Analytical methodologies based on X-Ray Fluorescence Spectrometry (XRF) and Inductively Couple Plasma Spectroscopy (ICP) for the assessment of metal dispersal around mining environments

La investigació que es presenta en aquesta tesi es centra en l'aplicació i millora de metodologies analítiques existents i el desenvolupament de nous procediments que poden ser utilitzats per a l'estudi dels efectes ambientals de la dispersió dels metalls entorn a les zones mineres abandonades. En primer lloc, es van aplicar diferents procediments d'extracció simple i seqüencial per a estudiar la mobilitat, perillositat i bio-disponibilitat dels metalls continguts en residus miners de característiques diferents. Per altra banda, per a estudiar les fonts potencials de Pb en la vegetació de les zones mineres d'estudi, una metodologia basada en la utilització de les relacions isotòpiques de Pb determinades mitjançant ICP-MS va ser avaluada. Finalment, tenint en compte l'elevat nombre de mostres analitzades per a avaluar l'impacte de les activitats mineres, es va considerar apropiat el desenvolupament de mètodes analítics d'elevada productivitat. En aquest sentit la implementació d'estratègies quantitatives així com l'aplicació de les millores instrumentals en els equips de XRF han estat avaluades per a aconseguir resultats analítics fiables en l'anàlisi de plantes. A més, alguns paràmetres de qualitat com la precisió, l'exactitud i els límits de detecció han estat curosament determinats en les diverses configuracions de espectròmetres de XRF utilitzats en el decurs d'aquest treball (EDXRF, WDXRF i EDPXRF) per a establir la capacitat de la tècnica de XRF com a tècnica alternativa a les clàssiques comunament aplicades en la determinació d'elements en mostres vegetals.

Croig Cave: a late Bronze Age ornament deposition and 3,500 years of coastal foraging in NW Mull, Scotland

Activity within caves provides an important element of the later prehistoric and historic settlement pattern of western Scotland. This contribution reports on a small-scale excavation within Croig Cave, on the coast of north-west Mull, that exposed a 1.95m sequence of midden deposits and cave floors that dated bewteen c 1700 BC and AD 1400. Midden analysis indicated the processing of a .... 950 BC, a penannular copper bracelet a discrete ritual episode within the cycle of otherwise potentially mundane activities. Lead isotope analysis indicates an Irish origin for the copper ore. A piece of iron slag within later midden deposits, dated to c 400 BC, along with high frequencies of wood charcoal, suggest that smithing or smelting may have occurred within the cave. High zinc levels in the historic levels of the midden c AD 1200 might indicate intensive processing of seaweed.

U Pb and Sm Nd geochronologic studies of the eastern Borborema Province, Northeastern Brazil: initial conclusions

