Coral reefs benefit from reduced land-sea impacts under ocean warming.

Coral reef ecosystems are being fundamentally restructured by local human impacts and climate-driven marine heatwaves that trigger mass coral bleaching and mortality1. Reducing local impacts can increase reef resistance to and recovery from bleaching2. However, resource managers lack clear advice on targeted actions that best support coral reefs under climate change3 and sector-based governance means most land- and sea-based management efforts remain siloed4. Here we combine surveys of reef change with a unique 20-year time series of land-sea human impacts that encompassed an unprecedented marine heatwave in Hawai'i. Reefs with increased herbivorous fish populations and reduced land-based impacts, such as wastewater pollution and urban runoff, had positive coral cover trajectories predisturbance. These reefs also experienced a modest reduction in coral mortality following severe heat stress compared to reefs with reduced fish populations and enhanced land-based impacts. Scenario modelling indicated that simultaneously reducing land-sea human impacts results in a three- to sixfold greater probability of a reef having high reef-builder cover four years postdisturbance than if either occurred in isolation. International efforts to protect 30% of Earth's land and ocean ecosystems by 2030 are underway5. Our results reveal that integrated land-sea management could help achieve coastal ocean conservation goals and provide coral reefs with the best opportunity to persist in our changing climate.

Role of Electrostatics in Influencing the Pathway by Which the Excited State of [Ru(bpy)3]2+ Is Deactivated by Ferrocene Derivatives.

Excited states of tris(2,2'-bipyridine)ruthenium(II), [Ru(bpy)3]2+, can be deactivated by a wide range of ferrocene derivatives. The pathway by which deactivation takes place, either energy transfer (EnT) or electron transfer (ET), depends on several factors inherent to each specific donor-acceptor (D···A) system. In this work, we provide mechanistic insight into bimolecular quenching between [Ru(bpy)3]2+* and several ferrocene (Fc) derivatives in a variety of solvents. By introducing various functional groups onto the cyclopentadienyl ring of ferrocene, the chemical properties of the organometallic complexes were altered by tuning the oxidation potentials and charge of the iron complexes, and the manner in which the [Ru(bpy)3]2+ excited state is quenched by each ferrocene complex in solvents of various dielectric constants, including anhydrous acetonitrile (ACN), dimethylformamide (DMF), dimethyl sulfoxide (DMSO), and water (pH 10), was assessed. Through the use of transient absorption (TA) spectroscopy, the mechanism of [Ru(bpy)3]2+* quenching by each of five ferrocene derivatives (i.e., either EnT or ET) in the aforementioned solvents was evaluated. On the basis of these studies, electrostatic factors relating to the charge on the ferrocene moiety were found to influence the quenching pathway(s) for the [Ru(bpy)3]2+···Fc systems under interrogation. When the ferrocene moiety is positively charged, the [Ru(bpy)3]2+ excited state is quenched by EnT to Fc, while when the ferrocene moiety is neutral or negatively charged, the [Ru(bpy)3]2+ excited state is quenched via reductive ET.

pH-Driven Mechanistic Switching from Electron Transfer to Energy Transfer between [Ru(bpy)3]2+ and Ferrocene Derivatives.

The metal-to-ligand charge transfer excited states of [Ru(bpy)3]2+ (bpy = 2,2'-bipyridine) may be deactivated via energy transfer or electron transfer with ferrocene derivatives in aqueous conditions. Stern-Volmer quenching analysis revealed that the rate constant for [Ru(bpy)3]2+ excited-state quenching depends on solution pH when a ferrocenyl-amidinium derivative (Fc-am) containing a proton-responsive functionality tethered to the ferrocene center was present. By contrast, the rate constant with which the [Ru(bpy)3]2+ excited state is quenched by an analogous ferrocene derivative (ferrocenyl-trimethylammonium, Fc-mam) that lacks a protonic group does not depend on pH. These results show that the presence (or absence) of a readily transferrable proton modulates quenching rate constants in bimolecular events involving [Ru(bpy)3]2+ and ferrocene. More surprisingly, transient absorption spectroscopy reveals that the mechanism by which the [Ru(bpy)3]2+ excited state is quenched by Fc-am appears to be modulated by solution proton availability, switching from energy transfer at low pH when Fc-am is protonated, to electron transfer at high pH when Fc-am is deprotonated. The mechanistic switching that is observed for this system cannot be aptly explained using a simple driving force dependence argument, suggesting that more subtle factors dictate the pathway by which the [Ru(bpy)3]2+ excited state is deactivated by ferrocene in aqueous solutions.

