Patterns and variability in ocean acidification conditions in Puget Sound and the Strait of Juan de Fuca

The Washington Ocean Acidification Center is working with NOAA and other partners to increase understanding of ocean acidification dynamics and spatial variability in the Salish Sea, and how these correlate with planktonic responses. These data are critical for assessing water quality, areas with higher or lower OA stress, and to understand effects on the food web. Two main strategies are employed; seasonal ship cruises provide spatial coverage and the ability to collect plankton, while mooring buoys provide information on mechanisms and the range of variation due to the high-resolution and constant coverage they provide. Results show a strong degree of depth, seasonal, and spatial variation in pH and aragonite saturation state. In general, the lowest pH and aragonite saturation state values are at depth, particularly in stratified areas, though this can shift during seasonal localized upwelling, e.g., Southern Hood Canal, and in mixed water columns, e.g., the Main Basin. Seasonal patterns are spatially diverse, with stratified areas exhibiting strong vertical gradients with depth during summer and more homogenous conditions during winter; well-mixed areas show less variation year-round. This implies that species encounter quite different OA conditions in various parts of the Salish Sea between the seasons. Mooring CO2 data reveal higher variation during late fall through early spring at sites within the Salish Sea, due to winter mixing of stratified waters, yet the reverse pattern off the Washington coast, due to summer upwelling. In both cases, these mechanisms (winter mixing and summer upwelling) operate across a gradient, bringing relatively deeper lower pH / aragonite saturation state waters in contact with surface waters with higher values. Such changes in the spatial and depth distribution of corrosive conditions have broad implications for sensitive marine life

Phosphate and Silicate Analysis in Seawater using Programmable Flow Injection: Optimization and Applications of Benchtop and In Situ Methodologies

Oceanographic nutrient monitoring efforts still largely rely on discrete sampling at irregular intervals, hindering the advancement of high-resolution biogeochemical observations and models. Benchtop analytical instrumentation for macronutrient analysis is expensive, complex, and requires large reagent volumes and highly trained operators. This thesis describes the development and optimization of a novel and commercially available class of automated nutrient analyzers called programmable Flow Injection (pFI) for benchtop and unattended in situ operations with a focus on phosphate and silicate analysis. While pFI is an ideal candidate for unattended deployments due to its compact size, low reagent volume requirements, and ability measure multiple analytes from a single device, this type of instrumentation has only been used for benchtop applications to date. The composition of reagents and standards were optimized to remain stable for more than 30 days at a range of temperatures. In addition, online dilutions were implemented to produce autonomous calibrations. A field-deployable pFI analyzer was developed using open-source software and low-cost commercially available hardware. The instrument was successfully deployed at a coastal shore station, revealing nutrient variability driven by the transport of high-nutrient water into the nearshore via internal tidal waves. The work presented in this thesis will showcase pFI as a robust technique for advancing the field of analytical chemistry and inspiring wider use of this technology

Programmable flow injection: a versatile technique for benchtop and autonomous analysis of phosphate and silicate in seawater

High-resolution, autonomous monitoring of phosphate and silicate in the marine environment is essential to understand their complex dynamics and implications for the functioning of marine ecosystems. In the absence of dependable reagent-less sensors for these nutrients, leveraging established colorimetric techniques using miniaturized analyzers, such as programmable Flow Injection (pFI), offers the best immediate solution to meet oceanographic accuracy and precision standards. In this work, we further optimize the phosphomolybdate and silicomolybdate assays recently adapted for use with pFI, laying the groundwork for the technique’s use for long-term, autonomous operations. For both assays, we show that only a narrow range of acidities and molybdate concentrations can maximize sensitivity while minimizing salt effects. In addition, we demonstrate the stability of our optimized colorimetric reagent formulations, ensuring that analytical sensitivity remains within 10% of initial levels for at least 35 days of continuous use. We then applied our optimized protocols to produce oceanographically consistent phosphate and silicate profiles at the Hawaii Ocean Time Series (HOTS) and Southern Ocean Time Series (SOTS), respectively, which compared favorably against a reference method and historical data. Using certified reference materials for nutrients in seawater, we show that our pFI protocols, optimized for long-term operations, achieve a shipboard precision better than 6% and a relative combined uncertainty (k=1) of 4.5% for phosphate (0.45 - 2.95 µmol L-1) and 6.2% for silicate (2.2 to 103 µmol L-1). To demonstrate pFI’s potential as a versatile tool for autonomous monitoring, we report a five-day hourly phosphate time series at a coastal shore station in central California (n=121 analyses), examine phosphate uptake by seaweed at five-minute intervals at a seaweed aquaculture facility (n=103), and discuss a unique, high-resolution surface silicate transect spanning multiple frontal zones in the Australian sector of the Southern Ocean (n=249). These data, obtained using a commercially available pFI analyzer, confirm that pFI is a viable technology for autonomous monitoring of phosphate and silicate, paving the way for more ambitious, long-term deployments in a variety of settings

