was increased in Z and BZ amended soils. Acid phosphomonoesterase activity was higher in the untreated soil than in the other soils; the alkaline phosphomonoesterase, phosphodiesterase and protease activities were increased by Z and BZ treatments, whereas B amendment had less positive effects. Genetic fingerprinting using Denaturing Gradient Gel Electrophoresis (DGGE) revealed shifts in the composition of eubacterial and fungal communities of the amended soils. Microbial species richness decreased rather than increased in the treated soils, regardless of reduced trace element availability and increased soil microbial biomass and activity.     

Use of the BCR three-step sequential extraction procedure for the study of the partitioning of Cd, Pb and Zn in various soil samples

A slightly modified three-step sequential extraction procedure proposed by the Community Bureau of Reference (BCR) for analysis of sediments was successfully applied to soil samples. Contaminated soil samples from the lead and zinc mining area in the Mezica valley (Slovenia) and natural soils from a non-industrial area were analysed. The total concentrations of Cd, Pb and Zn and their concentrations in fractions after extraction were determined by flame or electrothermal atomic absorption spectrometry (FAAS, ETAAS). Total metal concentrations in natural soils ranged from 0.3 to 2.6 mg kg^-1 for Cd, from 20 to 45 mg kg^-1 for Pb and from 70 to 140 mg kg^-1 for Zn, while these concentrations ranged from 0.5 to 35 mg kg^-1 for Cd, from 200 to 10000 mg kg^-1 for Pb and from 140 to 1500 mg kg^-1 for Zn in soils from contaminated areas. The results of the partitioning study applying the slightly modified BCR three-step extraction procedure indicate that Cd, Pb and Zn in natural soils prevails mostly in sparingly soluble fractions. Cd in natural soils is bound mainly to Fe and Mn oxides and hydroxides, Pb to organic matter, sulphides and silicates, while Zn is predominantly bound to silicates. In contaminated soils, Cd, Pb and Zn are distributed between the easily and sparingly soluble fractions. Due to the high total Cd, Pb and Zn concentrations in contaminated soil close to the smelter, ! and their high proportions in the easily soluble fraction (80% of Cd, 50% of Pb and 70% of Zn), the soil around smelters represents an environmental hazard.     

Relationship Between Extractable Metals in Acid Soils and Metals Taken Up by Tea Plants

Abstract

The accumulation of heavy metals in plants is related to concentrations andchemical fractions of the metals in soils. Understanding chemical fractions and availabilities of the metals in soils is necessary for management of the soils. In this study, the concentrations of copper (Cu), cadmium (Cd), lead (Pb), and zinc (Zn) in tea leaves were compared with the total and extractable contents of these heavy metals in 32 surface soil samples collected from different tea plantations in Zhejiang province, China. The five chemical fractions (exchangeable, carbonate‐bound, organic matter‐bound, oxides‐bound, and residual forms) of the metals in the soils were characterized. Five different extraction methods were also used to extract soil labile metals. Total heavy metal contents of the soils ranged from 17.0 to 84.0 mgCukg^?1, 0.03 to 1.09 mg Cd kg^?1, 3.43 to 31.2 mg Pb kg^?1, and 31.0 to 132.0 mg Zn kg^?1. The concentrations of exchangeable and carbonate‐bound fractions of the metals depended mainly on the pH, and those of organic matter‐bound, oxides‐bound, and residual forms of the metals were clearly controlled by their total concentrations in the soils. Extractable fractions may be preferable to total metal content as a predictor of bioconcentrations of the metals in both old and mature tea leaves. The metals in the tea leaves appeared to be mostly from the exchangeable fractions. The amount of available metals extracted by 0.01 mol L^?1 CaCl₂, NH₄OAc, and DTPA‐TEA is appropriate extractants for the prediction of metals uptake into tea plants. The results indicate that long‐term plantation of tea can cause sol acidification and elevated concentrations of bioavailable heavy metals in the soil and, hence, aggravate the risk of heavy metals to tea plants.     

