Non‐Matrix‐Matched Calibration for the Multi‐Element Analysis of Geological and Environmental Samples Using 200 nm Femtosecond LA‐ICP‐MS: A Comparison with Nanosecond Lasers

LA‐ICP‐MS is one of the most promising techniques for in situ analysis of geological and environmental samples. However, there are some limitations with respect to measurement accuracy, in particular for volatile and siderophile/chalcophile elements, when using non‐matrix‐matched calibration. We therefore investigated matrix‐related effects with a new 200 nm femtosecond (fs) laser ablation system (NWRFemto200) using reference materials with different matrices and spot sizes from 10 to 55 μm. We also performed similar experiments with two nanosecond (ns) lasers, a 193 nm excimer (ESI NWR 193) and a 213 nm Nd:YAG (NWR UP‐213) laser. The ion intensity of the 200 nm fs laser ablation was much lower than that of the 213 nm Nd:YAG laser, because the ablation rate was a factor of about 30 lower. Our experiments did not show significant matrix dependency with the 200 nm fs laser. Therefore, a non‐matrix‐matched calibration for the multi‐element analysis of quite different matrices could be performed. This is demonstrated with analytical results from twenty‐two international synthetic silicate glass, geological glass, mineral, phosphate and carbonate reference materials. Calibration was performed with the certified NIST SRM 610 glass, exclusively. Within overall analytical uncertainties, the 200 nm fs LA‐ICP‐MS data agreed with available reference values.     

Theoretical interpretation of the 0.7820 μm CO2 band and 0.8226 μm H2O line on Venus

We have analyzed the P6, P8, and P10 lines in the 0.7820 μm CO₂ band of Venus using a scattering model. Our new results compare favorably with previous results from the 1.05 μm CO₂ band. We considered nonabsorbing and absorbing clouds. We found that the anisotropic scattering mean free path for both models at the 0.2atm level is between 0.55 and 0.73km, a range close to the value of 1 km for terrestrial hazes. We used our scattering models to synthesize the 0.8226 μm H₂O line, assuming that the clouds are composed of sulfuric acid drops, and found our nonabsorbing cloud required a sulfuric acid concentration of 82% by weight, while our thicker absorbing cloud required a concentration of 89%. A comparison of the variation of optical depth with height for our cloud models with the variation reported by Prinn (1973, Science182, 1132–1134) showed that, within a factor of 2, the variation for Prinn's thinnest cloud agreed with ours. Whitehill and Hansen (1973, Icarus20, 146–152) have recently confirmed the work of Regas et al. (1973a, J. Quant. Spectry. Radiative Transfer13, 461–463) which showed that two cloud layers are not required to explain the CO₂ phase variation of Venus. Prinn's recent photochemical study of sulfuric acid clouds further supports a single, continuous cloud layer in the line formation region instead of two cloud layers with an extensive clear region between. The single layer model appears more likely because the maximum particle density in Prinn's cloud occurs in the clear region between the two layers in the models of Hunt (1972, J. Quant. Spectry. Radiative Transfer12, 405–419) and Carleton and Traub (1972, Bull. Amer. Astron. Soc.4, 362.).     

A numerical-physical planetary boundary layer model

A numerical-physical model for the planetary boundary layer has been formulated for the purpose of predicting the winds, temperatures and humidities in the lowest 1600 m of the atmosphere. An application of the model to the synoptic situation of 30 August, 1972, demonstrates its ability to produce useful forecasts for a period of 24 h. Results are illustrated in terms of horizontal maps and time-height sections of winds and temperatures. The model is divided in the vertical direction into three layers that are governed, respectively, by different physical formulations. At the lowest level, which is the surface of the earth, forecasts of temperature and humidity are computed from empirical relations. In the first layer, the surface layer, application is made of the similarity theories of Monin-Obukhov, Monin-Kazanski and Businger’s form of the universal functions. The second layer, the Ekman layer, is 1550 m deep and is governed by diagnostic momentum and time-dependent thermodynamic and humidity equations. External input to the model are large-scale pressure gradients and middle-level cloudiness. Cressman’s objective analysis procedure is applied to conventional surface and upper air data over a horizontal region of about 2500 km by 2500 km, centered about Lake Ontario. With a grid distance of 127 km and a time interval of 30 min, the computer time required on Control Data Cyber 76 for a 24 h forecast for the case study is less than two minutes.     

