Measurements of CO2, its stable isotopes, O2/N2, and 222Rn at Bern, Switzerland

A one-year time series of atmospheric CO2 measurements from Bern, Switzerland, is presented. O2/N2 and Ar/N2 ratios as well as stable carbon and oxygen isotopes of CO2 and δ29N2, δ34O2 and δ36Ar were measured periodically during a one year period. Additionally, the 222Rn activity was measured during three months in the winter 2004. Using the correlation from short-term fluctuations of CO2 and 222Rn we estimated a mean CO2 flux density between February 2004 and April 2004 in the region of Bern of 95±39 tC km–2month–1. The continuous observations of carbon dioxide and associated tracers shed light on diurnal and seasonal patterns of the carbon cycle in an urban atmosphere. There is considerable variance in nighttime δ13C and δ18O of source CO2 throughout the year, however, with generally lower values in winter compared to summertime. The O2:CO2 oxidation ratio during the nighttime build-up of CO2 varies between –0.96 and –1.69 mol O2/mol CO2. Furthermore, Ar/N2 measurements showed that artifacts like thermal fractionation at the air intake are relevant for high precision measurements of atmospheric O2

Measurements of CO₂, its stable isotopes, O₂/N₂, and ²²²Rn at Bern, Switzerland

A one-year time series of atmospheric CO₂ measurements from Bern, Switzerland, is presented. O₂/N₂ and Ar/N₂ ratios as well as stable carbon and oxygen isotopes of CO₂ and δ²⁹N₂, δ³⁴O₂ and δ³⁶Ar were measured periodically during a one year period. Additionally, the ²²²Rn activity was measured during three months in the winter 2004. Using the correlation from short-term fluctuations of CO₂ and ²²²Rn we estimated a mean CO₂ flux density between February 2004 and April 2004 in the region of Bern of 95±39 tC km^–2month^–1. The continuous observations of carbon dioxide and associated tracers shed light on diurnal and seasonal patterns of the carbon cycle in an urban atmosphere. There is considerable variance in nighttime δ¹³C and δ¹⁸O of source CO₂ throughout the year, however, with generally lower values in winter compared to summertime. The O₂:CO₂ oxidation ratio during the nighttime build-up of CO₂ varies between –0.96 and –1.69 mol O₂/mol CO₂. Furthermore, Ar/N₂ measurements showed that artifacts like thermal fractionation at the air intake are relevant for high precision measurements of atmospheric O₂

An automatic static chamber for continuous 220Rn and 222Rn flux measurements from soil

A closed-circuit analytical system for the (quasi)-continuous measurement of radon fluxes from soil consisting of a static accumulation chamber and two radon detectors operated in series is described. The first detector measures the (220Rn + 222Rn) activity, the second one the remaining 222Rn activity after the 220Rn atoms (half-life 56 s) have decayed when the air passes a delay volume between the two detectors. A step-motor driven cover closes the chamber at the beginning of a flux measurement interval of e.g. 3 h. In between measurements the chamber remains open to maintain soil and vegetation inside the chamber as closely as possible to the conditions outside. A mathematical description of the temporal evolution of Rn activities in the analytical system is presented from which procedures are derived to calculate Rn fluxes (Bq m−2 s−1) from the measured activities in the two detectors. Examples from field tests illustrate the performance of the experimental set-up and possible complications due to technical and/or environmental difficulties

Helium transfer from water into quartz crystals: A new approach for porewater dating

