Abstract. Topography and climate play an integral role in the spatial variability and annual dynamics of aboveground carbon sequestration. Despite knowledge of vegetation-climate-topography relationships on the landscape and hillslope scales, little is known about the influence of complex terrain coupled with hydrologic and topoclimatic variation on tree growth and physiology at the catchment scale. Climate change predictions for the semi-arid, western United States include increased temperatures, more frequent and extreme drought events, and decreases in snowpack, all of which put forests at risk of drought induced mortality and enhanced susceptibility to disturbance events. In this study, we determine how speciesspecific tree growth patterns and water use efficiency respond to interannual climate variability and how this response varies with topographic position. We found that Pinus contorta and Pinus ponderosa both show significant decreases in growth with water-limiting climate conditions, but complex terrain mediates this response by controlling moisture conditions in variable topoclimates. Foliar carbon isotope analyses show increased water use efficiency during drought for Pinus contorta, but indicate no significant difference in water use efficiency of Pinus ponderosa between a drought year and a non-drought year. The responses of the two pine species to climate indicate that semi-arid forests are especially susceptible to changes and risks posed by climate change and that topographic variability will likely play a significant role in determining the future vegetation patterns of semi-arid systems.

Multiple, simultaneous environmental changes, in climatic/abiotic factors, interacting species, and direct human influences, are impacting natural populations and thus biodiversity, ecosystem services, and evolutionary trajectories. Determining whether the magnitudes of the population impacts of abiotic, biotic, and anthropogenic drivers differ, accounting for their direct effects and effects mediated through other drivers, would allow us to better predict population fates and design mitigation strategies. We compiled 644 paired values of the population growth rate (λ) from high and low levels of an identified driver from demographic studies of terrestrial plants. Among abiotic drivers, natural disturbance (not climate), and among biotic drivers, interactions with neighboring plants had the strongest effects on λ. However, when drivers were combined into the 3 main types, their average effects on λ did not differ. For the subset of studies that measured both the average and variability of the driver, λ was marginally more sensitive to 1 SD of change in abiotic drivers relative to biotic drivers, but sensitivity to biotic drivers was still substantial. Similar impact magnitudes for abiotic/biotic/anthropogenic drivers hold for plants of different growth forms, for different latitudinal zones, and for biomes characterized by harsher or milder abiotic conditions, suggesting that all 3 drivers have equivalent impacts across a variety of contexts. Thus, the best available information about the integrated effects of drivers on all demographic rates provides no justification for ignoring drivers of any of these 3 types when projecting ecological and evolutionary responses of populations and of biodiversity to environmental changes.

Artificial photosynthesis strives to convert the energy of sunlight into sustainable, eco-friendly solar fuels. However, systems with light-driven water oxidation reaction (WOR) at pH = 1 are rare. Broadly used [Ru(bpy) 3 ] 2 + (bpy = 2,2'-bipyridine) photosensitizer has a fixed + 1.23 V potential which is insufficient to drive most water oxidation catalysts (WOCs) in acid, while Fe 2 O 3 , featuring the highly oxidizing holes, is not stable at low pH. Here, the key examples of Fe-based metal-organic framework (MOF) water oxidation photoelectrocatalysts active at pH = 1 are presented. Fe-MIL-126 and Fe MOF-dcbpy structures were formed with 4,4'-biphenyl dicarboxylate (bpdc), 2,2'-bipyridine-5,5'-dicarboxylate (dcbpy) linkers and their mixtures. Presence of dcbpy linkers allows integration of metalbased catalysts via coordination to 2,2'-bipyridine fragments. Fe-based MOFs were doped with Ru-based precursors to achieve highly active MOFs bearing [Ru(bpy)(dcbpy)(H 2 O) 2 ] 2 + WOC. Materials were analyzed with X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier transform infra-red (FTIR) spectroscopy, resonance Raman, X-ray absorption spectroscopy, fs optical pump-probe, electron paramagnetic resonance (EPR), diffuse reflectance and electric conductivity measurements and were modeled by band structure calculations. It is shown that under reaction conditions, Fe III and Ru III oxidation states are present, indicating rate-limiting electron transfer in MOF. Fe 3 O nodes emerge as photosensitizers able to drive prolonged O 2 evolution in acid. Further developments are possible via MOF's linker modification for enhanced light absorption, electrical conductivity, reduced MOF solubility in acid, Ru-WOC modification for faster WOC catalysis, or Ru-WOC substitution to 3d metal-based systems. The findings give further insight for development of light-driven water splitting systems based on Earth-abundant metals.

SummaryShifts in pollination may drive adaptive diversification of reproductive systems within plant lineages. The monophyletic genus Schiedea is a Hawaiian lineage of 32 extant species, with spectacular diversity in reproductive systems. Biotic pollination is the presumed ancestral condition, but this key element of the life history and its role in shaping reproductive systems has remained undocumented.We observed floral visitors to two species of Schiedea and conducted field experiments to test pollinator effectiveness. We used choice tests to compare attraction of pollinators to species hypothesized to be biotically vs wind-pollinated.Pseudoschrankia brevipalpis (Erebidae), a recently described moth species known only from O'ahu, visited hermaphroditic Schiedea kaalae and S. hookeri and removed nectar from their unique tubular nectary extensions. Pseudoschrankia brevipalpis effectively pollinates S. kaalae; single visits to emasculated flowers resulted in pollen transfer. In choice tests, P. brevipalpis strongly preferred these hermaphroditic species over two subdioecious species capable of wind pollination.A shift from biotic to abiotic pollination is clearly implicated in the diversification of reproductive systems within Schiedea. Abundant pollination by a previously unknown native moth in experimental and restored populations suggests the potential for restoration to re-establish native plant-pollinator interactions critical for production of outcrossed individuals with high fitness.