Phosphate in the form of organic compounds can be bound in soils containing the aluminosilicate allophane. A significant part of this phosphorus is believed to be present as nucleic acids. The interaction of yeast RNA with allophane was studied to further the understanding of the allophane/organic macro molecule interaction as well as the binding of organic phosphorus by allophanic soils. The extent of RNA adsorption on the allophane was dependent upon the pH, the charge and concentration of simple cations, the concentration of RNA, and the time of interaction. From a mixture containing 145 mg/liter RNA and 2.9 g/liter allophane in 10−2 M NaCl, the amount of RNA adsorbed increased from 6% at pH 10 to 98% at pH 3. The adsorption also increased as the concentration of added NaCl was increased from 10−4 M to 10−1 M, but only when the pH was greater than 5, i.e., above the isoelectric point of the clay. Mg2+ and Ca2+ were equally much more effective at promoting adsorption than Na+ at the same concentrations. There was no difference in the effectiveness of SO4−2, Cl−, or NO3− at pH 5 or higher. The adsorption isotherm at pH 7 can be described by the Langmuir equation; the apparent adsorption maximum was 38 mg/g. Van der Waals and simple electrostatic forces appear to dominate the interaction leading to the adsorption of RNA by allophane.

The adsorption of sodium, chloride, and phosphate ions by allophane, imogolite, and halloysite has been studied in relation to the surface structure of the mineral samples. The high adsorption of phosphate (>200 μmole/g) and chloride (10–30 meq/100 g at pH 4) by allophane is ascribed to the small particle size of allophane, its high surface area (∼800 m2/g), and the presence at the surface of Al-OH-Al groups and defect sites. In contrast, halloysite has a relatively large particle size and a Si-O-Si surface. Accordingly, the adsorption of phosphate (5–10 μmole/g) and chloride (1 meq/100 g) by halloysite is very much lower as compared with allophane. Phosphate adsorption by halloysite is also related to particle morphology and the number of edge sites. Thus, a sample consisting entirely of spheroidal particles adsorbed only 5 μmole/g at a solution concentration of 1 × 10−4 M, whereas the tubular types of comparable surface area adsorbed 7–10 μmole/g at the same concentration. This is because spheroidal halloysite particles have few, if any, edge sites at which phosphate can adsorb. The relative degree of order and hydration of halloysite, as indicated by infrared spectroscopy, also affects phosphate adsorption. However, this factor is apparently less important than particle morphology and surface structure. Although imogolite also has an Al-OH-Al surface, it contains relatively few defect sites where phosphate can adsorb. Consequently, much less phosphate (120 μmole/g) was adsorbed as compared with allophane.

The Excello Shale is one of the best exposed and most laterally continuous of the Pennsylvanian cyclothemic black shales in the midcontinent region of the United States. Its petrology and paleoenvi-ronmental significance were studied to understand the nature of cyclic black shales in general and how they relate to the habitat of hydrocarbon source beds. The Excello is thinly laminated, fissile where weathered, and rich in organic matter and phosphate nodules; it is 90–120 cm thick. Its thin laminations, fine particle size, and high total organic carbon (TOC) content suggest that it was deposited in a quiet water environment of an epeiric sea having anaerobic bottom water. The Excello Shale consists of two lithofacies: non-bioturbated black shale and bioturbated yellow-brown shale. Petrographic studies show that the black shale contains wavy to straight laminations and that the yellow-brown shale contains discontinuous and random laminae and mottled stratification. The close association of organic matter and phosphate-controlled nodule morphology (spherical, elongated, bladed, and platy) appear to be related to progressive decreases in nutrient supply of the sea water from the ancient ocean (Panthalassa).

