The boiling 5-M-NaOH treatment was found to aid in the identification and characterization of goethite and hematite by effectively concentrating the two Fe oxides in kaolinitic-gibbsitic soil clays. No transformations of goethite to hematite or hematite to goethite were detected, but poorly crystalline, highly Al-substituted goethite was found to dissolve and recrystallize into a more well-crystalline, less Al-substituted goethite in samples low in Si. The Si released from kaolinite was sufficient to block goethite dissolution and recrystallization in kaolinitic samples, but noncrystalline silica had to be added to samples rich in gibbsite to minimize this effect.

South Africa is a net importer of fertilizer products, importing all of its potassium, as well as 60–70% of its nitrogen requirements. Thus, domestic prices are impacted significantly by international prices, shipping costs, and exchange rates. Producing these fertilizers locally would be far more economical. Phlogopite, a rich source of potassium, is discarded in large quantities during mining operations; the objective of the present study, therefore, was to determine the acid-leaching characteristics and behavior of phlogopite as a means of releasing potassium. Phlogopite samples were leached with nitric acid (source of nitrogen for fertilizers) at various concentrations, temperatures, and reaction times. The feed phlogopite and leached residue samples corresponding to conversions of 14% (LP1), 44% (LP2), and 100% (LP3) were collected and analyzed using X-ray fluorescence spectroscopy (XRF), X-ray diffractometry (XRD), attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR), Brunauer–Emmett–Teller surface area and porosity analysis (BET), thermogravimetric analysis (TGA), and field emission gun-scanning electron microscopy (FEG-SEM). The feed phlogopite was highly crystalline. The absence of defects in the lattice meant that the motion of H+ atoms penetrating into the lattice was restricted, suggesting internal diffusion-controlled leaching. Furthermore, results obtained from the various analytical techniques corroborated each other in terms of the release of cations during leaching. All leaching experiments were conducted batchwise, in a closed system. The gravimetric data from the experiments were used to identify a suitable model which predicts accurately the leaching behavior. The reaction was found to be internal diffusion-controlled, and the D1 model, which represents one-dimensional diffusion through a flat plate, predicts the leaching behavior most accurately. The observed activation energies (Ea) and pre-exponential constants (k0) varied with initial nitric acid concentration ([H+]0).

Gray-black kaolinitic claystones of industrial value are abundant in Upper Carboniferous–Lower Permian coal-bearing strata of the Datong Coalfield of northern China. The main types are tonsteins and cryptocrystalline kaolinitic claystones, distinguished by the thinness and greater crystallinity of kaolinite in the former and by the presence of detrital illite and authigenic pyrite in the latter. In order to determine the formation history of these two types of kaolinitic claystone, the petrological, mineralogical, and geochemical characteristics of borehole samples from the Upper Carboniferous Taiyuan Formation which comprises siliciclastics and coal seams deposited in a coastal environment, were analyzed. In addition to kaolinite, the claystones contain subordinate illite, quartz, pyrite, anatase, feldspar, siderite, and calcite. The tonsteins and cryptocrystalline kaolinitic claystones have different sources, as shown by petrographic data, elemental ratios, and chondrite-normalized rare earth element (REE) patterns. The volcanic origin of the tonsteins is revealed by an abundance of volcanic quartz and vitric fragments as well as Al2O3/TiO2, Zr/Hf, and Nb/Ta ratios consistent with a felsic igneous source. Their REE fraction was derived from feldspars or micas of the parent rocks, and the fraction decreased with alteration of these minerals to kaolinite. The sedimentary origin of the cryptocrystalline kaolinitic claystones is revealed by an abundance of detrital quartz and illite grains derived from either granite or sedimentary upper crust, and by the total REE contents (ΣREE) and (La/Yb)N values which are consistent with granitic material. Their depositional environment was in a transitional (coastal) setting (as shown by intermediate Sr/Ba ratios) hosting an open acidic hydrologic system (as shown by high chemical index of alteration (CIA) values indicative of intensive chemical weathering) that was suboxic to anoxic (as shown by high U/Th ratios and trace-metal enrichment factors). The present chemistry of these claystones was thus controlled by a combination of parent rock type and diagenetic alteration.

