Description: The eastern boundary region of the southeastern Pacific Ocean hosts one of the world's most dynamic and productive upwelling systems with an associated oxygen minimum zone (OMZ). The variability in downward export fluxes in this region, with strongly varying surface productivity, upwelling intensities and water column oxygen content, is however poorly understood. Thorium-234 (234Th) is a powerful tracer to study the dynamics of export fluxes of carbon and other elements, yet intense advection and diffusion in nearshore environments impact the assessment of depth-integrated 234Th fluxes when not properly evaluated. Here we use VmADCP current velocities, satellite wind speed and in situ microstructure measurements to determine the magnitude of advective and diffusive fluxes over the entire 234Th flux budget at 25 stations from 11°S to 16°S in the Peruvian OMZ. Contrary to findings along the GEOTRACES P16 eastern section, our results showed that weak surface wind speed during our cruises induced low upwelling rates and minimal upwelled 234Th fluxes, whereas vertical diffusive 234Th fluxes were important only at a few shallow shelf stations. Horizontal advective and diffusive 234Th fluxes were negligible because of small alongshore 234Th gradients. Our data indicated a poor correlation between seawater 238U activity and salinity. Assuming a linear relationship between the two would lead to significant underestimations of the total 234Th flux by up to 40% in our study. Proper evaluation of both physical transport and variability in 238U activity is thus crucial in coastal 234Th flux studies. Finally, we showed large temporal variations on 234Th residence times across the Peruvian upwelling zone, and cautioned future carbon export studies to take these temporal variabilities into consideration while evaluating carbon export efficiency.

Description: Intercomparision of 234Th measurements in both water and particulate samples was carried out between 15 laboratories worldwide, as a part of GEOTRACES inter-calibration program. Particulate samples from four different stations namely BATS (both shallow and deep) and shelf station (shallow) in Atlantic and SAFE (both shallow and deep) and Santa Barbara station (shallow) in Pacific were used in the effort. Particulate inter-calibration results indicate good agreement between all the participating labs with data from all labs falling within the 95% confidence interval around the mean for most instances. Filter type experiments indicate no significant differences in 234Th activities between filter types and pore sizes (0.2–0.8 μm). The only exception are the quartz filters which are associated with 10-20% higher 234Th activities attributed to sorption of dissolved 234Th. Flow rate experiments showed a trend of decreasing 234Th activities with increasing flow rates (2-9 L min-1) for 〉51μm size particles, indicating particle loss during the pumping process. No change in 234Th activities on small particles was observed with increasing flow-rates. 234Th inter-calibration results from deep water samples at SAFe station indicate a variability of 〈3% amongst labs while dissolved 234Th data from surface water at Santa Barbara Station show a less robust agreement, possibly due to the loss of 234Th from decay and large in-growth corrections as a result of long gap between sample collection and processing.

Description: 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): 631-644, doi:10.4319/lom.2012.10.631.

Description: Intercomparision of 234Th measurements in both water and particulate samples was carried out between 15 laboratories worldwide, as a part of GEOTRACES inter-calibration program. Particulate samples from four different stations namely BATS (both shallow and deep) and shelf station (shallow) in Atlantic and SAFE (both shallow and deep) and Santa Barbara station (shallow) in Pacific were used in the effort. Particulate intercalibration results indicate good agreement between all the participating labs with data from all labs falling within the 95% confidence interval around the mean for most instances. Filter type experiments indicate no significant differences in 234Th activities between filter types and pore sizes (0.2-0.8 μm). The only exception are the quartz filters, which are associated with 10% to 20% higher 234Th activities attributed to sorption of dissolved 234Th. Flow rate experiments showed a trend of decreasing 234Th activities with increasing flow rates (2-9 L min-1) for 〉 51 μm size particles, indicating particle loss during the pumping process. No change in 234Th activities on small particles was observed with increasing flow-rates. 234Th intercalibration results from deep water samples at SAFe station indicate a variability of 〈 3% amongst labs while dissolved 234Th data from surface water at Santa Barbara Station show a less robust agreement, possibly due to the loss of 234Th from decay and large in-growth corrections as a result of long gap between sample collection and processing.

Description: This research is funded by NSF Chemical Oceanography program. LM will like to thank Fisheries and Oceans Canada for support. PM is supported through ICREA Academia funded by Generalitat de Catalunya. The International Atomic Energy Agency is grateful to the Government of the Principality of Monaco for the support provided to its Environment Laboratories.

