Leaching and volatilization of N from urea, and precipitation and fixing of Zn by commercial fertilizers, has led to excessive costs for farmers and problems for the environment. Incorporating fertilizers in a porous material such as diatomite can prevent these losses by slowing the nutrient release. A new fertilizer formulation, based on the urea-zinc (UZn) complex in the eutectic solution of salt-urea was prepared. In the following, UZn was incorporated into diatomite and nano-diatomite by using hydroxypropyl methylcellulose (HPMC) as a binder. The treatments included the following: U: urea; UZn: urea-Zn; UZn-D: urea-Zn-diatomite; UZn-ND: urea-Zn-nano-diatomite; UZn-D-B: urea-Zn-diatomite-binder; and UZn-ND-B: urea-Zn-nano-diatomite-binder. The slow-release urea fertilizers (SRUFs) were characterized using FESEM/EDS, FTIR, CHN, XRD, DLS, and zeta potential techniques. Urea slow-release behavior, kinetics in water, and available Zn and N-forms leaching in the soil column were evaluated compared with conventional urea and zinc fertilizers. The pattern of release of urea in water was sigmoidal and after 12 h, only 20% of urea was released from fertilizers containing diatomite and HPMC. The NO3– release pattern in the soil started with a 12-day delay, and after that, the rate of NO3– leaching decreased by two to three times in the application of fertilizers containing HPMC compared with urea. The Zn concentration in the leachates of columns supplied with SRUFs was 35% less than for those supplied with ZnSO4. The results showed that the SRUFs make N and Zn available in the soil and but reduce the rate of their release.

Integrated intensities of the fundamental modes of vibrations of ammonium in heat-treated, NH4+-exchanged swelling minerals permits (1) a quantitative determination of the amount of tetrahedral substitutions of Si4+ by M3+ in dioctahedral smectites, and (2) an estimate of the degree of interlayer surface heterogeneity in trioctahedral minerals to be made. This is possible because NH4+ cations balancing the negative charge of tetrahedral sites that are not influenced by an excess positive charge of the octahedral layer have a symmetry lower (probably C3v) than the usual tetrahedral Td symmetry of NH4+. In C3v symmetry the ν1 band is infrared active whereas it is only Raman active in Td symmetry. Protons left after deammoniating dioctahedral smectites with tetrahedral substitutions form interlayer silanol groups, the stretching vibration of which give a band that is distinct from that of octahedral OH-stretching modes.

Naturally occurring ammonium illites have been discovered in black shales surrounding a stratiform base metal deposit in the DeLong Mountains, northern Alaska. Infrared spectra of the samples exhibit pronounced absorption at 1430 cm−1, the resonant-banding frequency for NH4+ coordinated in the illite interlayer. X-ray powder diffraction characteristics of the ammonium illites include an expanded d(001) spacing, with values as large as 10.16 Å, and ratios for I001/I003 and I002/I005 of about 2. Infrared analyses of physical mixtures of NH4Cl with a standard illite, and comparisons with synthetic ammonium micas indicate significant substitution (>50%) of NH4+ for K+ in the illite interlayer position. Nitrogen determinations on two ammonium illites after removal of carbonaceous matter gave values of 1.48 wt. % NH4+ and 1.44 wt. % NH4+. A survey of more than 150 different shale horizons indicates that the NH4+ content of the illites increases in proximity to the stratiform base metal mineralization.

Clinoptilolite from the Fort LaClede deposit in Sweetwater County, Wyoming, shows a moderate selectivity for NH4− over Na+ in aqueous solution. At 30°C, the standard free energy of this replacement reaction is −0.7 kcal/mole at an ionic strength of 0.05 M and −0.8 kcal/mole at 0.5 M. The Na+-NH4+ exchange is complete within 3 days in agitated solution and proceeds to the same extent from the clinoptilolite saturated with either cation.

