Todd R. Martz

Divergent ecosystem responses within a benthic marine community to ocean acidification

Ocean acidification is predicted to impact all areas of the oceans and affect a diversity of marine organisms. However, the diversity of responses among species prevents clear predictions about the impact of acidification at the ecosystem level. Here, we used shallow water CO2 vents in the Mediterranean Sea as a model system to examine emergent ecosystem responses to ocean acidification in rocky reef communities. We assessed in situ benthic invertebrate communities in three distinct pH zones (ambient, low, and extreme low), which differed in both the mean and variability of seawater pH along a continuous gradient. We found fewer taxa, reduced taxonomic evenness, and lower biomass in the extreme low pH zones. However, the number of individuals did not differ among pH zones, suggesting that there is density compensation through population blooms of small acidification-tolerant taxa. Furthermore, the trophic structure of the invertebrate community shifted to fewer trophic groups and dominance by generalists in extreme low pH, suggesting that there may be a simplification of food webs with ocean acidification. Despite high variation in individual species’ responses, our findings indicate that ocean acidification decreases the diversity, biomass, and trophic complexity of benthic marine communities. These results suggest that a loss of biodiversity and ecosystem function is expected under extreme acidification scenarios.

Diel variability in seawater pH relates to calcification and benthic community structure on coral reefs.

Community structure and assembly are determined in part by environmental heterogeneity. While reef-building corals respond negatively to warming (i.e. bleaching events) and ocean acidification (OA), the extent of present-day natural variability in pH on shallow reefs and ecological consequences for benthic assemblages is unknown. We documented high resolution temporal patterns in temperature and pH from three reefs in the central Pacific and examined how these data relate to community development and net accretion rates of early successional benthic organisms. These reefs experienced substantial diel fluctuations in temperature (0.78°C) and pH (>0.2) similar to the magnitude of ‘warming’ and ‘acidification’ expected over the next century. Where daily pH within the benthic boundary layer failed to exceed pelagic climatological seasonal lows, net accretion was slower and fleshy, non-calcifying benthic organisms dominated space. Thus, key aspects of coral reef ecosystem structure and function are presently related to natural diurnal variability in pH.

Near-shore Antarctic pH variability has implications for the design of ocean acidification experiments

Understanding how declining seawater pH caused by anthropogenic carbon emissions, or ocean acidification, impacts Southern Ocean biota is limited by a paucity of pH time-series. Here, we present the first high-frequency in-situ pH time-series in near-shore Antarctica from spring to winter under annual sea ice. Observations from autonomous pH sensors revealed a seasonal increase of 0.3 pH units. The summer season was marked by an increase in temporal pH variability relative to spring and early winter, matching coastal pH variability observed at lower latitudes. Using our data, simulations of ocean acidification show a future period of deleterious wintertime pH levels potentially expanding to 7–11 months annually by 2100. Given the presence of (sub)seasonal pH variability, Antarctica marine species have an existing physiological tolerance of temporal pH change that may influence adaptation to future acidification. Yet, pH-induced ecosystem changes remain difficult to characterize in the absence of sufficient physiological data on present-day tolerances. It is therefore essential to incorporate natural and projected temporal pH variability in the design of experiments intended to study ocean acidification biology.

Deep-Sea DuraFET: A Pressure Tolerant pH Sensor Designed for Global Sensor Networks

Increasing atmospheric carbon dioxide is driving a long-term decrease in ocean pH which is superimposed on daily to seasonal variability. These changes impact ecosystem processes, and they serve as a record of ecosystem metabolism. However, the temporal variability in pH is observed at only a few locations in the ocean because a ship is required to support pH observations of sufficient precision and accuracy. This paper describes a pressure tolerant Ion Sensitive Field Effect Transistor pH sensor that is based on the Honeywell Durafet ISFET die. When combined with a AgCl pseudoreference sensor that is immersed directly in seawater, the system is capable of operating for years at a time on platforms that cycle from depths of several km to the surface. The paper also describes the calibration scheme developed to allow calibrated pH measurements to be derived from the activity of HCl reported by the sensor system over the range of ocean pressure and temperature. Deployments on vertical profiling platforms enable self-calibration in deep waters where pH values are stable. Measurements with the sensor indicate that it is capable of reporting pH with an accuracy of 0.01 or better on the total proton scale and a precision over multiyear periods of 0.005. This system enables a global ocean observing system for ocean pH.