Characterization of zinc in contaminated soils: complementary insights from isotopic exchange,batch extractions and XAFS spectroscopy

Isotopic exchange (IE) of trace metals is an established method for characterizing metal reactivity in soils, but it is still unclear which metal species are isotopically exchangeable. In this study, we used IE to quantify ‘labile’ zinc (Zn) in 51 contaminated soils that were previously studied by Zn K‐edge X‐ray absorption fine structure (XAFS) spectroscopy and sequential extraction (SE). All soils had been contaminated by runoff water from 17‐ to 74‐year‐old galvanized power‐line towers. They covered a wide range in pH (4.0–7.7), organic carbon (0.9–10.2%), clay (3.8–45.1%) and Zn concentrations (251–30 090 mg kg^?1). Isotopic exchange was also performed on selected Zn minerals used as references for linear combination fitting of XAFS spectra. The isotopically exchangeable fraction (%E) of Zn generally decreased with increasing pH, but small %E values were also observed for acidic soils with a large fraction of Zn in hydroxy‐interlayered minerals (Zn‐HIM). The fraction of Zn identified by XAFS spectroscopy as (tetrahedrally and octahedrally coordinated) ‘sorbed Zn’ agreed reasonably well with the isotopically exchangeable fraction but was in many cases larger than the %E, indicating that some ‘sorbed Zn’ may be isotopically non‐exchangeable, such as Zn sorbed in micropores of Fe oxyhydroxides. Zinc identified by XAFS spectroscopy as Zn precipitates (Zn phyllosilicates, Zn‐layered double hydroxide (Zn‐LDH) or hydrozincite) or as Zn‐HIM was largely isotopically non‐exchangeable (‘non‐labile’). Comparison between IE and extraction results suggested that the isotopically exchangeable Zn was mainly extracted in the first two fractions of the SE. However, non‐labile Zn was also extracted in these first two fractions for some soils, including a hydrozincite‐containing soil. Despite the presence of Zn‐LDH and/or Zn phyllosilicates in almost all soils, the Zn concentrations in solution and labile Zn increased with increasing soil total Zn at a given pH, which contradicts the concept of precipitation control by a single phase. Solution Zn was well predicted from the labile Zn following a sorption model.     

An anion resin membrane technique to overcome detection limits of isotopically exchanged P in P-sorbing soils

Isotopically exchanged phosphorus is difficult to determine in soils that strongly sorb P (so that there is little P in solution) and in soils with large concentrations of colloidal P in soil suspensions. A method is proposed in which anion exchange membranes (AEM) are added to the soil suspension after an initial period of isotopic exchange with ³²P‐labelled phosphate ions. Isotopically exchanged P, termed E_AEM, is calculated from the ratio of labelled phosphate ions to the total phosphate ions on the membrane. The E_AEM was compared with the E value measured in an aqueous soil extract (E_{Water extract}) for 14 soils with different degrees of P sorption. The two methods gave similar results in soils with large P concentrations in an aqueous soil extract. However, E_{Water extract} values significantly exceeded the E_AEM values by up to 18‐fold when soluble P was near the determination limit (0.008 mg P l^?1). In a second experiment, two Ferralsols received further P from inorganic and plant sources and were incubated for 7 days. Treatment effects on labile P were erroneous as detected by the E_{Water extract} but were significant as detected with the AEM method. Third, E_AEM values were followed in a Lixisol and a Ferralsol which received labelled phosphate ions with carrier just before the beginning of a 23‐day incubation. The approximate recovery of added inorganic P in the E_AEM value suggested that this method adequately samples labile P in P‐sorbing soils. All these results showed that errors in the determination of E values for soils with very small concentrations of P in the soil solution are reduced using the proposed method.     

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.     

Methods for determining labile cadmium and zinc in soil

Isotopically exchangeable cadmium and zinc (‘E values’) were measured on soils historically contaminated by sewage sludge and ones on zinc‐rich mine spoil. The E‐value assay involves determining the distribution of an added metal isotope, e.g. ¹⁰⁹Cd, between the solid and solution phases of a soil suspension. The E values for both metals were found to be robust to changes in the position of the metal solid?solution equilibrium, even though the concentration of dissolved metal varied substantially with electrolyte composition and soil:solution ratio. Concentration of labile metal was also invariant over isotope equilibration times of 2–6 days. The use of a submicron filtration procedure, in addition to centrifuging at 2200 g , proved unnecessary if 0.1 m Ca electrolyte was used to suspend the soils. The proportion of ‘fixed’ metal, in non‐labile forms, apparently increased with increasing pH, although there was considerable variation in both sets of contaminated soil. Zinc and cadmium in the sludged soils were similarly labile. Several possible methods for the measurement of chemically reactive metal were explored for comparison with E values, including single extraction with 1 m CaCl₂ and a ‘pool depletion’ (PD) method. The latter involves comparing solid?solution metal equilibria in two electrolytes with differing degrees of (solution) complex formation, 0.1 m Ca(NO₃)₂ and CaCl₂. Both the single extraction and the PD method gave good estimates of E value for Cd, although the single extraction was more consistent. Neither technique was a useful substitute for determining labile Zn, because of weak chloro‐complexation of Zn^2+. We therefore suggest that 1 m CaCl₂ extraction of Cd alone be used as an alternative to E values to avoid the inconvenience of isotopic dilution procedures.     

