Gardar Province Research Articles

Assimilation and extensive metasomatism of agpaitic rocks from the transitional layered kakortokite, Ilímaussaq Intrusion, South Greenland

AbstractThe peralkaline Ilímaussaq Intrusion of the Gardar Province in South Greenland consists of several intrusive phases that have been related to different magmatic pulses and igneous cumulate processes. The lowermost exposed part of the intrusion is kakortokite, a eudialyte‐nepheline syenite, with distinctive sub‐horizontal layering which passes upwards into lujavrite, a fine‐grained melanocratic eudialyte‐nepheline syenite. Along the contact between kakortokite and lujavrite lies a transitional layered kakortokite, which has been defined previously based on textural and mineralogical criteria. However, published literature presents conflicting descriptions of this sequence in terms of thickness, layering, contacts, and mode of origin. Our own and previous field and petrographic investigations suggest that parts of the eudialyte‐rich zones in the transitional layered kakortokite comprise metasomatized and partially assimilated naujaite autoliths, a sodalite‐rich eudialyte nepheline syenite, detached probably from the roof of the intrusion. Here, we focus on the nature of the transitional layered kakortokite and conclude, in contrast to the conventional model, that it was formed by metasomatic transformation and assimilation of naujaite autoliths. We propose that the breakdown and replacement of sodalite locally increased chlorine and sodium concentrations, which may have catalyzed the precipitation of eudialyte. In detail, we suggest that the uppermost four eudialyte‐rich horizons were strongly influenced by metasomatic processes caused by mineral‐melt reaction, and were not simply the result of conventional igneous magmatic cumulate formation, as has been inferred for the underlying kakortokite layered units. Recognition of a significant metasomatic process has important bearing on the distribution of minerals with specific elements, like REE in eudialyte, both from a petrological and an economic perspective.

Mantle sources and magma evolution in Europe's largest rare earth element belt (Gardar Province, SW Greenland): New insights from sulfur isotopes

Alkaline igneous complexes are often rich in rare earth elements (REE) and other metals essential for modern technologies. Although a variety of magmatic and hydrothermal processes explain the occurrence of individual deposits, one common feature identified in almost all studies, is a REE-enriched parental melt sourced from the lithospheric mantle. Fundamental questions remain about the origin and importance of the mantle source in the genesis of REE-rich magmas. In particular, it is often unclear whether localized enrichments within an alkaline province reflect heterogeneity in the mantle source lithology (caused by prior subduction or plume activity) or variations in the degree of partial melting and differentiation of a largely homogeneous source. Sulfur isotopes offer a means of testing these hypotheses because they are unaffected by high temperature partial melting processes and can fingerprint different mantle sources. Although one must be careful to rule out subsequent isotope fractionation during magma ascent, degassing and crustal interactions.Here, we present new S concentration and isotope (δ34S) measurements, as well as a compilation of major and trace element data, for a suite of alkaline magmatic units and crustal lithologies from the Mesoproterozoic Gardar Province. Samples span all phases of Gardar magmatism (1330–1140 Ma) and include regional dykes, rift lavas and the alkaline complexes Motzfeldt and Ilímaussaq, which represent two of Europe's largest REE deposits. We show that the vast majority of our 115 samples have S contents >100 ppm and δ34S of −1 to 5‰. Only 8 samples (with low S contents, <100 ppm) show evidence for crustal interactions, implying that the vast majority of Gardar melts preserve the S isotopic signature of their magma source. Importantly, samples from across the Gardar Province have δ34S above the canonical mantle range (≤−1.4‰) and therefore require recycled surface S in their mantle source. Elevated δ34S values are explained by a period of Andean-style subduction and mantle metasomatism which took place ∼500 Ma before rift onset and are also supported by trace elements signatures (e.g. Ba/La) which match modern subduction zones.Comparing the various generations of Gardar magmas, we find that δ34S values, large ion lithophile elements (K, Ba, P) and selective incompatible elements (Nb and light REE) are particularly enriched in the Late Gardar dykes, alkaline complexes and clusters of silica-undersaturated dykes spatially associated with the alkaline complexes. These data indicate that subduction-related metasomatism of the Gardar mantle was spatially heterogeneous, and that alkaline complexes are sourced from localized mantle domains highly enriched in 34S, REE, alkalis and volatiles (particularly, F). Since alkalis and volatiles play an essential role in driving extreme differentiation of alkaline melts and fluids, we suggest the co-location of these species plus incompatible metals at high concentrations in the lithospheric mantle is a critical first-step in the genesis of a world-class alkaline REE deposit. S isotopes are powerful tools for identifying enriched mantle domains and the sources of mineralized alkaline igneous bodies.