Spatial distribution and sources of nutrients at two coastal developments in South Kohala, Hawai'i.

Nutrient sources to coastal waters with coral reefs are not well-characterized. This study documented spatial distributions of nutrients within coastal waters along two developments with coral reefs, and identified nutrient sources through nutrient mixing plots, δ15N measurements in macroalgal tissue, and NO3- stable isotope mixing models. Nutrients decreased from fresh groundwaters to offshore waters, with some surface waters higher in concentrations than benthic ones. Conservative and non-conservative mixing between fresh and ocean waters occurred, the latter suggestive of local nutrient sources and biological removal. δ15N in macroalgal tissue and NO3- concurred that fresh groundwater, ocean water, and fertilizers were dominant nutrient sources. Benthic salinity and NO3- + NO2- concentrations illustrated that submarine groundwater discharge delivered nutrients to reefs in pulses ranging from minutes to days. Information generated from this study is imperative for developing management actions to improve water quality and make coral reefs more resilient to stressors.

Coral taxonomy and local stressors drive bleaching prevalence across the Hawaiian Archipelago in 2019.

The Hawaiian Archipelago experienced a moderate bleaching event in 2019-the third major bleaching event over a 6-year period to impact the islands. In response, the Hawai'i Coral Bleaching Collaborative (HCBC) conducted 2,177 coral bleaching surveys across the Hawaiian Archipelago. The HCBC was established to coordinate bleaching monitoring efforts across the state between academic institutions, non-governmental organizations, and governmental agencies to facilitate data sharing and provide management recommendations. In 2019, the goals of this unique partnership were to: 1) assess the spatial and temporal patterns of thermal stress; 2) examine taxa-level patterns in bleaching susceptibility; 3) quantify spatial variation in bleaching extent; 4) compare 2019 patterns to those of prior bleaching events; 5) identify predictors of bleaching in 2019; and 6) explore site-specific management strategies to mitigate future bleaching events. Both acute thermal stress and bleaching in 2019 were less severe overall compared to the last major marine heatwave events in 2014 and 2015. Bleaching observed was highly site- and taxon-specific, driven by the susceptibility of remaining coral assemblages whose structure was likely shaped by previous bleaching and subsequent mortality. A suite of environmental and anthropogenic predictors was significantly correlated with observed bleaching in 2019. Acute environmental stressors, such as temperature and surface light, were equally important as previous conditions (e.g. historical thermal stress and historical bleaching) in accounting for variation in bleaching during the 2019 event. We found little evidence for acclimation by reefs to thermal stress in the main Hawaiian Islands. Moreover, our findings illustrate how detrimental effects of local anthropogenic stressors, such as tourism and urban run-off, may be exacerbated under high thermal stress. In light of the forecasted increase in severity and frequency of bleaching events, future mitigation of both local and global stressors is a high priority for the future of corals in Hawai'i.

A linked land-sea modeling framework to inform ridge-to-reef management in high oceanic islands.