Clay-mineral assemblages consist mainly of detrital illite, kaolinite, chlorite, and illite/smectite (I/S). Grain size and amount of these clays increase and TOC decreases shoreward towards the probable source areas of the clay minerals in the northern Ouachita region and northern Iowa. Quartz, carbonate-fluor-apatite, carbonate fossil fragments, and minor feldspar and pyrite are the principal minerals in the Excello Shale. Minor amounts of fine-silt-size carbonate minerals are present in some samples. Limestone concretions, 90–150 cm in diameter and 30 cm thick, were found at only one locality in Missouri where the Excello is a maximum of about 3 m thick. Fissility increases with weathering along the bedding plane, and laminae are separated by a limonite film. Four petrographically distinct microfabric variations of the Excello Shale appear to be related to the TOC content and bioturbation. Textural and structural properties of the shale are more developed with increasing organic matter content.

Ebnerite and epiebnerite, both with the ideal formula NH4ZnPO4, are new mineral species from the Rowley mine, Maricopa County, Arizona, USA. They occur in an unusual bat-guano-related, post-mining assemblage of phases. Epiebnerite grows epitactically on ebnerite and replaces it. Ebnerite and epiebnerite are found in intimate association with alunite, halite, mimetite, newberyite, sampleite, struvite and wulfenite on hematite-rich quartz–baryte matrix. Crystals of ebnerite are colourless narrow prisms up to ~0.3 mm in length. The streak is white, lustre is vitreous, Mohs hardness is ~2, tenacity is brittle and fracture is splintery. The density is 2.78(2) g⋅cm–3. Ebnerite is optically uniaxial (–) with ω = 1.585(2) and ɛ = 1.575(2). Epiebnerite occurs as colourless prisms or blades, up to about 10 × 3 × 2 μm, in parallel growth forming ribs with serrated edges epitactic on ebnerite prisms. The streak is white, lustre is vitreous, Mohs hardness is probably ~2, tenacity is brittle. The calculated density is 2.851 g⋅cm–3. Epiebnerite is optically biaxial with all indices of refraction near 1.580. Electron microprobe analysis gave the empirical formula [(NH4)0.89K0.06]Σ0.95(Zn0.96Cu0.07)Σ1.03[(P0.97Si0.03)Σ1.00O4] for ebnerite and [(NH4)0.67K0.28]Σ0.95(Zn0.99Cu0.02)Σ1.02(P1.00O4) for epiebnerite. Ebnerite is hexagonal, P63, with a = 10.67051(16), c = 8.7140(2) Å, V = 859.25(3) Å3 and Z = 8. Epiebnerite is monoclinic, P21, with a = 8.796(16), b = 5.457(16), c = 8.960(16) Å, β = 90.34(6)°, V = 430.1(17) Å3 and Z = 4. The structures of ebnerite (R1 = 0.0372 for 1168 Io > 2σI reflections) and epiebnerite (known from synthetic monoclinic NH4ZnPO4) are zeolite-like frameworks based upon corner-sharing linkages between alternating ZnO4 and PO4 tetrahedra with channels in the frameworks hosting the NH4 groups. The two structures are topologically distinct. Ebnerite belongs to the family of ‘stuffed derivatives’ of tridymite, whereas epiebnerite possesses an ABW-type zeolite structure.

The effect of phosphate on the formation of Fe oxides from Fe(II) salts is important because phosphate is a ubiquitous anion in natural environments. For this reason, the products formed by oxidation of phosphate-containing Fe(II)SO4 solutions neutralized with bicarbonate were characterized. The rate of oxidation of Fe(II) increased with increasing P/Fe atomic ratio to 0.2 in the initial solution. Goethite (α-FeOOH) or lepidocrocite (γ-FeOOH) or both were produced and identified by powder X-ray diffraction (XRD). The ratio between lepidocrocite and goethite increased with increasing P/Fe. In the 5–8.5 pH range, the formation of goethite predominated at P/Fe < 0.005, but only lepidocrocite was detected by XRD for P/Fe > 0.02. Thus, phosphate favors lepidocrocite formation because lepidocrocite has (1) a layered structure (like its precursor green rust), and (2) a structure less dense than that of goethite, thereby requiring less complete removal of the green-rust interlayer phosphate to form. The lepidocrocite crystals were platy, with prominent {010} faces and the thickness of the plates decreased with increasing P/Fe from >25 nm for P/Fe < 0.005 to <5 nm for P/Fe > 0.1. The solubility of lepidocrocite in acid oxalate was nearly complete for P/Fe > 0.03. The lepidocrocite contained occluded phosphate, i.e., phosphate that could not be desorbed by alkali treatment. The decrease in the b unit-cell length with increasing P/Fe suggests that lepidocrocite may contain structural P.

