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The Humboldt Current System along the Pacific coast of South America creates one of the most productive ecosystems on Earth. To trace the origin of the water masses in this area, we measured neodymium isotope compositions (ԑNd) in tooth enameloid of two genera of coastal sharks from latest Oligocene to early Pleistocene strata in the Pisco and Sacaco basins in southern Peru. Most ԑNd values range from −4 to −1, with a strong negative excursion in the late Miocene (∼8–7 million years ago [Ma]) with values as low as −9.2. The overall trend of the ԑNd values resembles that of equatorial Pacific deep waters, though with an offset of about +2 ԑNd units until about 6 Ma. With a major input of hinterland weathering considered unlikely, we interpret this pattern as reflecting a modern-type upwelling regime, though with a lower contribution of Antarctic waters than today. Starting about 6 Ma, the contribution of Antarctic waters to the upwelling waters increased approximately to present-day levels, coincident with, and possibly driven by, increased Antarctic glaciation and the Andes reaching their present-day elevation, both of which likely enhanced the counter-clockwise circulation in the South Pacific Ocean. The negative excursion of ԑNd values in the Pisco/Sacaco basins ∼8–7 Ma coincides with a late Miocene biogenic bloom in the Pacific Ocean and elsewhere, and with a strongly increased northward bottom current observed on the Nazca Drift System just offshore our sampling area. Thus, the negative excursion of ԑNd values in the Pisco/Sacaco basins likely resulted from a southern sourced input of nutrient-rich, unradiogenic water, which could have been an important contributor to the biogenic bloom.

Studies on the involvement of intrusive magmatism in hydrocarbon generation within sedimentary basins have gained momentum owing to increasing appraisal of the role that such processes may play in controlling global carbon cycle perturbations, and the exploration potential of the volcanic sedimentary basins. Nevertheless, for many areas the causal link between the intrusions and surrounding hydrocarbon systems remains disputed, encouraging a search for methods that could aid in identifying different hydrocarbon sources. Here, we have performed a multi-proxy geochemical study of the middle Cretaceous methane-seep deposits of the Basque-Cantabrian Basin, an early-stage, peri-cratonic rift marking the Mesozoic opening of the Bay of Biscay. Infilled by a thick sedimentary succession intruded by shallow-level igneous bodies, the basin shares analogies with modern young, sedimented rifts that sustain hydrocarbon seepage. We have applied a novel approach that uses the Nd isotope composition of the seep deposits to constrain the relationship between hydrocarbon seepage and igneous activity, and to explore the general potential of Nd isotopes to trace magmatic-influenced fluids in volcanic sedimentary basins. The Nd isotope data have been combined with rare earth element analyses and carbon and oxygen isotope measurements, providing broad insight into the former composition of the seeping fluids. For three out of four investigated seeps, the Nd isotope ratios observed in authigenic seep carbonates include signatures markedly more radiogenic than that reconstructed for background seawater-derived pore waters. The level of this Nd-143-enrichment varies both between and within individual deposits, reflecting spatial and temporal differences in fluid composition typical of seep-related environments. The radiogenic Nd isotope signals provide evidence of subseafloor interactions between the seeping fluids and mafic igneous materials, supporting the model of an igneous control on the mid-Cretaceous methane expulsion in the Basque-Cantabrian Basin. The thermogenic origin of the methane is in accord with the moderately negative delta C-13 values and paragenetic successions observed in the studied seep carbonates. For a single deposit, its relatively unradiogenic Nd isotope composition can be attributed to the smallest size and shallowest emplacement depth of the underlying intrusion, likely resulting in a short-lived character and limited hydrocarbon-generation potential of the associated contact metamorphism. The study demonstrates that Nd isotope analyses of seep carbonates offer a tool in disentangling methane fluxes from different organic matter alteration pathways for the numerous, both fossil and modern sedimented rifts for which the involvement of various methane sources remains insufficiently understood. This work was supported by the National Science Centre, Poland (grant No. 2016/23/D/ST10/00444; to MJ) , and the Eusko Jaurlaritza (Ikerketa Taldeak IT930-16) and the Spanish State Research Agency (project PID2019-105670GB-I00/AEI/10.13039/501100011033; both to LMA)

