Patterns of Nd and Sr isotopic ratios produced by magmatic and post-magmatic processes in the Shiant Isles Main Sill, Scotland

The Shiant Isles Main Sill of the British Tertiary Igneous Province is a classic example of a differentiated, alkaline basic sill. Four separate intrusions, each emplaced internally in rapid succession, form a 165-m-thick sill hosted by Lower Jurassic sedimentary rocks. Extensive Nd and Sr isotopic studies were conducted on samples from a vertical section through the sill where the relationships of samples to one another are well defined. The results illuminate patterns of modification of isotopic ratios and clarify the petrogenesis (magma sources, crustal contamination), magmatic processes (bulk mixing, interstitial liquid mixing), and post-magmatic alteration (hydrothermal effects on Sr and Nd). Overall, the whole-rock initial ⁸⁷Sr/⁸⁶Sr ratios range from ∼0.7037 to 0.7061 while initial ¹⁴³Nd/¹⁴⁴Nd ratios vary from ∼0.51243 to 0.51286 (ɛ_Nd∼−0.7 to +5.7) – values that contrast markedly with those of the country rock. Acid leaching (HCl) of the whole-rock samples that removes analcime indicates that most of the scatter in the ⁸⁷Sr/⁸⁶Sr is caused by the ubiquitous sub-solidus, aqueous alteration during which more-radiogenic Sr was introduced into the sill, especially along the margins, and also reveals magmatic isotopic ratios. In contrast, Nd was immobile during fluid interaction so that the sill ¹⁴³Nd/¹⁴⁴Nd ratios were not affected, even <1 m from the country-rock contact. Using leached rock values, ⁸⁷Sr/⁸⁶Sr and ¹⁴³Nd/¹⁴⁴Nd ratios are inversely correlated from magmatic processes. Magmas with two distinct isotopic compositions were involved: a more primitive one with ¹⁴³Nd/¹⁴⁴Nd ∼0.51285 and ⁸⁷Sr/⁸⁶Sr ∼0.7035 that produced the first two intrusions and a more evolved one (with 0.51252 and 0.7048) that produced the third intrusion. Mixing of the two magmas was very limited, restricted to near contacts between units, and apparently occurred by interstitial melt migration. The more evolved crinanitic magma was probably produced from a batch of the more primitive picritic melt by a small degree of crustal contamination and crystal fractionation during a short crustal residence prior to ascent and emplacement. Received: 20 December 1999 / Accepted: 5 May 2000     

The structural relationships of the Loch Borrolan Complex,Scotland

The Borrolan Complex comprises earlier and later rock suites which are separated by an intrusive junction. The earlier suite forms a conformable sheeted complex which has been punched through by a later plug-like body and includes several distinct magma types; while the later suite differentiated gravitationally in place. Field and microscopic evidence suggests that some of the earlier rocks were emplaced prior to the principal movements on the Assynt Thrust Plane, while the later suite post-dates the development of the Assynt Thrust, although it is affected by a deformation. It is suggested that the emplacement of the greater bulk of the Borrolan rocks after movement on the Assynt Thrust Plane had ceased excludes the possibility of the Borrolan, and nearby Loch Ailsh, intrusions being the trigger mechanism which set off the great duplication of strata in the Assynt Culmination.     