Competitive adsorption between glyphosate and phosphate on goethite was evaluated. The influence of background electrolyte on the adsorption of glyphosate and phosphate was also investigated by using 0.01 M KCl, 0.1 M KCl and 0.01 M CaCl2 as background electrolytes. Experiments showed that phosphate displaced adsorbed glyphosate from goethite, whereas glyphosate did not displace phosphate. Results also showed that the background electrolyte had a strong effect on phosphate adsorption, but little effect on glyphosate adsorption. Thus, there are differences between the adsorption of glyphosate and phosphate. The study also showed that 0.01 M KCl caused dispersion of goethite, resulting in inefficient filtering, and that phosphate precipitated as calcium phosphates in 0.01 M CaCl2 background electrolyte solutions. The results suggest that 0.1 M KCl is a more suitable background electrolyte to determine competitive adsorption processes involving glyphosate and phosphate.

Competitive adsorption between phosphate, tartrate and oxalate was studied on two hydroxy aluminum montmorillonite complexes (AlMt1.6 and AlMt6), which were prepared by adding a base to pH 5.5 to samples containing 1.6 and 6.0 mol Al per kg clay. The quantities of phosphate, tartrate and oxalate adsorbed were more closely related to the amount of OH-Al species coatings on the montmorillonite than to the surface area of the complexes. The adsorption capacity of phosphate was much greater than that of tartrate or oxalate for both samples. Adding molar amounts of oxalate and tartrate resulted in an oxalate/tartrate adsorption ratio (Rf) of ∼1. However, in the presence of phosphate, Rf values were <1.0, and the Rf values decreased with increasing amounts of added phosphate, indicating that tartrate competed with phosphate more effectively than oxalate. The presence of tartrate also reduced phosphate adsorption by the complexes. The efficiency of tartrate in reducing phosphate adsorption increased by increasing the initial tartrate/phosphate molar ratio and by adding tartrate 2 h before phosphate addition. Tartrate and oxalate added as a mixture in equimolar quantities were much more effective in inhibiting phosphate sorption than tartrate alone under the same organic ligand concentrations, probably because more sites with high affinity for both the organic ligands were occupied by tartrate and oxalate than by tartrate alone. The efficiency of tartrate alone, or combined with oxalate, in preventing phosphate adsorption was greater for the complex containing a lesser amount of OH-Al species coating the montmorillonite surfaces. This result may be attributable to a greater proportion of sites specific for organic ligands present on AlMt1.6 compared to AlMt6 complex.

Although phosphate sorption by goethite and other less-abundant Fe oxides strongly influences the concentration of this anion in the soil solution and aquatic environments, relatively little is known on the P-sorption characteristics of natural goethites. For this reason, we examined the P-sorption capacity and time course of P sorption of 10 goethite-rich soil, ferricrete and lake ore samples, in which the content and nature of mineral impurities were unlikely to affect P sorption significantly. Phosphate sorption could be adequately described by a modified Freundlich equation including a time term. The amount of P sorbed after 1 day of equilibration at a concentration of 1 mg P/liter ranged widely (0.36–2.04 /μmol P/m2). The total P sorbed after 75 days of equilibration varied less, in relative terms (1.62–3.18 μmol P/m2), i.e., a higher slow sorption tended to compensate for a lower initial (fast) sorption. Total sorbed P (X̄ = 2.62, SD = 0.52 μmol P/m2) was similar to the sorption capacity of synthetic goethites, suggesting a common sorption mechanism and the predominance of one type of crystal face, which, according to previous transmission electron microscope observations, might be the (110).