The Ca2+-Na+ exchange also is complete within 3 days in agitated aqueous solution and proceeds to the same extent from either the calcium or the sodium form of the zeolite. Using test methods which take into account the slower equilibration of Ca2+-loaded clinoptilolite, the cation-exchange capacity is substantially the same over the full range of loading by Ca2+ and Na+. Ca2+ replaces Na+ with decreasing selectivity as Ca2+ loading increases to about 80% at 30°C (95% at 63°C), above which the selectivity reverses. The standard free energy of replacement of two Na+ ions by one Ca2+ ion in 0.05 M solution is −1.2 ± 0.2 kcal/mole at 63°C and −0.3 to −0.8 kcal/mole at 30°C.

The crystal growth of NH4-illite (NH4-I) from the hydrothermal system of Harghita Bãi (Eastern Carpathians) was deduced from the shapes of crystal thickness distributions (CTDs). The <2 mm and the <2-0.2 mm fractions of clay samples collected from the argillized andesite rocks consist of NH4-illite-smectite (I-S) interstratified structures (R1, R2, and R3-type ordering) with a variable smectite-layer content. The NH4-I-S (40-5% S) structures were identified underground in a hydrothermal breccia structure, whereas the K-I/NH4-I mixtures were found at the deepest level sampled (-110 m). The percentage of smectite interlayers generally decreases with increasing depth in the deposit. This decrease in smectite content is related to the increase in degree of fracturing in the breccia structure and corresponds to a general increase in mean illite crystal thickness. In order to determine the thickness distributions of NH4-I crystals (fundamental illite particles) which make up the NH4-I-S interstratified structures and the NH4-I/K-I mixtures, 27 samples were saturated with Li and aqueous solutions of PVP-10 to remove swelling and then were analyzed by X-ray diffraction. The profiles for the mean crystallite thickness (Tmean) and crystallite thickness distribution (CTD) of NH4-I crystallites were determined by the Bertaut-Warren-Averbach method using the MudMaster computer code. The Tmean of NH4-I from NH4-I-S samples ranges from 3.4 to 7.8 nm. The Tmean measured for the NH4-I/K-I mixture phase ranges from 7.8 nm to 11.7 nm (NH4-I) and from 12.1 to 24.7 nm (K-I).

The CTD shapes of NH4-I fundamental particles are asymptotic and lognormal, whereas illites from NH4-I/K-I mixtures have bimodal shapes related to the presence of two lognormal-like CTDs corresponding to NH4-I and K-I.

The crystal-growth mechanism for NH4-I samples was simulated using the Galoper code. Reaction pathways for NH4-I crystal nucleation and growth could be determined for each sample by plotting their CTD parameters on an α-ß2 diagram constructed using Galoper. This analysis shows that NH4-I crystals underwent simultaneous nucleation and growth, followed by surface-controlled growth without simultaneous nucleation.

Illite-smectite (I-S) minerals isolated from Upper Jurassic oil-source rock shales from Denmark and the North Sea have been investigated by X-ray diffraction, thermal analysis, infrared, Mössbauer, and solid-state nuclear magnetic resonance spectroscopies and chemical analysis. Detailed structures have been determined in order to reveal the diagenetic transformation mechanism in these shales. Generally, in oil-source rocks of sedimentary basins, oil generation takes place simultaneously with the diagenetic transformation of I-S. We demonstrate a link between the two reactions: NH3 released from kerogen during maximum oil generation is fixed as NH4+ in the NH4-bearing mica or tobelite layers formed from smectite or vermiculite layers in I-S, in a diagenetic interval which we name the ‘tobelitization window’. Due to this solid-state transformation, mixed-layer structures have been formed consisting of interstratified illite, tobelite, smectite and vermiculite layers (I-T-S-V) and having maximum ordering of illite + tobelite and smectite layers for R = 1. The tobelitization of smectite in I-S is probably typical for all oil-source rock shales.

