The adsorption of citrate, at 10 4−10−3 M initial concentration, by pseudoboehmite suspended in 0.02 M NaC1O4 was investigated at varying pH. Citrate shows a strong affinity for the pseudoboehmite surface, as seen in the adsorption isotherm at pH 6. Adsorption envelopes of adsorbed citrate vs. pH for a given initial citrate concentration are characteristic for the adsorption of a polyprotic acid by a variable-charge mineral. The envelope data were fit well by the Constant Capacitance Model assuming a ligand-exchange adsorption mechanism, three monodentate surface species of citrate, and a reactive surface OH density of 0.4 mol kg−1. Aqueous speciation calculations suggest that solubility equilibrium with pseudoboehmite was attained at pH > 9 and that particulate or polymeric Al may have existed at 6 < pH < 9. Dissolved Al appeared to reduce the adsorption of citrate at pH < 5.5 via solution complexation reactions.

The rate of Fe(II) oxidation at a constant rate of oxygen supply in the presence of citrate was measured at pH 6.0 at various citrate/Fe(II) molar ratios at 23.5°C in 0.01 M ferrous Perchlorate system. The kinetics followed a first-order reaction with respect to Fe(II) concentration at constant pH (6.0) and aeration (5 ml/min). The rate constant decreased exponentially from 41.3 × 10-4 to 7.6 × 10-4/min with an increase in the citrate/Fe(II) molar ratio from 0 to 0.1.

The nature of the hydrolytic products formed after 120 min of oxidation was arrived at by X-ray powder diffraction (XRD), infrared spectrometry (IR), and transmission electron microscopic (TEM) analyses. In the absence of citrate, goethite (α-FeOOH) and poorly crystalline lepidocrocite (γ-FeOOH) were the oxidation products formed at pH 6.0. The formation of lepidocrocite was promoted at the expense of goethite at citrate/Fe(II) molar ratios of 0.0005 to 0.005. The formation of lepidocrocite was especially pronounced at a citrate/Fe(II) molar ratio of 0.001, as observed from the width at half height (WHH) and the area of the 020 XRD peak of lepidocrocite. At a citrate/Fe(II) molar ratio of 0.01, however, the crystallization was perturbed resulting in the formation of noncrystalline Fe oxides, and no precipitate was observed at a citrate/Fe molar ratio of 0.1. The strong complexation of Fe(II) with citrate retarded the kinetics of Fe(II) oxidation and the formation and hydrolysis of Fe(III). The complexation, electrostatic, and steric effects of the coexisting citrate anions in solution apparently influenced the oxygen coordination and the way by which the double rows of edge-sharing Fe(O,OH)6 octahedra linked during crystallization, resulting in the formation of lepidocrocite.

The degree of flocculation of aqueous suspensions of microcrystalline goethite was measured in salts of monovalent, divalent and trivalent cations at pH 6.0–6.5 over a range of ionic strengths using light scattering measurements at 650 nm. Varying concentrations of soluble humic material as well as the organic ligands, salicylate and citrate, were tested for their effect on flocculation. It was found that KCl and NaCl induced flocculation at lower ionic strength than CaCl2, while AlCl3 favored dispersion at all ionic strengths tested. The simple organic ligands promoted flocculation at low concentration, with citrate having a more pronounced effect than salicylate. At higher concentrations, these ligands reversed their effect, inducing a more dispersed state of the oxide. The organic ligand effect on dispersibility was modified by the particular metal cation present, with Ca2+ being more conducive to flocculation than K+. Soluble humic materials affected goethite flocculation in a qualitatively similar way to that of the simple organic ligands, that is low concentrations favored flocculation while high concentrations induced dispersion. This dispersing effect was partially suppressed by the presence of Ca2+, and completely suppressed by Al3+. Thus, soluble humic substances at relatively high concentrations appear to have a marked dispersing effect on goethite in the absence of polyvalent cations, and a strongly flocculating effect in their presence.

