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As global ocean monitoring programs and marine carbon dioxide removal methods expand, so does the need for scalable biogeochemical sensors. Currently, pH sensors are widely used to measure the ocean carbonate system on a variety of autonomous platforms. This paper assesses a commercially available optical pH sensor (optode) distributed by PyroScience GmbH for oceanographic applications. Results from this study show that the small, solid‐state pH optode demonstrates a precision of 0.001 pH and relative accuracy of 0.01 pH using an improved calibration routine outlined in the manuscript. A consistent pressure coefficient of 0.029 pH/1000 dbar is observed across multiple pH optodes tested in this study. The response time is investigated for standard and fast‐response versions over a range of temperatures and flow rates. Field deployments include direct comparison to ISFET‐based pH sensor packages for both moored and profiling platforms where the pH optodes experience sensor‐specific drift rates up to 0.006 pH d−1. In its current state, the pH optode potentially offers a viable and scalable option for short‐term field deployments and laboratory mesocosm studies, but not for long term deployments with no possibility for recalibration like on profiling floats. [ABSTRACT FROM AUTHOR]

Background/Objectives: The coagulation cascade due to tissue damage is considered to be one of the causes of poor prognostic outcomes in patients with acute exacerbations of interstitial lung disease (AE-ILD). This study aimed to confirm coagulopathy in AE-ILD by evaluating the differences in the clinical characteristics of coagulation/fibrinolysis markers between stable ILD and AE-ILD. Methods: Overall, 81 patients were enrolled in this retrospective study and categorized into the following two groups: a chronic ILD group comprising 63 outpatients and an acute ILD group comprising 18 inpatients diagnosed with AE-ILD. Serum markers, including thrombin–antithrombin III complex (TAT), D-dimer, plasmin–α2 plasmin inhibitor complex (PIC), and surfactant protein D (SP-D), were compared between the groups. Results: Among the 18 patients with acute ILD, 17 did not meet the International Society of Thrombosis and Hemostasis scoring system for disseminated intravascular coagulation. In acute ILD, the SP-D levels were statistically significantly positively correlated with TAT, D-dimer, and PIC levels, while the Krebs von den Lungen 6 (KL-6) levels showed no correlation with any of these coagulation/fibrinolytic markers. A positive correlation was observed between SP-D levels and TAT, D-dimer, and PIC levels in acute ILD. Serum TAT, D-dimer, and PIC all showed good area under the receiver operating characteristic (ROC) curve (AUC) values in ROC analysis for the diagnosis of acute ILD. Conclusions: In the clinical setting of AE-ILD, it may be important to focus not only on alveolar damage markers such as SP-D but also on coagulation/fibrinolytic markers including TAT, D-dimer, and PIC. [ABSTRACT FROM AUTHOR]

The ocean carbonate system is critical to monitor because it plays a major role in regulating Earth's climate and marine ecosystems. It is monitored using a variety of measurements, and it is commonly understood that all components of seawater carbonate chemistry can be calculated when at least two carbonate system variables are measured. However, several recent studies have highlighted systematic discrepancies between calculated and directly measured carbonate chemistry variables and these discrepancies have large implications for efforts to measure and quantify the changing ocean carbon cycle. Given this, the Ocean Carbonate System Intercomparison Forum (OCSIF) was formed as a working group through the Ocean Carbon and Biogeochemistry program to coordinate and recommend research to quantify and/or reduce uncertainties and disagreements in measurable seawater carbonate system measurements and calculations, identify unknown or overlooked sources of these uncertainties, and provide recommendations for making progress on community efforts despite these uncertainties. With this paper we aim to (1) summarize recent progress toward quantifying and reducing carbonate system uncertainties; (2) advocate for research to further reduce and better quantify carbonate system measurement uncertainties; (3) present a small amount of new data, metadata, and analysis related to uncertainties in carbonate system measurements; and (4) restate and explain the rationales behind several OCSIF recommendations. We focus on open ocean carbonate chemistry, and caution that the considerations we discuss become further complicated in coastal, estuarine, and sedimentary environments. [ABSTRACT FROM AUTHOR]

