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1. Biological, Physical, and Atmospheric Controls on the Distribution of Cadmium and Its Isotopes in the Pacific Ocean

   https://doi.org/10.1029/2022GB007441  

   Sieber, Matthias; Lanning, Nathan T.; Bunnell, Zachary B.; Bian, Xiaopeng; Yang, Shun‐Chung; Marsay, Chris M.; Landing, William M.; Buck, Clifton S.; Fitzsimmons, Jessica N.; John, Seth G.; et al (January 2023, Global Biogeochemical Cycles)

   Abstract Despite the Pacific being the location of the earliest seawater Cd studies, the processes which control Cd distributions in this region remain incompletely understood, largely due to the sparsity of data. Here, we present dissolved Cd and δ¹¹⁴Cd data from the US GEOTRACES GP15 meridional transect along 152°W from the Alaskan margin to the equatorial Pacific. Our examination of this region's surface ocean Cd isotope systematics is consistent with previous observations, showing a stark disparity between northern Cd‐rich high‐nutrient low‐chlorophyll waters and Cd‐depleted waters of the subtropical and equatorial Pacific. Away from the margin, an open system model ably describes data in Cd‐depleted surface waters, but atmospheric inputs of isotopically light Cd likely play an important role in setting surface Cd isotope ratios (δ¹¹⁴Cd) at the lowest Cd concentrations. Below the surface, Southern Ocean processes and water mass mixing are the dominant control on Pacific Cd and δ¹¹⁴Cd distributions. Cd‐depleted Antarctic Intermediate Water has a far‐reaching effect on North Pacific intermediate waters as far as 47°N, contrasting with northern‐sourced Cd signatures in North Pacific Intermediate Water. Finally, we show that the previously identified negative Cd* signal at depth in the North Pacific is associated with the PO₄maximum and is thus a consequence of an integrated regeneration signal of Cd and PO₄at a slightly lower Cd:P ratio than the deep ocean ratio (0.35 mmol mol⁻¹), rather than being related to in situ removal processes in low‐oxygen waters. 

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2. Noble gas isotopes reveal degassing-derived eruptions at Deception Island (Antarctica): implications for the current high levels of volcanic activity

   https://doi.org/10.1038/s41598-022-23991-3  

   Álvarez-Valero, Antonio M.; Sumino, Hirochika; Caracausi, Antonio; Sánchez, Antonio Polo; Burgess, Ray; Geyer, Adelina; Borrajo, Javier; Rodríguez, José A.; Albert, Helena; Aulinas, Meritxell; et al (December 2022, Scientific Reports)

   Abstract Deception Island is one of the most active volcanoes in Antarctica with more than twenty explosive eruptions in the past two centuries. Any future volcanic eruption(s) is a serious concern for scientists and tourists, will be detrimental to marine ecosystems and could have an impact to global oceanographic processes. Currently, it is not possible to carry-out low and high frequency volcanic gas monitoring at Deception Island because of the arduous climatic conditions and its remote location. Helium, neon and argon isotopes measured in olivine samples of the main eruptive events (pre-, syn- and post caldera) offer insights into the processes governing its volcanic history. Our results show that: (i) ascending primitive magmas outgassed volatiles with a MORB-like helium isotopic signature ( 3 He/ 4 He ratio); and (ii) variations in the He isotope ratio, as well as intensive degassing evidenced by fractionated 4 He/ 40 Ar * values, occurred before the beginning of the main eruptive episodes. Our results show how the pre-eruptive noble gas signals of volcanic activity is an important step toward a better understanding of the magmatic dynamics and has the potential to improve eruption forecasting. 

