Verhalten von Schwermetallen in Böden. 2. Extraktion mobiler Schwermetalle mittels CaCl2 und NH4NO3

Behaviour of heavy metals in soils. 2. Extraction of mobile heavy metals with CaCl₂ and NH₄NO₃ 156 soil samples from arable fields, grassland and forest stands were analysed for the CaCl₂^? and NH₄NO₃^? extractable contents of Cd, Zn, Mn, Cu and Pb. The average amounts of Cd, Zn, Cu and Pb extracted with CaCl₂ are higher compared with NH₄NO₃ whereas the relation for Mn is vice versa. The proportion of the NH₄NO₃^? extractable contents in percent of the CaCl₂^? extractable contents of Cd, Zn and Pb decrease with increasing pH, whereas the contents of Mn and Cu increase. Inspite of a differing extraction behaviour of the two salt solutions the CaCl₂^? and NH₄NO₃^? extractable amounts of Cd, Mn, Zn und Pb are highly correlated and can be converted one into another. The mobile (CaCl₂, NH₄NO₃) proportion of the corresponding total, EDTA and DTPA heavy metal contents is in close relation to the pH of the soils. Using CaCl₂ solution the threshold pH values for an increasing mobility decrease in the order Cd > Mn > Zn > Cu > Pb, using NH₄NO₃ as extractant the order is Mn > Cd > Zn > Cu > Pb. In the case of CaCl₂ as extractant soluble chloro-Cd-complexes will be formed so that the Cd mobility in soils will be overestimated in most cases.     

Cadmium and Nutrient Heavy Metals Uptake by Rice,Barley, and Spinach as Affected by Four Ammonium Salts

This experiment was conducted to investigate the influence of ammonium salts on the uptake of cadmium (Cd) and nutritional heavy metals (copper (Cu), zinc (Zn), manganese (Mn), and iron (Fe)) by rice, barley, and spinach. These plants were grown in Cd, Cu, and Zn contaminated entisol (ES) or andisol (AS). The following ammonium salts were used: ammonium nitrate (NH₄NO₃), ammonium sulfate ((NH₄)₂SO₄), ammonium chloride (NH₄Cl), and ammonium dihydrogen phosphate (NH₄H₂PO₄). In ES, the Cd concentrations in three plant shoots were higher with NH₄Cl than with the other salts. The concentrations of Cd in soil solutions collected from ES were higher with NH₄Cl. Thus, the increase of Cd uptake by three plants with NH₄Cl treatment would be caused by the increased concentration of Cd in the soil solution. In contrast, in AS, the concentrations of the heavy metals in the shoots of all plants were not different among NH₄ applications, with one exception, the Mn concentration in rice increased with NH₄Cl in both ES and AS.     

Extractability and plant uptake of heavy metals in alum shale soils

Abstract

Fifty soil samples (0–20 cm) with corresponding numbers of grain, potatoes, cabbage, and cauliflower crops were collected from soils developed on alum shale materials in Southeastern Norway to investigate the availability of [cadmium (Cd), copper (Cu), zinc (Zn), lead (Pb), nickel (Ni), and manganese (Mn)] in the soil and the uptake of the metals by these crops. Both total (aqua regia soluble) and extractable [ammonium nitrate (NH₄NO₃) and DTPA] concentrations of metals in the soils were studied. The total concentration of all the heavy metals in the soils were higher compared to other soils found in this region. Forty‐four percent of the soil samples had higher Cd concentration than the limit for application of sewage sludge, whereas the corresponding values for Ni, Cu, and Zn were 60%, 38%, and 16%, respectively. About 70% the soil samples had a too high concentration of one or more of the heavy metals in relation to the limit for application of sewage sludge. Cadmium was the most soluble of the heavy metals, implying that it is more bioavailable than the other non‐essential metals, Pb and Ni. The total (aqua regia soluble) concentrations of Cd, Cu, Zn, and Ni and the concentrations of DTPA‐extractable Cd and Ni were significantly higher in the loam soils than in the sandy loam soils. The amount of NH₄NCyextractable metals did not differ between the texture classes. The concentrations of DTPA‐extractable metals were positively and significantly correlated with the total concentrations of the same metals. Ammonium nitrate‐extractable metals, on the other hand, were not related to their total concentrations, but they were negatively and significantly correlated to soil pH. The average concentration of Cd (0.1 mg kg^‐1 d.w.) in the plants was relatively high compared to the concentration previously found in plants grown on the other soils. The concentrations of the other heavy metals Cu, Zn, Mn, Ni, and Pb in the plants were considered to be within the normal range, except for some samples with relatively high concentrations of Ni and Mn (0–11.1 and 3.5 to 167 mg kg‘¹ d.w., respectively). The concentrations of Cd, Cu, Zn, Ni, and Mn in grain were positively correlated to the concentrations of these respective metals in the soil extracted by NH₄NO₃. The plant concentrations were negatively correlated to pH. The DTPA‐extractable levels were not correlated with plant concentration and hence DTPA would not be a good extractant for determining plant availability in these soils.     

