Phosphate amendment of metalliferous waste rocks, Century Pb-Zn mine, Australia: Laboratory and field trials

The aim of the study was to determine whether the application of phosphate compounds (phosphorite rock, phosphate fertilizer) to polyminerallic waste rocks can inhibit sulfide oxidation and metal mobility (Cu, Pb, Zn, Cd, Ni, Mn, Mg). Waste rocks comprised sulfidic carbonaceous shales and were sourced from the Century Pb-Zn mine, NW Queensland, Australia. The acid producing, Pb-Zn rich rocks consisted of major quartz, muscovite/illite, dolomite, siderite and kaolinite as well as smaller amounts of sulfide minerals (e.g. galena, sphalerite, pyrite). Laboratory leach experiments were conducted on finely granulated phosphate-treated waste rocks (>2 to <30 mm) over 13 weeks, whereas phosphate amendment of coarsely granulated waste rocks (sand to boulder size) was investigated using heap leach piles at the mine site over an 11 months period. Results of the laboratory experiments demonstrate that the treatment of finely granulated waste rocks with phosphorite rock produced leachates with near-neutral pH values due to calcite dissolution. This in turn did not allow the leaching of apatite, formation of secondary phosphate phases and phosphate stabilization to occur. Metal mobility in these amended wastes was restricted by the dissolution of calcite and the resultant near-neutral pH conditions. By contrast, the application of the water-soluble phosphate fertilizer MKP (KH₂PO₄) to polyminerallic sulfidic waste rocks during the short-term laboratory experiments led to the formation of phosphate coatings and precipitates and inhibited acid and metal release (Cd, Mn, Ni, Pb, Zn). At least in the short term, the application of phosphate fertilizers proved to be an effective method. However, results of the long-term field trials demonstrate that coarsely granulated waste rocks were not coated by secondary phosphate phases and that amendment by phosphorite rock or superphosphate fertilizer did not improve leachate quality compared to the unamended waste. Thus, phosphate stabilization appears ineffective in suppressing oxidation of sulfides in coarsely granulated mine wastes.     

An occurrence of cadmiferous phosphorite soil concretions in Jamaica

Bauxite exploration drilling revealed the presence of phosphate minerals through the chemical and XRD analysis of recovered drill hole samples at Spitzbergen, in Manchester Parish, Jamaica. A subsequent pit led to the discovery of phosphorite concretions composed of hard competent masses of finely crystalline fluorapatite, with some minor crandallite. The phosphorite contains anomalously high levels of Zn (>5000 mg kg⁻¹), Cd (>1.1%), Ag (>20 mg kg⁻¹), Be (>80 mg kg⁻¹) and, to a lesser extent, U. Textural and geochemical evidence indicates that the phosphorite concretions were most likely formed by the replacement of limestone by secondary deposition proximal to fossil guano deposits, postulated to be Late Miocene or Pliocene sea-bird colonies. Mechanical dispersion of the phosphorite concretions through karst weathering processes has led to their wider spatial distribution than the original guano deposits. Subsequent weathering of the concretions and the admixture of their decomposition products into the bauxitic and Terra Rossa soils is postulated to be the cause of the widespread anomalous levels of Zn, Cd and Be in these soils in central Jamaica, and the elevated levels of P in the bauxite.     

荆襄地区陡山沱组磷块岩的类型、成因和沉积环境

本文根据野外调查和室内初步研究成果并结合有关地质资料,分析、讨论了荆襄陡山沱组含磷岩系的磷块岩类型、成因和沉积环境。通过分析可知,组成磷块岩的磷灰石有不同的形成方式;磷块岩沉积在海退旋回中粘土和硅质沉积向碳酸盐沉积的转变阶段;磷块岩矿床形成在陆缘海内与深水有联系的浅水地带。 矿区含磷岩系特征综合于图1。     

Trace fossils of a cyclic chalk-marl succession; the upper Maastrichtian Rørdal Member, Denmark

