Influence of soil pH on inorganic phosphorus sorption and desorption in a humid brazilian Ultisol

Liming is a common practice to raise soil pH and increase phosphorus (P) bioavailability in tropical regions. However, reports on the effect of liming on P sorption and bioavailability are controversial. The process of phosphorus desorption is more important than P sorption for defining P bioavailability. However few studies on the relationship between soil pH and P desorption are available, and even fewer in the tropical soils. The effects of soil pH on P sorption and desorption in an Ultisol from Bahia, Brazil, were investigated in this study. Phosphorus sorption decreased by up to 21 and 34 % with pH increases from 4.7 to 5.9 and 7.0, respectively. Decreasing Langmuir K parameter and decreasing partition coefficients (Kd) with increasing pH supported this trend. Phosphorus desorption was positively affected by increased soil pH by both the total amount of P desorbed and the ratio of desorbed P to initially sorbed P. A decreased K parameter and increased Kd value, particularly at the highest pH value and highest P-addition level, endorsed this phenomenon. Liming the soil had the double effect of reducing P sorption (up to 4.5 kg ha-1 of remaining P in solution) and enhancing P desorption (up to 2.7 kg ha-1 of additionally released P into solution).

Dispersion of natural arsenic in the Malcantone watershed, Southern Switzerland: field evidence for repeated sorption-desorption and oxidation-reduction processes

In recent years, elevated arsenic concentrations have been found in waters and soils of many, countries, often resulting in a health threat for the local population. Switzerland is not an exception and this paper deals with the release and subsequent fate of arsenic in a 200-km(2) mountainous watershed, characterized by crystalline silicate rocks (gneisses, schists, amphibolites) that contain abundant As-bearing sulfide ore deposits, some of which have been mined for iron and gold in the past. Using analytical methods common for mineralogical, ground water and soil studies (XRD, XRF, XAS-XANES and -EXAFS, electron microprobe, extraction, ICP, AAS with hydride generator, ion chromatography), seven different field situations and related dispersion processes of natural arsenic have been studied: (1) release by rock weathering, (2) transport and deposition by water and ice; (3) release of As to the ground and surface water due to increasing pH; (4) accumulation in humic soil horizons; (5) remobilization by reduction in water-saturated soils and stagnant ground waters; (6) remobilization by using P-rich fertilizers or dung and (7) oxidation, precipitation and dilution in surface waters. Comparison of the results with experimental adsorption studies and speciation diagrams from the literature allows us to reconstruct and identify the typical behavior of arsenic in a natural environment under temperate climatic conditions. The main parameters identified are: (a) once liberated from the primary minerals, sorption processes on Fe-oxy-hydroxides dominate over Al-phases, such as Al-hydroxides or clay minerals and limit the As concentrations in the spring and well waters between 20 and 300 mug/l. (b) Precipitation as secondary minerals is limited to the weathering domain, where the As concentrations are still high and not yet too diluted by rain and soils waters. (c) Although neutral and alkaline pH conditions clearly increase the mobility of As, the main factor to mobilize As is a low redox potential (Eh close or below 0 mV), which favors the dissolution of the Fe-oxy-hydroxides on which the As is sorbed. (d) X-ray absorption spectroscopy (XAS) of As in water-logged humic forest soils indicates that the reduction to As III only occurs at the solid-water interface and that the solid contains As as As V (e) A and Bh horizons of humic cambisols can effectively capture As when As-rich waters flow through them. Complex spatial and temporal variation of the various parameters in a watershed results in repeated mobilization and immobilization of As, which continuously transports As from the upper to the lower part of a watershed and ultimately to the ocean. (C) 2004 Elsevier B.V. All rights reserved.