This study reports a leaching process along with a novel physical pretreatment technique to remove iron impurities from kaolin using oxalic acid. A detailed examination of the physical properties of the minerals confirmed that almost none of the leaching-resistant iron oxides, specifically hematite, was completely interlocked with the clay minerals. Accordingly, a pre-agitating technique followed by high-pressure washing of the sample on a 600 μm sieve were applied. In this method, by discarding up to 20% of the raw material, >54% of the total iron content of the raw kaolin was removed, and the iron content was reduced from 9.75% in the initial sample to <6.00% in the passing fraction. Application of this pretreatment method rendered the leaching process successful at 97°C using 0.3 M oxalic acid solutions for 1 h under atmospheric pressure. Compared to the leaching of the raw material without pretreatment, which consumed at least 0.5 M oxalic acid over a minimum period of 2 h, the method used was very cost-effective and favourable, reducing the iron content of the product to <1% and producing high-quality kaolin.

Reliable radiocarbon (14C) ages of foraminifera are a prerequisite to generate robust high-resolution age-depth models or to obtain precise understanding of past carbon cycle dynamics. With the advance of small-scale 14C measurements, instrumental precision and levels of contamination (extraneous carbon introduced during sample pretreatment or analysis) became increasingly important to consider. To reduce the effect of carbon contamination, an attempt can be made to remove it by leaching the surface with weak acids. Alternatively, mathematical corrections (e.g., subtraction) based on processing blanks can be applied. We report on 14C analyses of monospecific foraminifera samples compared between different blank corrections (correction against 14C-free CO2, IAEA-C1 and foraminifera) and sample treatments (i) to examine whether chemical pretreatment and mathematical blank subtraction are comparable, and (ii) to determine limitations hindering reliable 14C dating with ever smaller sample sizes. The data show that chemical pretreatment of foraminifera corrected against IAEA-C1 does remove surface contamination and that the same effect can be achieved for untreated samples that were mathematically corrected for blank values determined from sample size-matched 14C-free foraminifera. Leaching only has a beneficial effect on 14C data for older samples, where the isotopic difference between untreated and chemically pretreated samples exceeds the analytical precision.

Vegetables are widely cultivated in high rainfall and mountainous regions in Sri Lanka with poor soil conservation practices. Accumulation of essential mineral and toxic trace elements in the soils and widely cultivated vegetables of this region are poorly understood. One hundred soil and vegetable (i.e. cabbage, carrot and potato) samples were collected at the time of harvest and analysed for element concentrations. Soils contained high concentrations of essential mineral (N, P, K, Cu, Zn and Mn) and toxic trace elements (As, Cd and Pb). When comparing edible parts, cabbage contained the highest concentrations of mineral and toxic trace elements, and potato contained the lowest. Irrespective of the crop, edible parts contained high concentrations of N, P, K (14–35, 2–6, 15–24 g/kg, respectively), and Cu, Zn, Mn (2.5–6.7, 11–30, 8–147 mg/kg, respectively). Vegetables also contained As, Cd and Pb (0.04–1, 0.02–0.15, 0.02–0.26 mg/kg, respectively), but did not exceed the maximum permissible limits. Irrespective of the crop, 36–64 kg N, 6–11 kg P and 35–45 kg K per ha were removed with the harvest. According to the current rate of vegetable consumption by Sri Lankans (i.e. 240 g fresh weight (FW) per day), per capita consumption of 0.05–0.2 mg Cu, 0.45–0.65 mg Zn and 0.5–2 mg Mn per day through these vegetables was observed, i.e. 5–23% Cu, 7.5–11% Zn and 22–87% Mn of the recommended daily intake. Vegetables grown in the region served as a key source of essential mineral elements. However, agronomic mitigation strategies are needed to improve soil health and sustainability of these cropping systems.

