Real-time analysis of δ13C- and δD-CH4 in ambient air with laser spectroscopy: method development and first intercomparison results

In situ and simultaneous measurement of the three most abundant isotopologues of methane using mid-infrared laser absorption spectroscopy is demonstrated. A field-deployable, autonomous platform is realized by coupling a compact quantum cascade laser absorption spectrometer (QCLAS) to a preconcentration unit, called trace gas extractor (TREX). This unit enhances CH4 mole fractions by a factor of up to 500 above ambient levels and quantitatively separates interfering trace gases such as N2O and CO2. The analytical precision of the QCLAS isotope measurement on the preconcentrated (750 ppm, parts-per-million, µmole mole−1) methane is 0.1 and 0.5 ‰ for δ13C- and δD-CH4 at 10 min averaging time. Based on repeated measurements of compressed air during a 2-week intercomparison campaign, the repeatability of the TREX–QCLAS was determined to be 0.19 and 1.9 ‰ for δ13C and δD-CH4, respectively. In this intercomparison campaign the new in situ technique is compared to isotope-ratio mass spectrometry (IRMS) based on glass flask and bag sampling and real time CH4 isotope analysis by two commercially available laser spectrometers. Both laser-based analyzers were limited to methane mole fraction and δ13C-CH4 analysis, and only one of them, a cavity ring down spectrometer, was capable to deliver meaningful data for the isotopic composition. After correcting for scale offsets, the average difference between TREX–QCLAS data and bag/flask sampling–IRMS values are within the extended WMO compatibility goals of 0.2 and 5 ‰ for δ13C- and δD-CH4, respectively. This also displays the potential to improve the interlaboratory compatibility based on the analysis of a reference air sample with accurately determined isotopic composition.

Identfying predictors of St. Louis encephalitis activity in Houston Texas

Generalized linear Poisson and logistic regression models were utilized to examine the relationship between temperature and precipitation and cases of Saint Louis encephalitis virus spread in the Houston metropolitan area. The models were investigated with and without repeated measures, with a first order autoregressive (AR1) correlation structure used for the repeated measures model. The two types of Poisson regression models, with and without correlation structure, showed that a unit increase in temperature measured in degrees Fahrenheit increases the occurrence of the virus 1.7 times and a unit increase in precipitation measured in inches increases the occurrence of the virus 1.5 times. Logistic regression did not show these covariates to be significant as predictors for encephalitis activity in Houston for either correlation structure. This discrepancy for the logistic model could be attributed to the small data set.^ Keywords: Saint Louis Encephalitis; Generalized Linear Model; Poisson; Logistic; First Order Autoregressive; Temperature; Precipitation. ^

(Table 4) Mean diameter of Orbulina universa d'Orbigny at DSDP Leg 54 Holes

On Deep Sea Drilling Project Leg 54, we recovered upper Pliocene (Globigerinoides obliquus: PL6 zone) to Pleistocene sediments from the equatorial East Pacific Rise (EPR) and Galapagos spreading center (GSC). Progressively older sediments were drilled at increasing distances from the crest, with the exception of the sediment drilled in the deepest trough known in the Siqueiros fracture zone. The anomalous age obtained at the latter site suggests that the basalt which was drilled may represent fracture zone volcanism. Paleoenvironmental analysis using the planktonic foraminifers at the EPR sites indicated the presence of environmental cycles of shorter wave length during the interval from 0 to 0.24 Ma, whereas cycles of longer wave length occurred from 0.43 to 2.17 Ma. The planktonic foraminiferal taphocoenoses at the EPR sites were strongly affected by selective dissolution which indicated that these EPR sites have been near either the lysocline or carbonate compensation surface since the upper Pliocene. The planktonic foraminiferal thanatocoenoses at the GSC sites were preserved better than those at the EPR sites. The number of planktonic foraminiferal species generally was greatly reduced in the green mud associated with the GSC hydrothermal mounds. More species were found in older than in younger green mud; this suggests that there probably was an increase in the rate of production of green mud sometime after the initiation of the hydrothermal system.