Phosphate adsorption and availability plant of phosphate

Summary The effects of phosphate buffer capacity on the plant-availability of labile soil phosphate, when measured as intensity (I) or quantity (Q), are described and tested using results from a greenhouse experiment on 24 Sherborne soils. In multiple regression studies, phosphate buffer capacity with I or Q measurements as independent variables accounted for up to 94% of the variance in P uptake by ryegrass, the maximum buffer capacity being generally more useful than the equilibrium buffer capacity.When the quantity of soil P is measured (Q), its availability (i.e. ease of desorption) to plant roots is inversely related to the Langmuir bonding energy parameter and the buffer capacity. When the intensity of soil P is measured (I), its availability (i.e. resistance to change) is directly related to the adsorption and buffer capacities. The levels of Q or I, therefore, which are optimal for plant uptake vary with the buffer capacity of the soil. There is little or no correlation between the adsorption capacity and the bonding energy in many soils and consequently phosphate buffer capacity is only poorly correlated with the total adsorption capacity.     

择伐干扰对小兴安岭阔叶红松林土壤磷吸附解吸的影响

以小兴安岭地区阔叶红松林经过轻度、中度和强度择伐干扰后形成的天然林以及未经干扰的原始林(对照)林地表层(0～10 cm)土壤为对象,对土壤磷素的最大吸附量、吸附强度、最大缓冲容量、最大解吸量、平均解吸率和易解吸磷量等指标进行测定,研究不同干扰强度导致土壤磷吸附解吸的规律性变化,分析择伐干扰对阔叶红松林土壤磷吸附解吸特征的影响.结果表明: 各林地土壤磷最大吸附量为1383.93～1833.34 mg·kg^-1,中度和强度干扰林地显著高于轻度干扰林地和原始林地;磷吸附强度为0.024～0.059 L·mg^-1,强度和轻度干扰显著增加了林地土壤磷吸附强度;最大缓冲容量为35.68～97.97 L·kg^-1,强度干扰林地土壤的最大缓冲容量最高.择伐干扰显著降低了林地土壤的供磷潜力.各样地土壤磷最大解吸量、平均解吸率和易解吸磷量分别为526.32～797.54 mg·kg^-1、14.7%～25.5%和1.79～5.41 mg·kg^-1,林地土壤磷素释放能力随干扰强度的增加显著降低.择伐干扰通过降低林地土壤磷的供应及释放能力改变了阔叶红松林土壤磷吸附与解吸特征.     

退耕还湖后湿地土壤对磷的吸附解吸特性

以安徽菜子湖区不同退耕年限(3、5、9和11年)湿地为研究对象,以相邻油菜地和原始湿地为对照(共6个样地),研究退耕还湖后湿地土壤对磷的吸附解吸特性变化.结果表明: 退耕湿地土壤对磷的等温吸附曲线与Langmuir和Freundlich吸附方程拟合程度均达极显著水平(P<0.01);6个样地土壤对磷的最大吸附量(X_m)、吸附常数(K)和最大缓冲容量(MBC)范围分别为478～1074 mg·kg^-1、0.14～0.61和68.6～661.5 mg·kg^-1,且退耕湿地的这些参数均随着退耕年限的延长而升高,但未达到原始湿地水平;6个样地土壤磷的平均解吸率为6.2%～14.6%,且退耕湿地土壤磷解吸率随着退耕年限的延长呈先增高后降低的趋势,但均显著高于原始湿地.表明随着退耕年限的增加,湿地土壤对外源磷的固持能力不断增强,而土壤有机质和粘粒含量是影响湿地土壤对外源磷固持能力的重要因子.     

A new metal chelate affinity adsorbent for cytochrome C

We have prepared a novel metal-chelate adsorbent utilizing N-methacryloyl-L-histidine methyl ester (MAH) as a metal-chelating ligand. MAH was synthesized by using methacryloyl chloride and l-histidine methyl ester dihydrochloride. Spherical beads with an average diameter of 75-125 microm were produced by suspension polymerization of 2-hydroxyethyl methacrylate (HEMA) and MAH carried out in an aqueous dispersion medium. Then, Cu(2+) ions were chelated directly on the chelating beads. Cu(2+)-chelated beads were used in the adsorption of cytochrome c (cyt c) from aqueous solutions. The maximum cyt c adsorption capacity of the Cu(2+)-chelated beads (658.2 micromol/g Cu(2+) loading) was found to be 31.7 mg/g at pH 10 in phosphate buffer. The nonspecific cyt c adsorption on the naked PHEMA beads was 0.2 mg/g. Cyt c adsorption increased with increasing Cu(2+) loading. Cyt c adsorption capacity was demonstrated for the buffer types with the effects in the order phosphate > HEPES > MOPS > MES > Tris-HCl. Cyt c molecules could be adsorbed and desorbed five times with these adsorbents without noticeable loss in their cyt c adsorption capacity.     

