Posts Tagged 'methods'

Evaluating the sensor-equipped autonomous surface vehicle C-Worker 4 as a tool for identifying coastal ocean acidification and changes in carbonate chemistry

The interface between land and sea is a key environment for biogeochemical carbon cycling, yet these dynamic environments are traditionally under sampled. Logistical limitations have historically precluded a comprehensive understanding of coastal zone processes, including ocean acidification. Using sensors on autonomous platforms is a promising approach to enhance data collection in these environments. Here, we evaluate the use of an autonomous surface vehicle (ASV), the C-Worker 4 (CW4), equipped with pH and pCO2 sensors and with the capacity to mount additional sensors for up to 10 other parameters, for the collection of high-resolution data in shallow coastal environments. We deployed the CW4 on two occasions in Belizean coastal waters for 2.5 and 4 days, demonstrating its capability for high-resolution spatial mapping of surface coastal biogeochemistry. This enabled the characterisation of small-scale variability and the identification of sources of low pH/high pCO2 waters as well as identifying potential controls on coastal pH. We demonstrated the capabilities of the CW4 in both pre-planned “autonomous” mission mode and remote “manually” operated mode. After documenting platform behaviour, we provide recommendations for further usage, such as the ideal mode of operation for better quality pH data, e.g., using constant speed. The CW4 has a high power supply capacity, which permits the deployment of multiple sensors sampling concurrently, a shallow draught, and is highly controllable and manoeuvrable. This makes it a highly suitable tool for observing and characterising the carbonate system alongside identifying potential drivers and controls in shallow coastal regions.

Continue reading ‘Evaluating the sensor-equipped autonomous surface vehicle C-Worker 4 as a tool for identifying coastal ocean acidification and changes in carbonate chemistry’

Retrieving monthly and interannual total-scale pH (pHT) on theEast China Sea shelf using an artificial neural network:ANN-pHT-v1 (update)

While our understanding of pH dynamics has strongly progressed for open-ocean regions, for marginal seas such as the East China Sea (ECS) shelf progress has been constrained by limited observations and complex interactions between biological, physical and chemical processes. Seawater pH is a very valuable oceanographic variable but not always measured using high-quality instrumentation and according to standard practices. In order to predict total-scale pH (pH(T)) and enhance our understanding of the seasonal variability of pHT on the ECS shelf, an artificial neural network (ANN) model was developed using 11 cruise datasets from 2013 to 2017 with coincident observations of pHT, temperature (T), salinity (S), dissolved oxygen (DO), nitrate (N), phosphate (P) and silicate (Si) together with sampling position and time. The reliability of the ANN model was evaluated using independent observations from three cruises in 2018, and it showed a root mean square error accuracy of 0.04. The ANN model responded to T and DO errors in a positive way and S errors in a negative way, and the ANN model was most sensitive to S errors, followed by DO and T errors. Monthly water column pHT for the period 2000-2016 was retrieved using T, S, DO, N, P and Si from the Changjiang biology Finite-Volume Coastal Ocean Model (FVCOM). The agreement is good here in winter, while the reduced performance in summer can be attributed in large part to limitations of the Changjiang biology FVCOM in simulating summertime input variables.

Continue reading ‘Retrieving monthly and interannual total-scale pH (pHT) on theEast China Sea shelf using an artificial neural network:ANN-pHT-v1 (update)’

From particle attachment to space-filling coral skeletons

Reef-building corals and their aragonite (CaCO3) skeletons support entire reef ecosystems, yet their formation mechanism is poorly understood. Here we used synchrotron spectromicroscopy to observe the nanoscale mineralogy of fresh, forming skeletons from six species spanning all reef-forming coral morphologies: Branching, encrusting, massive, and table. In all species, hydrated and anhydrous amorphous calcium carbonate nanoparticles were precursors for skeletal growth, as previously observed in a single species. The amorphous precursors here were observed in tissue, between tissue and skeleton, and at growth fronts of the skeleton, within a low-density nano- or microporous layer varying in thickness from 7 to 20 µm. Brunauer-Emmett-Teller measurements, however, indicated that the mature skeletons at the microscale were space-filling, comparable to single crystals of geologic aragonite. Nanoparticles alone can never fill space completely, thus ion-by-ion filling must be invoked to fill interstitial pores. Such ion-by-ion diffusion and attachment may occur from the supersaturated calcifying fluid known to exist in corals, or from a dense liquid precursor, observed in synthetic systems but never in biogenic ones. Concomitant particle attachment and ion-by-ion filling was previously observed in synthetic calcite rhombohedra, but never in aragonite pseudohexagonal prisms, synthetic or biogenic, as observed here. Models for biomineral growth, isotope incorporation, and coral skeletons’ resilience to ocean warming and acidification must take into account the dual formation mechanism, including particle attachment and ion-by-ion space filling.

