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.     

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.     

柠檬酸—硝酸铝溶剂溶解磷灰石中全磷

试验了用柠檬酸＿Ａｌ（ＮＯ３）３溶液做溶剂分解磷灰石的预处理方法。结果表明，在微沸加热６ｍｉｎ条件下，质量浓度分别为３２ｇ／Ｌ和９０ｇ／Ｌ的柠檬酸＿Ａｌ（ＮＯ３）３混合溶剂可以有效地分解磷灰石，测定全磷的回收率＞９９％，与王水溶样结果相符，并用测定磷灰石标样中全磷进行验证，说明方法可靠。     

乌梁素海和岱海沉积磷形态分布的差异性研究

湖泊沉积物中磷的含量及形态分布等地球化学信息可以用来反演湖泊流域的古环境及污染历史。本文以乌梁素海和岱海两个不同类型的湖泊为研究对象,对两个湖泊沉积柱芯中磷形态分布的差异性进行了研究。结果表明,乌梁素海和岱海沉积柱芯中沉积磷的主导形态均为ACa P、De P和 Or P,但乌梁素海表层沉积物和沉积柱芯中Al P和 ACa P的含量水平明显高于岱海,而Ex P、De P和 Or P的含量水平明显低于岱海。两个湖泊沉积磷形态分布的差异性能较好地揭示出湖泊流域的地理环境、化学风化程度以及湖泊富营养化类型的差异性,沉积柱芯中ACa P含量及其分布特征能很好的指示湖泊自身发展过程中的富营养化水平,而De P含量及其分布特征则能较好的揭示出整个湖泊流域的古环境古气候信息。     

Abundance and Chemical Speciation of Phosphorus in Sediments of the Mackenzie River Delta, the Chukchi Sea and the Bering Sea: Importance of Detrital Apatite

Utilizing a sequential extraction technique this study provides the first quantitative analysis on the abundance of sedimentary phosphorus and its partitioning between chemically distinguishable phases in sediments of the Bering Sea, the Chukchi Sea and the Mackenzie River Delta in the western Arctic Ocean. Total sedimentary phosphorus (TSP) was fractionated into five operationally defined phases: (1) adsorbed inorganic and exchangeable organic phosphorus, (2) Fe-bound inorganic phosphorus, (3) authigenic carbonate fluorapatite, biogenic apatite and calcium carbonate-bound inorganic and organic phosphorus, (4) detrital apatite, and (5) refractory organic phosphorus. TSP concentrations in surface sediments increased from the Chukchi Sea (18 μmol g⁻¹ of dried sediments) to the Bering Sea (22 μmol g⁻¹) and to the Mackenzie River Delta (29 μmol g⁻¹). Among the five pools, detrital apatite phosphorus of igneous or metamorphic origin represents the largest fraction (~43%) of TSP. The second largest pool is the authigenic carbonate fluorapatite, biogenic apatite as well as CaCO₃ associated phosphorus (~24% of TSP), followed by the Fe-bound inorganic phosphorus, representing ~20% of TSP. The refractory organic P accounts for ~10% of TSP and the readily exchangeable adsorbed P accounts for only 3.5% of TSP. Inorganic phosphorus dominates all of phosphorus pools, accounting for an average of 87% of the TSP. Relatively high sedimentary organic carbon and total nitrogen contents and low δ¹³C values in the Mackenzie River Delta together with the dominance of detrital apatite in the TSP demonstrate the importance of riverine inputs in governing the abundance and speciation of sedimentary phosphorus in the Arctic coastal sediments.     

长江悬浮颗粒物中磷的赋存形态

2006年9~10月在长江采集悬浮颗粒物样品,应用改进后的SEDEX法对磷的赋存形态进行了分析.结果表明,自生磷灰石磷是长江悬浮颗粒物中磷的主要赋存形态.涪陵至万州江段,碎屑磷灰石磷的含量较高,弱吸附态磷和有机磷含量较低,磷的赋存形态主要受悬浮颗粒物含量的影响;香溪至葛洲坝下江段,弱吸附态磷和有机磷含量较高,碎屑磷灰石磷含量较低,磷的赋存形态主要受浮游植物生长及泥沙粒径的影响;城陵矶至大通江段,有机磷、碎屑磷灰石磷和铁结合态磷含量较高,弱吸附态磷含量较低,磷的赋存形态主要受泥沙粒径和洞庭湖输入的影响.长江悬浮颗粒物中生物可利用磷占颗粒态磷的45.6%,长江上游水体中生物可利用磷含量较低,下游含量较高.     