In recent years, Nd isotopes have seen increasingly common use in studies of hydrocarbon seeps. Given the distinct Nd isotope signature of mafic igneous rocks, particular emphasis in these investigations has been on reconstructing former interactions between the seeping fluids and volcanic materials. The results of our case studies on ancient seeps underlain by mafic volcanic bodies, including Cretaceous seep carbonates of the Outer Carpathians (Czech Republic) and Basque-Cantabrian Basin (Spain), as well as Eocene seeps of the Cascadia convergent margin (Washington) consistently document their significant enrichment in volcanogenic Nd, reflected in their increased Nd isotope ratios (εNd values). The extent of this 143Nd-enrichment varies depending on the geological context of given seeps, most notably the εNd signatures and thickness of the volcanics and overlying sedimentary piles, and the Nd isotope signal of background local pore waters. The highest εNd values are observed in seep carbonates very shallowly underlain by thick mafic volcanics: the Cretaceous seep of the Carpathians and Eocene seeps of Cascadia. For the former, the εNd values are up to 7.5 units higher than the signature of coeval non-seep pore water, whereas for the latter the εNd values are as high as +1.9, close to the highest value ever recorded for seawater. More moderate 143Nd-enrichment typifies the Cretaceous seeps of Spain, for which the volcanic intrusions were emplaced at considerable depths below the seafloor. In such cases, the Nd isotope signature of the fluid-volcanic interactions was partially obscured by subsequent interactions between the fluids and the overlying sediments. Rather than focusing solely on exploring the new geochemical tool, the primary aim of our studies was to address broader questions regarding the tectonic architecture and geological history of the sedimentary basins that host given seep deposits. For the Eocene seeps of Washington, the Nd isotope data served to document interactions between the methane-rich fluids and the volcanic terrane of Siletzia, which underlies the Cascadia forearc; these results placed important stratigraphic and structural constraints on the activation and earliest history of convergence in Cascadia, following Siletzia accretion. For the studied Cretaceous seeps, all hosted by early, sediment-covered rifts, the studies demonstrated that Nd isotopes offer a valuable new tool of deconvolving methane fluxes from different organic matter alteration pathways for the very complex, sedimentary-magmatic systems of incipient rifts. At the same time, these studies emphasized important limitations of Sr isotopes, the system most commonly used to document interactions between the seeping fluids and igneous rocks. Because of the much higher Sr/Nd ratios observed in pore waters than in igneous rocks, the potential of Sr isotopes to record fluid-volcanic interactions is considerably lower than that of Nd isotopes. Thus, broader use of Nd isotopes can assist in identifying potential volcanogenic fluid endmembers for the numerous sedimented rifts for which evidence for magmatic involvement in the fluid expulsion remains equivocal.This work was supported by the National Science Centre, Poland, grant No. 2016/23/D/ST10/00444

Middle Miocene crystals of sabre gypsum and subcrystal of giant gypsum intergrowth cropping out in southern Poland near Busko have been analysed for their Sr isotope composition. The new isotopic data revealed fluctuations in 87Sr/86Sr values within the primary gypsum crystals providing new insight into paleohydrological conditions during the Badenian salinity crisis in the Polish part of the Carpathian Foredeep Basin. The isotopic composition of a glassy gypsum subcrystal decreased progressively with the subcrystal growth, ranging from 0.70892 to 0.70884 near the crystal apex. The 87Sr/86Sr ratios of the sabre gypsum crystals are in the range of 0.70887–0.70934 and there are significant fluctuations within each gypsum layer tested. Similar intra-layer fluctuation patterns observed in various sections provide a strong argument for the synchronous origin of the investigated portions of the sulphate successions. The studied primary gypsum has a more radiogenic composition than the Badenian seawater. Its isotope signatures reflect spatial and temporal changes in the supply of continental derived radiogenic Sr to the Carpathian Foredeep Basin. Contrary to previous studies, the Palaeozoic clastic rocks of the Holy Cross Mountains are suggested as potential sources of radiogenic strontium. The new Sr isotope data support a salina model for the evaporitic basin of the Carpathian Foredeep.This study was supported by the Polish National Science Centre, grant No. 2017/27/B/ST10/00493.

