Recent Advances of the Halogen–Zinc Exchange Reaction

For the preparation of zinc organometallics bearing highly sensitive functional groups such as ketones, aldehydes or nitro groups, especially mild halogen–zinc exchange reagents have proven to be of great potential. In this Minireview, the latest research in the area of the halogen–zinc exchange reaction is reported, with a special focus lying on novel dialkylzinc reagents complexed with lithium alkoxides. Additionally, the preparation and application of organofluorine zinc reagents and transition‐metal‐catalyzed halogen–zinc exchange reactions are reviewed

Coupled radon, methane and nitrate sensors for large-scale assessment of groundwater discharge and non-point source pollution to coastal waters

Author Posting. © The Author(s), 2009. This is the author's version of the work. It is posted here by permission of Elsevier B.V. for personal use, not for redistribution. The definitive version was published in Journal of Environmental Radioactivity 101 (2010): 553-563, doi:10.1016/j.jenvrad.2009.12.004.We constructed a survey system of radon/methane/nitrate/salinity to find sites of submarine groundwater discharge (SGD) and groundwater nitrate input. We deployed the system in Waquoit Bay and Boston Harbor, MA where we derived SGD rates using a mass balance of radon with methane serving as a fine resolution qualitative indicator of groundwater. In Waquoit Bay we identified several locations of enhanced groundwater discharge, out of which two (Childs and Quashnet Rivers) were studied in more detail. The Childs River was characterized by high nitrate input via groundwater discharge, while the Quashnet River SGD was notable but not a significant source of nitrate. Our radon survey of Boston Harbor revealed several sites with significant SGD, out of these Inner Harbor and parts of Dorchester Bay and Quincy Bay had groundwater fluxes accompanied by significant water column nitrogen concentrations. The survey system has proven effective in revealing areas of SGD and non-point source pollution.R. Camilli acknowledges the National Ocean Partnership Program (NOPP) for supporting the development of the TETHYS mass spectrometer through research grant #OCE-0537173. H. Dulaiova, M. A. Charette and R. Camilli acknowledge funding support from the WHOI Coastal Institute and MIT Sea Grant College Program under NOAA grant number NA06OAR4170019, project number 5710002173. H. Dulaiova was funded by the WHOI Academic Program’s postdoctoral scholarship

Increased fluxes of shelf-derived materials to the central Arctic Ocean

© The Author(s), 2018. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Science Advances 4 (2018): eaao1302, doi:10.1126/sciadv.aao1302.Rising temperatures in the Arctic Ocean region are responsible for changes such as reduced ice cover, permafrost thawing, and increased river discharge, which, together, alter nutrient and carbon cycles over the vast Arctic continental shelf. We show that the concentration of radium-228, sourced to seawater through sediment-water exchange processes, has increased substantially in surface waters of the central Arctic Ocean over the past decade. A mass balance model for 228Ra suggests that this increase is due to an intensification of shelf-derived material inputs to the central basin, a source that would also carry elevated concentrations of dissolved organic carbon and nutrients. Therefore, we suggest that significant changes in the nutrient, carbon, and trace metal balances of the Arctic Ocean are underway, with the potential to affect biological productivity and species assemblages in Arctic surface waters.This work was funded by NSF awards OCE-1458305 to M.A.C. and OCE-1458424 to W.S.M. The Mackenzie River sampling was supported by a Graduate Student Research Award from the North Pacific Research Board to L.E.K. L.E.K. also acknowledges support from a National Defense Science and Engineering Graduate Fellowship. I.G.R. acknowledges funding by the contributors to the U.S. Interagency Arctic Buoy Program, which include the U.S. Coast Guard, the Department of Energy, NASA, the U.S. Navy, the National Oceanic and Atmospheric Administration, and NSF

Revisiting 228Th as a tool for determining sedimentation and mass accumulation rates