Protein adsorption on histidyl-aminohexyl-Sepharose 4B: I. Study of the mechanistic aspects of adsorption for the separation of human serum albumin from its non-enzymatic glycated isoforms (advanced glycosylated end products)

The characteristics of albumin adsorption on histidyl-aminohexyl-Sepharose 4B were investigated. In particular, the adsorption capacity of the gel was studied as a function of conductivity and pH of the running buffer. The adsorption was maximum at low salt concentration around neutral pH, involving electrostatic and hydrophobic interactions. Kinetic aspects were also investigated. Dissociation constant (K_D) and maximum capacity (Q_x) were, respectively, estimated to be 4.5×10⁻⁵ M (medium affinity) and 93.3 mg (high capacity) of human serum albumin per ml of adsorbent. According to these preliminary results, separation of HSA and its non-enzymatically glycated isoforms (conventionally named advanced glycated end products: AGEs) was achieved. Chromatographic potential of this separation tool is discussed.     

Methacryloylamidohistidine in affinity ligands for immobilized metal-ion affinity chromatography of ferritin

A new metal-chelate adsorbent utilizing 2-methacryloylamidohistidine (MAH) was prepared as a metalchelating ligand. MAH was synthesized using methacryloly chloride and histidine. Monosize nanospheres with an average diameter of 450 nm were produced by emulsion polymerization of 2-hydroxyetylmethacrylate (HEMA) and MAH. Then, Fe³⁺ ions were chelated directly onto the monosize nanospheres. Mon-poly(HEMA-MAH) nanospheres were characterized by Fourier transform infrared spectroscopy, scanning electron microscopy, and elemental analysis. Fe³⁺ chelated monosize nanospheres were used in ferritin adsorption from an aqueous solution. The maximum ferritin adsorption capacity of Fe³⁺-chelated mon-poly(HEMAMAH) nanospheres was 202 mg/g at pH 4.0 in acetate buffer. The non-specific ferritin adsorption on the monpoly( HEMA-MAH) nanospheres was 20 mg/g. The adsorption behavior of ferritin could be modeled using both Langmuir and Freundlich isotherms. The adsorption capacity decreased with increasing ionic strength of the binding buffer. High desorption ratios (> 95% of the adsorbed ferritin) were achieved with 1.0 M NaCl at pH 7.0. Ferritin could be repeatedly adsorbed and desorbed with the Fe³⁺-chelated mon-poly(HEMA-MAH) nanospheres without significant loss of adsorption capacity.     

Iron:phosphorus ratio in surface sediment as an indicator of phosphate release from aerobic sediments in shallow lakes

Analysis of Danish lakes showed that both mean winter and mean summer concentrations of lake water total phosphorus in the trophogenic zone correlated negatively with the total iron to total phosphorus ratio (Fe:P) in surface sediments. No correlation was found between the water total phosphorus concentration and either the sediment phosphorus concentration alone or with sediment calcium concentration. The increase in total phosphorus from winter to summer, which is partly a function of net internal P-loading, was lowest in lakes with high Fe:P ratios in the surface sediment.A study of aerobic sediments from fifteen lakes, selected as representative of Danish lakes with respect to the sediment Fe and phosphorus content, showed that the release of soluble reactive phosphorus was negatively correlated with the surface sediment Fe:P ratio. Analysis of phosphate adsorption properties of surface sediment from 12 lakes revealed that the capability of aerobic sediments to buffer phosphate concentration correlated with the Fe:P ratio while the maximum adsorption capacity correlated with total iron. Thus, the Fe:P ratio may provide a measure of free sorption sites for orthophosphate ions on iron hydroxyoxide surfaces.The results indicate that provided the Fe:P ratio is above 15 (by weight) it may be possible to control internal P-loading by keeping the surface sediment oxidized. Since the Fe:P ratio is easy to measure, it may be a useful tool in the management of shallow lakes.     