花岗质岩浆作用及后期演化过程：来自矿物原位微区成分与同位素组成的制约

花岗岩作为大陆地壳的重要组成部分, 其岩浆作用过程一直是地学领域研究的热点。传统上利用全岩地球化学和同位素数据来示踪花岗岩成因和演化过程的方法已不够准确, 为此, 本文系统总结了近年来报导的花岗岩中单矿物的原位微区成分——这些数据记录了全岩数据无法识别的单矿物颗粒内部和不同矿物颗粒之间元素和同位素组成的变异特征, 明显提高了对花岗质岩浆作用及后期演化过程的认识。首先, 矿物原位微区成分对花岗质岩浆的源区性质和混合过程具有指示意义。花岗岩中岩浆锆石Hf同位素组成的变异可能暗示其源区在深熔作用过程中发生了锆石的不平衡和选择性熔融, 而未必是壳幔混合作用的结果, 这是对"锆石效应"概念新的扩展; 同一花岗岩样品中分选出的磷灰石颗粒可以具有完全不同的稀土元素配分模式、Eu异常、Sr含量和Sr-Nd同位素组成等, 表明它们中的部分颗粒是岩浆形成和上升过程中从围岩捕获的, 是小规模地壳混染作用的产物; 榍石的微区成分分带记录了多种岩浆混合过程, 也反映了熔体成分、氧逸度和温度等因素的变化; 花岗岩与其中发育的包体、捕虏体和相关围岩的锆石Hf-O同位素和磷灰石Sr-Nd同位素组成可以记录上述岩石在形成过程中经历岩浆混合和同化混染等作用。其次, 矿物原位微区成分可以反映花岗质岩浆的分离结晶过程。岩浆成因磷灰石不同的稀土元素配分模式可能指示它们受到了其他矿物分离结晶作用的影响, 如帘石族、榍石、角闪石、斜长石等; 花岗伟晶岩系统中岩浆成因独居石Sm/Nd值在不同岩带中的规律性变化揭示了岩浆分离结晶程度的差异; 榍石的多种微区元素含量和它们之间的协变关系受控于花岗质岩浆的结晶分异过程和氧化还原状态; 岩浆成因绿帘石族矿物的震荡环带表明在绿帘石结晶的晚期阶段花岗质岩浆中的Fe3+含量降低, 且结晶过程中褐帘石和绿帘石并不能形成完全连续的固溶体, 因此晚期结晶的绿帘石环边与褐帘石核具有成分间断; 根据角闪石的电子探针数据可以计算得到花岗质岩浆结晶时的温度、压力和fO2, 并据此推断出岩浆起源的深度。此外, 矿物原位微区成分可以记录花岗质岩石晚期经历的构造热事件和矿化作用过程。经历晚期变质/交代作用改造的花岗岩中的磷灰石具有低的轻稀土元素含量和变化很大的Nd同位素组成, 导致花岗岩具有Nd-Hf位素体系解耦的特点; 晚期变质/交代作用同样会改变磷灰石和榍石的δ18O值, 造成各副矿物之间δ18O值相互解耦的现象; 蚀变独居石的元素和U-Th-Pb同位素体系指示流体交代过程中多种置换反应的发生以及普通Pb混染和Pb丢失的过程; 热液成因绿帘石族矿物的成分环带表明氧化环境下热液流体成分会不断演化, 根据矿物-流体平衡模型, 可以利用绿帘石成分计算出成矿作用发生的温度以及流体的pH值, 研究表明绿帘石向流体中释放的大量Ca2+有效促进了硫化物矿床的成矿作用进程。综上, 单矿物原位微区成分分析技术的不断提高使我们对花岗质岩浆作用及后期演化过程的认识有了很大进步, 在未来的研究中, 如何取长补短, 将这些数据进行良好地运用是本领域的重要方向。     

Generation and metamorphism of new crust in magmatic arcs: a case study from northern Chile

In a deep section of the Jurassic Andean arc, coastal Cordillera of northern Chile, south of Antofagasta, basic magmas from a mantle source accreted large masses of crust in an early stage of arc development. These gabbroic intrusions were isochemically metamorphosed at moderate pressures (≤ 5 kbar) and high temperatures (∼ 800°C) into uniform garnet-absent dino+ortho-pyroxene gneisses (granulites). Subsequently they were partly transformed into amphibolites ( T ≤ 700°C) during tectonically controlled access of fluid without major changes in whole rock chemistry. Locally migmatization occurs in the amphibolites. The metamorphic unit was diversified by enduring magmatic activity in the form of chemically distinct gabbroic and quartz dioritic intrusions. Formation and composition of continental crust might be a typical example for the deeper plutonic sections of this continental magmatic arc.     

