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.

Land‐ocean dissolved organic matter (DOM) transport is a significant and changing term in global biogeochemical cycles which is increasing as a result of human perturbation, including land‐use change. Knowledge of the behavior and fate of transported DOM is lacking, particularly in the tropics and subtropics where land‐use change is occurring rapidly. We used Parallel Factor (PARAFAC) Analysis to investigate how land‐use influenced the composition of the DOM pool along a subtropical land‐use gradient (from near‐pristine broadleaf forest to agri‐urban settings) in Belize, Central America. Three humic‐like and two protein‐like components were identified, each of which was present across land uses and environments. Land‐use mapping identified a strong (R² = 0.81) negative correlation between broadleaf forest and agri‐urban land. All PARAFAC components were positively associated with agri‐urban land‐use classes (cropland, grassland, and/or urban land), indicating that land‐use change from forested to agri‐urban exerts influence on the composition of the DOM pool. Humic‐like DOM exhibited linear accumulation with distance downstream and behaved conservatively in the coastal zone whilst protein‐like DOM exhibited nonlinear accumulation within the main river and nonconservative mixing in coastal waters, indicative of differences in reactivity. We used a hydrodynamic model to explore the potential of conservative humics to reach the region's environmentally and economically valuable coral reefs. We find that offshore corals experience short exposures (10 ± 11 days yr⁻¹) to large (∼120%) terrigenous DOM increases, whilst nearshore corals experience prolonged exposure (113 ± 24 days yr⁻¹) to relatively small (∼30%) terrigenous DOM increases.

Coral reefs are subject to degradation by multiple environmental stressors which are predicted to intensify. Stress can alter ecosystem composition, with shifts from hard coral to macroalgae dominated reefs often accompanied by an increase in soft corals and sponges. Such changes may alter net ecosystem metabolism and biogeochemistry by shifting the balance between photosynthesis, respiration, calcification and dissolution. We deployed high temporal resolution pH and dissolved oxygen (DO) sensors at four Caribbean reef sites with varying covers of hard and soft corals, sponges and macroalgae. The resultant data indicated that the strength of the “metabolic pulse”, specifically the co‐variation in daily pH and DO oscillations, was driven by the net balance of light ‐dependent and ‐independent metabolism. pH and DO were positively correlated over the diel cycle at coral dominated sites, suggesting that photosynthesis and respiration were the major controlling processes, and further indicated by agreement with a simple production:respiration model. Whereas, at a site with high macroalgal cover, pH and DO decoupling was observed during daylight hours. This indicates that an unidentified light‐driven process altered the expected pH:DO relationship. We hypothesize that this could be mediated by the higher levels of macroalgae, which either stimulated bacterial‐mediated carbonate dissolution via the production and release of allelopathic compounds or retained oxygen, evolved during photosynthesis, in the gaseous form in seawater (ebullition). Our work demonstrates that high resolution monitoring of pH and DO provides insight into coral reef biogeochemical functioning and can be key for understanding long‐term changes in coral reef metabolism.

A decrease in ocean pH of 0.3 units will likely double the proportion of dissolved copper (Cu) present as the free metal ion, Cu²⁺, the most bioavailable form of Cu, and one of the most common marine pollutants. We assess the impact of ocean acidification and Cu, separately and in combination, on calcification, photosynthesis and respiration of sub-colonies of a single tropical Stylophora pistillata colony. After 15 days of treatment, total calcification rates were significantly decreased in corals exposed to high seawater pCO₂ (∼1000-μatm, 2100 scenario) and at both ambient (1.6-1.9 nmols) and high (2.5-3.6 nmols) dissolved Cu concentrations compared to controls. The effect was increased when both stressors were combined. Coral respiration rates were significantly reduced by the combined stressors after 2 weeks of exposure, indicating the importance of experiment duration. It is therefore likely rising atmospheric CO₂ will exacerbate the negative effects of Cu pollution to S. pistillata.