Declining natural resources have led to a cultural renaissance across the Pacific that seeks to revive customary ridge-to-reef management approaches to protect freshwater and restore abundant coral reef fisheries. Effective ridge-to-reef management requires improved understanding of land-sea linkages and decision-support tools to simultaneously evaluate the effects of terrestrial and marine drivers on coral reefs, mediated by anthropogenic activities. Although a few applications have linked the effects of land cover to coral reefs, these are too coarse in resolution to inform watershed-scale management for Pacific Islands. To address this gap, we developed a novel linked land-sea modeling framework based on local data, which coupled groundwater and coral reef models at fine spatial resolution, to determine the effects of terrestrial drivers (groundwater and nutrients), mediated by human activities (land cover/use), and marine drivers (waves, geography, and habitat) on coral reefs. We applied this framework in two 'ridge-to-reef' systems (Ha'ena and Ka'upulehu) subject to different natural disturbance regimes, located in the Hawaiian Archipelago. Our results indicated that coral reefs in Ka'upulehu are coral-dominated with many grazers and scrapers due to low rainfall and wave power. While coral reefs in Ha'ena are dominated by crustose coralline algae with many grazers and less scrapers due to high rainfall and wave power. In general, Ka'upulehu is more vulnerable to land-based nutrients and coral bleaching than Ha'ena due to high coral cover and limited dilution and mixing from low rainfall and wave power. However, the shallow and wave sheltered back-reef areas of Ha'ena, which support high coral cover and act as nursery habitat for fishes, are also vulnerable to land-based nutrients and coral bleaching. Anthropogenic sources of nutrients located upstream from these vulnerable areas are relevant locations for nutrient mitigation, such as cesspool upgrades. In this study, we located coral reefs vulnerable to land-based nutrients and linked them to priority areas to manage sources of human-derived nutrients, thereby demonstrating how this framework can inform place-based ridge-to-reef management.

Resetting predator baselines in coral reef ecosystems.

What did coral reef ecosystems look like before human impacts became pervasive? Early efforts to reconstruct baselines resulted in the controversial suggestion that pristine coral reefs have inverted trophic pyramids, with disproportionally large top predator biomass. The validity of the coral reef inverted trophic pyramid has been questioned, but until now, was not resolved empirically. We use data from an eight-year tag-recapture program with spatially explicit, capture-recapture models to re-examine the population size and density of a key top predator at Palmyra atoll, the same location that inspired the idea of inverted trophic biomass pyramids in coral reef ecosystems. Given that animal movement is suspected to have significantly biased early biomass estimates of highly mobile top predators, we focused our reassessment on the most mobile and most abundant predator at Palmyra, the grey reef shark (Carcharhinus amblyrhynchos). We estimated a density of 21.3 (95% CI 17.8, 24.7) grey reef sharks/km2, which is an order of magnitude lower than the estimates that suggested an inverted trophic pyramid. Our results indicate that the trophic structure of an unexploited reef fish community is not inverted, and that even healthy top predator populations may be considerably smaller, and more precarious, than previously thought.

Growth and life history variability of the grey reef shark (Carcharhinus amblyrhynchos) across its range.

For broadly distributed, often overexploited species such as elasmobranchs (sharks and rays), conservation management would benefit from understanding how life history traits change in response to local environmental and ecological factors. However, fishing obfuscates this objective by causing complex and often mixed effects on the life histories of target species. Disentangling the many drivers of life history variability requires knowledge of elasmobranch populations in the absence of fishing, which is rarely available. Here, we describe the growth, maximum size, sex ratios, size at maturity, and offer a direct estimate of survival of an unfished population of grey reef sharks (Carcharhinus amblyrhynchos) using data from an eight year tag-recapture study. We then synthesized published information on the life history of C. amblyrhynchos from across its geographic range, and for the first time, we attempted to disentangle the contribution of fishing from geographic variation in an elasmobranch species. For Palmyra's unfished C. amblyrhynchos population, the von Bertalanffy growth function (VBGF) growth coefficient k was 0.05 and asymptotic length L∞ was 163.3 cm total length (TL). Maximum size was 175.5 cm TL from a female shark, length at maturity was estimated at 116.7-123.2 cm TL for male sharks, maximum lifespan estimated from VBGF parameters was 18.1 years for both sexes combined, and annual survival was 0.74 year-1. Consistent with findings from studies on other elasmobranch species, we found significant intraspecific variability in reported life history traits of C. amblyrhynchos. However, contrary to what others have reported, we did not find consistent patterns in life history variability as a function of biogeography or fishing. Ultimately, the substantial, but not yet predictable variability in life history traits observed for C. amblyrhynchos across its geographic range suggests that regional management may be necessary to set sustainable harvest targets and to recover this and other shark species globally.