The incorporation of boron (B) and nitrogen (N) into illite is the key demand-side process responsible for the diagenetic budget of these elements in sedimentary basins, with important implications for pore-water chemistry, natural-gas composition, and borehole geophysics. The purpose of the present study was to take advantage of recent advances in quantitative mineral analysis of sedimentary rocks which have opened new possibilities for investigating this particular process. In order to avoid complications with recycled (detrital) N and B, clays from pyroclastic horizons of sedimentary rocks (bentonites) were used. The B and N contents in illite-smectite were measured in samples from different sedimentary basins, representing a complete range of diagenetic alteration. The bulk-rock chemical measurements, performed on raw rock samples in order to avoid any loss of exchangeable B and N, were referred to the contents of illite-smectite clays and to the content of illite alone, both measured by a combination of XRD and chemistry-based techniques.

Both B and N (as NH4) are present in illite, so their contents in illite-smectite clay increase in a more or less linear manner with progressing illitization. Thus, during diagenesis, the illite-smectite clay is a net consumer of B and N from the pore water. The amount of N in individual illite layers decreases during diagenesis and the amount of B either decreases or remains stable. Bentonitic illite must acquire both B and N from outside of the bentonite bed. In one diagenetic cycle, bentonitic illite fixes up to 800–1000 ppm B and up to >1% N expressed as (NH4)2O, corresponding to >20% of the fixed cation sites.

Vermiculite is a common layered silicate clay mineral which has good adsorption and ion-exchange properties, and which is used to remove pollutants from groundwater. The adsorption by vermiculite from Heibei Province, China, of low-concentration ammonium in water was assessed here to evaluate the effects of adsorption time, particle size, adsorbent dose, pH, and temperature. Using Fourier-transform infrared spectroscopy, the concentration of NH4+ at 1430 cm−1 was evaluated after ammonium was adsorbed by vermiculite. Based on Langmuir-model analysis, the adsorption capacity of the Chinese vermiculite (in the particle-size range 0.025–0.075 mm) for ammonium was 18 mg/g after 3 h of equilibration. Optimal adsorption occurred at pH 6–7 and 60°C, which is different from that at high ammonium concentrations. Smaller particle-size fractions showed greater degrees of adsorption. Increase in Mg2+, K+, or Na+ concentrations influenced ammonium adsorption and, therefore, indicated that cation exchange was the mechanism for ammonium uptake from low-concentration solutions.

For purposes of mass-rearing fruit flies, nutrient intake through artificial diets is a challenge, artificial food content and processing should promote sufficient absorption and availability to ensure fly fitness. Bulking agents play an essential role in creating a quality diet, but its physical characteristics, such as particle size, may establish a better microenvironment for feeding and development. Currently, there is a lack of information about protein metabolism in mass-reared fruit flies. Therefore, we evaluated whether the particle size of the bulking agent affects the absorption and excretion of the proteins, as well as their effect on the life-history traits of Anastrepha obliqua. We determined the protein content of hemolymph and feces, as well as the presence of nitrogen end-products as indicators of their level of absorption in a diet elaborated with coarse and fine corn cob particles as a bulking agent. The bromatological composition showed that coarse particles increased the bioavailability and content of crude, digestible, and soluble protein for the diet and hemolymph protein of larvae alike. We found an inverse relationship between the protein content of the hemolymph and feces of the larvae. Ammonium was determined to be a product of the catabolism of proteins. Also, A. obliqua improved its development (yield and pupal weight) and fitness (adult emergence and flight ability) when larvae were reared on a coarse particle diet. In conclusion, a diet elaborated with a coarse bulking agent features increased protein bioavailability and nutritional quality, which, in turn, increases the life-history traits of A. obliqua.

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.

FTIR spectroscopy has been applied to NH4+-exchanged dioctahedral clay minerals to determine the molecular environment of NH4+ and to quantify N concentration. FTIR under vapourpressure control, coupled with heating and freezing treatments has shown that NH4+ ion symmetry varies with the nature of clay minerals. NH4+ has a perfect tetrahedral symmetry in hydrated or dehydrated smectites and belongs to the Td symmetry group. The NH4+-bending vibration is centred at 1450 and 1425 cm–1.