New insights from field observations of the Younger giant dyke complex and mafic lamprophyres of the Gardar Province on Tuttutooq island, South Greenland

The Gardar Province of south Greenland is defined by the products of alkaline igneous magmatism during the Mesoproterozoic. The most laterally extensive Gardar intrusions are a series of giant dyke complexes best exposed on the Tuttutooq archipelago. We present new field observations and a geological map of north-east Tuttutooq island that provide fresh insights into the temporal evolution of the Younger giant dyke complex and two associated ultramafic lamprophyres. Our data demonstrate that distinctive crystallisation regimes occurred in different sectors of the dyke complex, leading to the formation of marginal gabbros and ovoid pod-like domains displaying lamination, modal layering and/or more evolved differentiates. We infer that at least two pulses of magma contributed to the formation of the Younger giant dyke complex. In addition, the relative ages of two ultramafic lamprophyre diatremes are constrained and attributed to two distinct phases of rifting in the Gardar Province.

Petrography, geochemistry and magnetic susceptibility of the Isortoq Fe-Ti-V deposit, Isortoq Giant Dykes, South Greenland

The Isortoq Giant Dykes in the Proterozoic Gardar Province, South Greenland, include the Isortoq South giant dyke and the Isortoq North giant dyke. The fine-grained Fe-Ti-V deposit hosted by the Isortoq South giant dyke, referred to as the Isortoq Fe-Ti-V deposit, is considered a good test site for the use of magnetic susceptibility for the mapping of ore grades. Here, we test this and show that the Fe, Ti and V distribution is controlled by titanomagnetite disseminated throughout fine-grained troctolite. The deposit displays a clear correlation between magnetic susceptibility and Fe, Ti and V grades in bulk samples of consecutive 2 m sections from 11 drill cores, totalling 2671 m in length. We observe that Fe, Ti and V are almost entirely hosted in titanomagnetite, which controls the magnetic susceptibility. Field measurements of the magnetic susceptibility can thus be considered as a reliable exploration tool for this type of mineralisation. We further consider the origins of the deposit by reconnaissance petrography, mineral and bulk rock chemistry of the large mass of aphanitic Fe-rich troctolite in the Isortoq South giant dyke. We suggest that the deposit may represent the base of a basanitic to trachybasaltic magma chamber, in which Fe-rich immiscible melts accumulated, crystallised and fractionated. The processes suggested here may apply to other giant dykes and intrusions of the Gardar Province.

The characteristics of zircon as the evidence for post-magmatic remobilization of REE and HFSE in the northern Motzfeldt alkaline igneous complex, southern Greenland

The Motzfeldt intrusions in the Gardar Province, southern Greenland, split into syenitic plutonic and hypabyssal rocks, in which the latter include ring dykes and sheet intrusions. Sheet intrusions, considered as the source for rare earth elements (REE) and high field strength elements (HFSE), comprise sheets of peralkaline microsyenite (SPM), syenitic pegmatite (SP), and peralkaline microsyenite (PM). SP exhibits extremely high concentrations of REE and HFSE, which are positively correlated with increasing alkalinity from early towards late intrusion, caused by magmatic processes. In contrast, some of the SPM and PM are also significantly enriched in REE and HFSE, caused by post-magmatic fluids. The REE-and HFSE-rich phases in SP consist mainly of zircon and allanite with smaller amounts of pyrochlore in pseudomorph from the inferred eudialyte, whereas some of the PM and SPM consist of pyrochlore, REE-carbonate, and zircon in the matrix. The zircon grains in the Motzfeldt So Formation (MSF) syenite occur in interstitial spaces, exhibiting an association with magnetite and a bipyramidal form in texture. They are characterized by a highly fractured and embayed rim. Zircons from PM and SP are clearly enriched in Fe, Al, Ca, Na, Y, P, Hf, Y, P, Nb, Ta, and REE, and are depleted in Zr and Si in comparison with magmatic zircon. They also show a clear trend of higher LREE/HREE and Eu/Eu* ratios, and lower Ce/Ce* ratios, which define them as typical hydrothermal zircons. In contrast, zircons from the MSF syenite show a relatively lower LREE/HREE ratio and Eu and Ce anomalies of a similar magnitude compared with those from SP and PM. The occurrence and mineral composition of the zircon suggest that post-magmatic fluids have played an important role in the remobilization of REE and HFSE as well as the primary concentration of REE and HFSE, caused by magmatic processes.

