Comparison of Five Digestion Procedures for Recovery of Nutrients and Trace Elements in Plant Tissue

Comparison of five digestion procedures for recovery of nutrients and trace elements in plant tissue were examined. The objectives of this study were to compare five digestion procedures: AOAC (dry ashing), two nitric acid, (NA1, commonly used and NA2, our modification), and two aqua regia (AR1, commonly used and AR2, our modification) procedures for recovery of 15 plant nutrients and trace elements in corn, swiss chard, thorn apple, and barley flour (certified material). Generally, the recovery of various elements depended on the digestion procedure used and the plant species. In most instances, NA2 recovered more phosphorus (P), potassium (K), sulfur (S), and manganese (Mn) than the AOAC or the two AR procedures. Also, overall NA2 recovered more K and magnesium (Mg) than NA1. Extractants AR1 and AR2 recovered more iron (Fe) than the two NA procedures, and the same as the AOAC. The AR2 recovered very similar concentrations of nutrients as the AOAC; and in corn tissue, AR2 recovered more zinc (Zn), chromium (Cr), nickel (Ni), copper (Cu), and boron (B) than the AOAC. The AOAC recovered less S and B than the other procedures tested. For instance, in barley flour, AOAC recovered eight to nine times less S, while in corn tissue AOAC recovered around three times less S than the NA procedures. Overall, there are three important findings: (1) NA procedures may be used for recovery of most elements in plant tissue; (2) AR2 procedure is comparable to the official AOAC method for recovery of nutrients and trace elements in plant tissue, and (3) the official AOAC method used in Canadian plant testing laboratories may underestimate the concentration of S and B in plant tissue.     

Total elemental analysis digestion method evaluation on soils and clays

Abstract

The standard digestion method for total elemental analysis of soil material by the Soil Survey Laboratory (USDA Natural Resources Conservation Service) uses a 2‐mL clay suspension with hydrofluoric acid (HF) in a closed Teflon digestion vessel (method HF‐SUS). The accuracy and efficiency of elemental recovery by method HF‐SUS was compared to: (a) modification of HF‐SUS by use of a dried sample (method HF‐DRI); (b) modification of HF‐SUS by use of a dried sample and HF+aqua regia (method HF+AR); (c) sample digestion by Li metaborate fusion (method FUS); and (d) microwave digestion of samples with HF+aqua regia in Teflon bombs (method MICRO). Three replications of three standard reference materials (SRMs), fine‐earth (<2 mm) from 12 soils, and the clay (<2 urn) from 10 of those soils were analyzed. Method HF+AR shows the most consistent statistical agreement with the certified SRM values. Analysis of variance (ANOVA) indicates significant effects (α=0.05) for method of digestion, nonsignificant effects for method times SRM and method times clay, but significant effects for method times fine‐earth. Composition and/or variability of material are significant factors in the method of digestion. Method HF+AR yields significantly higher experimental means of A1₂O₃, Fe₂O₃, and K₂O contents and oxide recovery (summation of experimental means for oxides of all reported elements) than all other methods.     

Nitric acid dissolution and multi‐element analysis of soils and sediments by inductively coupled plasma spectrometry

Abstract

A method was developed for the simultaneous analysis of P, K, Cu, Cd, Zn, Fe, Mn and Pb in soils and sediments by inductively coupled plasma spectrometry (ICP) after digestion in nitric acid. The procedure extracted 82 to 94% of the totals of the heavy metals, 78% of total P and 34% of total K. Inter‐element interference correction data are given for the ICP method. The method gave results similar to those obtained by other analytical procedures. The precision of the method was satisfactory but was lowest for Cd which had the lowest concentrations (<2.7 mg/kg) of the elements determined.     