© The Author(s), 2022. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Tamborski, J., Cai, P., Eagle, M., Henderson, P., & Charette, M. Revisiting 228Th as a tool for determining sedimentation and mass accumulation rates. Chemical Geology, 607, (2022): 121006, https://doi.org/10.1016/j.chemgeo.2022.121006.The use of 228Th has seen limited application for determining sedimentation and mass accumulation rates in coastal and marine environments. Recent analytical advances have enabled rapid, precise measurements of particle-bound 228Th using a radium delayed coincidence counting system (RaDeCC). Herein we review the 228Th cycle in the marine environment and revisit the historical use of 228Th as a tracer for determining sediment vertical accretion and mass accumulation rates in light of new measurement techniques. Case studies comparing accumulation rates from 228Th and 210Pb are presented for a micro-tidal salt marsh and a marginal sea environment. 228Th and 210Pb have been previously measured in mangrove, deltaic, continental shelf and ocean basin environments, and a literature synthesis reveals that 228Th (measured via alpha or gamma spectrometry) derived accumulation rates are generally equal to or greater than estimates derived from 210Pb, reflecting different integration periods. Use of 228Th is well-suited for shallow (<15 cm) cores over decadal timescales. Application is limited to relatively homogenous sediment profiles with minor variations in grain size and minimal bioturbation. When appropriate conditions are met, complimentary use of 228Th and 210Pb can demonstrate that the upper layers of a core are undisturbed and can improve spatial coverage in mapping accumulation rates due to the higher sample throughput for sediment 228Th.This research was undertaken thanks in part to funding from the Canada First Research Excellence Fund, through the Ocean Frontier Institute. This project was supported by U.S. Geological Survey Coastal and Marine Hazards and Resources Program. Any use of trade, firm or product names is for descriptive purposes only and does not imply endorsement by the U.S. Government. PC acknowledges the support of the Natural Science Foundation of China (NSFC) through Grants No. 92058205

Lingering radioactivity at the Bikini and Enewetak Atolls

© The Author(s), 2017. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Science of The Total Environment 621 (2018): 1185-1198, doi:10.1016/j.scitotenv.2017.10.109.We made an assessment of the levels of radionuclides in the ocean waters, seafloor and groundwater at Bikini and Enewetak Atolls where the US conducted nuclear weapons tests in the 1940's and 50's. This included the first estimates of submarine groundwater discharge (SGD) derived from radium isotopes that can be used here to calculate radionuclide fluxes in to the lagoon waters. While there is significant variability between sites and sample types, levels of plutonium (239,240Pu) remain several orders of magnitude higher in lagoon seawater and sediments than what is found in rest of the world's oceans. In contrast, levels of cesium-137 (137Cs) while relatively elevated in brackish groundwater are only slightly higher in the lagoon water relative to North Pacific surface waters. Of special interest was the Runit dome, a nuclear waste repository created in the 1970's within the Enewetak Atoll. Low seawater ratios of 240Pu/239Pu suggest that this area is the source of about half of the Pu in the Enewetak lagoon water column, yet radium isotopes suggest that SGD from below the dome is not a significant Pu source. SGD fluxes of Pu and Cs at Bikini were also relatively low. Thus radioactivity associated with seafloor sediments remains the largest source and long term repository for radioactive contamination. Overall, Bikini and Enewetak Atolls are an ongoing source of Pu and Cs to the North Pacific, but at annual rates that are orders of magnitude smaller than delivered via close-in fallout to the same area.Finally, none of this would have been possible without the generous financial support from the Dalio Explore Fund (WHOI #25531513) for the vessel and our post cruise analyses that together resulted in this unique and successful research program

Underground gamma-ray measurements of radium isotopes from hydrothermal plumes in the deep Pacific Ocean