More than 80% of soybean [Glycine max (L.) Merr.] in Brazil is cultivated in no-till systems, and although cover crops benefit the soil, they may reduce the amount of residual herbicides reaching the soil, thereby decreasing herbicide efficacy. The objective of this study was to evaluate sulfentrazone applied alone, sequentially after glyphosate, and in a tank mixture with glyphosate before planting no-till soybean. Experiments were performed in two cover crop systems: (1) pearl millet [Pennisetum glaucum (L.) R. Br.] and (2) forage sorghum [Sorghum bicolor (L.) Moench ssp. bicolor]. The treatments tested were: glyphosate (720 g ae ha−1) at 20 d before sowing (DBS) followed by sulfentrazone (600 g ai ha−1) at 10 DBS; glyphosate + sulfentrazone (720 g ae ha−1 + 600 g ai ha−1) for cover crop desiccation at 10 DBS; and sulfentrazone alone at 10 DBS without a cover crop. The accumulation of straw was 31% greater using sorghum rather than pearl millet. In the sorghum system, the concentration of sulfentrazone at 0 to 10 cm was 57% less with sequential application and 92% less with the tank mixture compared with the treatment without cover crop straw at 1 d after application (DAA). The same occurred in the pearl millet system, where the reduction was 33% and 80% for the sequential application and tank mixture, respectively. The absence of a cover crop resulted in greater sulfentrazone concentrations in the top layer of the soil when compared with the sequential application or tank mixture. At 31 and 53 DAA, the concentration of sulfentrazone at 10 to 20 and 20 to 40 cm did not differ among treatments. Precipitation of 90 mm was enough to remove the herbicide from the cover crop straw at 31 DAA when using sequential application. An additional 90-mm precipitation was necessary to promote the same result when using the tank mixture.

The radiocarbon (14C) content of irradiated graphite is the most important problem for the management of Spanish irradiated graphite (Vandellós I NPP) as L&ILW, due to this material exceeding the maximum 14C inventory for the C.A. El Cabril repository. Therefore, the encapsulation of graphite in an impermeable matrix and making an appropriate waste form are indicated as potential management options to be studied. The conversion of the graphite to a long-term stable glass matrix, called IGM (impermeable graphite matrix), uses a long-term stable inorganic binder which additionally encloses the graphite pore system. The world’s first IGM samples made with irradiated graphite have been manufactured in CIEMAT facilities. The durability of the matrix is investigated in leaching experiments in deionized water and granitic bentonite water. The results show that ∼0.05% of 14C is leached. A species of organic carbon was found as formate and oxalate (∼10–1 mg/L). CO was detected as volatile specie in both media in the first leaching steps; for deionized water (∼3.101 mg/L) and in granitic bentonite water (ranging 1.101–3.101 mg/L). These low values demonstrated the durability of the IGM glass matrix for final disposal.

Radiocarbon (14C or carbon-14, half-life 5730 yr) is a key radionuclide in the assessment of the safety of a geological disposal facility (GDF) for radioactive waste. In particular, the radiological impact of gaseous carbon-14 bearing species has been recognized as a potential issue. Irradiated steels are one of the main sources of carbon-14 in the United Kingdom’s radioactive waste inventory. However, there is considerable uncertainty about the chemical form(s) in which the carbon-14 will be released. The objective of the work was to measure the rate and speciation of carbon-14 release from irradiated 316L(N) stainless steel on leaching under high-pH anoxic conditions, representative of a cement-based near field for low-heat generating wastes. Periodic measurements of carbon-14 releases to both the gas phase and to solution were made in duplicate experiments over a period of up to 417 days. An initial fast release of carbon-14 from the surface of the steel is observed during the first week of leaching, followed by a drop in the rate of release at longer times. Carbon-14 is released primarily to the solution phase with differing fractions released to the gas phase in the two experiments: about 1% of the total release in one and 6% in the other. The predominant dissolved carbon-14 releases are in inorganic form (as 14C-carbonate) but also include organic species. The predominant gas-phase species are hydrocarbons with a smaller fraction of 14CO (which may include some volatile oxygen-containing carbon-species). The experiments are continuing, with final sampling and termination planned after leaching for a total of two years.

The understanding of the 14C behavior in waste packages could lead, in the Spanish context, to a revision of the management strategies for radioactive waste and a revaluation of the near surface repository devoted to the disposal of waste containing this radionuclide in high concentrations. To achieve this objective, and in the context of the EU project Carbon-14 Source Term (CAST), the authors of the work presented in this paper have performed leaching experiments with irradiated graphite considering two different scenarios. One, in which the leaching solution simulates some of the expected conditions in a repository where a granite/bentonite mixture has been used as backfill material, and the other, using deionized water as a high efficiency chemical removal agent and for comparison purposes. The analytical approach to measure the release rate and speciation of 14C from irradiated graphite samples in the aqueous and gaseous phase is also described. The main results obtained shows that, after 359 days of leaching, no 14C activity was detected above the detection limits, and only leaching rates regarding beta-gamma emitters were observed: 2×10–6 cm/day for 137Cs and 1×10–5 cm/day for 60Co in granite/bentonite water media and 4×10–6 cm/day for 137Cs in pure water.

