Origin of Phosphate-bearing Carbonate Concretions in the Upper Triassic Lacustrine Black Shales of the Southern Ordos Basin,China

Carbonate concretions are conspicuous in organic-rich shales and are generally related to decomposition of organic matter.The black shales from the Chang 7 Member of the Upper Triassic Yanchang Formation of the southern Ordos Basin host abundant carbonate concretions,which provide a unique record of depositional and early diagenetic conditions of the paleo-lake sediments.However,little attention has been given to the genesis and growth processes of the concretions in these lacustrine petroleum source rocks.New petrographic observations and geochemical analysis show that the concretions are composed of calcite,phosphate fossil fragments,K-NH_4-feldspar,quartz,bitumen,and minor Fedolomite.Phosphate minerals,mainly carbonate fluorapatite (CFA),show pervasive replacement by calcite,most of which contains phosphorus,ranging in concentration from 0.26 to 2.35 wt%.This suggests that the phosphate minerals are the precursors for concretion growth.Positiveδ~(13)C (+5.6 to+12.4‰V-PDB) signatures and the absence of pyrite indicate that microbial methanogenesis was the dominant driver for concretion growth,rather than bacterial sulfate reduction.Quartz,bitumen,and Fe-dolomite are the last cements that occurred,at deep burial depths and high temperatures.The formation of phosphate minerals might have been induced by upwelling of phosphate-enriched deep water in the Late Triassic paleolake,which promoted phytoplankton blooms and further enrichment of organic matter.Extremely slow sedimentation rates of fine-grained detrital minerals,relative to dead organism accumulation,led to the high permeabilities of the organic-rich sediments and rapid concretion growth during shallow burial.The close association of phosphate-bearing carbonate concretions and organic-rich shales reflects that upwelling played a critical role in the formation of the high-quality petroleum source rocks in the Triassic paleo-Ordos lake.     

海州湾近岸海域水质状况调查与风险评价

随着我国沿海经济的快速发展,人类活动强度不断加剧,对海洋生态系统的干扰和破坏不断加剧。为了解海州湾近岸海域水质状况,本文于2016年4月、9月对海州湾近岸海域表层海水的温度、盐度、pH值、悬浮物(SS)、溶解氧(DO)、化学需氧量(CODMn)、亚硝酸盐(NO2--N)、硝酸盐(NO3--N)、铵氮(NH4+-N)、活性磷酸盐(PO34--P)、铜、铅、锌、镉、石油类等指标进行了两次采样调查,应用分光光度法和ICP-MS等技术分析各指标;应用单因子法、富营养化指数法和有机污染指数法对该海域海水的质量状况进行了评价分析,以期为研究区环境预警、环境管理和保护提供依据。结果表明:研究海域表层海水中CODMn在4月均值为1. 34mg/L,9月为1. 22mg/L;石油类4月均值为0. 031mg/L,9月为0. 034mg/L;活性磷酸盐4月均值为0. 013mg/L,9月为0. 012mg/L;溶解无机氮4月均值为0. 34mg/L,9月为0. 16mg/L; CODMn、石油类、活性磷酸盐、溶解无机氮的质量浓度大致呈现出由西南部向东北部海域降低的趋势,且无机氮总体浓度水平较高,为该海域主要的污染物。根据营养化评价模式和有机污染指数计算结果,本研究认为海州湾近岸海域表层水质总体营养水平较高,处于氮限制的潜在性富营养水平,有机污染程度属于Ⅱ级,水质已受到污染。     