In upwelling systems, fluctuations in seawater pH, dissolved oxygen (DO), and temperature can expose species to extremes that differ greatly from the mean conditions. Understanding the nature of this exposure to extremes, including how exposure to low pH, low DO concentrations, and temperature varies spatiotemporally and in the context of other drivers, is critical for informing global change biology. Here, we use a 4‐yr time series of coupled pH, DO, and temperature observations at six nearshore kelp forest sites spanning the coast of California to characterize the variability and covariance among these drivers. We further compare observed properties to those derived from a high‐resolution coupled physical‐biogeochemical simulation for the central California current system. We find the intensity, duration, and severity of exposure to extreme conditions beyond heuristic, biologically relevant pHT (< 7.7), and DO (< 4.6 mg L−1) values were greatest at sites with strong upwelling. In contrast, sites with relatively weaker upwelling had little exposure to pH or DO conditions below these heuristic values but had higher and more variable temperature. The covariance between pH, DO, and temperature was highest in sites with strong upwelling and weakest in sites with limited upwelling. These relationships among pH, DO, and temperature at the observation locations were mirrored in the model, and model output highlighted geographic differences in exposure regimes across the California marine protected area network. Together, these results provide important insight into the conditions marine ecosystems are exposed to relevant to studies of global change biology. [ABSTRACT FROM AUTHOR]

Author(s): Rebecca Albright (corresponding author) [1, 2]; Yuichiro Takeshita [1, 3]; David A. Koweek [1]; Aaron Ninokawa [4]; Kennedy Wolfe [5]; Tanya Rivlin [6, 7]; Yana Nebuchina [1]; Jordan Young [...]

Acidification‐induced changes in neurological function have been documented in several tropical marine fishes. Here, we investigate whether similar patterns of neurological impacts are observed in a temperate Pacific fish that naturally experiences regular and often large shifts in environmental pH/pCO2. In two laboratory experiments, we tested the effect of acidification, as well as pH/pCO2 variability, on gene expression in the brain tissue of a common temperate kelp forest/estuarine fish, Embiotoca jacksoni. Experiment 1 employed static pH treatments (target pH = 7.85/7.30), while Experiment 2 incorporated two variable treatments that oscillated around corresponding static treatments with the same mean (target pH = 7.85/7.70) in an eight‐day cycle (amplitude ± 0.15). We found that patterns of global gene expression differed across pH level treatments. Additionally, we identified differential expression of specific genes and enrichment of specific gene sets (GSEA) in comparisons of static pH treatments and in comparisons of static and variable pH treatments of the same mean pH. Importantly, we found that pH/pCO2 variability decreased the number of differentially expressed genes detected between high and low pH treatments, and that interindividual variability in gene expression was greater in variable treatments than static treatments. These results provide important confirmation of neurological impacts of acidification in a temperate fish species and, critically, that natural environmental variability may mediate the impacts of ocean acidification. [ABSTRACT FROM AUTHOR]