Kinetics of phosphorus sorption in soils in the state of Paraíba¹

The soil P sorption capacity has been studied for many years, but little attention has been paid to the rate of this process, which is relevant in the planning of phosphate fertilization. The purpose of this experiment was to assess kinetics of P sorption in 12 representative soil profiles of the State of Paraíba (Brazil), select the best data fitting among four equations and relate these coefficients to the soil properties. Samples of 12 soils with wide diversity of physical, chemical and mineralogical properties were agitated in a horizontal shaker, with 10 mmo L-1 CaCl2 solution containing 6 and 60 mg L-1 P, for periods of 5, 15, 30, 45, 60, 90, 120, 420, 720, 1,020, and 1,440 min. After each shaking period, the P concentration in the equilibrium solution was measured and three equations were fitted based on the Freundlich equation and one based on the Elovich equation, to determine which soil had the highest sorption rate (kinetics) and which soil properties correlated to this rate. The kinetics of P sorption in soils with high maximum P adsorption capacity (MPAC) was fast for 30 min at the lower initial P concentration (6 mg L-1). No difference was observed between soils at the higher initial P concentration (60 mg L-1). The P adsorption kinetics were positively correlated with clay content, MPAC and the amount of Al extracted with dithionite-citrate-bicarbonate. The data fitted well to Freundlich-based equations equation, whose coefficients can be used to predict P adsorption rates in soils.

Phosphorus sorption and availability in soils amended with animal manures and sewage sludge

Soils that receive large applications of animal wastes and sewage sludge are vulnerable to releasing environmentally significant concentrations of dissolved P available to subsurface flow owing to the gradual saturation of the soil's P sorption capacity. This study evaluated P sorption (calculated from Langmuir isotherms) and availability of P (as CaCl2-P and resin P) in soils incubated for 20 d with poultry litter, poultry manure, cattle slurry, municipal sewage sludge, or KH2PO4, added on a P-equivalent basis (100 mg P kg(-1)). All the P sources had a marked negative effect on P sorption and a positive effect on P availability in all soils. In the cattle slurry- and KH2PO4- treated soils, the decreases in P sorption maximum (19-66%) and binding energy (25-89%) were consistently larger than the corresponding decreases (7-41% and 11-30%) in poultry litter-, poultry manure-, and sewage sludge-treated soils. The effects of cattle slurry and KH2PO4 on P availability were, in most cases, larger than those of the other P sources. In the poultry litter, poultry manure, and sewage sludge treatments, the increase in soil solution P was inversely related (R-2 = 0.75) to the input of Ca from these relatively high Ca (13.5-42 g kg(-1)) sources. Correlation analyses implied that the magnitude of the changes in P sorption and availability was not related to the water-extractable P content of the P sources. Future research on the sustainable application of organic wastes to agricultural soils needs to consider the non-P- as well as P-containing components of the waste.

Tillage and phosphorus management effects on enzyme-labile bioactive phosphorus availability in Cerrado Oxisols

Phosphorus (P) is an essential element in crop nutrition, which can be growth limiting or an environmental contaminant, if present in excess. Tillage practices have a direct effect on the behavior and availability of soil P. Sorption and availability of various P forms were evaluated in an incubation-fractionation study of three soils, a Typic Paleudults (CR soil) and two Cerrado Oxisols (Latossolo Vermelho-Amarelo [LVA] and Latossolo Vermelho [LV]) with distinct biogeochemical characteristics and tillage management history. Phosphate and myo-inositol hexakisphosphate (mIPH) were strongly sorbed by the soils. Maximum adsorption capacities (S(max)) were 2.2-6.9, 3.3-7.8, and 1.6-19.8 mmol kg(-1) for phosphate in the 0-40 cm depths of the CR, LV, and LVA soils, respectively. For mIPH, S. were 1.2-3.7, 3.7-5.5, and 4.6-5.2 mmol kg(-1). Saturation indices reflected the long-term effect of repeated manure applications on the Paleudults and the near saturation of its P holding capacity, in contrast to the recently cultivated Cerrado soils. Tillage method appeared to have altered P retention characteristics of the near-surface zone very slightly, while increases in ligand-exchangeable (EEP;) and enzyme-labile organic P (EDTA-PHP) forms were observed in no-till Oxisols. In the Paleudults, added manure P increased bioactive P fractions and P saturation of no-till near-surface soil zone. Estimates of all bioactive P fractions using the ligand-based enzymatic assay showed it to be an effective method for assessing P availability in soil and developing sustainable P management strategies, particularly in Cerrado Oxisols that were low in organic matter while having an extensive P-fixing capacity. Published by Elsevier B.V.