Concentrations and forms of heavy metals in Slovak soils

The risk assessment of heavy‐metal contamination in soils requires knowledge of the controls of metal concentrations and speciation. We tested the relationship between soil properties (pH, CEC, C_org, oxide concentrations, texture) and land use (forest, grassland, arable) and the partitioning of Al, Cd, Cr, Cu, Fe, Mn, Ni, Pb, and Zn among the seven fractions of a sequential extraction procedure in 146 A horizons from Slovakia. Using a cluster analysis, we identified 92 soils as representing background metal concentrations while the remaining 54 soils showed anthropogenic contamination. Among the background soils, forest soils had the lowest heavy‐metal concentrations except for Pb (highest), because of the shielding effect of the organic layer. Arable soils had the highest Cr, Cu, and Ni concentrations suggesting metal input with agrochemicals. Grassland soils had the highest Cd and Zn concentrations probably for geogenic reasons. Besides the parent material (highest metal concentrations in soils from carbonatic rock, lowest in quartz‐rich soils with sandy texture), pedogenic eluviation processes controlled metal concentrations with podzols showing depletion of most metals in E horizons. Partitioning among the seven fractions of the sequential extraction procedure was element‐specific. The pH was the overwhelming control of the contributions of the bioavailable fractions (fractions 1–4) of all metals and even influenced the contributions of Fe oxide‐associated metals (fractions 5 and 6) to total metal concentrations. For fractions 5 and 6, Fe concentrations in oxides were the most important control of contributions to total metal concentrations. After statistically separating the pH from land use, we found that the contributions of Cu in fractions 1–4 and of NH₄NO₃‐extractable Al, Cd, Pb, and Zn to total metal concentrations were significantly higher under forest than under grassland and in some cases arable use. Our results confirm that metal speciation in soils is mainly controlled by the pH. Furthermore, land use has a significant effect.     

Evaluation of Mehlich 3 reagent as a multielement extractant in mine soils

The usefulness of Mehlich 3 (M3) reagent was evaluated as a method to extract numerous elements from coalmine soils in As Pontes (Spain) showing a wide range of physicochemical properties. Critical levels (deficiency and/or toxicity) were established for plant available elements extracted by this reagent. The M3 method was compared to 1M NH₄Cl, Olsen, acid oxalate, and DTPA methods as extractants for exchangeable Ca, Mg and K, available P, non-crystalline aluminium, and available heavy metals, respectively. The M3 method correlated significantly to NH₄Cl for Ca, Mg and K (r=0·76, 0·84 and 0·87, respectively), to Olsen P (r=0·77) and to oxalate Al (r=0·77). Significant correlations were found between Fe, Cu, Zn and Cd extracted by M3 and DTPA; for Mn, Ni, Co and Pb different relationship between methods were obtained for acid and alkaline samples, so that critical levels were established for M3 metals as a function of soil pH. Copyright © 1999 John Wiley & Sons, Ltd.     

Verhalten von Schwermetallen in Böden 1. Untersuchungen zur Schwermetallmobilität