Characterization of an Ion Sensitive Field Effect Transistor and Chloride Ion Selective Electrodes for pH Measurements in Seawater

Characterization of several potentiometric cells without a liquid junction has been carried out in universal buffer, aqueous HCl, and artificial seawater media. The electrodes studied include Ion Sensitive Field Effect Transistor (ISFET) pH electrodes, and Chloride-Ion Selective Electrodes (Cl-ISE) directly exposed to the solution. These electrodes were compared directly to the conventional hydrogen electrode and silver-silver chloride electrode in order to report the degree to which they obey ideal Nernstian laws. These data provide a foundation for operating the ISFET|Cl-ISE pair in seawater as a pH sensor. In order to obtain the highest quality pH measurements from this sensor, its response to changes in pH and salinity must be properly characterized. Our results indicate near-ideal Nernstian response for both electrodes over a wide range of pH (2-12) and Cl(-) molality (0.01-1). We conclude that the error due to sub-Nernstian response of the cell ISFET|seawater|Cl-ISE over the range of seawater pH and salinity is negligible (<0.0001 pH). The cross sensitivity of the Cl-ISE to Br(-) does not seem to be a significant source of error (<0.003 pH) in seawater media in the salinity range 20-35.

Seasonal advection of Pacific Equatorial Water alters oxygen and pH in the Southern California Bight

Chemical properties of the California Undercurrent (CU) have been changing over the past several decades, yet the mechanisms responsible for the trend are still not fully understood. We present a survey of temperature, salinity, O2, pH, and currents at intermediate depths (defined here as 50–500 m) in the summer (30 June to 10 July) and winter (8–15 December) of 2012 in the southern region of the Southern California Bight. Observations of temperature, salinity, and currents reveal that local bathymetry and small gyres play an important role in the flow path of the California Undercurrent (CU). Using spiciness (π) as a tracer, we observe a 10% increase of Pacific Equatorial Water (PEW) in the core of the CU during the summer versus the winter. This is associated with an increase in π of 0.2, and a decrease in O2 and pH of 30 μmol kg−1 and 0.022, respectively; the change in pH is driven by increased CO2, while total alkalinity remains unchanged. The high-π, low-O2, and low-pH waters during the summer are not distributed uniformly in the study region. Moreover, mooring observations at the edge of the continental shelf reveal intermittent intrusions of PEW onto the shelf with concomitant decreases in O2 and pH. We estimate that increased advection of PEW in the CU could account for approximately 50% of the observed decrease in O2, and between 49 and 73% of the decrease in pH, over the past three decades.

Dynamic variability of biogeochemical ratios in the Southern California Current System

We use autonomous nitrate (NO3−), oxygen (O2), and dissolved inorganic carbon (DIC) observations to examine the relationship between ratios of C:N:O at an upwelling site in the Southern California Current System. Mean ratios and 95% confidence intervals observed by sensors over 8 months were NO3−:O2 = −0.11 ± 0.002, NO3−:DIC = 0.14 ± 0.001, and DIC:O2 = −0.83 ± 0.01, in good agreement with Redfield ratios. Variability in the ratios on the weekly time scale is attributable to shifts in biological demand and nutrient availability and shown to exhibit a spectrum of values ranging from near 100% New Production to 100% Regenerated Production.

