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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)

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.