An application of a modified microwave total dissolution technique for soils

Abstract

Application of a microwave dissolution technique to soil materials aided by acid digestion procedures has many advantages, but the incomplete dissolution of sandy soils has been noted. The objectives of this study were to modify a microwave oven digestion technique to facilitate the determination of the total elemental content of soils and geologic materials containing greater than 45% sand and apply these data to determine natural separations in parent materials. A microwave dissolution technique using aqua regia (HNO₃ and HCl) and hydrofluoric acid (HF) was modified such that the HF is added to the solid 16 hours prior to aqua‐regia addition and subsequent microwave heating. Elemental recoveries were validated using a NBS coal fly ash standard. This procedure was applied to soil core samples representing a wide range of geological and pedological weathering sequences and soil textural classes. Separations in the parent material were determined by observing natural breaks in the elemental concentrations and comparing them to soil morphology data.     

Effectiveness of three rapid digestion methods to estimate total lead in orchard soils

Abstract

High concentrations of lead in contaminated soils comprise a potential public health hazard. Limits between safe and dangerous levels are often based on total soil lead content. Current chemical procedures to determine total lead are unsuitable for routine soil analysis because they are time‐consuming and require highly trained personnel. This paper describes the effectiveness of three rapid extraction procedures to estimate total lead in a large number of lead arsenate‐contaminated orchard soils. Dissolution of soil lead in Kjeldahl flasks using a nitric acid‐perchloric acid mixture was virtually complete (98%) when compared to values for total lead measured by treatment with a mixture of HF, HNO₃ and KClO₄. Shaking of 5‐g samples in 50 ml of lN HCl or lN HNO₃ for 1½ hours extracted 95 and 93 percent of the total lead, respectively. Regression equations were derived to allow estimation of total lead from values obtained in the HNO₃‐HClO₄, HCl, or HNO₃ extracts. The HNO₃‐HClO₄ digestion procedure is preferred with atomic absorption spectrophotometry, while HCl extraction is suitable for routine soil analysis with inductively coupled argon plasma spectrophotometers or similar instrumentation.

Grinding of the soils to promote sample uniformity appeared unnecessary, at least in the silt loam soils tested.     

Evaluation of Decomposition Procedure to Determine Ba,Co, Cr,Cu, Ni,Mn, V,and Zn Total Content in Soil Samples

Different procedures have been proposed to decompose soil samples. Most of them regard determination with fertility aims. In this case, the contents available to the plants are considered. On the other hand, there are procedures to determine total content. The objective of this work was to propose a new decomposition procedure to determine barium (Ba), cobalt (Co), chromium (Cr), copper (Cu), manganese (Mn), nickel (Ni), vanadium (V), and zinc (Zn) total content in tropical soils with high content of oxides and silicate. According to the results, the digestion procedure proposed in this study provided satisfactory results for the contents recovery for the elements Ba, Co, Cr, Cu, Mn, Ni, V, and Zn, above 90%, and the use of inverted aqua regia, hydrogen peroxide (H₂O₂), hydrofluoric acid (HF), pre-digestions and agitation was shown as a new alternative for the high silicate content soil sample total digestion, such as the oxisols.     

Determination of trace elements in Saudi Arabian soils by inductively coupled plasma mass spectrometry (ICP‐MS)

Abstract

Saudi Arabian soil samples from different locations have been collected and analyzed for traces of barium (Ba), cobalt (Co), nickel (Ni), titanium (Ti), vanadium (V), silver (Ag), gold (Au), copper (Cu), lithium (Li), and lead (Pb). Inductively coupled plasma mass spectrometry (ICP/MS) has been found to be useful for soil analysis. Two commonly used digestion methods, one employing nitric acid and the other aqua regia, are employed for sample pretreatment. Percentage recovery of added element quantities are found to be within the 97.4 to 101.2% range for Ba, Co, Ni, Ti, and V using aqua regia digestion and within the 95.0 to 05.0% range for Ag, Au, Cu, Li, and Pb when using the nitric acid digestion method. The percentage relative standard deviation (% RSD) for five replicate samples for the two digestion procedures is less than 5% for the analyzed elements.     