云南安宁磷矿中稀土元素分布规律和赋存状态研究

磷矿伴生稀土元素是获取稀土资源的重要途径。我国磷块岩型稀土矿分布广,稀土含量高,具有综合回收价值,是仅次于独立稀土矿床的伴生稀土资源。本文主要研究云南安宁磷矿中稀土元素分布规律和赋存状态,并比较了磷矿石中稀土元素总量与磷含量的关系,结果表明磷矿石中稀土氧化物总量为72×10^-6～1 050×10^-6,与磷含量呈一定的正相关关系。另外通过光学显微镜及电子显微镜观察发现,安宁磷矿中缺乏独立的稀土矿物,只在部分海绿石中找到了独立的稀土矿物(可能为独居石和褐帘石)。LA-ICP-MS分析结果表明,胶磷矿单矿物稀土元素含量在770×10^-6～920×10^-6之间,而白云石单矿物稀土元素含量均低于34×10^-6,石英单矿物的稀土元素平均含量为180×10^-6。由于部分独立的稀土矿物的存在,海绿石矿物中稀土元素总量可高达2 947.27×10^-6～3 159.87×10^-6。综合分析结果表明,安宁磷矿中稀土元素主要以类质同像的...     

Physical and thermal treatment of phosphate ores — An overview

The annual consumption of phosphate rock approached 150 million tons. The marketable phosphate is usually 30% P₂O₅ or higher. The run-of-mine material is mostly of lower grade which needs processing or upgrading. The processing techniques of phosphate ores depend mostly on the type of associated gangue minerals present in the mined rock. In some cases, simple, inexpensive techniques are enough to produce the required grade. For example, crushing and screening is used to get rid of the coarse hard siliceous material, and attrition scrubbing and desliming is used to remove the clayey fine fraction. If silica is the main gangue material, single-stage or double-stage flotation is the conventional mineral processing technique used in this case. If the ore is igneous carbonatitic alkaline or ultra basic phosphate deposit, crushing, grinding, scrubbing, and flotation associated with other steps such as magnetic and/or gravity separation is proved to be successful in upgrading this type of ore. The sedimentary phosphate ores having carbonate-apatite as the main phosphate minerals and containing carbonates (calcite and/or dolomite) represent a challenge in the field of phosphate concentration due to similarity in the physico-chemical properties of surfaces of the ore constituents. Also, if considerable amount of organic matter constitutes the main gangue material, upgrading of the ore becomes difficult. New flotation systems (techniques and reagents) are being developed to treat these challenging phosphate ores. Furthermore, calcination is another solution for upgrading these difficult-to-treat types of ores. However, calcination is indicted with some controversial drawbacks. This overview discusses and summarizes the State-of-the-Art and the existing efforts to overcome these problems and to produce a high-grade phosphate product suitable for fertilizers and other phosphate compounds.     

电感耦合等离子体发射光谱法测定磷矿石中常量元素硅磷硫钙镁铝铁钛锰

以粒状氢氧化钠作熔剂,样品在银坩锅中700℃熔融,热水浸取后用盐酸酸化,溶液冷却定容后直接用电感耦合等离子体发射法测定磷矿石中硅、磷、硫、钙、镁、铝、铁、钛、锰9种常量元素,采用基体匹配和离峰扣背景等方式有效消除了测定的干扰。对样品分解条件、试剂用量、元素分析谱线的选择、干扰的影响及消除等进行了优化处理和讨论。方法精密度(RSD)为0.28%~1.85%(n=12),回收率为97.92%~107.1%,具有快捷、成本低等特点。经国家一级标准物质分析验证,结果满意,适用于磷矿石中常量元素的快速分析。     

