Agricultural gypsum (CaSO4.2H2O) stands out as an effective source of calcium and sulfur, and to control aluminum saturation in the soil. Labeled as 34S it can elucidate important aspects of the sulfur cycle. Ca34SO4.2H2O was obtained by chemical reaction between Ca(OH)2 and H2(34)SO4, performed under slow agitation. The acid was produced by ion exchange chromatography using the Dowex 50WX8 cation exchange resin and a Na2(34)SO4 eluting solution. After precipitation, the precipitate was separated and dried in a ventilated oven at 60ºC. From 2.2 L H2SO4 0.2 mol L-1 and 33.6 g Ca(OH)2, 73.7 ± 0.6 g Ca34SO4.2H2O were produced on average in the tests, representing a mean yield of 94.6 ± 0.8%, with 98% purity. The 34SO2 gas was obtained from Ca34SO4.2H2O in the presence of NaPO3 in a high vacuum line and was used for the isotopic determination of S in an ATLAS-MAT model CH-4 mass spectrometer.
sulfur 34; stable isotope; isotopic determination
O gesso agrícola (CaSO4.2H2O) destaca-se como fonte eficiente de cálcio e enxofre e na redução da saturação de alumínio no solo. O 34S como traçador isotópico pode elucidar aspectos importantes no ciclo do enxofre. Para tanto o Ca34SO4.2H2O foi obtido por reação química entre o Ca(OH)2 e solução de H2(34)SO4, realizada sob agitação lenta. O ácido foi produzido por cromatografia de troca iônica, utilizando resina catiônica Dowex 50WX8 e solução eluente de Na2(34)SO4. Após a precipitação foi separado o precipitado e realizada a secagem em estufa ventilada à temperatura de 60ºC. Nos testes, a partir de 2,2 L de H2SO4 0,2 mol L-1 e 33,6 g de Ca(OH)2, foram produzidos em média 73,7 ± 0,6 g de Ca34SO4.2H2O representando um rendimento médio de 94,6 ± 0,8%, com pureza de 98%. A partir do Ca34SO4.2H2O na presença de NaPO3, em linha de alto vácuo, obteve-se o gás 34SO2 utilizado para a determinação isotópica do S no espectrômetro de massas ATLAS-MAT modelo CH-4.
enxofre 34; isótopo estável; determinação isotópica
Production of 34S-labeled gypsum (Ca34SO4.2H2O)
Produção de gesso (Ca34SO4.2H2O), marcado com 34S
Alexssandra Luiza Rodrigues Molina RosseteI; José Albertino BendassolliI,* * Corresponding author < firstname.lastname@example.org> ; Everaldo MáximoI; Carlos Roberto Sant Ana FilhoI; Raquel de Fátima de IgnotoII
IUSP/CENA - Lab. de Isótopos Estáveis, C.P. 96 - 13400-970 - Piracicaba, SP - Brasil
IIUniversidade do Grande ABC - UniABC, AV. Industrial, 3.330 - Campus Universitário - 09080-511 - Santo André, SP - Brasil
Agricultural gypsum (CaSO4.2H2O) stands out as an effective source of calcium and sulfur, and to control aluminum saturation in the soil. Labeled as 34S it can elucidate important aspects of the sulfur cycle. Ca34SO4.2H2O was obtained by chemical reaction between Ca(OH)2 and H234SO4, performed under slow agitation. The acid was produced by ion exchange chromatography using the Dowex 50WX8 cation exchange resin and a Na234SO4 eluting solution. After precipitation, the precipitate was separated and dried in a ventilated oven at 60ºC. From 2.2 L H2SO4 0.2 mol L-1 and 33.6 g Ca(OH)2, 73.7 ± 0.6 g Ca34SO4.2H2O were produced on average in the tests, representing a mean yield of 94.6 ± 0.8%, with 98% purity. The 34SO2 gas was obtained from Ca34SO4.2H2O in the presence of NaPO3 in a high vacuum line and was used for the isotopic determination of S in an ATLAS-MAT model CH-4 mass spectrometer.
