Comparative Evaluation of Inductively Coupled Plasma–Atomic Emission Spectroscopy and Colorimetric Methods for Determining Hot-Water-Extractable Boron in Soils

Frequency of boron (B) deficiency is increasing in rainfed systems, and hence there is a need to diagnose the deficiency. Colorimetric methods are still widely used in soil-testing laboratories in India for measuring B. Little information is available on the comparative evaluation of the colorimetric and inductively coupled plasma (ICP) methods for determining extractable B in soils. We describe results of the comparative evaluation of these methods for measuring extractable B in 57 soil samples with pH values ranging from 5.3 to 9.5. There was a significant correlation between B values determined by the two methods, and the correlation coefficient was greater for soil samples with pH in the neutral to alkaline range. Interaction between soil samples and methods (ICP or colorimetric) was significant except for soil samples in the pH range of 8.0 to 9.5. Precision for B determination was greater with the ICP than with the colorimetric method.     

Spectrophotometric and Inductively Coupled Plasma–Optical Emission Spectroscopy Determination of Gallium in Natural Soils and Soils Polluted by Industry: Relationships between Elements

The aim of this work was to determine gallium contents in different soils of Poland using a sensitive spectrophotometric method based on the complex of Ga(III) with chrome azurol S and benzyldodecyldimethylammonium bromide and inductively coupled plasma–optical emission spectrometry technique. The total content of gallium in the soils clearly depends on the soil location and properties and ranged from 41.7 to 437 μg g^–1. The contents of gallium determined in 10% nitric acid and 1 M of magnesium chloride extract ranges respectively from 38.0 to 81.9% and 20–40% of the total content of this element. A strong correlation has been found between gallium and zinc, cadmium, lead, and copper. The high Pearson correlation coefficient values and the proportional relationship between the concentrations of Ga and these metals may make it possible to treat gallium as an indicator of soil contamination with heavy metals.     

Analysis of Arsenic Uptake by Plant Species Selected for Growth in Northwest Ohio by Inductively Coupled Plasma–Optical Emission Spectroscopy

Abstract

Arsenic (As) contamination is widespread in the industrial areas of northwest Ohio. Plant species that both take up As and are appropriate for the climate and growth conditions of the region are needed for phytoremediation to be successfully employed. Actively growing plants from 22 species of native genera were exposed to As in hydroponics systems (either 0, 10, or 50 mg As L^?1; 1 week) and commercially available potting mix (either 0, 10, 25, 100, or 250 mg As L^?1; 2 weeks), depending on their growth conditions. Aboveground plant tissues were harvested and digested, and concentrations of As were determined by inductively coupled plasma–optical emission spectrometry. The highest tissue concentrations of As (mg As kg^?1 dw) were recorded in seven plant species: Rudbeckia hirta (661), Helenium autumnale (363 in tissues formed after exposure to As), Lupinus perennis (333), Echinacea purpurea (298), Coreopsis lanceolata (258), Lepidium virginicum (214), and Linum lewisii (214). These seven species are ecologically diverse, which suggests that phytoremediation of As using diverse assemblages of plants may be an option for a variety of environments.     

Comparison of New Ultrasonic Digestion Approaches for Plant Matrices in the Analysis of Trace Metals by Inductively Coupled Plasma–Optical Emission Spectroscopy Analysis: Contrast with USEPA Method 3050B

An ultrasonic method using two approaches, A and B, along with a reference Environmental Protection Agency (EPA) Method 3050B [i.e., a mixture of 30 mL of nitric acid–hydrochloric acid–hydrogen peroxide–water (HNO₃-HCl-H₂O₂-H₂O)] were contrasted for leaching of a plant matrix. The trace metals were arsenic, cadmium, cobalt, chromium, copper, mercury, manganese, nickel, lead, selenium, and zinc (As, Cd, Co, Cr, Cu, Hg, Mn, Ni, Pb, Se and Zn) and quantified by ICP-OES followed by an investigation into residue formation and the impact of digestion time. Approach B was the most accurate and precise with percent recoveries ranging between 99 and 120%, whereas ultrasonic approach A and the USEPA method 3050B gave similar results with poor accuracies and precisions. In the optimization of the digestion time using approach B, the total metal recovery was fairly the same over a period of 120 min except for Cr and Cu, which showed slight variations.     