贵州凯里梁山组高硫煤中稀土元素的富集及其地质成因

基于电感耦合等离子质谱、X射线衍射等测试结果,分析了贵州省东部凯里地区下二叠统梁山组高硫煤中稀土元素的分布特征,探讨了稀土元素在煤中赋存方式和地质成因。结果表明:凯里煤中稀土元素含量远高于中国煤、美国煤和世界煤中稀土元素含量的平均值,轻稀土元素相对富集,煤层中稀土元素的物质来源具有一致性。研究认为:煤中稀土元素的赋存与黄铁矿有关,也存在一部分稀土元素通过原生富集而赋存在惰质组和壳质组中的可能性;相对较弱的泥炭沼泽水动力条件以及偏碱性还原的环境更有利于稀土元素在煤中的富集,海水对泥炭沼泽的影响是造成煤中富硫以及利于稀土元素富集环境条件发育的一个重要原因。     

The Rare Earth Elements and Uranium in Garnets from the Beinn an Dubhaich Aureole, Skye, Scotland, UK: Constraints on Processes in a Dynamic Hydrothermal System

Garnets from skarns in the Beinn an Dubhaich granite aureole,Isle of Skye, Scotland, have a large range of concentrationsof uranium (0·2–358 ppm) and the rare earth elements(REE) (23–4724 ppm). Variations in these concentrationscorrelate with major element zonation within the garnets, andwith changes in the shape of REE patterns. Typical patternsin most garnets display light REE (LREE) enrichment, flat heavyREE (HREE) distribution and a negative Eu anomaly. These patternsare interpreted to represent equilibrium trace element exchangebetween pre-existing pyroxene, hydrothermal fluid and calcicgarnets. Iron-rich zones are characterized by positive Eu anomaliesand an increase in the abundance of the LREE relative to theHREE. These patterns are interpreted as resulting from changesin REE speciation related to the introduction of externallybuffered fluid to the skarn system. Relatively Fe-poor zonesshow strongly HREE-enriched patterns with negative Eu anomaliesand in some instances depletions in Y relative to Ho and Dy,which are interpreted as resulting from surface sorption ofthe REE during rapid, disequilibrium garnet growth. Strong correlationsbetween U abundance and the REE patterns indicate that the sameprocesses have affected U distribution. Both types of patterncan be modified by the effects of closed-system crystallizationon REE abundance in the fluid, and changes in fluid major elementchemistry. KEY WORDS: fractionation; garnet; hydrothermal; rare earth elements; skarn     

Genesis for Rare Earth Elements Enrichment in the Permian Manganese Deposits in Zunyi,Guizhou Province,SW China

The Zunyi manganese deposits, which formed during the Middle to Late Permian period and are located in northern Guizhou and adjacent areas, are the core area of a series of large-medium scale manganese enrichment minerogenesis in the southern margin and interior of the Yangtze platform, Southern China. This study reports the universal enrichment of rare earth elements(REEs) in Zunyi manganese deposits and examines the enrichment characteristics, metallogenic environment and genesis of REEs. The ...     

稀土元素对鲁西铜石、铜井、龙宝山杂岩体的同源性制约

20世纪80年代,在山东省平邑县发现归来庄大型金矿床,实现了鲁西黄金找矿的重大突破。此后,鲁西相继发现卓家庄、磨坊沟和龙宝山金矿。近年,又在沂南金矿的深部发现新的矿体,鲁西良好的金矿成矿前景引起了地质学界的广泛关注。目前,鲁西发现的金矿床主要分布在铜石、铜井和龙宝山等燕山期杂岩体的附近。这些岩体在成因上有什么关系值得研究。通过对上述岩体稀土元素的地球化学分析,每种岩体不同期次侵入的岩浆岩的稀土元素分布形式和3种岩体综合稀土元素分布形式均呈向右陡倾的弧形线,且配分曲线形态基本相似,都没有明显的Ce、Eu异常,指示了岩体之间存在同源性,均来自深部同一岩浆房。该认识对于指导鲁西黄金找矿具有一定的意义。     