The results can be explained qualitatively by a simple oxide surface charge model, in which chemi-sorption of multivalent cations or organic ligands alters the surface charge. Reactions that increase the magnitude of positive or negative surface charge favor dispersion, while those that reduce the magnitude of charge favor flocculation.

The citrate-induced desorption kinetics of pre-adsorbed Se from montmorillonite (Mt) and its complexes with hydroxyaluminum (HyA-Mt) and hydroxyaluminosilicate (HAS-Mt) were studied. The mole fraction of pre-adsorbed Se released in 24 h from different clays followed the trends of Mt>> HAS-Mt> HyA-Mt with a significant increase with elevated citrate concentration in the desorbing solution. In contrast, the amount of Se adsorbed per unit mass of different clays followed a clear-cut opposite trend of HyA-Mt>HAS-Mt>>Mt. The Se desorption kinetics in different systems indicated multiple rate characteristics; where an initial fast reaction (0.25–2 h) was followed by a slow reaction (2–16 h). Of the six different kinetic models tested (zero-, first-, and second-order; power function, Elovich, and parabolic diffusion), the second-order rate equation showed the overall best fit to the fast and slow desorption kinetic data from the clays. Based on second-order rate constants, the rates of the mole fraction of Se desorption by citrate from different clay systems at 298 K followed the order Mt > HAS-Mt >> HyA-Mt. For both fast and slow reaction, the rates of desorption increased proportionally with the level of citrate. Replicate experiments conducted across a range of temperature (288–318 K) yielded Arrhenius parameters that followed the order HyA-Mt > HAS-Mt >> Mt. Considering that a lower mole fraction of Se desorption after a particular reaction period, slower desorption kinetics, and a greater activation energy of desorption are the indices of increased adsorption bond strength, the results clearly indicate that HyA- and HAS-interlayering and coatings on Mt not only augmented its Se adsorption affinity and capacity, but also increased the adsorption bond strength. Silication in HyA not only reduced the Se adsorption capacity, but also weakened the adsorption bond strength. This establishes a significant role of HyA/HAS-interlayering and coating on Mt in influencing the rate of citrate-induced release of Se. Reduction in surface-positive potential following citrate adsorption on the clay surface, a direct ligand exchange between Se and citrate, and structural dissolution are possible mechanisms responsible for citrate-induced Se desorption in the present study.

We investigated the sorption of Ni to gibbsite of two different surface areas at pH 7.5, in the presence and absence of citrate, over a time period of 180 days. Extended X-ray absorption fine-structure spectroscopy was employed to elucidate the sorption mechanisms at the molecular level. In agreement with former results, Ni-Al layered double hydroxide (LDH) formed in the presence of gibbsite of low surface area. However, gibbsite of high surface area suppressed the formation of the surface precipitate. Instead, two Al atoms neighboring Ni at distances of 2.95–2.98 Å indicated formation of an inner-sphere sorption complex, where each NiO6-octahedron shares edges with two AlO6-octahedra. Focused multiple scattering arising from Al atoms at a distance of 6 Å suggest that sorbed Ni(OH)2(OH2)4 monomers epitaxially extend the hexagonal arrangement of Al atoms in gibbsite. Only after 30 days or more was a small amount of LDH formed. The presence of citrate prevented the formation of LDH, while maintaining the formation of inner-sphere sorption complexes.

Citrate is distributed widely in the Earth’s surface environments as a biological product released by microbes and plants. Citrate is also often used as a chelating agent for the selective dissolution of iron coatings and free iron oxides in soils. Adsorption experiments of Cs+ and IO3− before and after the complexation of citrate with the pseudoboehmite surface were conducted to evaluate the effects of citrate on the adsorption of these ions on the surface of pseudoboehmite. Additional adsorption experiments of Cs+ and IO3− after the decomposition of citrate adsorbed on the pseudoboehmite surface were also performed to confirm the recovery of the original surface properties. Citrate decomposition was carried out by means of 10% H2O2 treatments at 75°C and pH 5, 7, and 9. The results indicated that citrate complexation decreased remarkably the adsorption of both Cs+ and IO3− in the pH range 3–10, which was due to a decrease in the number of active charged sites available for adsorption of these ions. Decomposition of citrate adsorbed on the pseudoboehmite surface was found to be complete after three rounds of treatment with 10% H2O2 at 75°C and pH > 7. After the decomposition of citrate adsorbed on the pseudoboehmite surface, the adsorption of both Cs+ and IO3− was restored completely to the initial amounts before citrate complexation, and the inhibition effect of citrate on the adsorption of these ions disappeared under all pH conditions.