DataSheet_1_Programmable flow injection: a versatile technique for benchtop and autonomous analysis of phosphate and silicate in seawater.pdf

High-resolution, autonomous monitoring of phosphate and silicate in the marine environment is essential to understand their complex dynamics and implications for the functioning of marine ecosystems. In the absence of dependable reagent-less sensors for these nutrients, leveraging established colorimetric techniques using miniaturized analyzers, such as programmable Flow Injection (pFI), offers the best immediate solution to meet oceanographic accuracy and precision standards. In this work, we further optimize the phosphomolybdate and silicomolybdate assays recently adapted for use with pFI, laying the groundwork for the technique’s use for long-term, autonomous operations. For both assays, we show that only a narrow range of acidities and molybdate concentrations can maximize sensitivity while minimizing salt effects. In addition, we demonstrate the stability of our optimized colorimetric reagent formulations, ensuring that analytical sensitivity remains within 10% of initial levels for at least 35 days of continuous use. We then applied our optimized protocols to produce oceanographically consistent phosphate and silicate profiles at the Hawaii Ocean Time Series (HOTS) and Southern Ocean Time Series (SOTS), respectively, which compared favorably against a reference method and historical data. Using certified reference materials for nutrients in seawater, we show that our pFI protocols, optimized for long-term operations, achieve a shipboard precision better than 6% and a relative combined uncertainty (k=1) of 4.5% for phosphate (0.45 - 2.95 µmol L-1) and 6.2% for silicate (2.2 to 103 µmol L-1). To demonstrate pFI’s potential as a versatile tool for autonomous monitoring, we report a five-day hourly phosphate time series at a coastal shore station in central California (n=121 analyses), examine phosphate uptake by seaweed at five-minute intervals at a seaweed aquaculture facility (n=103), and discuss a unique, high-resolution surface silicate transect spanning multiple frontal zones in the Australian sector of the Southern Ocean (n=249). These data, obtained using a commercially available pFI analyzer, confirm that pFI is a viable technology for autonomous monitoring of phosphate and silicate, paving the way for more ambitious, long-term deployments in a variety of settings.</p

Improving access to ocean and coastal data: how the Northwest Association of Networked Ocean Observing Systems serves the Pacific Northwest

The Northwest Association of Networked Ocean Observing Systems (NANOOS), the regional association of U.S. Integrated Ocean Observing System (U.S. IOOS) for the United States Pacific Northwest, developed its NANOOS Visualization System (NVS - http://nvs.nanoos.org/) to provide users with a rich interface to access observations, forecasts, and satellite overlays from a wide range of ocean and coastal assets in a user-friendly format. The NVS interface is available via the web, on tablets and smart phones, and other devices. While this is a major service to our various user groups, we note that the rich assortment of data streams NANOOS has been able to harness can be overwhelming to users. Our more recent developments with NVS focus on an improved interface for access to ocean and coastal data and models that allows user interface applications (apps) for specific user groups. The technical structure of NVS was made in way that it simplifies the process for developing new and more targeted web apps, saving time and money to program and design apps in the future, thus enabling NANOOS to develop applications tailored to meet specific user needs more readily. Here we will emphasize many of the apps and data types of highest utility and interest to the ecosystem assessment and management community

A decade-long biogeochemical cruise time-series from the Salish Sea and Washington coast: Regional connections to large-scale ocean climate drivers of ocean acidification and hypoxia