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3. The Helium and Carbon Isotope Characteristics of the Andean Convergent Margin

   https://doi.org/10.3389/feart.2022.897267  

   Barry, P. H.; De Moor, J. M.; Chiodi, A.; Aguilera, F.; Hudak, M. R.; Bekaert, D. V.; Turner, S. J.; Curtice, J.; Seltzer, A. M.; Jessen, G. L.; et al (June 2022, Frontiers in Earth Science)

   Subduction zones represent the interface between Earth’s interior (crust and mantle) and exterior (atmosphere and oceans), where carbon and other volatile elements are actively cycled between Earth reservoirs by plate tectonics. Helium is a sensitive tracer of volatile sources and can be used to deconvolute mantle and crustal sources in arcs; however it is not thought to be recycled into the mantle by subduction processes. In contrast, carbon is readily recycled, mostly in the form of carbon-rich sediments, and can thus be used to understand volatile delivery via subduction. Further, carbon is chemically-reactive and isotope fractionation can be used to determine the main processes controlling volatile movements within arc systems. Here, we report helium isotope and abundance data for 42 deeply-sourced fluid and gas samples from the Central Volcanic Zone (CVZ) and Southern Volcanic Zone (SVZ) of the Andean Convergent Margin (ACM). Data are used to assess the influence of subduction parameters (e.g., crustal thickness, subduction inputs, and convergence rate) on the composition of volatiles in surface volcanic fluid and gas emissions. He isotopes from the CVZ backarc range from 0.1 to 2.6 R A ( n = 23), with the highest values in the Puna and the lowest in the Sub-Andean foreland fold-and-thrust belt. Atmosphere-corrected He isotopes from the SVZ range from 0.7 to 5.0 R A ( n = 19). Taken together, these data reveal a clear southeastward increase in 3 He/ 4 He, with the highest values (in the SVZ) falling below the nominal range associated with pure upper mantle helium (8 ± 1 R A ), approaching the mean He isotope value for arc gases of (5.4 ± 1.9 R A ). Notably, the lowest values are found in the CVZ, suggesting more significant crustal inputs (i.e., assimilation of 4 He) to the helium budget. The crustal thickness in the CVZ (up to 70 km) is significantly larger than in the SVZ, where it is just ∼40 km. We suggest that crustal thickness exerts a primary control on the extent of fluid-crust interaction, as helium and other volatiles rise through the upper plate in the ACM. We also report carbon isotopes from ( n = 11) sites in the CVZ, where δ 13 C varies between −15.3‰ and −1.2‰ [vs. Vienna Pee Dee Belemnite (VPDB)] and CO 2 / 3 He values that vary by over two orders of magnitude (6.9 × 10 8 –1.7 × 10 11 ). In the SVZ, carbon isotope ratios are also reported from ( n = 13) sites and vary between −17.2‰ and −4.1‰. CO 2 / 3 He values vary by over four orders of magnitude (4.7 × 10 7 –1.7 × 10 12 ). Low δ 13 C and CO 2 / 3 He values are consistent with CO 2 removal (e.g., calcite precipitation and gas dissolution) in shallow hydrothermal systems. Carbon isotope fractionation modeling suggests that calcite precipitation occurs at temperatures coincident with the upper temperature limit for life (122°C), suggesting that biology may play a role in C-He systematics of arc-related volcanic fluid and gas emissions. 

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4. Dissolved and Particulate Barium Distributions Along the US GEOTRACES North Atlantic and East Pacific Zonal Transects (GA03 and GP16): Global Implications for the Marine Barium Cycle

   https://doi.org/10.1029/2022GB007330  

   Rahman, Shaily; Shiller, Alan M.; Anderson, Robert F.; Charette, Matthew A.; Hayes, Christopher T.; Gilbert, Melissa; Grissom, Karen R.; Lam, Phoebe J.; Ohnemus, Daniel C.; Pavia, Frank J.; et al (June 2022, Global Biogeochemical Cycles)

