Tracking the magmatic evolution of island arc volcanism : insights from a high-precision Pb isotope record of Montserrat, Lesser Antilles

The volcanic succession on Montserrat provides an opportunity to examine the magmatic evolution of island arc volcanism over a ∼2.5 Ma period, extending from the andesites of the Silver Hills center, to the currently active Soufrière Hills volcano (February 2010). Here we present high-precision double-spike Pb isotope data, combined with trace element and Sr-Nd isotope data throughout this period of Montserrat's volcanic evolution. We demonstrate that each volcanic center; South Soufrière Hills, Soufrière Hills, Centre Hills and Silver Hills, can be clearly discriminated using trace element and isotopic parameters. Variations in these parameters suggest there have been systematic and episodic changes in the subduction input. The SSH center, in particular, has a greater slab fluid signature, as indicated by low Ce/Pb, but less sediment addition than the other volcanic centers, which have higher Th/Ce. Pb isotope data from Montserrat fall along two trends, the Silver Hills, Centre Hills and Soufrière Hills lie on a general trend of the Lesser Antilles volcanics, whereas SSH volcanics define a separate trend. The Soufrière Hills and SSH volcanic centers were erupted at approximately the same time, but retain distinctive isotopic signatures, suggesting that the SSH magmas have a different source to the other volcanic centers. We hypothesize that this rapid magmatic source change is controlled by the regional transtensional regime, which allowed the SSH magma to be extracted from a shallower source. The Pb isotopes indicate an interplay between subduction derived components and a MORB-like mantle wedge influenced by a Galapagos plume-like source.

Spatial subdivision among assemblages of Spanish mackerel, Scomberomorus commerson (Pisces: Scombridae) across northern Australia: implications for fisheries management

Aim: This study investigated the use of stable δ13C and δ18O isotopes in the sagittal otolith carbonate of narrow-barred Spanish mackerel, Scomberomorus commerson, as indicators of population structure across Australia. Location: Samples were collected from 25 locations extending from the lower west coast of Western Australia (30°), across northern Australian waters, and to the east coast of Australia (18°) covering a coastline length of approximately 9500 km, including samples from Indonesia. Methods: The stable δ13C and δ18O isotopes in the sagittal otolith carbonate of S. commerson were analysed using standard mass spectrometric techniques. The isotope ratios across northern Australian subregions were subjected to an agglomerative hierarchical cluster analysis to define subregions. Isotope ratios within each of the subregions were compared to assess population structure across Australia. Results: Cluster analysis separated samples into four subregions: central Western Australia, north Western Australia, northern Australia and the Gulf of Carpentaria and eastern Australia. Isotope signatures for fish from a number of sampling sites from across Australia and Indonesia were significantly different, indicating population separation. No significant differences were found in otolith isotope ratios between sampling times (no temporal variation). Main conclusions: Significant differences in the isotopic signatures of S. commerson demonstrate that there is unlikely to be any substantial movement of fish among these spatially discrete adult assemblages. The lack of temporal variation among otolith isotope ratios indicates that S. commerson populations do not undergo longshore spatial shifts in distribution during their life history. The temporal persistence of spatially explicit stable isotopic signatures indicates that, at these spatial scales, the population units sampled comprise functionally distinct management units or separate ‘stocks’ for many of the purposes of fisheries management. The spatial subdivision evident among populations of S. commerson across northern and western Australia indicates that it may be advantageous to consider S. commerson population dynamics and fisheries management from a metapopulation perspective (at least at the regional level).

Stable carbon isotope ratios in Asian elephant collagen: implications for dietary studies

Stable carbon isotope ratios in bone collagen have been used in a variety of dietary studies in modern and fossil animals, including humans. Inherent in the stable isotope technique is the assumption that the isotopic signature is a reflection of the diet and is persistent in collagen because this is a relatively inert protein. Carbon isotope analyses of bones from a southern Indian population of Asian elephant (Elephas maximus), a long-lived mammal that alternates seasonally between a predominantly C3 (browse) and C4 (grass) plant diet, showed two patterns that have important implications for dietary interpretation based on isotopic studies. Relative to the quantity of the two plant types consumed on average, the ?13C signal in collagen indicated that more carbon was incorporated from C3 plants, possibly due to their higher protein contribution. There was a much greater variance in ?13C values of collagen in sub-adult (range -10.5� to-22.7�, variance=14.51) compared to adult animals (range -16.0� to -20.3�, variance=1.85) pointing to high collagen turnover rates and non-persistent isotopic signatures in younger, growing animals. It thus seems important to correct for any significant relative differences in nutritive value of food types and also consider the age of an animal before drawing definite conclusions about its diet from isotope ratios.