Compositional variation of apatite from rift-related alkaline igneous rocks of the Gardar Province, South Greenland

Textural and compositional variations of apatite from rift-related gabbros, syenogabbros, syenites, quartz-syenites, and nepheline syenites of the Mid-Proterozoic Gardar Province (South Greenland) are presented and compared to apatite compositions from other rock suites. The observed zoning textures of apatite are interpreted to represent (1) primary growth zonation (concentric and oscillatory) that formed during magmatic differentiation and (2) secondary irregular overgrowths, patchy zonation, and resorption textures, assigned to metasomatic overprinting due to interaction with fluids/melts and intra-crystalline diffusion. Compositional variation in the apatites is mainly due to coupled substitutions of Ca and P by variable amounts of Si, Na, and REE, which show increasing concentrations during magmatic differentiation. Furthermore, F concentrations in apatites increase from gabbroic through syenogabbroic to syenitic rocks, whereas Cl concentrations show the opposite trend. Compared to apatite compositions from gabbroic, dioritic, and granitic rocks in general, apatites from alkaline rock suites are characterized by exceptionally high contents of REE and Si and in some alkaline rocks they attain Sr contents comparable to those reported from carbonatites. Typical low Mn and S contents are probably a result of low oxygen fugacity during crystallization at relatively high temperatures.

Mesoproterozoic dykes in the Timmiarmiit area, Southeast Greenland: evidence for a continuous Gardar dyke swarm across Greenland’s North Atlantic Craton

During the Proterozoic, several mafic dykes with variable trends and mineralogies intruded the Archaean basement of Southeast Greenland. Some of the younger ENE-trending dykes are interpreted to represent a prolongation of the Mesoproterozoic Gardar Province, and have been termed Timmiarmiit dykes. Extrapolations of their trends across the inland ice sheet coincide with the northernmost so-called brown dykes (BD’s) which are part of the Gardar Province. Baddeleyite U–Pb ID-TIMS analyses for three ENE-trending Timmiarmiit dykes give ages of 1277 ± 4, 1275 ± 3 and 1268 ± 4 Ma, which are slightly younger than the oldest (BD0 = 1284–1279 ± 3 Ma, Upton 2013) and only dated generation of dykes in the Gardar Province, and thereby indirectly provide a possible age for the two younger dyke generations (BD1 and BD2). The Timmiarmiit–Gardar correlation is strengthened by a rigorous multivariate statistical analysis, on the basis of all major and trace elements. Thus, a coherent ENE-trending trans-Greenlandic dyke swarm is constituted. The major and trace element data of the Timmiarmiit dykes show that they crystallised from comparably evolved mantle-derived magma with minor crustal contamination and indicate a strong contribution of a metasomatised subcontinental lithospheric mantle component in the evolution of melts. This component was probably influenced by supra-subduction zone metasomatism during the Palaeoproterozoic Ketilidian orogeny. The data presented here, in addition to recent plate reconstruction models, give new evidence for a petrogenetic link between rift-related Mesoproterozoic magmatism in North America, South Greenland and Central Scandinavia which possibly formed in response to back-arc basin formation.

Petrological and geochemical characteristics of Mesoproterozoic dyke swarms in the Gardar Province, South Greenland: Evidence for a major sub-continental lithospheric mantle component in the generation of the magmas

AbstractThe Mesoproterozoic Gardar Province in South Greenland developed in a continental rift-related environment. Several alkaline intrusions and associated dyke swarms were emplaced in Archaean and Ketilidian basement rocks during two main magmatic periods at 1300–1250 Ma and 1180–1140 Ma. The present investigation focuses on mafic dykes from the early magmatic period ('Older Gardar') and the identification of their possible mantle sources.The rocks are typically fine- to coarse-grained dolerites, transitional between tholeiitic and alkaline compositions with a general predominance of Na over K. They crystallized from relatively evolved, mantle-derived melts and commonly show minor degrees of crustal contamination. Selective enrichment of the large ion lithophile elements Cs, Ba and K and the light rare-earth elements when compared to high field-strength elements indicate significant involvement of a sub-continental lithospheric mantle (SCLM) component in the generation of the magmas. This component was affected by fluid-dominated supra-subduction zone metasomatism, possibly related to the Ketilidian orogeny ∼500 Ma years prior to the onset of Gardar magmatism. Melt generation in the SCLM is further documented by the inferential presence of amphibole in the source region, negative calculated εNd(i) values (–0.47 to –4.40) and slightly elevated87Sr/86Sr(i) (0.702987 to 0.706472) ratios when compared to bulk silicate earth as well as relatively flat heavy rare-earth element (HREE) patterns ((Gd/Yb)N= 1.4 –1.9) indicating melt generation above the garnet stability field.The dyke rocks investigated show strong geochemical and geochronological similarities to penecontemporaneous mafic dyke swarms in North America and Central Scandinavia and a petrogenetic link is hypothesized. Considering recent plate reconstructions, it is further suggested that magmatism was formed behind a long-lived orogenic belt in response to back-arc basin formation in the time interval between 1290–1235 Ma.