Key words: sulfur 34, stable isotope, isotopic determination
O gesso agrícola (CaSO4.2H2O) destaca-se como fonte eficiente de cálcio e enxofre e na redução da saturação de alumínio no solo. O 34S como traçador isotópico pode elucidar aspectos importantes no ciclo do enxofre. Para tanto o Ca34SO4.2H2O foi obtido por reação química entre o Ca(OH)2 e solução de H234SO4, realizada sob agitação lenta. O ácido foi produzido por cromatografia de troca iônica, utilizando resina catiônica Dowex 50WX8 e solução eluente de Na234SO4. Após a precipitação foi separado o precipitado e realizada a secagem em estufa ventilada à temperatura de 60ºC. Nos testes, a partir de 2,2 L de H2SO4 0,2 mol L-1 e 33,6 g de Ca(OH)2, foram produzidos em média 73,7 ± 0,6 g de Ca34SO4.2H2O representando um rendimento médio de 94,6 ± 0,8%, com pureza de 98%. A partir do Ca34SO4.2H2O na presença de NaPO3, em linha de alto vácuo, obteve-se o gás 34SO2 utilizado para a determinação isotópica do S no espectrômetro de massas ATLAS-MAT modelo CH-4.
Palavras-chave: enxofre 34, isótopo estável, determinação isotópica
Gypsum is widely used in agriculture as an important nutrient input to obtain productivity increase. This compound has a two-fold function, as an effective source of calcium and sulfur, and as an aluminum saturation reducer in deeper soil layers (Vitti & Malavolta, 1985; Paolinelli et al., 1990). Gypsum is used notably in the recovery of soils with excess of sodium in order to improve root environment of acid subsoils, and is based upon the ion exchange reaction of calcium with sodium in the soil (Raij, 1988; Malavolta, 1979).
Sulfur presents four stable isotopes: 32S, 33S, 34S, and 36S, with natural abundances of 95.02; 0.75; 4.21; and 0.02 (atom %), respectively (Krouse et al., 1996). Most studies performed to date using S as a tracer have employed the 35S radioisotope; this has been very useful in studies involving the dynamics of this nutrient (Lal & Dravid, 1990; Arora et al., 1990; Sharma & Kamath, 1991; Bansal & Motiramani, 1993; Patnaik & Santhe, 1993; Fitzgorald et al., 1999). However, compounds labeled with the 34S stable isotope present some advantages over the radioisotope, including the following: they are not radioactive; the experiments are not limited by time; there is no exposition to radiation; and no safety measures against radiation are required.
At present, the international tendency of using non-radioactive techniques whenever possible in isotopic tracer experiments must not be forgotten, especially in field work (Zhao et al., 2001). The first studies using the 34S isotopic tracer were developed by Hamilton et al. (1991) and Awonaike et al. (1993), and in Brazil by Trivelin et al. (2002).
Recently, laboratories in the USA and Europe started to produce 34S highly-enriched compounds, however, at prohibited prices. In Brazil, the first studies targeted to sulfur isotope separation (especially 34S) were initiated by Bendassolli et al. (1997). They used the exchange reaction between a H2SO3 solution (SO2 aq) and bisulfite anions (HSO3-) adsorbed to anion resins of the quaternary ammonium type. Obtaining enriched aqueous 34SO2 allowed the production of several compounds labeled with this isotope, including: Na234SO4; (15NH4)234 SO4; K234SO4; Ca34SO4.2H2O; and H234SO4, among others (Maximo et al., 2000; Rossete, 2002). With such products available, the production of 34S (Ca34SO4.2H2O) isotope-labeled gypsum was possible, here made through the reaction between H234SO4 and Ca(OH)2 which is the objective of this note.
ATLAS-MAT, model CH4 mass spectrometer (120º radius of tube curvature; electronic impact ionization; molecular-flow admission system; simple, Faraday-cup ion collector; and mass scan analysis system).
Pyrex glass and quartz Vacuum line; model 2M8 EDWARDS mechanical vacuum pump; model E050 EDWARDS high vacuum diffusion pump; AGD EDWARDS active vacuum gauge; APG-M EDWARDS Pirani vacuum sensor filament.