Measurements of pH and nitrate from the Southern Ocean Carbon and Climate Observations and Modeling array of profiling floats were used to assess the ratios of dissolved inorganic carbon (DIC) and nitrate (NO3) uptake during the spring to summer bloom period throughout the Southern Ocean. Two hundred and forty‐three bloom periods were observed by 115 floats from 30°S to 70°S. Similar calculations were made using the Takahashi surface DIC and nitrate climatology. To separate the effects of atmospheric CO2 exchange and mixing from phytoplankton uptake, the ratios of changes in DIC to nitrate of surface waters (ΔDIC/ΔNO3) were computed in the Biogeochemical Southern Ocean State Estimate (B‐SOSE) model. Phytoplankton uptake of DIC and nitrate are fixed in B‐SOSE at the Redfield Ratio (RR; 6.6 mol C/mol N). Deviations in the B‐SOSE ΔDIC/ΔNO3 must be due to non‐biological effects of CO2 gas exchange and mixing. ΔDIC/ΔNO3 values observed by floats and in the Takahashi climatology were corrected for the non‐biological effects using B‐SOSE. The corrected, in situ biological uptake ratio (C:N) occurs at values similar to the RR, with two major exceptions. North of 40°S biological DIC uptake is observed with little or no change in nitrate giving high C:N. In the latitude band at 55°S, the Takahashi data give a low C:N value, while floats are high. This may be due to a change in CO2 air‐sea exchange in this region from uptake during the Takahashi reference year of 2005 to outgassing of CO2 during the years sampled by floats. Plain Language Summary: Phytoplankton take up dissolved inorganic carbon (DIC) and nitrate as they grow. This results in a decrease in DIC and nitrate during the spring through summer bloom periods each year. The ratio of DIC to nitrate uptake is typically near 6.6 mol C/mol N, a value termed the Redfield Ratio (RR). Here, we used sensor data from an array of profiling floats deployed by the Southern Ocean Carbon and Climate Observations and Modeling program in the Southern Ocean to examine the ratio of C:N uptake by phytoplankton during 243 bloom periods from October through February. We find uptake occurred at values near the RR throughout the Southern Ocean, with two exceptions. North of 40°S, C:N ratios exceed the Redfield value, most likely due to phytoplankton production of a gel‐like organic matter deficient in nitrogen. Near 55°S in the Antarctic Southern Zone, an apparent increase in the C:N ratio over the past decade may reflect a change from an air‐sea flux of CO2 into the ocean to a flux out of the ocean. Key Points: Carbon:nitrate uptake ratios by phytoplankton are near the Redfield Ratio in Southern Ocean waters south of 40°SCarbon:nitrate uptake ratios north of 40°S are much higher, likely due to production of dissolved organic matter with little nitrogenA change in air‐sea CO2 flux during October to February from a sink in 2005 to a source in recent years may have occurred near 55°S [ABSTRACT FROM AUTHOR]

Spectrophotometric pH measurements of seawater (pHspec) are routinely made by the oceanographic community for a wide variety of studies. However, obtaining consistent measurements between laboratories that meet stringent thresholds such as the "weather" (± 0.02) and "climate" (± 0.003) standards, has been a challenge. One of the main sources of error for pHspec measurements is gas exchange of carbon dioxide during sample handling. Here, we present a simple method where pHspec measurements on the total scale are made directly in the sampling bottle, which minimizes sample handling errors because the solution is not transferred during analysis. We compared the performance of this method to a standard automated benchtop system on a hydrography cruise, and the two methods were consistent to 0.003 ± 0.0033 (1σ). This demonstrates that this simple method can produce pHspec that approaches climate quality, and comfortably meets weather quality standards. Additional benefits include high sample throughput, and the ability to rapidly quantify dye perturbation effects for each sample. The latter should be particularly useful for low salinity samples such as those taken from estuaries, insofar as modifications specific to the pHspec measurements of estuarine waters are employed. [ABSTRACT FROM AUTHOR]

