Association of cadmium,zinc, copper,and nickel with components in naturally heavy metal‐rich soils studied by parallel and sequential extractions

Abstract

In this study, a new parallel and sequential extraction procedure was proposed to investigate the solubility of metals [cadmium (Cd), zinc (Zn), copper (Cu), and nickel (Ni)] and their association with soil components in naturally metal‐rich soils of Norway. Two different soils, alum shale (clay loam) and moraine (loam), developed on alum shale minerals were used. Each soil had two pH levels. For parallel and successive extractions, H₂O, 0.1M NH₄OAc (soil pH), 0.3M NH₄OAc (soil pH), 1M NH₄OAc (soil pH), and 1M NH₄OAc (pH 5.0) were used. A significant amount of Cd was extracted by NH₄O Ac related to concentration of NH₄OAc in the extracting solution. The amounts of Zn, Cu, and Ni extracted by these reagents were almost negligible except with 1M NH₄OAc (pH 5.0). Thus these metals were strongly bound to soil components. A seven step sequential extraction procedure was applied to evaluate the association of metals with soil constituents. The extractions were performed sequentially by extracting the soil with reagents having an increasing dissolution strength: 1M NH₄OAc (soil pH), 1M NH₄OAc (pH 5.0), 1M NH₂OH.HCl (in 25% HOAc), 1M NH₂OH.HCl (in 0.1M HNO₃), 30% H₂O₂ (in 0.1M HNO₃), 30% H₂O₂ (1M HNO₃), and aqua regia. In both soils at both pH levels investigated, appreciable percentages of total Cd (20–50%) were found associated with the NH₄OAc extractable fraction (mobile fraction). For Zn, Cu, and Ni, the percentage of total metal extracted with NH₄OAc was low (<4%), but it increased significantly by introducing a reducing agent (NH₂OH.HCl). The NH₂OH.HCl‐extractable fraction was the greatest fraction (>60%) for all four metals examined. These results suggest that among the metals studied, only Cd was easily desorbed from soil and should be considered mobile and potentially bioavailable. Other metals (Zn, Cu, and Ni) were strongly associated with the soil components and should be considered less available to plants. Using the sequential fractionation technique as a measure of availability, mobility and potential bioavailability of these four metals in the alum shale soils were: Cd>Zn>Ni>Cu.     

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.     

Vergleich zwischen Total- und königswasserextrahierbaren Elementgehalten in natürlichen Böden und Sedimenten

Comparison between total- and aqua regia extractable contents of elements in natural soils and sediments Total- and aqua regia extractable contents of 19 elements from 28 soil samples with widely varying composition of the ISE ring analytical program (INTERNATIONAL SOIL-ANALYTICAL EXCHANGE) of the year 1995 to 1997 have been taken to find out the comparability between the two fractions. The relations between the two fractions and pH, organic matter and clay content were considered by means of single and multiple regressions. The correlations between the total and aqua regia extractable contents of As, Ca, Cd, Co, Cr, Cu, Fe, Hg, Mg, Mn, Ni, P, Pb and Zn are very close, whereas Al, Ba, K, Na and Sr are not or only weakly correlating. The multiple regressions show that the content of some aqua regia extractable elements and the proportion (in %) of the total contents is correlated with pH, organic matter and/or content of clay. In the same way the proportion of aqua regia extractable elements is closely related (except Fe and Hg) to the soil pH. Hereby the proportion of the aqua regia extractable content increases with increasing pH in the range 3,5—7,7. The determined equations are tested for As, Cd, Co, Cr, Cu, Hg, Mn, Ni, Pb and Zn by using the values of certified reference material. The estimated aqua regia extractable contents are being compared with values of reference material. The average proportion of the calculated to the measured aqua regia contents of an element in percent are 99 for Zn, 98 for Co, Cu and Mn, 94 for Cd, 90 for Ni, 88 for Cr, 105 for Hg, 113 for As and 114 for Pb.     