Chemical Extractability of Lead in Field-Contaminated Soils: Implications for Estimating Total Lead

Lead (Pb) is frequently present in urban soils at concentrations of concern for human health. Regulations for Pb are based on total soil concentrations as determined by acid digestion, but a less expensive screening test for Pb would be useful in facilitating more thorough soil testing of urban areas if it could be shown to correlate strongly to total soil Pb. In this study, three extractants (0.1 M citrate, MM, and 1 M nitric acid) were evaluated for their ability to estimate the total Pb in contaminated soils. Nitric acid not only extracted a greater fraction of total soil Pb but also produced the strongest correlation to total Pb and is concluded to be the superior extractant for a soil Pb screening test. As the spatial distribution of Pb was observed in selected soils to be highly heterogeneous on the micron scale, thorough soil homogenization prior to testing is recommended.     

Determination of low concentrations of organic phosphorus in soil solution

Abstract

Phosphorus (P) export from agricultural land is an important source of water‐quality deterioration in many areas of the world. Part of the total phosphorus in the soil solution is represented by dissolved organic P at concentrations that can be as low as 1x10^‐6 M of P. The suitability of four digestion methods for the destruction of organic P and determination of orthophosphate at low concentrations and small volumes using the malachite green method has been evaluated. The acid digestion procedures evaluated were 1) sulfuric and perchloric acid, 2) sulfuric acid and potassium persulphate, 3) nitric acid, and 4) nitric and perchloric acid. As inositol hexaphosphate (IHP) represents one of the more resistant molecules to acid hydrolysis in soils, this compound has been chosen to assess the recovery assay of the recommended procedure. The digestion procedures were adapted for the malachite green spectrophotometric method, in order to obtain lower analytical limits for P determination. The sulfuric‐perchloric acid digestion gave excellent recovery and reproducibility, and can therefore be used for determining organic P in solution at concentrations as low as 6.45x10^‐7 M.     

A comparison of some methods for soil organic carbon determination

Abstract

This study compared three dichromate‐oxidation methods adapted for use with 100‐mL digestion tubes and 40‐tube block digester (for controlled heating), the Walkley‐Black method, a loss‐on‐ignition procedure and an automated dry combustion method for the determination of organic carbon in soils of the northwestern Canadian prairie. The Walkley‐Black method required a correction factor of 1.40. The modified Tinsley method and the Mebius procedure, adapted for use with 100‐mL digestion tubes, recovered 95% and 98%, respectively, of soil carbon against the dry combustion procedure. The presence of elemental carbon in some soils probably caused, at least partially, the slightly incomplete recovery; thermal decomposition of dichromate may not have been accurately corrected for. A dichromate‐oxidation procedure with controlled digestion at 135°C gave 100% recovery, but somewhat more variable results. The loss‐on‐ignition procedure, even when allowance was made for clay content of the soils, was the least satisfactory of the methods tested. All procedures produced correlation coefficients of 0.980 or better against the dry combustion method.     

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     

Analysis of Environmental Samples Using Microwave-Assisted Acid Digestion and Inductively Coupled Plasma Mass Spectrometry: Maximizing Total Element Recoveries