Information on marine CO 2 system variability has been limited along the northeast Pacific Inside Passage despite the region's rich biodiversity, abundant fisheries, and developing aquaculture industry. Beginning in 2017, the Alaska Marine Highway System M/V Columbia has served as a platform for surface underway data collection while conducting twice weekly ∼1600 km transits between Bellingham, Washington, and Skagway, Alaska. Marine CO 2 system patterns were evaluated using measurements made over a 2-year period, which revealed the seasonal cycle as the dominant mode of temporal variability. The amplitude of this signal varied spatially and was modulated by the relative influences of tidal mixing, net community production, and the magnitude and character of freshwater input. Surface water pH T (total hydrogen ion scale) and aragonite saturation state (Ωarag) were determined using carbon dioxide partial pressure (p CO 2) data with alkalinity derived from a regional salinity-based relationship, which was evaluated using intervals of discrete seawater samples and underway pH measurements. High- p CO 2 , low-pH T , and corrosive Ωarag conditions (Ωarag<1) were seen during winter and within persistent tidal mixing zones, and corrosive Ωarag values were also seen in areas that receive significant glacial melt in summer. Biophysical drivers are shown to dominate p CO 2 variability over most of the Inside Passage except in areas highly impacted by glacial melt. pH T and Ωarag extremes were also characterized based on degrees of variability and severity, and regional differences were evident. Computations of the time of detection identified tidal mixing zones as strategic observing sites with relatively short time spans required to capture secular trends in seawater p CO 2 equivalent to the contemporary rise in atmospheric CO 2. Finally, estimates of anthropogenic CO 2 showed notable spatiotemporal variability. Changes in total hydrogen ion content ([H + ] T), pH T , and Ωarag over the industrial era and to an atmospheric p CO 2 level consistent with a 1.5 ∘ C warmer climate were theoretically evaluated. These calculations revealed greater absolute changes in [H + ] T and pH T in winter as opposed to larger Ωarag change in summer. The contemporary acidification signal everywhere along the Inside Passage exceeded the global average, with specific areas, namely Johnstone Strait and the Salish Sea, standing out as potential bellwethers for the emergence of biological ocean acidification (OA) impacts. Nearly half of the contemporary acidification signal is expected over the coming 15 years, with an atmospheric CO 2 trajectory that continues to be shaped by fossil–fuel development. [ABSTRACT FROM AUTHOR]

Climate change is causing decreases in pH and dissolved oxygen (DO) in coastal ecosystems. Canopy‐forming giant kelp can locally increase DO and pH through photosynthesis, with the most pronounced effect expected in surface waters where the bulk of kelp biomass resides. However, limited observations are available from waters in canopies and measurements at depth show limited potential of giant kelp to ameliorate chemical conditions. We quantified spatiotemporal variability of surface biogeochemistry and assessed the role of biological and physical drivers in pH and DO modification at two locations differing in hydrodynamics inside and outside of two kelp forests in Monterey Bay, California in summer 2019. pH, DO, dissolved inorganic carbon (DIC), and temperature were measured at and near the surface, in conjunction with physical parameters (currents and pressure), nutrients, and metrics of phytoplankton and kelp biological processes. DO and pH were highest, with lower DIC, at the surface inside kelp forests. However, differences inside vs. outside of kelp forests were small (DO 6–8%, pH 0.05 higher in kelp). The kelp forest with lower significant wave height and slower currents had greater modification of surface biogeochemistry as indicated by larger diel variation and slightly higher mean DO and pH, despite lower kelp growth rates. Differences between kelp forests and offshore areas were not driven by nutrients or phytoplankton. Although kelp had clear effects on biogeochemistry, which were modulated by hydrodynamics, the small magnitude and spatial extent of the effect limits the potential of kelp forests to mitigate acidification and hypoxia. [ABSTRACT FROM AUTHOR]

We introduce three new Empirical Seawater Property Estimation Routines (ESPERs) capable of predicting seawater phosphate, nitrate, silicate, oxygen, total titration seawater alkalinity, total hydrogen scale pH (pHT), and total dissolved inorganic carbon (DIC) from up to 16 combinations of seawater property measurements. The routines generate estimates from neural networks (ESPER_NN), locally interpolated regressions (ESPER_LIR), or both (ESPER_Mixed). They require a salinity value and coordinate information, and benefit from additional seawater measurements if available. These routines are intended for seawater property measurement quality control and quality assessment, generating estimates for calculations that require approximate values, original science, and producing biogeochemical property context from a data set. Relative to earlier LIR routines, the updates expand their functionality, including new estimated properties and combinations of predictors, a larger training data product including new cruises from the 2020 Global Data Analysis Project data product release, and the implementation of a first‐principles approach for quantifying the impacts of anthropogenic carbon on DIC and pHT. We show that the new routines perform at least as well as existing routines, and, in some cases, outperform existing approaches, even when limited to the same training data. Given that additional training data has been incorporated into these updated routines, these updates should be considered an improvement over earlier versions. The routines are intended for all ocean depths for the interval from 1980 to ~2030 c.e., and we caution against using the routines to directly quantify surface ocean seasonality or make more distant predictions of DIC or pHT. [ABSTRACT FROM AUTHOR]