滇池现代沉积物中磷的地球化学及其对环境影响

湖泊沉积物中,磷是产生富营养化的重要元素.湖泊中磷元素含量、地球化学行为以及它的复杂矿物学特征,使人们对磷的研究极为重视.滇池湖中总磷超标10.3倍,底泥沉积物中P2O5平均含量0.52%,最高可达1.92%.滇池地处磷矿区,是磷质来源最丰富的湖泊,统计表明,磷含量每年在不断增长.滇池沉积物中磷主要以吸附态、有机态、铁结合态、钙结合态、铝结合态等几种形式存在.这些形态磷在底泥中是不稳定的,它们在环境改变条件下,又将磷释放到水体中.微生物在磷的循环过程中起了重要作用,乳酸菌对不溶性磷酸盐的分解,使湖泊中可溶磷含量增高.聚磷菌对磷元素的富集以及聚磷菌死亡后发生有机磷的矿化作用,是湖泊中水合磷酸盐矿物沉积的重要途径.当湖泊中这种不稳定的水合磷酸盐矿物在条件具备的情况下,经沉积物覆盖成岩作用后,最终形成磷灰石。     

Phosphorus burial as a function of paleoproductivity and redox conditions in Arabian Sea sediments

In this study the response of sedimentary phosphorus (P) burial to changes in primary productivity and bottom water oxygen concentrations during the Late Quaternary is investigated, using two sediment cores from the Arabian Sea, one recovered from the continental slope and the other from the deep basin. The average solid-phase P speciation in both cores is similar, authigenic and biogenic (fish debris) apatite make up the bulk of the P inventory (ca. 70%);whereas P adsorbed to iron oxides, organic P, and detrital apatite constitute minor fractions. Postdepositional redistribution has not significantly altered the downcore distribution of total solid-phase P. Phosphorus burial efficiencies are generally lower during periods of increased paleoproductivity. This is caused by (a) partial decoupling of the P export flux, consisting primarily of particulate organic P, and the P burial flux, consisting primarily of biogenic and authigenic apatite; and (b) the lack of increased rates of authigenic CFA formation during periods of higher P deposition. In addition, fluctuations in bottom water oxygen concentrations may have affected P burial in continental slope sediments. The results of this study indicate that higher primary productivity induces more efficient P cycling. On time scales exceeding the oceanic P residence time, this process may induce higher surface water productivity, thus creating a positive feedback loop. In the Arabian Sea, this feedback mechanism may have contributed to changes in sea surface productivity on sub-Milankovitch time scales because P, regenerated on the continental slopes of the Oman and Somalian coastal upwelling zones, is reintroduced into the photic zone relatively fast.     

Phosphorus speciation in the sediment and mass balance for the central region of the Great Barrier Reef continental shelf (Australia)

Solid phase P speciation has been determined in sediments from a transect across the central section of the continental shelf and slope of the Great Barrier Reef (GBR) lagoon. This region is characterized by a gradient of riverine aluminosilicate clay and silt nearshore, seawards of which biogenic carbonate sediment predominates. Phosphorus speciation results show large variations along this transect. Organic P and authigenic (apatite) P are the major chemical forms of phosphorus in the central GBR continental shelf sediments. Post-depositional reorganization of P was also observed, converting organic P and iron bound P (Fe-P) to authigenic (apatite) P. Phosphorus burial rate was estimated from measurements of total P concentration and excess ²¹⁰Pb sediment mass accumulation rates. Burial efficiency varies significantly over the shelf. Inshore areas showed significant P remobilization from sediments to the water column (up to ∼50%). The mid and the outer shelf showed little evidence for remobilization (except for coral reef platform sediments), with more of the sediment P being in the less reactive authigenic apatite phases. An appreciable fraction of this non-labile authigenic apatite phase was identified as fish bone. P sources and sinks over the central part of the GBR shelf were quantified using a mass balance approach. This showed that Coral Sea shelf edge upwelling events are essential to satisfy the large P nutrient demand of the whole GBR lagoon. P inputs due to upwelling events were greater than those contributed by local rivers over an average year.     