Tracing the source of bottled water using stable isotope techniques

The Indian Summer Monsoon (ISM) precipitation recharges ground water aquifers in a large portion of the Indian subcontinent. Monsoonal precipitation over the Indian region brings moisture from the Arabian Sea and the Bay of Bengal (BoB). A large difference in the salinity of these two reservoirs, owing to the large amount of freshwater discharge from the continental rivers in the case of the BoB and dominating evaporation processes over the Arabian Sea region, allows us to distinguish the isotopic signatures in water originating in these two water bodies. Most bottled water manufacturers exploit the natural resources of groundwater, replenished by the monsoonal precipitation, for bottling purposes. The work presented here relates the isotopic ratios of bottled water to latitude, moisture source and seasonality in precipitation isotope ratios. We investigated the impact of the above factors on the isotopic composition of bottled water. The result shows a strong relationship between isotope ratios in precipitation (obtained from the GNIP data base)/bottled water with latitude. The approach can be used to predict the latitude at which the bottled water was manufactured. The paper provides two alternative approaches to address the site prediction. The limitations of this approach in identifying source locations and the uncertainty in latitude estimations are discussed. Furthermore, the method provided here can also be used as an important forensic tool for exploring the source location of bottled water from other regions. Copyright (C) 2011 John Wiley & Sons, Ltd.

Time-Domain TeraHertz Spectroscopy and Observational Probes of Prebiotic Interstellar Gas and Ice Chemistry

Understanding the origin of life on Earth has long fascinated the minds of the global community, and has been a driving factor in interdisciplinary research for centuries. Beyond the pioneering work of Darwin, perhaps the most widely known study in the last century is that of Miller and Urey, who examined the possibility of the formation of prebiotic chemical precursors on the primordial Earth [1]. More recent studies have shown that amino acids, the chemical building blocks of the biopolymers that comprise life as we know it on Earth, are present in meteoritic samples, and that the molecules extracted from the meteorites display isotopic signatures indicative of an extraterrestrial origin [2]. The most recent major discovery in this area has been the detection of glycine (NH₂CH₂COOH), the simplest amino acid, in pristine cometary samples returned by the NASA STARDUST mission [3]. Indeed, the open questions left by these discoveries, both in the public and scientific communities, hold such fascination that NASA has designated the understanding of our "Cosmic Origins" as a key mission priority.

Despite these exciting discoveries, our understanding of the chemical and physical pathways to the formation of prebiotic molecules is woefully incomplete. This is largely because we do not yet fully understand how the interplay between grain-surface and sub-surface ice reactions and the gas-phase affects astrophysical chemical evolution, and our knowledge of chemical inventories in these regions is incomplete. The research presented here aims to directly address both these issues, so that future work to understand the formation of prebiotic molecules has a solid foundation from which to work.

From an observational standpoint, a dedicated campaign to identify hydroxylamine (NH₂OH), potentially a direct precursor to glycine, in the gas-phase was undertaken. No trace of NH₂OH was found. These observations motivated a refinement of the chemical models of glycine formation, and have largely ruled out a gas-phase route to the synthesis of the simplest amino acid in the ISM. A molecular mystery in the case of the carrier of a series of transitions was resolved using observational data toward a large number of sources, confirming the identity of this important carbon-chemistry intermediate B11244 as l-C₃H⁺ and identifying it in at least two new environments. Finally, the doubly-nitrogenated molecule carbodiimide HNCNH was identified in the ISM for the first time through maser emission features in the centimeter-wavelength regime.

In the laboratory, a TeraHertz Time-Domain Spectrometer was constructed to obtain the experimental spectra necessary to search for solid-phase species in the ISM in the THz region of the spectrum. These investigations have shown a striking dependence on large-scale, long-range (i.e. lattice) structure of the ices on the spectra they present in the THz. A database of molecular spectra has been started, and both the simplest and most abundant ice species, which have already been identified, as well as a number of more complex species, have been studied. The exquisite sensitivity of the THz spectra to both the structure and thermal history of these ices may lead to better probes of complex chemical and dynamical evolution in interstellar environments.