Global‐scale ocean acidification has spurred interest in the capacity of seagrass ecosystems to increase seawater pH within crucial shoreline habitats through photosynthetic activity. However, the dynamic variability of the coastal carbonate system has impeded generalization into whether seagrass aerobic metabolism ameliorates low pH on physiologically and ecologically relevant timescales. Here we present results of the most extensive study to date of pH modulation by seagrasses, spanning seven meadows (Zostera marina) and 1000 km of U.S. west coast over 6 years. Amelioration by seagrass ecosystems compared to non‐vegetated areas occurred 65% of the time (mean increase 0.07 ± 0.008 SE). Events of continuous elevation in pH within seagrass ecosystems, indicating amelioration of low pH, were longer and of greater magnitude than opposing cases of reduced pH or exacerbation. Sustained elevations in pH of >0.1, comparable to a 30% decrease in [H+], were not restricted only to daylight hours but instead persisted for up to 21 days. Maximal pH elevations occurred in spring and summer during the seagrass growth season, with a tendency for stronger effects in higher latitude meadows. These results indicate that seagrass meadows can locally alleviate low pH conditions for extended periods of time with important implications for the conservation and management of coastal ecosystems. [ABSTRACT FROM AUTHOR]

Two Argo floats equipped with oxygen, chlorophyll (Chl), backscatter, and nitrate sensors conducted daily vertical profiles of the water column from a depth of 2000 m to the sea surface in the western North Pacific from January to April of 2018. Data for calibrating each sensor were obtained via shipboard sampling that occurred when the floats were deployed and recovered. Float backscatter observations were converted to particulate organic carbon (POC) concentrations using an empirical relationship derived from contemporaneous float profiles of backscatter and shipboard observations of suspended organic carbon particles. During the float deployment periods, repeated meteorological disturbances (storms) passed over the study area and caused the mixed layer to deepen. During these events, nitrate was entrained from deeper layers into the surface mixed layer, while Chl and POC in the surface mixed layer were redistributed into deeper layers. After the storms, the upper layer gradually restratified, nitrate concentrations in the surface layer decreased, and Chl and POC concentrations increased. When the floats observed the same water mass, the net community production within the euphotic layer (0-70 m), determined from the increases in POC, was 126-664 mg C m-2 d-1 (10.5-55.3 mmol C m-2 d-1) close to the values reported from a nearby area. The C/N ratio of the increase in POC and the decrease in nitrate was closed to the Redfield ratio, which indicates that the sensors were able to observe the net biochemical processes in this area despite the relatively low concentrations of nitrate and POC. To determine the fate of particles transported from the surface ocean to the twilight layer, the ratio of oxygen consumption and nitrate regeneration rates were compared. This O2/N ratio approached the Redfield ratio when the floats followed the same water mass continuously, but the consumption rate of POC was significantly lower than what would be expected based on the oxygen consumption and nitrate release rates. This suggests that dissolved organic carbon was the main substrate for the respiration in the twilight layer. [ABSTRACT FROM AUTHOR]

Global and local anthropogenic stressors such as climate change, acidification, overfishing, and pollution are expected to shift the benthic community composition of coral reefs from dominance by calcifying organisms to dominance by non‐calcifying algae. These changes could reduce the ability of coral reef ecosystems to maintain positive net calcium carbonate accretion. However, relationships between community composition and calcification rates remain unclear. We performed field experiments to quantify the metabolic rates of the two most dominant coral reef substrate types, live coral and dead coral substrate colonized by a mixed algal assemblage, using a novel underwater respirometer. Our results revealed that calcification rates in the daytime were similar for the live coral and dead coral substrate communities. However, in the dark, while live corals continued to calcify at slower rates, the dead coral substrate communities exhibited carbonate dissolution. Daytime net photosynthesis of the dead coral substrate communities was up to five times as much as for live corals, which we hypothesize may have created favorable conditions for the precipitation of carbonate minerals. We conclude that: (1) calcification from dead coral substrate communities can contribute to coral reef community calcification during the day, and (2) dead coral substrate communities can also contribute to carbonate mineral dissolution at night, decreasing ecosystem calcification over a diel cycle. This provides evidence that reefs could shift from slow, long‐term accretion of calcium carbonate to a state where large daily cycling of calcium carbonate occurs, but with little or no long‐term accumulation of the carbonate minerals needed to sustain the reef against erosional forces. [ABSTRACT FROM AUTHOR]