A novel magnetic adsorbent for immunoglobulin-g purification in a magnetically stabilized fluidized bed

A novel magnetic poly(ethylene glycol dimethacrylate-N-methacryloly-L-histidinemethylester) [m-poly(EGDMA-(MAH)] support was prepared for purification of immunoglobulin G (IgG) in a magnetically stabilized fluidized bed by suspension polymerization. Elemental analysis of the magnetic beads for nitrogen was estimated as 70 micromol MAH/g polymer. Magnetic poly(EGDMA-MAH) beads were used in the separation of immunoglobulin-G (IgG) from aqueous solutions and/or human plasma in a magnetically stabilized fluidized bed system. IgG adsorption capacity of the beads decreased with an increase in the flow rate. The maximum IgG adsorption was observed at pH 6.0 for MES buffer. IgG adsorption onto the m-poly(EGDMA) was negligible. Higher adsorption values (up to 262 mg/g) were obtained in which the m-poly(EGDMA-MAH) sorbents were used from aqueous solutions. Higher amounts of IgG were adsorbed from human plasma (up to 320 mg/g) with a purity of 87%. IgG molecules could be repeatedly adsorbed and desorbed with these sorbents without noticeable loss in their IgG adsorption capacity.     

Nonspecific interaction of proteoglycans with chromatography media and surfaces: effect of this interaction on the isolation efficiencies

Nonspecific adsorption of proteoglycans to chromatography media and surfaces is demonstrated. This adsorption is highly dependent on the nature of the chromatography media and the precise buffer conditions. For a given buffer the amount of adsorption decreases as the pH of the buffer is increased. It is also highly dependent on buffer concentration and increases as the buffer concentration is increased. The effect of salts such as LiCl, NaCl, KCl, and MgCl2 was generally small and complex so that the presence of the salt both increased and decreased the amount of adsorption depending on the buffer conditions. In contrast, the effect due to the presence of guanidine hydrochloride (Gdn-HCl) was relatively large and complex. At low Gdn-HCl concentrations there generally was a large increase in the amount of adsorption, reaching a maximum at approximately 0.5 M Gdn-HCl and decreasing with further increases in Gdn-HCl concentration. Detergents such as 3-[(3-cholamidopropyl)dimethylammonio]-1-propanesulfonate (Chaps) and sodium dodecylsulfate generally reduced the amount of nonspecific adsorption, although in the presence of both the detergent and Gdn-HCl, the effect due to Gdn-HCl predominated. In commonly used buffers such as 0.5 M sodium acetate (NaOAc), pH 7.0 (buffer F), and 4 M Gdn-HCl in 0.05 M NaOAc, pH 5.8 (buffer D), adsorption to surfaces and chromatography media such as Sepharose CL-2B, cellulose, and controlled pore glass (CPG) is highly significant and it is particularly large for cellulose and CPG.(ABSTRACT TRUNCATED AT 250 WORDS)     

Application of dye-ligands affinity adsorbent in capturing of rabbit immunoglobulin G

The applicability of dye-ligands attached to an expanded bed chromatography quartz base matrix (Streamline™) for the affinity bioseparation of rabbit immunoglobulin G (IgG) was investigated. Reactive Green 5 (RG-5) immobilized onto adsorbent was selected for capturing of rabbit-IgG due to its higher binding capacity compared to other dye-ligands possessing similar ligand density. Adsorption parameters such as pH, temperature, ionic strength and initial rabbit-IgG concentration were optimized for the adsorption of rabbit-IgG on the RG-5-immobilized adsorbent. The highest rabbit-IgG adsorption was recorded in pH 7.0, while the maximum binding capacity for BSA was achieved at pH 4.0. The adsorption of rabbit-IgG on RG-5-immobilized adsorbent was declined as the increase of ionic strength. There is no significant influence of temperature against adsorption efficiency of RG-5-immobilized adsorbent for rabbit-IgG. The adsorption phenomenon of rabbit-IgG on RG-5-immobilized adsorbent appeared to follow the Langmuir–Freundlich adsorption isotherm model. The theoretically maximum binding capacity (q_m) of RG-5-immobilized adsorbent estimated from this isotherm was 49.3 mg ml⁻¹, which is very close to that obtained experimentally (49.0 mg ml⁻¹). About 50% of bound BSA on RG-5-immobilized adsorbent in binary adsorption system was removed with washing buffer containing 1 M NaCl.     