Remediation of a soil contaminated with heavy metals by immobilizing compounds

The labile fraction of heavy metals (HM) in soils is the most important for toxicity for plants and microorganisms. Thus, it is crucial to reduce this fraction in contaminated soils to decrease the negative effect of HM. In a greenhouse experiment, the effects of several additives on the labile fractions of Zn, Cd, Cu, Ni, and Pb were investigated in a soil contaminated during long‐term sewage‐sludge application. The accumulation of HM was studied in the aboveground biomass of wheat (Triticum aestivum L.). The additives used were the clay minerals Na‐bentonite, Ca‐bentonite, and zeolite; the Fe oxides hematite and goethite; the phosphate fertilizers superphosphate and Novaphos. Wheat was planted three times during 5 months, allowed to grow for 7 w, and harvested. Dry matter and HM content of shoots were determined after each harvest. Soil samples were taken after the first and third harvest, and the NH₄NO₃‐extractable HM contents were determined. After the addition of 2% Na‐bentonite as well as 2% Ca‐bentonite, a strong reduction of the labile HM soil fraction and shoot HM concentration was observed. At the end of the experiment, the labile fraction was reduced due to the addition of Na‐bentonite and Ca‐bentonite by 24% and 31% for Zn, by 37% and 36% for Cd, by 41% and 43% for Cu, by 54% and 61% for Ni, and by 48% and 41% for Pb, respectively. Furthermore, the shoot HM concentrations with the exception of Zn were reduced below the phytotoxicity range. Accordingly, the shoot dry‐matter production was significantly increased. The addition of phosphate fertilizers (notably Novaphos) strongly reduced the bioavailability of Pb for wheat plants. By addition of 0.05% Novaphos, the labile fraction and the shoot concentration of Pb were lowered by 39% and 64%, respectively. However, the addition of Fe oxides and zeolite resulted only in a small reduction in HM bioavailability to wheat plants. Among the studied additives, Na‐bentonite and Ca‐bentonite have the most promising potential to reduce the bioavailability for the studied HM.     

Quantification of anthropogenic lead in Slovak forest and arable soils along a deposition gradient with stable lead isotope ratios

Isotope ratios of Pb may provide the opportunity to determine the contribution of Pb from a point source to Pb concentrations in soil. Our objective was to quantify the contribution of anthropogenic Pb to total Pb and chemical Pb fractions in contaminated soil profiles with the help of ²⁰⁶Pb/²⁰⁷Pb isotope ratios. We sampled 5 forest and 5 arable Cambisols along a transect from a Cu smelter and determined Pb concentrations and ²⁰⁶Pb/²⁰⁷Pb isotope ratios in total digests of all horizons and in 7 chemical fractions of the A horizons. In the organic layer under forest, Pb concentrations decreased from 2155 mg kg^—1 at 1.1 km distance from the smelter to 402 mg kg^—1 at 8 km distance; in the Ap horizons, it decreased from 126 to 72 mg kg^—1. In the total digests, ²⁰⁶Pb/²⁰⁷Pb isotope ratios could be explained by simple mixing of smelter‐ and background‐Pb as indicated by the correlation between the inverse of the Pb concentration and the ²⁰⁶Pb/²⁰⁷Pb ratio (r = 0.93). The mean proportion of smelter‐Pb in soil horizons decreased with depth from 87% (Oi) to 21% (C) under forest and from 64% (A) to 30% (B) in the arable soils. The smelter‐Pb proportions in the B horizons ranged from 6 to 66% and were independent of the distance from the smelter indicating variable leaching rates. The ²⁰⁶Pb/²⁰⁷Pb ratios in the chemical fractions could not be explained by a simple mixing model. Thus, the ²⁰⁶Pb/²⁰⁷Pb ratios may be used to determine the contribution of anthropogenic Pb in total digests but not in chemical Pb fractions.     