Equimolal tris (2-amino-2-hydroxymethyl-propane-1,3-diol) buffer in artificial seawater is a well characterized and commonly used standard for oceanographic pH measurements. We evaluated the stability of tris pH when stored in purportedly gas-impermeable bags across a variety of experimental conditions, including bag type and storage in air vs. seawater over 300 d. Bench-top spectrophotometric pH analysis revealed that the pH of tris stored in bags decreased at a rate of 0.0058±0.0011 yr-1 (mean slope ±95 % confidence interval of slope). The upper and lower bounds of expected pH change at t=365 d , calculated using the averages and confidence intervals of slope and intercept of measured pH change vs. time data, were - 0.0042 and - 0.0076 from initial pH. Analyses of total dissolved inorganic carbon confirmed that a combination of CO2 infiltration and/or microbial respiration led to the observed decrease in pH. Eliminating the change in pH of bagged tris remains a goal, yet the rate of pH change is lower than many processes of interest and demonstrates the potential of bagged tris for sensor calibration and validation of autonomous in situ pH measurements. [ABSTRACT FROM AUTHOR]

Ion‐sensitive field effect transistor‐based pH sensors have been shown to perform well in high frequency and long‐term ocean sampling regimes. The Honeywell Durafet is widely used due to its stability, fast response, and characterization over a large range of oceanic conditions. However, potentiometric pH monitoring is inherently complicated by the fact that the sensors require careful calibration. Offsets in calibration coefficients have been observed when comparing laboratory to field‐based calibrations and prior work has led to the recommendation that an in situ calibration be performed based on comparison to discrete samples. Here, we describe our work toward a self‐calibration apparatus integrated into a SeapHOx pH, dissolved oxygen, and CTD sensor package. This Self‐Calibrating SeapHOx is capable of autonomously recording calibration values from a high quality, traceable, primary reference standard: equimolar tris buffer. The Self‐Calibrating SeapHOx's functionality was demonstrated in a 6‐d test in a seawater tank at Scripps Institution of Oceanography (La Jolla, California, U.S.A.) and was successfully deployed for 2 weeks on a shallow, coral reef flat (Lizard Island, Australia). During the latter deployment, the tris‐based self‐calibration using 15 on‐board samples exhibited superior reproducibility to the standard spectrophotometric pH‐based calibration using > 100 discrete samples. Standard deviations of calibration pH using tris ranged from 0.002 to 0.005 whereas they ranged from 0.006 to 0.009 for the standard spectrophotometric pH‐based method; the two independent calibration methods resulted in a mean pH difference of 0.008. We anticipate that the Self‐Calibrating SeapHOx will be capable of autonomously providing climate quality pH data, directly linked to a primary seawater pH standard, and with improvements over standard calibration techniques. [ABSTRACT FROM AUTHOR]

