Particle Fluxes In The North Pacific: An Assessment Of Pseudonitzschia And Domoic Acid In The Santa Barbara Basin, And Of Mercury, Carbon And Nitrogen In The Central Pacific

Particle fluxes are an integral part of marine biogeochemical cycling and mediate the transfer of material from the surface ocean to depth. Throughout this process, particles are subjected to a suite of biological and physical processes that influence element and compound composition. Understanding these myriad factors is therefore critical for examining an array of marine biogeochemical questions that range from the role of particles in sequestering anthropogenic carbon dioxide, to serving as a food source and as vector for the removal and/or bioaccumulation of toxic chemicals. This thesis examines spatial and temporal changes in particle formation and export of nutrients, carbon, the neurotoxin domoic acid, and mercury using a combination of water column 238U-234Th disequilibria, in situ pumps, and sediment traps. In Chapter 2, water column bulk Pseudo-nitzschia abundance and dissolved and particulate domoic acid (DA) concentrations were measured in the coastal waters of the Santa Barbara Basin (SBB), California from 2009-2013 and compared to bulk Pseudonitzschia abundance and DA concentrations and fluxes in sinking particles collected using moored sediment traps at 147 m and 509 m. Our results indicate that while a variety of Pseudo-nitzschia spp. exist in the SBB, specific species likely drive toxicity in response to a suite of environmental conditions that are complicated by physical processes and bloom stage. This work demonstrates that dissolved DA is a significant component of the water column and should not be ignored when examining potential vi allelopathic impacts on competitors or deterrents to grazers. Water column Pseudonitzschia abundance and pDA concentrations were poorly correlated with sediment trap concentrations and fluxes, with Pseudo-nitzschia trap fluxes decreasing by an order of magnitude with increasing depth and DA fluxes increasing by a factor of three. However, DA toxicity is likely associated with senescent blooms that rapidly sink to the seafloor, adding another potential source of DA to benthic organisms. In Chapter 3, the downward fluxes of particulate carbon (PC), nitrogen (PN) and total mercury (PHg) were measured at Station ALOHA in the North Pacific Subtropical Gyre using a combination of sediment traps and in situ pumps coupled with 238U -234Th disequilibria. While highest absolute PC fluxes were observed during the summer, our findings indicate that zooplankton exert more influence over both small and large PC (and PN) fluxes in February than in September or May, when heterotrophic bacteria play a proportionally larger role in particle remineralization and cycling. PHg fluxes were also seasonally variable and highest in May and September yet were influenced by different biogeochemical cycling processes than PC in the subsurface. PHg fluxes in May and September were higher than those previously measured in the equatorial Pacific and continue to be high (\u3e 250 pmol Hg m-2 d-1) down to 400 m, thereby providing a significant source of Hg that may be incorporated into the mesopelagic food web. In Chapter 4, the role of dissolved oxygen in PC, PN, and PHg was explored using a combination of sediment traps and in situ pumps coupled with 238U -234Th disequilibria by sampling a transect within the central North Pacific Ocean along 155oW between 5 and 17oN. Results indicate that particle fluxes at 150 m throughout this region are very low, among the lowest measured. Water column profiles of fluorescence across vii both oxygenated waters (5oN) and across the oxygen minimum zone (8oN) were similar, yet the magnitude of particle export was significantly higher in oxygenated waters, by a factor of 3 to 7 for PC, PN, and PHg. Furthermore, the peak in PHg fluxes occurred below the depth of maximum PC export. Combined, our results suggest that PC and PN production may have been influenced by a lack of small grazers, while PHg fluxes were additionally influenced by enhanced solubility in low oxygen waters. Thus, while oxygenation may influence particle production and remineralization rates in the upper water column, fluxes across 150 m remain low regardless of oxygen concentratio

A Time Series of Water Column Distributions and Sinking Particle Flux of Pseudo-Nitzschia and Domoic Acid in the Santa Barbara Basin, California

Water column bulk Pseudo-nitzschia abundance and the dissolved and particulate domoic acid (DA) concentrations were measured in the Santa Barbara Basin (SBB), California from 2009–2013 and compared to bulk Pseudo-nitzschia cell abundance and DA concentrations and fluxes in sediment traps moored at 147 m and 509 m. Pseudo-nitzschia abundance throughout the study period was spatially and temporally heterogeneous (L−1 to 3.8 × 106 cells L−1 , avg. 2 × 105 ± 5 × 105 cells L−1 ) and did not correspond with upwelling conditions or the total DA (tDA) concentration, which was also spatially and temporally diverse (1000 cells L−1 and tDA = 200 ng L−1 ) measured as deep as 150 m. Our results highlight that dDA should not be ignored when examining bloom toxicity. Although water column abundance and pDA concentrations were poorly correlated with sediment trap Pseudo-nitzschia abundance and fluxes, DA toxicity is likely associated with senescent blooms that rapidly sink to the seafloor, adding another potential source of DA to benthic organisms