The Borborema Province of NE Brasil comprises the central part of a wide Pan-African-Brasiliano orogenetic belt that formed as a consequence of late Neoproterozoic convergence and collision of the São Luis-West Africa craton and the São Francisco-Congo-Kasai cratons. New Sm Nd and U Pb results from the eastern part of this province help to define the basic internal architecture and pre-collisional history of this province, with particular emphasis on delineating older cratonic terranes, their fragmentation during the Mesoproterozoic, and their assembly into West Gondwana during the Pan African-Brasiliano orogeny at ca. 600 Ma. The region can be divided into three major geotectonic domains: a) Rio Piranhas-Caldas Brandão massif, with overlying Paleoproterozoic to Neoproterozoic supracrustal rocks, north of the Patos Lineament; b) the Archean to Paleoproterozoic São Francisco craton (SFC) to the south; and c) a complex domain of Paleoproterozoic to Archean basement blocks with several intervening Mesoproterozoic to Neoproterozoic fold belts in the center (south of Patos Lineament and north of SFC). The northern and central domains comprise the Borborema Province. Archean basement gneiss and Transamazonian granulite of northern SFC are exposed in the southern part of the central domain, underlying southern parts of the Sergipano fold belt. Basement in the Rio Piranhas massif appears to consist mostly of Transamazonian (2.1 to 2.2 Ga) gneissic rocks; Nd model ages (TDM) of ca. 2.6 Ga for 2.15 Ga gneisses indicate a substantial Archean component in the protoliths to these gneisses. The Caldas Brandão massif to the east yields both Transamazonian and Archean U Pb zircon and Nd (TDM) ages, indicating a complex architecture. Metasedimentary rocks of the Jucurutu Formation yield detrital zircons with original crystallization ages as young as 1.8 Ga, indicating that these rocks may be late Paleoproterozoic and correlate with other ca. 1.8 Ga cratonic supracrustal rocks in Brazil such as the Roraima Group and Espinhaço Group. Most metavolcanic and pre-Brasiliano granitic units of the Sergipano (SDS), Pajeú-Paraíba (SPP), Riacho Pontal (SRP), and Piancó-Alto Brígida (SPAB) fold belts in the central domain formed ~ 1.0 ± 0.1 Ga, based on U Pb ages of zircons. Nd model ages (TDM) for these same rocks, as well as Brasiliano granites intruded into them and large parts of the Pernambuco-Alagoas massif, are commonly 1.3-1.7 Ga, indicating that rocks of the fold belts were not wholly derived from either older (> 2.1 Ga) or juvenile (ca. 1.0 Ga) crust, but include mixtures of both components. A simple interpretation of Brasiliano granite genesis and the Nd data implies that there is no Transamazonian or Archean basement underlying large parts of these fold belts or of the Pernambuco-Alagoas massif. An exception is a belt of syenitic Brasiliano plutons (Syenitoid Line) and host gneisses between SPAB and SPP that clearly has a Transamazonian (or older) source. In addition, there are several smaller blocks of Archean to Transamazonian gneiss that can be defined within and among these fold belts. These blocks do not appear to constitute a continuous basement complex, but appear to be isolated older crustal fragments. Our data support a model in which ca. 1.0 Ga rifting was an important tectonic and crust-forming event along the northern edge of the São Francisco craton. Our data also show that significant parts of the Borborema Province are not remobilized Transamazonian to Archean crust, but that Mesoproterozoic crust is a major feature of the Province. There are several small remnants of older crust within the area dominated by Mesoproterozoic crust, suggesting that the rifting event created several small continental fragments that were later incorporated into the Brasiliano collisional orogen. We cannot at present determine if the Rio Piranhas-Caldas Brandão massifs and the older crustal blocks of the central domain were originally part of the São Francisco craton or whether some (or all) of them came from more exotic parts of the Proterozoic Earth. Finally, our data have not yet revealed any juvenile terranes of either Transamazonian or Brasiliano age. © 1995.

Magmatismo há ca. 660 - 640 Ma no Domínio Socorro: Registros de convergência-colisional na Aglutinação do Gondwana Ocidental

Uranium-lead zircon ages between 660 and 640 Ma, obtained from a series of calc-alkaline orthogneisses and plutons in southeast Brazil's Central Mantiqueira Province, suggest that a significant period of magmatism occurred in this region prior to the collisional assembly of West Gondwana (presently constrained in the region between ca. 625 and 580 Ma). While the nature of this earlier magmatism is presently unclear, some preliminary Sm-Nd data suggest that these magmas were not solely derived from the Paleoproterozoic lithosphere, but appear to represent hybrid products of Paleoproterozoic and Neoproterozoic sources. As such hybrid mixtures have been most commonly observed in continental are settings, it is possible that the 660 to 640 Ma magmatism represents are magmatism that resulted from subduction of Neoproterozoic oceanic crust during early precollisional convergence and closure of a branch of either the Adamastor or Goianides oceans.

Evidence for 2.35 to 2.30 Ga juvenile crustal growth in the northwest Borborema Province, NE Brazil

The c. 600 Ma Brasiliano Borborema Province of NE Brazil comprises a complex collage of Precambrian crustal blocks cut by a series of continental-scale shear zones. The predominant basement rocks in the province are 2.1-2.0 Ga Transamazonian gneisses of both juvenile and reworked nature. U-Pb zircon and Sm-Nd whole-rock studies of tonalite-trondhjemite-granodiorite basement gneisses in the NW Ceará or Médio Coreaú domain in the northwestern part of the Borborema Province indicate that this represents a continental fragment formed by 2.35-2.30 Ga juvenile crust. This block has no apparent genetic affinity with any other basement gneisses in the Borborema Province, and it does not represent the tectonized margin of the c. 2.1-2.0 Ga São Luis Craton to the NW. The petrological and geochemical characteristics, as well as the Nd-isotopic signatures of these gneisses, are consistent with their genesis in an island arc setting. This finding documents a period of crustal growth during a period of the Earth's history which is known for its tectonic quiescence and paucity of crust formation. © Geological Society of London 2009.