© The Author(s), 2019. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Hult, M., Charette, M., Lutter, G., Marissens, G., Henderson, P., Sobiech-Matura, K., & Simgen, H. Underground gamma-ray measurements of radium isotopes from hydrothermal plumes in the deep Pacific Ocean. Applied Radiation and Isotopes, 153, (2019): 108831, doi:10.1016/j.apradiso.2019.108831.The radium isotopes 226Ra and 228Ra can provide important data on the dynamics of deep-sea hydrothermal plumes that travel the oceans for decades and have great impact on the ocean chemistry. This study focuses on parameters important for obtaining low detection limits for 228Ra using gamma-ray spectrometry. It is present at mBq-levels in samples collected during the US GEOTRACES 2013 cruise to the Southeast Pacific Ocean.The work of the HADES-staff of Euridice at SCK•CEN is gratefully acknowledged. We are most grateful to Dr. Faidra Tzika for her work in the precursor to this project. Many thanks to Heiko Stroh for quality control and measurements in HADES. This research was supported in part by grants from the U.S. National Science Foundation, Ocean Sciences division (OCE-1232669 and OCE-1736277)

Shelf-basin interactions and water mass residence times in the western Arctic Ocean: Insights provided by radium isotopes

Author Posting. © American Geophysical Union, 2019. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Journal of Geophysical Research-Oceans 124(5), (2019): 3279-3297, doi: 10.1029/2019JC014988.Radium isotopes are produced through the decay of thorium in sediments and are soluble in seawater; thus, they are useful for tracing ocean boundary‐derived inputs to the ocean. Here we apply radium isotopes to study continental inputs and water residence times in the Arctic Ocean, where land‐ocean interactions are currently changing in response to rising air and sea temperatures. We present the distributions of radium isotopes measured on the 2015 U.S. GEOTRACES transect in the Western Arctic Ocean and combine this data set with historical radium observations in the Chukchi Sea and Canada Basin. The highest activities of radium‐228 were observed in the Transpolar Drift and the Chukchi shelfbreak jet, signaling that these currents are heavily influenced by interactions with shelf sediments. The ventilation of the halocline with respect to inputs from the Chukchi shelf occurs on time scales of ≤19–23 years. Intermediate water ventilation time scales for the Makarov and Canada Basins were determined to be ~20 and >30 years, respectively, while deep water residence times in these basins were on the order of centuries. The radium distributions and residence times described in this study serve as a baseline for future studies investigating the impacts of climate change on the Arctic Ocean.We thank the captain and crew of the USCGC Healy (HLY1502) and the chief scientists D. Kadko and W. Landing for coordinating a safe and successful expedition. We thank the members of the pump team, P. Lam, E. Black, S. Pike, X. Yang, and M. Heller for their assistance with sample collection and for their unfailingly positive attitudes during this 65‐day expedition. We also appreciate sampling assistance from P. Aguilar and M. Stephens, and MATLAB assistance from B. Corlett, A. Pacini, P. Lin, and M. Li. The radium data from the HLY1502 expedition are available through the Biological & Chemical Oceanography Data Management Office (https://www.bco‐dmo.org/dataset/718440) and the radium measurements from the SHEBA, AWS‐2000, and SBI expeditions can be found in the supporting information. This work was funded by NSF awards OCE‐1458305 to M.A.C., OCE‐1458424 to W.S.M., and PLR‐1504333 to R.S.P. This research was conducted with Government support under and awarded by a DoD, Air Force Office of Scientific Research, National Defense Science and Engineering Graduate (NDSEG) Fellowship awarded to L.E.K., 32 CFR 168a.2019-10-2

Erratum : GEOTRACES radium isotopes interlaboratory comparison experiment

Author Posting. © Association for the Sciences of Limnology and Oceanography, 2012. This article is posted here by permission of Association for the Sciences of Limnology and Oceanography for personal use, not for redistribution. The definitive version was published in Limnology and Oceanography: Methods 10 (2012): 617, doi:10.4319/lom.2012.10.617.In our original paper, Charette, M. A., H. Dulaiova, M. E. Gonneea, P. B. Henderson, W. S. Moore, J. C. Scholten, and M. K. Pham. 2012. GEOTRACES radium isotopes interlaboratory comparison experiment. Limonol. Oceanogr.: Methods 10:451, the incorrect headers were used for Table 9

