Sources of dehydration fluids underneath the Kamchatka arc.

Fluids mediate the transport of subducted slab material and play a crucial role in the generation of arc magmas. However, the source of subduction-derived fluids remains debated. The Kamchatka arc is an ideal subduction zone to identify the source of fluids because the arc magmas are comparably mafic, their source appears to be essentially free of subducted sediment-derived components, and subducted Hawaii-Emperor Seamount Chain (HESC) is thought to contribute a substantial fluid flux to the Kamchatka magmas. Here we show that Tl isotope ratios are unique tracers of HESC contribution to Kamchatka arc magma sources. In conjunction with trace element ratios and literature data, we trace the progressive dehydration and melting of subducted HESC across the Kamchatka arc. In succession, serpentine (<100 km depth), lawsonite (100-250 km depth) and phengite (>250 km depth) break down and produce fluids that contribute to arc magmatism at the Eastern Volcanic Front (EVF), Central Kamchatka Depression (CKD), and Sredinny Ridge (SR), respectively. However, given the Tl-poor nature of serpentine and lawsonite fluids, simultaneous melting of subducted HESC is required to explain the HESC-like Tl isotope signatures observed in EVF and CKD lavas. In the absence of eclogitic crust melting processes in this region of the Kamchatka arc, we propose that progressive dehydration and melting of a HESC-dominated mélange offers the most compelling interpretation of the combined isotope and trace element data.

Strong Margin Influence on the Arctic Ocean Barium Cycle Revealed by Pan-Arctic Synthesis.

Early studies revealed relationships between barium (Ba), particulate organic carbon and silicate, suggesting applications for Ba as a paleoproductivity tracer and as a tracer of modern ocean circulation. But, what controls the distribution of barium (Ba) in the oceans? Here, we investigated the Arctic Ocean Ba cycle through a one-of-a-kind data set containing dissolved (dBa), particulate (pBa), and stable isotope Ba ratio (δ138Ba) data from four Arctic GEOTRACES expeditions conducted in 2015. We hypothesized that margins would be a substantial source of Ba to the Arctic Ocean water column. The dBa, pBa, and δ138Ba distributions all suggest significant modification of inflowing Pacific seawater over the shelves, and the dBa mass balance implies that ∼50% of the dBa inventory (upper 500 m of the Arctic water column) was supplied by nonconservative inputs. Calculated areal dBa fluxes are up to 10 µmol m-2 day-1 on the margin, which is comparable to fluxes described in other regions. Applying this approach to dBa data from the 1994 Arctic Ocean Survey yields similar results. The Canadian Arctic Archipelago did not appear to have a similar margin source; rather, the dBa distribution in this section is consistent with mixing of Arctic Ocean-derived waters and Baffin Bay-derived waters. Although we lack enough information to identify the specifics of the shelf sediment Ba source, we suspect that a sedimentary remineralization and terrigenous sources (e.g., submarine groundwater discharge or fluvial particles) are contributors.

Fossil records of early solar irradiation and cosmolocation of the CAI factory: A reappraisal.

Calcium-aluminum­rich inclusions (CAIs) in meteorites carry crucial information about the environmental conditions of the nascent Solar System prior to planet formation. Based on models of 50V­10Be co-production by in-situ irradiation, CAIs are considered to have formed within ~0.1 AU from the proto-Sun. Here, we present vanadium (V) and strontium (Sr) isotopic co-variations in fine- and coarse-grained CAIs and demonstrate that kinetic isotope effects during partial condensation and evaporation best explain V isotope anomalies previously attributed to solar particle irradiation. We also report initial excesses of 10Be and argue that CV CAIs possess essentially a homogeneous level of 10Be, inherited during their formation. Based on numerical modeling of 50V­10Be co-production by irradiation, we show that CAI formation during protoplanetary disk build-up likely occurred at greater heliocentric distances than previously considered, up to planet-forming regions (~1AU), where solar particle fluxes were sufficiently low to avoid substantial in-situ irradiation of CAIs.

Vanadium Stable Isotopes in Biota of Terrestrial and Aquatic Food Chains.

Vanadium, a potentially toxic metal, is enriched in the environment from anthropogenic releases, particularly during fossil fuel production and use and steel manufacturing. Metal stable isotopes are sophisticated tools to trace pollution; however, only recent analytical advances have allowed for the accurate and precise measurement of vanadium isotope ratios (δ51V). To examine its potential as a tracer in terrestrial and aquatic ecosystems, δ51V was measured in soil, plant, lichen, marten, and lake sediment from sites near vanadium emissions at oil sands mines (Alberta, Canada) and in the sediment and biota (algae, zooplankton, fish) from a remote subarctic lake (Northwest Territories, Canada). Samples from Alberta had distinct δ51V values with marten liver the lowest (-1.7 ± 0.3‰), followed by lichen (-0.9 ± 0.1‰), soil (-0.7 ± 0.1‰), sediment (-0.5 ± 0.2‰), and plant root (-0.3 ± 0.2‰). Average values were lower than Alberta bitumen and petroleum coke (-0.1 ± 0.1‰). Plant roots had systematically higher δ51V than the soil from which they grew (Δ51Vplant-soil = 0.4 ± 0.1‰), while δ51V of lichen and aquatic biota were lower (0.1-0.3‰) than likely crustal sources. These δ51V measurements in terrestrial and aquatic biota demonstrate promise for tracer applications, although further study of its biological fractionation is needed.

Isotopic evidence for the formation of the Moon in a canonical giant impact.

