(Supporting Information) 14Cage plateau tuning of local Atlantic sediment cores

Modeling studies predict that changes in radiocarbon (14C) reservoir ages of surface waters during the last deglacial episode will reflect changes in both atmospheric 14C concentration and ocean circulation including the Atlantic Meridional Overturning Circulation. Tests of these models require the availability of accurate 14C reservoir ages in well-dated late Quaternary time series. We here test two models using plateau-tuned 14C time series in multiple well-placed sediment core age-depth sequences throughout the lower latitudes of the Atlantic Ocean. 14C age plateau tuning in glacial and deglacial sequences provides accurate calendar year ages that differ by as much as 500-2500 years from those based on assumed global reservoir ages around 400 years. This study demonstrates increases in local Atlantic surface reservoir ages of up to 1000 years during the Last Glacial Maximum, ages that reflect stronger trades off Benguela and summer winds off southern Brazil. By contrast, surface water reservoir ages remained close to zero in the Cariaco Basin in the southern Caribbean due to lagoon-style isolation and persistently strong atmospheric CO2 exchange. Later, during the early deglacial (16 ka) reservoir ages decreased to a minimum of 170-420 14C years throughout the South Atlantic, likely in response to the rapid rise in atmospheric pCO2 and Antarctic temperatures occurring then. Changes in magnitude and geographic distribution of 14C reservoir ages of peak glacial and deglacial surface waters deviate from the results of Franke et al. (2008) but are generally consistent with those of the more advanced ocean circulation model of Butzin et al. (2012).

Cyclostratigraphy and eccentricity tuning of the early Oligocene through early Miocene record from Walvis Ridge

Few astronomically calibrated high-resolution (<=5 kyr) climate records exist that span the Oligocene-Miocene time interval. Notably, available proxy records show responses varying in amplitude at frequencies related to astronomical forcing, and the main pacemakers of global change on astronomical time-scales remain debated. Here we present newly generated X-ray fluorescence core scanning and benthic foraminiferal stable oxygen and carbon isotope records from Ocean Drilling Program Site 1264 (Walvis Ridge, southeastern Atlantic Ocean). Complemented by data from nearby Site 1265, the Site 1264 benthic stable isotope records span a continuous ~13-Myr interval of the Oligo-Miocene (30.1-17.1 Ma) at high resolution (~3.0 kyr). Spectral analyses in the stratigraphic depth domain indicate that the largest amplitude variability of all proxy records is associated with periods of ~3.4 m and ~0.9 m, which correspond to 405- and ~110-kyr eccentricity, using a magnetobiostratigraphic age model. Maxima in CaCO3 content, d18O and d13C are interpreted to coincide with ~110 kyr eccentricity minima. The strong expression of these cycles in combination with the weakness of the precession- and obliquity-related signals allow construction of an astronomical age model that is solely based on tuning the CaCO3 content to the nominal (La2011_ecc3L) eccentricity solution. Very long-period eccentricity maxima (~2.4-Myr) are marked by recurrent episodes of high-amplitude ~110-kyr d18O cycles at Walvis Ridge, indicating greater sensitivity of the climate/cryosphere system to short eccentricity modulation of climatic precession. In contrast, the responses of the global (high-latitude) climate system, cryosphere, and carbon cycle to the 405-kyr cycle, as expressed in benthic d18O and especially d13C signals, are more pronounced during ~2.4-Myr minima. The relationship between the recurrent episodes of high-amplitude ~110-kyr d18O cycles and the ~1.2-Myr amplitude modulation of obliquity is not consistent through the Oligo-Miocene. Identification of these recurrent episodes at Walvis Ridge, and their pacing by the ~2.4-Myr eccentricity cycle, revises the current understanding of the main climate events of the Oligo-Miocene.

