Search

Ground-based observations are indispensable for the long-term monitoring of atmospheric constituents. In this work, we take advantage of multiple collocated instruments to analyze potential biases and drifts in ground-based ozone observations, within the context of the HEGIFTOM (Harmonization and Evaluation of Ground-based Instruments for Free Tropospheric Ozone Measurements) working group in the Tropospheric Ozone Assessment Report, Phase II (TOAR-II). This work is performed at Lauder (New Zealand), Boulder (Colorado), and Mauna Loa (Hawaii) where comparisons are made between Fourier Transform Infrared (FTIR) spectroscopy, Dobson Umkehr, and ozonesonde observations. The validation is performed with respect to FTIR as arbitrary reference, while considering the differences between the a priori profile information for the techniques that employ these as well as accounting for the different vertical resolution of each measurement technique. Such intercomparison is done for a handful discrete altitude partial columns, defined to have independent pieces of information also in the case of the low vertical resolution techniques (FTIR and Umkehr). This leads to 4 independent vertical layers to be compared, including one in the troposphere where ozone plays an important role as a greenhouse gas and as a risk to human health. In this tropospheric layer we compare the FTIR, Dobson Umkehr and ozonesonde techniques and derive a consistent bias from the FTIR data of about 5%, which we attribute in part to the assumed spectroscopy. Fitting the time series of the relative measurement differences using multiple linear regression, we obtain a linear trend, which quantifies the drift between pairs of techniques. Within the uncertainties, we find no significant drift between FTIR and Umkehr or ozone sonde data in the troposphere.

Clouds and aerosols, as well as overhead ozone, can have large effects on ultraviolet (UV) irradiances. We use statistical methods to remove cloud effects and mean aerosol effects from spectral UV irradiance measurements to investigate the relationship between UV and total column ozone. We show that for fixed solar zenith angles (SZA), seasonal changes in ozone lead to marked changes in clear-sky UV irradiances. Such effects are larger at mid-latitudes than in the tropics. At mid-latitudes, the minimum ozone amount over the course of a year can be about 50 percent of its maximum, with the lowest values in autumn and the highest values in spring. These seasonal ozone changes lead to UV Index (UVI) values in autumn that can exceed those in spring at the same SZA by nearly a factor of two. Differences are even larger for UV spectra weighted by the action spectra for DNA-damaging UV, and for cutaneous previtamin D production. In some cases, the seasonal increase exceeds a factor of 4. The analysis experimentally demonstrates the limits of applicability of the concept of constant Radiative Amplification Factors (RAFs) for estimating effects of changes in ozone for some weighting functions. Changes in DNA-weighted UV and erythemally weighted UV are well represented by the published RAFs. However, there are large SZA dependencies in the case of UVB and vitamin D-weighted UV. For all weightings considered, RAFs calculated from the observations as a function of SZA show similar dependencies between sites, in good agreement with published values, independently of the ozone data source. High quality measurements show that natural variations in ozone are responsible for huge variations in biologically damaging UV, with seasonal changes at fixed solar zenith angles sometimes exceeding a factor of four. The measured changes from thousands of spectra agree well with calculations over a wide range of solar zenith angles.

We use ground-based spectroscopic remote sensing measurements of the stratospheric trace gases O3, HCl, ClO, BrO, HNO3, NO2, OClO, ClONO2, N2O and HF, along with radiosonde profiles of temperature ...

We present 20 years (1996–2015) of austral springtime measurements of chlorine monoxide (ClO) over Antarctica from the Chlorine Oxide Experiment (ChlOE1) ground-based millimeter wave spectrometer at Scott Base, Antarctica, as well 12 years (2004–2015) of ClO measurements from the Aura Microwave Limb Sounder (MLS). From August onwards we observe a strong increase in lower stratospheric ClO, with a peak column amount usually occurring in early September. From mid-September onwards we observe a strong decrease in ClO. In order to study interannual differences, we focus on a 3-week period from 28 August to 17 September for each year and compare the average column ClO anomalies. These column ClO anomalies are shown to be highly correlated with the average ozone mass deficit for September and October of each year. We also show that anomalies in column ClO are strongly anti-correlated with 30 hPa temperature anomalies, both on a daily and an interannual timescale. Making use of this anti-correlation we calculate the linear dependence of the interannual variations in column ClO on interannual variations in temperature. By making use of this relationship, we can better estimate the underlying trend in the total chlorine (Cly = HCl + ClONO2 + HOCl + 2 × Cl2 + 2 × Cl2O2 + ClO + Cl). The resultant trends in Cly, which determine the long-term trend in ClO, are estimated to be −0.5 ± 0.2, −1.4 ± 0.9, and −0.6 ± 0.4 % year−1, for zonal MLS, Scott Base MLS (both 2004–2015), and ChlOE (1996–2015) respectively. These trends are within 1σ of trends in stratospheric Cly previously found at other latitudes. The decrease in ClO is consistent with the trend expected from regulations enacted under the Montreal Protocol.