Trace fossils from an upper Maastrichtian cyclic chalk-marl succession, the Rørdal Member, exposed in the Rørdal quarry, Denmark, are analysed in order to test whether the changes in substrate lithology exerted any control over the ichnodiversity, tiering complexity, and density of the infauna. The cyclicity is interpreted as caused by orbital changes within the Milankovitch frequency band. The carbonate content varies between 71 and 82 weight% in the marl and 82-92 weight% in the chalk beds. The material is based on 19 samples collected from six chalk and marl beds. The investigated bedding-normal sample surfaces vary in area between 29 and 155 cm². Eight ichnogenera and two undetermined ichnogenera are recognised. The member is characterised by three ichnofabrics (A, B and C). The ichnofabric analysis is based on texture and internal structure of the sediments resulting from bioturbation. Ichnofabric A is found only in chalk samples and shows a poor preservation of trace fossils, whereas ichnofabric C is found in a few chalk and all marl samples and comprises a very dense, diverse and well preserved ichnofauna representing a high tiering complexity. Ichnofabric B represents an intermediate situation between ichnofabrics A and C and occurs in chalk samples immediately adjacent to marl beds. The observed changes in ichnofabrics between chalk and marl are related to the amount of clay in the samples and the differences in the occurrence of trace fossils are interpreted as due to differences in the visibility of traces between chalk and marl and not due to differences in ecological stress upon the endobenthic community of the two lithologies. The study thus provides an excellent example of how the effect of taphonomic factors may give a misleading and biased impression of apparent differences in the endobenthic community between chalk and marl.     

朝阳磷矿磷块岩的类型和成因特征

朝阳磷矿的磷块岩有五种类型,即泥晶磷块岩、球粒磷块岩、鲕粒磷块岩、内碎屑磷块岩和细晶磷块岩。其中内碎屑磷块岩占优势。磷酸盐岩沉积在海退旋回中,是处于深水向浅水过渡的层位。磷块岩的沉积环境主要是隆起附近的浅水带。     

Composition of manganese nodules and manganese carbonates from Loch Fyne,Scotland

Manganese nodules and manganese carbonate concretions occur in the upper 10–15 cm of the Recent sediments of Loch Fyne, Argyllshire in water depths of 180–200 m. The nodules are spherical, a few mm to 3 cm in diameter, and consist of a black, Mn-rich core and a thin, red, Fe-rich rim. The carbonate occurs as irregular concretions, 0.5–8 cm in size, and as a cement in irregular nodule and shell fragment aggregates. It partially replaces some nodule material and clastic silicate inclusions, but does not affect aragonitic and calcitic shell fragments.The nodules are approximately 75% pure oxides and contain 30% Mn and 4% Fe. In the cores, the principal mineral phase is todorokite, with a Mn/Fe ratio of 17. The rim consists of X-ray amorphous Fe and Mn oxides with a Mn/Fe ratio of 0.66. The cores are enriched, relative to Al, in K, Ba, Co, Mo, Ni and Sr while the rims contain more P, Ti, As, Pb, Y and Zn.The manganese carbonate has the composition (Mn_47.7 Ca_45.1 Mg_7.2) CO₃. Apart from Cu, all minor elements are excluded from significant substitution in the carbonate lattice.Manganese nodules and carbonates form diagenetically within the Recent sediments of Loch Fyne. This accounts for the high Mn/Fe ratios in the oxide phases and the abundance of manganese carbonate concretions. Mn concentrations in the interstitial waters of sediment cores are high (ca. 10 ppm) as also, by inference, are the dissolved carbonate concentrations.     

A comparative study of Pleistocene phosphorites from the continental slope off western India

