Sr and Nd isotope compositions of atmospheric mineral dust at the summit of Mt. Sefuri, north Kyushu, southwest Japan: A marker of the dust provenance and seasonal variability

We analyzed Rb-Sr-Nd isotope ratios of mineral dust in total aerosol load collected with rainwater continuously from 1998 to 2006 at the summit of Mt. Sefuri, northern Kyushu, southwestern Japan. During this period, the total mass of the dust generally increased in late winter, peaked in early spring, and then decreased.⁸⁷Sr/⁸⁶Sr in atmospheric mineral dust varied from 0.7096 to 0.7180, and εNd(0)_CHUR from −19.9 to −3.5. During heavy deposition periods, the dust had high ⁸⁷Sr/⁸⁶Sr isotope ratios and low to middle εNd(0)_CHUR values, respectively. These compositions are comparable to those of sand and loess in arid areas of Northeast China, Takla Makan and Western Beijing. Such particles were transported by westerlies from those areas to northern Kyushu in winter and spring. In summer and autumn, the isotopic compositions of the dust varied greatly; however, during light deposition periods, the Sr isotope composition was low. In these seasons, the contributions to the dust from Japanese soils and volcanic ash, transported by southern winds, were relatively larger than in winter and spring because of decreased mineral dust particle transport from the continent. Nevertheless, fine sandy desert particles and loess in general accounted for most mineral dust deposition in northern Kyushu year-round, even in summer. Local soils derived from weathered granite and volcanic ash were minor components only.The net mass of water-insoluble inorganic matter in the collected mineral dust fluctuated from year-to-year; deposition on Mt. Sefuri was relatively large before 2001, decreased from 2002 to 2005, and increased greatly in spring 2006. These year-to-year differences probably reflected changes in the strength of the westerlies and in climate conditions in the arid source areas.     

Sr isotopes as a tracer of weathering processes and dust inputs in a tropical granitoid watershed, Luquillo Mountains, Puerto Rico

Sr isotope data from soils, water, and atmospheric inputs in a small tropical granitoid watershed in the Luquillo Mountains of Puerto Rico constrain soil mineral development, weathering fluxes, and atmospheric deposition. This study provides new information on pedogenic processes and geochemical fluxes that is not apparent in watershed mass balances based on major elements alone. ⁸⁷Sr/⁸⁶Sr data reveal that Saharan mineral aerosol dust contributes significantly to atmospheric inputs. Watershed-scale Sr isotope mass balance calculations indicate that the dust deposition flux for the watershed is 2100 ± 700 mg cm⁻² ka⁻¹. Nd isotope analyses of soil and saprolite samples provide independent evidence for the presence of Saharan dust in the regolith. Watershed-scale Sr isotope mass balance calculations are used to calculate the overall short-term chemical denudation velocity for the watershed, which agrees well with previous denudation rate estimates based on major element chemistry and cosmogenic nuclides. The dissolved streamwater Sr flux is dominated by weathering of plagioclase and hornblende and partial weathering of biotite in the saprock zone. A steep gradient in regolith porewater ⁸⁷Sr/⁸⁶Sr ratio with depth, from 0.70635 to as high as 0.71395, reflects the transition from primary mineral-derived Sr to a combination of residual biotite-derived Sr and atmospherically-derived Sr near the surface, and allows multiple origins of kaolinite to be identified.     

Pb, Sr and Nd isotope study of two co-existing magmas in the Nízke Tatry Mountains, Western Carpathians (Slovakia)

Summary Two co-existing plutonic rocks (diorite and granodiorite) were studied from an intrusion of Variscan age in the Raztocna Valley – Nízke Tatry Mountains, Western Carpathians. Geochemical analyses of major and trace elements constrain a volcanic arc as emplacement environment and give the first hints of a mixture of two magmatic end-members: the so-called Prasivá granodiorite and the Raztocna diorite. The ⁸⁷Sr/⁸⁶Sr₍₀₎ ratios vary between 0.7075 and 0.7118, the ε Nd₍₀₎ values range from −1.4 to −5.0. Common Pb isotopes reveal a dominant crustal source with minor influences from a mantle and a lower crustal source. Modelling based on Sr and Nd isotope data and using three component mixing calculations indicates that mixing of 2/3 of upper mantle material with 1/3 upper crustal material can produce the isotopic composition of the Raztocna diorite. Very minor amounts of lower crust were incorporated in the diorite. For the Prasivá granodiorite, the mixing ratio of upper mantle and upper crust is similar, but a lower crustal reservoir contributed about 5–10% of the source material.     