Lipase purification by affinity precipitation with a thermo-responsive polymer immobilized Cibacron Blue F3GA ligand

A thermo-responsive polymer (P_NNB) was synthesized with lower critical solution temperature 27.5°C and over 95% recovery. The adsorption of porcine pancreatic lipase on Cibacron Blue F3GA-conjugated P_NNB (P_NNB-CB) closely followed the bi-Langmuir adsorption isotherm. The maximum adsorption capacity was found at pH 5.0, with a ligand density of 18.4 μmol/g polymers. The optimized eluent was a 0.01 M phosphate buffer solution at pH 8.0 containing 20% ethylene glycol. Six adsorptiondesorption recycles indicated excellent reusability of the affinity adsorbent. P_NNB-CB was applied to separate porcine pancreatic lipase from its crude material giving a lipase activity recovery of 81.6% with a 16-fold purification factor. Lipase could be purified to single-band purity, according to gel electrophoresis. The purification strategy is therefore feasible and efficient for purifying proteins of interest.     

Amphoteric, buffering chromatographic beads for proteome prefractionation. I: theoretical model

The possibility is reported here of fractionating proteins on amphoteric, buffering resins via ion-exchange chromatography. A given protein's adsorption to a particular amphoteric buffering resin is characterized by a bell-shaped curve in which the maximum protein binding capacity is observed at an optimum pH value lying approximately midway between the isoelectric point values (pI) of the resin and the protein. On either side of this maximum the protein binding capacity declines steadily, reaching zero at the pI of either the protein or exchanger. For instance, on beads of pI equal to 8, four proteins, two acidic (bovine albumin and ovalbumin) and two basic (cytochrome c and lysozyme), exhibit binding curves reaching zero values for the whole set when the exchanger is conditioned at pH 8.0. Away from the pI, and on both sides of the pH scale, the bell-shaped adsorption curves reach a maximum, for each protein, at a pH located at the midpoint between the pI values of each protein and that of the exchanger, and decline steadily to reach zero at the pI value of each protein species. Separation of model proteins using different amphoteric buffering resins of various pI was possible at different pH values according to both the pI of the proteins and of the exchangers. It was also demonstrated, using surface enhanced laser desorption/ionization mass spectrometry and two dimensional electrophoretic mapping, that separation of an Escherichia coli cell lysate on columns packed with amphoteric buffering resins of different pI and titrated to a particular pH value, delivered two distinctly different fractions, i.e. characteristically composed of, on the one hand, proteins having a pI below the buffer pH (the 'adsorbed' fraction), and on the other, of alkaline proteins possessing a pI above the pH of the buffer (the 'unadsorbed' fraction). This approach represents an attractive addition and/or alternative to the armory of protein pre-fractionation techniques currently employed in proteomics.     

Adsorption of BSA on QAE-dextran: equilibria

Equilibrium isotherms for adsorption of bovine serum albumin (BSA) on a strong-base (QAE) dextran-type ion exchanger have been determined experimentally. They were not affected by the initial concentration of BSA but were affected by pH considerably. They were correlated by the Langmuir equation when pH >/= 5.05 and by the Freundlich equation of pH 4.8, which is close to pl approximately 4.8 of BSA. The contribution of ion exchange to adsorption of BSA on the ion exchanger was determined experimentally. The maximum amounts of inorganic anion exchanged for BSA were 1% and 0.4% of the exchange capacity of the ion exchanger at pH 6.9, respectively. Since the effect of the ion exchange on the adsorption appeared small, BSA may be adsorbed mainly by electrostatic attraction when pH >/= 5.05 and by hydrophobic interaction or hydrogen bonding at pH 4.8. When NaCl coexisted in the solution, the shape of the isotherm was similar to the Langmuir isotherm, but it is shifted to the right. When the concentration of NaCl was 0.2 mol/dm(3), BsA was not adsorbed on the resin. When BSA was dissolved in pure water, the saturation capacity of BSA on HPO(4) (2-),-orm resin was about 2 times larger than that for adsorption from the solution with buffer (pH 6.9 and 8.79). The saturation capacity for adsorption of BSA in pure water on HPO(4) (2-) + H(2)O(4) (-)-from resin was much smaller than that from the solution with buffer. The isotherms for univalent Cl(-)-and H(2)PO(4) (-)-form resin was peculiar; that is, the amount of BSA adsorbed decreased with increasing the liquid-phase equilibrium concentration of BSA. (c) 1993 John Wiley & Sons, Inc.     