利用液态磷渣制备乳浊玻璃

为实现炼磷排放的高温液态磷渣的热能、物质的同步回收利用, 并消除其环境污染问题, 通过现场试验, 以高温液态磷渣为主要原料, 直接与16.5%的石英粉和8.5%的高岭土热配合, 再经1450℃熔炼、浇铸成型和850℃乳化热处理, 制得了乳浊玻璃板材.磷渣乳浊玻璃的抗折强度为43.68MPa, 耐酸性为0.51%, 耐碱性为0.04%, 能满足建筑装饰材料的质量要求.ESEM、XRD和EDS分析结果共同表明, 母玻璃的乳浊机理在于主体玻璃中析出了富Ca元素的粒径为0.1~0.4μm的非晶质球形颗粒.由于高温液态磷渣掺量高达75%, 改性剂掺量低且成本低廉, 生产线易于配置, 本研究具有较高的工业化生产可行性、较佳的经济效益和应用前景.      

Phosphorus Cycle in the Ocean

The behavior of phosphorus is considered at major stages of the sedimentary cycle beginning with supply sources for its delivery into the ocean to precipitation and its sedimentation, localization and subsequent diagenetic redistribution in bottom sediments. River runoff represents the main phosphorus source in the ocean. It delivers annually about 1.5 Mt of dissolved phosphorus and more than 20 Mt of suspended phosphorus into the ocean. Up to 80% of the suspended phosphorus incorporated in the lithogenic material precipitates within submarine continental margins. Phosphorus dissolved in seawater repeatedly participates in biogeochemical processes owing to its assimilation by phytoplankton that annually consumes from 1.5 to 2.5 Gt of phosphorus. Dissolved phosphorus is incorporated in organic remains and precipitates from seawater by a biogenic mechanism, too. Only a part of phosphorus settled onto the bottom is buried in sediments. Due to reducing diagenetic processes, up to 30–40% of the primarily precipitated phosphorus diffuses from the upper layer of sediments into bottom water. Diffusion flux into the ocean significantly exceeds the supply of dissolved phosphorus from river runoff. The absolute mass phosphorus dispersed in sediments is several orders of magnitude greater than the mass concentrated in phosphorite deposits. However, the majority of phosphorite formation epochs coincide with the intensification of total phosphorus accumulation in marine sediments in conditions of humid climate, intense chemical weathering of rocks on continents, and considerable expansion of the oceanic shelf area.     

Sulfur partitioning between apatite and melt and effect of sulfur on apatite solubility at oxidizing conditions

The effect of sulfur on phosphorus solubility in rhyolitic melt and the sulfur distribution between apatite, ±anhydrite, melt and fluid have been determined at 200 MPa and 800–1,100 °C via apatite crystallization and dissolution experiments. The presence of a small amount of sulfur in the system (0.5 wt.% S) under oxidizing conditions increases the solubility of phosphorus in the melt, probably due to changing calcium activity in the melt as a result of the formation of Ca-S complexing cations. Apatite solubility geothermometers tend to overestimate temperature in Ca-poor, S-bearing system at oxidizing conditions. In crystallization experiments, the sulfur content in apatite decreases with decreasing temperature and also with decreasing sulfur content of the melt. The sulfur partition coefficient between apatite and rhyolitic melt increases with decreasing temperature (Kd_S^apatite/melt=4.5–14.2 at T=1,100–900 °C) under sulfur-undersaturated conditions (no anhydrite). The sulfur partition coefficient is lower in anhydrite-saturated melt (~8 at 800 °C) than in anhydrite-undersaturated melt, suggesting that Kd_S^apatite/melt depends not only on the temperature but also on the sulfur content of the melt. These first results indicate that the sulfur content in apatite can be used to track the evolution of sulfur content in a magmatic system at oxidizing conditions.Editorial responsibility: J. Hoefs     

Geochemistry of Cadmium in Mesozoic Phosphorites of the East European Platform

Cadmium is the most toxic admixture in mineral fertilizers. The Cd concentration in Mesozoic phosphorites, which are widespread in the East European Platform, has not been investigated. The present study was stimulated by the scanty and contradictory nature of the published data on this issue. We determined Cd concentration in 21 phosphorite samples from major deposits and checked the reliability of obtained results by external replicate analyses. It has been established that the Cd concentration in phosphorites varies from 5 ppm in the Late Jurassic–Early Cretaceous basin to 2 ppm in the Late Cretaceous basin. Cadmium does not enter the structure of phosphate and sulfide minerals. The Cd concentration is independent of the phosphorus abundance. However, all studied samples show a positive correlation of Cd with organic matter mainly contained in phosphates, supporting the biophilic nature of Cd. Mesozoic phosphorites of the East European Platform accumulated in epicontinental basins. They are significantly depleted in Cd relative to Mesozoic–Cenozoic phosphorites in pericontinental basins of the southern margin of the Tethys Ocean. The Cd concentration is more stable in Mesozoic phosphorites than in Mesozoic–Cenozoic deposits.     