Caracterização ambiental da bacia hidrogáfica do Rio São Domingos a partir da análise geoquímica e isotópica Pb/Pb

A bacia hidrográfica do rio São Domingos constitui uma das sub-bacias do rio Muriaé pertencente ao sistema Paraíba do Sul e, tem seus limites coincidentes com os limites do município de São José de Ubá, sendo este o segundo maior produtor de tomate do estado do Rio de Janeiro, com sua principal fonte econômica baseada na agropecuária. Este tipo de atividade resulta em utilização de produtos químicos nas lavouras e juntamente a ocupação inadequada resulta em modificação das paisagens e da mata nativa, resultando em diversos tipos de impactos no ambiente. Neste estudo foram abordados os impactos relacionados a concentração de metais e sua proveniência através das assinaturas isotópicas Pb/Pb, utilizando para tal o procedimento analítico de lixiviação dos sedimentos de corrente e abertura total de rochas para a obtenção de razões isotópicas e concentrações de metais por ICP-MS. Os resultados mostraram que as contribuições nos sedimentos de corrente se dão a partir de cinco fontes compreendidos no intervalo de assinatura isotópica 206Pb/207Pb 1,1229 e 1,1949, representadas em intervalos bem definidos. Por correlação com as respectivas concentrações se observa que, preferencialmente, existe maior influência das rochas do embasamento, seguido de atividade antrópicas como a urbanização e disposição de lixo doméstico. As maiores concentrações estão associadas ao cobre, chumbo, estrôncio, níquel e zinco. Contudo todas as concentrações de metais obtidas se encontram abaixo da legislação vigente. Desta forma a contaminação antrópica é limitada a regiões de maior densidade populacional e as influências naturais predominam na área da bacia.

Petrogênese e geocronologia das intrusões alcalinas de Morro Redondo, Mendanha e Morro de São João: caracterização do magmatismo alcalino no Estado do Rio de Janeiro e implicações geodinâmicas

Os modelos para a formação de plútons alcalinos da Província Alcalina do Sudeste Brasileiro ou Alinhamento Poços de Caldas-Cabo Frio associam a gênese destas rochas a grandes reativações ou a passagem de uma pluma mantélica, registrada pelo traço de um hot spot. O objetivo desta tese é, apresentar novos dados e interpretações para contribuir com a melhor elucidação e discussão destes modelos. Os estudos incluem mapeamento, petrografia, litogeoquímica, geoquímica isotópica de Sr, Nd e Pb e datação 40Ar/39Ar. As intrusões selecionadas correspondem ao Morro Redondo, Mendanha e Morro de São João, no Rio de Janeiro, localizados em posições distintas no alinhamento Poços de Caldas-Cabo Frio. A intrusão alcalina do Morro Redondo é composta majoritariamente de nefelina sienitos e sienitos com nefelina, com rara ocorrência de rochas máficas e é caracterizada por uma suíte alcalina sódica insaturada em sílica, de caráter metaluminosa a peralcalina. Esta intrusão foi datada em aproximadamente 74 Ma (idade-platô 40Ar/39Ar). A intrusão alcalina do Mendanha é composta por diversos tipos de rochas sieníticas, além de brechas e estruturas subvulcânicas, como rochas piroclásticas e diques e caracteriza-se por ser uma suíte alcalina sódica saturada em sílica, de caráter metaluminosa, diferente do que ocorre no Marapicu, este subsaturado em sílica. Esta intrusão apresentou duas idades-platô 40Ar/39Ar distintas de magmatismo: 64 Ma para as rochas do Mendanha e 54 Ma em dique de lamprófiro, registrando magmatismo policíclico. O Morro do Marapicu foi datado em aproximadamente 80 Ma. Já a intrusão alcalina do Morro de São João possui uma ampla variedade de litotipos saturados a subsaturados em sílica, tais como sienitos, álcali-sienitos e monzossienitos (alguns portadores de pseudoleucita), com variedades melanocráticas, tais como malignitos e fergustios. Estas rochas definem suas distintas suítes alcalinas subsaturadas em sílica: Uma de composição sódica e outra potássica. Há também uma suíte alcalina saturada em sílica, definida por gabros alcalinos e shonkinitos. A petrogênese destas intrusões corresponde ao modelo de cristalização fracionada, com assimilação de rochas encaixantes (AFC) como indicado pela alta variabilidade de razões isotópicas de estrôncio. No Morro de São João é sugerido o modelo de mistura magmática. Estas intrusões foram geradas a partir de magmas mantélicos enriquecidos, possivelmente associados à antiga zona de subducção relacionada ao orógeno Ribeira. Em razão das novas idades obtidas, o modelo de hot spot proposto fica prejudicado, visto que o Marapicu é de idade mais antiga das intrusões analisadas, o que era esperado para o Morro Redondo. Alguns modelos projetam plumas mantélicas com aproximadamente 1000 km de diâmetro, o que poderia explicar o Mendanha ser contemporâneo ao Morro de São João. As assinaturas isotópicas obtidas para as intrusões não se associam à assinatura isotópica de Trindade e, caso o modelo de plumas mantélicas seja o correto, a pluma que teria maior semelhança de assinatura isotópica é a pluma de Tristão da Cunha.