Anomalous Concentrations of Rare Metal Elements, Rare-scattered (Dispersed) Elements and Rare Earth Elements in the Coal from Iqe Coalfield, Qinghai Province, China

Total of 23 bench samples were taken from the No. 7 Coal of Iqe Coalfield, Qinghai Province, China, following Chinese Standard Method GB/T 482-2008 (2008). These samples were analyzed by powder X-ray diffraction (XRD), inductively coupled plasma mass spectrometry (ICP-MS) and X-ray fluorescence (XRF). The results indicate that the No. 7 Coal belongs to a low rank (Ro,ran =0.659%) and high-ash coal (40.54%). Compared to common Chinese and world low-rank coals, the Iqe coal contains anomalous concentrations of rare metal elements, rare-scattered (dispersed) elements and rare earth elements. The highest contents of Rb, Cs, Ga and REY reach to 180, 26, 37, and 397 ppm, respectively. Their average contents of these elements are 10.9, 15, 4.8 and 3.5 times higher than those of world coals, respectively. Minerals in the coal include kaolinite, quartz, muscovite, siderite, and traces of rutile, and brookite. Kaolinite could be main host minerals of Rb, Cs, Ga and REY. The anomalous rare element Rb and Cs accumulation in the Iqe coal is related to both organic and inorganic matter. The REY concentrations may be related to circulation of thermal solutions, contained or sorbed by clayey particles, and organic matter as well.     

Relative contribution of magmatic and post-magmatic processes in the genesis of the Thompson Mine Ni-Co sulfide ores,Manitoba, Canada