Do decomposing organic matter residues reduce phosphorus sorption in highly weathered soils?

Many studies have shown a reduction in P sorption in highly weathered soils when organic matter (OM) is applied, suggesting competition between OM decomposition products and P for sorption sites. However, such studies seldom consider the P released from the added OM. To delineate the effects of OM addition on P availability through sorption competition and P addition, water leachate from incubated soybean (SB) [Glycine mar (L.) Merr.] and Rhodes grass (RG) (Chloris gayana Knuth cv. Callide) was used in competitive P sorption studies both undiluted and after acidification (i.e., the fulvic acid [FA] component). Addition of two rates (0.2 and 2 mL) of SB leachate to an Oxisol significantly increased P sorption at the higher rate, while a similar trend was observed following RG leachate addition at the same rates. Extending the range of highly weathered soils examined (two Oxisols, an Ultisol, and an acidic Vertisol) resulted in no observed decrease in P sorption following addition of OM leachate. Surprisingly, SB leachate transiently increased P sorption in the two Oxisol soils. Addition of the FA component of the leachates resulted in a transient (< 6 d) decrease in P sorption in three of the four soils examined and constituted the only evidence in this study that decomposing OM residues reduced P sorption. This research provides further evidence contradicting the long held assumption that inhibition of P sorption by dissolved organic compounds, derived from decomposing OM, is responsible for increased P phytoavailability when P fertilizer and OM are applied together.

Competitive sorption and desorption of phosphate and citrate in clayey and sandy loam soils

The increase of organic acids in soils can reduce phosphorus sorption. The objective of the study was to evaluate the competitive sorption of P and citrate in clayey and sandy loam soils, using a stirred-flow system. Three experiments were performed with soil samples (0-20 cm layer) of clayey (RYL-cl) and sandy loam (RYL-sl) Red Yellow Latosols (Oxisols). In the first study, the treatments were arranged in a 2 × 5 factorial design, with two soil types and five combinations of phosphorus and citrate application (only P; P + citrate; and citrate applied 7, 22, 52 min before P); in the second, the treatments were arranged in a 2 × 2 factorial design, corresponding to two soils and two forms of P and citrate application (only citrate and citrate + P); and in the third study, the treatments in a 2 × 2 × 6 factorial design consisted of two soils, two extractors (citrate and water) and six incubation times. In the RYL-cl and RYL-sl, P sorption was highest (44 and 25 % of P application, respectively), in the absence of citrate application. Under citrate application, P sorption was reduced in all treatments. The combined application of citrate and P reduced P sorption to 25.8 % of the initially applied P in RYL-cl and to 16.7 % in RYL-sl, in comparison to P without citrate. Citrate sorption in RYL-cl and RYL-sl was highest in the absence of P application, corresponding to 32.0 and 30.2 % of the citrate applied, respectively. With P application, citrate sorption was reduced to 26.4 and 19.7 % of the initially applied citrate in RYL-cl and RYL-sl, respectively. Phosphorus desorption was greater when citrate was used. Phosphorus desorption with citrate and water was higher in the beginning (until 24 h of incubation of P) in RYL-cl and RYL-sl, indicating a rapid initial phase, followed by a slow release phase. This suggests that according to the contact time of P with the soil colloids, the previously adsorbed P can be released to the soil solution in the presence of competing ligands such as citrate. In conclusion, a soil management with continuous input of organic acids is desirable, in view of their potential to compete for P sorption sites, especially in rather weathered soils.