Two types of phosphorite recovered from the continental slope off western India are described. The first type, phosphorite 1, comprises a hard, grey nodule composed of carbonate fluorapatite (CFA) and calcite as major minerals. The phosphorite consists of light‐brown microcrystalline apatite containing a few skeletal fragments and planktonic foraminifera. Scanning electron microscope (SEM) studies show evidence of dissolution of skeletal calcite and filling of the resulting cavities by phosphate composed of ovoid to rod‐shaped apatite microparticles. Apatite also occurs as coatings on these particles. The P₂O₅ content of the phosphorite is 29%, and the CO₂ content of the CFA is about 4·5%. The rare‐earth element (REE) abundance (ΣREE=2·02 μg g^–1) is lower than in other modern phosphorites. The ⁸⁷Sr/⁸⁶Sr ratio and ?Nd value of this sample are 0·70921 and –9·9 respectively. The ¹⁴C age found through accelerator mass spectrometry (AMS) dating (18 720 ± 120 years BP) is much younger than that determined by the U‐series method (100 ka). The second type, phosphorite 2, comprises a friable, light‐brown nodule consisting of CFA as the only major mineral, with a CO₂ content of the CFA of 4·5%. In thin section, the phosphate is light brown and homogeneous, and a few bone fragments are present. The P₂O₅ content is 33%, and REE contents (ΣREE = 0·18 μg g^–1) are lower than in phosphorite 1. The age of phosphorite 2 is >300 ka. Phosphorite 1 appears to have formed during the late Pleistocene through replacement of carbonate by phosphate; phosphorite 2 is also of Pleistocene age but is much older than phosphorite 1. The initial substrate for phosphorite 2 was a fish coprolite, which was subsequently phosphatized during slow sedimentation under low‐energy conditions. Microbial mediation is evident in both phosphorites. The colour, density and P₂O₅ content of the phosphorites are found to be dependent on the nature of the initial substrates and physico‐chemical conditions during phosphatization. The CO₂ content of the CFA is not related to the precursor carbonate phase. The nature of sediments, rates of sedimentation and the time spent undergoing phosphogenesis at the sediment–water interface may control REE concentrations in phosphorites.     

Pb-Pb age and Sr isotopic characteristic of the Middle Riphean phosphorite concretions: The Zigaza-Komarovo Formation of the South Urals

The Pb-Pb age of phosphorite concretions of the Zigaza-Komarovo Formation, which composes the intermediate horizons of the Riphean stratotype of the South Urals, was determined in fractions resulting from the stepwise dissolution of concretions in 0.1 N, 0.5 N, and 1 N HCl. The determination of the Sr isotopic composition in phosphate fractions was favorable for rejection the fractions polluted with extraneous material. On the ²⁰⁷Pb/²⁰⁴Pb-²⁰⁶Pb/²⁰⁴Pb diagram, the isochron based on 31 points corresponds to 1330 ± 20 Ma (MSWD = 1.12), which is in agreement with the stratigraphic position of the Zigaza-Komarovo Formation. The decreased μ₂ value of 9.57 for the phosphorite concretions relative to that of the average earthly lead based on the Stacey-Kramers model (9.74) is related to the rocks with an admixture of mantle lead, which occur in the run-off area of the Zigaza-Komarovo sediments.     

陕南天台山、茶店一带磷块岩的时代和成因特征

陕西南部汉中天台山、勉县茶店和略阳何家岩、金家河一带磷块岩的时代,目前有三种看法,即:泥盆纪、震旦纪和寒武纪。这一带磷块岩的成因也比较复杂。在磷酸盐沉积、成岩以后,又受到变质、褶皱、断裂和水溶液活动影响。本文对天台山、茶店一带的磷块岩的成矿时代和生成特点提出一些初步意见。     

Animals and Mineralization of Phosphorus: Ore-Forming Mechanism of Insular Phosphorites1

Abstract Phosphorite, or guano, or insular phosphorite, commonly containing 10-35% P₂O₅, is one of the sources of phosphatic fertilizer. Taking the modern insular phosphorite on the Xisha Islands as an example, this paper discusses the ore-forming mechanism of phosphate and the important contribution made by animals to this process. The phosphorite occurs in the middle part of carbonate sand cays of coral reef surrounded by longshore sandbanks, which assumes a dish-shape. The surface of the cays is covered by unconsolidated guano. The phosphorite, yellowish brown to dark brown, is made up of thick-bedded sand and gravel cemented by collophanite; and partly replaced by carbonate apatite. The mechanism of mineralization is as follows: The average content of phosphorus in the sea water is only 0. 07 ppm, but through the sea food. chain concentration, phosphorus content may become higher. The phytoplanktons, as producers, suck up phosphorus out of sea water. The primary consumers, zooplanktons, obtain phosphorus by eating phytoplanktons, then they are followed by the second and third consumers. Sea birds living on fish, as the third consumers, concentrate and transport the phosphorus to the carbonate sand cays. Finally layers of guano are deposited under the arbores. Under the tropical climatic conditions with high temperature and plentiful rainfall, soluble matters are leached out of the guano and infiltrated into deeper horizon. In alkaline groundwater with pH greater than 7. 0, the phosphoritization takes place, bioclastics are cemented and replaced by collophanite or carbonate apatite. Finally, the phosphorus is fixed and phosphate formed.     