Determination of Major and Trace Elements in Plant Samples by Inductively Coupled Plasma–Mass Spectrometry

The determination of several trace elements [arsenic (As), cadmium (Cd), cobalt (Co), chromium (Cr), copper (Cu), molybdenum (Mo), nickel (Ni), and lead (Pb)] in plant samples using inductively coupled plasma–mass spectrometry (ICP‐MS) was evaluated. It was established experimentally that moderate amounts (0.2–2%) of dissolved solids decreased the analyte signals significantly. Internal standardization with Rh was efficiently used to compensate for these matrix effects. The accuracy of the method was verified using reference materials digested according to two different procedures: dry ashing and microwave digestion. No significant differences were observed between measured concentrations and certified values. The investigation was next extended for the determination of major elements [aluminum (Al), boron (B), calcium (Ca), iron (Fe), potassium (K), magnesium (Mg), manganese (Mn), sodium (Na), phosphorus (P), and zinc (Zn)] on the same reference materials. The ICP‐MS values agree well with the values supplied. However, it appeared that Sc was the most useful internal standard for major elements.     

Evaluation of Extractants and Quantity–Intensity Relationship for Estimation of Available Potassium in Some Calcareous Soils of Western Iran

Accurate estimation of the available potassium (K⁺) supplied by calcareous soils in arid and semi‐arid regions is becoming more important. Exchangeable K⁺, determined by ammonium acetate (NH₄OAc), might not be the best predictor of the soil K⁺ available to crops in soils containing micaceous minerals. The effectiveness of different extraction methods for the prediction of K‐supplying capacities and quantity–intensity relationships was studied in 10 calcareous soils in western Iran. Total K⁺ uptake by wheat grown in the greenhouse was used to measure plant‐available soil K⁺. The following methods extracted increasingly higher average amounts of soil K⁺: 0.025 M H₂SO₄ (45 mg K⁺ kg^?1), 1 M NaCl (92 mg K⁺ kg^?1), 0.01 M CaCl₂ (104 mg K⁺ kg^?1), 0.1 M BaCl₂ (126 mg K⁺ kg^?1), and 1 M NH₄OAc (312 mg K⁺ kg^?1). Potassium extracted by 0.01 M CaCl₂, 1 M NaCl, 0.1 M BaCl₂, and 0.025 M H₂SO₄ showed higher correlation with K⁺ uptake by the crop (P < 0.01) than did NH₄OAc (P < 0.05), which is used to extract K⁺ in the soils of the studied area. There were significant correlations among exchangeable K⁺ adsorbed on the planar surfaces of soils (labile K⁺) and K⁺ plant uptake and K⁺ extracted by all extractants. It would appear that both 0.01 M CaCl₂ and 1 M NaCl extractants and labile K⁺ may provide the most useful prediction of K⁺ uptake by plants in these calcareous soils containing micaceous minerals.     

Comparison of Multi-element to Single‐Element Extractants for Macro‐ and Micronutrients in Acid Soils from Spain

Abstract

Different chemical reagents are used to assess plant‐available nutrients from soils with similar properties. The use of different extractants is a serious limitation when comparing results between different soil‐testing laboratories, often leading to large differences in fertilizer recommendations for similar crops.

In this study, 80 samples from acid soils from Galicia (Spain) were used to compare several soil nutrient extractants. Traditional and tested extractants for acid soil such as Bray 2 and ammonium acetate were used to evaluate multielement extractants such as ethylenediaminetetraacetic acid–ammonium acetate (EDTA‐aa), ammonium bicarbonate–diethylenetriaminepentaacetic acid (AB‐DTPA), and Mehlich 3.