The crystal structure of strontium hydrogen citrate monohydrate has been solved using laboratory X-ray powder diffraction data, refined using both laboratory and synchrotron data, and optimized using density functional techniques. Strontium hydrogen citrate monohydrate crystallizes in space group C2/c (#15) with a = 25.15601(17), b = 10.90724(6), c = 6.37341(4) Å, β = 91.9846(6)°, V = 1747.704(12) Å3, and Z = 8. The Sr coordination and the hydrogen bonding result in a layered structure. The SrO8 coordination polyhedra share edges to form corrugated layers parallel to the bc-plane. Hydrogen bonds between the carboxylic acid groups and water molecules link the layers. Intermolecular hydroxyl–carboxyl hydrogen bonds also link the layers in a ring pattern with a graph set symbol R2,2(12). After storage for 2 years, partial re-crystallization occurred, to an as-yet unknown compound with a triclinic unit cell.

The aim of this work was to use X-ray diffraction to identify substances used for adulteration of raw milk and to determine if crystallographic analysis can detect extraneous substances in milk. Two unknown substances were sent anonymously by employers linked to the dairy chain, who claimed that they were added directly in milk prior to water addition by truck drivers. The samples were analyzed by X-ray diffraction and submitted to physicochemical analysis. The first substance was identified by X-ray diffraction as sodium citrate, complying with its physicochemical attributes, such as the powerful ability to decrease the freezing point. The second substance was identified by X-ray diffraction as sucrose and this result was also in agreement with its ability to increase the density, decrease the freezing point and finally, to be positive for sucrose in the resorcinol qualitative test. To evaluate if X-ray diffraction can detect extraneous substances already mixed in milk, fresh raw milk samples tampered with urea, sodium hydroxide, sodium citrate and sucrose were freeze dried and analyzed by X-ray diffraction, with no detection of any extraneous substances at any percentage. This is the first report of attempted diagnosis of extraneous substances in milk by X-ray diffraction. However, this technique can be useful only when applied to identify substances used for adulteration prior to its dilution in milk, since the amorphous nature of milk seems to be a limitation for the accurate detection of extraneous substances.

The crystal structures of (NH4)H2C6H5O7 and (NH4)3C6H5O7 have been determined using a combination of powder and single crystal techniques. The structure of (NH4)2HC6H5O7 has been determined previously by single crystal diffraction. All three structures were optimized using density functional techniques. The crystal structures are dominated by N-H⋅⋅⋅O hydrogen bonds, though O-H⋅⋅⋅O hydrogen bonds are also important. In (NH4)H2C6H5O7 very strong centrosymmetric charge-assisted O-H-O hydrogen bonds link one end of the citrate into chains along the b-axis. A more-normal O-H⋅⋅⋅O hydrogen bond links the other end of the citrate to the central ionized carboxyl group. In (NH4)2HC6H5O7, the very strong centrosymmetric O-H-O hydrogen bonds link the citrates into zig-zag chains along the b-axis. The citrates occupy layers parallel to the bc plane, and the ammonium ions link the layers through N-H⋅⋅⋅O hydrogen bonds. In (NH4)3C6H5O7, the hydroxyl group forms a hydrogen bond to a terminal carboxylate, and there is an extensive array of N-H⋅⋅⋅O hydrogen bonds. The energies of the density functional theory-optimized structures lead to a correlation between the energy of an N-H⋅⋅⋅O hydrogen bond and the Mulliken overlap population: E(N-H⋅⋅⋅O) (kcal/mole) = 23.1(overlap)½. Powder patterns of (NH4)H2C6H5O7 and (NH4)3C6H5O7 have been submitted to International Centre for Diffraction Data for inclusion in the powder diffraction file.