Sorption and desorption of phosphate on biochar and biochar-soil mixtures

The term biochar refers to materials with diverse chemical, physical and physicochemical characteristics that have potential as a soil amendment. The purpose of this study was to investigate the P sorption/desorption properties of various slow biochars and one fast pyrolysis biochar and to determine how a fast pyrolysis biochar influences these properties in a degraded tropical soil. The fast pyrolysis biochar was a mixture of three separate biochars: sawdust, elephant grass and sugar cane leaves. Three other biochars were made by slow pyrolysis from three Amazonian tree species (Lacre, Ingá and Embaúba) at three temperatures of formation (400 °C, 500 °C, 600 °C). Inorganic P was added to develop sorption curves and then desorbed to develop desorption curves for all biochar situations. For the slow pyrolysis, the 600 oC biochar had a reduced capacity to sorb P (4-10 times less) relative to those biochars formed at 400 °C and 500 °C. Conversely, biochar from Ingá desorbed the most P. The fast pyrolysis biochar, when mixed with degraded tropical mineral soil, decreased the soil's P sorption capacity by 55% presumably because of the high soluble, inorganic P prevalent in this biochar (909 mg P/kg of biochar). Phosphorus desorption from the fast pyrolysis biochar/soil mixture not only exhibited a common desorption curve but also buffered the soil solution at a value of ca. 0.2 mg/L. This study shows the diversity in P chemistry that can be expected when biochar is a soil amendment and suggests the potential to develop biochars with properties to meet specific objectives. © 2013 British Society of Soil Science.

Étude de la sorption et de la désorption de neuf contaminants émergents dans les boues usées

Des études de sorption/désorption ont été effectuées pour neuf contaminants émergents sélectionnés (caféine, sulfaméthoxazole, déséthylatrazine, carbamazépine, atrazine, estradiol, éthinylestradiol, noréthindrone et diclofénac) dans les boues usées provenant de trois systèmes différents. Les contaminants incluent une variété de classes de composés (pesticides, hormones et pharmaceutiques) qui possèdent des propriétés physicochimiques différentes. L’objectif de ces travaux est de modéliser leur comportement dans une station d’épuration, en présence d’une phase particulaire et d’une phase aqueuse, et du même coup, de mieux comprendre leur devenir lors de leur rejet dans l’environnement. Le coefficient octanol-eau (log Kow) permet de bien interpréter les résultats et nous permet de classer les composés selon deux types de comportements observés : les composés avec un log Kow inférieur à 3 montrent peu ou pas de sorption alors que les composés avec un log Kow supérieur à 3 montrent une sorption variant de 30 à 90 % durant les premières minutes, suivi d’une sorption lente durant les heures suivantes. Une augmentation du contenu organique favorise la sorption des composés hydrophobes alors qu’un changement de pH peut modifier la charge à la surface des particules et également la charge des analytes. Les résultats ont montré que seul le diclofénac était sensible aux variations de pH étudiés. Dans une telle situation, il est nécessaire d’utiliser le facteur d’hydrophobicité corrigé en fonction du pH (log Dow). Le coefficient de distribution solide-eau (log Kd) a été déterminé pour chaque composé à la fin de chaque expérience de sorption et se situe entre -0.3 et 2.6. Avec l’augmentation de l’hydrophobicité, la désorption diminue avec le temps et avec l’étape de rinçage. Pour simuler le relargage dans les systèmes aquatiques, les facteurs de rinçage ont été déterminés pour estimer le nombre de rinçages qui seraient nécessaire pour désorber 50 et 99 % de la concentration initialement sorbée. Les bilans de masse ont été effectués après chaque expérience dans le but de ne pas surestimer les capacités de sorption d’un composé et se situent entre 7 et 25 % pour l’estradiol, la noréthindrone et le sulfaméthoxazole et entre 44 et 103 % pour l’éthinylestradiol, l’atrazine, la déséthylatrazine, la carbamazépine, la caféine et le diclofénac.