Linear regression analyses were performed to relate the amount of each nutrient obtained by traditional soil extractants to the amount obtained by multielement extractants. Strong correlation was found between extractable Bray 2 P and Mehlich 3 P (r²=0.97, slope=0.87, and intercept=?0.48). The slope of the regression line between EDTA‐aa‐extractable calcium (Ca) and that from ammonium acetate (Aa) approached 1∶1 (r²=0.86). Similar results were obtained for magnesium (Mg) (r²=0.99). Soil zinc (Zn) concentrations extracted by Mehlich 3 and EDTA‐aa were similar; slope of the regression line was 0.95 (r²=0.88). With regard to copper (Cu), Mehlich 3 extracted approximately 20% more Cu than EDTA‐aa.

The results showed that Mehlich 3 and EDTA‐aa are suitable for assessment of plant available phosphorus (P), potassium (K), Ca, Mg, Cu, Zn, and iron (Fe) in acid soils.     

Graphite Furnace Atomic Absorption Spectrometry After Dispersive Liquid–Liquid Microextraction for the Determination of Selenium in the Anodic Slime

In the present study, a method based on dispersive liquid–liquid microextraction (DLLME) followed by graphite furnace atomic absorption spectrometry (GFAAS) determination was proposed for the determination of selenium by using ammonium pyrrolidine dithiocarbamate (APDC) as the chelating reagent. The main factors influencing the DLLME were investigated systematically. Under the optimal conditions, the limit of detection for Se(IV) was 0.02 ng mL^?1. The relative standard deviation was 4.1% (C_Se(IV) = 0.2 ng mL^?1, n = 8) with an enhancement factor of 135.8-fold from only 5 mL of the water sample. The proposed method was successfully applied to the determination of Se(IV) in anodic slime and electrolyte samples. In order to validate the proposed method, a Certified Reference Material (trace elements in water, 1643e, NIST) was analyzed, and the determined value obtained was in good agreement with the certified value.     

Nitrogen‐Supplying Capacity of Soils for Rice and Wheat and Nitrogen Availability Indices in Soils of Northwest India

Abstract

Quantitative assessment of soil nitrogen (N) that will become available is important for determining fertilizer needs of crops. Nitrogen‐supplying capacity of soil to rice and wheat was quantified by establishing zero‐N plots at on‐farm locations to which all nutrients except N were adequately supplied. Nitrogen uptake in zero‐N plots ranged from 41.4 to 110.3 kg N ha^?1 for rice and 33.7 to 123.4 kg N ha^?1 for wheat. Availability of soil N was also studied using oxidative, hydrolytic, and autoclaving indices, salt‐extraction indices, light‐absorption indices, and aerobic and anaerobic incubation indices. These were correlated with yield and N uptake by rice and wheat in zero‐N plots. Nitrogen extracted by alkaline KMnO₄ and phosphate borate buffer and nitrogen mineralized under aerobic incubation were satisfactory indices of soil N supply. For rice, 2 M KCl and alkaline KMnO₄ were the best N‐availability indices. Thus, alkaline KMnO₄ should prove a quick and reliable indicator of indigenous soil N supply in soils under a rice–wheat cropping system.     

Evaluation of Distribution and Chemical Associations between Cobalt and Manganese in Soils by Continuous‐Flow Sequential Extraction

Abstract

In this study, a strong association between cobalt (Co) and manganese (Mn) in different geochemical soil phases (fractions) was evaluated using a continuous‐flow sequential extraction technique employing a modified Tessier extraction scheme. With the flow system, detailed extraction profiles of Co and Mn in soils could be obtained by plotting concentrations of the elements extracted against extraction time (plots referred to as extractograms). Extractograms may be used as an indicator of whether the elements dissolving in the same extraction step are closely associated, or are merely extractable with the same reagent. From the soil samples studied, the coincidence of Co and Mn peaks seems to indicate a close association of these elements in the exchangeable, reducible, and oxidizable fractions. Analysis of flow extraction data suggested that the association between Co and Fe is not as strong as reported in previous studies based on the statistical analysis of batch fractionation data.     