Continue reading ‘From particle attachment to space-filling coral skeletons’

Development of an autonomous dissolved inorganic carbon sensor for oceanic measurements

Since the industrial revolution the CO2 concentrations in the atmosphere have increased from 280 ppm to over 400 ppm, and each year the oceans take up approximately 25% of the annually emitted anthropogenic CO2. This increase in CO2 in the oceans has had a measure able impact on the marine carbonate system, and the resultant increase in the acidity of the ocean is a potential stressor for a range of ecosystems. In order to fully quantify the marine carbonate system there are four variables that can be measured, these are dissolved inorganic carbon (DIC), pH, total alkalinity and partial pressure of CO2. By measuring two of the four variables the others can be determined. Of these variables DIC is the only one without either an underway or in situ sensor, despite being one half of the preferred pairs for observing the carbonate system. To address this technological gap and increase the measurement coverage there is a clear need for an autonomous sensor capable of making quality measurements while having a robust, small physical size, and low power requirements. Presented here are the results of developmental work that has led to a full ocean depth rated autonomous DIC sensor, based on a microfluidic “Lab On Chip” (LOC) design. The final version of the DIC LOC sensor operates by acidifying < 1 ml of seawater, converting the DIC to CO2, which is diffused across a gas permeable membrane into an acceptor solution. The CO2 reacts with the acceptor resulting in a conductivity drop that is measured using a Capacitively Coupled Contactless Conductivity Detector (C4D). Each measurement takes ~15 minutes and the sensor can be set up to perform calibrations in situ. Laboratory testing demonstrated this system has a precision of < 1 µmol kg-1. The sensor was deployed as part of a large EU project aiming to detect a simulated sub-seabed leak of CO2. Over multiple deployments in the North Sea the sensor collected data used to locate the leak. A number of field tests have established the sensor has a precision of < 10 µmol kg-1. This work has demonstrated that this sensor offers potential to fill the current technological gap and collect data that will enhance understanding of the marine carbonate system.

Continue reading ‘Development of an autonomous dissolved inorganic carbon sensor for oceanic measurements’

Polymorphs and morphological changes during dissolution in aging of CaCO₃

In this study, an experimental setup was designed to achieve accelerated aging of CaCO₃ crystals in the laboratory to simulate the aging of calcite precipitates and biominerals caused by ocean acidification. CaCO₃ was formed in the calcium aqueous solution through the inflow of CO₂ from the atmosphere, and CaCO₃ aging was conducted in the absence and presence of polyacrylic acid (PAA). When PAA increased, the maximum amount of deposited CaCO₃ reduced, and the time to reach the maximum CaCO₃ deposition was longer. However, there was a late onset of dissolution during aging. In the absence of PAA, typical rhombohedra eroded in the form of a plate or irregular sheet, but in the presence of PAA, some calcite nanofibers broke into nanoparticles. During aging, the calcite polymorph was not changed, but the relative intensity of the (104) plane to other peaks became weaker. This observation implied that the crack in the calcite crystals propagated mainly in the (104) plane during aging. This experimental setup demonstrated that CaCO₃ aging caused by ocean acidification can be simulated in the laboratory.

Continue reading ‘Polymorphs and morphological changes during dissolution in aging of CaCO₃’

Experimental techniques to assess coral physiology in situ: current approaches and novel insights

Coral reefs are declining worldwide due to global changes in the marine environment. The increasing frequency and severity of massive bleaching events in the tropics are highlighting the need to better understand the stages of coral physiological responses to extreme conditions. Moreover, like many other coastal regions, coral reef ecosystems are facing additional localized anthropogenic issues such as nutrient loading, increased turbidity, and coastal development. The changes in coral metabolism under local or global stress conditions is studied largely through laboratory manipulation and field observations. Different strategies have been developed to measure the health status of a damaged reef, ranging from the resolution of individual polyps to an entire coral community, but techniques for measuring coral physiology in situ are not yet widely implemented. For instance, while there are many studies of the coral holobiont response in single or limited-number multiple stressor experiments, they provide only partial insights to metabolic performance under more complex temporally and spatially variable natural conditions. Here, we discuss the current status of coral reefs and their global and local stressors in the context of current experimental techniques that measure core processes in coral metabolism (respiration, photosynthesis, and biocalcification) and their role in indicating the health status of colonies and communities. The state of the art of in situ techniques for experimental and monitoring purposes is explored. We highlight the need to improve the capability of in situ studies in order to better understand the resilience and stress response of corals under multiple global and local scale stressors.

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Ideas and perspectives: when ocean acidification experiments are not the same, reproducibility is not tested

Can experimental studies on the impacts of ocean acidification be trusted? That question was raised in early 2020 when a high-profile paper failed to corroborate previously-observed impacts of high CO2 on the behavior of coral reef fish. New information on the methodologies used in the replicated studies now provides the explanation: the experimental conditions were substantially different. High sensitivity to test conditions is characteristic of ocean acidification research; such response variability shows that effects are complex, interacting with many other factors. Open-minded assessment of all research results, both negative and positive, remains the best way to develop process-based understanding of those responses. Whilst replication studies can provide valuable insights and challenges, they can unfortunately also be counter-productive to scientific advancement if carried out in a spirit of confrontation rather than collaboration.