Sulfur mineralization in two soils amended with organic manures,crop residues,and green manures

The mineralization of sulfur (S) was investigated in a Vertisol and an Inceptisol amended with organic manures, green manures, and crop residues. Field‐moist soils amended with 10 g kg^—1 of organic materials were mixed with glass beads, placed in pyrex leaching tubes, leached with 0.01 M CaCl₂ to remove the mineral S and incubated at 30 °C. The leachates were collected every fortnight for 16 weeks and analyzed for SO₄‐S. The amount of S mineralized in control and in manure‐amended soils was highest in the first week and decreased steadily thereafter. The total S mineralized in amended soils varied considerably depending on the type of organic materials incorporated and soil used. The cumulative amounts of S mineralized in amended soils ranged from 6.98 mg S (kg soil)^—1 in Inceptisol amended with wheat straw to 34.38 mg S (kg soil)^—1 in Vertisol amended with farmyard manure (FYM). Expressed as a percentage of the S added to soils, the S mineralized was higher in FYM treated soils (63.5 to 67.3 %) as compared to poultry manure amended soils (60.5 to 62.3 %). Similarly the percentage of S mineralization from subabul (Leucaena leucocephala) loppings was higher (53.6 to 55.5 %) than that from gliricidia (Gliricidia sepium) loppings (50.3 to 51.1 %). Regression analysis clearly indicated the dependence of S mineralization on the C : S ratio of the organic materials added to soil. The addition of organic amendments resulted in net immobilization of S when the C : S ratio was above 290:1 in Vertisol and 349:1 in Inceptisol. The mineralizable S pool (S_o) and first‐order rate constant (k) varied considerably among the different types of organic materials added and soil. The S_o values of FYM treated soils were higher than in subabul, gliricidia, and poultry manure treated soils.     

贵州铅锌冶炼区农田土壤镉铅有效性评价与预测模型研究

农田土壤重金属的不同活性库分布和土壤-溶液分配模型能够提供重金属的生物有效性和浸出能力等信息,因而在风险评价和修复实践中非常重要。本研究采集毕节铅锌冶炼区30个历史污染农田土壤,同时在贵州省范围内采集5种类型背景土壤制成不同浓度Pb/Cd单一污染土壤;经3个月老化,分别测定由0.43 mol/L HNO_3、0.1 mol/L HCl和0.005 mol/L DTPA提取态表征的重金属反应活性库以及由0.01 mol/L CaCl_2提取态表征的直接有效库;分析铅锌冶炼区农田土壤Cd、Pb不同有效库的分布特征,建立土壤-溶液分配模型,并讨论土壤理化性质的影响。结果表明:历史污染土壤中Cd和Pb的直接有效库占全量比例分别比人工污染土壤低4倍和223倍,然而历史污染土壤Cd和Pb的反应活性库(0.43 mol/L HNO_3提取态)占全量比例要高于相应人工污染土壤中的比例。拓展Freundlich形式吸附方程能够准确描述各提取态表征的Cd和Pb活性库与土壤全量Cd和Pb的关系,尤其0.43 mol/L HNO_3提取方法能够克服土壤理化性质对土壤Cd和Pb提取的影响而与总量建立极显著的相关关系。pH依附性Freundlich吸附方程准确描述了Cd和Pb的总反应活性库分别与土壤溶液Cd和Pb的关系,对于Pb而言,还要考虑土壤有机质和有效磷的影响。本研究可为矿区农田土壤重金属污染评价、修复以及农田有效态标准的推导提供参考。     

Speciation in metal contaminated soils as revealed by an ion exchange resin membrane fractionation procedure

Abstract

Ion exchangers have proven to be a useful tool in the study of metal speciation in aquatic environments, but have seen little application in the study of metal behavior in soil environments. The labile metal species in polluted soils were evaluated by equilibrating soil suspensions with ion exchange resin membranes of different types at pH values ranging from 3 to 9. The total soluble metal content of cadmium (Cd), chromium (Cr), nickel (Ni), and lead (Pb) contaminated Western Canadian soils was subdivided into (i) low‐pH labile, (ii) weak‐acid labile, (iii) weak‐base labile, (iv) high‐pH labile, and (v) non‐adsorbable forms using cation and anion exchange membranes. Soil suspension is mixed overnight with different types of resin membranes and the cations transferred from the soil are subsequently eluted from the membranes using 1N HCl. The HCl extract is then analyzed for Cd, Cr, Ni, and Pb. The aqueous phase remaining in contact with the soil residue is considered the amount of released non‐labile, non‐adsorbable species. The low‐pH labile fraction constituted the largest proportion of the added metal in poorly buffered (sandy) soils. Weak‐acid and base labile fractions were typically highest in highly buffered soils. Clearly, metal contaminated soils most likely to cause environmental damage are sandy textured soils subject to acidification, although the production of chelating substances by roots and microorganisms may also mobilize considerable quantities of metal in soils of high clay content.     