Distribution and Availability of Heavy Metals in Raw and Acidulated Phosphate Rock–Amended Soils

Abstract

The effectiveness of the application of raw (PR‐1), and partially acidulated phosphate rock (PR), at 25% (PR‐25) and at 50% (PR‐50), was investigated to reduce extractability and plant uptake of Pb, Cd, Cu, Ni, and Zn in three calciorthids soils.Furthermore, the effects of soil treatments on metal extractability were evaluated by sequential extraction. Similarly, such effects were assessed on the phytoavailability of metals of maize (Zea mays L.) through a pot experiment. Water‐soluble and exchangeable metal fractions (the bioavailable fractions) were influenced distinctively by PR treatments and soil properties. In addition, decrease of soluble and exchangeable metal fractions was compensated by an increase in metal extracted from other fractions. Most bioavailable soil metals correlated significantly with their associated level in plant tissue. Finally, plant metal uptake decreased with PR treatments, suggesting that PR application was likely to be effective in controlling metal immobilization in these soils.     

Potassium Fixation and Release Characteristics in Rhizosphere and Nonrhizosphere Soils for a Rapeseed–Rice Cropping Sequence

Potassium (K) fixation and release in soil are important factors in the long-term sustainability of a cropping system. Changes in K concentration and characteristics of K fixation and release in rhizosphere and nonrhizosphere soils in the rapeseed (Brassica napus L.)–rice (Oryza sativa L.) rotation were investigated using a rhizobox system. The concentrations of different forms of K in both rhizosphere and nonrhizosphere soils decreased with plants compared to without plants, regardless of K fertilizer application. Potassium uptake by crops mainly came from the rhizosphere soil. In the treatment without K fertilizer (–K), the main form of K supplied by the soil to the crops was 1.0 mol L^?1 nitric acid (HNO₃) nonextractable K, followed by nonexchangeable K, and then exchangeable K. In the treatment with K fertilizer (+K), the main K forms supplied by the soil to the crops were exchangeable K and nonexchangeable K. The amount and rate of K fixation after one cycle of the rapeseed–rice rotation was greater in rhizosphere soil than in nonrhizosphere soil. The amount and rate of K fixation of soil in the +K treatment were significantly less than in the –K treatment. The cumulative amounts of K released with 1.0 mol L^?1 ammonium acetate (NH₄OAc) and 1.0 mol L^?1 HNO₃ extraction increased with the increasing numbers of extractions, but the K-releasing power of soil by successive extraction decreased gradually and finally became almost constant. The release of K was less in rhizosphere soil than in nonrhizosphere soil. The release of K in the +K treatment was similar to that in the –K treatment in rhizosphere soil, but the K release in nonrhizosphere soil was greater with the +K than the –K treatment. Overall, the information obtained in this study will be helpful in formulating more precise K fertilizer recommendations for certain soils.     

Gas Chromatography–Mass Spectroscopy Analysis of Carbofuran and Its Metabolite 3-Hydroxy-carbofuran in Maize and Soil in Field

In this article, a simple and efficient method using gas chromatography–mass spectrometry (GC-MS) was developed to determine carbofuran and 3-hydroxy carbofuran in maize and soil. Field experiments were carried out to investigate the dissipation of carbofuran and its metabolite 3-hydroxy carbofuran in soil and maize plants and their accumulation in maize. Results showed that the half-lives of carbofuran were 4.7 and 5.3 days in maize plants and 8.5 and 7.6 days in soil for Beijing and Jinan trial sites, respectively. The final residues of carbofuran and 3- hydroxy carbofuran in the soils and maize grain were not detected. This study suggests that carbofuran is acceptable to apply to maize in the recommended dosage and can be a good alternative to other highly toxic insecticides.     