Pore water exchange-driven inorganic carbon export from intertidal salt marshes

© The Author(s), 2021. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Tamborski, J. J., Eagle, M., Kurylyk, B. L., Kroeger, K. D., Wang, Z. A., Henderson, P., & Charette: 1774-1792, https://doi.org/10.1002/lno.11721.Respiration in intertidal salt marshes generates dissolved inorganic carbon (DIC) that is exported to the coastal ocean by tidal exchange with the marsh platform. Understanding the link between physical drivers of water exchange and chemical flux is a key to constraining coastal wetland contributions to regional carbon budgets. The spatial and temporal (seasonal, annual) variability of marsh pore water exchange and DIC export was assessed from a microtidal salt marsh (Sage Lot Pond, Massachusetts). Spatial variability was constrained from 224Ra : 228Th disequilibria across two hydrologic units within the marsh sediments. Disequilibrium between the more soluble 224Ra and its sediment-bound parent 228Th reveals significant pore water exchange in the upper 5 cm of the marsh surface (0–36 L m−2 d−1) that is most intense in low marsh elevation zones, driven by tidal overtopping. Surficial sediment DIC transport ranges from 0.0 to 0.7 g C m−2 d−1. The sub-surface sediment horizon intersected by mean low tide was disproportionately impacted by tidal pumping (20–80 L m−2 d−1) and supplied a seasonal DIC flux of 1.7–5.4 g C m−2 d−1. Export exceeded 10 g C m−2 d−1 for another marsh unit, demonstrating that fluxes can vary substantially across salt marshes under similar conditions within the same estuary. Seasonal and annual variability in marsh pore water exchange, constrained from tidal time-series of radium isotopes, was driven in part by variability in mean sea level. Rising sea levels will further inundate high marsh elevation zones, which may lead to greater DIC export.This research was undertaken thanks in part to funding from the Canada First Research Excellence Fund, through the Ocean Frontier Institute. Additional funding was provided by the U.S. Geological Survey (USGS) Coastal & Marine Geology Program and the USGS Land Change Science Program's LandCarbon program

GEOTRACES radium isotopes interlaboratory comparison experiment

Author Posting. © Association for the Sciences of Limnology and Oceanography, 2012. This article is posted here by permission of Association for the Sciences of Limnology and Oceanography for personal use, not for redistribution. The definitive version was published in Limnology and Oceanography: Methods 10 (2012): 451-463, doi:10.4319/lom.2012.10.451.In anticipation of the international GEOTRACES program, which will study the global marine biogeochemistry of trace elements and isotopes, we conducted a multi-lab intercomparison for radium isotopes. The intercomparison was in two parts involving the distribution of: (1) samples collected from four marine environments (open ocean, continental slope, shelf, and estuary) and (2) a suite of four reference materials prepared with isotopic standards (circulated to participants as 'unknowns'). Most labs performed well with 228Ra and 224Ra determination, however, there were a number of participants that reported 226Ra, 223Ra, and 228Th (supported 224Ra) well outside the 95% confidence interval. Many outliers were suspected to be a result of poorly calibrated detectors, though other method specific factors likely played a role (e.g., detector leakage, insufficient equilibration). Most methods for radium analysis in seawater involve a MnO2 fiber column preconcentration step; as such, we evaluated the extraction efficiency of this procedure and found that it ranged from an average of 87% to 94% for the four stations. Hence, nonquantitative radium recovery from seawater samples may also have played a role in lab-to-lab variability.This work was funded by grants from the National Science Foundation (OCE- 0751461to M.A.C and H.D. and OCE- 0751867 to W.S.M.)