Simulation of crop yields using ERA-40: Limits to skill and nonstationarity in weather-yield relationships

Reanalysis data provide an excellent test bed for impacts prediction systems. because they represent an upper limit on the skill of climate models. Indian groundnut (Arachis hypogaea L.) yields have been simulated using the General Large-Area Model (GLAM) for annual crops and the European Centre for Medium-Range Weather Forecasts (ECMWF) 40-yr reanalysis (ERA-40). The ability of ERA-40 to represent the Indian summer monsoon has been examined. The ability of GLAM. when driven with daily ERA-40 data, to model both observed yields and observed relationships between subseasonal weather and yield has been assessed. Mean yields "were simulated well across much of India. Correlations between observed and modeled yields, where these are significant. are comparable to correlations between observed yields and ERA-40 rainfall. Uncertainties due to the input planting window, crop duration, and weather data have been examined. A reduction in the root-mean-square error of simulated yields was achieved by applying bias correction techniques to the precipitation. The stability of the relationship between weather and yield over time has been examined. Weather-yield correlations vary on decadal time scales. and this has direct implications for the accuracy of yield simulations. Analysis of the skewness of both detrended yields and precipitation suggest that nonclimatic factors are partly responsible for this nonstationarity. Evidence from other studies, including data on cereal and pulse yields, indicates that this result is not particular to groundnut yield. The detection and modeling of nonstationary weather-yield relationships emerges from this study as an important part of the process of understanding and predicting the impacts of climate variability and change on crop yields.

A comparison of the reactivity of germylene and dimethylgermylene with some methylgermanes. Direct kinetic and quantum chemical studies

Time-resolved studies of germylene, GeH2, and dimethygermylene, GeMe2, generated by the 193 nm laser flash photolysis of appropriate precursor molecules have been carried out to try to obtain rate coefficients for their bimolecular reactions with dimethylgermane, Me2GeH2, in the gas-phase. GeH2 + Me2GeH2 was studied over the pressure range 1-100 Torr with SF6 as bath gas and at five temperatures in the range 296-553 K. Only slight pressure dependences were found (at 386, 447 and 553 K). RRKM modelling was carried out to fit these pressure dependences. The high pressure rate coefficients gave the Arrhenius parameters: log(A/cm(3) molecule(-1)s(-1)) = -10.99 +/- 0.07 and E-a = -(7.35 +/- 0.48) kJ mol(-1). No reaction could be found between GeMe2 + Me2GeH2 at any temperature up to 549 K, and upper limits of ca. 10(-14) cm(3) molecule(-1)s(-1) were set for the rate coefficients. A rate coefficient of (1.33 +/- 0.04) x 10(-11)cm(3) molecule(-1)s(-1) was also obtained for GeH2 + MeGeH3 at 296 K. No reaction was found between GeMe2 and MeGeH3. Rate coefficient comparisons showed, inter alia, that in the substrate germane Me-for-H substitution increased the magnitudes of rate coefficients significantly, while in the germylene Me-for-H substitution decreased the magnitudes of rate coefficients by at least four orders of magnitude. Quantum chemical calculations (G2(MP2,SVP)// B3LYP level) supported these findings and showed that the lack of reactivity of GeMe2 is caused by a positive energy barrier for rearrangement of the initially formed complexes. Full details of the structures of intermediate complexes and the discussion of their stabilities are given in the paper.