Evaluation of alternatives for human lysozyme purification from transgenic rice: impact of phytic acid and buffer

Producing economically competitive recombinant human lysozyme from transgenic rice demands an inexpensive purification process for nonpharmaceutical applications. Human lysozyme is a basic protein, and thus, cation exchange chromatography was the selected method for lysozyme purification. Similar to other protein production systems, the identification of critical impurities in the rice extract was important for the development of an efficient purification process. Previous adsorption data indicated that phytic acid was probably responsible for an unacceptably low cation exchange adsorption capacity. In this study, we confirm that reducing phytic acid concentration improves lysozyme binding capacity and investigate alternative process conditions that reduce phytic acid interference. Compared with the previous best process, the adsorption capacity of human lysozyme was increased from 8.6 to 19.7 mg/mL when rice extract was treated with phytase to degrade phytic acid. Using tris buffer to adjust pH 4.5 extract to pH 6 before adsorption reduced phytic acid interference by minimizing phytic acid-lysozyme interactions, eliminated the need for phytase treatment, and increased the binding capacity to 25 mg/mL. Another method of reducing phytic acid concentration was to extract human lysozyme from rice flour at pH 10 with 50 mM NaCl in 50 mM sodium carbonate buffer. A similar binding capacity (25.5 mg/mL) was achieved from pH 10 extract that was clarified by acidic precipitation and adjusted to pH 6 for adsorption. Lysozyme purities ranged from 95 to 98% for all three processing methods. The tris-mediated purification was the most efficient of the alternatives considered.     

Phosphorus adsorption characteristics of Hawaiian soils and their relationships to equilibrium phosphorus concentrations required for maximum growth of Millet

Summary Phosphorus adsor tion isotherms were constructed for six Latosols and one calcareous soil from Hawaii which differed greatly in their phosphorus adsorption capacities. Equilibration was in 0.01M CaCl₂ at 25°C for 6 or 8 days. P adsorption properties of the soils were characterised employing the linear form of Langmuir's equation and also by calculating the amount of P adsorbed between equilibrium concentrations of 0.25 to 0.35 ppm (estimates of P buffering capacities), following the procedure of Oaanne and Shaw¹³. The isotherms of all the soils were found to fit the Langmuir equation at low equilibrium concentrations (< 5 ppm) and the P adsorption maxima ranged from 520 to 10 500 ppm. The buffering capacity estimates correlated closely (r = 0.950) with the adsorption maxima of soils. However, in two soils, the estimates were much lower than expected from their adsorption maxima.Millet (Pennisetum typhoides) was grown in these soils in pots, at 6 phosphorus levels corresponding to 6 equilibrium concentrations chosen from the phosphorus adsorption isotherms. Equilibrium concentrations at maximum growth of millet (C_max) in Latosols varied inversely with the adsorption maxima of the soils. The relationship between these two parameters was expressed by the equation CmaX = a,b^–k, where C_max = equilibrium P concentration at maximum growth of millet, b = P adsorption maximum and a and k are constants. Quantitative expression of the constants are useful as they enable predictions of CmaX for a particular crop from the phosphorus adsorption maximum. This relation was found to hold also for the data on limed acid soils published by Woodruff and Kamprath²⁰.A part of the Ph.D. Thesis approved by the University of Hawaii, Honolulu, Hawaii, U.S.A. (1971).     

The role of sediments for phosphorus retention in the Kirinya wetland (Uganda)

Phosphorus dynamics were examined and modelled in a Cyperus papyrus and Phragmites mauritanus wetland on the Ugandan coast of Lake Victoria receiving secondary treated wastewater. Using a series of transversal transects, concentrations of nitrogen (N) and phosphorus (P) were found to decrease gradually as water moved downstream, giving nutrient retention capacities which ranged between 40% and 60%. Near-zero oxygen and nitrate concentrations were observed as well. To investigate the phosphorus retention characteristics in more detail, laboratory experiments were carried out on sediment samples and sediment cores retrieved from points along the wetland. Following a P shock load to cores of the wetland sediment, it was possible to determine a sediment P uptake rate of 0.016 day⁻¹. Sediment P adsorption studies were also performed, showing significant Freundlich and Langmuir isotherm behaviour. With these data a maximum P adsorption capacity of 4 mg P/g for the wetland sediment could be estimated. A plug-flow model was used to evaluate the phosphorus retention dynamics of the Kirinya wetland. A good correspondence between the actual and simulated P retention was observed. Comparing the daily P uptake (g/m³day) in the Kirinya wetland with the maximum sediment P uptake capacity, it can be concluded that the total P retention capacity of the wetland will only be sufficient for 30 more years under the present P loading and wetland management.     