海水溶解磷酸盐氧同位素组成的测定

生物磷酸盐和水分子间的氧同位素分馏主要受温度和生物活动控制,因此磷酸盐氧同位素组成既可以测量古温度又可以示踪磷循环.近年来磷酸盐氧同位素研究受到较多关注,除了传统的生物体磷灰石古温度测量外,这些研究大多是关于磷循环的.磷酸盐的氧同位素组成可以示踪海洋中磷的源区和生物对磷的利用效率.由于海水的组成十分复杂,测量前必须对样品进行富集、分离和纯化处理.目前,加州大学(Santa Cruz)Paytan 教授和耶鲁大学 Blake 教授的实验室已建立了海水溶解磷酸盐氧同位素的测量方法,二者各有优缺点.我们结合了这两种方法的优点,并对一些步骤进行了改进,建立了海水溶解磷酸盐氧同位素组成的测量方法.通过向海水样品中加入 NaOH,形成 Mg(OH)2来富集海水中的 PO43-,也可同时除去部分杂质离子和溶解有机质;通过将 PO43-转化为 CePO4沉淀来进一步除去杂质离子,然后用阳离子交换树脂除 Ce3+,再通过阴离子交换树脂柱来除溶解有机质.最后将磷酸盐转换为Ag3PO4沉淀,在1350℃裂解Ag3PO4,产生的O2和石墨反应形成CO用IRMS测定.结果显示富集、分离和纯化过程可以获得纯的Ag3PO4颗粒,不会产生PO43-的氧同位素分馏.测量Ag3PO4用量仅为0.3 mg,标准偏差在±0.2‰~±0.3‰之间.     

河口表层沉积物中磷酸盐释放的动力学特征

研究与探讨了胶州湾李村河河口区3个采样点表层沉积物中磷酸盐释放行为及盐度、温度、波浪强度、悬浮物浓度对磷酸盐释放动力学过程的影响。认为磷酸盐释放的动力学过程大致可分为3个阶段:①0~1 h快速释放阶段;②1~8 h缓慢释放阶段;③8 h之后的平衡阶段。盐度升高可以促进磷酸盐释放,当盐度从0升高到10时,磷酸盐释放量增幅最大,说明磷酸盐释放对水相盐度的突变有较强的敏感性。温度升高有利于磷酸盐释放,在低温(20 ℃)条件下磷酸盐释放的过程有明显差异;温度较低时快速释放速率与缓慢释放速率相当,而温度较高时快速释放速率是缓慢释放速率的10倍。波浪强度对磷酸盐释放过程的影响与温度类似,当沉积物处于充分悬浮状态时,磷酸盐释放量会有大幅度提高;当悬浮物浓度降低时,快速释放速率与缓慢释放速率都有大幅度提高,释放总量也显著增加。     

The relationships between particulate and soluble alkaline phosphatase activities and the concentration of phosphorus dissolved in the seawater of Toulon Bay (NW Mediterranean)

The activities of particulate and soluble phosphatase were analyzed monthly for 1 year in the coastal ecosystems of the NW Mediterranean Sea. The mean contribution of the particulate activity increased from 56% at an MUF-P concentration of 30 μM to 77% at 0.04 μM. This particulate activity was negatively correlated with the DIP, DOP and TDP concentrations when the activities were related to the seawater volume, chlorophyll a or the protein concentration. The TDP correlations were highly significant (p: 0.001). The DOP correlations were significant (p: 0.04) and became highly significant (p: 0.009) at low DIP concentrations (<0.13 μM). The DIP correlations were significant (p: 0.04) only at low DOP concentrations (<0.18 μM). Thus, the effects of seawater DIP and DOP were found to be linked. The soluble activity exhibited distinct phosphatase fractions with high (0.5–29.5 μM) and low (0.02–2 μM) Km values, but none exhibited significant correlations with phosphorus compounds.     

氯化铁对磷酸铁锂中锂浸出性能研究

随着新能源电动汽车的发展,磷酸铁锂(LiFePO₄,LFP)电池的报废量逐年剧增,由于其有价金属锂含量低,回收经济性差,近年来废旧LFP的低成本回收成为研究热点。基于同构诱导置换浸出,以FeCl₃为浸出剂,在固-液反应体系中探究了FeCl₃对LFP中的锂浸出的影响因素,利用未反应核收缩模型探究了两个浸出阶段的宏观动力学。结果表明,增大FeCl₃/LFP摩尔比、减小固液比和升高反应温度可以显著促进锂的浸出;在浸出前4 min内,锂浸出速率主要受固态产物层内扩散过程控制,表观活化能为6.68 kJ/mol; 4 min后锂浸出速率受流体膜外扩散、产物层内扩散和化学反应混合机制的控制。