Prediction of available heavy metals by six chemical extractants in a sewage sludge‐amended soil

Abstract

In a field experiment conducted during three years in a sandy‐loam, calcareous soil, one aerobically digested sewage sludge (ASL) and another anaerobically digested sewage sludge (ANSL) were applied at rates of 400, 800, and 1,200 kg N/ha/year, and compared with mineral nitrogen fertilizer at rates of 0, 200, 400, and 600 kg N/ha/year in a cropping sequence of potato‐corn, potato‐lettuce, and potato, the first, second, and third year, respectively. Results showed that the highest values of soil extractable metals were obtained with aqua regia, whereas the lowest levels with DTPA. All metal (Zn, Cu, Cd, Ni, Pb, and Cr) gave significant correlations between metal extracted with the different extractants and metal loading applied with the sludges. The metal extractable ion increased over the control for Zn, Cu, Cd, Ni, Pb, and Cr extracted with DTPA, EDTA (pH 8.6) and 0.1 N HC1, for Zn, Cd, Ni, Pb, and Cr extracted with EDTA (pH 4.65) and AB‐DTPA, and for Zn, Cd, Ni, and Cr extracted with aqua regia. The level of metal‐DTPA extractable resulted highly correlated with that obtained by the other methods, except the Ni‐aqua regia extractable. The soil extractable elements which showed significant correlations with metals in plant were: Zn, Cu, Cd, and Ni in potato leaves, Cd, Ni, and Pb in corn grain, and Zn and Cd for lettuce wrapper leaves. In general, all the chelate based extractants (DTPA, EDTA pH 4.6, EDTA pH 8.6, AB‐DTPA) were equally useful as indicator of plant available metals in the soil amended with sludge.     

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.     

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.     

Effect of Grinding on Soil Extraction by Aqua Regia, 2 M Nitric Acid,and Mehlich 3

Abstract

The effect of grinding on soil extraction was determined for two soil fractions and three extractants. Arsenic (As), beryllium (Be), cadmium (Cd), cobalt (Co), chromium (Cr), copper (Cu), nickel (Ni), lead (Pb), vanadium (V), and zinc (Zn) were extracted by aqua regia and 2 M nitric acid. Mehlich 3 extractant was used for determination of potassium (K), magnesium (Mg), calcium (Ca), phosphorus (P), iron (Fe), and aluminum (Al). One hundred forty‐seven agricultural soil samples representing all major soil types, climatic regions, and proportions of agronomic cultures in the Czech Republic were collected for the study. Particle size fractions smaller than 2 mm and smaller than 0.150 mm were chosen for investigation. Extraction of elements by aqua regia was similar for both size fractions of soil. Cold 2 M nitric acid is a weaker extractant than aqua regia, and a statistically significant increase in extractable Be (5%), Cd (6%), Co (11%), Cu (5%), Ni (5%), and V (2%) was measured with the finely ground soils. An increase for the finer fraction for K (10%) and Mn (25%) was found for Mehlich 3. A more complex nonlinear relationship was found for Mehlich 3 extractable Al and Fe. This was probably caused by a more intensive re‐adsorption of Fe and Al to the finely ground soils.     

Chemical extractability of heavy metals during and after long-term applications of sewage sludge to soil

Sequential extractions were used on soils from a long-term experiment treated with either metal-contaminated sewage sludge or inorganic fertilizers between 1942 and 1961. The four extracts employed were CaCl₂, NaOH, EDTA and aqua regia. These showed that large increases in the proportions of Pb, Cu, Zn, Ni and Cd in at least one of the first three fractions occurred during the first 10 years of sewage sludge additions. Cr always remained predominantly in the aqua regia-soluble fraction. For 30 years after this, including a period of more than 20 years after application of sludges to the field had ceased, there was very little change in the percentage of each metal extracted by each reagent. Although the ‘residual’ (aqua regia-soluble) and EDTA fractions usually contained the largest amounts of metals in either sludge- or fertilizer-treated soils, there were clear differences between the metals: Pb represented the largest fraction of any metal extracted by EDTA, Cu of any metal extracted by NaOH and Cd of any metal extracted by CaCl₂. The same extractions were made of the sewage sludges that were applied to the field, and the distributions of the metals differed from those found in the treated soils. It was particularly apparent that more Pb and Cu was present as the ‘residual’ (aqua regia) fraction in sludges than in the soils.     