Performance of hydrophobic chromatography in purification of alpha-amylase

Hydrophobic ligands were introduced onto agarose beads, and the adsorption capacity of the beads was measured. The adsorption capacity increased with increase in the carbon number of the ligand, ionic strength of the buffer solution, and temperature. Crude alpha-amylase was purified with these hydrophobic adsorbents and the breakthrough and elution curves were estimated based on the mass transfer theory. Under strongly hydrophobic conditions, impurities contained in crude feeds and the lack of uniformity of packing caused by aggregation of beads affected adsorption and elution behaviors.     

Batch and continuous adsorption of strontium by plant root tissues

Strontium (Sr) ions in aqueous solutions could be adsorbed by root tissue powders of Amaranthus spinosus, a common weed found in the fields. The adsorption isotherm could be fitted by either the Langmuir or the Freundlich model with the maximum adsorption capacity being 12.89 mg/g from the Langmuir isotherm. The maximum adsorption capacity of the biosorbent decreased with increasing temperature, whereas alkaline pretreatment enhanced the adsorption capacity 1.9 fold. Alginate gel beads (1 mm diameter) containing the root tissue powders were prepared and packed in a column for continuous adsorption/desorption of Sr in solution. Efficient desorption of Sr could be carried out with 0.1 CaCl₂ to give a concentrated Sr solution with 94% recovery.     

Behavior of human immunoglobulin G adsorption onto immobilized Cu(II) affinity hollow‐fiber membranes

Iminodiacetic acid (IDA) and tris(2‐aminoethyl)amine (TREN) chelating ligands were immobilized on poly(ethylene vinyl alcohol) (PEVA) hollow‐fiber membranes after activation with epichlorohydrin or butanediol diglycidyl ether (bisoxirane). The affinity membranes complexed with Cu(II) were evaluated for adsorption of human immunoglobulin G (IgG). The effects of matrix activation and buffer system on adsorption of IgG were studied. Isotherms of batch IgG adsorption onto finely cut membranes showed that neither of the chelates, IDA‐Cu(II) or TREN‐Cu(II), had a Langmuirean behavior with negative cooperativity for IgG binding. A comparison of equilibrium and dynamic maximum capacities showed that the dynamic capacity for a mini‐cartridge in a cross‐flow filtration mode (52.5 and 298.4 mg g^?1 dry weight for PEVA‐TREN‐Cu(II) and PEVA‐IDA‐Cu(II), respectively) was somewhat higher than the equilibrium capacity (9.2 and 73.3 mg g^?1 dry weight for PEVA‐TREN‐Cu(II) and PEVA‐IDA‐Cu(II), respectively). When mini‐cartridges were used, the dynamic adsorption capacity of IDA‐Cu(II) was the same for both mini‐cartridge and agarose gel. Copyright © 2013 John Wiley & Sons, Ltd.     

Thermodynamics of statherin adsorption onto hydroxyapatite

Statherin is a salivary protein that inhibits the nucleation and growth of hydroxyapatite crystals in the supersaturated environment of the oral cavity. The thermodynamics of adsorption of statherin onto hydroxyapatite crystals have been characterized here by isothermal titration calorimetry and equilibrium adsorption isotherm analysis. At 25 degrees C, statherin adsorption is characterized by an exothermic enthalpy of approximately 3 kcal/mol that diminishes to zero at approximately 25% surface coverage. The initial heat of statherin adsorption increases with temperature, displaying a positive heat capacity change of 194 +/- 7 cal K(-)(1) mol(-)(1) at 25 degrees C. The heat of adsorption during this initial phase is strongly dependent on the buffer species, and from the differential heats of buffer ionization, it can be calculated that approximately one proton is taken up by the crystal or protein upon adsorption. The free energy of adsorption is dominated at all coverages by a large positive entropy (>or=23 cal K(-)(1) mol(-)(1)), which may be partially due to the loss of organized water that hydrates the protein and the mineral surface prior to adsorption. These results are interpreted using a two-site model for adsorption of statherin onto the hydroxyapatite crystals.