Diffusion controls the ventilation of a Pacific Shadow Zone above abyssal overturning.

Mid-depth North Pacific waters are rich in nutrients and respired carbon accumulated over centuries. The rates and pathways with which these waters exchange with the surface ocean are uncertain, with divergent paradigms of the Pacific overturning: one envisions bottom waters upwelling to 1.5 km depth; the other confines overturning beneath a mid-depth Pacific shadow zone (PSZ) shielded from mean advection. Here global inverse modelling reveals a PSZ where mean ages exceed 1400 years with overturning beneath. The PSZ is supplied primarily by Antarctic and North-Atlantic ventilated waters diffusing from below and from the south. Half of PSZ waters re-surface in the Southern Ocean, a quarter in the subarctic Pacific. The abyssal North Pacific, despite strong overturning, has mean re-surfacing times also exceeding 1400 years because of diffusion into the overlying PSZ. These results imply that diffusive transports - distinct from overturning transports - are a leading control on Pacific nutrient and carbon storage.

Decadal trends in the ocean carbon sink.

Measurements show large decadal variability in the rate of [Formula: see text] accumulation in the atmosphere that is not driven by [Formula: see text] emissions. The decade of the 1990s experienced enhanced carbon accumulation in the atmosphere relative to emissions, while in the 2000s, the atmospheric growth rate slowed, even though emissions grew rapidly. These variations are driven by natural sources and sinks of [Formula: see text] due to the ocean and the terrestrial biosphere. In this study, we compare three independent methods for estimating oceanic [Formula: see text] uptake and find that the ocean carbon sink could be responsible for up to 40% of the observed decadal variability in atmospheric [Formula: see text] accumulation. Data-based estimates of the ocean carbon sink from [Formula: see text] mapping methods and decadal ocean inverse models generally agree on the magnitude and sign of decadal variability in the ocean [Formula: see text] sink at both global and regional scales. Simulations with ocean biogeochemical models confirm that climate variability drove the observed decadal trends in ocean [Formula: see text] uptake, but also demonstrate that the sensitivity of ocean [Formula: see text] uptake to climate variability may be too weak in models. Furthermore, all estimates point toward coherent decadal variability in the oceanic and terrestrial [Formula: see text] sinks, and this variability is not well-matched by current global vegetation models. Reconciling these differences will help to constrain the sensitivity of oceanic and terrestrial [Formula: see text] uptake to climate variability and lead to improved climate projections and decadal climate predictions.

Biological uptake and reversible scavenging of zinc in the global ocean.

Zinc (Zn) is a key micronutrient for marine phytoplankton, with a global distribution that is similar to silicic acid. The processes that govern this relationship, despite the very different biological cycling of Zn and silica, remain poorly understood. Here, we use diagnostic and mechanistic models to show that only a combination of Southern Ocean biological uptake and reversible scavenging of Zn onto sinking particles can explain the observations. The distinction between organic and adsorbed Zn can also reconcile the vertical distribution and mass balance of Zn isotopes, which previously appeared at odds. This holistic understanding explains the Zn deficiencies observed throughout the low-latitude ocean and implies a greater sensitivity of the marine Zn cycle to climate-driven changes in organic matter cycling than previously recognized.

Recent increase in oceanic carbon uptake driven by weaker upper-ocean overturning.

The ocean is the largest sink for anthropogenic carbon dioxide (CO2), having absorbed roughly 40 per cent of CO2 emissions since the beginning of the industrial era. Recent data show that oceanic CO2 uptake rates have been growing over the past decade, reversing a trend of stagnant or declining carbon uptake during the 1990s. Here we show that ocean circulation variability is the primary driver of these changes in oceanic CO2 uptake over the past several decades. We use a global inverse model to quantify the mean ocean circulation during the 1980s, 1990s and 2000s, and then estimate the impact of decadal circulation changes on the oceanic CO2 sink using a carbon cycling model. We find that during the 1990s an enhanced upper-ocean overturning circulation drove increased outgassing of natural CO2, thus weakening the global CO2 sink. This trend reversed during the 2000s as the overturning circulation weakened. Continued weakening of the upper-ocean overturning is likely to strengthen the CO2 sink in the near future by trapping natural CO2 in the deep ocean, but ultimately may limit oceanic uptake of anthropogenic CO2.

Carbon isotope records reveal precise timing of enhanced Southern Ocean upwelling during the last deglaciation.

The Southern Ocean plays a prominent role in the Earth's climate and carbon cycle. Changes in the Southern Ocean circulation may have regulated the release of CO2 to the atmosphere from a deep-ocean reservoir during the last deglaciation. However, the path and exact timing of this deglacial CO2 release are still under debate. Here we present measurements of deglacial surface reservoir ¹4C age changes in the eastern Pacific sector of the Southern Ocean, obtained by ¹4C dating of tephra deposited over the marine and terrestrial regions. These results, along with records of foraminifera benthic-planktic ¹4C age and δ¹³C difference, provide evidence for three periods of enhanced upwelling in the Southern Ocean during the last deglaciation, supporting the hypothesis that Southern Ocean upwelling contributed to the deglacial rise in atmospheric CO2. These independently dated marine records suggest synchronous changes in the Southern Ocean circulation and Antarctic climate during the last deglaciation.

Recent changes in the ventilation of the southern oceans.

Surface westerly winds in the Southern Hemisphere have intensified over the past few decades, primarily in response to the formation of the Antarctic ozone hole, and there is intense debate on the impact of this on the ocean's circulation and uptake and redistribution of atmospheric gases. We used measurements of chlorofluorocarbon-12 (CFC-12) made in the southern oceans in the early 1990s and mid- to late 2000s to examine changes in ocean ventilation. Our analysis of the CFC-12 data reveals a decrease in the age of subtropical subantarctic mode waters and an increase in the age of circumpolar deep waters, suggesting that the formation of the Antarctic ozone hole has caused large-scale coherent changes in the ventilation of the southern oceans.

Photochemical synthesis of aldehydes in the solid phase.

A substituted anthraquinone (AQ), previously shown to photochemically generate benzaldehyde in methanol solution, was attached to a commercially available resin via an 11 carbon tether and an amide bond. Photolysis of the polymer-bound AQ with visible or 350 nm UV light resulted in the formation of benzaldehyde in yields of 50-55% as determined by HPLC. The phenolic positions in the polymer were then alkylated using benzyl bromide and 1-iodo-3-(4-nitrophenyl)propane in a coupling reaction with K(2)CO(3) as a base and a solution-phase proton shuttle. Photolysis of these alkylated polymers resulted in the formation of benzaldehyde (54-89%) and 3-(4-nitrophenyl)-propanal (58-67%). The yields of both aldehydes dropped considerably with subsequent realkylation and photolysis, and the polymer beads began to show signs of deterioration. This is the first time that aldehydes have been made photochemically on a solid-supported phase.