Over the past decades, neodymium isotopes have received considerable attention in palaeoceanography as a tool for reconstructing past seawater circulation, local weathering inputs, and sea-level changes. In this study, we have investigated the Nd isotope composition of Serpukhovian (Carboniferous) carbonates of a shallow-water succession to test icehouse cyclicity and seawater dynamics on the Karatau carbonate platform in southern Kazakhstan. The cyclic succession formed in response to glacio-eustasy and composed of subtidal and intertidal limestones displays a large variation in the εNd(326 Ma) values from –1.6 to +4.3, corresponding to differences in the isotopic composition of two seawater masses present in the adjacent Uralian–Turkestan Ocean during the Serpukhovian, highly radiogenic deep water and less radiogenic surface water. The Nd isotope excursions within the icehouse cycles are more complex than simple transgressive-regressive cycles. They probably reflect a temporal pattern of the sub-Milankovitch climatic perturbations during the interglacial periods in the Carboniferous. The episodic appearance of rich brachiopod communities was forced by the inflow of highly radiogenic, nutrient-rich waters, presumably driven by upwelling. Nd isotope analyses of cyclic intertidal and subtidal carbonates have great potential to produce high-resolution records of seawater dynamics on shallow-water carbonate platforms.This study was supported by the Polish National Science Centre, grant No. 2013/11/B/ST10/04751.

This study presents first isoscape maps of strontium isotope signatures and their spatial variation in Poland, based on ~900 samples of rocks, sediments, surface water, and flora. This dataset is supplemented by

The neodymium isotope composition of micritic limestones from the Devonian–Carboniferous carbonate platform of the Greater Karatau (southern Kazakhstan) was investigated to test the ability of calcite micrite to archive Nd isotope signatures of seawater. The carbonate fraction that displays seawater-like rare earth element (REE + Y) signatures is often more radiogenic than the dispersed terrigenous material in the samples. Hence, its Nd isotope composition is interpreted to correspond to the seawater from which the micrite was precipitated. The seawater on the Karatau platform exhibited an extremely wide range of eNd(t) values from –9.3 to +4.3 (the most radiogenic value measured for past seawater to date) and very uniform Sm/Nd ratios, from 0.19 to 0.22, lying within the range characteristic for modern oceanic water. The temporal trend in eNd(t) values is interpreted to document the final closure of the Uralian–Turkestan Ocean. It shows that the subduction along Kazakhstan9s active margin had already started at the beginning of the Tournaisian (c. 355 Ma), at least 23 Myr earlier than previously thought. The application of Nd isotope time series on biostratigraphically dated carbonates opens a new direction for geotectonic studies. This approach has the potential to provide useful constraints for the precise dating of the duration of geotectonic and volcanic events. Supplementary material: Nd isotope and REE concentration data, summary of stratigraphic and lithological data, field photographs and additional geochemical plots are available at: https://doi.org/10.6084/m9.figshare.c.5110163

The carbonates forming at deep-sea hydrocarbon seeps provide an archive for the source and migration pathways of the seeping fluids. Interpretation of the archived isotopic and elemental signatures is, however, not straightforward because of mixing between the signals of fluids and ambient seawater, limited understanding of subseafloor fluid circulation, and effects of diagenetic alteration. The Nd isotope system is among the most widely used tracers of circulation patterns in modern and past oceans, but to date Nd isotopes have been rarely used in investigations of fluid migration pathways at hydrocarbon seeps. To test the sensitivity of Nd isotope signals of seep carbonates to record past interactions between the seeping fluids and 143Nd-enriched, volcanic-derived mineral components, we performed Nd, Sr and stable isotope analyses of the Lower Cretaceous (Barremian) seep carbonates found in Baska (Czech Carpathians). These seep deposits are directly underlain by a complex of mafic igneous rocks, which the methane-charged fluids must have passed through on their way to the seafloor. The eNd(t) values measured in the seep carbonates are significantly more radiogenic than the inferred signal of contemporaneous local seawater, and shifted towards the composition typical of the underlying basaltoids. This is in agreement with the 87Sr/86Sr ratios, which are markedly lower that the coeval seawater signature. Consistent co-variance trends are observed among the measured eNd(t), 87Sr/86Sr and δ13C values, attesting increasing role of the volcanic-derived fluid component with increasing contribution of methane-derived carbon. The results of the present approach reveal the potential of Nd isotopes to fingerprint exotic fluid end-members present in plumbing systems of both fossil and modern methane discharges. The method can be of particular use in studies of seeps associated with plate margins, where 143Nd-enriched igneous materials are commonly encountered in the basement or in the sediment column.