Sr isotope chemostratigraphy of Upper Jurassic carbonate rocks in the Demerdzhi Plateau (Crimean Mountains)

The first Sr chemostratigraphic data are obtained for the Upper Jurassic carbonate sections in the Demerdzhi Plateau of the Crimean Mountains. The oncoid, microbial, and organogenic-detrital limestone varieties representing shallow-water marine microfacies of the carbonate platform served as material for these studies. The limestone samples for reconstructing the isotopic parameters of depositional environments were selected using geochemical criteria (Mn/Sr < 0.2, Fe/Sr < 1.6, Mg/Ca < 0.024) and subjected to the preliminary treatment in a 1 N ammonium acetate solution. The ⁸⁷Sr/⁸⁶Sr value in the least altered samples increases up the section from 0.70701 to 0.70710. The obtained ⁸⁷Sr/⁸⁶Sr values are correlated with the Sr isotope properties of belemnite rostrae characterizing the Pectinatites scitulus-Pavlovia rotunda ammonite zone in the zonal scale of the Boreal realm, Hyponoticeras hybonotum-M. ponti/B. peroni Zone in the zonal scale of the Tethyan realm, and lower part of the Dorsoplanites panderi Zone in the zonal scale for the transitional domain of the East European Platform. The Sr chemostratigraphic correlation indicates the early Tithonian age of sediments developed in the eastern part of the Demerdzhi Plateau and restricts the upper boundary of the limestone section redeposited within carbonate breccia of Mount Severnaya Demerdzhi to the terminal early Tithonian. The Sr isotope data are used for calculating the sedimentation rates for limestones. They are estimated to be at least 0.23 m/1000 years, which is an anomalously high value for pre-Quaternary carbonate platforms.     

Reconciling the elemental and Sr isotope composition of Himalayan weathering fluxes: insights from the carbonate geochemistry of stream waters

Determining the relative proportions of silicate vs. carbonate weathering in the Himalaya is important for understanding atmospheric CO₂ consumption rates and the temporal evolution of seawater Sr. However, recent studies have shown that major element mass-balance equations attribute less CO₂ consumption to silicate weathering than methods utilizing Ca/Sr and ⁸⁷Sr/⁸⁶Sr mixing equations. To investigate this problem, we compiled literature data providing elemental and ⁸⁷Sr/⁸⁶Sr analyses for stream waters and bedrock from tributary watersheds throughout the Himalaya Mountains. In addition, carbonate system parameters (P_CO2, mineral saturation states) were evaluated for a selected suite of stream waters. The apparent discrepancy between the dominant weathering source of dissolved major elements vs. Sr can be reconciled in terms of carbonate mineral equilibria. Himalayan streams are predominantly Ca²⁺-Mg²⁺-HCO₃⁻ waters derived from calcite and dolomite dissolution, and mass-balance calculations demonstrate that carbonate weathering contributes ∼87% and ∼76% of the dissolved Ca²⁺ and Sr²⁺, respectively. However, calculated Ca/Sr ratios for the carbonate weathering flux are much lower than values observed in carbonate bedrock, suggesting that these divalent cations do not behave conservatively during stream mixing over large temperature and P_CO2 gradients in the Himalaya.The state of calcite and dolomite saturation was evaluated across these gradients, and the data show that upon descending through the Himalaya, ∼50% of the streams evaluated become highly supersaturated with respect to calcite as waters warm and degas CO₂. Stream water Ca/Mg and Ca/Sr ratios decrease as the degree of supersaturation with respect to calcite increases, and Mg²⁺, Ca²⁺, and HCO₃⁻ mass balances support interpretations of preferential Ca²⁺ removal by calcite precipitation. On the basis of patterns of saturation state and P_CO2 changes, calcite precipitation was estimated to remove up to ∼70% of the Ca²⁺ originally derived from carbonate weathering. Accounting for the nonconservative behavior of Ca²⁺ during riverine transport brings the Ca/Sr and ⁸⁷Sr/⁸⁶Sr composition of the carbonate weathering flux into agreement with the composition of carbonate bedrock, thereby permitting consistency between elemental and Sr isotope approaches to partitioning stream water solute sources. These results resolve the dissolved Sr²⁺ budget and suggest that the conventional application of two-component Ca/Sr and ⁸⁷Sr/⁸⁶Sr mixing equations has overestimated silicate-derived Sr²⁺ and HCO₃⁻ fluxes from the Himalaya. In addition, these findings demonstrate that integrating stream water carbonate mineral equilibria, divalent cation compositional trends, and Sr isotope inventories provides a powerful approach for examining weathering fluxes.     