Continue reading ‘Ideas and perspectives: when ocean acidification experiments are not the same, reproducibility is not tested’

Spectrophotometric loop flow analyzer for high-precision measurement of seawater pH


  • Spectrophotometric seawater pH analyzer was developed based on loop flow analysis.
  • The pH analyzer can be used for underway and in situ measurements
  • The precision of in situ measurement system first reached 0.0004.
  • The pH analyzer showed good stability and accuracy in various environments.


Automated instrument for long-term measurement of seawater pH is important for documenting the changes of the marine carbonate system and the impacts of ocean acidification. An automated pH analyzer based on loop flow analysis (LFA-pH) was developed to achieve precise and accurate measurements of seawater pH. The circulating loop allows complete mixing of an indicator and seawater, constant mixing volume of two solutions, and correcting indicator perturbation for each measurement. During laboratory testing, the LFA-pH precision achieved 0.0004, and the accuracy was 0.0017±0.0038 compared with the certified standard buffer at different temperatures. During the 59 day underway measurement across the mid and high latitudes, more than 2500 pH measurements were carried out. LFA-pH showed good stability with high temperature and salinity changes, and measurement results were consistent with the discrete surface seawater pH measurement data. In situ testing of two LFA-pHs was completed near the Zhongyuan pier in Qingdao. The average pH offset between the two LFA-pHs was 0.0010±0.0032 (n=788), with the accuracies of the two LFA-pHs of 0.0012±0.0033 and 0.0005±0.0035 compared to discrete measurements. For continuous measurement, the average power consumption is 3.6 W at a 10 min measurement frequency. Given its low power consumption, high precision, and accuracy, FLA-pH could be adapted for underway and in situ measurements of ocean acidification observations.

Continue reading ‘Spectrophotometric loop flow analyzer for high-precision measurement of seawater pH’

Reaching consensus on assessments of ocean acidification trends

Scientists are working to establish a common methodology for evaluating rates of change in—and the various mechanisms that affect—acidification across ocean environments.

Media coverage concerning carbon dioxide (CO2) emissions into Earth’s atmosphere most often focuses on how these emissions affect climate and weather patterns. However, atmospheric CO2 is also the primary driver for ocean acidification, because the products of atmospheric CO2 dissolving into seawater reduce seawater’s pH and its concentration of carbonate ions. Since the beginning of the Industrial Revolution, the acidity of the ocean has increased by over 30%.

Some organisms in the ocean may struggle to adapt to increasingly acidified conditions, and even resilient life-forms may have a harder time finding food. Higher CO2 levels in ocean water also make it difficult for shellfish to build their shells and corals to form their reefs, both of which are made of carbonate compounds.Ocean acidification affects the overall health of marine ecosystems as well as societal concerns about food security.Ocean acidification, which affects the overall health of marine ecosystems as well as societal concerns about food security, has emerged as a major concern for decision-makers on local, regional, and global scales. Indeed, ocean acidification is now a headline climate indicator for the World Meteorological Organization.

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Autonomous measurement of seawater total alkalinity as an enhancement of ocean carbon observations: from performance characterization to long-term field deployment

Since around the mid of the 18th century, the global atmospheric carbon dioxide (CO2) concentration has significantly increased due to anthropogenic activities. For 2018, around 11.5 GtC yr−1 were emitted by fossil fuel combustion and cement production, and land use changes. A sink for the atmospheric CO2 is the ocean, which has taken up around 2.6 GtC yr−1 in 2018. The relative good understanding of the current global mean oceanic uptake of anthropogenic CO2 is contrasted by a lack of knowledge how the natural carbon cycle will respond regionally to changes introduced by anthropogenic CO2 emissions, like global warming, ocean acidification or ocean deoxygenation. In view of the central role of the oceanic CO2 sink and its vulnerability to these changes, extensive ocean carbon observations are necessary. Over several years, the Ships of Opportunity (SOOP) network provides high-quality CO2 partial pressure (p(CO2)) data of the surface ocean, and, therefore, forms the backbone of the global observation system for the oceanic CO2 sink. However, to get full insight into the marine CO2 system, at least two of the four measurable carbonate variables are required, which are p(CO2), total alkalinity (AT), dissolved inorganic carbon (CT) and pH. The so far common workaround is the prediction of AT by using established temperature-salinity based parameterizations. However, compared with direct measurements, this procedure leads to higher uncertainties and spatiotemporal biases. Therefore, autonomous SOOP-based AT measurements are of great interest and, in the end, should enhance ocean carbon observations. In order to achieve this enhancement, this thesis goals to provide an example of a successful implementation of a novel autonomous analyzer for seawater AT, the CONTROS HydroFIA TA (-4H-JENA engineering GmbH, Germany), on a Carbon-SOOP station operating in the subpolar North Atlantic (together with fundamental guidelines and recommendations leading to high-quality AT data).

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Ocean acidification in the IPCC AR5 WG II

OUP book