Comparative evaluation of residual and total metal analyses in polluted soils

Abstract

Two digestion procedures, employing aqua regia‐HF (ARHF) and HNO₃‐HCIO4‐HF (HHH), were used to analyze residual metals (following a chemical fractionation scheme) and total metal content of two soils, one moderately polluted by municipal sludge applications and the other a grossly‐contaminated sample (20.8% Pb) from a battery recycling site. Although commonly used in sequential extraction analyses, the ARHF method solubilized only 53% (significant at p = 0.05) of the HHH‐determined residual Pb in the battery soil. For the sludge‐amended soil, residual Cd, Pb, and Zn were not statistically different by the two methods. For the battery soil, a single ARHF extraction also underestimated total Pb and Cu relative to HHH, but both methods gave statistically‐similar total Cd, Cu, Pb, and Zn for the sludge‐amended soil. As the sample metal concentration increased, the ability of ARHF to solubilize HHH‐equivalent metal quantities generally decreased. Since the degree of contamination is often unknown for environmental samples, the HHH method is more reliable for assessing residual and total metals in polluted soils     

Phosphorus fractions and profile distribution in newly formed wetland soils along a salinity gradient in the Yellow River Delta in China

Soil P availability has been identified as one of the key factors controlling wetland productivity, structure, and function. Soil P fractions at different depths in newly formed wetlands along a salinity gradient in Yellow River Delta (China) were studied using a modified Hedley fraction method. The total P (P_t) content ranged from 471.1 to 694.9 mg kg^–1, and diluted HCl‐extractable inorganic P (Dil‐HCl‐P_i) ranged from 324 to 524.2 mg kg^–1. The Dil‐HCl‐P_i is the predominant P form in all profiles, with on average 70% of the P_t extracted as P_i. Organic P (P_o) comprised (4.2 ± 2.0)% (mean ± SD) of the P_t, due to low organic‐matter content in coastal salt marsh ecosystems. The labile P (resin‐P, NaHCO₃‐P_i, and NaHCO₃‐P_o) and moderately labile P (NaOH‐P_i and NaOH‐P_o) concentrations were both low, ranged from 11.6 to 38.1 and 2.8 to 21.3 mg kg^–1, respectively, constituting (3.7 ± 1.1)% and (2.0 ± 0.7)%, respectively, of P_t, suggesting low availability of P to plants in these soils. Our results suggested that vegetation cover significantly influenced soil P dynamics and availability. In particular, the labile P content under Tamarix chinensis increased significantly by 23.2%–145.5% compared with adjacent soils. These findings have important implications for wetland conservation or restoration and long‐term sustainable management of newly formed wetland ecosystems in the Yellow River Delta.     

Phosphorus fractions in soils from an area with high density of livestock population

The concentrations of total phosphorus and its distribution in fractions of different solubility have been investigated in 6 different organic manures and in 69 soil samples from two counties with high concentrations of livestock population (Cloppenburg and Vechta, Lower Saxony). In the manures, large proportions of total P (means: 24% and 44%) were extracted by H₂O and anion exchange resin so that increases in labile soil P fractions can be expected if these manures are applied. The high total P-concentrations of the soils up to 8173 mg kg^?1 were related to pedogenesis and soil use. Data such as soil P test (H₂O-P, DL-P) values above the P-fertilizer recommendations and considerably larger proportions of soluble and labile P-fractions (7%-47% of total soil P) than in other regions strongly suggested that significant P-losses from the soils are likely. Therefore, reductions of P inputs to soils and measures to reduce the P-solubility and mobility are necessary for water conservation in this region.     

Residual effects of organic Zn fertilizers applied before the previous crop on Zn availability and Zn uptake by flax (Linum usitatissium)