The Ni-Co-(PGE) sulfide deposits of the Thompson Nickel Belt (TNB) in Northern Manitoba, Canada are part of the fifth largest nickel camp in the world based on contained nickel; past production from the TNB deposits is 2500 kt Ni. The Thompson Deposit is located on the eastern and southern flanks of the Thompson Dome structure, which is a re-folded nappe structure formed during collision of the Trans-Hudson Orogen with the Canadian Shield at 1.9–1.7 Ga. The Thompson Deposit is almost entirely hosted by P2 member sulfidic metasedimentary rocks of the Paleoproterozoic Ospwagan Group. Variably serpentinised and altered dunites, peridotites and pyroxenites contain disseminated sulfides and have a spatial association with sediment-hosted Ni sulfides which comprise the bulk of the ore types. These rocks formed from rift-related komatiitic magmas that were emplaced at 1.88 Ga, and subsequently deformed by boudinage, thinning, folding, and stacking.Disseminated sulfide mineralization in the large serpentinised peridotite and dunite intrusions that host the Birchtree and Pipe Ni-Co sulfide deposits typically has 4–6 wt% Ni in 100% sulfide. The disseminated sulfides in the less abundant and much smaller boudinaged serpentinised peridotite and dunite bodies associated with the Thompson Deposit have 7–10 wt% Ni in 100% sulfide. The majority of Thompson Mine sulfides are hosted in the P2 member of the Pipe Formation which is a sulfidic schist developed from a shale prololith; the mineralization in the schist includes both low Ni tenor (<1 wt% Ni in sulfide) and barren sulfide (<200 ppm Ni) and a Ni-enriched sulfide with 1–18 wt% Ni in 100% sulfide. The semi-massive and massive sulfide ores show a similar range in Ni tenor to the metasediment-hosted mineralization, but there are discrete populations with maximum Ni tenors of ∼8, 11 and 13 wt% Ni in 100% sulfide. The variations in Ni tenor are related to the Ni/Co ratio (high Ni/Co correlates with high Ni tenor sulfide) and this relationship is produced by the different Ni/Co ratios in sulfides with a range in proportions of pyrrhotite and pentlandite. Geological models of the ore deposit, host rocks, and sulfide geochemical data in three dimensions reveal that the Thompson Deposit forms an anastomosing domain on the south and east flanks of a first order D3 structure which is the Thompson Dome. In detail, a series of second order doubly-plunging folds on the eastern and southern flank control the geometry of the mineral zones. The position of these folds on the flank of the Thompson Dome is a response to the anisotropy of the host rocks during deformation; ultramafic boudins and layers of massive quartzite in ductile metasedimentary rocks control the geometry of the doubly-plunging F3 structures. The envelope of mineralization is almost entirely contained within the P2 member of the Pipe formation, so the deposit is clearly folded by the first order and second order D3 structures. The sulfides with highest Ni tenor (typically >13 wt% Ni in sulfide) define a systematic trend that mirrors the configuration of the second order doubly-plunging F3 structures on the flanks of the Dome. Although moderate to high Ni tenor mineralization is sometimes localized in fold hinges, more typically the highest Ni tenor mineralization is located on the flanks of the fold structures.There is no indication of the mineralogical and geochemical signatures of sedimentary exhalative or hydrothermal processes in the genesis of the Thompson ores. The primary origin of the mineralization is undoubtedly magmatic and this was a critical stage in the development of economic mineralization. Variations in metal tenor in disseminated sulfides contained in ultramafic rock indicate a higher magma/sulfide ratio in the Thompson parental magma relative to Birchtree and Pipe. The variation in Ni tenor of the semi-massive and massive sulfide broadly supports this conclusion, but the variations in metal tenor in the Thompson ores was likely created partly during deformation. The sequence of rocks was modified by burial and loading of the crust (D2 events) to a peak temperature of 750 °C and pressure of 7.5 kbar. The third major phase of deformation (D3) was a sinistral transpression (D3 event) which generated the dome and basin configuration of the TNB. These conditions allowed for progressive deformation and reformation of pyrrhotite and pentlandite into monosulfide solid solution as pressure and temperature increased; this process is termed sulfide kinesis. Separation of the ductile monosulfide solid solution from granular pentlandite would result in an effective separation of Ni during metamorphism, and the monosulfide solid solution would likely be spread out in the stratigraphy to form a broad halo around the main deposit to produce the low Ni tenor sulfide. Reformation of pentlandite and pyrrhotite after the peak D2 event would explain the broad footprint of the mineral system. The effect of the D3 event at lower pressure and temperature would have been to locally redistribute, deform, and repeat the lenses of sulfide.The understanding of the relationships between petrology, stratigraphy, structure, and geochemistry has assisted in formulating a predictive exploration model that has triggered new discoveries to the north and south of the mine, and provides a framework for understanding ore genesis in deformed terrains and the future exploration of the Thompson Nickel Belt.     

Deglaciation of the younger dryas or Loch Lomond Stadial ice-field in the northern Highlands,Scotland

When viewed from the air, Scottish ‘hummocky moraine’ can be resolved into a series of linear ridges that resemble those found at the margins of actively retreating glaciers today. Recent work has supported the interpretation of these linear ridges as ice-marginal landforms and the authors believe that the majority of ‘hummocky moraine’ deposits can be interpreted in this way. Consequently the pattern of deglaciation can be established fairly precisely from the pattern of linear ridges. This approach is applied to the landforms of the northern part of the Loch Lomond Stadial ice-field in order to reconstruct the regional pattern of deglaciation. This leads to important inferences about the significance of topographic control during deglaciation and more importantly it provides fresh insight into the environment of the British Isles during the Loch Lomond Stadial.     