Inoculation of Earthworms and Plant Growth–Promoting Rhizobacteria (PGPR) for the Improvement of Vegetable Growth via Enhanced N and P Availability in Soils

A pot trial was conducted to investigate the single, dual, and triple inoculation of earthworms or plant growth–promoting rhizobacteria (PGPR), including nitrogen-fixing bacteria (NFB) (Azotobacter chroococcum HKN-5) and phosphate-solubilizing bacteria (PSB) (Bacillus megaterium HKP-1), on the growth of Brassica parachinenesis and nitrogen (N) and phosphorus (P) availability in soils. All of the five inoculation treatments significantly (P < 0.05) increased the shoot growth of B. parachinenesis. The greatest shoot and root biomass were recorded in the triple inoculation of earthworm, NFB, and PSB. All of the five inoculation treatments significantly (P < 0.05) increased the concentrations of ammonium (NH₄ ⁺)-N, NO_x-N, and sodium bicarbonate (NaHCO₃)–extractable P in soils. Based on plant growth and availability of N and P in soils, the present study suggested that the triple inoculation may be a promising approach for reducing the need for chemical fertilizers in growing vegetables.     

Carbon Stock in Sandy and Loamy Soils of Coniferous–Broadleaved Forests at Different Succession Stages

Eurasian Soil Science - A comparative assessment of the carbon stock in loamy soils (Albic Retisols) of coniferous–broadleaved forests on the Moskvoretsko-Oksky Plain and sandy soils (Albic...     

Evaluation of Water–Nitrogen Schemes for Rice in Iran,Using ORYZA2000 Model

The model ORYZA2000 simulates the growth and development of rice under conditions of potential production and water and nitrogen (N) limitations. Crop simulation models could provide an alternative, less time-consuming, and inexpensive means of determining the optimum crop N and irrigation requirements under varied irrigation and nitrogen conditions. Water productivity (WP) is a concept of partial productivity and denotes the amount or value of product over volume or value of water used. For the evaluated ORYZA2000 model in Iran, a study was carried out in a randomized complete block design between 2005 and 2007, with three replications at the Rice Research Institute of Iran, Rasht. Irrigation management (three regimes) was the main plot and N application (four levels) was the subplot. In this study, simulation modeling was used to quantify water productivity and water balance components of water and nitrogen interactions in rice. Evaluation simulated and measured total aboveground biomass and yield, by adjusted coefficient of correlation, T test of means, and absolute and normalized root mean square errors (RMSE). Results showed that with normalized root mean square errors (RMSE_n) of 5–28%, ORYZA2000 satisfactorily simulated crop biomass and yield that strongly varied among irrigation and nitrogen fertilizer conditions. Yield was simulated with an RMSE of 237–443 kg ha^?1 and a normalized RMSE of 5–11%. Results showed that the significant (28–56%) share of evaporation into evapotranspiration, using the actual yield (measured) and simulated water balance (ORYZA2000), the calculated average WP_ET was significantly lower than the average WP_T: 37%. The average WP_I, WP_I+R, WP_ET, WP_T, and WP_ETQ were 1.4, 1.07, 1.07, 1.57, and 0.82 kg m^?3. Results also showed that irrigation with 8-day intervals and 60 kg N ha^?1, nitrogen level was the optimum irrigation regime and nitrogen level.     

Evaluation of press mud cake as a source of nitrogen and phosphorus for rice–wheat cropping system in the Indo-Gangetic plains of India

Press mud cake (PMC) is an important organic source available for land application in India. Adequate information regarding availability of nitrogen and phosphorous contained in PMC to rice–wheat (RW) cropping system is lacking. In field experiments conducted for 4 years to study the effect of PMC application to rice as N and P source in RW system, application of 60 kg N ha⁻¹ along with PMC (5 t ha⁻¹) produced grain yield of rice similar to that obtained with the 120 kg N ha⁻¹ in unamended plots. In the following wheat, the residual effects of PMC applied to preceding rice were equal to 40 kg N and 13 kg P ha⁻¹. Immobilization of soil and fertilizer N immediately after the application of PMC was observed in laboratory incubation. The net amount of N mineralized from the PMC ranged from 16% at 30 days to 43% at 60 days after incubation. Available P content in the soil amended with PMC increased by about 60% over the unamended control within 10 days of its application. The P balance for the no-PMC treatment receiving recommended dose of 26 kg P ha⁻¹ year⁻¹ was −13.5 kg P ha⁻¹ year⁻¹. The P balance was positive (+42.3 to 53.5 kg P ha⁻¹ year⁻¹) when PMC was applied to rice. Application of PMC increased total N, organic carbon, and available P contents in the soil.     