The objective of this study was to compare the residual effect of zinc (Zn) from three Zn chelates (Zn‐aminelignosulfonate, Zn‐AML; Zn‐polyhydroxyphenylcarboxylate, Zn‐PHP; and Zn‐ethylenediaminedisuccinate, Zn‐EDDS), applied at two rates (5 and 10 mg Zn [kg soil]^–1, respectively) to a previous crop, for a flax crop (Linum usitatissimum L.). For the greenhouse experiment, two different soils were used: a weakly acidic soil, classified as Typic Haploxeralf (Soil_acid), and a calcareous soil, classified as Typic Calcixerept (Soil_calc). Plant availability of soil Zn was evaluated using the DTPA‐triethanolamine (TEA), Mehlich 3, and low‐molecular‐weight organic acids (LMWOAs) methods. Easily leachable Zn was determined, and soil Zn status was characterized based on the Zn distribution in different fractions obtained by a sequential extraction. The Zn reserves after the previous crop were substantial and ranged from 2.85% to 5.61% of available Zn (Mehlich 3‐extractable) with respect to the applied Zn. Plant parameters such as dry‐matter yield, total Zn, and soluble Zn concentrations were measured, and Zn utilization by plants was calculated. In both soils, the highest concentrations of available Zn were associated with the application of Zn‐AML at a rate of 10 mg Zn kg^–1. In Soil_acid the largest quantity of easily leachable Zn was also observed with Zn‐AML fertilizer. Similarly, Zn‐AML resulted in the highest Zn concentration in flax seeds (229 mg Zn kg^–1 and 72 mg Zn kg^–1 for the highest rate of Zn application to Soil_acid and Soil_calc, respectively). The results suggest that these Zn chelates resulted in a residual effect in soils with appropriate concentrations of the most labile fractions of Zn and available Zn, particularly when Zn‐AML was applied at the highest rate. This chelate was more effective in Soil_acid than in Soil_calc. In the weakly acidic soil at the lowest Zn level it was associated with the highest percentage of Zn utilization by the flax plant and the most effective Zn transfer from soil to the plant.     

Production of the forage halophyte Atriplex amnicola in metal‐contaminated soils

Clean‐up of contaminated soils is a costly and slow process that requires long periods of time to be effective. Therefore, direct use of contaminated sites with appropriate management is often likely to be a more efficient use of such land. Consequently, the production of safe animal forages from contaminated soils was the aim of this research. Field studies were conducted to evaluate the growth and elemental composition of river saltbush (Atriplex amnicola) grown on a metal‐contaminated soil. The soil was amended with compost at rates of 0, 15 and 30 t/ha to assess its role on plant growth and metal uptake. Compost application significantly (P < 0.05) increased biomass yield, crude protein (CP) and ash content of river saltbush; in contrast, it decreased the Zn and Pb concentrations in shoot tissues. When 30 t/ha of compost was added, the Pb concentrations in the stems and leaves decreased by 32 and 38%, respectively. Despite the large total and extractable content of metals in the studied soil, shoot concentrations of these metals in A. amnicola were always maintained below potentially toxic levels. The biomass material of A. amnicola had a high nutritive value compared to conventional forage crops and could safely be used as animal forage. This work demonstrates that an Atriplex spp, A. amnicola, has significant potential for use as a safe forage crop in the sustainable on‐site management of contaminated soils.     

Heavy‐metal mobilization and uptake by mycorrhizal and nonmycorrhizal willows (Salix × dasyclados)

Ectomycorrhizal fungi have been shown to affect metal transfer from the soil to the host plant, but the use of these fungi for increased phytoextraction of heavy metals has been scarcely investigated. Therefore, a two‐factorial pot experiment was conducted with Salix × dasyclados and (1) two contaminated soils with different concentrations of NH₄NO₃‐extractable metals and (2) two strains of the ectomycorrhizal fungus Paxillus involutus (one strain originating from a noncontaminated site—Pax1, and another from a contaminated site—Pax2). The inoculation with Pax2 increased the phytoavailability of Cd in the soils. Inoculation with both fungal strains increased the stem and root biomass, but had no effect on metal concentrations in the stems. Decreased Cd and increased Cu concentrations were observed in the roots of inoculated willows. The inoculation with P. involutus increased Cd (up to 22%), Zn (up to 48%), and Cu content in the stems. Decreased Pb content (Cu and Pb content were always <1 mg per plant) occurred in the stems from plants at the soil with the higher concentration of NH₄NO₃‐extractable metals. Contrary to this, in the soil with lower concentrations of NH₄NO₃‐extractable metals, the inoculation had no significant effects on the total uptake of Zn and Cu and even caused decreased Cd (Pax2) and Pb (Pax1) contents in the stems. Strain Pax2 had higher colonization densities, but the plants had lower mycorrhizal dependencies in the contaminated soils than after inoculation with the strain Pax1. Generally, metal extractability in the soils substantially affected the mycorrhizal dependency and heavy‐metal uptake of the willows. We concluded, that the inoculation with P. involutus offers an opportunity to particularly increase the phytoextraction of Zn, but the metal extractability and fungal strain effects have to be tested.