Relative contributions of silicate and carbonate rocks to riverine Sr fluxes in the headwaters of the Ganges

Exhumation of the Himalayan-Tibetan orogen is implicated in the marked rise in seawater ⁸⁷Sr/⁸⁶Sr ratios since 40 Ma. However both silicate and carbonate rocks in the Himalaya have elevated ⁸⁷Sr/⁸⁶Sr ratios and there is disagreement as to how much of the ⁸⁷Sr flux is derived from silicate weathering. Most previous studies have used element ratios from bedrock to constrain the proportions of silicate- and carbonate-derived Sr in river waters. Here we use arrays of water compositions sampled from the head waters of the Ganges in the Indian and Nepalese Himalaya to constrain the end-member element ratios. The compositions of tributaries draining catchments restricted to a limited range of geological units can be described by two-component mixing of silicate and carbonate-derived components and lie on a plane in multicomponent composition space. Key elemental ratios of the carbonate and silicate components are determined by the intersection of the tributary mixing plane with the planes Na = 0 for carbonate and constant Ca/Na for silicate. The fractions of Sr derived from silicate and carbonate sources are then calculated by mass-balance in Sr-Ca-Mg-Na composition space. Comparison of end-member compositions with bedrock implies that secondary calcite deposition may be important in some catchments and that dissolution of low-Mg trace calcite in silicate rocks may explain discrepancies in Sr-Ca-Na-Mg covariation. Alternatively, composition-dependent precipitation or incongruent dissolution reactions may rotate mixing trends on cation-ratio diagrams. However the calculations are not sensitive to transformations of the compositions by incongruent dissolution or precipitation processes provided that the transformed silicate and carbonate component vectors are constrained. Silicates are calculated to provide ∼50% of the dissolved Sr flux from the head waters of the Ganges assuming that discrepancies between Ca-Mg-Na covariation and the silicate rock compositions arise from addition of trace calcite. If the Ca-Mg-Na mixing plane is rotated by composition-dependent secondary calcite deposition, this estimate would be increased. Moreover, when ⁸⁷Sr/⁸⁶Sr ratios of the Sr inputs are considered, silicate Sr is responsible for 70 ± 16% (1σ) of the ⁸⁷Sr flux forcing changes in seawater Sr-isotopic composition. Since earlier studies predict that silicate weathering generates as little as 20% of the total Sr flux in Himalayan river systems, this study demonstrates that the significance of silicate weathering can be greatly underestimated if the processes that decouple the water cation ratios from those of the source rocks are not properly evaluated.     

Hydrogeochemistry and strontium isotopes of spring and mineral waters from Monte Vulture volcano,Italy

This paper describes the results of a study that was conducted to determine the relationship between hydrogeochemical composition and ⁸⁷Sr/⁸⁶Sr isotope ratios of the Mt. Vulture spring waters. Forty samples of spring waters were collected from local outcrops of Quaternary volcanites. Physico-chemical parameters were measured in the field and analyses completed for major and minor elements and ⁸⁷Sr/⁸⁶Sr isotopic ratios. A range of water types was distinguished varying from alkaline-earth bicarbonate waters, reflecting less intense water–rock interaction processes to alkali bicarbonate waters, probably representing interaction with volcanic rocks of Mt. Vulture and marine evaporites. The average ⁸⁷Sr/⁸⁶Sr isotope ratios suggest at least 3 different sources. However, some samples have average Sr isotope ratios (0.70704–0.70778) well above those of the volcanites. These ratios imply interaction with other rocks having higher ⁸⁷Sr/⁸⁶Sr ratios, probably Triassic evaporites, which is substantiated by their higher content of Na, SO₄ and Cl. The Sr isotope ratios for some samples (e.g. Toka and Traficante) are intermediate between the value for the Vulture volcanites and that for the local Mesozoic rocks. The salt content of these samples also lies between the value for waters interacting solely with the volcanites and the value measured in the more saline samples. These waters are thus assumed to result from the mixing of waters circulating in volcanic rocks with waters presumably interacting with the sedimentary bedrock (marine evaporites).     

Geodynamic setting of the Zijinshan porphyry–epithermal Cu–Au–Mo–Ag ore system,SW Fujian Province,China: Constrains from the geochronology and geochemistry of the igneous rocks