The extent of the slow reaction correlated to the ratio between micropore surface area and total surface area, as well as to oxalate-extractable Fe, which is an estimation of the ferrihydrite content. Ferrihydrite impurities might affect the slow reaction by contributing to the microporosity of some samples. Silicate adsorbed on the surface of the goethites was readily desorbed during phosphate sorption and did not significantly affect the extent of the slow sorption process.

We investigated the crystallization of ferrihydrite prepared by hydrolysis of Fe(NO3)3 solutions containing phosphate. Crystallization was studied at different pH (3–9), temperatures (298, 323, and 373 K), and initial P/Fe atomic ratios for periods to 730 d. Generally, crystallization was inhibited or only poorly crystallized lepidocrocite was formed at P/Fe > 2.5%. Phosphate favored the formation of hematite over goethite at all temperatures for most of the pH and P/Fe ranges investigated. This result is consistent with a model in which phosphate acts as a template for hematite formation, in analogy with other anions, such as oxalate. However, goethite was preferentially formed at alkaline pH and P/Fe > 1%, probably because high phosphate concentration resulted in a large increase in the negative charge of the ferrihydrite particles. This resulted in turn in less aggregation, a process that is known to precede dehydration to hematite. Phosphate greatly influenced the morphology of hematite and goethite. Hematite was often ellipsoidal or spindle-shaped. Twinned goethite crystals with a hematite core were formed at alkaline pH at P/Fe > 1%. Both hematite and goethite particles incorporated phosphate in an occluded form not desorbable by repeated alkali treatments.

Because layered Fe(II)Fe(III)-hydroxides (Green rusts, GRs) are anion exchangers, they represent potential orthophosphate sorbents in anoxic soils and sediments. To evaluate this possibility, two types of experiments with synthetic sulphate-interlayered GRs (GRSO4 = Fe2+4Fe3+2(OH)12SO4 ×H2O) were studied. First, sorption of phosphate in GRSO4 was followed by reacting suspensions of pure GRSO4 synthesized by oxidation of Fe(II) with an excess of Na2HPO4 (pH 9.3). Second the possible incorporation of phosphate in GR during formation by Fe(II)-induced reductive dissolution of phosphate-containing ferrihydrites was examined in systems containing an excess of Fe(II) (pH 7). With excess phosphate in solution, GRSO4 initially sorbed phosphate in the interlayer producing a basal layer spacing of 1.04 nm, but only ~50% of the interlayer sulphate was exchanged with phosphate. This GR slowly transformed to vivianite within months. In the Fe(II)-rich systems, reaction with synthetic ferrihydrites produced GRSO4 similar to that produced by air oxidation. Reaction of Fe(II) with phosphate-containing ferrihydrites initially produced amorphous greenish phosphate containing precipitates which, after 3–4 h, crystallized to GRSO4 and vivianite. In these solutions, stable phosphate-free GRSO4 can form since precipitation of vivianite produced low phosphate activity. Consequently, in both systems GR or amorphous greenish precipitates act as reactive intermediates, but vivianite is the stable end-product limiting phosphate concentration in solution. It is also inferred that Fe(OH)2 is an unlikely phosphate sorbent in mixed Fe(II)-Fe(III) systems because GR phases are more stable (less soluble) than Fe(OH)2.