磷灰石结晶法降低天然水体中磷浓度Ⅱ．反应物浓度及其他影响条件试验

在磷灰石、钙、氟的共同作用下，可以使水体中的磷浓度显著降低。以此为基础，在含磷水溶液中调节反应物（磷灰石、钙、氟）浓度，通过监测水溶液中磷浓度的变化，探讨了加入物浓度对降磷效果的影响，初步确定了适合的反应物加入量，并试验了其他因素如震荡作用和催化剂对降磷的影响。最后探讨了固化沉淀的反应速率。     

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。     

水环境中氮磷形态分析方法研究进展

归纳总结了近年来国内外水环境中氮、磷形态分析方法的研究新进展,并着重介绍了氮、磷在水环境中赋存形态的分类、分析测定方法,这对于深入揭示水环境中氮、磷的赋存形态及研究环境与生物地球化学循环有着重要的指导意义。     

Expériences sur la précipitation directe de l'apatite dans l'eau de mer: Implication dans la genèse des phosphorites

The direct precipitation of apatite in seawater is inhibited by Mg ions. The action of various factors on this precipitation is studied: addition of Ca, addition of F, reduction of pH and simultaneous effect of reduction of pH and addition either of F or of Ca. It is established that the reduction of the pH of seawater to 7 allows the precipitation of the apatite with a Ca/Mg ratio in the water of 1.2. The favourable environment for the settlement of natural apatite must then be either neutral or acid. This result is corroborated by the re-study of Gulbrandsen's equation. Such an acid environment with a high phosphorus content may be the result of oxidation of large quantities of organic matter due to previous intense biological activity. The acidity is probably brought about by bubbling of CO₂.     

兴神保磷矿含磷岩系沉积环境分析

兴神保磷矿赋存于震旦系陡山沱组中下部,磷块岩主要为原地生物、生物化学成因的团粒、藻菌粒、壳粒、叠层石组成。它们形成于低能还原-弱氧化条件的浅水盆地,泻湖及浪基面附近的浅滩环境。按含磷岩系沉积特征划分出三个沉积相区。古隆起控制着磷块岩的时空分布。     

滇池地区沉积磷块岩中胶磷矿矿物学特征及其研究意义

本文从物理性质、化学成分及其成因结构等方面,对云南滇池地区胶磷矿进行了矿物学特征研究。提出该区胶磷矿主要以三种形式赋存在磷块岩中。对不同矿石类型中胶磷矿做扫描电镜研究,得知胶磷矿主要由超微晶低碳氟磷灰石集合体、磷酸盐显微莓群以及纤维放射状磷灰石等构成。经化学分析、红外、晶胞参数测定,不同胶磷矿有一定差异,特别是碳和磷,经矿物学对比发现,反映随变质作用的加深,胶磷矿有向晶质氟磷灰石演化的趋势,脱碳作用表现明显。本区胶磷矿稀土元素含量不高,钇族较富,铈族较贫。球粒陨石标准化后为铈亏损型模式。     

Phosphorus in lamprophyre and lamproid rocks

The P₂O₅-content of 300 samples of lamprophyre, lamproid and some acid dyke rocks from three areas of the Bohemian Massif has been determined colorimetrically. The values established range from 0.02% in microgranite to 2.38% in an alkaline minette. A negative correlation exists between P₂O₅ and SiO₂, and Al₂O₃, respectively, a positive one between P₂O₅ and TiO₂, CaO and F, respectively. In the alkaline dykes most of the calcium is found in apatite. The main factor controlling the distribution of P₂O₅ in the rocks studied is their saturation with aluminium. Theoretically, this may be explained according to Shcherbina's (1966) acidity concept. If the chemical composition of a dyke remains approximately constant, the same holds good also for phosphorus, in spite of considerable differences in the mode. In the course of the differentiation of the kersantite type magma, P₂O₅ increases at first in agreement with the Al₂O₃ saturation of the magma, but falls off in the final stages. Due to local factors, there exist considerable differences between the P₂O₅- contents of the individual rock types of various areas.