Stratigraphic and structural context of the early evolution of the Cascadia convergent margin, following major subduction reconfiguration associated with accretion of the igneous Siletzia terrane at 50−45 Ma, remains insufficiently understood. Here, we have applied a novel approach that uses combined Nd, Sr and stable isotope analyses of ancient methane-seep carbonates to constrain the early hydrogeological regime of the Cascadia margin. Analyses included the oldest-known seep deposits of Cascadia, formed during mid-Eocene time (42.5−40.5 Ma). A combination of exceptionally high εNd and low 87Sr/86Sr signatures observed in these carbonates consistently point to former interactions between the seeping fluids and mafic, igneous constituents of the forearc basement. Moderately negative δ13Ccarbonate values imply thermogenic origin of hydrocarbons at three out of four studied seeps, with likely contribution of biogenic methane at a single, landward-most site. When combined with structural constraints, the recorded signals point to discharges of fluids originating from deep portions of the young subduction wedge, and their channeled ascent through the Siletzia terrane. The results document the presence of a fluid expulsion system indicative of active convergence prior to maturation of typical arc magmatism in the Cascades at 40 Ma. The exceptionally pronounced role of exotic, 143Nd-enriched, 87Sr- and 18O-depleted fluids recorded for early Cascadia reflects its distinctive structural architecture, including the relatively thin sedimentary cover of the young forearc, its extensional tectonics, and the near-trench position of the volcanic terrane that the descending plate-derived fluids must have migrated through prior to reaching the seafloor.

International audience; Spectacular Early Devonian carbonate buildups exposed in the eastern Anti-Atlas of southern Morocco and widely known as the Kess-Kess mounds constitute a classical example of deep-water mud mounds interpreted to be related to hydrothermal venting. They developed on the Hamar Laghdad elevation, located near Erfoud, created by a submarine volcanic eruption and composed of peperites and tuffs displaying geochemical characteristics of typical intra-plate basalts. During late Emsian time, reactivation of magmatic processes caused doming of the volcanic complex and the overlying sedimentary strata, and in consequence, a network of radial and tangential faults originated. Most of the mounds developed over the cross-points of these faults. One of the characteristic features of the Kess-Kess mounds is the presence of small caves and rock shelters. They represent fragments of larger fissures, originally open and connected to the seafloor through vent outlets. This system has formed simultaneously with the formation of mounds or immediately after. The irregular and/or pipe-shaped geometry of fissures points to chemical corrosion processes rather than to a tectonic mechanism for their origin. Dissolution of carbonates appears to be in contradiction with enhanced carbonate production, characteristic for the rapid mound growth, but it can easily be explained by mixing of two different carbonate solutions, hydrothermal fluids and seawater. It is suggested that during the formation of the Kess-Kess mounds dissolution took place in zones dominated by hydrothermal fluid-rich mixtures, and precipitation progressed with dilution of the vent fluids by seawater.