Zijinshan is a large porphyry–epithermal Cu–Au–Mo–Ag ore system located in the Zijinshan mineral field (ZMF) of southwestern Fujian Province, China. Although it is commonly accepted that the early Cretaceous magmatism and the metallogenesis of the mineral field are closely related, the tectonic setting for the ore-forming event(s) has been controversial and regarded as either extensional or subduction-related. New U–Pb zircon geochronology, Sr–Nd–Pb isotopic systematics, and geochemical data presented here from granites and volcanic rocks in the mineral field help to clarify this uncertainty.LA–MC–ICP-MS U–Pb zircon analyses yield weighted mean ages of between ca. 165 and 157 for the monzogranite, ca. 112 Ma for granodiorite, and between ca. 111 and 102 Ma for nine samples of volcanic units in the study area. These dates, integrated with previous geochronological data, indicate that there were two magmatic events in the area during the Middle to Late Jurassic and the Early Cretaceous. Major and trace element geochemistry indicates that these rocks are high-K, calc-alkaline granites, are enriched in LREE and Th, U, Ta, Nd, Sm and Yb, and depleted in Ba, K, Sr, P, Ti and Y. These features are characteristic of volcanic-arc granites or active-continental margin granites. The Middle to Late Jurassic monzogranitic plutons in the region have initial ⁸⁷Sr/⁸⁶Sr ratios of 0.7096 to 0.7173, εNd_T values of − 10.1 to − 7.6, ²⁰⁶Pb/²⁰⁴Pb isotope ratios of 18.51–18.86, ²⁰⁷Pb/²⁰⁴Pb isotope ratios of 15.64–15.73, and ²⁰⁸Pb/²⁰⁴Pb isotope ratios of 38.76–39.18. The Early Cretaceous granodiorite and volcanic rocks are distinctly different with initial ⁸⁷Sr/⁸⁶Sr ratios of 0.7055–0.7116, εNd_T values of − 8 to 0.5, ²⁰⁶Pb/²⁰⁴Pb ratios ranging between 18.49 and 19.77, ²⁰⁷Pb/²⁰⁴Pb ratios of 15.63–15.71, and ²⁰⁸Pb/²⁰⁴Pb ratios of 38.71–40.62. These characteristics suggest that the source for the Middle to Late Jurassic monzogranitic plutons is a partially melted Mesoproterozoic substrate, with a minor component from Paleozoic material, whereas the Early Cretaceous granodiorite and volcanic rocks may represent mixing of crustal and mantle-derived melts. It is therefore suggested that the Middle to Late Jurassic monzogranitic plutons, and the Early Cretaceous granodiorite and volcanic rocks in the ZMF are the result of an active continental-margin setting related to the subduction of the Paleo-Pacific Plate beneath the Eurasian continent. Given that the mineralization and the early Cretaceous granodiorite and volcanic rocks in the area are genetically related, the Zijinshan porphyry–epithermal ore system formed in the subduction-related tectonic setting.     

High oxidation magmatic evolution in the Naruo porphyry Cu deposit,Tibet, China

The Naruo porphyry Cu deposit is the third largest deposit discovered in the Duolong metallogenic district. Previous research has focused mainly on the geochemistry of the ore-bearing granodiorite porphyry; the metallogenesis remains poorly understood. In the present work, on the basis of outcrops and drilling core geological mapping, phases of early mineralization diorite, two inter-mineralization granodiorite porphyries, and late-mineralization granodiorite porphyry have been distinguished. Furthermore, the alteration zones were outlined, and the vein sequence was identified. The diorite and three porphyry phases were subjected to Laser Ablation Inductively Coupled Plasma Mass Spectrometry (La–ICP–MS) zircon U–Pb dating and in situ Hf isotope analyses as well as bulk major element, trace element, and Sr–Nd isotopic analyses. Molybdenite Re–Os dating was also conducted.The zircon U–Pb dating results show that the diorite and porphyry intrusions were emplaced at about 120 Ma, and the molybdenite Re–Os isochron age is 118.8 ± 1.9 Ma; this indicates that the Naruo porphyry Cu deposit was formed during a continuous magmatic–hydrothermal process. All of the diorite and granodiorite porphyry samples showed arc magmatic characteristics. Moreover, the moderate (⁸⁷Sr/⁸⁶Sr)_i ratios and low ε_Nd(t) and ε_Hf(t) values of the diorite and porphyry intrusions suggest the source region of the juvenile lower crust. The lower (⁸⁷Sr/⁸⁶Sr)_i and (¹⁴³Nd/¹⁴⁴Nd)_i ratios and higher ε_Nd(t) values and incompatible element concentrations than those in the granodiorite porphyry samples indicate a two-stage magmatic generation process for the intrusions. The early mineralization diorite has a high Cu concentration, implying that the source is enriched in Cu. However, the slightly lower Cu content of the late-mineralization granodiorite porphyry samples might imply Cu release from magmas and deposition within the metallogenic stage. The multiple stages of intrusions and subsequent volcanism within the Duolong metallogenic district, together with high Sr/Y features, indicate persistent magmatism during the metallogenic epoch, which is necessary for maintaining the activity of magmatic–hydrothermal and mineralization processes. Thus, the high Cu content in the source region, mantle-derived melt upwelling, and multiple stages of persistent magmatism were favorable for the formation of the Naruo porphyry Cu deposit.The high Fe₂O₃/FeO ratios of the diorite and granodiorite porphyry intrusions show very high oxidation features, which is coincident with estimated magmatic oxidation state calculated by the zircon trace element compositions. The high oxidation facilitates sulfur and chalcophile metals to be scavenged into the magmatic–hydrothermal systems, which is crucial for the metallogenesis of the Naruo porphyry Cu deposit.     