Several important fundamental and applied problems require a quantification of slow rates of groundwater flow. To resolve these problems helium appears to be a promising tracer. In this contribution we discuss a new approach, which gives the helium inventory in a rock – pore water system by using the relevant mineral record, i.e., without extraction and investigation of the porewater samples. Some U- and Th-poor minerals such as quartz (quartz separates from Permo-Carboniferous Formation, sandstone–shale interlayering, Molasses Basin, Northern Switzerland, hereafter PCF, are used in this study) contain excessive helium having migrated into their internal helium-accessible volume (HAV) from the surrounding porewater [I.N. Tolstikhin, B.E. Lehmann, H.H. Loosli, A. Gautschi, Helium and argon isotopes in rocks, minerals and related groundwaters: a case study in Northern Switzerland, Geochim. Cosmochim. Acta 60 (1996) 1497–1514]. These volumes are estimated by using helium as a nano-size penetrating tool, i.e., by saturation of the minerals with helium under controlled pressure–temperature conditions and subsequent measurements of the helium-saturated concentrations. In the quartz separates HAV/total volume ratios vary from 0.017% to 0.16%; along with the measured initial (unsaturated) He concentration the HAV gives the internal helium pressure, the mean value obtained for 7 samples (25 sample aliquots) is P=0.45F0.15 atm (1 r). The product of helium pressure and solubility (7.35_10_3 cc STP He/cc H2O for the temperature and salinity of PCF aquifers reported in [F.J. Pearson, W. Balderer, H.H. Loosli, B.E. Lehmann, A. Matter, T. Peters, H. Schmassmann, A. Gautschi, Applied Isotope Hydrogeology–A Case Study in Northern Switzerland, Elsevier Amsterdam, 1991, 439 pp.]) is the mineral-derived He concentration in the respective porewater, CPW=0.0035F0.0017 cc He/cc H2O. This value is in full accord with measured He concentrations in PCF aquifers, CPCF, varying from 0.0045 to 0.0016 cc He/cc H2O. This agreement validates the proposed approach and also shows that the mineral–porewater helium–concentration equilibrium has been established. Indeed, estimates of the He-migration rates through our quartz samples show that in ~6000 years the internal pressure should equilibrate with He-concentration in related porewater of PCF, and this time interval is short compared to independent estimates [I.N. Tolstikhin, B.E. Lehmann, H.H. Loosli, A. Gautschi, Helium and argon isotopes in rocks, minerals and related groundwaters: a case study in Northern Switzerland, Geochim. Cosmochim. Acta 60 (1996) 1497–1514]. The helium inventory in the rock–porewater assemblage shows that helium abundance in pore waters is indeed important. In shale samples (with ~15% porosity) porewaters contain more helium than the host minerals altogether. Porewater heliumconcentration profiles, available from the mineral record, along with helium production rates are input parameters allowing model(s) of helium migration through a hydrological structure to be developed. Quite high helium concentrations in PCF porewaters imply slow removal mechanisms, which will be discussed elsewhere

Turbulence characteristics in grassland canopies and implications for tracer transport

In-canopy turbulence is a required input to study pollutant cycling and chemistry within plant canopies and to link concentrations and sources. Despite the importance of grasslands worldwide, most previous work has focused on forests and crops. Here, turbulence parameters in a mature agricultural grassland canopy were measured with a combination of a small ultrasonic anemometer, hotwire anemometry and a radon (Rn) tracer technique, as part of a measurement to study ammonia (NH3) exchange with grassland. The measurements are used to derive vertical profiles of basic turbulent parameters, for quadrant-hole analysis of the two-parametric frequency distributions of u'−w' and to derive in-canopy eddy diffusivities as input for models of in-canopy tracer transport. The results are in line with previous measurements on taller canopies, but shows increased decoupling between in-canopy flow and above-canopy turbulence. The comparison of sonic anemometry and Rn measurements implies that Lagrangian time-scales must decrease sharply at the ground, with important implications for estimating the magnitude of ground-level and soil emissions from concentration measurements. Atmospheric stability above and within the canopy has little influence on the standard deviation of vertical wind component inside the canopy. Use of the turbulence parameters in an analytical Lagrangian framework, which is here validated for heat transfer, suggests that measured in-canopy profiles of NH3 are consistent with a ground-level source, presumably from senescent plant parts, which is recaptured by the overlying canopy. [Abstract from: http://www.biogeosciences.net/6/1519/2009/bg-6-1519-2009.html

Enhancing the Performance of Sensitized Solar Cells with PbS/CH3NH3PbI3 Core/Shell Quantum Dots

We report on the fabrication of PbS/CH3NH3PbI3 (=MAP) core/shell quantum dot (QD)sensitized inorganic organic heterojunction solar cells on top of mesoporous (mp) TiO2 electrodes with hole transporting polymers (P3HT and PEDOT:PSS). The PbS/MAP core/shell QDs were in situ-deposited by a modified successive ionic layer adsorption and reaction (SILAR) process using PbI2 and Na2S solutions with repeated spin-coating and subsequent dipping into CH3NH3I (=MAI) solution in the final stage. The resulting device showed much higher efficiency as compared to PbS QD-sensitized solar cells without a MAP shell layer, reaching an overall efficiency of 3.2% under simulated solar illumination (AM1.5, 100 mW.cm(-2)). From the measurement of the impedance spectroscopy and the time-resolved photoluminescence (PL) decay, the significantly enhanced performance is mainly attributed to both reduced charge recombination and better charge extraction by MAP shell layer. In addition, we demonstrate that the MAP shell effectively prevented the photocorrosion of PbS, resulting in highly improved stability in the cell efficiency with time. Therefore, our approach provides method for developing high performance QD-sensitized solar cellsclos