The volcano–pluton interface; The Longonot (Kenya) and Kûngnât (Greenland) peralkaline complexes

An important step in studying volcanic processes is to consider the coeval processes in the subjacent magma reservoir(s). The trachytic caldera volcano Longonot (Kenya Rift Valley) and the Kûngnât syenite complex (Gardar province, Greenland) are taken to represent complementary magmatic systems, providing evidence of the volcanic and plutonic stages of evolution, respectively. The systems show many features in common; they have similar sizes, experienced two periods of caldera collapse, and were dominated by trachytic magmas, with smaller volumes of basic magma. Magmatic differentiation was dominantly by fractional crystallization of basaltic parents, with minor episodes of magma mixing and, at Kûngnât, some crustal contamination of parental basalts. A model is presented of a single, hypothetical trachytic centre, showing how evidence from one complex can be used to infer processes at the other. For example, an active convective system, with formation of wall and floor syenitic cumulates, can be inferred to exist in the Longonot magma chamber. At Kûngnât, the intermittent development of compositionally zoned caps to the magma chamber is postulated and the nature of syn-caldera eruptive activity is outlined.

Geochemistry of pyrochlore minerals from the Motzfeldt Center, South Greenland: The mineralogy of a syenite-hosted Ta, Nb deposit

Pyrochlore minerals are common accessory phases in the syenite and nepheline syenite rocks of the Motzfeldt alkaline center, Gardar Province, South Greenland, and are of important economic interest due to their exceptional ability to host various high field strength elements. In this study pyrochlore from two distinct intrusive units within the Motzfeldt Center have been studied. The largely homogeneous syenite and nepheline syenite rocks of the Flinks Dal formation host oscillatory and sector-zoned pyrochlore, which have experienced minor alteration in the presence of high-temperature, dominantly juvenile magmatic fluids. Alteration is characterized by variable decrease in the Na, Ca, and F contents and addition of Sr and K, accompanied by introduction of A and Y site vacancies. Pyrochlore from the more heterogeneous and intensely altered syenite rocks of the Motzfeldt So Formation are pervasively altered through interaction with lower temperature evolved hydrothermal fluids. During this phase of alteration cations are preferentially leached from the A and Y sites, accompanied by progressively increasing hydration. In both formations the proportion of B -site cations remains unaltered regardless of the degree of alteration. The alteration encoded in the pyrochlores of the Motzfeldt Center records the different hydrothermal conditions the two formations experienced during the subsolidus, showing how evolution of fluids within one intrusive unit can vary both spatially and temporally.

A tale of two intrusions—where familiar rock names no longer suffice

Two contrasting intrusions in Greenland are described which both have extreme compositions and mineralogy. Ilímaussaq is part of the Mezoproterozoic Gardar Province of southern West Greenland. It developed by extreme fractionation in the crust of non‐remarkable weakly alkaline basic magmas leading to extraordinarily high levels of many rare elements. Indeed, in this intrusion the zirconium mineral, eudialyte, attains rock‐forming status. Gardiner in the East Greenland sector of the Palaeogene North Atlantic Igneous Province, was formed from nephelinitic magmas formed at great depth in the mantle by very low degrees of partial melting. Here, the magmas were so silica‐poor that there are large amounts of rocks composed of the melilite group of minerals, generally with perovskite (CaTiO4) as a major phase. Thus, extreme compositions at Ilímaussaq were caused by fractionation to very small amounts of melt while at Gardiner it was caused by very small degrees of mantle melting. Both intrusions are known for fine specimens of rare minerals; in the case of Ilímaussaq over 200 have been described. Rocks such as those found here require their own names as they cannot be accommodated in the usual petrological nomenclature.

Independent ages of magmatic and hydrothermal activity in alkaline igneous rocks: The Motzfeldt Centre, Gardar Province, South Greenland

The Motzfeldt Centre is one of four major alkaline centres belonging to the Igaliko complex, part of the Mid-Proterozoic Gardar province of South Greenland. Motzfeldt comprises syenites and nepheline syenites displaying complex magmatic and subsolidus histories. Ta, Nb and REE-rich zones are associated with a pervasive hydrothermal alteration process in the North and East of the complex, part of a subdivision of the Centre called the Motzfeldt So Formation (MSF). The zircons from the MSF show textures that are both magmatic and altered, whereas the textures of pyrochlore have a predominantly subsolidus chemistry. We compare and contrast the radiogenic isotope geochemistry of the zircon and pyrochlore to obtain independent age estimates of the magmatic and hydrothermal episodes. Selected analyses of magmatic zircons are concordant with an age of 1,273 ± 6 Ma. Altered zircons are normally discordant with one intercept at 1,261 ± 28 Ma and the other at 349 ± 49 Ma. This younger age would appear on face value to date the hydrothermal event at Motzfeldt to ~900 Ma after the magmatism. However, the Pb–Pb isotope systematics from altered pyrochlore define an isochron age of 1,267 ± 6 Ma for isotopic closure of the pyrochlore following alteration during the subsolidus. There is no known magmatic event in Southern Greenland at ~350 Ma and discordant points have high common lead. We therefore infer that the younger intercept age is spurious. The overlap between the magmatic U–Pb zircon and the Pb–Pb pyrochlore age suggests that alteration of the Motzfeldt centre occurred shortly after magmatism.

