The total quantity of P and plant‐available P often differ greatly in soils of the tropics, which typically range in weathering intensity. Assessing available P is fundamental to managing P in many of these soils. Phosphorus availability in some soils has been inferred from the Hedley sequential extraction assuming that each P fraction reflects similar plant availability in different soils. However, experimental measurements of plant P availability were either of short duration or involved multiple P applications, which complicates assessment of the plant availability of P fractions. The objectives of this study were to examine the changes in P fractions under exhaustive cropping on diverse soils and to discern the differences in plant availability among P fractions. Eight soils ranging in weathering from Vertisols and Mollisols to Ultisols and Oxisols were amended with Ca(H2PO4)·H2O to raise soil solution P to 0.2 mg L−1 and planted for 14 crops to remove available P. The results indicated that the Fe‐impregnated strip–P and inorganic NaHCO3–P (NaHCO3–Pi) decreased the most in response to plant P withdrawal in all soils. The inorganic NaOH‐P (NaOH‐Pi) also declined with plant P uptake in all soils. The HCl‐P and residual P seemed to act as a buffer for the strip‐P and the NaHCO3–Pi in the slightly weathered soils, whereas NaOH‐Pi seemed to act as a buffering pool for strip‐P and NaHCO3–Pi in the highly weathered soils. Residual P in the slightly weathered soils was plant‐available on a relatively short time scale. In contrast, residual P in the highly weathered soils accumulated in the presence of intensive plant P removal, indicating that it was unavailable to plants. Organic P (NaHCO3‐ and NaOH‐Po) fractions were not significant contributors to available P in these soils that received high levels of inorganic P. Phosphorus fractions separated by the same sequential method were not of equal availability to plants in all soils.

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Pressurized fluid extraction (PFE) is a new sample extraction method operated at elevated temperatures and pressures with liquid solvents. The use of PFE was investigated for the extraction of four Hawaiian clayey soils fortified with the selected chloroacetanilide and nitrogen heterocyclic herbicides Alachlor, Bromacil, Hexazinone, Metribuzin, and Tebuthiuron. The effects of operation temperature, pressure, flush volume, and static cycles on PFE performance were studied. Water was the most effective modifier of PFE for quantitative recoveries of the five herbicides in soils. The simple extraction method required pretreatment of the soil with 37.6% water and subsequent two-static-cycle extraction with a total of 32 mL of acetone at 1500 psi and 100 degrees C. Average recoveries of Alachlor, Bromacil, Hexazinone, Metribuzin, and Tebuthiuron ranged from 93 to 103% by the water-assisted PFE, compared with only 68-83% recoveries of the corresponding chemicals when no water was used. The extraction time and total organic solvent consumption were reduced from 18 h and 300 mL by Soxhlet to 22 min or less and 80 mL or less of organic solvent by PFE.

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Supercritical carbon dioxide (SC-CO(2)) is effective in extracting nonpolar and slightly polar chemicals from soils. However, pure SC-CO(2) is unsatisfactory for recovering polar chemicals in soils. A simple supercritical fluid extraction (SFE) procedure was developed to quantitatively recover polar and nonpolar chemicals from soils. The polar chemicals tested were aromatic acids and phenols. The nonpolar and slightly polar chemicals used as model compounds were common pesticides and environmental pollutants such as polycyclic aromatic hydrocarbons. The procedure required pretreatment of the samples with 15% water (g/g), 5% (ethylenedinitrilo)tetraacetic acid tetrasodium salt (Na(4)EDTA) (g/g), and 50% methanol (mL/g) prior to extractions using SC-CO(2) at 60 °C and 34.5 MPa. Recoveries ranged from 90 to 106% for the aromatic acids using the Na(4)EDTA-assisted SFE compared with only 7-63% recoveries of the corresponding chemicals when no Na(4)EDTA was used. The method quantitatively extracted 2,4-D and its close analogues aged in the soil for 2-30 days. The Na(4)EDTA-assisted SFE was also adequate for extracting phenolic analytes including picric acid and pentachlorophenol with recoveries from 85 to 104%. Na(4)EDTA is a good enhancer for extraction of the 29 analytes representing a wide range of polarity from the soil using SC-CO(2). The method is valuable for the analysis of parent pollutants and transformed products, particularly oxygen-borne metabolites in the environment.