This paper presents the results of acidic leaching of kaolinite from the flotation waste of the RTB Bor copper mine, Serbia. The kaolinitic concentrate from the flotation waste contains 32% Al2O3. Kinetic investigations were conducted on the leaching of kaolinite roasted at 750°C for 60 min under air using H2SO4, HNO3 and HCl. Activation energies for the process were 74, 63 and 63.2 kJ mol–1 for sulphuric, nitric and hydrochloric acids, respectively. The kinetic function D3: [1 – (1 – α)1/3]2 = kt was chosen to describe the fractional conversion dependence on time and temperature. This enabled effective management of the leaching process to be carried out.

A china clay sample from Jharkhand State, India, containing 65.0 wt.% SiO2, 22.7% Al2O3, 1.77% Fe2O3 and 9.10% LOI was subjected to physical beneficiation and acid leaching studies to improve its quality. The clay was characterized by optical microscopy, XRD, and wet chemical analysis methods. Quartz and goethite are the two major impurities. High intensity magnetic separation removed only 10% of the total iron. Experiments with oxalic acid were carried out to establish the leaching kinetics of iron and the effects of acid concentration, time and temperature on iron leaching were also examined. The study demonstrated that ∼90% of total iron could be removed using 5% oxalic acid. The dissolution of iron from clay is best described by diffusion of ions through the product layer of constant size spherical particles. The activation energy of the leaching process over the temperature range was calculated to be 51.14 kJ/mol.

Lead, zinc and arsenic mobilization/attenuation processes during interactions between smelter slag and water show differences depending on the origin of the slag. The studied samples, waste from ore and car-battery processing, were submitted to long-term (365 days) batch leaching at two different initial pH values. The leachate analyses were input to the EQ3NR speciation-solubility code to speciate the solutions and determine the degree of saturation with respect to different phases, and a mineralogical investigation was made of the newly formed phases. An ‘oxidizing’ scenario can be proposed for slag waste disposal, considering that cerussite (PbCO3) at pH >6 becomes a major solubility-controlling phase for Pb, and newly formed hydrous ferric oxides (HFO – common secondary phases under oxidizing conditions) efficiently adsorb As. No efficient scavenging mechanism was found for Zn, which was progressively leached from the slag and in particular from the ore-processing slag. Quenched glass-rich slag from old car-battery processing was found to release significant amounts of Pb, especially in acidic environments. Neither slag would therefore be suitable for recycling for civil engineering purposes. Conversely, extremely low releases of Pb, Zn and As were observed for recent car-battery processing slag, which could therefore be considered for road construction.

Most countries intend to dispose of their high-level radioactive wastes by converting them into a solidified wasteform which is to be buried within the earth. SYNROC is a titanate ceramic wasteform which has been designed for this purpose on the basis of geochemical principles. It comprises essentially rutile TiO2, ‘hollandite’ Ba(Al,Ti)Ti6O16, zirconolite CaZrTi2O7, and perovskite CaTiO3. The latter three phases have the capacity to accept the great majority of radioactive elements occurring in high-level wastes into their crystal lattice sites. These minerals (or their close relatives) also occur in nature, where they have demonstrated their capacity to survive for many millions of years in a wide range of geological environments. The properties of SYNROC and the crystal chemistry of its constituent minerals are reviewed in some detail and current formulations of SYNROC are summarized. A notable property of SYNROC it its extremely high resistance to leaching by groundwaters, particularly above 100°C. In addition, it can be shown that the capacity of SYNROC minerals to immobilize high-level waste elements is not markedly impaired by high levels of radiation damage. Current investigations are focused on developing a satisfactory production technology for SYNROC and progress towards this objective is described. The high leach resistance of SYNROC at elevated temperatures increases the range of geological environments in which the waste may be finally interred; in particular, SYNROC is well adapted for disposal in deep drill-holes, both in continental and marine environments. The fact that SYNROC is comprised of minerals which have demonstrated long-term geological stability is significant in establishing public confidence in the ability of the nuclear industry to immobilize high-level wastes for the very long periods required.

