Coralline algal Barium as indicator for 20th century northwestern North Atlantic surface ocean freshwater variability

During the past decades climate and freshwater dynamics in the northwestern North Atlantic have undergone major changes. Large-scale freshening episodes, related to polar freshwater pulses, have had a strong influence on ocean variability in this climatically important region. However, little is known about variability before 1950, mainly due to the lack of long-term high-resolution marine proxy archives. Here we present the first multidecadal-length records of annually resolved Ba/Ca variations from Northwest Atlantic coralline algae. We observe positive relationships between algal Ba/Ca ratios from two Newfoundland sites and salinity observations back to 1950. Both records capture episodical multi-year freshening events during the 20th century. Variability in algal Ba/Ca is sensitive to freshwater-induced changes in upper ocean stratification, which affect the transport of cold, Ba-enriched deep waters onto the shelf (highly stratified equals less Ba/Ca). Algal Ba/Ca ratios therefore may serve as a new resource for reconstructing past surface ocean freshwater changes

Robotic observations of high wintertime carbon export in California coastal waters

Biologically mediated particulate organic and inorganic carbon (POC and PIC) export from surface waters is the principal determinant of the vertical oceanic distribution of pH and dissolved inorganic carbon and thus sets the conditions for air-sea exchange of CO2; exported organic matter also provides the energy fueling communities in the mesopelagic zone. However, observations are temporally and spatially sparse. Here we report the first hourly-resolved optically quantified POC and PIC sedimentation rate time series from an autonomous Lagrangian Carbon Flux Explorer (CFE), which monitored particle flux using an imaging optical sedimentation recorder (OSR) at depths below 140m in the Santa Cruz Basin, CA, in May 2012, and in January and March 2013. Highest POC vertical flux (∼ 100-240mmolCm-2d-1) occurred in January, when most settling material was millimeter- to centimeter-sized aggregates but when surface biomass was low; fluxes were ∼ 18 and ∼ 6mmolCm-2d-1, respectively, in March and May, under high surface biomass conditions. An unexpected discovery was that January 2013 fluxes measured by CFE were 20 times higher than that measured by simultaneously deployed surface-tethered OSR; multiple lines of evidence indicate strong undersampling of aggregates larger than 1mm in the latter case. Furthermore, the January 2013 CFE fluxes were about 10 times higher than observed during multiyear sediment trap observations in the nearby Santa Barbara and San Pedro basins. The strength of carbon export in biologically dynamic California coastal waters is likely underestimated by at least a factor of 3 and at times by a factor of 20

Global Spatial and Temporal Variation of Cd:P in Euphotic Zone Particulates

Concentrations of Cd and P were determined in particle samples collected using the multiple unit large volume in situ filtration system (MULVFS) from 50 profiles at 34 different locations throughout the Atlantic, Pacific, and Southern Oceans since 1991. Consistent methodology has been used. This data set of Cd:P in size fractionated particles gives insight into the processes that lead to differences in regional Cd:P particle values as well as how the formation and remineralization of these particles lead to dissolved deep water ratios that increase from the North Atlantic to the North Pacific. With large spatial and temporal variation, this data set allows us to study the effects of an El Niño, upwelling, large-scale in situ Fe fertilization, low-oxygen conditions, and seasonal variation on the Cd:P in particles. Overall, Cd:P tends to be higher (~1–2 mmol/mol) in particles gathered in biologically dynamic waters and is much lower (typically ~0.1 mmol/mol) in oligotrophic regions. Using multiple linear regression analysis, we investigate how euphotic zone parameters important to photosynthesis including nitrate, phosphate, silicate, temperature, and euphotic zone depth affect the Cd:P ratio in particles. Using the results of the analysis, we create global seasonal maps of predicted particulate Cd:P distributions. We find that three factors—local dissolved nitrate, silicate concentrations, and euphotic zone depth—can predict 59% of the variation in particulate Cd:P. We verified our projections using in situ filtration samples collected during GEOTRACES expeditions GA03 (North Atlantic) and GP16 (South Pacific)

Carbon export and fate beneath a dynamic upwelled filament off the California coast