Kelp forests are among the world's most productive marine ecosystems, and they have the potential to locally ameliorate ocean acidification (OA). In order to understand the contribution of kelp metabolism to local biogeochemistry, we must first quantify the natural variability and the relative contributions of physical and biological drivers to biogeochemical changes in space and time. We deployed an extensive instrument array in Monterey Bay, CA, inside and outside of a kelp forest to assess the degree to which giant kelp (Macrocystis pyrifera) locally ameliorates present‐day acidic conditions which we expect to be exacerbated by OA. Temperature, pH, and O2 variability occurred at semidiurnal, diurnal (tidal and diel), and longer upwelling event periods. Mean conditions were driven by offshore wind forcing and the delivery of upwelled water via nearshore internal bores. While near‐surface pH and O2 were similar inside and outside the kelp forest, surface pH was elevated inside the kelp compared to outside, suggesting that the kelp canopy locally increased surface pH. We observed the greatest acidification stress deeper in the water column where pCO2 reached levels as high as 1,300 μatm and aragonite undersaturation (ΩAr < 1) occurred on several occasions. At this site, kelp canopy modification of seawater properties, and thus any ameliorating effect against acidification, is greatest in a narrow band of surface water. The spatial disconnect between stress exposure at depth and reduction of acidification stress at the surface warrants further assessment of utilizing kelp forests as provisioners of local OA mitigation. Plain Language Summary: Anthropogenic emissions increase atmospheric carbon dioxide (CO2), leading to increased dissolved CO2 in the ocean. Elevated CO2 concentrations increase the ocean's acidity (ocean acidification), threatening marine ecosystems. When kelp photosynthesizes, CO2 is removed from seawater (reducing acidity), and oxygen is produced. We do not know if kelp photosynthesis is enough to reduce acidity and protect the local ecosystem from acidification. To understand how kelp impacts its local environment over time, depth, and space, we deployed a novel array of monitoring instruments in Monterey Bay, CA. We observed patterns in temperature, pH (acidity), and oxygen over days to weeks related to the strength of offshore winds and the movement of deep, cold, acidic, low‐oxygen water into the shallow kelp environment. Below the surface, pH and oxygen were similar inside and outside of the kelp forest. Interestingly, surface pH was slightly higher (less acidic) inside the kelp relative to outside, suggesting that the kelp canopy reduced acidity. However, we observed the highest acidity in deep water, indicating that the impact of the kelp canopy (reducing surface acidity) does not extend to where we see the greatest acidification. Therefore, the ability for kelp to lessen acidification stress may be greater at the surface. Key Points: Offshore processes drove event‐scale variability and mean pH, O2, and temperature inside and outside a central California kelp forestThe influence of the kelp canopy on local biogeochemistry was greatest within the upper several meters of the surfaceThere was a spatial disconnect between maximum exposure to acidification stress at the bottom and the potential refuge at the surface [ABSTRACT FROM AUTHOR]

Coral reefs are facing intensifying stressors, largely due to global increases in seawater temperature and decreases in pH. However, there is extensive environmental variability within coral reef ecosystems, which can impact how organisms respond to global trends. We deployed spatial arrays of autonomous sensors across distinct shallow coral reef habitats to determine patterns of spatiotemporal variability in seawater physicochemical parameters. Temperature and pH were positively correlated over the course of a day due to solar heating and light‐driven metabolism. The mean temporal and spatial ranges of temperature and pH were positively correlated across all sites, with different regimes of variability observed in different reef types. Ultimately, depth was a reliable predictor of the average diel ranges in both seawater temperature and pH. These results demonstrate that there is widespread environmental variability on diel timescales within coral reefs related to water column depth, which needs to be included in assessments of how global change will locally affect reef ecosystems. [ABSTRACT FROM AUTHOR]

The role of immune checkpoint inhibitors in metastatic lung cancer has been established in recent years and the pretherapeutic profiles of the tumor microenvironment in responders have been increasingly reported. The role of salvage surgery and the immune profiles of the posttherapeutic specimens in patients achieving an objective response have rarely been studied. We report a case of metastatic lung cancer treated by anti‐programmed death‐1 Ab followed by surgical resection. The immune status of the tumor was assessed, showing germinal center formation, memory B cell infiltration, and a high frequency of interferon gamma ‐secreting T cells. [ABSTRACT FROM AUTHOR]

• A 73-year-old man had hyperpigmentation on the dorsum of the tongue. • His-symptoms were consistent with addison's disease from metastatic adrenal tumors. • Hyperpigmentation in addison's disease can occur anywhere due to various stimuli. • Hyperpigmentation could indicate susceptibility to acute adrenal insufficiency. [ABSTRACT FROM AUTHOR]