Application of Sr isotopes to geochemical mapping and provenance analysis: The case of Aichi Prefecture,central Japan

Geochemical maps expressing areal distributions of chemical elements in the earth’s land surface have been published in several countries in relation to various global environment issues. The authors have applied a radiogenic isotope ratio, ⁸⁷Sr/⁸⁶Sr, to geochemical mapping in order to understand the geological origin, transportation and dispersion system of chemical elements in the earth’s land surface. The Sr isotope ratio is a useful tracer for distinguishing the geological origin of surficial deposits, especially in areas where surface exposure of bedrocks is low, because it is not significantly altered by the processes of weathering and transportation. Most bedrocks in the Japanese islands are covered by plants, soils and urban areas. In this study, 142 of 1219 stream sediments (<180 μm) collected from the northeastern part of Aichi Prefecture, in the central part of Japan (75 km × 30 km), were analyzed. Their Sr isotope ratios range from 0.7086 to 0.7315 with an average of 0.7129, except for one sample. This average is higher than the mean of the upper crust of the Japan Arc (the Japanese Island Crustal Composite, JICC), 0.7077. This difference can be attributed to the below-average presence of young volcanic rocks, generally having lower ⁸⁷Sr/⁸⁶Sr values, and the above-average presence of granitic rocks, in the study area compared with the surface exposure of the Japan Arc. The first factor controlling the distribution of Sr isotope ratios is the bedrock distributed around the sampling points. Regional variation in the ⁸⁷Sr/⁸⁶Sr value shows that it is higher in the western and southeastern parts, where sedimentary rocks and metamorphic rocks are distributed, and that it is lower mainly in the central part, where granitic rocks are distributed. The ⁸⁷Rb/⁸⁶Sr–⁸⁷Sr/⁸⁶Sr plot for stream sediments more clearly reveals the differences and similarities of bedrocks. In some locations, the distribution of Sr isotope ratios does not correspond to that of bedrocks on the geological map. One reason is the existence of unmapped bedrock, for example, small intrusive masses of granite. The other is fluvial transportation and dispersion. The distribution of the isotope ratios suggests that some stream sediments include surficial deposits from a few km upstream. Application of the Sr isotope ratio to geochemical mapping is useful for revealing both the distribution of unexposed bedrocks and the transportation of surficial deposits. Information on unexposed bedrocks will be expected to contribute to the improvement of geological mapping.     

Comparison of stable carbon and oxygen isotopes in Picea glauca tree rings and Sphagnum fuscum moss remains from subarctic Canada

Stable isotope ratios from tree rings and peatland mosses have become important proxies of past climate variations. We here compare recent stable carbon and oxygen isotope ratios in cellulose of tree rings from white spruce (Picea glauca), growing near the arctic tree line; and cellulose of Sphagnum fuscum stems, growing in a hummock of a subarctic peatland, in west-central Canada. Results show that carbon isotopes in S. fuscum correlate significantly with July temperatures over the past ~20 yr. The oxygen isotopes correlate with both summer temperature and precipitation. Analyses of the tree-ring isotopes revealed summer temperatures to be the main controlling factor for carbon isotope variations, whereas tree-ring oxygen isotope ratios are controlled by a combination of spring temperatures and precipitation totals. We also explore the potential of combining high-frequency (annual) climate signals derived from long tree-ring series with low-frequency (decadal to centennial) climate signals derived from the moss remains in peat deposits. This cross-archive comparison revealed no association between the oxygen isotopes, which likely results from the varying sensitivity of the archives to different seasons. For the carbon isotopes, common variance could be achieved through adjustments of the Sphagnum age model within dating error.     

Comparative behaviour of recently deposited radiostrontium and atmospheric common strontium in soils (Vosges mountains,France)

The vertical distribution of atmospheric ⁸⁷Sr/⁸⁶Sr isotope ratios in soil is compared to the distribution of recent atmospheric ⁹⁰Sr deposition. ⁸⁷Sr/⁸⁶Sr isotope ratios of soil leachates are correlated with ⁹⁰Sr activities. Samples from the uppermost part of a soil profile have low ⁸⁷Sr/⁸⁶Sr ratios and high ⁹⁰Sr activities. Samples from the deeper part of the soil profile, however, have high ⁸⁷Sr/⁸⁶Sr but low ⁹⁰Sr activities. This points to mixing between an atmospheric and a geogenic component. Mixing calculations indicate that 50–80% of the Sr in the topsoil of a small catchment in the Vosges mountains is of atmospheric origin. Similarly ⁸⁷Sr/⁸⁶Sr of roots point to the presence of an atmospheric and geogenic component. ⁸⁷Sr/⁸⁶Sr ratios of soil leachates and corresponding roots are very similar indicating, that the roots integrate at each level of the soil profile the leachable Sr of the corresponding soil.     