Crop uptake and extractability of cadmium in soils naturally high in metals at different pH levels

Abstract

A greenhouse experiment was conducted for three years to study the effect of different pH levels on metal concentrations in plants and the cadmium (Cd) extractability by DTPA and NH₄NO₃. The soils used were an alum shale (clay loam) and a moraine (loam), which were adjusted to pH levels of 5.5, 6.5, 7.0, and 7.5. Wheat (Triticum aestivum), carrot (Daucus carota L.), and lettuce (Lactuca sativa) were grown as test crops. Crop yields were not consistently affected at increasing soil pH levels. The concentration of Cd in plant species decreased with increasing soil pH in both soils and in all three years. Significant concentration differences between soil pH levels were only seen in wheat and carrot crops. Increasing soil pH also decreased the nickel (Ni) and zinc (Zn) concentrations in plants in the first year crop but the copper (Cu) concentration was not consistently affected by soil pH. The effect of pH was more pronounced in the moraine then the alum shale soil. The DTPA‐and NH₄NO₃‐extractable Cd was decreased with the increasing soil pH and the pH effect was more pronounced with NH₄NO₃ extractable Cd. Both extractants were found equally effective in relation to the Cd concentration in plants in this study.     

Reference concentrations for heavy metals in mineral soils, oat, and orchard grass (Dáctylis glomeráta) from three agricultural regions in Norway

Background values for heavy metals are necessary for the assessment of metal pollution of soils and plants. Samples of cultivated and uncultivated soils, oat grain, and seed heads of orchard grass (Dáctylis glomeráta) were collected from central, southeastern, and southwestern Norway. Total and easily extractable concentrations of As, Cd, Cr, Cu, Hg, Ni, Pb, and Zn were determined in soil samples and total concentrations in plant samples. Element distributions have been correlated with petrology of soil parent material, type of mineral deposit, soil depth, geographic area, and land use. Concentrations of heavy metals are generally within the lower part of the normal global range. The petrology of the soil parent material has the greatest influence on aqua regia extracted metal concentrations among the factors studied. DTPA extracted metals show less dependence on rock types. Presence of alum shale results in particularly high values for Cd in both soil extracts and in oat grain. Soil cultivation seems to influence the relative concentration of metals in the topsoil. The ratios of easily extractable to total concentrations of metals are primarily related to the organic matter content. Metal concentrations in oat grain can best be predicted by concentrations in DTPA extracts and soil pH among the factors studied. Seed heads of orchard grass are less affected by concentrations in the soil and appear therefore to be a poor indicator of heavy metals in soils.     

Comparison of methods for measuring heavy metals and total phosphorus in soils contaminated by different sources

The relationships between the concentrations of zinc (Zn), lead (Pb), copper (Cu), nickel (Ni) and chromium (Cr) as measured by X-ray fluorescence analysis (XRF), aqua regia, and HNO₃ pressure digestion were studied in soil samples covering a wide range of heavy metal concentrations. The soils were contaminated by sewage sludge, exhaust depositions, river sediments of mining residues, and dump material. The question was addressed whether the source of heavy metals or other soil properties affect the relationship between these three methods. The aqua regia-digestible fraction of the five heavy metals reached on average 64% of the XRF-detectable content. The pressure accelerated HNO₃-digestible fraction of the five heavy metals was on average 71% of the XRF-detectable content; the respective phosphorus (P) fraction reached a median of 75%. This suggests that HNO₃ pressure digestion can also be used for characterizing the total P content of soils. Aqua regia extraction and HNO₃ pressure digestion gave similar values for Zn, Pb, and Cu, which dominate the heavy metal load of most contamination sources. Significantly higher Cr values were obtained by HNO₃ pressure digestion than by aqua regia extraction. Additionally, the Cr contents were affected by the source, e.g. sewage sludge had relatively high contents of aqua regia and HNO₃ pressure extractable contents in comparison to the XRF values. The element-specific relationships between the three methods were all highly significant. However, the respective multiple linear regression models were in most cases affected by soil organic carbon (C), in some cases by clay or soil pH.     

Solubility and uptake of heavy metals from a Swedish soil

Samples of the surface layer (Ap) and of grass, collected from: (1) grass ley fertilized in the normal way; (2) permanent pasture fertilized in the normal way; and (3) permanent pasture treated with large amounts of sewage sludge five years earlier, were analysed for Mn, Zn, Cu, Cr, Co, Ni, Pb, and Cd.The soil samples were extracted with: (1) distilled water saturated with CO₂; (2) 1 M neutral ammonium acetate; (3) ammonium acetate + acetic acid, pH 4.75; and (4) 2 M nitric acid on a waterbath. The efficiency of these extractants differed greatly and, in relative values, was: 1 for H₂O + CO₂, 3.4 for NH₄OAc, 20.7 for NH₄OAc + HOAc, and 343 for 2 M HNO_3- The dissolving effects of the extractants differed markedly with the kind of element.Grass from the field treated with sewage sludge showed much higher contents of Mn and Zn and somewhat higher contents of Cu and Pb than grass from the untreated field. The levels of Cr, Co, Ni, and Cd were practically uninfluenced by the treatment. Grass from a field close to a highway accumulated large amounts of air-borne Pb and Cd during the summer.It is concluded that the total contents of heavy metals in soils have only limited importance for the uptake by plants. Weak extractants therefore give better information about the plant-available amounts in soils.     