Behaviour of heavy metals in soils. 1. Heavy metal mobility 158 soil samples with widely varying composition were analysed for their total, EDTA, DTPA and CaCl₂ extractable contents of Cd, Zn, Mn, Cu and Pb. By means of single and multiple regressions the relations between the different heavy metal fractions and the pH, organic carbon and clay content were considered. The correlations between the total, EDTA and DTPA extractable contents are very close, whereas the CaCl₂ extractable contents are not or only weakly correlated with these fractions. According to these statistical results the former fractions are considered to be the total quantity (total content) and the reactive quantity (EDTA and DTPA extractable contents) of the heavy metals, whereas the CaCl₂ extractable fraction represents the mobile fraction of the heavy metals in soils. The multiple regressions show that the mobile content of heavy metals is closely correlated with each of the quantity fractions and with soil pH. In the same way the proportion of the mobile fraction (in %) of the total, EDTA and DTPA extractable heavy metal content of the soil samples is closely related to the soil pH. Hereby the proportion of the mobile content of the various elements increases in the pH range 6,5 - 3 below element-specific threshold pH values (in brackets) in the order Cd (6,5) > Mn (5,7) > Zn (5,3) > Cu (4,5) > Pb (3,5). In the pH range 6,5 - 7,5 mainly Cu and to a lesser degree also Pb show an increasing mobility due to the influence of soluble organic substances.     

Effects of ammonium nitrate encapsulated with coal combustion byproducts on nutrient accumulation by corn and rye

Ammonium nitrate is a fertilizer and an explosive. Encapsulation of ammonium nitrate (NH₄NO₃) with coal combustion byproducts (fly ash or flue gas desulfurization gypsum) reduces the explosiveness of NH₄NO₃. A field study was conducted to determine the effects of encapsulated NH₄NO₃ on corn (Zea mays L.) and rye (Secale cereal L.) yield and accumulation of nitrogen (N), arsenic (As), cadmium (Cd), iron (Pb), copper (Cu), manganese (Mn), and zinc (Zn). Nitrogen rates were 56 and 112 kg ha^?1. Yields and concentrations of N and metals in corn grain, ear-leaf, and stover and in rye shoots were not affected by N source. Increased N rate resulted in increased corn ear-leaf, grain, and stover N, ear-leaf Cu, Mn, and Zn, and rye shoot yield, Cu, and Zn. For both species, metal levels did not exceed normal ranges. Coal byproduct-encapsulated NH₄NO₃ is as effective as non-encapsulated NH₄NO₃ for corn or rye production, without increasing plant metal concentrations above normal levels.     

Redistribution of cadmium,copper, lead,nickel, and zinc among soil fractions in a contaminated calcareous soil after application of nitrogen fertilizers

This study was conducted to evaluate the redistribution of the heavy metals Cd, Cu, Pb, Ni, and Zn among different soil fractions by N fertilizers. In a lab experiment, soil columns were leached with distilled water, KNO₃, NaNO₃, NH₄NO₃, or Ca(NO₃)₂ · 4H₂O. After leaching, soil samples were sequentially extracted for exchangeable (EXCH), carbonate (CARB), organic‐matter (OM), Mn oxide (MNO), Fe oxide (FEO), and residual (RES) fractions. Distilled water significantly increased the concentrations of Cd and Ni in EXCH fraction, while concentration of Cu and Zn did not change significantly. Application of KNO₃, NaNO₃, NH₄NO₃, or Ca(NO₃)₂ · 4H₂O significantly increased the concentrations of Cd and Zn in EXCH fraction, while concentration of Pb and Ni was decreased. Application of all fertilizers caused an increase of Cu in the OM fraction. Moreover, leaching with these solutions significantly increased Cd [except in Ca(NO₃)₂ · 4H₂O], Cu, and Zn concentrations in the CARB fraction, while Pb and Ni concentrations were decreased. With application of all leaching solutions, Zn in the EXCH, CARB, FEO, and MNO fractions was significantly increased, while Zn in the OM fraction did not change. The mobility index indicated that Ca(NO₃)₂ · 4H₂O increased the mobility of Cd, Cu, and Zn in the soil, whereas NaNO₃ decreased the mobility of Pb and Ni in the soil. The mobility index of Pb decreased by all leaching solutions. Thus, these results suggest that applying N fertilizers may change heavy‐metal fractions in contaminated calcareous soil and possibly enhance metal mobility and that N‐fertilization management therefore may need modification.     