Sr and Nd isotopes as tracers in pedogenic studies: Evidence for Saharan dust contribution to the soils of Muravera (Sardinia,Italy)

Sr and Nd isotopes were applied to 5 soil profiles from the Muravera area, in south-eastern Sardinia.All the soils, which have developed during the Quaternary on the Lower Paleozoic metamorphic basement except for one on Eocene carbonates, are located far from major sources of pollution. Therefore, they are suitable for testing pedogenic processes and geochemical evolution to benefit for environmental studies.The Sr isotopic ratios range largely (δ⁸⁷Sr = 1.7–65.9‰), even in each soil profile. In particular, the observed increase of δ⁸⁷Sr with depth in the most of the metamorphic rock-based soils can be accounted for by the downward decrease of Sr contributions from organic matter and Saharan dust, both displaying lower isotopic ratios than the soil bedrocks. The carbonate rock-based soil exhibits δ⁸⁷Sr higher (1.7–18.1‰) than the bedrock, indicating a significant contribution of radiogenic Sr from the siliciclastic fraction of the soil, and probably from dust input. The Nd isotopic ratios are slightly variable through the profiles (ɛ_Nd from −7.8 to −14.5), confirming little mobility of Nd and Sm during the pedogenesis. Among the minerals present in the soils, phosphates, albite, and calcite are those important in providing low radiogenic Sr and Nd to organic matter of the soils.Lastly, this isotopic study has in particular allowed for evaluating the potential proportion of contribution of Saharan dust to south-eastern Sardinia, thus corroborating the findings of other studies related to soils from the central-western Mediterranean.     

Chemistry of rainwater in the Massif Central (France): a strontium isotope and major element study

Atmospheric aerosols (sea salt, crustal dust, and biogenic aerosols) are the primary source of dissolved species in rainwater as well as one of the sources of dissolved species in river water. Chemical weathering studies require quantification of this atmospheric input. The crustal component of atmospheric input can have various origins, both distant and local. The proportions of the various inputs (marine, distant or local) are determined in this study.Strontium isotope ratios and Ca, Na, K, Mg, Al, Cl, SO₄, NO₃ and Sr concentrations were measured in rainwater samples collected in the Massif Central (France) over a period of one year. Each sample, collected automatically, represents a monthly series of rain events. Chemical composition of the rainwater samples varied considerably and the ⁸⁷Sr/⁸⁶Sr ratios ranged between 0.709198 and 0.713143.Using Na as an indicator of marine origin, and Al for the crustal input in rain samples, the proportion of marine and crustal elements was estimated from elemental ratios. A marine origin of 4 to 100% of Cl, of 0.6 to 20% of the SO₄, of <1 to 10% of Ca, <1 to 40% of K, 4 to 100% of Mg and 1 to 44% of Sr was determined.Strontium isotopes were used to characterize the crustal sources. The ⁸⁷Sr/⁸⁶Sr ratios of the crustal sources varied considerably from 0.7092 to 0.71625 and indicate the occurrence of multiple sources for the crustal component in the analysed rainwaters.     

Minor-element and Sr-isotope geochemistry of tertiary stocks,Colorado mineral belt

Rocks of the northeast portion of the Colorado mineral belt form two petrographically, chemically and geographically distinct rock suites: (1) a silica oversaturated granodiorite suite; and (2) a silica saturated, high alkali monzonite suite. Rocks of the granodiorite suite generally have Sr contents less than 1000 ppm, subparallel REE patterns and initial ⁸⁷Sr/ ⁸⁶Sr ratios greater than 0.707. Rocks of the monzonite suite are restricted to the northeast part of the mineral belt, where few rocks of the granodiorite suite occur, and generally have Sr contents greater than 1000 ppm, highly variable REE patterns and ⁸⁷Sr/⁸⁶Sr initial ratios less than 0.706.Despite forming simple, smooth trends on major element variation diagrams, trace element data for rocks of the granodiorite suite indicate that they were not derived from a single magma. These rocks were derived from magmas having similar REE patterns, but variable Rb and Sr contents, and Rb/Sr ratios. The preferred explanation for these rocks is that they were derived by partial melting of a mixed source, which yielded pyroxene granulite or pyroxenite residues.The monzonite suite is chemically and petrographically more complex than the granodiorite suite. It is subdivided here into alkalic and mafic monzonites, and quartz syenites, based on the textural relations of their ferromagnesian phases and quartz. The geochemistry of these three rock types require derivation from separate and chemically distinct magma types. The preferred explanation for the alkalic monzonites is derivation from a heterogeneous mafic source, leaving a residue dominated by garnet and clinopyroxene. Early crystallization of sphene from these magmas was responsible for the severe depletion of the REE observed in the residual magmas. The lower Sr content and higher Rb/Sr ratios of the mafic monzonites requires a plagioclase-bearing source.The Sr-isotope systematics of the majority of these rocks are interpreted to be largely primary, and not the result of crustal contamination. The positive correlation of Rb/Sr and ⁸⁷Sr/⁸⁶Sr ratios for the least fractionated samples indicate that the sources from which parent magmas of both the granodiorite and monzonite suites were derived are Precambrian in age.     