Strontium isotopes have seen common use as a tracer of volcanic-influenced fluids at hydrothermal vents and cold seeps hosted by sedimented rifts. However, for some fluid emissions, no apparent contribution of volcanogenic Sr has been observed, despite geological or seismic evidence suggesting magmatic involvement in the fluid expulsion. Here, we explore the behaviour of Sr during fluid-rock interactions in a sedimented rift based on the isotope and elemental composition of Albian hydrocarbon-seep carbonates of the Basque-Cantabrian Basin, Pyrenees. The basin represents a peri-cratonic rift formed during the opening of the Bay of Biscay and infilled with organic-rich siliciclastics affected by subvolcanic intrusions. The intrusions stimulated thermogenic hydrocarbon generation in the sediments and resulted in enrichment of the associated seep carbonates in volcanic-derived, radiogenic Nd. In contrast, none of the 87Sr/86Srcarbonate ratios observed in this study provide evidence for subseafloor interactions between the seeping fluids and igneous materials. Instead, all four studied seep deposits show various degrees of 87Sr-enrichment, bearing the fingerprint of interactions with the rift-filling siliciclastics, rather than a volcanogenic signature. Furthermore, for three deposits, the observed unusual, positive correlation between the Sr and Nd isotope ratios attests to a presence of an evolved, deep-seated fluid end-member enriched in both 87Sr and 143Nd. This isotope decoupling can be explained by the different responses of Nd and Sr to subseafloor fluid-volcanic interactions, with a moderate degree of elemental exchange able to modify the fluid Nd isotope signal, but insufficient to affect the fluid Sr isotope signature. The study shows that for many sedimented seeps and vents, and especially for low-temperature, hydrocarbon-dominated emissions, volcanic-influenced fluids can be more reliably traced using the Nd isotope system, whereas Sr isotopes cannot provide standalone evidence for their absence.

The Sr isotope composition ( 87 Sr/ 86 Sr) and Sr content of waters of the Warta River (central-western Poland) and its tributaries were used to fingerprint water sources and their interactions in space and time. Dissolved Sr in river water of the Warta is characterized by a relatively narrow range of the 87 Sr/ 86 Sr values, from 0.7090 to 0.7105, which contrasts with a strong variation in isotopic signatures of the tributaries, from 0.7080 to 0.7121. With the exception of three streams, which include inputs of mine waters, the waters of tributaries are more enriched in 87 Sr than the master stream. The overall Sr budget of the Warta watershed is determined by the relative contributions of carbonate dissolution and silicate weathering. It can be accounted for by mixing between waters from three reservoirs: 1) groundwater charged with Sr through interaction with Sr-bearing clay minerals, 2) groundwater related to weathering (dissolution) of carbonate rocks, and 3) atmospheric waters charged with Sr from the near-surface weathering and wash-out of Quaternary glaciogenic deposits. Superimposed on the natural Sr isotope systematics is impact of mine waters and fertilizers. The former providing non-radiogenic Sr from the Permian/Mesozoic aquifers constitutes an important anthropogenic element of the Sr budget, whereas the impact of the latter is presumably common but of minor importance. The present-day Sr isotope systematics of the Warta is temporary and different from that of the pre-industrial times.

During the Final Eneolithic the Corded Ware Complex (CWC) emerges, chiefly identified by its specific burial rites. This complex spanned most of central Europe and exhibits demographic and cultural associations to the Yamnaya culture. To study the genetic structure and kin relations in CWC communities, we sequenced the genomes of 19 individuals located in the heartland of the CWC complex region, south-eastern Poland. Whole genome sequence and strontium isotope data allowed us to investigate genetic ancestry, admixture, kinship and mobility. The analysis showed a unique pattern, not detected in other parts of Poland; maternally the individuals are linked to earlier Neolithic lineages, whereas on the paternal side a Steppe ancestry is clearly visible. We identified three cases of kinship. Of these two were between individuals buried in double graves. Interestingly, we identified kinship between a local and a non-local individual thus discovering a novel, previously unknown burial custom.

This study presents first isoscape maps of strontium isotope signatures and their spatial variation in Poland, based on ~900 samples of rocks, sediments, surface water, and flora. This dataset is supplemented by 87Sr/86Sr ratios predicted for several carbonate rock units. High, radiogenic Sr isotope ratios (>0.72), related to the Pleistocene glacial deposits, are omnipresent throughout the country and are also found in the Sudetes and the Holy Cross Mountains, where igneous and clastic Palaeozoic rocks are widely exposed. The lowest Sr signatures (