A Time Series of Water Column Distributions and Sinking Particle Flux of Pseudo-Nitzschia and Domoic Acid in the Santa Barbara Basin, California

Water column bulk Pseudo-nitzschia abundance and the dissolved and particulate domoic acid (DA) concentrations were measured in the Santa Barbara Basin (SBB), California from 2009–2013 and compared to bulk Pseudo-nitzschia cell abundance and DA concentrations and fluxes in sediment traps moored at 147 m and 509 m. Pseudo-nitzschia abundance throughout the study period was spatially and temporally heterogeneous (L−1 to 3.8 × 106 cells L−1, avg. 2 × 105 ± 5 × 105 cells L−1) and did not correspond with upwelling conditions or the total DA (tDA) concentration, which was also spatially and temporally diverse (−1 to 2.2 × 105 ng L−1, avg. 7.8 × 103 ± 2.2 × 104 ng L−1). We hypothesize that the toxicity is likely driven in part by specific Pseudo-nitzschia species as well as bloom stage. Dissolved (dDA) and particulate (pDA) DA were significantly and positively correlated (p \u3c 0.01) and both comprised major components of the total DA pool (pDA = 57 ± 35%, and dDA = 42 ± 35%) with substantial water column concentrations (\u3e1000 cells L−1 and tDA = 200 ng L−1) measured as deep as 150 m. Our results highlight that dDA should not be ignored when examining bloom toxicity. Although water column abundance and pDA concentrations were poorly correlated with sediment trap Pseudo-nitzschia abundance and fluxes, DA toxicity is likely associated with senescent blooms that rapidly sink to the seafloor, adding another potential source of DA to benthic organisms

High-resolution spatial and temporal measurements of particulate organic carbon flux using thorium-234 in the northeast Pacific Ocean during the EXport processes in the ocean from RemoTe sensing field campaign

© The Author(s), 2020. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Buesseler, K. O., Benitez-Nelson, C. R., Roca-Marti, M., Wyatt, A. M., Resplandy, L., Clevenger, S. J., Drysdale, J. A., Estapa, M. L., Pike, S., & Umhau, B. P. High-resolution spatial and temporal measurements of particulate organic carbon flux using thorium-234 in the northeast Pacific Ocean during the EXport processes in the ocean from RemoTe sensing field campaign. Elementa: Science of the Anthropocene, 8(1), (2020): 030, https://doi.org/10.1525/elementa.030.The EXport Processes in the Ocean from RemoTe Sensing (EXPORTS) program of National Aeronautics and Space Administration focuses on linking remotely sensed properties from satellites to the mechanisms that control the transfer of carbon from surface waters to depth. Here, the naturally occurring radionuclide thorium-234 was used as a tracer of sinking particle flux. More than 950 234Th measurements were made during August–September 2018 at Ocean Station Papa in the northeast Pacific Ocean. High-resolution vertical sampling enabled observations of the spatial and temporal evolution of particle flux in Lagrangian fashion. Thorium-234 profiles were remarkably consistent, with steady-state (SS) 234Th fluxes reaching 1,450 ± 300 dpm m−2 d−1 at 100 m. Nonetheless, 234Th increased by 6%–10% in the upper 60 m during the cruise, leading to consideration of a non-steady-state (NSS) model and/or horizontal transport, with NSS having the largest impact by decreasing SS 234Th fluxes by 30%. Below 100 m, NSS and SS models overlapped. Particulate organic carbon (POC)/234Th ratios decreased with depth in small (1–5 μm) and mid-sized (5–51 μm) particles, while large particle (>51 μm) ratios remained relatively constant, likely influenced by swimmer contamination. Using an average SS and NSS 234Th flux and the POC/234Th ratio of mid-sized particles, we determined a best estimate of POC flux. Maximum POC flux was 5.5 ± 1.7 mmol C m−2 d−1 at 50 m, decreasing by 70% at the base of the primary production zone (117 m). These results support earlier studies that this site is characterized by a modest biological carbon pump, with an export efficiency of 13% ± 5% (POC flux/net primary production at 120 m) and 39% flux attenuation in the subsequent 100 m (POC flux 220 m/POC flux 120m). This work sets the foundation for understanding controls on the biological carbon pump during this EXPORTS campaign.The authors would like to acknowledge support from the National Aeronautics and Space Administration (NASA) as part of the EXport Processes in the Ocean from RemoTe Sensing (EXPORTS) program awards 80NSSC17K0555 and 80NSSC17K0662; the Woods Hole Oceanographic Institution’s Ocean Twilight Zone study for KOB and MRM, and the National Science Foundation Graduate Research Fellowship Program (NSF-GRFP) for funding and support of AW