Differences in phosphorus retention and release in soils amended with animal manures and sewage sludge

Excessive levels of P in agricultural soils pose a threat to local water quality. This study evaluated (i) time-dependent changes in soil P sorption (expressed as a phosphorus sorption index, PSI) and P availability (as resin P) during incubation (100 d) with poultry litter, cattle slurry, sewage sludge, or KH2PO4, added on a P-equivalent basis (100 mg P kg(-1)), and (ii) the subsequent kinetics of P release, measured by repeated extractions with a mixed cation-anion exchange resin. Soil exchangeable Ca and ammonium oxalate-extractable Fe and Al were also determined at 100 d of incubation. The small decrease in P sorption in the litter and sludge treatments (25%), compared with that in the slurry and KH2PO4 treatments (52%) between 20 and 100 d of incubation was attributed partly to the formation of new adsorption sites for P. Subsequent P release was described by a power equation: Resin P = a(extraction number)(b), where the constants a and b represent resin P obtained with a single extraction and the rate of P release per resin extraction, respectively. On average, the rate of P release decreased in the order: KH2PO4 and slurry > litter > sludge, and was inversely related to exchangeable Ca content of the incubated soils (R-2 = 0.57). The slower rates of P release in the litter and sludge treatments (P < 0.001) are attributed to the large values for exchangeable Ca (1050-2640 and 1070-2710 mg kg(-1), respectively) in these amended soils. Future research concerned with short-term declines in environmentally harmful levels of P in recently amended soils should consider the differential effects of the amendments on soil P dynamics.

Disponibilidade de nutrientes no solo: decomposição e liberação de compostos orgânicos de resíduos vegetais

O objetivo principal desta revisão foi reunir informações a respeito da ação de compostos orgânicos produzidos por plantas na disponibilidade de nutrientes nos solos, principalmente sobre os cátions Ca, Mg e K e sobre o ânion fosfato. O sistema de cultivo adotado ocasiona mudanças nas propriedades químicas e físicas do solo, especialmente na disponibilidade de nutrientes e condicionamento físico do solo. Tem-se observado o acúmulo de nutrientes nas camadas superficiais do solo no sistema de semeadura direta, pelo não-revolvimento do solo e pela deposição de resíduos de culturas na superfície. Os ácidos orgânicos provenientes de plantas podem interagir com a fase sólida e ocupar os sítios de adsorção de nutrientes, competindo diretamente com eles e aumentando sua disponibilidade no solo. A adição de resíduos vegetais pode promover, antes da humificação, a elevação do pH, por promover complexação de H e Al com compostos do resíduo vegetal, deixando Ca, Mg e K mais livres em solução, o que pode ocasionar aumento na saturação da CTC por estes cátions de reação básica. Também é normal observar o aumento na disponibilidade de P no solo com a adição de resíduos vegetais, tanto pelo P presente no resíduo como por competição de compostos orgânicos dos resíduos pelos sítios de troca no solo. A persistência dos compostos orgânicos também é fator que tem grande interferência nos processos de sorção/dessorção de cátions e ânions, dependendo da atividade microbiana, da disponibilidade metabólica do substrato carbonado e da sorção aos colóides do solo.

Determination of copper, iron, nickel and zinc in gasoline by FAAS after sorption and preconcentration on silica modified with 2-aminotiazole groups

Silica gel chemically modified with 2-aminotiazole groups (SiAT), was used for preconcentration of cupper, zinc, nickel and iron from gasoline, normally used as a engine fuel. Surface characteristics and surface area of the silica gel were obtained before and after chemical modification using FT-IR, Kjeldhal and surface area analysis (B.E.T.). The retention and recovery of the analyte elements were studied by applying batch and column techniques. The experimental parameters, such as shaking time in batch technique, flow rate and concentration of the eluent (HCl-0.25-2.00 mol 1(-1)) and the amount of silica, on retention and elution, have been investigated. Detection limits of the method for cupper, iron, nickel and zinc are 0.8, 3, 2 and 0.1 mug 1(-1), respectively. The sorption-desorption of the studied metal ions made possible the development of a preconcentration method for metal ions at trace level in gasoline using flame AAS for their quantification. (C) 2004 Published by Elsevier Ltd.