   Abstract Processes controlling dissolved barium (dBa) were investigated along the GEOTRACES GA03 North Atlantic and GP16 Eastern Tropical Pacific transects, which traversed similar physical and biogeochemical provinces. Dissolved Ba concentrations are lowest in surface waters (∼35–50 nmol kg⁻¹) and increase to 70–80 and 140–150 nmol kg⁻¹in deep waters of the Atlantic and Pacific transects, respectively. Using water mass mixing models, we estimate conservative mixing that accounts for most of dBa variability in both transects. To examine nonconservative processes, particulate excess Ba (pBa_xs) formation and dissolution rates were tracked by normalizing particulate excess²³⁰Th activities. Th‐normalized pBa_xsfluxes, with barite as the likely phase, have subsurface maxima in the top 1,000 m (∼100–200 μmol m⁻² year⁻¹average) in both basins. Barite precipitation depletes dBa within oxygen minimum zones from concentrations predicted by water mass mixing, whereas inputs from continental margins, particle dissolution in the water column, and benthic diffusive flux raise dBa above predications. Average pBa_xsburial efficiencies along GA03 and GP16 are ∼37% and 17%–100%, respectively, and do not seem to be predicated on barite saturation indices in the overlying water column. Using published values, we reevaluate the global freshwater dBa river input as 6.6 ± 3.9 Gmol year⁻¹. Estuarine mixing processes may add another 3–13 Gmol year⁻¹. Dissolved Ba inputs from broad shallow continental margins, previously unaccounted for in global marine summaries, are substantial (∼17 Gmol year⁻¹), exceeding terrestrial freshwater inputs. Revising river and shelf dBa inputs may help bring the marine Ba isotope budget more into balance. 

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5. Influence of infrastructure on water quality and greenhouse gas dynamics in urban streams

   https://doi.org/10.5194/bg-14-2831-2017  

   Smith, Rose M.; Kaushal, Sujay S.; Beaulieu, Jake J.; Pennino, Michael J.; Welty, Claire (January 2017, Biogeosciences)

   Streams and rivers are significant sources of nitrous oxide (N₂O), carbon dioxide (CO₂), and methane (CH₄) globally, and watershed management can alter greenhouse gas (GHG) emissions from streams. We hypothesized that urban infrastructure significantly alters downstream water quality and contributes to variability in GHG saturation and emissions. We measured gas saturation and estimated emission rates in headwaters of two urban stream networks (Red Run and Dead Run) of the Baltimore Ecosystem Study Long-Term Ecological Research project. We identified four combinations of stormwater and sanitary infrastructure present in these watersheds, including: (1) stream burial, (2) inline stormwater wetlands, (3) riparian/floodplain preservation, and (4) septic systems. We selected two first-order catchments in each of these categories and measured GHG concentrations, emissions, and dissolved inorganic and organic carbon (DIC and DOC) and nutrient concentrations biweekly for 1 year. From a water quality perspective, the DOC : NO₃⁻ ratio of streamwater was significantly different across infrastructure categories. Multiple linear regressions including DOC : NO₃⁻ and other variables (dissolved oxygen, DO; total dissolved nitrogen, TDN; and temperature) explained much of the statistical variation in nitrous oxide (N₂O, r² =  0.78), carbon dioxide (CO₂, r² =  0.78), and methane (CH₄, r² =  0.50) saturation in stream water. We measured N₂O saturation ratios, which were among the highest reported in the literature for streams, ranging from 1.1 to 47 across all sites and dates. N₂O saturation ratios were highest in streams draining watersheds with septic systems and strongly correlated with TDN. The CO₂ saturation ratio was highly correlated with the N₂O saturation ratio across all sites and dates, and the CO₂ saturation ratio ranged from 1.1 to 73. CH₄ was always supersaturated, with saturation ratios ranging from 3.0 to 2157. Longitudinal surveys extending form headwaters to third-order outlets of Red Run and Dead Run took place in spring and fall. Linear regressions of these data yielded significant negative relationships between each gas with increasing watershed size as well as consistent relationships between solutes (TDN or DOC, and DOC : TDN ratio) and gas saturation. Despite a decline in gas saturation between the headwaters and stream outlet, streams remained saturated with GHGs throughout the drainage network, suggesting that urban streams are continuous sources of CO₂, CH₄, and N₂O. Our results suggest that infrastructure decisions can have significant effects on downstream water quality and greenhouse gases, and watershed management strategies may need to consider coupled impacts on urban water and air quality. 

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