Sr-Nd-Pb isotopic constraints on the nature of the mantle sources involved in the genesis of the high-Ti tholeiites from northern Paraná Continental Flood Basalts (Brazil)

There has been little research on geochemistry and isotopic compositions in tholeiites of the Northern region from the Paraná Continental Flood Basalts (PCFB), one of the largest continental provinces of the world. In order to examine the mantle sources involved in the high-Ti (Pitanga and Paranapanema) basalt genesis, we studied Sr, Nd, and Pb isotopic systematics, and major, minor and incompatible trace element abundances. The REE patterns of the investigated samples (Pitanga and Paranapanema magma type) are similar (parallel to) to those of Island Arc Basalts' REE patterns. The high-Ti basalts investigated in this study have initial (133Ma) 87Sr/86Sr ratios of 0.70538-0.70642, 143Nd/144Nd of 0.51233-0.51218, 206Pb/204Pb of 17.74-18.25, 207Pb/204Pb of 15.51-15.57, and 208Pb/204Pb of 38.18-38.45. These isotopic compositions do not display any correlation with Nb/Th, Nb/La or P2O5/K2O ratios, which also reflect that these rocks were not significantly affected by low-pressure crustal contamination. The incompatible trace element ratios and Sr-Nd-Pb isotopic compositions of the PCFB tholeiites are different to those found in Tristan da Cunha ocean island rocks, showing that this plume did not play a substantial role in the PCFB genesis. This interpretation is corroborated by previously published osmium isotopic data (initial γOs values range from+1.0 to+2.0 for high-Ti basalts), which also preclude basalt generation by melting of ancient subcontinental lithospheric mantle. The geochemical composition of the northern PCFB may be explained through the involvement of fluids and/or small volume melts related to metasomatic processes. In this context, we propose that the source of these magmas is a mixture of sublithospheric peridotite veined and/or interlayered with mafic components (e.g., pyroxenites or eclogites). The sublithospheric mantle (dominating the osmium isotopic compositions) was very probably enriched by fluids and/or magmas related to the Neoproterozoic subduction processes. This sublithospheric mantle region may have been frozen and coupled to the base of the Parana basin lithospheric plate above which the Paleozoic subsidence and subsequent Early Cretaceous magmatism occurred. © 2013 Elsevier Ltd.

U-Pb SHRIMP and 40Ar/39Ar constraints on the timing of mineralization in the Paleoproterozoic Caxias orogenic gold deposit, São Luís cratonic fragment, Brazil

Caxias é um depósito de ouro orogênico do fragmento cratônico São Luís, que é correlacionável aos terrenos Riacianos do Cráton Oeste-Africano. O depósito se formou após o metamorfismo regional (estimado em 2100 ± 15 Ma) e está hospedado em zona de cisalhamento que secciona xistos do Grupo Aurizona (2240 ± 5 Ma) e o Microtonalito Caxias. O microtonalito foi aqui datado em 2009 ± 11 Ma, e representa um estágio magmático tardio na evolução do fragmento cratônico São Luís. Cristais de zircão com idades de 2139 ± 10 Ma foram herdados da fonte magmática ou são produto de contaminação durante a intrusão. A composição dos isótopos de chumbo sugere que granitoides de arco de ilhas de ca. 2160 Ma são a fonte provável para o Pb incorporado na pirita relacionada com o minério. Sericita hidrotermal mostra idade ⁴⁰Ar/³⁹Ar de 1990 ± 30 Ma, que, combinada com a idade de posicionamento do microtonalito hospedeiro, limita o evento mineralizador ao intervalo 2020-1960 Ma.