Analyses of the Nd isotope composition of conodonts from the Anti-Atlas (Morocco), the Montagne Noire (France) and the Rhenohercynian domain (Germany) provide insight into the temporal and lateral variations in seawater geochemistry in the western part of the Variscan Sea during the Late Devonian. Most of the isotopic excursions accurately record changes in sea level. The eNd values decreased during regression phases when erosion accelerated supply of unradiogenic Nd from old continental sources. A rise in sea level generated a positive shift in eNd values due to input of more radiogenic oceanic water into the seawater reservoir of the shelf areas. The method has great potential for sea-level research, paleoceanography and correlation because sea-level changes can be precisely recognized even in successions with uniform, monotonous lithologies. However, it has a significant limitation being valid only in epeiric seas and shelf areas. We have used the Nd isotope record to reconstruct the eustatic sea-level changes in late Frasnian–early Famennian time. The onset of the organic-rich Kellwasser units coincides with negative trends in eNd values. This accords with oxygen deficiency at the sea bottom being initiated by short-term regressive events, which in turn would be consistent with cooling periods of glacial origin, as previous authors have suggested.

A fauna of bivalve molluscs is described from methane seep carbonates of the Middle Devonian (c. 390 Ma) Hollard Mound in the eastern Anti-Atlas, Morocco. We describe a new modiomorphid genus Ataviaconcha gen. nov. with the type species Ataviaconcha wendti sp. nov. This is a very large, semi-infaunal species occurring in large colonies similar to those formed by Recent chemosymbiotic cold-seep and hydrothermal vent bivalves. It is the second modiomorphid bivalve known from Palaeozoic chemosynthesis-based ecosystems, after the roughly coeval Sibaya ivanovi Little, Maslennikov, Morris & Gubanov, 1999, from the Sibay hydrothermal vent deposit in the Ural Mountains, Russia. The second and much less numerous bivalve species described in this paper is the solemyid Dystactella? eisenmanni sp. nov., belonging to a genus known also from Ordovician to Devonian marine environments distinct from cold seeps and hydrothermal vents. As with other fossil and Recent solemyids, it was an infaunal burrower, most likely livi...

Stratigraphic and structural constraints on the initiation and early evolution of the Cascadia convergent margin, following accretion of the igneous Siletzia terrane at 50–45 Ma, remain elusive. This study applies a novel approach based on the combination of Nd, Sr, C and O isotope analyses of the oldest-known methane-seep carbonates (Humptulips Formation, middle Eocene, 42.5–40.5 Ma) of Cascadia to provide insight into its early hydrogeological regime and incipient subduction history. Both anomalously high eNd and low 87Sr/86Sr signatures of the studied carbonates attest to interactions between the seeping fluids and mafic, igneous components of the forearc basement. Moderately negative δ13Ccarbonate values imply a predominantly thermogenic origin of hydrocarbons at three out of four studied seeps, with likely an important contribution of biogenic methane at a site that was closer to the ancient shoreline. When combined with structural constraints, the recorded signals point to discharge of fluids originating mostly from deep portions of the young subduction wedge underthrust beneath the accreted Siletzia terrane, and their channelled ascent through its thick volcanic succession. These results document the presence of a fluid generation and migration system typical of active convergent margins prior to maturation of typical, calc-alkaline arc magmatism in the Cascades at 40 Ma. The strongly pronounced involvement of the exotic, 143Nd-enriched and 87Sr-depleted fluids reflects the distinctive structural architecture of the newly reorganised subduction zone. Of particular importance was the combination of a relatively thin sedimentary cover of the infant forearc, its extensional tectonics, and the proximity of the young trench to the volcanic backstop that the deep, subducting plate-derived fluids must have interacted with before their seepage at the seafloor.