The following reagents, all of analytical grade, were used: sulfuric and hydrochloric acid; barium and calcium chloride; barium and calcium sulfate; calcium and sodium hydroxide; and monobasic sodium phosphate. Solutions were prepared with deionized water obtained by ion exchange (5-10 mWcm resistively).
Other material used: Dowex 50WX8 cation resin with the specifications: acid type polystyrene-divinilbenzene with 8% of DVB; sulfonic functional group; mesh 100-200.
Production of H234SO4 in Dowex 50W-X8 cation resin columns
H234SO4 was obtained by cation exchange chromatography, using an acrylic column 130 cm height and 2.1 cm diameter (system 1), and a second acrylic column of 50 cm height and 1.5 cm diameter (system 2), filled with cation resin.
The active sites of the resin were saturated with the R-H+ form by admitting 1.0 mol L-1 H2SO4 solution at the top of the column at a flow rate of 1 to 2 cm3 cm-2 min -1. The resin saturation status and the volume of H2SO4 solution to saturate the resin with the R-H+ form were determined by titration with a NaOH 0.1 mol L-1 solution in collected effluent volumes. Next, the excess acid remaining in the interstitial pores of the resin was eliminated with deionized water and later decompaction with water in a backwash process.
In the next step, a Na234SO4 30 g L-1 eluting solution of enrichment of 5.85 ± 0.01%, was admitted with substitution of H+ by Na+ ions, producing H234SO4 in the eluted solution. In the H+ elution step, the eluted volume was collected in 100 ml (system 1) or 25 ml batches (system 2); the H+ concentration in each fraction was determined by titration with 0.1 mol L-1 NaOH tritisol. This procedure allowed the determination of the H234SO4 mass that could be obtained in each column system.
The sodium sulfate solution (Na234SO4) enriched at 5.85 ± 0.01 atoms % of 34S was produced at the USP/CENA Stable Isotope Laboratory.
Production of 34S-labeled Ca34SO4 .2H2O
The gypsum (Ca34SO4.2H2O) was obtained from the stoichiometric ratio of the chemical reaction between Ca(OH)2 and the addition of the 34S-labeled H234SO4 solution.
In order to perform the Ca34SO4.2H2O production tests by the chemical reaction between H234SO4 and Ca(OH)2, a H2SO4 solution with natural isotopic abundance was used (4.22 atoms % of 34S ) but with a concentration of the acid similar to that obtained by ion exchange chromatography. The nomenclature of the isotopic reagent labeling had the objective of identifying the labeling source in the process to obtain Ca34SO4.2H2O; however, when the same physicochemical parameters are maintained, the process for the production of labeled Ca34SO4.2H2O must be reproduced when 34S-enriched compounds are used.
The reaction was performed under slow agitation. Because of the low solubility of gypsum (Ca34SO4.2H2O) in water (2.5 g L-1), precipitation begins after the solubility product is reached (Ksp = 1.0.10-5). The gypsum formation reaction can be observed in equation (1).
where: (aq) and (s) indicate the aqueous and solid phases, respectively.
After precipitation, the liquid (supernatant) and the solid (precipitate) phases were separated. The solid phase was dried in a ventilated oven at 50ºC and the gravimetric quantification of the Ca34SO4.2H2O mass was made.
A small fraction of precipitate was solubilized in 50 mL deionized water, and the S-SO42- concentration was determined by the turbidimetric method (Raij et al., 2001; Malavolta et al., 1997).
The S-SO42- concentration was obtained from the absorbance values (spectrophotometer), using a calibration curve obtained from S-Sulfate standards (5 to 20 mg L-1). This procedure allowed the calculation of the yield of the reaction by which Ca34SO4.2H2O was obtained, as well as its chemical purity.
The amount of soluble sulfate at the solution phase (supernatant) was also obtained by turbidimetry. The objective of this step was to quantify the soluble Ca34SO4.2H2O concentration and then balance the mass of the reaction in relation to sulfur.