From Reef to Table: Social and Ecological Factors Affecting Coral Reef Fisheries, Artisanal Seafood Supply Chains, and Seafood Security.

Ocean and coastal ecosystems provide critical fisheries, coastal protection, and cultural benefits to communities worldwide, but these services are diminishing due to local and global threats. In response, place-based strategies involve communities and resource users in management have proliferated. Here, we present a transferable community-based approach to assess the social and ecological factors affecting resource sustainability and food security in a small-scale, coral reef fishery. Our results show that this small-scale fishery provides large-scale benefits to communities, including 7,353 ± 1547 kg yr(-1) (mean ± SE) of seafood per year, equating to >30,000 meals with an economic value of $78,432. The vast majority of the catch is used for subsistence, contributing to community food security: 58% is kept, 33.5% is given away, and 8.5% is sold. Our spatial analysis assesses the geographic distribution of community beneficiaries from the fishery (the "food shed" for the fishery), and we document that 20% of seafood procured from the fishery is used for sociocultural events that are important for social cohesion. This approach provides a method for assessing social, economic, and cultural values provided by small-scale food systems, as well as important contributions to food security, with significant implications for conservation and management. This interdisciplinary effort aims to demonstrate a transferable participatory research approach useful for resource-dependent communities as they cope with socioeconomic, cultural, and environmental change.

Benthic communities at two remote Pacific coral reefs: effects of reef habitat, depth, and wave energy gradients on spatial patterns.

Kingman Reef and Palmyra Atoll in the central Pacific are among the most remote coral reefs on the planet. Here we describe spatial patterns in their benthic communities across reef habitats and depths, and consider these in the context of oceanographic gradients. Benthic communities at both locations were dominated by calcifying organisms (54-86% cover), namely hard corals (20-74%) and crustose coralline algae (CCA) (10-36%). While turf algae were relatively common at both locations (8-22%), larger fleshy macroalgae were virtually absent at Kingman (<1%) and rare at Palmyra (0.7-9.3%). Hard coral cover was higher, but with low diversity, in more sheltered habitats such as Palmyra's backreef and Kingman's patch reefs. Almost exclusive dominance by slow-growing Porites on Kingman's patch reefs provides indirect evidence of competitive exclusion, probably late in a successional sequence. In contrast, the more exposed forereef habitats at both Kingman and Palmyra had higher coral diversity and were characterized by fast-growing corals (e.g., Acropora and Pocillopora), indicative of more dynamic environments. In general at both locations, soft coral cover increased with depth, likely reflecting increasingly efficient heterotrophic abilities. CCA and fleshy macroalgae cover decreased with depth, likely due to reduced light. Cover of other calcified macroalgae, predominantly Halimeda, increased with depth. This likely reflects the ability of many calcifying macroalgae to efficiently harvest light at deeper depths, in combination with an increased nutrient supply from upwelling promoting growth. At Palmyra, patterns of hard coral cover with depth were inconsistent, but cover peaked at mid-depths at Kingman. On Kingman's forereef, benthic community composition was strongly related to wave energy, with hard coral cover decreasing and becoming more spatially clustered with increased wave energy, likely as a result of physical damage leading to patches of coral in localized shelter. In contrast, the cover of turf algae at Kingman was positively related to wave energy, reflecting their ability to rapidly colonize newly available space. No significant patterns with wave energy were observed on Palmyra's forereef, suggesting that a more detailed model is required to study biophysical coupling there. Kingman, Palmyra, and other remote oceanic reefs provide interesting case studies to explore biophysical influences on benthic ecology and dynamics.