Some of the illustrative concepts for the disposal of intermediate-level waste in a geological disposal facility in the UK employ a cementitious backfill around the waste packages. The concept for higher strength rocks would use a highly alkaline backfill composed of Portland cement (now known as CEM I), hydrated lime and limestone flour, referred to as Nirex reference vault backfill (NRVB).

This paper reports a study of the extensive leaching of cured NRVB in a range of generic leachant compositions (deionized water, 0.1 M and 1 M NaCl solutions) under flow-through conditions using a flexible wall permeameter. The experiments were designed to run for up to two years and to pass at least 1000 volumes of leachant (defined as the cumulative leachate volume produced/NRVB solid specimen volume) through the NRVB samples. Results for the pH evolution profiles of the leachates and the microstructural analysis of the unleached and leached samples are presented.

The reactivity of primary Pb metallurgical slags in high-molecular-weight (HMW) organic solutions has been studied in order to determine the processes of release and attenuation of metal and metalloid contaminants (Pb, Zn, Cu, As) in 'soil-like' environments. Slag was submitted to a 112-day batch leaching experiment in Suwannee River fulvic acid solution and peat water (∼50 mg DOC l–1). The leaching was coupled with investigation of the secondary phases (SEM/EDS, Raman microspectrometry) and thermodynamic speciation-solubility modelling using MINTEQA2. Metals and As are released in large amounts during the early stage of the experiment, followed by a decrease in the concentrations in the leachate as a result of adsorption on secondary (hydrous) ferric oxides (HFO/FO), predicted by MINTEQA2 calculations and confirmed on the leached slag surface by SEM and Raman spectrometry. Compared to other contaminants, Zn exhibits more pronounced mobility and is adsorbed on HFO/FO only at pH >7. Such a scavenging process may be predominant during the long-term interaction of slag with an HMW organic solution of real soil. As a result, the soil cover and subsequent re-vegetation of slag dumps may be considered as a possible scenario for slag management.

Extreme silver enrichment at the surface of the complex sulphide, tennantite (ideal formula: Cu12As4S13), occurs following exposure to alkaline solutions, and involves the development of an Ag-rich sulphide surface species. The tennantite has a low bulk Ag content of 0.3 at.%, and a percentage surface enrichment of Ag is thirty-six times that of the bulk. The techniques of X-ray photoelectron spectroscopy (XPS) and reflection extended X-ray absorption fine structure spectroscopy show the new phase to be a Ag sulphide species compositionally similar to cupriferous proustite ((Cu,Ag)3AsS3). Solution experiments and XPS depth profiling show that the surface is most depleted in Cu and Zn, and enriched in Ag compared to the bulk tennantite. Selective dissolution and reprecipitation at the tennantite surface cannot explain the enrichment of Ag relative to the bulk. Migration must have occurred and could have been driven by the leaching out of Cu which produces a metal-depleted surface, coupled to the relative incompatibility of Ag in the tennantite lattice. To account for the extreme enrichment at the surface, Ag must have diffused from depths of up to 9 nm, probably via structural weaknesses and vacancies in the tennantite lattice.

CSIRO Minerals is developing new technologies and approaches for the in situ recovery (ISR) of valuable metals. ISR provides opportunities to process small and/or deep deposits and could create additional revenue for conventional uneconomic mines. Unlike for conventional processing, no standard methodology exists for characterizing sample suitability for ISR. The authors are developing a workflow to understand sample and deposit amenability to ISR processing. A South Australian low-grade iron-oxide-copper-gold sulphide ore was studied. A total of 37 drill cores samples were obtained from the ore sample for detailed mineralogical and leaching characterization. A range of characterization techniques including chemical analysis, X-ray fluorescence mapping, quantitative evaluation of minerals by scanning electron microscopy, computed tomography scanning, and bulk- and micro-X-ray diffraction analyses were applied to understand the ore mineralogy. Leaching tests at 50 °C were performed on selected samples to understanding their leaching behaviour. Mineralogical characterization found that copper was present mostly as discrete secondary copper sulphides distributed in various areas and at various specimen depths, which, in theory should be readily available for leaching, provided sufficient solution access exists. Leaching results showed steady copper recovery under the conditions tested. This study provides insight into understanding the suitability of an ore for ISR processing.