Stable isotope changes in freshwater shrimps (Exopalaemon modestus and Macrobrachium nipponensis): trophic pattern implications

Trophic patterns of omnivorous freshwater shrimps, Exopalaemon modestus and Macrobrachium nipponensis, were investigated in two shallow eutrophic lakes by using stable isotope analysis. delta N-15 and delta C-13 of M. nipponensis and E. modestus increased with increasing body weight, which might be attributed to larger individuals ingesting organisms that feed higher up the food chain and/or increased assimilation of benthic food items with enriched isotopic signatures. Of the freshwater shrimps occurring in the studied lakes, those from Lake Taihu had significantly elevated delta N-15 and delta C-13 values (4.3% and 1.8%, respectively) compared with those from the less eutrophic Lake Chaohu, indicating that the isotopic signature might partially reflect the trophic states of their habitats. Mixing model results suggested that the benthic food web provides the primary carbon source for both shrimp species, and that E. modestus assimilated relatively more pelagic food sources than M. nipponensis in these lakes.

Stable isotope variations in particulate organic matter and a planktivorous fish in the Yangtze River

Temporal and spatial changes in delta(13) C and delta 15 N of particulate organic matter (POM) and Hemiculter leucisculus were studied in the Yangtze River of China. Isotopic signatures of POM showed seasonal variations, which was assumed to be associated with allochthonous organic input and autochthonous phytoplankton growth. delta C-13 of H. leucisculus was 1.1 % higher than that of POM, which suggested that the food source of H. leucisculus was mostly from the POM. A mass balance model indicated the trophic position of H. leucisculus in the food web of Yangtze River was estimated to be 2.0 - 2.1, indicating that this fish mainly feeds on planktonic organic matter, which agreed with previous gut content analysis.

Trophic relationship between the parasitic isopod ichthyoxenus japonensis and the fish carassius auratus auratus as revealed by stable isotopes

Stable carbon and nitrogen isotope analysis was used to investigate the host-parasite trophic relationship between the parasitic isopod Ichthyoxenus japonensis and one of its freshwater fish host Carassius auratus auratus from Lake Fuxian, China. No significant differences in delta C-13 and delta N-15 were observed between the heterosexual pairs of I. japonensis in the same host. delta C-13 and delta N-15 of I. japonensis were significantly lower than those of its host fish, and the isotopic ratios of the isopod increased with the increase of host fish isotopic signatures. Unlike isotopic fractionation patterns generally observed among consumers and their diets, isopod parasite was delta C-13 and N-15 depleted relative to the muscle tissue of this host fish. Differential isotopic fractionation patterns in the isopod parasite and the fish may be attributed to differences in parasite and host metabolism.

Characterization of stable isotope fractionation during methane production in the sediment of a eutrophic lake,lake dagow,germany

We measured delta C-13 of CO2, CH4, and acetate-methyl in profundal sediment of eutrophic Lake Dagow by incubation experiments in the presence and absence of methanogenic inhibitors chloroform, bromoethane sulfonate (BES), and methyl fluoride, which have different specificities. Methyl fluoride predominantly inhibits acetoclastic methanogenesis and affects hydrogenotrophic methanogenesis relatively little. Optimization of methyl fluoride concentrations resulted in complete inhibition of acetoclastic methanogenesis. Methane was then exclusively produced by hydrogenotrophic methanogenesis and thus allowed determination of the fractionation factors specific for this methanogenic pathway. Acetate, which was then no longer consumed, accumulated and allowed determination of the isotopic signatures of the fermentatively produced acetate. BES and chloroform also inhibited CH4 production and resulted in accumulation of acetate. The fractionation factor for hydrogenotrophic methanogenesis exhibited variability, e. g., it changed with sediment depth. The delta C-13 of the methyl group of the accumulated acetate was similar to the delta C-13 of sedimentary organic carbon, while that of the carboxyl group was by about 12 parts per thousand higher. However, the delta C-13 of the acetate was by about 5 parts per thousand lower in samples with uninhibited compared with inhibited acetoclastic methanogenesis, indicating unusual isotopic fractionation. The isotope data were used for calculation of the relative contribution of hydrogenotrophic vs. acetoclastic methanogenesis to total CH4 production. Contribution of hydrogenotrophic methanogenesis increased with sediment depth from about 35% to 60%, indicating that organic matter was only partially oxidized in deeper sediment layers.