To understand the vertical variations in carbon fluxes in biologically productive waters, four autonomous carbon flux explorers (CFEs), ship-lowered CTD-interfaced particle-sensitive transmissometer and scattering sensors, and surface-drogued sediment traps were deployed in a filament of offshore flowing, recently upwelled water, during the June 2017 California Current Ecosystem-Long Term Ecological Research process study. The Lagrangian CFEs operating at depths from 100-500 m yielded carbon flux and its partitioning with size from 30 μ m-1 cm at three intensive study locations within the filament and in waters outside the filament. Size analysis codes intended to enable long-term CFE operations independent of ships are described. Different particle classes (anchovy pellets, copepod pellets, and > 1000 μ m aggregates) dominated the 100-150 m fluxes during successive stages of the filament evolution as it progressed offshore. Fluxes were very high at all locations in the filament; below 150 m, flux was invariant or increased with depth at the two locations closer to the coast. Martin curve bfactors (± denotes 95 % confidence intervals) for total particulate carbon flux were + 0.37 ± 0.59, + 0.85 ± 0.31,-0.24 ± 0.68, and-0.45 ± 0.70 at the three successively occupied locations within the plume, and in transitional waters. Interestingly, the flux profiles for all particles < 400 μ m were a much closer fit to the canonical Martin profile (b-0.86); however, most (typically > 90 %) of the particle flux was carried by > 1000 μ m sized aggregates which increased with depth. Mechanisms to explain the factor of 3 flux increase between 150 and 500 m at the mid-plume location are investigated

Process dominance shift in solute chemistry as revealed by long-term high-frequency water chemistry observations of groundwater flowing through weathered argillite underlying a steep forested hillslope

Significant solute flux from the weathered bedrock zone - which underlies soils and saprolite - has been suggested by many studies. However, controlling processes for the hydrochemistry dynamics in this zone are poorly understood. This work reports the first results from a four-year (2009-2012) high-frequency (1-3day) monitoring of major solutes (Ca, Mg, Na, K and Si) in the perched, dynamic groundwater in a 4000m2 zero-order basin located at the Angelo Coast Range Reserve, Northern California. Groundwater samples were autonomously collected at three wells (downslope, mid-slope, and upslope) aligned with the axis of the drainage. Rain and throughfall samples, profiles of well headspace pCO2, vertical profiles and time series of groundwater temperature, and contemporaneous data from an extensive hydrologic and climate sensor network provided the framework for data analysis. All runoff at this soil-mantled site occurs by vertical unsaturated flow through a 5-25m thick weathered argillite and then by lateral flows to the adjacent channel as groundwater perched over fresher bedrock. Driven by strongly seasonal rainfall, over each of the four years of observations, the hydrochemistry of the groundwater at each well repeats an annual cycle, which can be explained by two end-member processes. The first end-member process, which dominates during the winter high-flow season in mid- and upslope areas, is CO2 enhanced cation exchange reaction in the vadose zone in the more shallow conductive weathered bedrock. This process rapidly increases the cation concentrations of the infiltrated rainwater, which is responsible for the lowest cation concentration of groundwater. The second-end member process occurs in the deeper perched groundwater and either dominates year-round (at the downslope well) or becomes progressively dominant during low flow season at the two upper slope wells. This process is the equilibrium reaction with minerals such as calcite and clay minerals, but not with primary minerals, suggesting the critical role of the residence time of the water. Collectively, our measurements reveal that the hydrochemistry dynamics of the groundwater in the weathered bedrock zone is governed by two end-member processes whose dominance varies with critical zone structure, the relative importance of vadose versus groundwater zone processes, and thus with the seasonal variation of the chemistry of recharge and runoff. © 2014 The Authors

Controls on solute concentration-discharge relationships revealed by simultaneous hydrochemistry observations of hillslope runoff and stream flow: The importance of critical zone structure