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.     

Application of Response Surface Methodology and Machine Learning Combined with Data Simulation to Metal Determination of Freshwater Sediment

A comparative study between conventional methods (EPA 3050B and ISO 11466.3) of metal extraction and a simple low-cost method, using aqua regia, was carried out in this work. Six elements (Mn, Cu, Zn, Pb, Ni, and Cd) were determined by flame atomic absorption spectrometry (FAAS) in a certified sample of sediment (CNS 392). Central composite design (CCD) and response surface methodology (RSM), as well as machine learning, were used to find the optimal conditions for metal extraction. The influence of the parameters—volume of nitric acid in aqua regia (v), time of extraction (t), and temperature (T)—on Mn, Cu, Zn, and Pb recoveries was investigated. The best condition for the recovery of all the metals was v = 2.5 mL of HNO₃, t = 2 h, and T = 90 °C. In comparison with the conventional methods, the aqua regia method was found to present better recovery values and lower standard deviations for all the metals studied.     

Schwermetallanreicherungen in Salzmarschen der südlichen Nordseeküste

Heavy metal accumulations in Salic Fluvisols of the southern North Sea coast The total contents of Cd, Pb, Cu and Zn (HNO₃ bomb digestion) and their EDTA extractable fractions in Salic Fluvisols were investigated. The mean total content of Cd was 0,09 mg/kg, of Pb 44,1 mg/kg, of Cu 11,4 mg/kg and of Zn 105,6 mg/kg. Mostly the highly developed soils showed higher contents than poorly developed ones. The EDTA extractable fractions were comparatively small: they were 59% (Cd), 44% (Pb), 15% (Cu) and 10% (Zn) of the total content. The heavy metal contents of the soils in Elisabeth-Außengroden were higher than of those in Jadebusen. The vertical heavy metal distribution showed a different sedimentation pattern over the last hundred years. Compared with the geological background values Cd was 2- to 3-fold enriched, Pb 7-fold, Cu 3- to 4-fold and Zn 3-fold in soils with high sedimentation rates. Even higher values are likely in soils with smaller sedimentation rates.     

Use of routine soil tests in predicting corn leaf zinc

Abstract

Zinc of index corn leaves samples from 91 Minnesota sites on numerous soil types was correlated with soil Zn extracted by four routine procedures. The EDTA?(NH₄)₂CO₃ ‐ extractable soil Zn was more closely correlated with leaf Zn than soil zinc extracted by 0.1N HCl, EDTA‐NH₄OAc, or by NH₄OAc ‐ dithizone. Soil pH, CaCO₃ equivalent, extractable P, and organic matter of both acid and calcareous soils were negatively correlated with leaf Zn. When EDTA ? (NH₄)₂CO₃ ‐ extractable Zn was included with routine soil tests, a prediction equation for corn leaf Zn was formulated and compared with analytical values. However, the use of 1.4 ppm EDTA ? (NH₃)₂CO₃, ‐ extractable soil Zn alone as a critical value was equally effective in predicting leaf Zn.     

Compost use in viticulture: Effect on heavy metal levels in soil and plants

Abstract

The purpose of this study was to examine the long‐term effect of compost application on the heavy metal content in soil, leaves, and fruit of grape (Vitis vinifera). Two types of compost were tested in a vineyard. One was compost with a low heavy metal content, which was derived from sewage sludge and bark (SB compost). The other type was compost with a higher concentration of metals, which was derived from municipal solid waste (MSW compost). For 6 years, the levels of zinc (Zn), copper (Cu), nickel (Ni), lead (Pb), cadmium (Cd), and chromium (Cr) in their total (aqua regia digestion), EDTA‐extractable, and DTPA‐extractable forms were monitored in soil, leaves, musts, and wines. The resulting data clearly demonstrate that SB compost did not cause any significant increase in heavy metal levels in the soil and the plants. Thus, this type of compost can be used for soil fertilization with no danger either to the environment or to crops. In contrast, the use of MSW compost caused a significant accumulation of Ni, Pb, Cd, and Cr in the soil, in vegetation, and in musts. Skin‐contact fermentation dramatically decreased the heavy metal content of the wines. The concentration of heavy metals in plant tissues was found to be positively correlated with the DTPA‐extractable form of the metals in the soil, but not correlated with the total or the EDTA‐extractable forms.     