Bulk sediment parameter of three sediment cores from permafrost lowlands, Alaska Arctic Coastal Plain

Arctic lowland landscapes have been modified by thermokarst lake processes throughout the Holocene. Thermokarst lakes form as a result of ice-rich permafrost degradation and they may expand over time through thermal and mechanical shoreline erosion. We studied proximal and distal sedimentary records from a thermokarst lake located on the Arctic Coastal Plain of northern Alaska to reconstruct the impact of catchment dynamics and morphology on the lacustrine depositional environment and to quantify carbon accumulation in thermokarst lake sediments. Short cores were collected for analysis of pollen, sedimentological and geochemical proxies. Radiocarbon and Pb/Cs dating, as well as extrapolation of measured historic lake expansion rates, were applied to estimate a minimum lake age of ~ 1,400 calendar years BP. The pollen record is in agreement with the young lake age as it does not include evidence of the "alder high" that occurred in the region ~ 4.0 cal ka BP. The lake most likely initiated from a remnant pond in a drained thermokarst lake basin (DTLB) and deepened rapidly as evidenced by accumulation of laminated sediments. Increasing oxygenation of the water column as shown by higher Fe/Ti and Fe/S ratios in the sediment indicate shifts in ice regime with increasing water depth. More recently, the sediment source changed as the thermokarst lake expanded through lateral permafrost degradation, alternating from redeposited DTLB sediments, to increased amounts of sediment from eroding, older upland deposits, followed by a more balanced combination of both DTLB and upland sources. The characterizing shifts in sediment sources and depositional regimes in expanding thermokarst lakes were therefore archived in the thermokarst lake sedimentary record. This study also highlights the potential for Arctic lakes to recycle old carbon from thawing permafrost and thermokarst processes.

Kinetic modeling of molecular motors: pause model and parameter determination from single-molecule experiments

Single-molecule manipulation experiments of molecular motors provide essential information about the rate and conformational changes of the steps of the reaction located along the manipulation coordinate. This information is not always sufficient to define a particular kinetic cycle. Recent single-molecule experiments with optical tweezers showed that the DNA unwinding activity of a Phi29 DNA polymerase mutant presents a complex pause behavior, which includes short and long pauses. Here we show that different kinetic models, considering different connections between the active and the pause states, can explain the experimental pause behavior. Both the two independent pause model and the two connected pause model are able to describe the pause behavior of a mutated Phi29 DNA polymerase observed in an optical tweezers single-molecule experiment. For the two independent pause model all parameters are fixed by the observed data, while for the more general two connected pause model there is a range of values of the parameters compatible with the observed data (which can be expressed in terms of two of the rates and their force dependencies). This general model includes models with indirect entry and exit to the long-pause state, and also models with cycling in both directions. Additionally, assuming that detailed balance is verified, which forbids cycling, this reduces the ranges of the values of the parameters (which can then be expressed in terms of one rate and its force dependency). The resulting model interpolates between the independent pause model and the indirect entry and exit to the long-pause state model

Parameter space of experimental chaotic circuits with high-precision control parameters

The authors thank Professor Iber^e Luiz Caldas for the suggestions and encouragement. The authors F.F.G.d.S., R.M.R., J.C.S., and H.A.A. acknowledge the Brazilian agency CNPq and state agencies FAPEMIG, FAPESP, and FAPESC, and M.S.B. also acknowledges the EPSRC Grant Ref. No. EP/I032606/1.

Characterizing the transition dynamics for multi-pulsing in mode-locked lasers

We consider experimentally and theoretically a refined parameter space near the transition to multi-pulse modelocking. Near the transition, the onset of instability is initiated by a Hopf (periodic) bifurcation. As cavity energy is increased, the band of unstable, oscillatory modes generates a chaotic behavior between single- and multi-pulse operation. Both theory and experiment are in good qualitative agreement and they suggest that the phenomenon is of a universal nature in mode-locked lasers at the onset of multi-pulsing from N to N + 1 pulses per round trip. This is the first theoretical and experimental characterization of the transition behavior, made possible by a highly refined tuning of the gain pump level. © 2010 Copyright SPIE - The International Society for Optical Engineering.

Lead oxide-modified TiO2 photocatalyst: tuning light absorption and charge carrier separation by lead oxidation state