Overweight and obesity have become epidemic worldwide and are linked to sedentary lifestyle and the consumption of processed foods and drinks. Citrate is a metabolite that plays central roles in carbohydrate and lipid metabolism. In addition, citrate is the additive most commonly used by the food industry, and therefore is highly consumed. Extracellular citrate can freely enter the cells via the constitutively expressed plasma membrane citrate transporter. Within the cytosol, citrate is readily metabolised by ATP-citrate lyase into acetyl-CoA – the metabolic precursor of endogenously produced lipids and cholesterol. We therefore hypothesised that the citrate ingested from processed foods and drinks could contribute to increased postprandial fat production and weight gain. To test our hypothesis, we administered citrate to mice through their drinking water with or without sucrose and monitored their weight gain and other metabolic parameters. Our results showed that mice receiving citrate or citrate+sucrose did not show increased weight gain or an increase in the weight of the liver, skeletal muscles or adipose tissues (AT). Moreover, the plasma lipid profiles (TAG, total cholesterol, LDL and HDL) were similar across all groups. However, the group receiving citrate+sucrose showed augmented fasting glycaemia, glucose intolerance and the expression of pro-inflammatory cytokines (TNF-α, IL-1β, IL-6 and IL-10) in their AT. Therefore, our results suggest that citrate consumption contributes to increased AT inflammation and altered glucose metabolism, which is indicative of initial insulin resistance. Thus, citrate consumption could be a previously unknown causative agent for the complications associated with obesity.

The assumption, that metabolites derived from the activity of the mammary gland epithelial cells reflect changes in milk secretion and its coagulation properties, was tested in dairy cows. The experiment included cows with uninfected udders and cows with one of the glands infected by different bacteria specie. Analysis were carried at the cow level (including all four glands), or at the gland level. High and significant correlations among the concentrations of lactose, glucose, glucose-6-posphate, milk related respiratory index (the ratio between the concentrations of citrate/lactate+malate in milk) and milk-derived glycolytic index (the ratio between glucose-6-phosphate and glucose in milk) and milk clotting parameters were found. The physiological basis for these relations and their ability to predict the deterioration in milk quality in subclinically infected glands and in glands previously clinically infected with Escherichia coli are discussed.

Precipitation of calcium phosphates occurs in dairy products and depending on pH and ionic environment, several salts with different crystallinity can form. The present study aimed to investigate the effects of NaCl and citrate on the characteristics of precipitates obtained from model solutions of calcium phosphate at pH 6·70 maintained constant or left to drift. The ion speciation calculations showed that all the starting solutions were supersaturated with respect to dicalcium phosphate dihydrate (DCPD), octacalcium phosphate (OCP) and hydroxyapatite (HAP) in the order HAP>OCP>DCPD. X-ray diffraction (XRD) and Fourier transform infrared (FTIR) analyses of the precipitates showed that DCPD was formed at drifting pH (acidic final pH) whereas poor crystallised calcium deficient apatite was mainly formed at constant pH (6·70). Laser light scattering measurements and electron microscopy observations showed that citrate had a pronounced inhibitory effect on the crystallisation of calcium phosphates both at drifting and constant pH. This resulted in the decrease of the particle sizes and the modification of the morphology and the microstructure of the precipitates. The inhibitory effect of citrate mainly acted by the adsorption of the citrate molecules onto the surfaces of newly formed nuclei of calcium phosphate, thereby changing the morphology of the growing particles. These findings are relevant for the understanding of calcium phosphate precipitation from dairy byproducts that contain large amounts of NaCl and citrate.