River network travel time is correlated with dissolved organic matter composition in rivers of the contiguous United States

Most terrestrial allochthonous organic matter enters river networks through headwater streams during high flow events. In headwaters, allochthonous inputs are substantial and variable, but become less important in streams and rivers with larger watersheds. As allochthonous dissolved organic matter (DOM) moves downstream, the proportion of less aromatic organic matter with autochthonous characteristics increases. How environmental factors converge to control this transformation of DOM at a continental scale is less certain. We hypothesized that the amount of time water has spent travelling through surface waters of inland systems (streams, rivers, lakes, and reservoirs) is correlated to DOM composition. To test this hypothesis, we used established river network scaling relationships to predict relative river network flow-weighted travel time (FWTT) of water for 60 stream and river sites across the contiguous United States (3090 discrete samples over 10 water years). We estimated lentic contribution to travel times with upstream in-network lake and reservoir volume. DOM composition was quantified using ultraviolet and visible absorption and fluorescence spectroscopy. A combination of FWTT and lake and reservoir volume was the best overall predictor of DOM composition among models that also incorporated discharge, specific discharge, watershed area, and upstream channel length. DOM spectral slope ratio (R² = 0.77) and Freshness Index (R² = 0.78) increased and specific ultraviolet absorbance at 254 nm (R² = 0.68) and Humification Index (R² = 0.44) decreased across sites as a function of FWTT and upstream lake volume. This indicates autochthonous-like DOM becomes continually more dominant in waters with greater FWTT. We assert that river FWTT can be used as a metric of the continuum of DOM composition from headwaters to rivers. The nature of the changes to DOM composition detected suggest this continuum is driven by a combination of photo-oxidation, biological processes, hydrologically varying terrestrial subsidies, and aged groundwater inputs.     

Heat and momentum transfer characteristics of adjacent fields of soybeans and maize

Measurements made as part of studies of the evolution of the planetary boundary layer (the Sangamon experiments of 1975 and 1976) are used to compare the surface eddy fluxes of heat and momentum over adjacent fields of soybeans and maize. Although the maize canopy was much taller and rougher than that of the soybeans, daytime eddy fluxes of momentum over the maize exceeded those over the soybeans by only about 35%, in good agreement with predictions based on PBL similarity theory. Heat flux was about 10% greater over the maize, probably as a consequence of greater evaporation over the soybeans. Infrared surface temperatures generally differed by less than 0.4 °C and net radiation by less than 10%. For the soybean canopy, the momentum displacement height was found to be located at approximately 90% of the crop height, and the roughness length was about 5%. The roughness length for sensible heat transfer was found to be 2–3% of the soybean canopy height. For the maize canopy, the momentum displacement height was about 60% of the crop height, and the roughness length about 7%.Work supported under the auspices of the U.S. Department of Energy.     

Long-term simulation of Indonesian rainfall with the MPI regional model

Simulations of the Indonesian rainfall variability using the Max Planck Institute regional climate model REMO have been performed using three different lateral boundary forcings: Reanalyses from the European Centre for Medium-Range Weather Forecasts (ERA15), the National Centers for Environmental Prediction and National Center for Atmospheric Research (NRA) as well as from ECHAM4 climate model simulation. The result of those simulations are compared to station data. REMO simulations were performed at 0.5° horizontal resolution for the whole archipelago and at 1/6° for Sulawesi Island. In general the REMO model, reproduces the spatial pattern of monthly and seasonal rainfall well over land, but overestimates the rainfall over sea. Superiority of REMO performance over land is due to a high-resolution orography, while over sea, REMO suffers from erroneously low surface fluxes. REMO reproduces variability during El Niño-Southern Oscillations years well but fails to show a good (wet and dry) monsoon contrast. Despite strong influences of the lateral boundary fields, REMO shows a realistic improvement of a local phenomenon over Molucca. Significant improvement for the step from the relatively high global 1.125° to 0.5° resolution is noticeable, but not from 0.5° into 1/6°. The REMO simulation driven by ERA15 has the best quality, followed by NRA and ECHAM4 driven simulations. The quality of ERA15 is the main factor determining the quality of REMO simulations. A predictability study shows small internal variability among ensemble members. However, there are systematic intrinsic climatological errors as shown in the predictability analysis. These intrinsic errors have monthly, seasonal and regional dependencies and the one over Java is significantly large. The intrinsic error study suggests the presence of the spring predictability barrier and a high level of predictability in summer.