Referencing of street-level flows measured during the DAPPLE 2004 campaign

Street-level mean flow and turbulence govern the dispersion of gases away from their sources in urban areas. A suitable reference measurement in the driving flow above the urban canopy is needed to both understand and model complex street-level flow for pollutant dispersion or emergency response purposes. In vegetation canopies, a reference at mean canopy height is often used, but it is unclear whether this is suitable for urban canopies. This paper presents an evaluation of the quality of reference measurements at both roof-top (height = H) and at height z = 9H = 190 m, and their ability to explain mean and turbulent variations of street-level flow. Fast response wind data were measured at street canyon and reference sites during the six-week long DAPPLE project field campaign in spring 2004, in central London, UK, and an averaging time of 10 min was used to distinguish recirculation-type mean flow patterns from turbulence. Flow distortion at each reference site was assessed by considering turbulence intensity and streamline deflection. Then each reference was used as the dependent variable in the model of Dobre et al. (2005) which decomposes street-level flow into channelling and recirculating components. The high reference explained more of the variability of the mean flow. Coupling of turbulent kinetic energy was also stronger between street-level and the high reference flow rather than the roof-top. This coupling was weaker when overnight flow was stratified, and turbulence was suppressed at the high reference site. However, such events were rare (<1% of data) over the six-week long period. The potential usefulness of a centralised, high reference site in London was thus demonstrated with application to emergency response and air quality modelling.

A cross-calibration of chlorine isotopic measurements and suitability of seawater as the international reference material

A collection of 24 seawaters from various worldwide locations and differing depth was culled to measure their chlorine isotopic composition (delta(37)Cl). These samples cover all the oceans and large seas: Atlantic, Pacific, Indian and Antarctic oceans, Mediterranean and Red seas. This collection includes nine seawaters from three depth profiles down to 4560 mbsl. The standard deviation (2sigma) of the delta(37)Cl of this collection is +/-0.08 parts per thousand, which is in fact as large as our precision of measurement ( +/- 0.10 parts per thousand). Thus, within error, oceanic waters seem to be an homogeneous reservoir. According to our results, any seawater could be representative of Standard Mean Ocean Chloride (SMOC) and could be used as a reference standard. An extended international cross-calibration over a large range of delta(37)Cl has been completed. For this purpose, geological fluid samples of various chemical compositions and a manufactured CH3Cl gas sample, with delta(37)Cl from about -6 parts per thousand to +6 parts per thousand have been compared. Data were collected by gas source isotope ratio mass spectrometry (IRMS) at the Paris, Reading and Utrecht laboratories and by thermal ionization mass spectrometry (TIMS) at the Leeds laboratory. Comparison of IRMS values over the range -5.3 parts per thousand to +1.4 parts per thousand plots on the Y=X line, showing a very good agreement between the three laboratories. On 11 samples, the trend line between Paris and Reading Universities is: delta(37)Cl(Reading)= (1.007 +/- 0.009)delta(37)Cl(Paris) - (0.040 +/- 0.025), with a correlation coefficient: R-2 = 0.999. TIMS values from Leeds University have been compared to IRMS values from Paris University over the range -3.0 parts per thousand to +6.0 parts per thousand. On six samples, the agreement between these two laboratories, using different techniques is good: delta(37)Cl(Leeds)=(1.052 +/- 0.038)delta(37)Cl(Paris) + (0.058 +/- 0.099), with a correlation coefficient: R-2 = 0.995. The present study completes a previous cross-calibration between the Leeds and Reading laboratories to compare TIMS and IRMS results (Anal. Chem. 72 (2000) 2261). Both studies allow a comparison of IRMS and TIMS techniques between delta(37)Cl values from -4.4 parts per thousand to +6.0 parts per thousand and show a good agreement: delta(37)Cl(TIMS)=(1.039 +/- 0.023)delta(37)Cl(IRMS)+(0.059 +/- 0.056), with a correlation coefficient: R-2 = 0.996. Our study shows that, for fluid samples, if chlorine isotopic compositions are near 0 parts per thousand, their measurements either by IRMS or TIMS will give comparable results within less than +/- 0.10 parts per thousand, while for delta(37)Cl values as far as 10 parts per thousand (either positive or negative) from SMOC, both techniques will agree within less than +/- 0.30 parts per thousand. (C) 2004 Elsevier B.V. All rights reserved.

Achieving accurate FTIR measurements on high performance bandpass filters

The sources of ordinate error in FTIR spectrometers are reviewed with reference to measuring small out-of-band features in the spectra of bandpass filters. Procedures for identifying instrumental artefacts are described. It is shown that features well below 0.01%T can be measured reliably.

Improvements to the accuracy of measurements of NO2 by zenith-sky visible spectrometers II: errors in zero using a more complete chemical model

Using a flexible chemical box model with full heterogeneous chemistry, intercepts of chemically modified Langley plots have been computed for the 5 years of zenith-sky NO2 data from Faraday in Antarctica (65°S). By using these intercepts as the effective amount in the reference spectrum, drifts in zero of total vertical NO2 were much reduced. The error in zero of total NO2 is ±0.03×1015 moleccm−2 from one year to another. This error is small enough to determine trends in midsummer and any variability in denoxification between midwinters. The technique also suggests a more sensitive method for determining N2O5 from zenith-sky NO2 data.

Ventilation effects on humidity measurements in thermometer screens

Relative humidity (RH) measurements, as derived from wet-bulb and dry-bulb thermometers operated as a psychrometer within a thermometer screen, have limited accuracy because of natural ventilation variations. Standard RH calculations generally assume a fixed screen psychrometer coefficient, but this is too small during poor ventilation. By comparing a reference humidity probe—exposed within a screen containing a psychrometer—with wind-speed measurements under controlled conditions, a wind-speed correction for the screen psychrometer coefficient has been derived and applicable when 2-metre wind speeds fall below 3 ms–1. Applying this to hourly-averaged data reduced the mean moist RH bias of the psychrometer (over the reference probe) from 1.2% to 0.4%, and reduced the inter-quartile range of the RH differences from 2.0% to 0.8%. This correction is particularly amenable to automatic measurement systems.

A multi-instrument comparison of integrated water vapour measurements at a high latitude site

We compare measurements of integrated water vapour (IWV) over a subarctic site (Kiruna, Northern Sweden) from five different sensors and retrieval methods: Radiosondes, Global Positioning System (GPS), ground-based Fourier-transform infrared (FTIR) spectrometer, ground-based microwave radiometer, and satellite-based microwave radiometer (AMSU-B). Additionally, we compare also to ERA-Interim model reanalysis data. GPS-based IWV data have the highest temporal coverage and resolution and are chosen as reference data set. All datasets agree reasonably well, but the ground-based microwave instrument only if the data are cloud-filtered. We also address two issues that are general for such intercomparison studies, the impact of different lower altitude limits for the IWV integration, and the impact of representativeness error. We develop methods for correcting for the former, and estimating the random error contribution of the latter. A literature survey reveals that reported systematic differences between different techniques are study-dependent and show no overall consistent pattern. Further improving the absolute accuracy of IWV measurements and providing climate-quality time series therefore remain challenging problems.