Lactoferrin (Lf) is a molecule naturally present in bovine milk that affects the availability and transport systems of iron. Lf also binds endotoxin (lipopolysaccharide, LPS) of Gram-negative bacteria and modulates the immunological response. In the present study, concentrations of bovine Lf (bLf) and citrate in milk were determined in early (EL) and late (LL) lactating dairy cows, using an experimentally induced endotoxin mastitis model and a crossover design. Nine clinically healthy Finnish Ayrshire cows were challenged twice with 100 μg endotoxin infused into one udder quarter. Milk samples were collected from the challenged and control quarters of each cow before and after endotoxin infusion during 3 d, and bLf and citrate concentrations were measured. In all cows, clinical signs of mastitis were seen at both times of challenge, but the response was more severe in EL than in LL. Concentration of bLf in the milk started to rise approximately 8 h after endotoxin infusion and was still higher than normal on the third day, especially in the late-lactating cows. In milk of the LL group, concentrations of bLf were significantly higher than in the EL group. In contrast, concentrations of citrate were higher in milk of the EL cows compared with the LL cows. Concentration of bLf and citrate varied substantially among cows. The molar ratio of citrate to bLf before and after challenge was significantly higher during the EL period. The results of this study partly explain why cows in early lactation are more susceptible to intramammary infections and why mastitis is more severe in them.

Excessive dietary NaCl in association with a paucity of plant foods, major sources of K alkaline salts, is a common feature in Western eating habits which may lead to acid–base disorders and to Ca and Mg wasting. In this context, to evaluate the effects of potato, rich in potassium citrate, on acid–base homeostasis and mineral retention, Wistar rats were fed wheat starch (WS) or cooked potato (CP) diets with a low (0·5 %) or a high (2 %) NaCl content during 3 weeks. The replacement of WS by CP in the diets resulted in a significant urinary alkalinisation (pH from 5·5 to 7·3) parallel to a rise in citrate and K excretion. Urinary Ca and Mg elimination represented respectively 17 and 62% of the daily absorbed mineral in rats fed the high-salt WS diet compared with 5 and 28% in rats fed the high-salt CP diet. The total SCFA concentration in the caecum was 3-fold higher in rats fed the CP diets compared with rats fed the WS diets, and it led to a significant rise in Ca and Mg intestinal absorption (Ca from 39 to 56 %; Mg from 37 to 60 %). The present model of low-grade metabolic acidosis indicates that CP may be effective in alkalinising urine, enhancing citrate excretion and ameliorating Ca and Mg balance.

We examined the effects of administering recombinant bovine cytokines to non-lactating dairy cows and measured mammary gland leucocytes and the involution process. After the final milking, groups of cows were given an intramammary infusion of cytokine in two quarters. These cytokines were recombinant bovine interleukin-2 (rboIL-2) (2×105 units, n=6), recombinant bovine granulocyte-macrophage colony stimulating factor (rboGM-CSF) (500 μg, n=4) and recombinant bovine interleukin-1β (rboIL-1β) (10 μg, n=10). Each animal also received an infusion of phosphate-buffered saline (PBS) in the other two quarters as controls. The rboIL-2 and rboGM-CSF were produced in a yeast expression system, while rboIL-1β was produced in Escherichia coli. Leucocyte numbers, bactericidal activity of leucocytes, and concentrations of citrate and lactoferrin in quarter secretion samples were monitored after infusion of cytokine or PBS. Infusion of rboIL-2 had minimal effect on leucocyte numbers and concentrations of citrate and lactoferrin. Both rboGM-CSF and rboIL-1β induced a rapid increase in the number of neutrophils and macrophages compared with control PBS quarters. Concentrations of lactoferrin in secretions were increased by rboGM-CSF and rboIL-1β compared with control PBS quarters. In addition, infusion of glands with rboIL-1β lowered the citrate[ratio ]lactoferrin molar ratio compared with PBS control quarters. The results indicate that intramammary infusion of either rboGM-CSF or rboIL-1β at cessation of milking immediately increased the number of phagocytic cells in the gland. These cytokines, in particular rboIL-1β, also increased the rate of mammary gland involution during the early dry period.