Investigation of Heavy Metals using Various Extraction Methods in Livestock Manures

The use of animal waste for a soil amendment is a viable option for waste management. For safe and sustainable management of waste, it is important to assess the concentrations of heavy metals (HM). An experiment was conducted to compare metals [copper (Cu), zinc (Zn), and manganese (Mn)] in cow manure (CM), duck litter (DL), poultry litter (PL), and poultry litter ash (PLA) using eight extraction solutions. Extractability of HM was highly dependent upon the type of waste as well as extracting agent. Manures differed for the release of HM in the order of PL > DL > CM. Marked decreases in extractable trace elements were observed after ashing of PL irrespective of extraction method. Except for water, extractions released HM in the order of Mn > Cu > Zn. For Zn and Mn, the amount extracted varied in the order 1 M nitric acid (HNO₃) > 0.1 M HNO₃ > 0.01 M HNO₃ ≈ ethylenediaminetetraacetic acid (EDTA) > ammonium nitrate (NH₄NO₃) > calcium chloride (CaCl₂) > ammonium acetate (NH₄OAc) > H₂O in PL and PLA. Peak concentration of Cu was achieved in 1 M HNO₃ solution and the lowest Cu was found in NH₄OAc solution. On the basis of these results, the low extractability of HM in ash could suggest that the use of burned PL would be less of a water-pollution problem in the fields.     

Plant uptake of metals,transfer factors and prediction model for two contaminated regions of Kosovo

The bioavailability and plant uptake of heavy metals (HM), as well as finding the most reliable methods for the prediction of availability, continues to be one of the most crucial problems in agricultural and environmental studies. In agricultural soils from two regions in Kosovo, known for its metal pollution, we collected 60 soil and plant samples (wheat, corn, potatoes, and grass). Heavy metals were extracted from soil with aqua regia (pseudototal concentration), NH₄OAc‐EDTA (potential bioavailable), and NH₄NO₃ (mobile fraction), plant samples were digested with HNO₃/H₂O₂ (microwave assisted extraction). The pseudo total content of Cd, Pb, and Zn showed high value in Mitrovice (mean: Cd–2.92, Pb–570.15, and Zn–522.86 mg kg^?1), whereas in Drenas region Ni and Cr showed high value with a mean 258.54 and 203.22 mg kg^?1. Also, the potential bioavailability and mobile form of these metals were increased in Mitrovice (mean: Cd–1.59, Pb–217.05, Zn–522.86 mg kg^?1, respectively Cd–0.17, Pb–0.64, and Zn–15.45 mg kg^?1), compared to Drenas. Cd and Pb were elevated in potato tubers (mean Cd–0.48 and Pb–0.85 mg kg^?1). The TF was higher for micronutrients (Zn and Cu) than for non‐essential metals (Cd and Pb). Multiple regression analysis showed a good model for prediction of Cd, Pb and Zn content in plant with significance 99.9%, whereas this model was not significant for Cu, Cr, and Ni. Soil pH played a significant role in the content of Cd and Zn in wheat and potato plants. Clay content also showed significance in Cd concentration in wheat and potato plants, while carbon content was significant for Cd in grass plants, as well as for Zn in wheat and grass plants.     

Groundwater Pollution by Heavy Metals in Historical Mining Area of Lavrio,Attica, Greece

This article deals with the impacts of past mining activities andinefficient water resources management on groundwater quality inthe Lavrio area. Thirty-three water samples were collectedduring March 1998 and were analyzed for major ions (Ca, Mg, Na,K, HCO₃, Cl, NO₃, SO₄, PO₄), trace elements(Fe, Pb, Ni, Zn, Mn, Cu, Cr, Cd) and water parameters (Temperature,pH, conductivity, hardness and SiO₂). High concentrationsof heavy metals (lead, cadmium, zinc, nickel) are recorded ingroundwater samples in the Lavrio area. The highestconcentrations are recorded in the unconfined aquifer (alluvialdeposits and schists), due to mining activities. Qualitydeterioration of groundwater is also decumented and attributedto seawater intrusion and nitrate pollution of agriculturalorigin. The data were subjected to simple correlation analysisand R-mode factor analysis in order to examine the relationshipsbetween the parameters. There is a relationship between theelements participating in the sulfide (Pb, Zn, Cu, Cd) andiron-manganese mineralization and a strong relationship betweenNi–Cr. In the factor analysis a four-factor model is suggested,which can explain 72.5% of the total variance. The contributionof each factor at every site is also computed and maps showingthe geographical distribution are illustrated. The areas withhigh concentrations of heavy metals are defined from these maps.     