三稀元素矿床类型及找矿标志

"三稀"元素是当前乃至今后一段时期地质勘查的热门矿种之一。通过对"三稀"元素组合及矿物组合规律的研究,根据成矿地质作用和成矿方式,将"三稀"元素矿床分为七个成矿系列、十四种成因类型,并重点介绍了与岩浆活动有关稀有稀土矿产特征;在此基础上,从控矿条件和矿化指示两方面总结出稀有稀土元素矿床的找矿标志,供广大地质工作者在地质找矿工作中参考。     

大同盆地沉积物REE分布特征及其对碘富集的指示

大同盆地是典型的干旱-半干旱内陆盆地,盆地中部地下水碘含量异常,对当地饮用水安全造成了严重威胁.对盆地高碘地下水分布区沉积物组成及稀土元素(REE) 进行了地球化学研究,结果表明,地下水系统呈弱碱性(pH值为7.18~9.64) 的偏还原环境,沉积物多为Ce正常或轻微负异常及Eu负异常;沉积物中碘含量为0~1.78×10-6;ΣREE含量较高,ΣLREE/ΣHREE比值为2.79~4.14,即富集轻稀土元素(LREE) 而亏损重稀土元素(HREE).ΣREE与碘含量呈负相关关系,虽然铁氧化物/氢氧化物矿物的还原性溶解可导致二者的释放,但由于沉积物有机质产生的低结晶矿物对碘的强吸附性,使沉积物中碘含量较高;弱碱性环境中REE的再吸附过程会导致沉积物中富集LREE;沉积物中碘含量与氧化还原敏感组分TOC、U、V及[Eu]_N的关系也表明,地下水系统的氧化还原条件及有机质含量是影响碘富集的重要因素.      

竹山和马鞍山绿松石微量元素和稀土元素特征

对竹山和马鞍山两地绿松石的微量元素和稀土元素特征作了对比研究,同时分析了两地绿松石矿物特征和结构特征。采用X射线能谱、电感耦合等离子体质谱、X射线衍射、红外吸收光谱和扫描电镜等测试技术对竹山和马鞍山地区的绿松石样品进行岩石矿物学特征分析。结果表明,竹山与马鞍山地区绿松石在微量元素的含量上存在较大的差别,但主成分含量基本一致;两地区绿松石的稀土元素均富集重稀土,二者的稀土配分模式图出现镨反向,马鞍山地区的绿松石表现出铕负异常;马鞍山绿松石的结晶程度优于竹山县绿松石。该方法对绿松石产地划分的研究具有应用价值。     

Microstructural evidence for crystallization regimes in mafic intrusions: a case study from the Little Minch Sill Complex,Scotland

The magma forming the 20 m thick crinanitic/picrodoleritic Dun Raisburgh sill, part of the Little Minch Sill Complex of NW Scotland, comprised a mafic carrier liquid with a crystal cargo of plagioclase and olivine (1 vol%). The olivine component of the cargo settled on the floor of the intrusion while the more buoyant plagioclase component remained suspended during solidification, resulting in a relatively high plagioclase content in the centre of the sill. The settled olivine grains form a lower fining-upwards sequence overlain by a poorly sorted accumulation formed of grains that grew within the convecting magma. The accumulation of olivine on the sill floor occurred over 5–10 weeks, synchronous with the upwards-propagation of a solidification front comprising a porous (~?70 vol% interstitial liquid) plagioclase-rich crystal mush.     

四川稀土精矿的稀土元素和微量元素地球化学特征及开发利用意义

四川省是我国轻稀土的重要产地,开采近二十年来生产了大量稀土精矿,精矿的稀土品位及其他有用元素组成对矿山资源评价及企业生存至关重要。本文对A、B、C三个稀土矿区稀土精矿的稀土元素和微量元素组成特征进行了研究。结果表明:不同矿区、不同选矿方法、不同企业生产的精矿,其稀土元素和微量元素含量存在显著差异;A矿区浮选精矿的稀土含量最低(ΣREEs=41.57%),而C矿区精矿的稀土含量最高(ΣREEs=55.83%);A矿区磁选精矿的稀土含量(ΣREEs=49.96%)高于浮选精矿(ΣREEs=41.57%);B矿区甲公司(ΣREEs=48.35%)精矿产品的稀土含量高于乙公司精矿产品(ΣREEs=42.92%)。精矿的稀土元素配分特征继承了原矿石的同时普遍亏损Tb和Yb,推测是选矿过程导致了元素的亏损。精矿中除了富集稀土元素,Mo、Bi、Pb、Ga、Th、U、W等有用元素也发生了不同程度的富集,综合利用价值高,尤其是Mo(0.56%)和Ga(0.036%)的含量已达到现行边界品位。本文提出,今后在提高精矿稀土品位的同时,需对富集的元素采取恰当的方式加以综合回收。     