The Mineralogical Diversity of Alkaline Igneous Rocks: Critical Factors for the Transition from Miaskitic to Agpaitic Phase Assemblages

Geochemically, the large family of alkaline plutonic rocks (both Qtz-undersaturated and -oversaturated compositions) can be subdivided into metaluminous [(Na 2 O + K 2 O) < Al 2 O 3 ] and peralkaline [(Na 2 O + K 2 O) > Al 2 O 3 ] types. In this paper, we discuss two important aspects of the mineralogical evolution of such rocks. With respect to their Fe–Mg phases, a major mineralogical transition observed is the precipitation of arfvedsonite or aegirine instead of fayalite or magnetite (± ilmenite). The relative stability of these phases is controlled by oxygen fugacity and Na activity in the crystallizing melts. If Na activity in the melt is high enough, arfvedsonite + aegirine form a common assemblage in peralkaline rocks under both reduced and oxidized conditions. Major mineralogical differences within this rock group exist with respect to their high field strength element (HFSE)-rich minerals: most syenitic rocks, known as miaskites, contain zircon, titanite or ilmenite as HFSE-rich minerals, whereas in agpaites complex Na–K–Ca–(Ti, Zr) silicates incorporate the HFSE. Similarly, only a small group of peralkaline granites are found to lack zircon, titanite or ilmenite but instead contain Na–K–Ca–(Ti, Zr) silicates. Here, we present a detailed phase petrological analysis of the chemical parameters (µNa 2 O, µCaO, µK 2 O) that influence the transition from miaskitic to agpaitic rocks. Based on the occurrence of Ti and Zr minerals, several transitional mineral assemblages are identified and two major evolution trends for agpaites are distinguished: a high-Ca trend, which is exemplified by the alkaline rocks of the Kola Province, Russia, and a Ca-depletion trend, which is displayed by the alkaline rocks of the Gardar Province, South Greenland. Both trends show significant Na-enrichment during magmatic evolution. High-Ca agpaites evolve from nephelinitic parental melts that did not crystallize large amounts of plagioclase. In contrast, agpaites showing Ca-depletion originate by extensive fractionation of plagioclase from basaltic parental melts. In some peralkaline granites evolutionary trends are observed that culminate in agpaite-like HFSE-mineral associations in the most evolved rocks.

Halogen and trace-element chemistry in the Gardar Province, South Greenland: Subduction-related mantle metasomatism and fluid exsolution from alkalic melts

XRF analyses of 152 magmatic dyke samples from a broad area (150×60km) of the Gardar Province in Southern Greenland span the time 1280 to 1163Ma and represent a wide compositional range (transitional olivine basalts to trachytes, alkalinity index of 0.3 to 1.5). Among those, 16 dyke samples were additionally analysed for Cl and Br.Generally, the dykes represent a continuous fractionation trend from relatively unfractionated basalts to more highly fractionated trachytes. Dykes from different areas exhibit a diverse geochemistry suggesting a heterogeneous and metasomatised mantle source. Enrichment in LILE, LREE and Sr and depletion in HFSE, Nb and Ti suggest that some of the metasomatism may have been associated with subduction processes pre-dating Gardar activity by some 600Ma (Ketilidian orogeny).The dykes are characterised by high F contents up to 1.2wt.%, particularly in the vicinity of the Ivigtut fluoride deposit. F was probably derived from partial melting of lithospheric mantle enriched in F-apatite and F-phlogopite. High Cl/Br (>500) and low Cl/F (<1) ratios of the dykes point to a fluid degassing/separation process which is supported by mineral/rock and fluid inclusion data from the Ilímaussaq and Ivigtut intrusions. There, the analysed rocks and minerals generally show high Cl/Br (>300) and low Cl/F (<1) weight ratios whereas the fluid inclusions have complementary low ratios (Cl/Br ±100; Cl/F >10). Our investigations are in accordance with experimental data which show that F is preferentially enriched in the melt whereas Cl and especially Br are lost with the fluid phase. Accordingly, the halogens show an increase in incompatible behaviour in the magma in the order of F<Cl<Br.