The growing use of nano titanium dioxide (TiO2) in consumer and agricultural products has accelerated its introduction into terrestrial environments, where its impact has not been documented extensively. TiO2 toxicity arises primarily from its ability to photochemically generate reactive oxygen species (ROS), including hydrogen peroxide (H2O2). While common ligands in soil porewaters can either hinder or enhance the degradation of organic contaminants by TiO2, their effects on ROS production by TiO2 have not been understood clearly. The objective of this study was to assess the effect of phosphate (P) and nitrate on UV-irradiated anatase, nano-TiO2. Accordingly, H2O2-generation kinetics experiments were conducted in UV-irradiated TiO2 under environmentally relevant concentrations of the ligands (0, 50, 100, and 250 μM) and pH values (4.00 ± 0.02 and 8.00 ± 0.02) from 0–100 min. Under all conditions, H2O2 grew logarithmically and reached between 5.38 and 22.98 μM after 100 min. At pH 4.00 ± 0.02, H2O2 production was suppressed by P but not by nitrate. Conversely, at pH 8.00 ± 0.02, nitrate did not affect H2O2 concentration while P increased it. Non-specific, minimal adsorption of nitrate prevented interference with the photoreactivity of TiO2. Due to the pH-dependent behavior of suspended TiO2 and H2O2 degradation rates, specific adsorption of P on TiO2 impeded its ability to produce H2O2 photochemically at pH 4.00 ± 0.02 but amplified it at pH 8.00 ± 0.02.

Adsorption by synthetic 2-line ferrihydrite and hematite of glyphosate and phosphate, separately and together, was compared with adsorption results for goethite, gibbsite and two kaolinites in order to determine adsorption differences and similarities, in particular competition and phosphate preference, of these variable-charge minerals. Hematite rapidly adsorbed both compounds, while adsorption by ferrihydrite was slow, in particular of glyphosate, probably because of very slow diffusion of the bulky glyphosate molecules into interior sites in ferrihydrite particles. Accordingly, the Langmuir adsorption capacity of glyphosate (GAC) was considerably smaller (1.85 µmol m−2)than GAC for hematite (2.61 µmol m−2). The phosphate adsorption capacities (PAC) for ferrihydrite and hematite were more alike, 2.91 µmol m−2 and 2.85 µmol m−2, respectively. Differences between surface coordination (mono- or bidentate) may also contribute to the observed differences but conflicting information about the nature of the surface complexes makes this a difficult contributary factor to assess. The minerals were found to exhibit great variation in extent of competition and phosphate preference. Little competition and phosphate preference characterized hematite adsorption, while phosphate almost completely outcompeted glyphosate on goethite; ferrihydrite adsorption fell between these extremes. These differences may be attributed to different numbers of common (competitive) and specific (selective) adsorption sites on the three Fe oxides with a decreasing number of common sites in the order: goethite>>ferrihydrite>hematite, i.e. almost all goethite sites are common but with strong phosphate preference, while most hematite sites are specific for either glyphosate or phosphate. Alternatively, the result may be explained by adsorption in more planes, e.g. glyphosate adsorption onto the inner-Helmholtz-plane-adsorbed phosphate. For all six minerals compared, desorption of glyphosate following phosphate addition was found to be significantly correlated with the difference between the amounts of phosphate and glyphosate adsorbed indicating that this difference may be used as a competition index for predicting the influence of phosphate on glyphosate adsorption.

Organic ligands, such as EDTA, accelerate the dissolution of silicate and oxide minerals. In natural systems, oxyanions can compete with organic ligands for mineral surface sites thereby affecting ligand-promoted dissolution rates, either enhancing or inhibiting dissolution, depending upon pH. The influence of selenite, molybdate and phosphate on the EDTA-promoted dissolution of goethite has been examined and a mechanism proposed for the observed differences in dissolution rates over a pH range of 4–8. We propose that the surface complex formed by EDTA is the controlling factor for the observed dissolution rate, with mononuclear complexes accelerating dissolution compared to bi- or multinuclear complexes. Dissolution results from our experiments suggest that EDTA forms multinuclear complexes at pH values ⩾6 and mononuclear complexes at pH values <6. Dissolution results show that when the oxyanion and the EDTA are present in the system at concentrations nearly equalling the surface sites available for adsorption, the oxyanion reduces the adsorption of EDTA and inhibits dissolution. However, if the oxyanion is present at lower concentrations at pH values ⩾6, EDTA is adsorbed but the number of carboxylic groups that can bind to the surface is reduced causing the formation of mononuclear complexes. This shift to a weaker surface complex enhances the EDTA-promoted dissolution of goethite in the presence of the oxyanions compared to EDTA-promoted dissolution in their absence.