Abstract: The Southern Ocean Carbon and Climate Observations and Modeling (SOCCOM) program currently operates >80 profiling floats equipped with pH sensors in the Southern Ocean. Theoretically, these floats have the potential to provide unique year‐around estimates of pCO2 derived from pH measurements. Here, we evaluate this approach in the field by comparing pCO2 estimates from pH sensors to directly measured pCO2. We first discuss data from a ship's underway system which covered a large range in temperature (2–30°C) and salinity (33.6–36.5) over 43 days. This pH sensor utilizes the same sensing technology but with different packaging than those on SOCCOM floats. The mean residual varied between −4.6 ± 4.1 and 8.6 ± 4.0 (1σ) μatm, depending on how the sensor was calibrated. However, the standard deviation of the residual, interpreted as the ability to track spatiotemporal variability, was consistently < 5 μatm and was independent of the calibration method. Second, we assessed the temporal stability of this approach by comparing pCO2 estimated from four floats over 3 years to the Hawaii Ocean Time‐series. Good agreement of −2.1 ± 10.4 (1σ) µatm was observed, with coherent seasonal cycles. These results demonstrate that pCO2 estimates derived from profiling float pH measurements appear capable of reproducing spatiotemporal variations in surface pCO2 measurements and should provide a powerful observational tool to complement current efforts to understand the seasonal to interannual variability of surface pCO2 in underobserved regions of the open ocean. [ABSTRACT FROM AUTHOR]

Performance of autonomous pH sensors is evaluated by comparing in situ data to independent bench-top measurements of pH and to co-located pH, O 2 , and p CO 2 sensors. While the best practice is always to deploy a properly calibrated sensor, the lengthy time period required for sensor conditioning and calibration often results in sensor deployment without comprehensive calibration. Quality control (QC) procedures are examined to determine the errors associated with different in situ calibration approaches and lay a framework for best practices. Sensor packages employing the Honeywell Durafet remained stable across multiple deployments for over nine months. However, sensor performance was often limited by biofouling. Regional empirical relationships for estimating carbonate system parameters are shown to enable identification of otherwise indistinguishable sensor offset and drift when multiple sensor types are co-located. Uncertainty is determined by calibration approach and must be quantified on a case-by-case basis. Our results indicate that the Durafet is capable of accuracy, relative to a chosen reference, of better than 0.03 pH units over multiple months. Accuracy is improved when a robust shore-side calibration is performed, an independent means of QC is available throughout a deployment, and effective biofouling prevention measures are taken. [ABSTRACT FROM AUTHOR]

The effect of Ocean Acidification (OA) on marine biota is quasi-predictable at best. While perturbation studies, in the form of incubations under elevated pCO2, reveal sensitivities and responses of individual species, one missing link in the OA story results from a chronic lack of pH data specific to a given species' natural habitat. Here, we present a compilation of continuous, high-resolution time series of upper ocean pH, collected using autonomous sensors, over a variety of ecosystems ranging from polar to tropical, open-ocean to coastal, kelp forest to coral reef. These observations reveal a continuum of month-long pH variability with standard deviations from 0.004 to 0.277 and ranges spanning 0.024 to 1.430 pH units. The nature of the observed variability was also highly site-dependent, with characteristic diel, semi-diurnal, and stochastic patterns of varying amplitudes. These biome-specific pH signatures disclose current levels of exposure to both high and low dissolved CO2, often demonstrating that resident organisms are already experiencing pH regimes that are not predicted until 2100. Our data provide a first step toward crystallizing the biophysical link between environmental history of pH exposure and physiological resilience of marine organisms to fluctuations in seawater CO2. Knowledge of this spatial and temporal variation in seawater chemistry allows us to improve the design of OA experiments: we can test organisms with a priori expectations of their tolerance guardrails, based on their natural range of exposure. Such hypothesis-testing will provide a deeper understanding of the effects of OA. Both intuitively simple to understand and powerfully informative, these and similar comparative time series can help guide management efforts to identify areas of marine habitat that can serve as refugia to acidification as well as areas that are particularly vulnerable to future ocean change. [ABSTRACT FROM AUTHOR]