The Magmatic and Fluid Evolution of the Motzfeldt Intrusion in South Greenland: Insights into the Formation of Agpaitic and Miaskitic Rocks

The 1� 275 Ga Motzfeldt intrusive complex in the Gardar failed-rift Province in South Greenland formed from six successively intruding melt batches (SM1^SM6) interpreted to be derived from a common magma source at depth. Five units (SM1^SM5) crystallized an alkaline to peralkaline, miaskitic mineral assemblage of amphibole, clinopyroxene, feldspar, nepheline, Fe^Ti oxides, zircon, apatite, fluorite and rarely olivine.The last magmatic batch (SM6) is characterized by an agpaitic mineral assemblage of aegirine, nepheline, alkali-feldspar, eudialyte and rare fluorite or sodalite. Coexisting mafic minerals constrain the crystallization conditions of the miaskitic rocks to about 850^6008C, whereas solidus temperatures below 5008C are indicated by coexisting alkali feldspars in the agpaitic rocks. Oxygen fugacities during the orthomagmatic stage are below the FMQ (fayalite^ magnetite^quartz) buffer (FMQ ^0 � 5t o ^2� 0) whereas late hematite provides evidence of a higher relative oxygen fugacity during late-stage alteration. The Nd and oxygen isotope compositions of amphiboles and pyroxenes are homogeneous throughout the complex and suggest a common, mantle-derived magma source for all six units which is comparable with other Gardar intrusions.The hydrogen isotopic composition of amphiboles (dD^99 to ^132%) indicates lowtemperature fluid^rock interaction with low fluid^rock ratios. Fluid inclusion studies indicate that H2O^NaCl fluids present during the magmatic stages in the miaskitic units had salinities of510 wt % NaCl eq. Calcite crystals in fluid inclusions within these rocks suggest that CO2 or HCO3 ^ was an important component of the original fluid phase. In contrast, the agpaitic unit is characterized by a CH4^H2O^ NaClfluid.The C^O^H isotope compositionsofthefluid inclusions in all units are consistent with mixing between a small volume of magmatic fluid and a large volume of meteoric water. The chemical evolution of the Motzfeldt complex is a type example of the connection of the transition from miaskitic to agpaitic mineral assemblages with redox-dependent fluid^solid equilibria.Thetransitionfromarelatively oxidized to a relatively reduced fluid is correlated with a change from a more reduced, Fe 2þ -bearing miaskitic (taramite^arfvedsonite, zircon, SM1^SM5) to a more oxidized, Fe 3þ -bearing agpaitic assemblage (aegirine, eudialyte, SM6).We suggest that coupled fluid^solid redox equilibria involving Fe 2þ ,F e 3þ ,C O2 and CH4 in this case were simply driven by temperature decrease and an overall increase in Na (þ K) in the melt.This observation sheds light on the heavily debated miaskite^ agpaite transition.The combined temperature and compositional effect stabilized Fe 3þ ,C H 4 and enhanced the solubility of Zr (possibly as Na^Zr^Si^O complexes) in the latest stage melt (SM6) resulting in the crystallization ofan agpaitic mineral assemblage. In terms of redox conditions during crystallization, the Motzfeldt rocks represent an intermediate case in the Gardar Province between more oxidized, CO2dominated intrusions such as the syenite^carbonatite complex of

Isotope, major, minor and trace element geochemistry of late-magmatic fluids in the peralkaline Ilímaussaq intrusion, South Greenland

The persodic, 1.16 Ga old Ilímaussaq intrusion consists of alkali granites, syenites, and agpaitic nepheline syenites. These rocks are cut by late-magmatic veins and lenses consisting of albite, aegirine, ussingite (Na 2AlSi 3O 8(OH)), fluorite, and occasionally quartz. Oxygen-isotope compositions of quartz indicates both orthomagmatic ( δ 18O qtz = 8.5‰) and country rock-influenced ( δ 18O qtz ~ 10‰) origin. While albite and aegirine do not contain fluid inclusions suitable for investigations, ussingite contains secondary hydrocarbon fluid inclusions, fluorite contains brine inclusions of primary and secondary origin with up to 26.3 wt.% NaCl equiv., and quartz contains predominantly secondary brine inclusions with up to 29.7 wt.% NaCl equiv. or CH 4–H 2O–NaCl mixtures. These fluids are interpreted to reflect fluids in equilibrium with late-stage melts at Ilímaussaq at ≤ 450 °C. The carbon- and hydrogen-isotope composition of CH 4 in ussingite ( δ 13C = − 6 to − 3‰, δD = ~− 121‰) is indicative of a magmatic abiogenic origin. However, the isotopic composition of CH 4 in fluid inclusions in quartz veins resembles the signature of thermogenic CH 4 ( δ 13C = − 43 to − 23‰, δD = − 176 to − 121‰), but the higher hydrocarbons are mostly 13C-depleted in relation to CH 4 (up to 7.3‰), which is typical of abiogenically-derived hydrocarbons. Ion-chromatography of fluid inclusion leachates from the late-stage veins reveals Cl/Br ratios of ~ 100. As such values seem to be typical of peralkaline magmatic rocks, at least in the Gardar Province of South Greenland, it is suggested that this ratio is typical of Gardar magmatic fluids and may be characteristic of the Cl/Br ratio of the lithospheric mantle from which these alkaline melts are derived.