Concentrations, ratios, and sinking fluxes of major bioelements at Ocean Station Papa

© The Author(s), 2021. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Roca-Marti, M., Benitez-Nelson, C. R., Umhau, B. P., Wyatt, A. M., Clevenger, S. J., Pike, S., Horner, T. J., Estapa, M. L., Resplandy, L., & Buesseler, K. O. Concentrations, ratios, and sinking fluxes of major bioelements at Ocean Station Papa. Elementa: Science of the Anthropocene, 9(1), (2021): 00166, https://doi.org/10.1525/elementa.2020.00166.Fluxes of major bioelements associated with sinking particles were quantified in late summer 2018 as part of the EXport Processes in the Ocean from RemoTe Sensing (EXPORTS) field campaign near Ocean Station Papa in the subarctic northeast Pacific. The thorium-234 method was used in conjunction with size-fractionated (1–5, 5–51, and >51 μm) concentrations of particulate nitrogen (PN), total particulate phosphorus (TPP), biogenic silica (bSi), and particulate inorganic carbon (PIC) collected using large volume filtration via in situ pumps. We build upon recent work quantifying POC fluxes during EXPORTS. Similar remineralization length scales were observed for both POC and PN across all particle size classes from depths of 50–500 m. Unlike bSi and PIC, the soft tissue–associated POC, PN, and TPP fluxes strongly attenuated from 50 m to the base of the euphotic zone (approximately 120 m). Cruise-average thorium-234-derived fluxes (mmol m–2 d–1) at 120 m were 1.7 ± 0.6 for POC, 0.22 ± 0.07 for PN, 0.019 ± 0.007 for TPP, 0.69 ± 0.26 for bSi, and 0.055 ± 0.022 for PIC. These bioelement fluxes were similar to previous observations at this site, with the exception of PIC, which was 1 to 2 orders of magnitude lower. Transfer efficiencies within the upper twilight zone (flux 220 m/flux 120 m) were highest for PIC (84%) and bSi (79%), followed by POC (61%), PN (58%), and TPP (49%). These differences indicate preferential remineralization of TPP relative to POC or PN and larger losses of soft tissue relative to biominerals in sinking particles below the euphotic zone. Comprehensive characterization of the particulate bioelement fluxes obtained here will support future efforts linking phytoplankton community composition and food-web dynamics to the composition, magnitude, and attenuation of material that sinks to deeper waters.The authors would like to acknowledge support from the National Aeronautics and Space Administration as part of the EXport Processes in the Ocean from RemoTe Sensing program awards 80NSSC17K0555 and 80NSSC17K0662. They also acknowledge the funding from the Woods Hole Oceanographic Institution’s Ocean Twilight Zone study for MRM and KOB, the National Science Foundation Graduate Research Fellowship Program for AMW, and the Ocean Frontier Institute for MRM

Mercury Cycling in the North Pacific Subtropical Gyre as Revealed by Mercury Stable Isotope Ratios

The oceans are an important global reservoir for mercury (Hg), and marine fish consumption is the dominant human exposure pathway for its toxic methylated form. A more thorough understanding of the global biogeochemical cycle of Hg requires additional information on the mechanisms that control Hg cycling in pelagic marine waters. In this study, Hg isotope ratios and total Hg concentrations are used to explore Hg biogeochemistry in oligotrophic marine environments north of Hawaii. We present the first measurements of the vertical water column distribution of Hg concentrations and the Hg isotopic composition in precipitation, marine particles, and zooplankton near Station ALOHA (22°45â ²N, 158°W). Our results reveal production and demethylation of methylmercury in both the euphotic (0â 175 m) and mesopelagic zones (200â 1,000 m). We document a strong relationship between Hg isotopic composition and depth in particles, zooplankton, and fish in the water column and diurnal variations in Î 199Hg values in zooplankton sampled near the surface (25 m). Based on these observations and stable Hg isotope relationships in the marine food web, we suggest that the Hg found in large pelagic fish at Station ALOHA was originally deposited largely by precipitation, transformed into methylâ Hg, and bioaccumulated in situ in the water column. Our results highlight how Hg isotopic compositions reflect abiotic and biotic production and degradation of methylâ Hg throughout the water column and the importance of particles and zooplankton in the vertical transport of Hg.Key PointsMMHg bioaccumulated in fish is derived primarily from Hg (II) deposited in atmospheric precipitationMarine particles host the majority of Hg available for production of MMHg in the open oceanMethylation and demethylation of Hg occurs throughout the euphotic and mesopelagic zones in the North Pacific Subtropical GyrePeer Reviewedhttps://deepblue.lib.umich.edu/bitstream/2027.42/150543/1/gbc20883.pdfhttps://deepblue.lib.umich.edu/bitstream/2027.42/150543/2/gbc20883_am.pd