Metal Extractability in Binary and Multi-metals Spiked Calcareous Soils

In the present study, a laboratory experiment was designed to compare the 0.01 M calcium chloride (CaCl₂) and diethylenetriaminepentaacetic acid (DTPA) extraction methods for their ability to predict cadmium (Cd), copper (Cu), iron (Fe), Manganese (Mn), nickel (Ni), and zinc (Zn) availability and mobility in five calcareous soils. The soils were spiked with different amounts of metals (0, 50, 100, 200, and 400 mg kg^?1) both in binary (Cu and Zn; Ni and Cd; Fe and Mn) and in multi-systems (Cd, Cu, Fe, Mn, Ni, and Zn) and incubated for 1 months at field capacity. In metal-spiked soils, both extraction methods showed a linear relationship of extractable to total metals for all soils. The fraction of total metals extracted by DTPA was much higher than the fraction extracted by CaCl₂, which was attributed to the formation of soluble metal-complexes in the complexing extracts calculated by the Visual Minteq program. DTPA extraction method showed higher selectivity for Cu over other metals both in binary and in multi-systems. Different order of metals extractability was found in binary and multi-systems for both extraction methods. Solid/solution distribution coefficient (K_d) was calculated by the ratio of the solid phase to soil solution concentration of metals extracted by CaCl₂ or DTPA extraction methods. Both in binary and in multi-systems, the average K_d (l kg^?1) of metals by soils were in the order of Mn (5398) > Fe (4413) > Zn (3376) > Cu (2520) > Ni (969) > Cd (350) in the CaCl₂-extractable metals and Fe (35) ≥ Ni (34) > Zn (18) > Mn (11.2) > Cu (6.3) > Cd (4) in the DTPA-extractable metals. Results showed that among the six studied metals, Cd had the lowest K_d, implying a relative higher mobility in these calcareous soils. The Visual Minteq indicated that in the CaCl₂-extraction method and in both binary and multi-systems the dominant species for Cu, Mn, Ni, and Zn were Cu²⁺, Mn²⁺, Ni²⁺ and Zn²⁺, respectively, while for Cd and Fe, the dominant species were CdCl⁺ and Fe(OH)²⁺, respectively.     

一种通用型土壤有效元素高效提取方法及应用

Mehlich 3（M3）方法可同时提取土壤中磷、钾、钙、镁、铝、铁、锌、锰、铜等多种元素的有效态，提高土壤检测的效率；另外，M3法适用于钙质土、火山灰土、高度风化土等各类土壤，可作为一个“通用”型土壤有效元素提取试剂。但是硝酸铵（NH4NO3）由于管制不易获取，应用M3方法测定土壤有效元素含量时受到极大限制。因此，本研究用另一种易获取的惰性电解质氯化铵（NH4Cl）替代硝酸铵（NH4NO3），评价氯化铵替代硝酸铵M3法的适用性。Pearson相关分析结果表明，用氯化铵替代硝酸铵M3法测得的30种土壤有效磷、钾含量与M3法测定结果呈极显著正相关，其决定系数（R2）分别为0.99（P=2.31×10-55，n=60）和0.98（P=1.52×10-49，n=60）。同时，氯化铵替代硝酸铵M3法和M3法测定的有效钙、镁、铝、铁、锌、锰和铜含量极显著相关，R2值分别为0.98，1.00， 0.99，0.96，0.99，0.95和0.94。氯化铵替代硝酸铵M3–P与酸性、中性和碱性土壤的 Bray–P和Olsen–P极显著相关，R2分别为0.97和0.91 （P=1.42×10-15和1.00×10-21，n=20和40）。同时，利用氯化铵替代硝酸铵M3法测定酸性改良土壤有效磷含量，发现其得到显著提高。因此，氯化铵替代硝酸铵M3法可作为测定各种土壤，以及改良土壤中有效磷、钾和其他金属元素有效态含量的通用方法。     

Spatial distribution of soil heavy metal concentrations as indicator of pollution sources at Mount Križna (Great Fatra,central Slovakia)