碎屑锆石年龄和Nd-Hf同位素组成对扬子基底演化的制约

The South China craton was formed by the collision of the Yangtze and Cathaysia blocks during the Neoproterozoic Jiangnan orogeny (also termed as the Jingnin or Sibao orogeny in Chinese literature). Basement rocks within the Yangtze block consist mainly of Proterozoic sediments of the Lengjiaxi and Banxi Groups. U-Pb ages of detrital zircons obtained by the LA-ICP-MS dating technique imply that the deposition of the Lengjiaxi Group continued until the Neoproterozoic. The youngest detrital zircons suggest a maximum deposition age of ~830 Ma for the Lengjiaxi Group, consistent with the initiation time of the deposition of the overlying Banxi Group, likely indicating continuous deposition of these two groups and a short temporal hiatus (~10 Ma) between the Neoproterozoic sedimentary rocks distributed in the South China craton. Detrital zircons from both the Lengjiaxi and Banxi Groups have a wide range of εHf(t) values from -12 to 14.2 and a continuous Nd and Hf model age spectrum from ~820 Ma to 2200 Ma. Some grains have model ages ranging up to ca. 2.9-3.5 Ga, indicating that both juvenile mantle material and ancient crust provided sedimentary detritus. This is also consistent with the Nd isotopic signature of sedimentary rocks recorded in the Lengjiaxi Group, suggesting a back-arc tectonic setting. The Banxi Group has slightly enriched Nd isotopic signatures relative to the Lengjiaxi Group, implying a higher percentage of old continental material in the sedimentary source. Combined with previously published data, new results can help us to reconstruct the Neoproterozoic tectonic evolution of the South China craton. The age spectrum of detrital zircons and Nd-Hf isotopic composition suggests a two-stage collision: Between 1000 Ma to 870 Ma, a continental magmatic arc was build up along the eastern margin of the Yangtze block. Convergence led to continent-based back-arc extension, subsidence and formation of a back-arc basin. Detritus originating from arc-related magmatic and old basement rocks was transported into this back-arc basin resulting in formation of the Lengjiaxi Group and its equivalents. At around 870 Ma, a second (oceanic) arc was formed by extension of an inter-arc basin, subduction subsequently led to the first collision and the emplacement of the blueschist mélange. Accretion of the magmatic arc lasted until the closure of an oceanic basin between the Yangtze and Cathaysia blocks at about 830 Ma. Shortly after the collision, subsequent uplift, further extension of the former back-arc basin and post-collisional granitoid magmatism caused a tilting of the Lengjiaxi sediments. Between 830 Ma and 820 Ma, subsequent closure of the oceanic back-arc basin and formation of the Jiangnan orogen took place, leaving a regional unconformity above the Lengjiaxi Group. Above this unconformity the Banxi Group was immediately deposited during the post-tectonic stage.