For the routine determination of metals in environmental samples, we require microwave-assisted digestion methods that yield ‘total’ or ‘near-total’ recoveries while avoiding the use of HF acid. As inductively coupled plasma mass spectrometry (ICP-MS) is the method of detection, it is desirable to minimize the use of HCl to avoid spectral interferences caused by high Cl^– concentrations. Using certified reference materials, we performed a series of modifications to the US EPA method 3051 which included: increasing the temperature and durations of microwave digestion, varying the ratio of sample mass to acid volume, and alterations to the compositions of the acid digestion mixture. The experiments were conducted using urban particulate matter (NIST-1648), coal fly ash (NBS-1633) and six CANMET certified reference materials (Till-2, Till-3, Till-4, LKSD-1, LKSD-2 and LKSD-4), in two laboratories (Health Canada and Environment Canada) using different microwave digestion systems and different ICP-MS instruments. Our modified microwave-assisted nitric acid digestion method improved recoveries for Pb, Zn, V, Fe and Cu approaching ‘total’ recoveries in the same matrices determined using X-ray fluorescence (XRF) and instrumental neutron activation analysis (INAA) as reported in the certificates of analysis. Recoveries for other elements such as Cr and Ni compared well with ‘near-total’ recoveries yielded by traditional (non-assisted) acid digestion methods.     

Determination of total boron in soils by inductively coupled plasma atomic emission spectrometry using microwave‐assisted digestion

Abstract

A method is described in which total soil boron (B) was determined by inductively coupled plasma atomic emission spectrometry (ICP‐AES). The method is based on microwave‐assisted digestion of soil samples with nitric acid (HNO₃), hydrofluoric acid (HF) and hydrogen peroxide (H₂O₂). Excess HF was eliminated by adding silicon (IV) oxide (SiO₂). The B 208.959 nm line was chosen as the analytical line to avoid the spectral interferences of iron (Fe). A detection limit of 0.0045 mg L^‐1 was obtained with the selected analytical line under the optimized operating conditions. Four National Institute of Standards and Technology (NIST) standard reference materials (three soils and one river sediment) and four different type of practical soils were analyzed to test the reliability of the method. The total B concentration in selected samples ranged from 19 to 76 mg kg^‐1. The excellent recoveries of the spike (98.5–101%) indicate that the proposed procedure is effective and feasible for the determination of total B in soils.     

Evaluation of Multi-Mixtures of Acids for the Sample Preparation of Organic Soil Amendments for Multi-Element Determination by ICP OES

A method for the simultaneous determination of aluminum (Al), arsenic (As), calcium (Ca), cadmium (Cd), chromium (Cr), copper (Cu), iron (Fe), magnesium (Mg), manganese (Mn), phosphorus (P), lead (Pb), sulfur (S), selenium (Se), vanadium (V), and zinc (Zn) in organic soil amendments using microwave-assisted acid digestion and inductively coupled plasma optical emission spectroscopy (ICP OES) is proposed. Concentrated or diluted acids mixtures (HNO₃, HF, HBF₄, and H₃BO₃) combined or not with H₂O₂ were systematically evaluated in order to achieve the best digestion procedure for masses of around 150 mg of samples. Principal component analysis (PCA) was applied in order to choose the best acid mixture for digestion (3 mL HNO₃ + 1 mL HBF₄ + 2 mL H₂O). The determined concentrations were in accordance with certified values of CRM 029 at the 95% confidence level, according to the Student-t test. This acid mixture was successfully applied for the digestion of four organic soil amendment samples (organic fertilizers, substrates, and soil conditioners) and element determination.     

Improved Elemental Recoveries in Soils with Heating Boric Acid Following Microwave Total Digestion

Abstract

Microwave digestion of soils for elemental analysis commonly uses hydrofluoric acid (HF) because of insolubility of aluminosilicate minerals in other acids. Boric acid is added following digestion to complex F in solution. Low recoveries of calcium (Ca), aluminum (Al), and magnesium (Mg) of soil reference materials led to this investigation of a secondary heating of the boric acid with digested soil. The objectives were to evaluate boric acid (H₃BO₃) concentrations needed to complex F from 4 mL HF and to evaluate soil characteristics that may contribute to the formation of metal‐fluoride complexes that decrease recovery following digestion. Four standard soil reference materials and a variety of soil samples (n=75) were evaluated. Heating 20 mL 2.5% H₃BO₃ with a digested standard reference soil produced recoveries of 94, 98, and 99% for Al, Ca, and Mg, respectively, compared to 46% for Al and Mg and 37% recovery for Ca in extracts where H₃BO₃ was added but not heated. Two other concentrations of H₃BO₃ were tested with slightly improved recoveries, and results suggest that 20 mL of a 4.5% H₃BO₃ solution was sufficient to maximize recoveries. Digestion of soil samples by both the nonheated and heated H₃BO₃ methods showed that recovery difference between the two methods ranged from 0 to 100% for Al and Ca. Assuming that this difference in recovery was related to the formation of metal fluorides, correlation with clay and C in soils may reflect the positive or negative influence of these constituents on the formation of these complexes, respectively.     