贵州瓮安陡山沱组磷块岩的地球化学特征

贵州瓮安地区是震旦纪陡山沱期的一个磷块岩沉积区,生物作用是磷矿形成的重要因素。通过对贵州瓮安含磷岩系剖面地球化学特征的研究,认为磷块岩富集层是以P2O5与CaO构成的磷酸盐矿物为主,可分为白云质砂屑磷块岩和碳质磷块岩2个亚类;生物作用导致了磷块岩中Pb,As,Ba及Sr等微量元素的富集,其中亲硫元素Pb的含量最高达到1 446×10-6,反映了贵州瓮安震旦系陡山沱组磷块岩的成因与菌藻类生物作用密切相关。     

Proposed upgrading techniques for East Sibaiya phosphorites,Aswan area,southern Egypt

The Late Cretaceous (Campanian-Maastrichian), low-grade phosphorite sequence of East Sibaiya, Aswan area, which is known as the Duwi (phosphate) or Sibaiya Formation, is usually intercalated with marl, oyster limestone, and chert beds. These strata, which crop out in a generally east–west trending belt spanning the middle latitudes of Egypt, are phosphorite-rich sediments and of great economic importance. Representative samples were collected from the investigated area at several localities (e.g., Umm Tundubah-2 and Wadi El-Batur) and 200 kg of phosphate rocks was used for upgrading processes of low-grade phosphorites of the East Sibaiya area. The upgrading processes included two techniques: the first technique (gravity separation) comprises crushing, sieving, gravity separation by a shaking table, and magnetic separation. This technique raised the P₂O₅ in the head sample from 24.73 to 31.91% as a phosphate concentrate. The second technique (flotation technique) depends on certain flotation parameters such as pH, grain size, and phosphate collector dose (i.e., oleic acid). The flotation technique increased the P₂O₅% from 24.73 to 31.16% as a final product of the phosphate concentrate. These data were confirmed by X-ray fluorescence analyses of major elements.     

Characterization by electrical and electromagnetic geophysical methods of the shallow hydrogeological system at Hebron (West Bank,Palestine) in a semi-arid zone

Multi-electrode geo-electrical and transient electromagnetic surveys were carried out to characterize the nature of the subsurface infiltration zones (5 to 20 m) related to a series of groundwater outlets, and to reveal the geometry of the different aquifers at Bani-Naim, in the south-eastern foothills of the Hebron area, West Bank, Palestine. The purpose of the surveys was to understand the link between water storage/transfer and the characteristics of the geological formations. The strata in this semi-arid region are composed of alternate layers of chalky limestone, hard limestone, marl and chalk. A total of 30 ERT and 15 TDEM were conducted at Bani Naim-Jahir and Bani Naim-Birein. A correlation between the results indicates various infiltration pathways: fractures, feature heterogeneities, and porous chalk. The local heterogeneity on the eastern side were the major pathways for the water infiltration, whereas the thick marl layer underneath acts as a natural impermeable barrier preventing water from infiltrating deeper. A combination of the different geophysical results identified conductive features that correspond to the infiltration zones supplying the dug wells with water. Furthermore, it was established that the fractured chalk and porous chalky limestone act as an aquifer. A three-dimensional visualization of the resistivity allowed a useful reconstruction of the shallow hydrogeological system. Consequently, these studies contribute to regional sustainable development projects in this semi-arid region.     

Geochemistry of Phosphorus and Origin of Phosphorites: Communication 1. Role of Terrigenous Material in the Hypergene Phosphorus Geochemistry

Different hypotheses of phosphorite formation are discussed. The biogenic origin of phosphorites is most plausible. The important role of terrigenous material in P₂O₅ migration and concentration in the hypergenesis zone is emphasized. The mineralogical zoning of phosphate accumulations is described and the probable diagenetic alteration of accessory apatite in present-day seas and lakes is affirmed.     