REE systematics of fluorides, calcite and siderite in peralkaline plutonic rocks from the Gardar Province, South Greenland

The Gardar failed-rift Province is world-famous for its (per-)alkaline plutonic rocks. Elevated contents of F in the mantle source and F-enrichment in the parental melts have been suggested to account for the peculiarities of the Gardar rocks (e.g. their rare mineralogy, extreme enrichment of HFSE elements, Be or REE in the Ilímaussaq agpaites, and the formation of the unique Ivigtut cryolite deposit). To constrain the formation and chemical evolution of F-bearing melts and fluids, fluorides (fluorite, cryolite, villiaumite, cryolithionite), calcite and siderite from the Ilímaussaq, Motzfeldt and Ivigtut complexes were analysed for their trace element content focusing on the rare earth elements and yttrium (REE). The various generations of fluorite occurring in the granitic Ivigtut, agpaitic Ilímaussaq and miaskitic to agpaitic Motzfeldt intrusions all share a negative Eu anomaly which is attributed to (earlier) feldspar fractionation in the parental alkali basaltic melts. This interpretation is supported by the abundance of anorthositic xenoliths in many Gardar plutonic rocks. The primary magmatic fluorites from Ilímaussaq and Motzfeldt display very similar REE patterns suggesting a formation from closely related parental melts under similar conditions. Hydrothermal fluorites from these intrusions were used to constrain the multiple effects responsible for the incorporation of trace elements into fluorides: temperature dependence, fluid migration/interaction and complexation resulting in REE fractionation. Generally, the REE patterns of Gardar fluorides reflect the evolution and migration of a F/CO 2-rich fluid leading to the formation of fluorite and fluorite/calcite veins. In certain units, this fluid inherited the REE patterns of altered host rocks. In addition, there is evidence of an even younger fluid of high REE abundance which resulted in highly variable REE concentrations (up to three orders of magnitude) within one sample of hydrothermal fluorite. The REE patterns of the granitic Ivigtut intrusion show flat to slightly heavy-REE-enriched patterns characterised by a strong tetrad effect. This effect is interpreted to record extensive fluid–rock interaction in highly fractionated, Si-rich systems. Interestingly, the fluorides appear to record different source REE patterns, as the spatially close Motzfeldt and Ilímaussaq intrusions show strong similarities and contrast with the Ivigtut intrusion located 100 km NE. These variations may be attributed to differences in the tectonic position of the intrusions or mantle heterogeneities.

Trace element constraints on mantle sources during mid-Proterozoic magmatism: evidence for a link between the Gardar (South Greenland) and Abitibi (Canadian Shield) mafic rocks

Trace and major element compositions of mid-Proterozoic (1.20–1.16 Ga) basaltic lava flows and dikes from the Gardar Province (South Greenland) provide evidence for two geochemically distinct magma sources. Based on distinct features of incompatible trace element ratios, such as Th/Ta, Th/Tb, or Th/Hf, they differ by the composition of their mantle source and by their partial melting trends. One mantle source is compositionally transitional between mid-ocean ridge basalt (MORB)-type and ocean-island basalt (OIB)-type sources with relatively low Ta/Hf ratios (~0.2), moderate enrichment in light rare-earth elements (LREE), and slightly positive initial εNdvalues (+2). It can be attributed to either a lithospheric mantle source or a depleted astenospheric mantle plume component that has been enriched shortly prior to eruption. The other mantle source is characterized by high Ta/Hf ratios (~0.6), a more pronounced LREE enrichment, and initial εNdvalues around 0. Elevated CeN/YbN(7.0–9.8) and TbN/YbNratios (1.6–1.8) of the rocks derived from this source indicate the presence of garnet during melting, suggesting melt generation at depths &gt; 70 km. This mantle source has the geochemical characteristics of an OIB-type source and is interpreted as originating from a mantle plume. Samples from the slightly younger (1.14 Ga) Abitibi dike swarm (Superior Province, Canada), spatially connected to the Gardar Province, show very similar trace element characteristics and the same two distinct magma sources can be identified. The geochemical similarities between the magma sources in South Greenland and Canada support the idea of a genetic link between the two magmatic provinces. This link strengthens the idea that the system was a long-lived major intracontinental rift zone.

