Improved quantification of Chinese carbon fluxes using CO2/CO correlations in Asian outflow

[1] We use observed CO2:CO correlations in Asian outflow from the TRACE-P aircraft campaign (February–April 2001), together with a three-dimensional global chemical transport model (GEOS-CHEM), to constrain specific components of the east Asian CO2 budget including, in particular, Chinese emissions. The CO2/CO emission ratio varies with the source of CO2 (different combustion types versus the terrestrial biosphere) and provides a characteristic signature of source regions and source type. Observed CO2/CO correlation slopes in east Asian boundary layer outflow display distinct regional signatures ranging from 10–20 mol/mol (outflow from northeast China) to 80 mol/mol (over Japan). Model simulations using best a priori estimates of regional CO2 and CO sources from Streets et al. [2003] (anthropogenic), the CASA model (biospheric), and Duncan et al. [2003] (biomass burning) overestimate CO2 concentrations and CO2/CO slopes in the boundary layer outflow. Constraints from the CO2/CO slopes indicate that this must arise from an overestimate of the modeled regional net biospheric CO2 flux. Our corrected best estimate of the net biospheric source of CO2 from China for March–April 2001 is 3200 Gg C/d, which represents a 45 % reduction of the net flux from the CASA model. Previous analyses of the TRACE-P data had found that anthropogenic Chinese C

Towards understanding the variability in biospheric CO2 fluxes:Using FTIR spectrometry and a chemical transport model to investigate the sources and sinks of carbonyl sulfide and its link to CO2

Understanding carbon dioxide (CO2) biospheric processes is of great importance because the terrestrial exchange drives the seasonal and interannual variability of CO2 in the atmosphere. Atmospheric inversions based on CO2 concentration measurements alone can only determine net biosphere fluxes, but not differentiate between photosynthesis (uptake) and respiration (production). Carbonyl sulfide (OCS) could provide an important additional constraint: it is also taken up by plants during photosynthesis but not emitted during respiration, and therefore is a potential means to differentiate between these processes. Solar absorption Fourier Transform InfraRed (FTIR) spectrometry allows for the retrievals of the atmospheric concentrations of both CO2 and OCS from measured solar absorption spectra. Here, we investigate co-located and quasi-simultaneous FTIR measurements of OCS and CO2 performed at five selected sites located in the Northern Hemisphere. These measurements are compared to simulations of OCS and CO2 using a chemical transport model (GEOS-Chem). The coupled biospheric fluxes of OCS and CO2 from the simple biosphere model (SiB) are used in the study. The CO2 simulation with SiB fluxes agrees with the measurements well, while the OCS simulation reproduced a weaker drawdown than FTIR measurements at selected sites, and a smaller latitudinal gradient in the Northern Hemisphere during growing season when comparing with HIPPO (HIAPER Pole-to-Pole Observations) data spanning both hemispheres. An offset in the timing of the seasonal cycle minimum between SiB simulation and measurements is also seen. Using OCS as a photosynthesis proxy can help to understand how the biospheric processes are reproduced in models and to further understand the carbon cycle in the real world

Influence of Reduced Carbon Emissions and Oxidation on the Distribution of Atmospheric CO2: Implications for Inversion Analyses

Recent inverse analyses constraining carbon fluxes using atmospheric CO2 observations have assumed that the CO2 source from atmospheric oxidation of reduced carbon is released at the surface rather than distributed globally in the atmosphere. This produces a bias in the estimates of surface fluxes. We used a three-dimensional (3D) atmospheric chemistry model (GEOS-CHEM) to evaluate the magnitude of this effect on modeled concentrations and flux estimates. We find that resolving the 3D structure of the atmospheric CO2 source, as opposed to emitting this reduced carbon as CO2 at the surface, yields a decrease in the modeled annual mean interhemispheric gradient (N-S) of 0.21 ppm. Larger adjustments (up to −0.6 ppm) are apparent on a regional basis in and downwind of regions of high reduced carbon emissions. We used TransCom3 annual mean simulations from three transport models to evaluate the implications for inversion estimates. The main impacts are systematic decreases in estimates of northern continental land uptake (i.e., by 0.22 to 0.26 Pg C yr−1), and reductions in tropical land carbon efflux with smaller changes over oceans and in the Southern Hemisphere. These adjustments represent a systematic bias in flux estimates, accounting for changes of 9 to 27% in the estimated northern land CO2 sink for the three models evaluated here. Our results highlight the need for a realistic description of reduced carbon emission and oxidation processes in deriving inversion estimates of CO2 surface fluxes.Earth and Planetary SciencesEngineering and Applied Science

On the impact of transport model errors for the estimation of CO2 surface fluxes from GOSAT observations

A series of observing system simulation experiments is presented in which column averaged dry air mole fractions of CO2 (XCO2) from the Greenhouse gases Observing SATellite (GOSAT) are made consistent or not with the transport model embedded in a flux inversion system. The GOSAT observations improve the random errors of the surface carbon budget despite the inconsistency. However, we find biases in the inferred surface CO2 budget of a few hundred MtC/a at the subcontinental scale, that are caused by differences of only a few tenths of a ppm between the simulations of the individual XCO2 soundings. The accuracy and precision of the inverted fluxes are little sensitive to an 8-fold reduction in the data density. This issue is critical for any future satellite constellation to monitor XCO2 and should be pragmatically addressed by explicitly accounting for transport errors in flux inversion systems

A Breast Cancer Stem Cell-Selective, Mammospheres-Potent Osmium(VI) Nitrido Complex