Mineralogical sources of the buffer capacity in a granite catchment determined by strontium isotopes

The role of different minerals in base cation release and thus the increase of buffering capacity of groundwater against acid deposition is controversially discussed in the literature. The ⁸⁷Sr/⁸⁶Sr ratios and base cation concentration were investigated in whole rock leachates, mineral separates, precipitation, soil solution, groundwater and stream water samples in the Lehstenbach catchment (Germany) to identify the weathering sequence of the granite bedrock. Three different approaches were followed in parallel. It was assumed that the contribution of different minerals to base cation supply of the groundwater with increasing weathering intensity would be observed by investigating (1) unweathered rock leachates, deep groundwater and shallow groundwater, (2) groundwater samples from new groundwater wells, reflecting the initial weathering of the drilled bedrock, and groundwater from wells that were drilled in 1988, (3) stream water during baseflow, dominated by deep groundwater, and stream water during high flow, being predominantly shallow groundwater. Whereas the first approach yielded consistent patterns, there was some evidence that groundwater from the new wells initially reflected contamination by the filter gravel rather than cation release in an initial stage of weathering. Time series samples of stream water and groundwater solute concentrations and isotope ratios turned out to reflect varying fractions of soil water and precipitation water at baseflow and high flow conditions rather than varying contributions of different minerals that prevail at different stages of granite weathering.     

Metal sources of the Navan carbonate-hosted base metal deposit, Ireland: Nd and Sr isotope evidence for deep hydrothermal convection

Nd and Sr isotope analyses are presented for gangue mineral samples from the giant carbonate-hosted Navan Zn–Pb deposit, Ireland, and for rocks from which Navan metals may have been derived. Analysis of gangue minerals spanning the Navan paragenetic sequence reveals systematic evolution in the composition of the mineralising fluid. Early fluid represented by replacive dolomite exhibits the lowest initial ⁸⁷Sr/⁸⁶Sr ratio (0.7083–0.7086), closest to that of the host limestone and to Lower Carboniferous seawater, and the highest ¹⁴³Nd/¹⁴⁴Nd ratio (0.51161–0.51176). Later generations of dolomite, barite and calcite, which encompass sulphide precipitation, have higher initial ⁸⁷Sr/⁸⁶Sr ratios (maximum 0.7105) and lower initial ¹⁴³Nd/¹⁴⁴Nd ratios (minimum 0.51157). All samples have initial Nd isotope ratios that are too low to have been acquired only from the host limestone. Drill core samples of presumed Ordovician volcanic and sedimentary rocks from beneath the Navan orebody have ¹⁴³Nd/¹⁴⁴Nd and ⁸⁷Sr/⁸⁶Sr ratios at the time of mineralisation of 0.51184–0.51217 and 0.7086–0.7138, respectively. The data are interpreted to indicate mixing of sulphide-rich, limestone-buffered brine, with a metal-bearing hydrothermal fluid, which had passed through sub-Carboniferous rocks, consistent with published fluid inclusion and S isotope data. The ¹⁴³Nd/¹⁴⁴Nd ratio of this basement-derived fluid is too low to have been imparted by flow through the Devonian Old Red Sandstone, as required in models of regional fluid flow in response to Hercynian uplift. Irrespective of whether such regional fluid flow occurred, the hydrothermal Nd must have been derived from sub-Devonian rocks. These conclusions broadly support the hydrothermal convection cell model in which brines, ultimately of surface origin, penetrated to a depth of several kilometres, leaching metals from the rocks through which they passed. The data also support increasing depth of penetration of convection cells with time. Metals were subsequently precipitated in carbonate rocks at sites of mixing with cooler, sulphide-rich fluids. However, comparison of the Navan hydrothermal gangue Nd–Sr isotope data with data from Lower Palaeozoic rocks strongly suggests that the latter cannot alone account for the “basement” signature. As the Navan deposit lies immediately north of the Iapetus Suture, this suggests that the Laurentian margin includes Precambrian basement.     