Isotopic measurements of lunar and terrestrial rocks have revealed that, unlike any other body in the solar system, the Moon is indistinguishable from the Earth for nearly every isotopic system. This observation, however, contradicts predictions by the standard model for the origin of the Moon, the canonical giant impact. Here we show that the vanadium isotopic composition of the Moon is offset from that of the bulk silicate Earth by 0.18 ± 0.04 parts per thousand towards the chondritic value. This offset most likely results from isotope fractionation on proto-Earth during the main stage of terrestrial core formation (pre-giant impact), followed by a canonical giant impact where ~80% of the Moon originates from the impactor of chondritic composition. Our data refute the possibility of post-giant impact equilibration between the Earth and Moon, and implies that the impactor and proto-Earth mainly accreted from a common isotopic reservoir in the inner solar system.

Groundwater discharge impacts marine isotope budgets of Li, Mg, Ca, Sr, and Ba.

Groundwater-derived solute fluxes to the ocean have long been assumed static and subordinate to riverine fluxes, if not neglected entirely, in marine isotope budgets. Here we present concentration and isotope data for Li, Mg, Ca, Sr, and Ba in coastal groundwaters to constrain the importance of groundwater discharge in mediating the magnitude and isotopic composition of terrestrially derived solute fluxes to the ocean. Data were extrapolated globally using three independent volumetric estimates of groundwater discharge to coastal waters, from which we estimate that groundwater-derived solute fluxes represent, at a minimum, 5% of riverine fluxes for Li, Mg, Ca, Sr, and Ba. The isotopic compositions of the groundwater-derived Mg, Ca, and Sr fluxes are distinct from global riverine averages, while Li and Ba fluxes are isotopically indistinguishable from rivers. These differences reflect a strong dependence on coastal lithology that should be considered a priority for parameterization in Earth-system models.

Constraining oceanic oxygenation during the Shuram excursion in South China using thallium isotopes.

Ediacaran sediments record an unusual global carbon cycle perturbation that has been linked to widespread oceanic oxygenation, the Shuram negative C isotope excursion (NCIE). However, proxy-based estimates of global ocean redox conditions during this event have been limited largely due to proxy specificity (e.g., euxinic sediments for Mo and U isotopes). Modern global seawater documents a homogenous Tl isotope composition (ε205 Tl = -6.0) due to significant manganese oxide burial, which is recorded in modern euxinic sediments. Here, we provide new data documenting that sediments deposited beneath reducing but a non-sulfidic water column from the Santa Barbara Basin (ε205 Tl = -5.6 ± 0.1) also faithfully capture global seawater Tl isotope values. Thus, the proxy utilization of Tl isotopes can extend beyond strictly euxinic settings. Second, to better constrain the global redox conditions during the Shuram NCIE, we measured Tl isotopes of locally euxinic and ferruginous shales of the upper Doushantuo Formation, South China. The ε205 Tl values of these shales exhibit a decreasing trend from ≈-3 to ≈-8, broadly coinciding with the onset of Shuram NCIE. There are ε205 Tl values (-5.1 to -7.8) during the main Shuram NCIE interval that approach values more negative than modern global seawater. These results suggest that manganese oxide burial was near or even greater than modern burial fluxes, which is likely linked to an expansion of oxic conditions. This ocean oxygenation may have been an important trigger for the Shuram NCIE and evolution of Ediacaran-type biota. Subsequently, Tl isotopes show an increasing trend from the modern ocean value to values near the modern global inputs or even heavier (ε205 Tl ≈ -2.5 ~ 0.4), occurring prior to recovery from the NCIE. These records may suggest that there was a decrease in the extent of oxygenated conditions in the global oceans during the late stage of the Shuram NCIE.

Nitrogen Utilization and Toxin Production by Two Diatoms of the Pseudo-nitzschia pseudodelicatissima Complex: P. cuspidata and P. fryxelliana.

The toxigenic diatom Pseudo-nitzschia cuspidata, isolated from the U.S. Pacific Northwest, was examined in unialgal batch cultures to evaluate domoic acid (DA) toxicity and growth as a function of light, N substrate, and growth phase. Experiments conducted at saturating (120 µmol photons · m(-2)  · s(-1) ) and subsaturating (40 µmol photons · m(-2)  · s(-1) ) photosynthetic photon flux density (PPFD), demonstrate that P. cuspidata grows significantly faster at the higher PPFD on all three N substrates tested [nitrate (NO3 (-) ), ammonium (NH4 (+) ), and urea], but neither cellular toxicity nor exponential growth rates were strongly associated with one N source over the other at high PPFD. However, at the lower PPFD, the exponential growth rates were approximately halved, and the cells were significantly more toxic regardless of N substrate. Urea supported significantly faster growth rates, and cellular toxicity varied as a function of N substrate with NO3 (-) -supported cells being significantly more toxic than both NH4 (+) - and urea-supported cells at the low PPFD. Kinetic uptake parameters were determined for another member of the P. pseudodelicatissima complex, P. fryxelliana. After growth of these cells on NO3 (-) they exhibited maximum specific uptake rates (Vmax ) of 22.7, 29.9, 8.98 × 10(-3)  · h(-1) , half-saturation constants (Ks ) of 1.34, 2.14, 0.28 µg-at N · L(-1) , and affinity values (α) of 17.0, 14.7, 32.5 × 10(-3)  · h(-1) /(µg-at N · L(-1) ) for NO3 (-) , NH4 (+) and urea, respectively. These labo-ratory results demonstrate the capability of P. cuspidata to grow and produce DA on both oxidized and reduced N substrates during both exponential and stationary growth phases, and the uptake kinetic results for the pseudo-cryptic species, P. fryxelliana suggest that reduced N sources from coastal runoff could be important for maintenance of these small pennate diatoms in U.S. west coast blooms, especially during times of low ambient N concentrations.