The objective of this study was to test the suitability of a simple approach to identify the direction from where airborne heavy metals reach the study area as indication of their sources. We examined the distribution of heavy metals in soil profiles and along differently exposed transects. Samples were taken from 10 soils derived from the same parent material along N-, S-, and SE-exposed transects at 0—10, 10—20, and 20—40 cm depth and analyzed for total Al, Cd, Cr, Cu, Fe, Mn, Ni, Pb, and Zn concentrations. The heavy metal concentrations at 0—10 cm were larger than background concentrations in German arable soils except for Cr (Cd: 0.6—1.8 mg kg^—1; Cr: 39—67; Cu: 40—77; Ni: 87—156; Pb: 48—94; Zn: 71—129; Fe: 26—34 g kg^—1; Mn: 1.1—2.4). Decreasing Cd, Cu, Mn, and Pb concentrations with increasing soil depth pointed at atmospheric inputs. Aluminum and Ni concentrations increased with soil depth. Those of Fe, Cr, and Zn did not change with depth indicating that inputs at most equalled leaching losses. The Pb accumulation in the surface layer (i.e. the ratio between the Pb concentrations at 0—10 to those at 20—40 cm depth) was most pronounced at N-exposed sites; Pb obviously reached Mount Križna mainly by long-range transport from N where several industrial agglomerations are located. Substantial Cd, Cu, and Mn accumulations at the S- and SE-exposed sites indicated local sources such as mining near to the study area which probably are also the reason for slight Cr and Zn accumulations in the SE-exposed soils. Based on a principal component analysis of the total concentrations in the topsoils four metal groups may be distinguished: 1. Cr, Ni, Zn; 2. Mn, Cd; 3. Pb (positive loading), Cu (negative loading); 4. Al, Fe, indicating common sources and distribution patterns. The results demonstrate that the spatial distribution of soil heavy metal concentrations can be used as indication of the location of pollution sources.     

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.     

Trends in Water Chemistry of Acidified Bohemian Lakes from 1984 to 1995: II. Trace Elements and Aluminum

The concentrations of Al, Be, Cd, Cu, F, Fe, Mn, Pb, and Zn were monitored in five glacial lakes and one man-made lake in the southwestern part of the Czech Republic. The lakes had median pHs of 4.4 to 6.5 during 1984 to 1995. Decreases in the concentrations of Mn and Pb occurred in five acidified lakes. The concentrations of Al_T, Be, Cd, and F decreased in the four chronically acidified lakes, Zn decreased in two lakes. Concentrations of Cu and Fe remained unchanged. The decreases in Be, Mn, and Zn concentrations were proportional to the decrease in C_SA (C_SA = SO₄ ^2- + NO₃ ^-+ Cl^-); decreases in Al_T, Cd, and Pb concentrations were proportionately higher, while F was lower. The greater decrease in the Pb concentrations (61 to 79%, at a rate up to 0.15 μg L^-1yr^-1) was caused by pronounced decreases in deposition of Pb derived from mobile sources. The decrease of Al_T concentrations was dominated by a decrease in Al³⁺, whose concentration decreased by 51 to 86%. The concentrations of complexes Al(OH)²⁺, Al(OH)₂ ⁺, AlF²⁺, and AlH₃SiO₄ ²⁺ also decreased. The decrease in the concentrations of inorganic forms of Al (Al_i) compensated 65% of the decrease in C_SA. The Cd concentrations were highly variable in the years 1986 to 1988 because of variable amounts of accumulation on particles.     

Nitrate/ammonium ratio effects on mineral element uptake by sorghum 1

Abstract

Experiments were conducted using different NO₃ ^–/NH₄ ⁺ ratios to determine the effects of these sources of N on mineral element uptake by sorghum [Sorghum bicolor (L.) Moench] plants grown in nutrient solution. The NO₃ ^–/NH₄ ⁺ ratios in nutrient solution were 200/0, 195/5, 190/10, and 160/40 mg N L^–1. Nutrient solutions were sampled daily and plants harvested every other day during the 12‐day treatment period.

Moderately severe Fe deficiencies were observed on leaves of plants grown with 200/0 NO₃ ^–/NH₄ ⁺ solutions, but not on the leaves of plants grown with the other NO₃ ^–/NH₄ ⁺ ratios. As plants aged, less Fe, Mn, and Cu were translocated from the roots to leaves and leaf/root ratios of these elements decreased dramatically in plants grown with 200/0 NO₃ ^–/NH₄ ⁺ solutions. Extensive amounts of Fe, Mn, and Cu accumulated in or on the roots of plants grown with 200/0 NO₃ ^–/NH₄ ⁺ solutions. Manganese and Cu may have interacted strongly with Fe to inhibit Fe translocation to leaves and to induce Fe deficiency. As the proportion of NH₄ ⁺ in solution increased, K, Ca, Mg, Mn, and Zn concentrations decreased in the leaves, and Ca, Mg, Mn, and Cu concentrations decreased in roots. Potassium and Zn tended to increase in roots as NH₄ ⁺ in solution increased.     