四川稀土矿尾砂的稀土元素和微量元素地球化学特征及开发利用意义

四川是我国轻稀土的重要产地,稀土开采至今已有二十多年的历史,积存了大量尾砂。尾砂中仍然有丰富的稀土资源,但这部分资源究竟有多大的量、能不能再次回收,如何回收,则是当务之急。为查明稀土尾砂中各类元素的分布特征,本文对A、B、C、D四个稀土矿山的尾砂开展了稀土元素和微量元素地球化学特征的初步研究。结果表明:尾砂中稀土元素配分特征继承了原矿石,稀土氧化物含量普遍偏高(0.78%~2.12%),均超过了现行工业指标的边界品位(0.5%~1.0%),且老尾砂的稀土含量高于新尾砂;除了富集稀土元素之外,B尾砂中Sr含量超过10%,C矿区尾砂中Sr含量为2.7%,A矿区尾砂中Ba含量可达1.8%。同时,不同矿区的尾砂中Mo、Bi、Pb、Ag等有用元素发生了不同程度地富集(值得综合回收利用),尤其是Mo达到了边界品位(磁选后的尾砂Mo含量达到2.275%)。本文提出,今后不仅要加强保护四川稀土尾砂,而且需对富集的有用元素采取恰当的方式加以综合回收。     

A preliminary study of PGE in the Late Caledonian Loch Borralan and Loch Ailsh alkaline pyroxenite-syenite complexes,north-west Scotland

The Siluro-Ordovician Loch Borralan (c. 430 Ma) and Loch Ailsh Complexes (c. 439 Ma) comprise a suite of intrusive rocks ranging in composition from clinopyroxenites, through potassic melasyenites to quartz syenites. The rock suite at Loch Borralan also includes nepheline syenite. Geochemical data in the literature indicate that the intrusions are alkaline, with pronounced enrichments in LILE and LREE relative to contemporaneous calc-alkaline magmatic centres further to the south-east, although they share similar high LILE/Nb, subduction-related characteristics. The Loch Borralan Complex is associated with marginal gravity and magnetic anomalies which can be interpreted in terms of a shallow body less than 400 m thick. Analysis of rocks and drill core revealed widespread elevated Pt and Pd values in pyroxenites and syenites in both complexes. The highest concentrations, up to about 900 ppb Pt+Pd, occur in pyroxenites in the Loch Borralan Complex. Extensive archived drill core provides an excellent section through the marginal pyroxenites, which host the PGE at Loch Borralan. The pyroxenites show unusual petrological features; early clinopyroxene is followed by biotite, apatite, magnetite, sphene and plagioclase with later garnet, which might be metasomatic in origin. Sulphides occur in minor amounts. High-temperature shearing produced local granulation and mylonitisation. Later brittle deformation caused extensive micro-fracturing and the introduction of minor carbonate veining. Platinum-group minerals (PGM) were located in a number of samples with high PGE assay values. These occur as clusters of grains around 1–2 m in diameter, and are difficult to identify uniquely. A few grains appear to be magmatic; these are Pt and PtPd sulphides that occur enclosed in clinopyroxene or garnet. All other grains occur in late fractures or along grain boundaries. These include sperrylite (PtAs₂), Pd antimonides and PdBi tellurides, along with hessite (Ag₂Te). They occur in microfractures accompanied by carbonate and barite and fine-grained sulphides and are probably of secondary origin. The PGE in the pyroxenites may have been introduced during the magmatic phase of the intrusion but the observed distribution of PGM results from low-temperature, hydrothermal remobilisation following brittle deformation and introduction of fluids.

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.