Coastal and estuarine waters of the northern California Current Ecosystem and southern Salish Sea benefit from a comprehensive observation network for detecting and illuminating ocean acidification and hypoxia dynamics. Given the vulnerability of North Pacific ecosystems to ocean acidification and hypoxia, these observations provide critical insight into interactions among natural and anthropogenic processes as well as their combined effects on these valuable ecosystems. This time-series provides synoptic snapshots of conditions in Washington’s coastal and estuarine waters during conditions encompassing all ENSO phases and seasons, as well as throughout the North Pacific marine heat wave of 2013–2016. The cruises obtained high-quality carbon, physical, and other biogeochemical parameters through a combination of CTD casts to measure temperature, conductivity, pressure, and oxygen profiles and discrete water samples for analysis of dissolved inorganic carbon, oxygen, total alkalinity, and nutrient concentrations, with all carbonate system parameters calculated from these measured quantities. We compared average properties for each cruise with contemporaneous values of the North Pacific Gyre Oscillation (NPGO) index, Pacific Decadal Oscillation (PDO) index, Oceanic Niño Index (ONI), and Bakun upwelling anomaly for 48°N, as well as daylength (proxy for seasonality) and global atmospheric pCO2 (proxy for directional climate change). Preliminary regression results point to important roles for PDO, NPGO, seasonality, and directional climate change in shaping the biogeochemical dynamics of the southern Salish Sea. We anticipate these relationships will vary with water depth and sub-region within the study area upon further analysis and will provide a useful comparison to model results attributing variability to various drivers. This joint UW–PMEL observing effort has been supported by several state and federal funding sources. All observations meet or exceed the monitoring guidelines of the Global Ocean Acidification Observing Network, the U.S. National Oceanic and Atmospheric Administration\u27s Ocean Acidification Program, and ocean carbon community best practices

Supporting diverse Pacific NW marine data access needs via the NANOOS Visualization System (NVS) and data services

The Northwest Association of Networked Ocean Observing Systems, NANOOS, is the Pacific Northwest Regional Association of the U.S. Integrated Ocean Observing System (IOOS). For over 10 years, NANOOS has been making observation and model data available to a diverse set of stakeholders throughout the region through a user-friendly data visualization tool called the NANOOS Visualization System (NVS, http://nvs.nanoos.org). NVS is a web-based suite of thematic apps sharing a coherent user interface, common application components, and common capabilities for regional data processing, aggregation, subsetting and homogenization. We will discuss NVS capabilities, user experience, and NANOOS data services that support this suite of tailored NVS apps (including mobile apps) developed to serve the following NANOOS priority areas: Climate: Climatology and anomaly products from regional buoys, satellite time series, and shoreline change statistics to improve understanding of climate variation and change. Ecosystem assessment: Time-series and real-time observations and data products used to evaluate and forecast Harmful Algal Blooms (HABs), hypoxia, ocean acidification and water quality. Fisheries and biodiversity: Forecasts and data on the bio-physical environment enabling better-informed management decisions by fishers (from tuna fishers to shellfish growers) and regional managers. Mitigation of coastal hazards: Observations and analysis of topographic beach profiles, shoreline change, near-shore bathymetry, sea level change and waves to improve planning and response to coastal hazards, assist with engineering design and enhance coastal resiliency. Maritime operations: Water, wave and weather observations and forecasts to assist ship and boat operators with safe operations and planning

An Enhanced Ocean Acidification Observing Network: From People to Technology to Data Synthesis and Information Exchange

A successful integrated ocean acidification (OA) observing network must include (1) scientists and technicians from a range of disciplines from physics to chemistry to biology to technology development; (2) government, private, and intergovernmental support; (3) regional cohorts working together on regionally specific issues; (4) publicly accessible data from the open ocean to coastal to estuarine systems; (5) close integration with other networks focusing on related measurements or issues including the social and economic consequences of OA; and (6) observation-based informational products useful for decision making such as management of fisheries and aquaculture. The Global Ocean Acidification Observing Network (GOA-ON), a key player in this vision, seeks to expand and enhance geographic extent and availability of coastal and open ocean observing data to ultimately inform adaptive measures and policy action, especially in support of the United Nations 2030 Agenda for Sustainable Development. GOA-ON works to empower and support regional collaborative networks such as the Latin American Ocean Acidification Network, supports new scientists entering the field with training, mentorship, and equipment, refines approaches for tracking biological impacts, and stimulates development of lower-cost methodology and technologies allowing for wider participation of scientists. GOA-ON seeks to collaborate with and complement work done by other observing networks such as those focused on carbon flux into the ocean, tracking of carbon and oxygen in the ocean, observing biological diversity, and determining short-and long-term variability in these and other ocean parameters through space and time