Morphology and genesis of nodular chalks and hardgrounds in the Upper Cretaceous of southern England

The Upper Cretaceous chalks of southern England are a thick sequence of rhythmically bedded, bioturbated coccolith micrites, deposited in an outer shelf environment in water depths which varied between 50 and 200–300 m. The products of sea floor cementation are widely represented in the sequence, and a series of stages of progressive lithification can be recognized. These began with a pause in sedimentation and the formation of an omission surface, followed by (a) growth of discrete nodules below the sediment-water interface to form a nodular chalk, erosion of which produced intraformational conglomerates. (b) Further growth and fusion of nodules into continuous or semicontinuous layers: incipient hardgrounds. (c) Scour, which exposed the layer as a true hardground. At this stage, the exposed lithified chalk bottom was subject to boring and encrustation by a variety of organisms, whilst calcium carbonate was frequently replaced by glauconite and phosphate to produce superficial mineralized zones. In many cases, the processes of sedimentation, cementation, exposure and mineralization were repeated several times, producing composite hardgrounds built up of a series of layers of cemented and mineralized chalk, indicating a long and complex diagenetic history. Petrographic study of early cemented chalks indicates lithification was the result of the precipitation of small crystals on and between coccoliths and coccolith fragments. By analogy with known occurrences of early lithification in Recent deeper water carbonates, the cement is believed to have been either high magnesian calcite or aragonite, and more probably the former. The vast scale of operations involved in the cementation process precludes carbonate in expelled pore fluids as the source of cement, whilst quantities of aragonite incorporated in sediment are also inadequate. This, plus the observed association of horizons of early lithification with pauses in sedimentation associated with omission surfaces suggests seawater as a source of cementing materials. Stratigraphic studies indicate that processes of early lithification leading to hardground formation proceeded to completion in intervals to be measured in tens or hundreds of years. Regional studies suggest that early lithification characterized relatively shallow water phases associated with regional regression over the whole of the area, whilst in detail, the distribution of mature mineralized hardground complexes is strongly correlated with sedimentary thinning and condensation over small areas and the buried flanks of massifs. Early cementation in more basinal areas is typically in the form of nodular developments and incipient hardgrounds, whilst day contents in excess of a few percent appear to have inhibited early lithification. The striking rhythmicity of hardgrounds and nodular chalks is no more than a particular expression of the overall rhythmicity of chalk sequences. The stage of early lithification reached in any instance is dependent on sediment type, the time interval represented by the associated omission surface and the degree of associated scour and erosion (if any). Chalk hardgrounds differ from most others described in the geological literature in their widespread distribution (individual hardgrounds may cover up to 1500 km²), the presence of striking glauconite and phosphate replacements of lithified carbonate matrices, their frequently sparse epifaunas, and boring infaunas dominated by clionid sponges. These differences reflect the deeper water shelf setting of the chalk, and the more open marine, oceanic circulatory system, both strikingly different from the setting of other, shallower water hardgrounds. Litho- and biostratigraphic variation in the chalk sequences of the area studied are summarized in an appendix.     

震旦纪陡山沱组的泥晶磷块岩

泥晶磷块岩(micritic phosphorite)是磷块岩的主要类型之一。我国的磷块岩矿床也多有这种矿石。过去往往把组成泥晶磷块岩的磷酸盐矿物叫做胶磷矿(collophane)。扫描电镜、X-射线衍射等观察结果表明,胶磷矿实际上也是结晶质磷灰石,只是由于颗粒极其微小而已。由这种泥晶磷灰石组成的泥晶磷块岩也同样不像过去描述的那样单调,而是具有比较复杂的结构、构造。     

海州式磷矿床地质特征及其成矿模式

海州式磷矿成矿物质有多种来源。磷元素在地壳发展过程中，随着磷矿成矿作用不同阶段物化条件等改变而变化，将成矿划分为沉积、变质及改造三阶段。中元古代早期海州群锦屏组，肥东群双山 ，宿松群柳坪组和虎踏石组及红安群七角山组下段为其“源”，磷块岩形成后，由于变质、混合岩化交代和风化淋滤作用，使磷质活化，在一定的空间富集成矿。     

Uranium (U) concentration and its genetic significance in the phosphorites of the Paleoproterozoic Bijawar Group of the Lalitpur district,Uttar Pradesh,India