Sample preparation for the isotopic determination
A Ca34SO4.2H2O sample of about 10.0 mg (approximately 1.8 mg S), together with sodium metaphosphate (NaPO3) was placed in a quartz tube (Q1) of approximately 30 cm (Figure 1). The ratio between the Ca34SO4.2H2O mass and the reagent (NaPO3) was 1:3 (w/w) (Halas & Wolacewicz, 1981). This step has the purpose of obtaining 34SO2 gas from Ca34SO4.2H2O to determine the 34S isotopic abundance (atoms % of 34S) by mass spectrometry.
The NaPO3 was obtained burning the NaH2PO4.H2O in a muffle for 2 hours at 200ºC. This step is performed to remove the structural water from the compound and to eliminate possible organic impurities. Equation (2) shows the process by which NaPO3 is obtained.
A 2 g copper metal ring was added approximately 2 cm above the mixture (sample/reagents) using quartz wool. The metal copper is used to retain oxides formed during combustion and to convert possible SO3 into SO2, avoiding isotopic fractionation (Yanagisawa & Sakal, 1983; Rafter, 1957).
Next, the QT tube was connected to the high vacuum line and vacuum was established in the entire system using mechanical (MP) and diffusion pumps (DP). Traps Tr1 and Tr2 were later supplied with a dry ice and ethanol mixture ( 73ºC) or with liquid nitrogen (-196ºC), respectively. The Tr1 and Tr2 traps are designed to trap water and SO2 vapors, respectively, formed during combustion. The high vacuum line to obtain SO2 adapted from Bailey & Smith (1972) can be observed in Figure 1.
In the next step, the MF oven heated to 900ºC was displaced vertically up to the QT tube, where it remained for a 10-minute interval during which the Ca34SO4.2H2O combustion occurred in the presence of reagents, forming the SO2 gas (equation 3). Depending on the conditions (O2 partial pressure), the SO3 gas can be produced (equation 4). The formation of SO3 is not desirable, since it can cause isotopic fractionation. Equation 5 shows the conversion of SO3 to SO2 via reduced copper.
The SO2 gas entrapped in Tr2 was then transferred to the sample tube (ST), by alternating the liquid N2 ("trap") from Tr2 into the sample tube (ST).
Later, sample tube (ST) containing the SO2 gas was transferred from the high vacuum line and connected to the mass spectrometer admission system and the isotopic determination of S was made (atoms % of 34S).
The QT tube was cleaned after combustion of the sample in the high vacuum line. Initially, the quartz wool was removed from the oxidized copper ring (CuO), and the oxidized copper was then transferred to a glass container for later reduction (Cuº) in a vacuum line using hydrogen (Bendassolli et al., 2002).
Finally, the QT tube was scraped to remove residues from the reaction, and washed with HCl 6.0 mol L-1 so it could be reused in other combustions.
Isotopic determination of S
The mass spectrometry analysis of isotopic ratios or atoms % (abundance) of light elements, for the most part, is made on properly purified gaseous samples, and in a low- or medium-resolution-power mass spectrometer. To accomplish this, the sample preparation system involves some chemical transformations, and gases free from any atmospheric contaminant are required for their production.
For the isotopic determination of S in the SO2 gas samples contained in the storage flasks, the mass spectrometer worked with a heated admission system (70ºC) due to the polar nature of the SO2 and SO molecules, avoiding a memory effect between analyses.
A cryogenic trap containing dry ice and ethanol (-73ºC) was adapted on the mass spectrometer admission system, in order to retain water contained in the gas samples.
The abundance determination in atoms % of 34S in SO2 samples was performed in mass spectrometer according to Bendassolli et al., 1997.
The preliminary H234SO4 production tests were performed with natural Na234SO4. The labeled-H234SO4 production process must be reproduced, because the physicochemical parameters must be preserved when enriched 34S-isotope compounds are used.
In the process of production of H2 34SO4 using the 2.1 cm diameter (130 cm height) acrylic column, 3.0 L of H2SO4 solution were required for complete saturation of the active sites of the resin to the R-H+ form; 2.2 L deionized water were needed to eliminate the excess acid from the resin interstitial volume. Resin decompaction was performed later with deionized water.