The phosphate adsorption properties of three clay samples, with kaolinite as the dominant mineral, from different deposits in the Ivory Coast have been investigated. The clays contain varying amounts of crystalline Fe oxides and kaolinite with structural Fe. All measurements were made in dilute suspension under controlled conditions of temperature, pH, ionic strength and saturating cation. Data have been fitted to Langmuir adsorption isotherms. Both P adsorption and surface area measurements have been made on samples before and after chemical removal of Fe oxides. The samples have large P adsorption capacities, which are not entirely explained by their large specific surface areas. The presence of Fe oxides makes a strong contribution to the surface area and enhances the adsorption capacities. There is little evidence that structural Fe makes a strong contribution to the enhanced P adsorption capacity.

The use of waste materials from mineral ore processing has much potential for immobilizing pollutants such as arsenic (As) in natural soils and waters. The purpose of the present study was to investigate red mud (RM, a finely textured bauxite-ore residue) as a sequestering agent for arsenate and phosphate, including characterization of the types of surface complexes formed. The mineralogical and structural changes occurring in RM were investigated after exchange with arsenate [As(V)-RM] and phosphate [P(V)-RM] anions at pH 4.0, 7.0, and 10.0. Eight different phases were present in the untreated red mud (RMnt), though 80 wt.% of the crystalline phase consisted of sodalite, hematite, gibbsite, and boehmite. The X-ray diffraction (XRD) data for As(V)-RM revealed an anion-promoted dissolution of the gibbsite, suggesting that this phase was the most active for As(V) sequestration. In addition, the lattice parameters of cancrinite were different in As(V)-RM at pH 7.0 and 10.0 from those in RMnt. The changes may be related to the incorporation of arsenate in the cancrinite cages. X-ray diffraction patterns of P(V)-RM at pH 4.0 and 7.0 revealed the dissolution of sodalite, hematite, and gibbsite, and the formation of a novel phase, berlinite [(α,β)AlPO4]. The new phases detected through XRD and thermal (TG/DTG) analysis in P(V)-RM probably originated through an initial phosphate-promoted dissolution of some RM phases, followed by a precipitation reaction between the phosphate and Al/Fe ions. The results obtained suggest that phosphate and arsenate, though with different reactivities, were strongly bound to some RM phases, such as gibbsite, cancrinite, sodalite, and hematite through mechanisms such as chemical sorption and coprecipitation reactions. The knowledge acquired will be helpful in selecting alternative materials such as red muds, which currently pose critical economic and environmental challenges related to their disposal, for the decontamination of soils and waters polluted with As.

Cryosols from Maritime Antarctica have been less studied than soils from continental areas of Antarctica. In this work X-ray diffraction, difference X-ray diffraction, differential thermal analysis, thermogravimetry, transmission electron microscopy/energy dispersive spectroscopy and selective chemical dissolution were used to characterize the clay fraction of basaltic, acid sulfate and ornithogenic Cryosols from ice-free areas of Admiralty Bay, King George Island. Non-crystalline phases are important soil components and reach >75% of the clay fraction for some ornithogenic soils. Randomly interstratified smectite-hydroxy-Al-interlayered smectite is the main clay mineral of basaltic soils. Kaolinite, chlorite and regularly interstratified illite-smectite predominate in acid sulfate soils. Jarosite is also an important component of the clay fraction in these soils. Crystalline Al and Fe phosphates occur in the clay at sites directly affected by penguin activity and the chemical characteristics of these ornithogenic sites are controlled by highly reactive, non-crystalline Al, Si, Fe and P phases. Chemical weathering is an active process in Cryosols in Maritime Antarctica and is enhanced by the presence of sulfides for some parent materials, and faunal activity.