Rapid,Wet Oxidation Procedure for the Estimation of Silicon in Plant Tissue

Abstract

The quantification of silicon (Si) in plant samples is being requested more frequently, especially in agricultural laboratories associated with the determination of nutritional requirements of sugarcane (Saccharum officinarum L.) and rice (Oryza sativa L.). The analysis of plant material for Si can be protracted, especially if laboratories do not have access to X‐ray flourescence (XRF) instrumentation and large numbers of samples are involved. A simplified procedure using equipment considered standard in most agricultural laboratories is reported. Dry, ground plant material is subjected to nitric acid/peroxide oxidation in a low‐pressure laboratory microwave digestion system. The hydrated silica liberated from the organic matrix is dissolved in a small volume of sodium hydroxide solution also using the microwave digestion system. Silicon is measured by inductively coupled plasma atomic emission spectrometry (ICP‐AES). This method gives results that are linearly correlated with the much slower conventional techniques and avoids using hazardous chemicals (hydrofluoric acid) sometimes employed in other microwave methods.     

Comparison of Various Digestion and Extraction Procedures in Analysis of Heavy Metals in Sediments

Sediment analysis is very important ininvestigations of the heavy metal burden in theenvironment. In the present work various digestion andextraction procedures were evaluated in order toassess the extent of contamination with heavy metalsin sediments from the Moste hydroelectric reservoir.Total acid dissolution, aqua regia digestion andacetic acid extraction procedures were applied tosamples. Zn, Cd, Pb, Co, Ni, Cu and Cr were determinedby flame or electrothermal atomic absorptionspectrometry (FAAS, ETAAS) under optimized measurementconditions. A comparison of total acid dissolutionincluding hydrofluoric acid (HF) treatment and theaqua regia soluble fraction was made to estimatethe applicability of aqua regia digestion inanalysis of total metal concentrations in sediments.In general, good agreement of the results was observedfor Co, Pb, Cu and Zn, however for Cr, Ni and Cdsignificantly lower results were obtained in the aqua regia soluble fraction. In addition, an extraction procedure using 25% v/v acetic acid wasapplied for estimation of the extent of contaminationwith heavy metals originating from anthropogenicactivities. The results indicate that the sedimentsupstream of the reservoir are not contaminated, whilethe sediments from the hydroelectric reservoir showsa significant anthropogenic input of Ni, Zn and Pb,which corresponds well with pollution sources.     

土壤微量节肢动物组织中镉测定方法的改进

Highly precise and reliable determination of heavy metals in soil micro-arthropod tissues remains a challenge because of the small size of the animals and their typical low abundance in metal-contaminated agricultural soils. The present study sought to develop a method for cadmium(Cd) determination in soil micro-arthropods by optimizing the sample digestion procedure, reducing sample weight, modifying sample pre-treatment and validating the methodology with field samples. The optimized digestion conditions comprised a sample mass of 50–150 μg, digestion reagent of nitric acid:hydrogen peroxide(3:1), digestion temperature of 105℃,digestion period of 3 h and digestion volume of 30 μL. Defecation of the standard Collembola Folsomia candida(92 h) and the indigenous Collembola Onychiurus yodai(42 h) and ultrasonic cleaning of F. candida increased the accuracy of Cd determination.The recovery of Cd using the refined procedure was 98.9% and the limits of detection and quantification were 0.002 and 0.008 μg L~(-1), respectively. The within-batch precision values were 3%. The Cd concentrations in the tissues of the Collembola Isotoma sp.collected from a range of metal-contaminated fields determined by the improved method were consistent with the Cd concentrations in the field soils. The results indicate that the optimized method can be used for more accurate or reliable determination of Cd concentrations in soil micro-arthropod tissues.     