For the first time, Nd isotope signatures combined with rare earth element (REE) concentrations were used in investigations of ancient seep carbonates. The study was performed on the fossil hydrocarbon seep deposit of the Middle Devonian Hollard Mound (eastern Anti-Atlas, Morocco), where Nd isotopes, REE concentrations, and carbon and oxygen isotope ratios were measured to investigate the origin, former migration pathways and composition of fluids. Relatively high eNd values compared to local Eifelian seawater, as well as consistently appearing positive Eu anomalies in MREE-enriched shale-normalized REE patterns of the seep carbonates provided evidence for interaction between the seeping fluids and the Lower Devonian basaltic volcaniclastics underlying the studied seep deposit. Strongly reducing conditions and increased temperature of methane formation could have constituted an additional factor in the Eu-enrichment of the investigated carbonate phases. The presence of exclusively negative Ce anomalies in these carbonates is in line with observations of other workers that seep limestones may not necessarily display positive Ce anomalies indicative of precipitation under anoxic conditions. The negative Ce anomalies are attributed here to mixing between anoxic pore waters and oxic, Ce-depleted seawater, necessary to enable carbonate precipitation at seeps. The methane-rich fluids ascended most likely from below the volcaniclastic unit and inherited the enriched eNd signatures and positive Eu anomalies due to fluid–rock interactions during their seepage to the seafloor. The carbon isotope data are most consistent with thermogenic origin of methane, although contribution of abiotic and biogenic methane sources cannot be excluded. Our results indicate that neodymium isotope and rare earth element analyses constitute one of the most valuable tools for reconstructing former fluid migration patterns. The study shows also that Nd isotopes and Eu anomalies can serve as sensitive tracers of fluid–rock interactions at submarine springs.

Conodonts collected from sections near the small towns of Thong Pha Phum and Mae Sariang in the westernmost part of Thailand are used to reconstruct the neodymium (Nd) isotopic composition of seawater during the Late Devonian. The study provides the first Devonian seawater signatures recognized within the Australian shelf of northeastern Gondwana and the adjacent Paleotethys Ocean. At Thong Pha Phum site, the seawater was characterized by very low e Nd values (from − 13.1 to − 18.2) and very high Sm/Nd ratios (between 0.36 and 0.66). In contrast, the seawater at the Mae Sariang site was characterized by much more radiogenic signatures (e Nd values from − 8.7 to − 11.1) and uniform, low Sm/Nd ratios (between 0.20 and 0.23). Extremely low e Nd values recognized at Thong Pha Phum attest to a passive margin continental setting and a paleogeographic position very close to a continental area where Paleoproterozoic and Neoarchean rocks were eroded. Thus, the isotopic data provide strong evidence that during Late Devonian time the Sibumasu terrane was situated in the proximity to the Archean cratons of Western Australia, presumably adjacent to the Carnarvon intracratonic basin. Moreover, Sibumasu may not have been situated in an outboard position on the shelf, as previously suggested, but could have been directly attached to the Australian continental crust. By contrast, low and uniform Sm/Nd ratios of seawater at Mae Sariang resemble those of the Variscan and the present-day oceanic seawaters. Therefore, a pelagic setting within the Paleotethys Ocean is postulated for the Mae Sariang succession. This conclusion is also constrained by minor temporal changes in e Nd values and suggests that the Paleozoic of Mae Sariang is not part of the Sibumasu terrane but belongs to the Inthanon Zone.

An 11 m thick condensed sequence of Late Devonian limestones in northwestern Thailand exhibits faunal associations and sedimentological-/microfacies data which are indicative of a pelagic facies setting. The entire long-ranging section is completely free from clastic input. Similar successions are known worldwide in a few sections only. The Mae Sariang section is characterised by low sedimentation rates as recognised by a number of hardgrounds, neptunian dikes and Fe/Mn crusts. The succession comprises a number of pelagic faunal elements e.g. conodonts, cephalopods and pelagic ostracodes. The fauna records rare macrofossils and the faunal diversity is low. The very condensed section ranges from the Late rhenana to praesulcata conodont biozones, but contains some global events as undoubtedly shown by biostratigraphical and carbon-isotope results (including major Kellwasser and Hangenberg biotic crises). In terms of plate tectonics this important succession most probably belongs to the Inthanon Zone comprising remnants of the Paleotethys Ocean.

Neodymium isotope data obtained from conodonts collected in Morocco and Poland attest a geochemical decoupling of seawater in the Variscan realm during the Late Devonian. The water masses on the shelves were characterized by unradiogenic e Nd values, from about − 7 to − 12. The surface water in the bordering oceans (the Rheic Ocean and the Variscan Sea) yielded more radiogenic e Nd values, ranging from about − 1 to − 6. A compilation of Nd and C isotope signatures from the Moroccan Meseta suggests that the shelf and the surface oceanic water differed also in their carbon isotope evolution. The geochemical decoupling constrains a restricted water exchange between shelves and the ocean. Oceanic waters entered far into the shelf areas only during the semichatovae transgression in the Frasnian Zone 11. Sea-level fluctuations constituted the major force that modified circulation, and thus controlled the mixing of shelf and surface oceanic seawater. The Nd conodont data reveal that the surface water of the Variscan oceanic water resembled the seawater of the modern Pacific Ocean rather than those of the Atlantic and Indian oceans. The geochemical character of the Variscan oceanic water is consistent with the geotectonic regime of the Variscan realm in Late Devonian and Carboniferous times.