We investigated controls on concentration-discharge relationships of a catchment underlain by argillite by monitoring both groundwater along a hillslope transect and stream chemistry. Samples were collected at 1–3 day intervals over 4 years (2009–2013) in Elder Creek in the Eel River Critical Zone Observatory in California. Runoff at our study hillslope is driven by vadose zone flux through deeply weathered argillite (5–25 m thick) to a perched, seasonally dynamic groundwater that then drains to Elder Creek. Low flow derives from the slowly draining deepest perched groundwater that reaches equilibrium between primary and secondary minerals and saturation with calcite under high subsurface pCO2. Arriving winter rains pass through the thick vadose zone, where they rapidly acquire solutes via cation exchange reactions (driven by high pCO2), and then recharge the groundwater that delivers runoff to the stream. These new waters displayed lower solute concentrations than the deep groundwater by less than a factor of 5 (except for Ca). Up to 74% of the total annual solute flux is derived from the vadose zone. The deep groundwater's Ca concentration decreased as it exfiltrates to the stream due to CO2 degassing and this Ca loss is equivalent of 30% of the total chemical weathering flux of Elder Creek. The thick vadose zone in weathered bedrock and the perched groundwater on underlying fresh bedrock result in two distinct processes that lead to the relatively invariant (chemostatic) concentration-discharge behavior. The processes controlling solute chemistry are not evident from stream chemistry and runoff analysis alone

Controls on solute concentration-discharge relationships revealed by simultaneous hydrochemistry observations of hillslope runoff and stream flow: The importance of critical zone structure

We investigated controls on concentration-discharge relationships of a catchment underlain by argillite by monitoring both groundwater along a hillslope transect and stream chemistry. Samples were collected at 1–3 day intervals over 4 years (2009–2013) in Elder Creek in the Eel River Critical Zone Observatory in California. Runoff at our study hillslope is driven by vadose zone flux through deeply weathered argillite (5–25 m thick) to a perched, seasonally dynamic groundwater that then drains to Elder Creek. Low flow derives from the slowly draining deepest perched groundwater that reaches equilibrium between primary and secondary minerals and saturation with calcite under high subsurface pCO2. Arriving winter rains pass through the thick vadose zone, where they rapidly acquire solutes via cation exchange reactions (driven by high pCO2), and then recharge the groundwater that delivers runoff to the stream. These new waters displayed lower solute concentrations than the deep groundwater by less than a factor of 5 (except for Ca). Up to 74% of the total annual solute flux is derived from the vadose zone. The deep groundwater's Ca concentration decreased as it exfiltrates to the stream due to CO2 degassing and this Ca loss is equivalent of 30% of the total chemical weathering flux of Elder Creek. The thick vadose zone in weathered bedrock and the perched groundwater on underlying fresh bedrock result in two distinct processes that lead to the relatively invariant (chemostatic) concentration-discharge behavior. The processes controlling solute chemistry are not evident from stream chemistry and runoff analysis alone

Multiple sulfur isotope constraints on the modern sulfur cycle

We present 28 multiple sulfur isotope measurements of seawater sulfate (δ34SSO4 and δ33SSO4) from the modern ocean over a range of water depths and sites along the eastern margin of the Pacific Ocean. The average measured δ34SSO4 is 21.24‰ (±0.88‰, 2σ) with a calculated δ33SSO4 of +0.050‰ (±0.014‰, 2σ). With these values, we use a box-model to place constraints on the gross fraction of pyrite burial in modern sediments. This model presents an improvement on previous estimates of the global pyrite burial flux because it does not rely on the assumed value of δ34Spyrite, which is poorly constrained, but instead uses new information about the relationship between δ34S and δ33S in global marine sulfate. Our calculations indicate that the pyrite burial flux from the modern ocean is between 10% and 45% of the total sulfur lost from the oceans, with a more probable range between 20% and 35%. © 2014 The Authors

Optical techniques for remote and in-situ characterization of particles pertinent to GEOTRACES

Field and laboratory characterization of marine particles is laborious and expensive. Proxies of particle properties have been developed that allow researchers to obtain high frequency distributions of such properties in space or time. We focus on optical techniques used to characterize marine particles in-situ, with a focus on GEOTRACES-relevant properties, such as bulk properties including particle mass, cross-sectional area, particle size distribution, particle shape information, and also single particle optical properties, such as individual particle type and size. We also address the use of optical properties of particles to infer particulate organic or inorganic carbon. In addition to optical sensors we review advances in imaging technology and its use to study marine particles in situ. This review addresses commercially available technology and techniques that can be used as a proxy for particle properties and the associated uncertainties with particular focus to open ocean environments, the focus of GEOTRACES