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1. Nitrate chemistry in the northeast US – Part 2: Oxygen isotopes reveal differences in particulate and gas-phase formation

   https://doi.org/10.5194/acp-23-4203-2023  

   Kim, Heejeong; Walters, Wendell W; Bekker, Claire; Murray, Lee T; Hastings, Meredith G (January 2023, Atmospheric Chemistry and Physics)

   Abstract. The northeastern US represents a mostly urban corridorimpacted by high population and fossil fuel combustion emission density.This has led to historically degraded air quality and acid rain that hasbeen a focus of regulatory-driven emissions reductions. Detailing thechemistry of atmospheric nitrate formation is critical for improving themodel representation of atmospheric chemistry and air quality. The oxygenisotopic compositions of atmospheric nitrate are useful indicators intracking nitrate formation pathways. Here, we measured oxygen isotope deltas(Δ(17O) and δ(18O)) for nitric acid (HNO3)and particulate nitrate (pNO3) from three US EPA Clean AirStatus and Trends Network (CASTNET) sites in the northeastern US fromDecember 2016 to 2018. The Δ(17O, HNO3) and δ(18O, HNO3) values ranged from 12.9 ‰ to 30.9 ‰ and from 46.9 ‰ to 82.1 ‰, and the Δ(17O, pNO3) and δ(18O, pNO3) ranged from 16.6 ‰ to 33.7 ‰ and from 43.6 ‰ to 85.3 ‰, respectively. There was distinct seasonality ofδ(18O) and Δ(17O), with higher values observedduring winter compared to during summer, suggesting a shift in O3 to HOxradical chemistry, as expected. Unexpectedly, there was a statisticaldifference in Δ(17O) between HNO3 and pNO3, withhigher values observed for pNO3 (27.1 ± 3.8) ‰relative to HNO3 (22.7 ± 3.6) ‰, andsignificant differences in the relationship between δ(18O) andΔ(17O). This difference suggests atmospheric nitratephase-dependent oxidation chemistry that is not predicted in models. Basedon the output from GEOS-Chem and both the δ(18O) and Δ(17O) observations, we quantify the production pathways of atmosphericnitrate. The model significantly overestimated the heterogeneousN2O5 hydrolysis production for both HNO3 and pNO3, afinding consistent with observed seasonal changes in δ(18O) andΔ(17O) of HNO3 and pNO3, though large uncertaintiesremain in the quantitative transfer of δ(18O) from majoratmospheric oxidants. This comparison provides important insight into therole of oxidation chemistry in reconciling a commonly observed positive biasfor modeled atmospheric nitrate concentrations in the northeastern US. 

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2. Triple oxygen isotope evidence for a hot Archean ocean

   https://doi.org/10.1130/G50230.1  

   McGunnigle, J.P.; Cano, E.J.; Sharp, Z.D.; Muehlenbachs, K.; Cole, D.; Hardman, M.F.; Stachel, T.; Pearson, D.G. (May 2022, Geology)

   Triple oxygen isotope (δ17O and δ18O) values of high- and low-temperature altered oceanic crust and products of basalt alteration experiments were measured to better constrain ocean isotope compositions in deep time. The data define an array of δ18O and Δ′17O (Δ′17O=δ′17O – λRL × δ′18O + γ) values from mantle values toward 1‰ and –0.01‰, respectively, with a λ of ~0.523. The altered oceanic crust data were used to construct a model for estimating δ18O-Δ′17O values of the ancient oceans if the continental weathering flux (FCW) and/or hydrothermal oceanic crust alteration flux (FHT) changed through time. A maximum lowering of 7‰ and 4‰, respectively, is achieved in the most extreme cases. The δ18O value of the ocean cannot be raised by more than 1.1‰. Eclogites from the Roberts Victor kimberlite (South Africa), with a protolith age of 3.1 Ga, have δ18O-Δ′17O values that precisely overlap with those of the modern altered oceanic crust, suggesting that the Archean oceans had similar isotope values as today. Published triple isotope data for Archean cherts show that all samples have been altered to some degree and suggest an Archean ocean surface temperature of ~70–100 °C. An ocean as light as –2‰ is still consistent with our eclogite data and reduce our temperature estimates by 10 °C. 

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3. Looking upstream with clumped and triple oxygen isotopes of estuarine oyster shells in the early Eocene of California, USA

   https://doi.org/10.1130/G49634.1  

   Kelson, Julia R.; Petersen, Sierra V.; Niemi, Nathan A.; Passey, Benjamin H.; Curley, Allison N. (April 2022, Geology)