Spurenelemente in Bodensequenzen II. Zwei Pararendzina – Pseudogley – Sequenzen aus Löß

Trace elements in pedosequences II. Two Pararendzina-Pseudogley-sequences on loess Total amounts and fractions of Cu, Zn, Pb, Cd, Co and Ni extractable in boiling oxalate (replacing dithionite for analytical reasons), oxalate at room temperature and EDTA were determined in two hydro-pedosequences on loess ranging between Pararendzina-Braunerde-Parabraunerde-Pseudogley. The pedogenic influence on the depth functions of these trace elements was much weaker in the loess soils than in those on slates of part I of this study. With a few exceptions external additions seem to be masked by soil cultivation. Clay movement (Alfisols) produced maxima of Fe and Cu in the B_t horizon. Carbonates of the parent loess contain trace elements which are released into the soil during solum formation. As long as they exist in carbonates they are hardly extractable with oxalate but with EDTA. In contrast, after pedogenic decomposition of the carbonates in the B horizon their trace elements are now oxalate but no longer EDTA extractable. In the A horizon, where organic matter is involved the trace elements are again EDTA extractable. As in the soils from slate (part I) Cd behaves more similarly to Pb than to Zn. The total element balance indicates a slight gain of Pb and loss of Zn whereas the total amount of the other elements was essentially unchanged. Generally, the more mobile fractions increased during soil formation.     

Digestion Methods for Total Heavy Metals in Sediments and Soils

The objectives of this study were to analyze the total contents of Cd, Cr, Cu, Ni, Pb, and Zn in the freshwater sediments and the arable and non-arable soils of Taiwan, and to compare the different digestion methods for their determination. Two hundred and thirty-nine freshwater sediments were collected from the Fei-Tsui Reservoir Watershed (FTRW) in northern Taiwan. Forty-two surface (0–15 cm) and subsurface (15–30 cm) soil samples were likewise collected from 21 representative arable soils derived from various parent materials and with varying weathered degrees in different regions of Taiwan. In addition, one hundred and ninety-four non-arable soils were collected from the different forest regions, industrial parks, resident areas, and commercial areas. Several digestion methods including the aquaregia and different combinations of concentrated acids (HClO₄, HNO₃, H₂SO₄, or HF) were compared. All samples were digested both by the aqua regia method and the Baker and Amacher method for Cd, Cr, Cu, Ni, Pb, and Zn. The Reisenauer method was used for Cr and the Burau method for Pb further. The results indicate that the best digestion methods to analyze the total contents of heavy metals in the sediments and soils were recommended as follows: the Baker and Amacher method for Cd, Cr,Cu, Ni, and Zn; the Reisenauer method for Cr, but for simplicity the Baker and Amacher method is also recommended as the flexible method for the total analysis of Cr; the aqua regia method for Cu, Ni, and Zn; and the Burau method for Pb.     

Trace elements in some Northern Nigerian soils

Abstract

The concentrations of the more‐or‐less strongly retained trace elements present in the root zone of some northern Nigerian soils were determined. The soils were chosen to represent some of the more extensively distributed soil orders under cultivation in the Nigerian savanna zone. Extraction by concentrated HNO₃ was used to determine the so‐called “total”; amount of retained Cu, Zn, Pb, Ni, Cd, and B in the soils. Aqueous solutions of the chelating agents, EDTA and DTPA, were used to extract the more weakly retained Cu, Zn, Pb, Ni, and Cd; whereas, hot water was used to extract the weakly retained B. The “total”; and the more‐weakly‐retained contents of these trace elements were significantly correlated with the amount of clay, silt, and the oxalate‐extractable oxyhydroxides present in the soils; whereas, only the weakly retained elements were significantly correlated with the content of organic matter in the soil. Both the “total”; concentrations and weakly‐retained Cu, Zn, and B were so low that deficiency problems may develop in these sandy soils if cultivated more intensively on a commercial scale without due precautions. The concentrations of the weakly‐retained toxic elements, Pb, Ni, and Cd, were low indicating that industrial pollution has not yet occurred.