Tab. 2: U-Pb ion-microprobe ages from Taymyr peninsula

We present the initial results of a U-Th-Pb zircon ion-microprobe investigation on samples from the Central Belt of Taimyr, in order to constrain its tectono-magmatic evolution. The zircon samples are from a deformed twomica granite (Faddey Massif), deformed metamorphosed gabbroic dike entrained as pods and lenses within metamorphosed tholeiitic basalts of the Kunar-Mod volcanic suite (Klyaz'ma River region), a metamorphosed rhyolite of the same volcanic suite overlying the basic metavolcanic rocks, as well as an undeformed dolerite dike which intrudes the metamorphosed Kunar-Mod basic volcanic rocks. Preliminary results on zircons from the two-mica granite suggest a crystallization age of ~630 Ma for this rock, with inheritance from assimilated crust 840 Ma to 1.1 Ga in age. In the Klyaz'ma River region, zircons from the meta-rhyolite yield a concordant age of -630 Ma. Zircons from the entrained metagabbroic dikes have so far yielded an age of -615 Ma (1 grain), as well as Archean ages (5 grains, concordant at 2.6-2.8 Ga). It seems likely that the Archean grains represent assimilation of older crustal material. Zircons from the post-tectonic dolerite dike have a bimodal age distribution. A well-defined younger age of 281 ±9 Ma is interpreted to represent the crystallization age of the dike, while older, concordant ages of 2.6-2.9 Ga likely represent assimilation of Archean crust (Siberian craton at depth). Several important conclusions can be drawn from the data. (1) The mafic and felsic lithologies of the Kunar-Mod volcanic suite are genetically related and should be the same age. Ages of-630 Ma (meta-rhyolite) and -615 Ma (metagabbroic dikes representing the latest stage of mafic magmatism associated the Kunar-Mod suite) suggest that these lithologies may be the same age, but more data are required to confirm this hypothesis. (2) The 630 Ma two-mica granite is similar in age to the time of high-grade metamorphism, suggesting that syntectonic granite emplacement accompanied obduction of the accretionary Central Belt to the Siberian craton. (3) An Early Permian age is well defined for the undeformed dolerite dike. Dolerite dikes occur across the whole of Taimyr, but are deformed to the south. If related, this single magmatic event pre-dates Permo-Triassic Siberian trap magmatism. Furthermore, it suggests that deformation was localized to southeastern Taimyr.

Age determination on rock samples from Svalbard

A linear, N-S-trending belt of elliptical, positive magnetic anomalies occurs in central Nordaustlandet, northeast Svalbard. They extend from the Caledonian and older complexes in the vicinity of Duvefjorden, southwards beneath the western margin of Austfonna and the offshore areas covered by Carboniferous and younger strata, to the vicinity of Edge¯ya. One of the strongest anomalies occurs in inner Duvefjorden where it coincides with a highly magnetic quartz monzonite-granite pluton at Djupkilsodden. U-Pb and Pb-Pb zircon dating of this post-tectonic pluton defines an age of c. 415 Ma, this being based on the Pb-Pb analyses of three specimens (Pb-Pb ages of 414±10 Ma, 411±10 Ma and 408±10 Ma) and a U-Pb discordia with an upper intercept at 417+18/-7 Ma. Neighbouring felsic plutons in central Nordaustlandet, including the Rijpfjorden and Winsnesbreen granites, lack magnetic signatures in their exposed parts, but have a similar Caledonian age. The central Nordaustlandet magnetic anomalies appear to be part of a circa 300 km long linear belt of late Silurian or early Devonian post-tectonic plutonism that characterizes the Caledonian basement of eastern Svalbard. Felsic intrusions of similar age further west in Spitsbergen are likewise both highly magnetic (Hornemantoppen batholith) and largely non-magnetic (Newtontoppen batholiths / Chydeniusbreen granitoid suite). They all appear to have been intruded at the end of the main period of Caledonian terrane assembly of the northwestern Barents Shelf.

(Table 1) Isotopic and trace-element ratios of Emperor Seamount basalts

When a mantle plume interacts with a mid-ocean ridge, both are noticeably affected. The mid-ocean ridge can display anomalously shallow bathymetry, excess volcanism, thickened crust, asymmetric sea-floor spreading and a plume component in the composition of the ridge basalts (Schilling, 1973, doi:10.1038/242565a0; Verma et al., 1983, doi:10.1038/306654a0; Ito and Lin, 1995, doi:10.1130/0091-7613(1995)023<0657:OSCHIC>2.3.CO;2; Müller et al., 1998, doi:10.1038/24850). The hotspot-related volcanism can be drawn closer to the ridge, and its geochemical composition can also be affected (Ito and Lin, 1995, doi:10.1130/0091-7613(1995)023<0657:OSCHIC>2.3.CO;2; White et al., 1993, doi:10.1029/93JB02018; Kincaid et al., 1995, doi:10.1038/376758a0; Kingsley and Schilling, 1998, doi:10.1029/98JB01496 ). Here we present Sr-Nd-Pb isotopic analyses of samples from the next-to-oldest seamount in the Hawaiian hotspot track, the Detroit seamount at 51° N, which show that, 81 Myr ago, the Hawaiian hotspot produced volcanism with an isotopic signature indistinguishable from mid-ocean ridge basalt. This composition is unprecedented in the known volcanism from the Hawaiian hotspot, but is consistent with the interpretation from plate reconstructions (Mammerickx and Sharman, 1988, doi:10.1029/JB093iB04p03009) that the hotspot was located close to a mid-ocean ridge about 80 Myr ago. As the rising mantle plume encountered the hot, low-viscosity asthenosphere and hot, thin lithosphere near the spreading centre, it appears to have entrained enough of the isotopically depleted upper mantle to overwhelm the chemical characteristics of the plume itself. The Hawaiian hotspot thus joins the growing list of hotspots that have interacted with a rift early in their history.