In system 1, containing 426 cm3 cation resin in the R-H+ form (wet, balanced in water) 2.2 L Na234SO4 30 g L-1 solution was used for total elution of the H+ ions, and a final solution containing 44.2 g H234SO4 in 2.2 L (0.2 mol L-1) was obtained.
The chemical reaction of H234SO4 with Ca(OH)2 was performed at a stoichiometric ratio. The tests were performed in three replications using the same acid, but on different days. We used 2.2 L H234SO4 in each test at a concentration of 0.2 mol L 1, and 33.6 g Ca(OH)2 were added slowly, theoretically forming a precipitate containing approximately 78.0 g Ca34SO4.2H2O.
The Ca34SO4.2H2O mass produced in each test was determined in the precipitate by a gravimetric method. Using the theoretical value for the Ca34SO4.2H2O mass (78.0 g) and the mass obtained experimentally in the chemical reaction, the reaction yield and total mass of Ca34SO4.2H2O lost in the process could be calculated. Table 1 shows the Ca34SO4.2H2O mass produced, losses, and chemical reaction yields in each test. It can be observed that complete Ca34SO4.2H2O precipitation did not occur in any of the three tests. On average, 73.7 ± 0.6 g Ca34SO4.2H2O were produced in these tests, representing a mean yield of 94.6 ± 0.8%. There was no pronounced variability in Ca34SO4.2H2O mass loss; on average, this fraction represented 5.4 ± 0.8%. This is a relatively high value, since it is a labeled material with high added value.
Because complete gypsum precipitation did not occur, the supernatant of each test was analyzed in order to determine the mass lost in the reaction. The pH readings in the supernatant were in the range of 6.0 to 7.0, possibly indicating the complete consumption of H234SO4 in the chemical reaction with Ca(OH)2. Therefore, the H+ concentration in the solution (supernatant) was very reduced (10-6 to 10-7 mol L-1).
The S-34SO42- concentration in the supernatant was measured in the three tests, to estimate the Ca34SO4.2H2O mass solubilized in the volume. The data shown in Table 1 demonstrates that part of the 2.7 g Ca34SO4.2H2O not recovered in the chemical process were present in the supernatant volume. This solubilized Ca34SO4.2H2O fraction can be recovered in the chemical reaction process using 34S-enriched H234SO4.
From the results presented in Table 1, it can be verified that the Ca34SO4.2H2O mass lost in the chemical process was 1.5 g on average. Also, using the results from Table 1, the global mass balance for the chemical reaction process between H234SO4 and Ca(OH)2 to produce Ca34SO4.2H2O can be obtained. The mean for the global mass balance process can be observed in Table 2.
It can be observed from Table 2 that, on average, 64.3% of the Ca34SO4.2H2O losses of the chemical reaction process occurred in the supernatant, while 35.7% were not identified. From the same Table, it can be verified that only 2% of the total mass (Ca34SO4.2H2O) was really lost, which makes the process viable when 34S is used.
From the result presented in Table 2 it can also be observed that 3.4% of the Ca34SO4.2H2O mass lost in the process is solubilized in the supernatant, with a value equivalent to 50.2 mg 34S.
The S-SO42- concentration in the Ca34SO4.2H2O obtained through the chemical process (three assays) was determined by turbidimetry, indicating a purity of produced Ca34SO4.2H2O of 98%, on average.
The test using the 34S-labeled Na234SO4 solution with an abundance of 5.85 ± 0.01 atoms % performed in system 2, containing 33 cm3 cation resin in the R-H+ form (balanced in water) allowed to obtain about 3.0 g of 34S-labeled H234SO4.
From the chemical reaction between labeled H234SO4 and Ca(OH)2, under stoichiometric conditions, 5.2 g Ca34SO4.2H2O could be obtained in theory. The mass obtained in the reaction was 4.8 g Ca34SO4.2H2O, with a 91% yield.