Trace Element Analysis via Open‐Vessel or Microwave‐Assisted Digestion in Calcareous Mediterranean Soils

Abstract

Different digestion methods can be applied for analyzing trace elements in soils. Selection of the most useful and convenient method is critical for the adequate determination of their concentrations in each type of soil to appropriately detect potential environmental pollution. Open‐vessel digestion using a digester block (method 1) and microwave‐assisted digestion (method 2) were compared using a certified reference material (CRM) with similar properties and characteristics to calcareous Mediterranean soils. Both methods were contrasted in terms of accuracy by calculating the recovery of cobalt (Co), chromium (Cr), copper (Cu), nickel (Ni), lead (Pb), and zinc (Zn) in the CRM and precision of replicate analysis through the relative standard deviation (RSD). Recoveries from the digester block method were slightly higher than recoveries from microwave digestion because the use of perchloric acid (HClO₄), whereas RSD values for microwave digestion were generally lower but with higher measured precision than values obtained by open‐vessel digestion. The digestion methods were compared for analyzing trace elements in calcareous agricultural soils devoted to vegetable crops in the Alicante province (southeast Spain), as a representative area of the European Mediterranean region. Results of the paired‐sample t‐test showed significant differences between both methods for Co, Cr, Cu, and Pb in calcareous Mediterranean soils, whereas regression analysis indicated a good correlation between both methods for Cu, Ni, Pb, and Zn. Consequently, the choice of the digestion method is more relevant for minor elements such as Co and Cr. Microwave‐assisted digestion seems to be the best option to determine most of the trace elements in calcareous Mediterranean soils, because closed‐vessel digestion exhibited lower variability according to the RSD values obtained in the study area, particularly for Co and Cr. Trace element concentrations were in agreement with background levels, except for Cu and Pb in some soils, which seem to be related to anthropic activities.     

What Constitutes Plant-Available Molybdenum in Sandy Acidic Soils?

Molybdenum (Mo) is critical for the function of enzymes related to nitrogen cycling. Concentrations of Mo are very low in sandy, acidic soils, and biologically available Mo is only a small fraction of the total pool. While several methods have been proposed to measure plant-available Mo, there has not been a recent comprehensive analytical study that compares soil extraction methods as predictors of plant Mo uptake. A suite of five assays [total acid microwave digestion, ethylenediamenetetraaacetic acid (EDTA) extraction, Environmental Protection Agency (EPA) protocol 3050B, ammonium oxalate extraction, and pressurized hot water] was employed, followed by the determination of soil Mo concentrations via inductively coupled mass spectroscopy. The concentrations of soil Mo determined from these assays and their relationships as predictors of plant Mo concentration were compared. The assays yielded different concentrations of Mo: total digest > EPA > ammonium oxalate ≥ EDTA > pressurized hot water. Legume foliar Mo concentrations were most strongly correlated with ammonium oxalate–extractable Mo from soils, but an oak species showed no relationship with any soil Mo fraction and foliar Mo. Bulk fine roots in the 10- to 30-cm soil horizon were significantly correlated with the ammonium oxalate Mo fraction. There were significant correlations between ammonium oxalate Mo and the oxides of iron (Fe), manganese (Mn), and aluminum (Al). Results suggest that the ammonium oxalate extraction for soil Mo is the best predictor of plant-available Mo for species with high Mo requirements such as legumes and that plant-available Mo tracks strongly with other metal oxides in sandy, acidic soils.