Geochemistry of samples from Valtournenche, Western Italian Alps

Slices of polycyclic metasediments (marbles and meta-cherts) are tectonically amalgamated with the polydeformed basement of the Dent Blanche tectonic system along a major Alpine shear zone in the Western Alps (Becca di Salé area, Valtournenche Valley). A combination of techniques (structural analysis at various scales, metamorphic petrology, geochronology and trace element geochemistry) was applied to determine the age and composition of accessory phases (titanite, allanite and zircon) and their relation to major minerals. The results are used to reconstruct the polyphase structural and metamorphic history, comprising both pre-Alpine and Alpine cycles. The pre-Alpine evolution is associated with low-pressure high-temperature metamorphism related to Permo-Triassic lithospheric thinning. In meta-cherts, microtextural relations indicate coeval growth of allanite and garnet during this stage, at ~ 300 Ma. Textures of zircon also indicate crystallization at HT conditions; ages scatter from 263-294 Ma, with a major cluster of data at ~ 276 Ma. In impure marble, U-Pb analyses of titanite domains (with variable Al and F contents) yield apparent 206Pb/238U dates range from Permian to Jurassic. Chemical and isotopic data suggest that titanite formed at Permian times and was then affected by (extension-related?) fluid circulation during the Triassic and Jurassic, which redistributed major elements (Al and F) and partially opened the U-Pb system. The Alpine cycle lead to early blueschist facies assemblages, which were partly overprinted under greenschist facies conditions. The strong Alpine compressional overprint disrupted the pre-Alpine structural imprint and/or reactivated earlier structures. The pre-Alpine metamorphic record, preserved in these slices of metasediments, reflects the onset of the Permo-Triassic lithospheric extension to Jurassic rifting.

Pb concentrations, Pb isotopic composition, and amount of metalliferous components in pelagic sediments from the Pacific Ocean

The amount of lead annually transferred from oceanic crust to metalliferous sediments was estimated in order to test the hypothesis that a non-magmatic flux of lead causes the Pb surplus in the continental crust. A Pb surplus has been inferred from global crust-mantle lead mass balances derived from lead concentration correlations with other trace elements and from lead isotope systematics in oceanic basalts. DSDP/ODP data on the amount of metalliferous sediments in the Pacific Ocean and along a South Atlantic traverse are used to calculate the mean worldwide thickness of 3 (+/-1) m for purely metalliferous sediment componens. Lead isotope ratios of 39 metalliferous sediments from the Pacific define mixing lines between continent-derived (seawater) and mantle-derived (basaltic) lead, with the most metal-rich sediments usually having the most mantle-like Pb isotope composition. We used this isotope correlation and the Pb content of the 39 metalliferous sediments to derive an estimate of 130 (+/-70) µg/g for the concentration of mantle-derived lead in the purely metalliferous end-member. Mass balance calculations show that at least 12 (+/-8)% of the lead, annually transferred from upper mantle to oceanic crust at the ocean ridges, is leached out by hydrothermal processes and re-deposited in marine sediments. If all of the metalliferous lead is ultimately transferred to the continental crust during subduction, the annual flux of this lead from mantle to continental crust is 2.6 (+/-2.0) * 10**6 kg. Assuming this transfer rate to be proportional to the rate of oceanic plate production, one can fit the lead transfer to models of plate production rate variations through time. Integrating over 4 Ga, hydrothermal lead transfer to the continental crust accounts for a significant portion of the Pb surplus in the continental crust. It therefore appears to be one of the main reasons for the anomalous behavior of lead in the global crust-mantle system.