The 34S determination in atoms % of 34S was performed on three replicates for each test. For the evaluation of isotopic results a natural variation from -30 to +30 was taken into consideration (Krouse & Tabatabai, 1986). The natural variation values (-30 to +30) correspond to a variation from 4.15 to 4.38 atoms % of 34S. It must also be considered that the analytical precision of the mass spectrometer is in the order of 1%.
The results for isotopic determination of S in the SO2 gas samples obtained from the three Ca34SO4.2H2O production tests (natural abundance), one CaSO4.2H2O p.a. sample (natural abundance), and 34S-labeled Ca34SO4.2H2O test can be observed in Table 3.
The values presented in Table 3 concerning samples (CaSO4.2H2O) with natural variation, labeled material, or the p.a. product, are in accordance with the expected values (4.15 to 4.38 atoms % of 34S), demonstrating that the process for obtaining SO2 in the presence of NaPO3 and the isotopic determination of S in the mass spectrometer were suitable.
The result for isotopic determination of S (atoms % of 34S) in the test that used labeled material (Na234SO4 5.81 ± 0.01 atoms % of 34S) demonstrated that there was no isotopic fractionation in the process for the production of 34S-labeled Ca34SO4.2H2O.
The authors thank FAPESP for the financial support.
Received September 20, 2005
Accepted July 04, 2006
- ARORA, B.R.; HUNDAL, H.S.; SEKHON, G.S. Utilization of fertilizer sulphur by oat (Avena sativa L.) in different soils of Ludhiana. Journal of Nuclear Agriculture and Biology, v.19, p.92-96, l990.
- AWONAIKE, K.O.; DANSO, S.K.A.; ZAPATA, F. The use of a double isotope (N-15 and S-34) labeling technique to assess the suitability of various reference crops for estimating nitrogen-fixation in gliricidia-sepium and leucaena-leucocephala. Plant and Soil, v.155/156, p.325-328, 1993.
- BAILEY, S.A; SMITY, I.W. Improved method for the preparation of sulfur dioxide from Barium sulfate for isotope ratio studies. Analytical Chemistry, v.44, p.1542-1543, 1972.
- BANSAL, K.N.; MOTIRAMANI, D.P. Uptake of native and applied sulphur by soybean in vertisols of Madhya Pradesh. Journal of Nuclear Agriculture and Biology, v.22, p.42-46, l993.
- BENDASSOLLI, J.A.; TRIVELIN, P.C.O.; CARNEIRO JR., F.C. Stable sulfur isotope fractionation by anion exchange chromatography. Production of compounds enriched in 34S. Journal of Brazilian Chemical Society, v.8, p.13-17, 1997.
- BENDASSOLLI, J.A.; MORTATTI, J.; TRIVELIN, P.C.O.; IGNOTO, R.F.; BONASSI, J.A.; TAVARES, G.A. Reciclagem de cobre proveniente de analisador automático de carbono e nitrogênio. Química Nova, v.25, p.312-315, 2002.
- FITZGORALD, M.A.; UGALDE, T.D.; ANDERSON, J.W. Sulfur nutrition change the sources of S in vegetative tissues of wheat during generative growth. Journal of Experimental Botany, v.50, p.499-508, 1999.
- HALAS, S.; WOLACEWICZ, W. Direct extraction of sulfur dioxide from sulfates for isotopic analysis. Analytical Chemistry, v.53, p.686-689, 1981.
- HAMILTON, S.D.; CHALK, P.M.; UNDOVICH, M.J.; SMITH, C.J. The measurement of fertilizer-S uptake by plants using radioactive and stable isotopes. Applied Radiation and Isotopes, v.42, p.1099-1101, 1991.
- KROUSE, H.R.; TABATABAI, M.A. Stable sulphur isotopes. In: TABATABAI, M.A. (Ed.) Sulphur in agriculture Madison: ASA, 1986. p.169-205.
- KROUSE, H.R.; BERNHARD M.; SCHOENAU J.J. Applications of stable isotopes techniques to soil sulphur cycling. In: BOUTTON, T.W.; YAMASAKI, S. (Ed.) Mass spectrometry of soil New York: Marcel Dekker, 1996. p.246-285.