Nd and Sr isotope data were used to characterize the sources of the Upper Triassic (Keuper) siliciclastic rocks of Silesia in southern Poland. This continental succession, consisting predominantly of fine-grained mud- stones and siltstones, yields a remarkably uniform Nd isotopic composition. Nd model ages T 2DM vary from 1.56 to 1.69 Ga and e Nd values are in the range from –8.9 to –11.2, documenting old crust contribution in the provenance. In contrast, the Sr isotopic composition ( 87 Sr/ 86 Sr) of the clastics exhibits a relatively large variation from 0.710 to 0.723. The isotopic compositions indicate that the southern part of the Germanic Basin in Silesia was supplied with clastic material from the Bohemian Massif. The axis of the drainage area must have crossed from SW to NE the Saxothuringian units of the East Sudetes and most probably also the area of the Tepla–Barrandian Unit. There is no indication of any sediment transport from the Moravo-Silesian Belt and the Fore-Sudetic Block. It seems, that the Palaeozoic rocks of the latter domain must have been buried completely during Late Triassic times.

[1] The Nd isotope composition of conodonts is used for the first time as a paleoceanographic proxy to reconstruct seawater circulation. Conodonts from two stratigraphic levels in the eastern Anti-Atlas, the lower part of the Frasnian Zone 11 (base of the Kellwasser facies) and the boundary interval of the Uppermost crepida/rhomboidea zones (top of the Kellwasser facies), were selected for reconstruction of seawater circulation on the Moroccan shelf of Gondwana during Late Devonian times. The recognized lateral variations in ɛNd values are in very good agreement with current-related sedimentary features. They provide evidence for communication of the Moroccan shelf with the Rheic Ocean to the southwest and with the Variscan Sea to the north. In the Frasnian, the general seawater flow was directed from the southwest to the east and was influenced by a local riverine input of low radiogenic Nd from the south (the West African Craton and/or the Pan-African Ougarta Belt) and from the northwest (the Precambrian basement of the Anti-Atlas). The combined set of Nd isotopic records and directional data from the middle Famennian reveals a circulation pattern different from that of the Frasnian. It was dominated by a general westward flow with a countercurrent in the central Tafilalt area. The establishment of a new circulation system during the Famennian suggests essential changes in paleogeography of the western part of the Variscan realm.

Anthropogenic impact on surface waters and other elements in the environment was investigated in the Noteć River basin in central Poland. The approach was to trace changes in the Sr isotope composition ((87)Sr/(86)Sr) and concentration in space and time. Systematic sampling of the river water shows a very wide range of (87)Sr/(86)Sr ratios, from 0.7089 to 0.7127. This strong variation, however, is restricted to the upper course of the river, whereas the water in the lower course typically shows (87)Sr/(86)Sr values around 0.7104-0.7105. Variations in (87)Sr/(86)Sr are associated with a wide range of Sr concentrations, from 0.14 to 1.32mg/L. We find that strong variations in (87)Sr/(86)Sr and Sr concentrations can be accounted for by mixing of two end-members: 1) atmospheric waters charged with Sr from the near-surface weathering and wash-out of Quaternary glaciogenic deposits, and 2) waters introduced into the river from an open pit lignite mine. The first reservoir is characterized by a low Sr content and high (87)Sr/(86)Sr ratios, whereas mine waters display opposite characteristics. Anthropogenic pollution is also induced by extensive use of fertilizers which constitute the third source of Sr in the environment. The study has an important implication for future archeological studies in the region. It shows that the present-day Sr isotope signatures of river water, flora and fauna cannot be used unambiguously to determine the "baseline" for bioavailable (87)Sr/(86)Sr in the past.