Tropical coral reefs are both biologically diverse and economically important ecosystems, yet are under threat globally, facing a multitude of stressors including global warming, ocean acidification, nutrient loading, over-fishing and sedimentation. Reef building corals precipitate an aragonite skeleton (CaCO3), which forms the base of the coral reef ecosystem, but it is this skeleton, which makes them sensitive to changes in ocean pH. To precipitate their skeletons, corals raise their internal pH, as seawater pH decreases this increases the energy demands needed to facilitate calcification. Furthermore, reductions in coral calcification has significant implications for reef health, potentially altering community structure with reef-wide consequences. Global ocean pH is decreasing due to rising atmospheric concentrations of CO2, however, dynamic ecosystems, alongside carbon and freshwater input from land, may result in coastal ocean pH being lower than is predicted by open ocean models. While it is predicted than ocean pH will decrease by 0.3 units by 2100 if emissions are not curbed, coral reefs, particularly those near major river outflow, may already be experiencing pH values similar to that of future scenarios.Our aim was to determine the factors which influence pH in coastal reef systems and thus potentially mitigate or exacerbate atmospheric CO2 mediated ocean acidification. This was achieved by contrasting reefs in distinct environmental settings and collecting data over a sufficient temporal resolution to permit the identification of pertinent drivers. To accomplish this we deployed fixed point observatories in the distinct reefs of Belize (fore and back reef sites), Fiji and Dominica. These custom-built platforms were equipped with a spectrophotometric pH sensor and a conductivity, temperature and dissolved oxygen (CT-DO) sensor from which data was logged at 30-120 minute intervals.A strong diel cycle in pH, O2 and temperature was observed at all reef sites in response to the changing balance of respiration and photosynthesis. However, the range of these changes varied between the different sites - Belize fore reef (pH 7.849­ – 8.000), Belize back reef (pH 7.897 – 8.039), Fiji (pH 7.951 – 8.0950) and Dominica (pH 7.843 – 8.144). Meteorological conditions, such as wind direction, affected the amplitude of diurnal pH variability and its relationship with other parameters, likely by influencing mixing and the spatial distribution of seawater and freshwater endmembers. The relationship between pH and O2 varied between sites reflecting differences in ecosystem processes (e.g. calcification and primary production) and ecosystem composition (e.g. hard coral and algae cover, proximity to seagrass). Our data confirms that different reef sites are subject to varying degrees of ocean acidification and that controls on pH vary between environments. Furthermore, it highlights the need for widespread high-resolution monitoring to identify, and where possible enact protective measures, in vulnerable reef regions. As coral reefs continue to experience ocean acidification our data also serves to document baseline conditions against which future changes can be assessed. 

The Mesoamerican Barrier Reef, the second largest barrier reef in the world, is vitally important to the ecology and economy of Belize and neighbouring countries. Coral reefs are inherently vulnerable to ocean acidification and those exposed to significant riverine input may be under enhanced threat. In tropical rivers pCO2 levels may be linked to land use in their catchment, with conversion of pristine forest to agricultural land potentially enhancing carbon flux to the coastal ocean. We investigated the effect the Belize River may have on the carbonate chemistry of surrounding coastal ocean, applying a multidisciplinary methodology. Water samples were collected and measured for: total alkalinity; dissolved inorganic carbon (DIC); and δ13CDIC; and were complemented by pH and pCO2 data acquired from sensors mounted on an autonomous surface vehicle. Samples were collected from the source of the Belize river to the mouth and out past the barrier reef.  pCO2 measuring >1000-µatm at the mouth of the Belize River suggests local high levels of respiration and low pH water being discharged into the coastal ocean. δ13CDIC samples were taken to identify terrestrial DIC signatures and used in combination with sensor data to identify potential controls on coastal pH. There was a distinct difference in δ13CDIC along the river with a range of 27 ‰ to - 13‰, while coastal δ13CDIC was heavier with a range of  -11.5‰ to 1.5 ‰. These results demonstrate the complexity of processes that control coastal ocean acidification, which has implications for coastal economies that are heavily dependent on healthy coral reefs as a resource.