   The δ18O of carbonate minerals that formed at Earth’s surface is widely used to investigate paleoclimates and paleo-elevations. However, a multitude of hydrologic processes can affect δ18O values, including mixing, evaporation, distillation of parent waters, and carbonate growth temperatures. We combined traditional carbon and oxygen isotope analyses with clumped (Δ47) and triple oxygen isotopes (Δ′17O) analyses in oyster shells (Acutostrea idriaensis) of the Goler Formation in southern California (USA) to obtain insights into surface temperatures and δ18O values of meteoric waters during the early Eocene hothouse climate. The Δ47-derived temperatures ranged from 9 °C to 20 °C. We found a correlation between the δ18O of growth water (δ18Ogw) (calculated using Δ47 temperatures and δ18O of carbonate) and the δ13C values of shells. The Δ′17O values of shell growth waters (0.006‰–0.013‰ relative to Vienna standard mean ocean water–standard light Antarctic precipitation [VSMOW-SLAP]) calculated from Δ′17O of carbonate (–0.087‰ to –0.078‰ VSMOW-SLAP) were lower than typical meteoric waters. These isotopic compositions are consistent with oyster habitation in an estuary. We present a new triple oxygen isotope mixing model to estimate the δ18O value of freshwater supplying the estuary (δ18Ofw). The reconstructed δ18Ofw of –11.3‰ to –14.7‰ (VSMOW) is significantly lower than the δ18Ogw of –4.4‰ to –9.9‰ that would have been calculated using “only” Δ47 and δ18O values of carbonate. This δ18Ofw estimate supports paleogeographic reconstructions of a Paleogene river fed by high-elevation catchments of the paleo–southern Sierra Nevada. Our study highlights the potential for paired Δ47 and Δ′17O analyses to improve reconstructions of meteoric water δ18O, with implications for understanding ancient climates and elevations. 

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4. Orbital-pacing of South American Monsoon Strength and Regional Water Balance: New Evidence from Triple Oxygen Isotopes

   Katz, SA; Levin, N E; Rodbell, D T; Abbott, M B; Passey, B; Katz, S (December 2024, 2024 Fall Meeting, AGU)

   none (Ed.)

   Abstract The South American monsoon is central to the continent’s water and energy cycles, however, the relationships between the monsoon, regional water balance, and global climate change is poorly understood. Sediment records at Lake Junín (11°S, 76°W) provide an opportunity to explore these connections over the last 650 ka. Here, we focus on two interglacials, the Holocene (11.7–0 ka) and MIS 15 (621–563 ka), when sediment proxies suggest rapid regional hydroclimate fluctuations occurred. Clumped isotope distributions of lake carbonates reveal that interglacial water temperatures were similar to present, though analytical limitations preclude detecting the small temperature differences expected in the tropics (<2 °C). Combining the reconstructed water temperatures with carbonate oxygen (δ18O) and triple oxygen (Δ′17O) isotope values, we reconstruct precipitation δ18O values and lake water Δ′17O values. Precipitation δ18O values, a proxy of monsoon strength, range from -18.6 to -12.3 ‰ with lower values reflecting a stronger monsoon. Lake water Δ′17O values are -14 to 43 per meg and indicate the extent of lake water evaporation; lower values reflect a higher proportion of evaporation to inputs (i.e., more negative P-E). The precipitation δ18O and lake water Δ′17O values from both interglacials vary with the pacing of local summertime insolation, which follows an orbital pacing. These data document the close connection between Andean water balance, the South American monsoon, and global climate. Further, we analyze the relationship between precipitation δ18O and insolation, and we find that the relationship is consistent among interglacials, suggesting a similar response of the monsoon to orbital forcings over time. In contrast, while lake water Δ′17O and insolation are also correlated during both interglacials, water balance was overall more positive during MIS 15 than the Holocene. This suggests that either other global forcings or local basin dynamics can also contribute to water balance at Lake Junín. Together, these data provide new evidence of the connections between global climate, monsoon strength, and regional water balance. 

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5. Contamination of the Bushveld Complex (South Africa) magmas by basinal brines: Stable isotopes in phlogopite from the UG2 chromitite

   https://doi.org/10.1130/G49173.1  

   Zhou, Haoyang; Trumbull, Robert B.; Veksler, Ilya V.; Bindeman, Ilya N.; Glodny, Johannes; Kaufmann, Felix E.D.; Rammlmair, Dieter (July 2021, Geology)

   null (Ed.)

   There is abundant evidence for significant H2O in evolved melts from the platinum-rich UG2 chromitite and the Merensky Reef of the Bushveld Complex (South Africa), but there is no consensus about the source of H2O. We report triple-oxygen and hydrogen isotope ratios of interstitial, late-magmatic phlogopite from three localities of the UG2 layer. The phlogopite yielded δD values of –43‰ to –23‰, which is >30‰ higher than previously known from Bushveld rocks and far above the mantle values of ~–75‰. The phlogopite triple-oxygen isotope ratios are the first to be reported for Bushveld rocks, with values of Δ′17O0.5305 (17O excess relative to the reference line 0.5305) from –0.069‰ to –0.044‰ (δ18O 5.2‰–6.2‰). The oxygen data support existing models of as much as 30%–40% contamination of mantle-derived magmas in the lower to middle crust. However, the high δD values require a second step of contamination, which we attribute to brines from the marine sediments in the Transvaal Basin at the emplacement level. 

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