Evidence of hydrological control of Sr behavior in stream water (Strengbach catchment,Vosges mountains,France)

Strontium and particularly ⁸⁷Sr/⁸⁶Sr ratios in stream water have often been used to calculate weathering rates in catchments. Nevertheless, in the literature, discharge variation effects on the geochemical behavior of Sr are often omitted or considered as negligible. A regular survey of both Sr concentrations and Sr isotope ratios of the Strengbach stream water draining a granite (Vosges mountains, France) has been performed during one year. The results indicate that during low water flow periods, waters contain lower Sr concentrations and less radiogenic Sr isotope ratios (Sr=11.6 ppb and ⁸⁷Sr/⁸⁶Sr=0.7246 as an average, respectively) than during high water flow periods (Sr= 13 ppb and ⁸⁷Sr/⁸⁶Sr=0.7252 as an average, respectively). This is contrary to expected dilution processes by meteoric waters which have comparatively lower Sr isotopic ratios and lower Sr concentrations. Furthermore, ⁸⁷Sr/⁸⁶Sr ratios in stream water behave in 3 different ways depending on moisture and on hydrological conditions prevailing in the catchment. During low water flow periods (discharge < 9 l/s), a positive linear relationship exists between Sr isotope ratio and discharge, indicating the influence of radiogenic waters draining the saturated area during storm events. During high water flow conditions, rising discharges are characterized by significantly less radiogenic waters than the recession stages of discharge. This suggests a large contribution of radiogenic waters draining the deep layers of the hillslopes during the recession stages, particularly those from the more radiogenic north-facing slopes. These results allow one to confirm the negligible instantaneous incidence of rainwater on stream water chemistry during flood events, as well as the existence in the catchment of distinct contributive areas and reservoirs. The influence of these areas or reservoirs on the fluctuations of Sr concentrations and on Sr isotopic variations in stream water depends on both moisture and hydrological conditions. Hence, on a same bedrock type, ⁸⁷Sr/⁸⁶Sr ratios in surface waters can be related to flow rate. Consequently, discharge variations must be considered as a pre-requisite when using Sr isotopes for calculating weathering rates in catchments, particularly to define the range of variations of the end-members.     

Engelmann Spruce (Picea engelmannii) as a biological monitor of changes in soil metal loading related to past mining activity

Engelmann spruce (Picea engelmannii) is the dominant tree species in many abandoned mine areas of the Rocky Mountains. It is long-lived, and therefore, may act as a long term biological monitor of changes in soil chemistry caused by past mining activity. In this study, laser ablation inductively coupled mass spectrometry (LA-ICPMS) was used to analyze individual tree rings of Engelmann spruce for Fe, Zn, Cu, Cd, Mn, Pb and Sr concentrations. Cores were obtained from trees growing in tailings-impacted and control (non-tailings impacted) sites near the Waldorf mine (Waldorf, CO, USA). Zinc, Cu, Fe, Cd, Pb and Sr concentrations remained low and consistent over time in the control tree rings. However, in the tailings impacted cores, concentrations of Zn, Cu, Fe and Cd increase significantly in post-mining rings. In addition, Zn, Cu, Fe, and Cd concentrations in pre-mining rings of both the control and tailings impacted cores are similar, indicating that present day soil concentrations of these elements in the control area are a reasonable estimation of background for this area. Lead and Sr concentrations in control and tailings-impacted rings remained similar and relatively constant through time and are not useful in determining changes in soil chemistry due to past mining activity.     

The suitability of annual tree growth rings as environmental archives: Evidence from Sr,Nd, Pb and Ca isotopes in spruce growth rings from the Strengbach watershed

The combination of the Sr, Nd and Pb isotope systems, recognized as tracers of sources, with the Ca isotope system, known to reveal biology-related fractionations, allowed us to test the reliability of spruce (Picea abies) growth rings as environmental archives through time (from 1916 to 1983) in a forest ecosystem affected by acid atmospheric deposition. Sr and Pb isotopes have already been applied in former tree-ring studies, whereas the suitability of Nd and Ca isotope systems is checked in the present article. Our Sr and Nd isotope data indicate an evolution in the cation origin with a geogenic origin for the oldest rings and an atmospheric origin for the youngest rings. Ca isotopes show, for their part, an isotopic homogeneity which could be linked to the very low weathering flux of Ca. Since this flux is weak the spruces’ root systems have pumped the Ca mainly from the organic matter-rich top-soil over the past century. In contrast, the annual growth rings studied are not reliable and suitable archives of past Pb pollution.