The Si4+-Al3+ substitution in dioctahedral clay minerals induces the loss of symmetry elements of the NH4+ tetrahedron which acquires a C2v symmetry. As a consequence, the Td –C2v transition can be used to characterize the smectite–illite transition. Quantification of NH4+ content per half unit cell is provided by nNH4 = k[NH4]/[OH] where [NH4]/[OH] is the band area ratio of the NH4+-bending vibration to the OH-stretching vibration. k = 1.1 for hydrated smectite, 0.9 for dehydrated smectite and 0.8 for illite or tobelite. The bending vibration of NH4+ is chosen for the calculation because it is not affected by superimposed contributions.

The evolution of the nitrogen and boron content of shales during diagenesis and anchimetamorphism was studied in the Carboniferous rocks of Donbas by means of the bulk rock chemical analysis and the XRD quantification of mineral composition, aided by CEC and EGME sorption measurements. The contributions of the organic-bound N and B were taken into account, based on the literature data (B) and on the relationship established in the course of this study (N). 28–98% of the total N and 80–100% of the total B are contained in the mineral fraction of the investigated shales.

The mineral nitrogen is located mostly in illite and accounts for 3 to 64% of the sites available for its fixation in 1Md illite. The fixation of N by illite seems to diminish in the course of diagenesis, but additional fixation occurs in newly formed 2M1 illite during the anchimetamorphic stage. The volume of N contained in illite in most samples greatly surpasses the N available locally from the organic matter contained in shale. Modelling indicates that the measured level of N for K substitution in illite corresponds to the capture in 30 vol.% of shale of all N released in a basin containing 5 vol.% of coal.

Boron is held predominantly by the 1Md fraction (illite+smectite). During diagenesis boron is redistributed into the 1Md illite, and during anchimetamorphism it is released from the 1Md illite and incorporated into new 2M1 illite. No indication of the net enrichment of pore water in B due to the clay alteration process was found.

The percolation of water through waste landfill sites produces leachates with large amounts of pollutants. Clay barriers are often used to limit soil and underground water pollution. A better understanding of the interaction between ammonium smectite and carboxylic acids would contribute significantly to our understanding of such systems. The SWy-2 (Wyoming smectite) was exchanged with NH4+ and then batched with carboxylic acids (acetic, formic, chloroacetic and oxalic) in concentrations between 0.01 M and 1 M. The solid phases obtained were analysed chemically and characterized by infrared absorption spectroscopy (IR) and powder X-ray diffraction (XRD). Ionic chromatography was used for the quantitative measurement of ammonium ions in the solution after the interaction. For the four acids, the interaction was characterized by a cationic exchange of NH4+ to H3O+. A partial exchange to Al3+ due to a partial dissolution of the sample in strong acidic medium was observed with chloroacetic and oxalic acids for which adsorption of molecules on the clay sample occurs, mainly through H-bonding with the cation. Moreover, the intercalation of oxalic acid in the interlayer space was highlighted.

Ammonium analyses of representative rocks from the Rosses granite complex (Ireland) and their constituent mineral show that any variation of magmatic origin has been completely obscured by pervasive hydrothermal alteration. The altered rocks are strongly enriched in the ammonium ion, most of which is held by chloritized biotite and sericitized plagioclase. The present ammonium content of the Rosses granites averages 13 ppm, but the original ammonium content of the magmas is estimated to have been less than 5 ppm. Potassium feldspars may preserve a better record of the original magmatic ammonium content than the whole rocks or the biotites.

The ammonium content of pegmatites, aplites and granites from Alijó-Sanfins, northern Portugal, averages 162, 109 and 159 ppm respectively. There is no systematic difference in the NH4/K ratio between these rocks, and the variation in their ammonium content is mainly due to variations in the amount of potassium minerals they contain. The K-feldspars have higher NH4+ contents than the muscovites, but lower NH4/K ratios. The preference of NH4+ for micas rather than feldspars is not as great as that shown by rubidium. The ammonium content of pegmatites in general is highly variable, and is largely determined by the nature of the granites with which they are associated.