Bio-optical observations of the 2004 Labrador Sea phytoplankton bloom

[1] A unique time series of moored bio‐optical measurements documented the 2004 spring‐summer bloom in the southern Labrador Sea. In situ and satellite chlorophyll data show that chlorophyll levels in the 2004 bloom were at the upper end of those typically observed in this region. Satellite chlorophyll and profiling float temperature/salinity data show that the main bloom, which typically peaks in June/July, is often preceded by ephemeral mixed layer shoaling and a lesser, short‐lived bloom in May; this was the case in 2004. The particulate backscatter to beam attenuation ratio (bbp[470 nm]/Cp[660 nm]) showed peaks in the relative abundance of small particles at bloom initiation and during the decline of the bloom, while larger particles dominated during the bloom. Chlorophyll/Cp and bbp/chlorophyll were correlated with carbon export and dominated by changes in the pigment per cell associated with lower light levels due to enhanced attenuation of solar radiation during the bloom. An NPZ (nutrients, phytoplankton, zooplankton) model captured the phytoplankton bloom and an early July peak in zooplankton. Moored acoustic Doppler current profiler (ADCP) data showed an additional mid‐June peak in zooplankton biomass which was attributed to egg‐laying copepods. The data reported here represent one of the few moored time series of Cp, bbp and chlorophyll extending over several months in an open ocean region. Interpretation of data sets such as this will become increasingly important as these deployments become more commonplace via ocean observing systems. Moreover, these data contribute to the understanding of biological‐physical coupling in a biogeochemically important, yet poorly studied region.

Abiotic versus biotic drivers of ocean pH variation under fast sea ice in McMurdo Sound, Antarctica.

Ocean acidification is expected to have a major effect on the marine carbonate system over the next century, particularly in high latitude seas. Less appreciated is natural environmental variation within these systems, particularly in terms of pH, and how this natural variation may inform laboratory experiments. In this study, we deployed sensor-equipped moorings at 20 m depths at three locations in McMurdo Sound, comprising deep (bottom depth>200 m: Hut Point Peninsula) and shallow environments (bottom depth ∼25 m: Cape Evans and New Harbor). Our sensors recorded high-frequency variation in pH (Hut Point and Cape Evans only), tide (Cape Evans and New Harbor), and water mass properties (temperature and salinity) during spring and early summer 2011. These collective observations showed that (1) pH differed spatially both in terms of mean pH (Cape Evans: 8.009±0.015; Hut Point: 8.020±0.007) and range of pH (Cape Evans: 0.090; Hut Point: 0.036), and (2) pH was not related to the mixing of two water masses, suggesting that the observed pH variation is likely not driven by this abiotic process. Given the large daily fluctuation in pH at Cape Evans, we developed a simple mechanistic model to explore the potential for biotic processes – in this case algal photosynthesis – to increase pH by fixing carbon from the water column. For this model, we incorporated published photosynthetic parameters for the three dominant algal functional groups found at Cape Evans (benthic fleshy red macroalgae, crustose coralline algae, and sea ice algal communities) to estimate oxygen produced/carbon fixed from the water column underneath fast sea ice and the resulting pH change. These results suggest that biotic processes may be a primary driver of pH variation observed under fast sea ice at Cape Evans and potentially at other shallow sites in McMurdo Sound.

Assessment of net community production and calcification of a coral reef using a boundary layer approach

Coral reefs are threatened worldwide, and there is a need to develop new approaches to monitor reef health under natural conditions. Because simultaneous measurements of net community production (NCP) and net community calcification (NCC) are used as important indicators of reef health, tools are needed to assess them in situ. Here we present the Benthic Ecosystem and Acidification Measurement System (BEAMS) to provide the first fully autonomous approach capable of sustained, simultaneous measurements of reef NCP and NCC under undisturbed, natural conditions on time scales ranging from tens of minutes to weeks. BEAMS combines the chemical and velocity gradient in the benthic boundary layer to quantify flux from the benthos for a variety of parameters to measure NCP and NCC. Here BEAMS was used to measure these rates from two different sites with different benthic communities on the western reef terrace at Palmyra Atoll for 2 weeks in September 2014. Measurements were made every ∼15 min. The trends in metabolic rates were consistent with the benthic communities between the two sites with one dominated by fleshy organisms and the other dominated by calcifiers (degraded and healthy reefs, respectively). This demonstrates the potential utility of BEAMS as a reef health monitoring tool. NCP and NCC were tightly coupled on time scales of minutes to days, and light was the primary driver for the variability of daily integrated metabolic rates. No correlation between CO2 levels and daily integrated NCC was observed, indicating that NCC at these sites were not significantly affected by CO2.