Influence of Acidification and Liming on the Distribution of Trace Elements in Surface Waters

Metals in water have been monitored for up to 18 years in acidified regions of Sweden. The concentrations of metals (Al, Cd, Cu, Fe, Mn, Mo, Pb, Zn) were determined by AAS and ICP-MS, the dissolved fractions after separation by in-situ dialysis. Elements showing negative pH-correlation were primarily Al, Zn, Cd, Mn, and Pb, while Mo was positively correlated to pH, indicating a predominance of negatively charged ionic forms. Zn, Cd, and Mn occurred primarily in the dissolved fractions, especially at the lower pH levels. Fe, Al, Pb and Mn were further enriched in humic waters. During the study period, some of the sites were subject to lime treatment, which had a marked influence on most elements, causing the mean levels and the seasonal fluctuations to decrease. Treatment on the lake surface was less effective than wetland liming to reduce seasonal fluctuations, especially for metals mainly originating from the catchments, as Fe and Al.     

Heavy metals in the soil–plant system of the Don River estuarine region and the Taganrog Bay coast

Purpose

The aim of this work was to study the level and degree of mobility of heavy metals in the soil–plant system and to perform bioindication observations in the Don River estuarine region and the Russian sector of the Taganrog Bay coast.

Materials and methods

The objects of the study included samples of zonal soils (chernozem) and intrazonal soils (alluvial meadow and alluvial-stratified soils, Solonchak, sandy primitive soil) from monitoring stations of the Don river estuarine region and the Taganrog Bay coast, as well as their higher plants: Phragmites australis Cav., Typha angustifolia L., Carex riparia Curtis, Cichorium intybus L., Bolboschoenus maritimus L. Palla, and Rumex confertus Willd. The total concentrations of Mn, Ni, Cd, Cu, Zn, Pb, and Cr in the soils were determined by X-ray fluorescent scanning spectrometer. The concentration of heavy metal mobile forms exchangeable, complex compounds, and acid-soluble metal were extracted using the following reagents: 1 N NH₄Ac, pH 4.8; 1 % EDTA in NH₄Ac, pH 4.8; 1 N HCl, respectively. Heavy metals in plants were prepared for analysis by dry combustion at 450 °C. The heavy metal concentration in extracts from plants and soils was determined by AAS.

Results and discussion

The total contents of heavy metals in the soil may be described with a successively decreasing series: Mn?>?Cr?>?Zn?>?Ni?>?Cu?>?Pb?>?As?>?Cd. The total concentrations of As, Cd, and Zn in the soil exceed the maximum permissible concentrations levels. Contamination of alluvial soils in the estuarine zone with mobile Сu, Zn, Pb, and Cd has been revealed, which is confirmed by the high bioavailability of Cu and Zn and, to a lesser degree, Cd and Pb accumulating in the tissues of macrophytic plants. Data on the translocation of elements to plant organs have showed their predominant accumulation in the roots. Bioindication by the morphofunctional parameters of macrophytic plants (with a Typha L. species as an example) can be used for revealing the existence of impact zones with elevated contents of metals in aquatic ecosystems.

Conclusions

The results revealed that increased content of Zn, Pb, Cu, Ni, and As in soil have anthropogenic sources. The high content of Cr in the soils is related to the lithogenic factor and, hence, has a natural source.

     

Plant Availability of Cadmium in Soils: II. Factors Related to the Extractability and Plant Uptake of Cadmium in Cultivated Soils

Abstract

Eighty four soil samples collected from southeastern Norway were analyzed for Cd by extraction with NH₄OAc, DTPA, NH₄OAc-EDTA, NH₄NO₃, HCl and CaCl₂. The total Cd, pH, exchangeable K and Ca, dithionite-extractable Mn, available P and fine sand (0.2–0.02 mm) contents were the principal factors related to the extractable Cd, with some inter-extractant variations. Cadmium extracted by NH₄NO₃, NH₄OAc, HCl and CaCl₂ decreased with increasing soil pH, but the Cd extracted by all the extractants increased with increasing total Cd, exchangeable K and Ca, available P, and Mn-oxide contents in the soils. The Cd concentrations in plants were significantly related to the extractable Cd, exchangeable Ca and Mg, pH, Mn-oxides and organic matter content.