Water sorption of CH3- and CF3-Bis-GMA based resins with additives

Objectives: To evaluate the effect of additives on the water sorption characteristics of Bis-GMA based copolymers and composites containing TEGDMA, CH(3)Bis-GMA or CF(3)Bis-GMA. Material and methods: Fifteen experimental copolymers and corresponding composites were prepared combining Bis-GMA and TEGDMA, CH(3)Bis-GMA or CF(3)Bis-GMA, with aldehyde or diketone (24 and 32 mol%) totaling 30 groups. For composites, barium aluminosilicate glass and pyrogenic silica was added to comonomer mixtures. Photopolymerization was effected by 0.2 wt% each of camphorquinone and N,N-dimethyl-p-toluidine. Specimen densities in dry and water saturated conditions were obtained by Archimedes' method. Water sorption and desorption were evaluated in a desorption-sorption-desorption cycle. Water uptake (%WU), water desorption (%WD), equilibrium solubility (ES; mu g/mm(3)), swelling (f) and volume increase (%V) were calculated using appropriate equations. Results: All resins with additives had increased %WU and ES. TEGDMA-containing systems presented higher %WU, %WD, ES, f and %V values, followed by resins based on CH(3)Bis-GMA and CF(3)Bis-GMA. Conclusions: Aldehyde and diketone led to increases in the water sorption characteristics of experimental resins.

Occurrence and sorption of fluoroquinolones in poultry litters and soils from sao Paulo State, Brazil

Animal production is one of the most expressive sectors of Brazilian agro-economy. Although antibiotics are routinely used in this activity, their occurrence, fate, and potential impacts to the local environment are largely unknown. This research evaluated sorption-desorption and occurrence of four commonly used fluoroquinolones (norfloxacin, ciprofloxacin, danofloxacin, and enrofloxacin) in poultry litter and soil samples from Sao Paulo State, Brazil. The sorption-desorption studies involved batch equilibration technique and followed the OECD guideline for pesticides. All compounds were analyzed by HPLC, using fluorescence detector. Fluoroquinolones' sorption potential to the poultry litters (K-d <= 65 L kg(-1)) was lower than to the soil (K-d similar to 40,000 L kg(-1)), but was always high (>= 69% of applied amount) indicating a higher specificity of fluoroquinolones interaction with soils. The addition of poultry litter (5%) to the soil had not affected sorption or desorption of these compounds. Desorption was negligible in the soil (<= 0.5% of sorbed amount), but not in the poultry litters (up to 42% of sorbed amount). Fluoroquinolones' mean concentrations found in the poultry litters (1.37 to 6.68 mg kg(-1)) and soils (22.93 mu g kg(-1)) were compatible to those found elsewhere (Austria, China, and Turkey). Enrofloxacin was the most often detected compound (30% of poultry litters and 27% of soils) at the highest mean concentrations (6.68 mg kg(-1) for poultry litters and 22.93 mu g kg(-1) for soils). These results show that antibiotics are routinely used in poultry production and might represent one potential source of pollution to the environment that has been largely ignored and should be further investigated in Brazil. (C) 2012 Elsevier B.V. All rights reserved.

An investigation of phosphate adsorption from aqueous solution onto hydrous niobium oxide prepared by co-precipitation method

The synthetic hydrous niobium oxide has been used for phosphate removal from the aqueous solutions. The kinetic data correspond very well to the pseudo second-order equation The phosphate removal tended. to increase with a decrease of pH. The equilibrium data describe very well the Langmuir isotherm. The peak appearing at 1050 cm(-1) in IR spectra after adsorption was attributed to the bending vibration of adsorbed phosphate. The adsorption capacities are high, and increased with increasing temperature. The evaluated Delta G degrees and Delta H degrees indicate the spontaneous and endothermic nature of the reactions. The adsorptions occur with increase in entropy (Delta S positive) value suggest increase in randomness at the solid-liquid interface during the adsorption. A phosphate desorbability of approximately 60% was observed with water at pH 12, which indicated a relatively strong bonding between the adsorbed phosphate and the sorptive sites on the surface of the adsorbent. (C) 2008 Elsevier B.V. All rights reserved.