Preparation of Ammonium‐15N and Nitrate‐15N Samples by Microdiffusion for Isotope Ratio Analysis by Optical Emission Spectrometry

Abstract

A diffusion method for the preparation and measurement of ¹⁵N abundance of ammonium and nitrate in KCl extracts of soil using optical emission spectrometry (OES) was compared with conventional continuous flow isotope ratio mass spectrometry (IRMS). There were highly significant correlations between the values obtained by using OES and IRMS. The 99% confidence interval of the intercept included the value 0 and the 99% confidence interval of the slope included the value 1 for both nitrate and ammonium measurements, suggesting that the results from the two methods did not differ significantly. In another experiment, ¹⁵N values of nitrate and ammonium from soil extracts prepared by using the standard distillation procedures for OES were compared against the microdiffusion preparation method. Again, there was a highly significant correlation between the values: the 95% confidence interval of the intercept included the value 0, and the 95% confidence interval of the slope included the value 1, again suggesting that the two methods did not differ significantly. It was concluded that the diffusion technique is an appropriate and simple method of sample preparation for inorganic N analysis of KCl extracts using OES.     

Underestimation of Available Phosphorus by Resin–Bicarbonate and Olsen Tests in Calcareous Soils treated with Gypsum

In the present study, Olsen [0.5 M sodium bicarbonate (NaHCO₃), pH 8.5] and resin–bicarbonate (HCO₃) tests underestimated available phosphorus (P) in calcareous soils treated with gypsum (CaSO₄). The reaction of CaSO₄ and HCO₃ ^? ion or resin–HCO₃ to form calcium carbonate (CaCO₃) precipitate reduced the strength of the Olsen NaHCO₃ extractant and resin–HCO₃ strip for P extraction. The iron (Fe) oxide–impregnated filter paper (Pi strip) was independent of CaSO₄ influence and thus correctly estimated soil‐available P with respect to plant response to soil‐available P. Two greenhouse experiments were conducted with maize and wheat grown on calcareous soils treated with different rates of CaSO₄. The results confirmed that Olsen and resin–HCO₃ tests should not be used to measure available P or labile P in the P fractionation scheme in the calcareous soils containing significant amounts of gypsum.     

Evaluation of Soil Tests for Plant‐available Mercury in a Soil–Crop Rotation System

A reliable soil test is needed for estimating mercury (Hg) availability to crop plants. In this study, four extraction procedures including 0.1 M hydrochloric acid (HCl), 1 M ammonium acetate (NH₄OAc) (pH 7.0), 0.005 M diethylenetriaminepentaacetic acid (DTPA), and 0.1 M calcium chloride (CaCl₂) (pH5.0) were compared for their adequacy in predicting soil Hg availability to crop plants of a rice–cabbage–radish rotation system. The amounts of Hg extracted by each of the four procedures increased with increasing equilibrium time. The optimal time required for extraction of soil Hg was approximately 30 min, though it varied slightly among the four extractants. The amounts of Hg extracted decreased with increasing soil/solution ratio, and a soil/solution ratio of 1:5 appeared to be adequate for soil Hg availability tests. The amounts of Hg extracted increased in the order of NH₄OAc < CaCl₂ < DTPA < HCl in silty loam soil (SLS) soil, and the order was NH₄OAc < CaCl₂ ≈ DTPA < HCl in yellowish red soil (YRS) soil. Significant positive correlations among the four extractants were obtained in SLS soil. In contrast, the correlations were poor in YRS soil, especially for HCl. There were significant correlations between concentrations of Hg in edible tissue of three plants and the amounts of soil Hg extractable to the four extractants for soil–rice system and soil–radish system, but not for soil–Chinese cabbage system. The 0.1M HCl extraction overall provided the best estimation of soil‐available Hg and could be used to predict phytoavailability of Hg in soil–crop systems.