Description: The eastern boundary region of the southeastern Pacific Ocean hosts one of the world's most dynamic and productive upwelling systems with an associated oxygen minimum zone (OMZ). The variability in downward export fluxes in this region, with strongly varying surface productivity, upwelling intensities and water column oxygen content, is however poorly understood. Thorium-234 (234Th) is a powerful tracer to study the dynamics of export fluxes of carbon and other elements, yet intense advection and diffusion in nearshore environments impact the assessment of depth-integrated 234Th fluxes when not properly evaluated. Here we use vessel-mounted acoustic Doppler current profiler (VmADCP) current velocities, satellite wind speed and in situ microstructure measurements to determine the magnitude of advective and diffusive fluxes over the entire 234Th flux budget at 25 stations from 11 to 16∘ S in the Peruvian OMZ. Contrary to findings along the GEOTRACES P16 eastern section, our results showed that weak surface wind speed during our cruises induced low upwelling rates and minimal upwelled 234Th fluxes, whereas vertical diffusive 234Th fluxes were important only at a few shallow shelf stations. Horizontal advective and diffusive 234Th fluxes were negligible because of small alongshore 234Th gradients. Our data indicated a poor correlation between seawater 238U activity and salinity. Assuming a linear relationship between the two would lead to significant underestimations of the total 234Th flux by up to 40 % in our study. Proper evaluation of both physical transport and variability in 238U activity is thus crucial in coastal 234Th flux studies. Finally, we showed large temporal variations on 234Th residence times across the Peruvian upwelling zone and cautioned future carbon export studies to take these temporal variabilities into consideration while evaluating carbon export efficiency.

Description: The availability of the micronutrient iron (Fe) in surface waters determines primary production, N2 fixation, and microbial community structure in large parts of the world's ocean, and thus it plays an important role in ocean carbon and nitrogen cycles. Eastern boundary upwelling systems and the connected oxygen minimum zones (OMZs) are typically associated with elevated concentrations of redox-sensitive trace metals (e.g., Fe, manganese (Mn), and cobalt (Co)), with shelf sediments typically forming a key source. Over the last 5 decades, an expansion and intensification of OMZs has been observed and this trend is likely to proceed. However, it is unclear how trace-metal (TM) distributions and transport are influenced by decreasing oxygen (O2) concentrations. Here we present dissolved (d; 〈0.2 µm) and leachable particulate (Lp; 〉0.2 µm) TM data collected at seven stations along a 50 km transect in the Mauritanian shelf region. We observed enhanced concentrations of Fe, Co, and Mn corresponding with low O2 concentrations (〈50 µmol kg−1), which were decoupled from major nutrients and nutrient-like and scavenged TMs (cadmium (Cd), lead (Pb), nickel (Ni), and copper (Cu)). Additionally, data from repeated station occupations indicated a direct link between dissolved and leachable particulate Fe, Co, Mn, and O2. An observed dFe (dissolved iron) decrease from 10 to 5 nmol L−1 coincided with an O2 increase from 30 to 50 µmol kg−1 and with a concomitant decrease in turbidity. The changes in Fe (Co and Mn) were likely driven by variations in their release from sediment pore water, facilitated by lower O2 concentrations and longer residence time of the water mass on the shelf. Variations in organic matter remineralization and lithogenic inputs (atmospheric deposition or sediment resuspension; assessed using Al as indicator for lithogenic inputs) only played a minor role in redox-sensitive TM variability. Vertical dFe fluxes from O2-depleted subsurface-to-surface waters (0.08–13.5 µmol m−2 d−1) driven by turbulent mixing and vertical advection were an order of magnitude larger than atmospheric deposition fluxes (0.63–1.43 µmol m−2 d−1; estimated using dAl inventories in the surface mixed layer) in the continental slope and shelf region. Benthic fluxes are therefore the dominant dFe supply to surface waters on the continental margins of the Mauritanian upwelling region. Overall, our results indicated that the projected future decrease in O2 concentrations in OMZs may result in increases in Fe, Mn, and Co concentrations.

Description: The Peruvian upwelling zone is one of the most productive marine ecosystems in the world with a spectacular, pronounced oxygen minimum zone (OMZ). Globally OMZs are increasing in size and intensity with far-reaching consequences for the marine biological carbon pump and carbon export; thus, these zones need to be carefully monitored to be able to understand future climate change impacts. The current study was carried out in 2013 and 2017 to quantify the vertical flux of organic matter exported out of the productive surface layer by measuring 234Thsingle bond238U disequilibria in the water column. Samples were collected in January 2013 and May 2017 along an identical transect located at 12°S off the Peruvian coast near Lima, Peru. Th-234 fluxes ranged from 0 to 2088 ± 95 dpm m−2 d−1 in 2013 and 698 ± 63 to 3648 ± 113 dpm m−2 d−1 in 2017. The corresponding POC fluxes varied between 0 and 164.2 ± 7.9 mg C m−2 d−1 in 2013 and 22.7 ± 2.7 to 133.1 ± 15.2 mg C m−2 d−1 in 2017, with POC fluxes gradually decreasing with distance from the coast. Despite higher POC fluxes, the export efficiencies were found to be extremely low due to high particle remineralization rates observed within the euphotic zone.