Mercury Cycling in the North Pacific Subtropical Gyre as Revealed by Mercury Stable Isotope Ratios

The oceans are an important global reservoir for mercury (Hg), and marine fish consumption is the dominant human exposure pathway for its toxic methylated form. A more thorough understanding of the global biogeochemical cycle of Hg requires additional information on the mechanisms that control Hg cycling in pelagic marine waters. In this study, Hg isotope ratios and total Hg concentrations are used to explore Hg biogeochemistry in oligotrophic marine environments north of Hawaii. We present the first measurements of the vertical water column distribution of Hg concentrations and the Hg isotopic composition in precipitation, marine particles, and zooplankton near Station ALOHA (22°45′N, 158°W). Our results reveal production and demethylation of methylmercury in both the euphotic (0–175 m) and mesopelagic zones (200–1,000 m). We document a strong relationship between Hg isotopic composition and depth in particles, zooplankton, and fish in the water column and diurnal variations in Δ199Hg values in zooplankton sampled near the surface (25 m). Based on these observations and stable Hg isotope relationships in the marine food web, we suggest that the Hg found in large pelagic fish at Station ALOHA was originally deposited largely by precipitation, transformed into methyl‐Hg, and bioaccumulated in situ in the water column. Our results highlight how Hg isotopic compositions reflect abiotic and biotic production and degradation of methyl‐Hg throughout the water column and the importance of particles and zooplankton in the vertical transport of Hg

A Time Series of Water Column Distributions and Sinking Particle Flux of <i>Pseudo-Nitzschia</i> and Domoic Acid in the Santa Barbara Basin, California

Water column bulk Pseudo-nitzschia abundance and the dissolved and particulate domoic acid (DA) concentrations were measured in the Santa Barbara Basin (SBB), California from 2009&#8315;2013 and compared to bulk Pseudo-nitzschia cell abundance and DA concentrations and fluxes in sediment traps moored at 147 m and 509 m. Pseudo-nitzschia abundance throughout the study period was spatially and temporally heterogeneous (&lt;200 cells L&#8722;1 to 3.8 &#215; 106 cells L&#8722;1, avg. 2 &#215; 105 &#177; 5 &#215; 105 cells L&#8722;1) and did not correspond with upwelling conditions or the total DA (tDA) concentration, which was also spatially and temporally diverse (&lt;1.3 ng L&#8722;1 to 2.2 &#215; 105 ng L&#8722;1, avg. 7.8 &#215; 103 &#177; 2.2 &#215; 104 ng L&#8722;1). We hypothesize that the toxicity is likely driven in part by specific Pseudo-nitzschia species as well as bloom stage. Dissolved (dDA) and particulate (pDA) DA were significantly and positively correlated (p &lt; 0.01) and both comprised major components of the total DA pool (pDA = 57 &#177; 35%, and dDA = 42 &#177; 35%) with substantial water column concentrations (&gt;1000 cells L&#8722;1 and tDA = 200 ng L&#8722;1) measured as deep as 150 m. Our results highlight that dDA should not be ignored when examining bloom toxicity. Although water column abundance and pDA concentrations were poorly correlated with sediment trap Pseudo-nitzschia abundance and fluxes, DA toxicity is likely associated with senescent blooms that rapidly sink to the seafloor, adding another potential source of DA to benthic organisms

Seasonal and spatial changes in carbon and nitrogen fluxes estimated using 234Th:238U disequilibria in the North Pacific tropical and subtropical gyre

Peer Reviewedhttps://deepblue.lib.umich.edu/bitstream/2027.42/155778/1/Umhau_et_al_2019_Seasonal_and_Spacial.pd

Deep zooplankton rely on small particles when particle fluxes are low

The fate of organic matter (OM) in the deep ocean remains enigmatic, with little understood regarding the flux and its utilization by deep food webs. We used compound‐specific nitrogen stable isotope ratios of source amino acids measured in particle size classes and deep zooplankton (700–1500 m) to determine the contribution of small (0.7–53 μm) vs. large particles (> 53 μm) to their diet at four sites in the North Pacific. Our results show that small particles constitute between 9% and 98% of zooplankton diets, being the contribution higher at sites with lower flux regimes. The contribution of small particles to the diet of deep zooplankton was also higher when biomass of vertical migrators, and therefore actively transported OM, was lower. Climate‐driven changes in primary production and export are expected to shift particle fluxes to smaller size classes, and thus their importance in midwater food webs may become more widespread