山东西部中生代碳酸岩和火山岩的地球化学特征及其成因研究

On account of some very peculiar features, such as extremely high Sr and Nd contents which can buffer their primary isotopic signatures against crustal contamination, deep-seated origin within mantle, and quick ascent in lithosphere, carbonatites are very suitable for deciphering the nature of sub-continental lithospheric mantle(SCLM) and receiving widespread attentions all around the world. The Mesozoic carbonatites located in western Shandong was comprehensively investigated in this dissertation. The extremely high REE concentrations, similar spider diagrams to most other carbonatites around the world and high Sr. low Mn contents of apatite from carbonatites confirm their igneous origin. The K depletion of carbonatites from this studies reflect the co-existing of carbonatite melts with pargasite+phlogopite lherzolite rather than phlogopite lherzolite. Geological characteristics and their occumng without associated silicate rocks argue against their origin of fractionation of or liquid immisibility with carbonated silicate melts. In contrast to the low S7Sr/86Sr and high l43Nd/l44Nd of other carbonatites in the world, carbonatites of this studies show EMU features with high S7Sr/86Sr and low l4jNd/144Nd ratios, which imply that this enriched nature was formed through metasomatism of enriched mantle preexisted beneath the Sino-korean craton by partial melts of subducted middle-lower crust of Yangtze craton. In addition to carbonatites, the coeval Mesozoic volcanic rocks from western Shandong were also studied in this dissertation. Mengyin and Pingyi volcanic rocks, which located in the south parts of western Shandong are shoshonite geochemically. while volcanic rocks cropped out in other places are high-K calc-alkaline series. All these volcanic rocks enriched in LREE and LILE. depleted in HFSE, and show TNT(strong negative anomalies in Ta, Nb. Ti) patterns in spider diagrams which are common phenomena in arc-related volcanic rocks. The Sr-Nd-Pb isotopic systematics reveal that the volcanic rocks decrease gradually in 87Sr/86Sr, 206Pb/204Pb, 20SPb/204Pb and increase in TDM from south to north, suggesting the distinction of SCLM beneath Shandong in Mesozoic is more explicit in south-north trending than in east-west trending. The variable features of SCLM can be attributed to the subduction of Yangtze craton beneath Sino-Korean craton, and subsequent metasomatism of SCLM by partial melts of Yangtze lower crust in different extent.

Methane contamination of drinking water accompanying gas-well drilling and hydraulic fracturing.

Directional drilling and hydraulic-fracturing technologies are dramatically increasing natural-gas extraction. In aquifers overlying the Marcellus and Utica shale formations of northeastern Pennsylvania and upstate New York, we document systematic evidence for methane contamination of drinking water associated with shale-gas extraction. In active gas-extraction areas (one or more gas wells within 1 km), average and maximum methane concentrations in drinking-water wells increased with proximity to the nearest gas well and were 19.2 and 64 mg CH(4) L(-1) (n = 26), a potential explosion hazard; in contrast, dissolved methane samples in neighboring nonextraction sites (no gas wells within 1 km) within similar geologic formations and hydrogeologic regimes averaged only 1.1 mg L(-1) (P < 0.05; n = 34). Average δ(13)C-CH(4) values of dissolved methane in shallow groundwater were significantly less negative for active than for nonactive sites (-37 ± 7‰ and -54 ± 11‰, respectively; P < 0.0001). These δ(13)C-CH(4) data, coupled with the ratios of methane-to-higher-chain hydrocarbons, and δ(2)H-CH(4) values, are consistent with deeper thermogenic methane sources such as the Marcellus and Utica shales at the active sites and matched gas geochemistry from gas wells nearby. In contrast, lower-concentration samples from shallow groundwater at nonactive sites had isotopic signatures reflecting a more biogenic or mixed biogenic/thermogenic methane source. We found no evidence for contamination of drinking-water samples with deep saline brines or fracturing fluids. We conclude that greater stewardship, data, and-possibly-regulation are needed to ensure the sustainable future of shale-gas extraction and to improve public confidence in its use.

Denitrification and inference of nitrogen sources in the karstic Floridan Aquifer

Aquifer denitrification is among the most poorly constrained fluxes in global and regional nitrogen budgets. The few direct measurements of denitrification in groundwaters provide limited information about its spatial and temporal variability, particularly at the scale of whole aquifers. Uncertainty in estimates of denitrification may also lead to underestimates of its effect on isotopic signatures of inorganic N, and thereby confound the inference of N source from these data. In this study, our objectives are to quantify the magnitude and variability of denitrification in the Upper Floridan Aquifer (UFA) and evaluate its effect on N isotopic signatures at the regional scale. Using dual noble gas tracers (Ne, Ar) to generate physical predictions of N2 gas concentrations for 112 observations from 61 UFA springs, we show that excess (i.e. denitrification-derived) N2 is highly variable in space and inversely correlated with dissolved oxygen (O2). Negative relationships between O2 and δ15N NO3 across a larger dataset of 113 springs, well-constrained isotopic fractionation coefficients, and strong 15N:18O covariation further support inferences of denitrification in this uniquely organic-matter-poor system. Despite relatively low average rates, denitrification accounted for 32 % of estimated aquifer N inputs across all sampled UFA springs. Back-calculations of source δ15N NO3 based on denitrification progression suggest that isotopically-enriched nitrate (NO3-) in many springs of the UFA reflects groundwater denitrification rather than urban- or animal-derived inputs. © Author(s) 2012.