The new mineral therasiaite, ideally (NH4)3KNa2Fe2+Fe3+(SO4)3Cl5, was found in a mediumtemperature (∼250°C) intracrater active fumarole at La Fossa crater, Vulcano, Aeolian Islands, Sicily, Italy. It occurs on a pyroclastic breccia as brown to dark brown equant to short prismatic crystals up to 0.1 mm in length, in association with salammoniac, kremersite and adranosite. The mineral is monoclinic, space group: Cc (no. 9) with a = 18.284(4), b = 12.073(2), c = 9.535(2) Å, β = 108.10(3)°, V = 2000.6(7) Å3 and Z = 4. The six strongest reflections in the X-ray powder diffraction pattern are: [dobs in Å(I)(hkl)] 2.812(100)(23), 2.664(77)(13), 3.297(28)(33), 3.208(14)(2), 3.008(12)(040), 2.942(11)(331). The empirical formula (based on 17 anions per formula unit (p.f.u.)) is (NH4)2.68K1.32Na2.04Fe1.76Al0.12Mn0.12S2.98O11.95Cl5.05. The measured density is 2.41(1) g cm−3, dcalc = 2.395 g cm−3. The mineral is biaxial (−) with α= 1.585(3) β = 1.615(3) and γ = 1.630(3) (white light). Using single-crystal diffraction data, the structure was refined to a final R(F) = 0.0240 for 5574 independent observed reflections [I > 2σ(I)]. The structure of therasiaite displays a novel topology and contains two independent, distorted octahedral Fe sites, with the Fe atoms in oxidation state 3+ and 2+, respectively, each surrounded by three Cl atoms and three oxygens of the sulfate ions. The Fe octahedra and the three independent sulfate anions are connected to form chains running along [001]. Voids between the chains are occupied by three independent ammonium ions (partially replaced by K+), one K+ and two Na+ ions. The formula resulting from the structure refinement is [(NH4)2.25K0.75]KNa2Fe2(SO4)3Cl5.

Ammoniovoltaite, (NH4)2Fe2+5Fe3+3Al(SO4)12(H2O)18, is a new voltaite-group mineral. The mineral was discovered at the Severo-Kambalny (North-Kambalny) geothermal field, Kambalny volcanic ridge, Southern Kamchatka, Russia. Ammoniovoltaite forms at ~100°C around geothermal gas/steam vents in association with alunogen, tschermigite and pyrite. Crystals of ammoniovoltaite have euhedral habit, are up to 50 µm in size and grow on alunogen plates. Ammoniovoltaite is black with vitreous lustre, opaque, brittle and water-soluble. Neither cleavage nor parting is found, the fracture is conchoidal. The mineral is isotropic, with the refractive index n = 1.602(2) (589 nm). Infrared spectra contain an absorption band at 1433 cm–1 distinctive for the ammonium ion. The chemical composition is (iron content is given in accordance with Mössbauer data, H2O calculated from a crystal-structure refinement, wt.%): FeO 13.26, Fe2O3 11.58, MgO 2.33, ZnO 0.04, Al2O3 2.74, SO3 47.46, K2O 0.19, CaO 0.11, (NH4)2O 2.96, H2O 16.03, total 96.70. The empirical formula based on S = 12 atoms per formula unit is [(NH4)1.88K0.08Ca0.04]Σ2.00(Fe2+3.74Mg1.17Fe3+0.05Zn0.01)Σ4.97(Fe3+2.89Al0.09)Σ2.98Al1.00(SO4)12.00(H2O)18.00. The crystal structure has been refined to R1 = 0.031 and 0.030 on the basis of 1217 and 1462 unique reflections with I >2σ(I) collected at 100 K and room temperature, respectively. Ammoniovoltaite is the ammonium analogue of voltaite. The mineral is cubic, Fd$\bar{3}$c, a = 27.250(1) Å and V = 20234(3) Å3 (at 100 K); and a = 27.322(1) Å and V = 20396(3) Å3 (at RT), with Z = 16. The strongest lines of the powder X-ray diffraction pattern [d, Å (I, %) (hkl)] are: 9.67 (74) (022), 7.90 (56) (222), 5.58 (84) (422), 3.560 (100) (731), 3.418 (100) (008) and 2.8660 (37) (931). A brief review of ammonium minerals from various volcanically active geological environments is given.