The Tikiusaaq carbonatite: a new Mesozoic intrusive complex in southern West Greenland

Ultrabasic alkaline magmatic rocks are products of melts generated deep within or at the base of the lithospheric mantle. The magmas may reach the surface to form lavas and pyroclastic deposits; alternatively they crystallise at depth to form dykes or central complexes. The rocks are chemically distinct and may contain high concentrations of economically interesting minerals and chemical elements, such as diamonds, niobium, tantalum, rare earth elements, phosphorus, iron, uranium, thorium, and zirconium. Ultrabasic alkaline rocks are known from several provinces in Greenland, but extrusive facies have only been preserved at a few places; e.g. at Qassiarsuk in South Greenland where pyroclastic rocks occur, and in the Maniitsoq region, where a small volcanic breccia (‘Fossilik’) contains fragments of Palaeozoic limestone. Ultramafic lamprophyre and kimberlite are mainly emplaced as dykes, whereas carbonatite forms large intrusive bodies as well as dykes. The ultrabasic alkaline magmas that have been emplaced at certain times during the geological evolution of Greenland can be related to major episodes of continental break-up (Larsen &amp; Rex 1992). The oldest are Archaean and the youngest dated so far are Palaeogene. Figure 1 shows the distribution of known ultrabasic alkaline rocks in West Greenland. The large and well-exposed bodies of alkaline rocks and carbonatites in the Gardar Province were discovered already in the early 1800s (Ussing 1912), while less conspicuous bodies were discovered much later during geological mapping and mineral exploration. Many alkaline rock bodies, particularly dykes, are difficult to identify in the field because they weather more extensively than the country rock gneisses and form vegetated depressions in the landscape. However, their distinct chemistry and mineralogy render alkaline rocks identifiable in geochemical and geophysical survey data. Thus, the Sarfartôq carbonatite complex was discovered during regional airborne gamma-spectrometric surveying owing to its elevated uranium and thorium contents (Secher 1986). The use of kimberlite indicator minerals has led to the discovery of alkaline rocks such as kimberlites and ultramafic lamprophyres that carry fragments of deep lithospheric mantle. Such rocks may also contain diamonds. Kimberlite indicator minerals are high-pressure varieties of minerals, such as garnet, clinopyroxene, chromite and ilmenite that were formed in the lithospheric mantle. Exploration companies have processed thousands of till samples from southern West Greenland for kimberlite indicator minerals and found many new dykes.

Crystallisation of mela-aillikites of the Narsaq region, Gardar alkaline province, south Greenland and relationships to other aillikitic–carbonatitic associations in the province

Aillikites (carbonated, melilite-free ultramafic lamprophyres grading to carbonatites) are minor components of the Gardar alkaline igneous province. They occur principally as minor intrusions and as clasts in diatremes, but more voluminous aillikitic intrusions crop out near the Ilímaussaq Complex, which they predate by a few million years. These larger intrusions were emplaced at 1160 ± 5 Ma. They are essentially carbonate-free and, consisting almost wholly of ferromagnesian silicate and oxide minerals, are mela-aillikites. Typically the mela-aillikites are fine-grained rocks composed largely of olivine, clinopyroxene, phlogopite and magnetite that crystallised in open systems, permitting loss of volatile-rich residues. The petrography is highly complex, involving at least 28 mineral species. Pyroxenitic veins were emplaced while the host-rocks were still at high temperatures and represent channels through which fluorinated silico-carbonatitic residual melts escaped, with exsolving CO 2 as propellant. Precipitation of Ca-rich minerals including monticellite, perovskite, vesuvianite, wollastonite and cuspidine was a result of dissociation of the calcium carbonate in the residual melts. Late-stage crystallisation was in a highly oxidising environment in which the ‘common minerals’ attain extreme compositions (almost pure forsterite, ferrian-diopside, highly magnesian ilmenite, Ba–Ti-rich phlogopite and Sr-rich kaersutite). Spatially associated diatremes may be vents through which CO 2-rich gases erupted. The whole-rock compositions are considered to be well removed from those of co-existing melts: compaction and expulsion of highly mobile residual melts is inferred to have left the mela-aillikites as aberrant cumulates. The mela-aillikites are a late-Gardar manifestation of the aillikitic magmatism that occurred intermittently in the province for over 120 Ma. Repetitive formation of metasomite vein systems in the deep lithospheric mantle is postulated. These readily fusible metasomites had short residence histories, experiencing either adiabatic melting or thermal melting as a result of plume activity. The abnormally large volumes of ultramafic lamprophyre magma, from which the mela-aillikites crystallised, may denote the culmination of metasomatic processes in the closing stages of the evolution of the Gardar Province.