The effect of a newly developed osmium(VI) nitrido complex, 1, on breast cancer stem cells (CSCs) is reported. The complex displays selective toxicity for HMLER breast cancer cells enriched with CD44-positive, CSC-like cells over the same cells having reduced CSC character. Remarkably, 1 also reduces the proportion of CSCs within a heterogeneous breast cancer cell population and irreversibly inhibits the formation of free-floating mammospheres to an extent similar to that of salinomycin, a natural product that targets CSCs. Detailed mechanistic studies reveal that in breast cancer cells 1 induces DNA damage and endoplasmic reticulum stress, the latter being responsible for the CSC selectivity. The anti-CSC properties of 1 provide a strong impetus for the development of new metal-based compounds to target CSCs and to treat chemotherapy-resistant and relapsed tumors.National Cancer Institute (U.S.) (Grant CA034992)Misrock Foundation (Fellowship

Breast Cancer Stem Cell Potency of Nickel(II)-Polypyridyl Complexes Containing Non-steroidal Anti-inflammatory Drugs.

We report the breast cancer stem cell (CSC) potency of two nickel(II)-3,4,7,8-tetramethyl-1,10-phenanthroline complexes, 1 and 3, containing the non-steroidal anti-inflammatory drugs (NSAIDs), naproxen and indomethacin, respectively. The nickel(II) complexes, 1 and 3 kill breast CSCs and bulk breast cancer cells in the micromolar range. Notably, 1 and 3 display comparable or better potency towards breast CSCs than salinomycin, an established CSC-active agent. The complexes, 1 and 3 also display significantly lower toxicity towards non-cancerous epithelial breast cells than breast CSCs or bulk breast cancer cells (up to 4.6-fold). Mechanistic studies suggest that 1 and 3 downregulate cyclooxygenase-2 (COX-2) in breast CSCs and kill breast CSCs in a COX-2 dependent manner. Furthermore, the potency of 1 and 3 towards breast CSCs decreased upon co-treatment with necroptosis inhibitors (necrostatin-1 and dabrafenib), implying that 1 and 3 induce necroptosis, an ordered form of necrosis, in breast CSCs. As apoptosis resistance is a hallmark of CSCs, compounds like 1 and 3, which potentially provide access to alternative (non-apoptotic) cell death pathways could hold the key to overcoming hard-to-kill CSCs. To the best of our knowledge, 1 and 3 are the first compounds to be associated to COX-2 inhibition and necroptosis induction in CSCs

Error Correlation Between CO2 and CO as Constraint for CO2 Flux Inversions Using Satellite Data

Inverse modeling of CO2 satellite observations to better quantify carbon surface fluxes requires a chemical transport model (CTM) to relate the fluxes to the observed column concentrations. CTM transport error is a major source of uncertainty. We show that its effect can be reduced by using CO satellite observations as additional constraint in a joint CO2-CO inversion. CO is measured from space with high precision, is strongly correlated with CO2, and is more sensitive than CO2 to CTM transport errors on synoptic and smaller scales. Exploiting this constraint requires statistics for the CTM transport error correlation between CO2 and CO, which is significantly different from the correlation between the concentrations themselves. We estimate the error correlation globally and for different seasons by a paired-model method (comparing GEOS-Chem CTM simulations of CO2 and CO columns using different assimilated meteorological data sets for the same meteorological year) and a paired-forecast method (comparing 48- vs. 24-h GEOS-5 CTM forecasts of CO2 and CO columns for the same forecast time). We find strong error correlations (r2>0.5) between CO2 and CO columns over much of the extra-tropical Northern Hemisphere throughout the year, and strong consistency between different methods to estimate the error correlation. Application of the averaging kernels used in the retrieval for thermal IR CO measurements weakens the correlation coefficients by 15% on average (mostly due to variability in the averaging kernels) but preserves the large-scale correlation structure. We present a simple inverse modeling application to demonstrate that CO2-CO error correlations can indeed significantly reduce uncertainty on surface carbon fluxes in a joint CO2-CO inversion vs. a CO2-only inversion.Earth and Planetary SciencesEngineering and Applied Science

Scientific, Back-Illuminated CCD Development for the Transiting Exoplanet Survey Satellite

We describe the development of the fully depleted, back illuminated charge coupled devices for the Transiting Exoplanet Survey Satellite, which includes a set of four wide angle telescopes, each having a 2x2 array of CCDs. The devices are fabricated on the newly upgraded 200-mm wafer line at Lincoln Laboratory. We discuss methods used to produce the devices and present early performance results from the 100- micron thick, 15x15-microns, 2k x 4k pixel frame transfer CCDs

Necroptosis-Inducing Rhenium(V) Oxo Complexes

Rhenium(V) oxo complexes of general formula [ReO(OMe)(N^N)Cl₂], where N^N = 4,7-diphenyl-1,10-phenanthroline, 1, or 3,4,7,8-tetramethyl-1,10-phenanthroline, 2, effectively kill cancer cells by triggering necroptosis, a non-apoptotic form of cell death. Both complexes evoke necrosome (RIP1-RIP3)-dependent intracellular reactive oxygen species (ROS) production and propidium iodide uptake. The complexes also induce mitochondrial membrane potential depletion, a possible downstream effect of ROS production. Apparently, 1 and 2 are the first rhenium complexes to evoke cellular events consistent with programmed necrosis in cancer cells. Furthermore, 1 and 2 display low acute toxicity in C57BL/6 mice and reasonable stability in fresh human blood.National Cancer Institute (U.S.) (CA034992