- LAL, K.; DRAVID, M.S. Sulphur utilization by mustard as influenced by P, S, K2SiO3 and FYM in Tupic Ustipsamment. Journal of Nuclear Agriculture and Biology, v.19, p.87-91, l990.
- MALAVOLTA, E. Gesso agrícola seu uso e adubação e correção do solo São Paulo: Ultrafertil, Depto. de Serviços Técnicos Agronômicos, 1979. 30p.
- MALAVOLTA, E.; VITTI, G.C.; OLIVEIRA, S.A. Avaliação do estado nutricional das plantas: princípios e aplicações. 2.ed. Piracicaba: POTAFOS, 1997.
- MÁXIMO, E.; ROSSETE, A.L.R.M.; OLIVEIRA, C.R.; TRIVELIN, P.C.O.; BENDASSOLLI, J.A. Methodology for obtaining 15(NH4)34SO4 and H234SO4 from 15(NH4)34SO4 and Na234SO4 by ion exchange chromatography. In: INTERNATIONAL SYMPOSIUM ON THE SYNTHESIS AND APPLICATIONS OF ISOTOPES AND ISOTOPICALLY LABELED COMPOUNDS, 17., Dresden, 2000. p.44.
- PAOLINELLI, M.; OLIVEIRA, P.M.; SANTOS, P.R.R.S.; LEANDRO, V.P.; MORAES, W.V. Gesso agrícola São Paulo: Petrobrás, 1990. 16p.
- PATNAIK', M.C.; SANTHE, A. Influence of N, P, CaSO4 on utilization of sulphur by rice in red sandy loam soil. Journal of Nuclear Agriculture and Biology, v.22, p.75-79, l993.
- RAFTER, T.A. The preparation of sulfur dioxide for mass spectrometer examination. Journal of Science and Technology, v.38, p.849-857, 1957.
- RAIJ, B.V. Gesso agrícola na melhoria do ambiente radicular no subsolo São Paulo: ANDA, 1988.
- RAIJ, V.B.; ANDRADE, J.C.; CANTARELLA, H.; QUAGGIO, J.A. Análise química para avaliação da fertilidade de solos tropicais Campinas: Instituto Agronômico, 2001.
- ROSSETE, A.L.R.M. Produção de gesso (Ca34SO42H2O), marcado no 34S. Piracicaba: USP/CENA, 2002. 73p. (Dissertação - Mestrado).
- SHARMA, V.K.; KAMATH, M.B. Effect of sulphur, phosphorus and calcium on sulphur utilization by mustard (Brassica juncea L.) and Pea (Pissum sativum L.) Journal of Nuclear Agriculture and Biology, v.20, p.123-127, l991.
- TRIVELIN, P.C.O.; BENDASSOLLI, J.A.; CARNEIRO JR., F.; MUROAKA, T. Sulfur utilization by rice and Crotalaria juncea from sulfate - 34S applied to the soil. Scientia Agricola, v.59, p.205-207, 2002.
- VITTI, G.C.; MALAVOLTTA, E. Fosfogesso uso agrícola In: SEMINÁRIO SOBRE CORRETIVOS AGRÍCOLAS, Piracicaba, 1985. Campinas: Fundação Cargil, 1985. p.161-201.
- YANAGISAWA, F.; SAKAL, H. Thermal decomposition of barium sulfate-vanadium pentaoxide-silica glass mixtures for preparation of sulfur dioxide in sulfur isotope ratio measurements. Analytical Chemistry, v.55, p.985-987, 1983.
- ZHAO, F.J.; VERKAMPEN, K.C.J.; BIRDSEY, M.; BLAKE-KALFF, M.M.A.; MCGRATH, S.P. Use of the enriched stable isotope 34S to study sulfur uptake and distribution in wheat. Journal of Plant Nutrition, v.24, p.1551-1560, 2001.
Corresponding author <
Publication in this collection
20 Aug 2007
Date of issue
20 Sept 2005
04 July 2006