[1] Amazon forests are potentially globally significant sources or sinks for atmospheric carbon dioxide. In this study, we characterize the spatial trends in carbon storage and fluxes in both live and dead biomass (necromass) in two Amazonian forests, the Biological Dynamic of Forest Fragments Project (BDFFP), near Manaus, Amazonas, and the Tapajós National Forest (TNF) near Santarém, Pará. We assessed coarse woody debris (CWD) stocks, tree growth, mortality, and recruitment in ground-based plots distributed across the terra firme forest at both sites. Carbon dynamics were similar within each site, but differed significantly between the sites. The BDFFP and the TNF held comparable live biomass (167 ± 7.6 MgCÁha À1 versus 149 ± 6.0 MgCÁha À1 , respectively), but stocks of CWD were 2.5 times larger at TNF (16.2 ± 1.5 MgCÁha À1 at BDFFP, versus 40.1 ± 3.9 MgCÁha À1 at TNF). A model of current forest dynamics suggests that the BDFFP was close to carbon balance, and its size class structure approximated a steady state. The TNF, by contrast, showed rapid carbon accrual to live biomass (3.24 ± 0.22 MgCÁha À1 Áa À1 in TNF, 2.59 ± 0.16 MgCÁha À1 Áa À1 in BDFFP), which was more than offset by losses from large stocks of CWD, as well as ongoing shifts of biomass among size classes. This pattern in the TNF suggests recovery from a significant disturbance. The net loss of carbon from the TNF will likely last 10-15 years after the initial disturbance (controlled by the rate of decay of coarse woody debris), followed by uptake of carbon as the forest size class structure and composition continue to shift. The frequency and longevity of forests showing such disequilibruim dynamics within the larger matrix of the Amazon remains an essential question to understanding Amazonian carbon balance.

Since the pioneering work of Kochi in the 1970s, iron has attracted great interest for crosscoupling catalysis due to its low cost and toxicity as well as its potential for novel reactivity compared to analogous reactions with precious metals like palladium. Today there are numerous iron-based cross-coupling methodologies available, including challenging alkyl-alkyl and enantioselective methods. Furthermore, cross-couplings with simple ferric salts and additives like NMP and TMEDA (N-methylpyrrolidone and tetramethylethylenediamine) continue to attract interest in pharmaceutical applications. Despite the tremendous advances in iron cross-coupling methodologies, in situ formed and reactive iron species and the underlying mechanisms of catalysis remain poorly understood in many cases, inhibiting mechanism-driven methodology development in this field. This lack of mechanism-driven development has been due, in part, to the challenges of applying traditional characterization methods such as nuclear magnetic resonance (NMR) spectroscopy to iron chemistry due to the multitude of paramagnetic species that can form in situ. The application of a broad array of inorganic spectroscopic methods (e.g., electron paramagnetic resonance, 57 Fe Mössbauer, and magnetic circular dichroism) removes this barrier and has revolutionized our ability to evaluate iron speciation. In conjunction with inorganic syntheses of unstable organoiron intermediates and combined inorganic spectroscopy/gas chromatography studies to evaluate in situ iron reactivity, this approach has dramatically evolved our understanding of in situ iron speciation, reactivity, and mechanisms in iron-catalyzed cross-coupling over the past 5 years. This Account focuses on the key advances made in obtaining mechanistic insight in iron-catalyzed carboncarbon cross-couplings using simple ferric salts, iron-bisphosphines, and iron-N-heterocyclic carbenes (NHCs). Our studies of ferric salt catalysis have resulted in the isolation of an unprecedented iron-methyl cluster, allowing us to identify a novel reaction pathway and solve a decades-old mystery in iron chemistry. NMP has also been identified as a key to accessing more stable intermediates in reactions containing nucleophiles with and without β-hydrogens. In ironbisphosphine chemistry, we have identified several series of transmetalated iron(II)-bisphosphine complexes containing mesityl, phenyl, and alkynyl nucleophile-derived ligands, where mesityl systems were found to be unreliable analogues to phenyls. Finally, in iron-NHC cross-coupling, unique chelation effects were observed in cases where nucleophile-derived ligands contained *

Abstract.Observations of CO 2 were made in the upper troposphere and lower stratosphere in the deep tropics in order to determine the patterns of large-scale vertical transport and age of air in the Tropical Tropopause Layer (TTL). Flights aboard the NASA WB-57F aircraft over Central America and adjacent ocean areas took place in January and February, 2004 (Pre-AURA Validation Experiment, Pre-AVE) and 2006 (Costa Rice AVE, CR-AVE), and for the same flight dates of 2006, aboard the Proteus aircraft from the surface to 15 km over Darwin, Australia (Tropical Warm Pool International Cloud Experiment, TWP-ICE). The data demonstrate that the TTL is composed of two layers with distinctive features: (1) the lower TTL, 350-360 K (potential temperature(θ ); approximately 12-14 km), is subject to inputs of convective outflows, as indicated by layers of variable CO 2 concentrations, with air parcels of zero age distributed throughout the layer; (2) the upper TTL, from θ=∼360 K to ∼390 K (14-18 km), ascends slowly and ages uniformly, as shown by a linear decline in CO 2 mixing ratio tightly correlated with altitude, associated with increasing age. This division is confirmed by ensemble trajectory analysis. The CO 2 concentration at the level of 360 K was 380.0(±0.2) ppmv, indistinguishable from surface site values in the Intertropical Convergence Zone (ITCZ) for the flight dates. Values declined with altitude to 379.2(±0.2) ppmv at 390 K, implying that air in the upper TTL monotonically ages while ascending. In combination with the winter slope of the CO 2 seasonal cycle (+10.8±0.4 ppmv/yr), the vertical gradient of -0.78 (±0.09) ppmv gives a mean age of 26(±3) days for the air at 390 K and a mean ascent rate of 1.5(±0.3) mm s −1 . TheCorrespondence to: S. C. Wofsy (swofsy@deas.harvard.edu) TTL near 360 K in the Southern Hemisphere over Australia is very close in CO 2 composition to the TTL in the Northern Hemisphere over Costa Rica, with strong contrasts emerging at lower altitudes (<360 K). Both Pre-AVE and CR-AVE CO 2 observed unexpected input from deep convection over Amazônia deep into the TTL. The CO 2 data confirm the operation of a highly accurate tracer clock in the TTL that provides a direct measure of the ascent rate of the TTL and of the age of air entering the stratosphere.