Modification of TiO2 with metal oxide nanoclusters such as FeOx, NiOx has been shown to be a promising approach to the design of new photocatalysts with visible light absorption and improved electron–hole separation. To study further the factors that determine the photocatalytic properties of structures of this type, we present in this paper a first principles density functional theory (DFT) investigation of TiO2 rutile(110) and anatase(001) modified with PbO and PbO2 nanoclusters, with Pb2+ and Pb4+ oxidation states. This allows us to unravel the effect of the Pb oxidation state on the photocatalytic properties of PbOx-modified TiO2. The nanoclusters adsorb strongly at all TiO2 surfaces, creating new Pb–O and Ti–O interfacial bonds. Modification with PbO and PbO2 nanoclusters introduces new states in the original band gap of rutile and anatase. However the oxidation state of Pb has a dramatic impact on the nature of the modifications of the band edges of TiO2 and on the electron–hole separation mechanism. PbO nanocluster modification leads to an upwards shift of the valence band which reduces the band gap and upon photoexcitation results in hole localisation on the PbO nanocluster and electron localisation on the surface. By contrast, for PbO2 nanocluster modification the hole will be localised on the TiO2 surface and the electron on the nanocluster, thus giving rise to two different band gap reduction and electron–hole separation mechanisms. We find no crystal structure sensitivity, with both rutile and anatase surfaces showing similar properties upon modification with PbOx. In summary the photocatalytic properties of heterostructures of TiO2 with oxide nanoclusters can be tuned by oxidation state of the modifying metal oxide, with the possibility of a reduced band gap causing visible light activation and a reduction in charge carrier recombination.

Development of miniaturized antennas and adaptive tuning solutions for body sensor network applications

Wireless Sensor Networks (WSNs) are currently having a revolutionary impact in rapidly emerging wearable applications such as health and fitness monitoring amongst many others. These types of Body Sensor Network (BSN) applications require highly integrated wireless sensor devices for use in a wearable configuration, to monitor various physiological parameters of the user. These new requirements are currently posing significant design challenges from an antenna perspective. This work addresses several design challenges relating to antenna design for these types of applications. In this thesis, a review of current antenna solutions for WSN applications is first presented, investigating both commercial and academic solutions. Key design challenges are then identified relating to antenna size and performance. A detailed investigation of the effects of the human body on antenna impedance characteristics is then presented. A first-generation antenna tuning system is then developed. This system enables the antenna impedance to be tuned adaptively in the presence of the human body. Three new antenna designs are also presented. A compact, low-cost 433 MHz antenna design is first reported and the effects of the human body on the impedance of the antenna are investigated. A tunable version of this antenna is then developed, using a higher performance, second-generation tuner that is integrated within the antenna element itself, enabling autonomous tuning in the presence of the human body. Finally, a compact sized, dual-band antenna is reported that covers both the 433 MHz and 2.45 GHz bands to provide improved quality of service (QoS) in WSN applications. To date, state-of-the-art WSN devices are relatively simple in design with limited antenna options available, especially for the lower UHF bands. In addition, current devices have no capability to deal with changing antenna environments such as in wearable BSN applications. This thesis presents several contributions that advance the state-of-the-art in this area, relating to the design of miniaturized WSN antennas and the development of antenna tuning solutions for BSN applications.

Orbitally tuned time scale and astronomical forcing in the middle Eocene to early Oligocene determined on ODP and IODP sediment cores

Deciphering the driving mechanisms of Earth system processes, including the climate dynamics expressed as paleoceanographic events, requires a complete, continuous, and high-resolution stratigraphy that is very accurately dated. In this study, we construct a robust astronomically calibrated age model for the middle Eocene to early Oligocene interval (31-43 Ma) in order to permit more detailed study of the exceptional climatic events that occurred during this time, including the Middle Eocene Climate Optimum and the Eocene/Oligocene transition. A goal of this effort is to accurately date the middle Eocene to early Oligocene composite section cored during the Pacific Equatorial Age Transect (PEAT, IODP Exp. 320/321). The stratigraphic framework for the new time scale is based on the identification of the stable long eccentricity cycle in published and new high-resolution records encompassing bulk and benthic stable isotope, calibrated XRF core scanning, and magnetostratigraphic data from ODP Sites 171B-1052, 189-1172, 199-1218, and 207-1260 as well as IODP Sites 320-U1333, and -U1334 spanning magnetic polarity Chrons C12n to C20n. Subsequently we applied orbital tuning of the records to the La2011 orbital solution. The resulting new time scale revises and refines the existing orbitally tuned age model and the Geomagnetic Polarity Time Scale from 31 to 43 Ma. Our newly defined absolute age for the Eocene/Oligocene boundary validates the astronomical tuned age of 33.89 Ma identified at the Massignano (Italy) global stratotype section and point. Our compilation of geochemical records of climate-controlled variability in sedimentation through the middle-to-late Eocene and early Oligocene demonstrates strong power in the eccentricity band that is readily tuned to the latest astronomical solution. Obliquity driven cyclicity is only apparent during very long eccentricity cycle minima around 35.5 Ma, 38.3 Ma and 40.1 Ma.