The paper presents the uranium (U) concentration and distribution pattern in the Paleoproterozoic phosphorites of Lalitpur district of Uttar Pradesh. The study of thin sections, SEM and XRD reveal that apatite is the essential phosphate mineral while quartz and feldspars are the dominant gangue in the phosphorites of the investigated area. The collophane is observed to be mostly oolitic in form and microspherulitic in texture. The major element geochemistry indicated that the phosphorite samples are rich in P₂O₅, CaO, SiO₂ and Fe₂O₃ whereas depletion of MgO, MnO, K₂O and Al₂O₃ was observed. The CaO/P₂O₅ ratio ranges from 1.13 to 1.46 which is slightly lower than that of cations and anions substituted francolite (1.621) and close to that of carbonate-fluorapatite (1.318). The trace element geochemistry indicates that the phosphorites of Lalitpur have the significant range of U concentration (1.67 to 129.67 μg/g) which is more than that of Th (0.69 to 0.09 μg/g) among the analysed trace elements in the phosphorite samples of the area. The positive correlation of U with P₂O₅, CaO and U/P₂O₅ indicates a close association of U with phosphate minerals like collophane (apatite), whereas negative correlation of U with SiO₂ and Fe₂O₃ may be due to mutual replacement. The antipathetic relationship of U with Ni may be an indication of high oxidizing conditions, whereas sympathetic relationship of U with K₂O points towards higher alkaline conditions of the basin of deposition during phosphatization. The variable concentration of U and its relationship with significant major and trace elements in most of the phosphorite samples lead one to believe that the deposition of these phosphorites might have taken place in highly alkaline medium during fairly oxidizing to weakly reducing environmental conditions of geosynclinal basin.     

Phosphate deposits of Neogene age in Greece. Mineralogy, geochemistry and genetic implications

In Greece, several occurrences of phosphates have been located in Mesozoic and Cenozoic sedimentary rocks. The aim of the present paper is to describe the mineralogy, geochemistry and the origin of the phosphates deposited in marine and lacustrine basins of Neogene age in Greece. Phosphates of marine origin formed in an outer shelf-upper slope environment (Palliki Peninsula, Kefalonia Island) as well as in a hemipelagic environment (Heraklion, Crete Island). In both the deposits, the phosphate minerals belong to the apatite group. In Kefalonia Island, phosphatic material accumulations occur in the field as scattered or accumulated vertebrate bones, fish teeth and other biogenic components, hosted in a sandy limestone of Upper Tortonian age. On a microscopic scale, in the groundmass of the limestone, phosphate minerals are present as fillings and secondarily as replacements of foraminiferal and other calcareous microfossil tests. In Crete Island, burrowed cobbles and phosphatic concretions up to 10 cm in diameter have been detected east of Heraklion town. The phosphatic material is hosted in a sandy marlstone that is interbedded with diatomaceous rocks of Middle Pliocene age. Phosphates of lacustrine origin have been formed in the NW–SE-oriented Upper Miocene basins of Florina–Ptolemais and Elassona–Sarantaporo, located, respectively, in western Macedonia and Thessaly, Greece. The phosphate minerals are mainly represented by Ca/Fe phosphates such as anapaite and mitridatite and secondarily by Ca phosphates of the apatite group that are hosted in a thick succession of clayey diatomite rock. They usually form lenticular layers, asymmetric lenses, nodular and botryoidal aggregates, and faecal pellet replacements.

The major and trace element content of a representative set of rocks was studied. Their geochemistry was found to be controlled by the presence of detrital minerals, the host rock mineralogies, and the types of phosphate minerals present. The relatively high amounts of uranium, arsenic and barium detected in some of the phosphate rocks studied are mainly related with organic matter and are comparable to those detected in other phosphate deposits worldwide.

In the deposits studied, phosphogenesis was mainly promoted by the decay of organic substances derived from diatoms, fishes and other vertebrates, leaves and trunks, and faecal pellets in a highly reducing environment on or just below the sea or lake bottom, and secondarily by the feeding of the basin with phosphate-bearing nutrients that originated in the land.     

卡哈洛磷矿矿石特征及其成因分析

卡哈洛磷矿磷矿石以磷质碎屑（砂屑、鲕粒、砾屑、团块、生物碎屑）结构为主,次为胶状泥晶结构;原生磷块岩矿石主要有纹层-条带状和块状两种构造类型,矿石中磷酸盐矿物为泥晶磷灰石（胶磷矿）。矿床形成于水体较浅、水动力条件强、以波浪作用为主的潮下浅滩环境。