We present a 10-year (January 2007–December 2016) time series of continuous in situ measurements of methane ( CH4 ), carbon monoxide (CO) and nitrous oxide ( N2O ) made by an in situ Fourier transform infrared trace gas and isotope analyser (FTIR) operated at Lauder, New Zealand (45.04 S, 169.68 E, 370 m a. m. s. l.). Being the longest continuous deployed operational FTIR system of this type, we are in an ideal position to perform a practical evaluation of the multi-year performance of the analyser. The operational methodology, measurement precision, reproducibility, accuracy and instrument reliability are reported. We find the FTIR has a measurement repeatability of the order of 0.37 ppb (1 σ standard deviation) for CH4 , 0.31 ppb for CO and 0.12 ppb for N2O . Regular target cylinder measurements provide a reproducibility estimate of 1.19 ppb for CH4 , 0.74 ppb for CO and 0.27 ppb for N2O . FTIR measurements are compared to co-located ambient air flask samples acquired at Lauder since May 2009, which allows a long-term assessment of the FTIR data set across annual and seasonal composition changes. Comparing FTIR and co-located flask measurements show that the bias (FTIR minus flask) for CH4 of −1.02 ± 2.61 ppb and CO of −0.43 ± 1.60 ppb are within the Global Atmospheric Watch (GAW)-recommended compatibility goals of 2 ppb. The N2O FTIR flask bias of −0.01 ± 0.77 ppb is within the GAW-recommended compatibility goals of 0.1 ppb and should be viewed as a serendipitous result due to the large standard deviation along with known systematic differences in the measurement sets. Uncertainty budgets for each gas are also constructed based on instrument precision, reproducibility and accuracy. In the case of CH4 , systematic uncertainty dominates, whilst for CO and N2O it is comparable to the random uncertainty component. The long-term instrument stability, precision estimates and flask comparison results indicate the FTIR CH4 and CO time series meet the GAW compatibility recommendations across multiple years of operation (and instrument changes) and are sufficient to capture annual trends and seasonal cycles observed at Lauder. The differences between FTIR and flask N2O measurements need to be reconciled. Trend analysis of the 10-year time series captures seasonal cycles and the secular upward trend of CH4 and N2O . The CH4 and CO time series have the required precision and accuracy at a high enough temporal resolution to be used in inversion models in a data-sparse region of the world.

We use multi-year datasets of UV spectral irradiances, measured to the exacting standards required by the Network for the Detection of Atmospheric Composition Change (NDACC), to investigate the enhancement effects of clouds and their wavelength dependence at sites that span a wide range of altitudes. These enhancements are derived by comparing weighted UV irradiance measurements with corresponding model calculations at each site for clear skies. We find that the frequency, magnitude, and wavelength-dependence of cloud enhancements are insufficient to explain the repeatedly high values of UVB and UVI observed by Cabrol et al., 2014, and that ozone amounts lower than have ever been seen there would be required.

We review 25 years of solar spectral UV at Lauder, measured to the exacting standards of the Network for the Detection of Atmospheric Composition Change (NDACC) with the best systems available at the time. Recent reanalysis of the alignment, calibration, and data processing from all nine of the UV spectroradiometers used at Lauder and other NDACC sites has better characterised the effects of changes in instrument technology. There has been no detectable trend in solar UV radiation other than that resulting from ozone variation.

Monitoring ambient solar UVR levels provides information on how much there is in both real time and historically. Quality assurance of ambient measurements of solar UVR is critical to ensuring accuracy and stability and this can be achieved by regular intercomparisons of spectral measurement systems with those of other organizations. In October and November of 2013 a solar UVR spectroradiometer from Public Health England (PHE) was brought to Melbourne for a campaign of intercomparisons with a new Bentham spectrometer of Australian Radiation Protection and Nuclear Safety Agency (ARPANSA) and one at the Australian Bureau of Meteorology (BOM), supported by New Zealand's National Institute for Water and Atmosphere (NIWA). Given all three spectroradiometers have calibrations that are traceable to various national standards, the intercomparison provides a chance to determine measurement uncertainties and traceability that support UV measurement networks in Australia, New Zealand and the UK. UV Index measurements from all three systems were compared and ratios determined for clear sky conditions when the scans from each instrument were within 2 min of each other. While wavelengths below 305 nm showed substantial differences between the PHE unit and the two other systems, overall the intercomparison results were encouraging, with mean differences in measured UV Index between the BOM/NIWA and those of PHE and ARPANSA of

Measurements from sensors designed to measure erythemal UV irradiance were used to relate the UV incident on a horizontal surface to that incident on a surface maintained normal to the sun throughout the day at Lauder, New Zealand. These UV measurements were also related to variations in global radiation, total column ozone and atmospheric pressure at the surface. Strong correlations were found between these variables over the 37 day observation period in the summer of 1995/1996. Results from these cross-calibrated UV sensors show that the irradiance incident on a surface normal to the sun can be significantly different from that on a horizontal surface. On clear days, the normal-incidence signal can be 30-40% greater for solar zenith angles in the range 60-70 degrees. Consequently, the risk of UV damage can be greater than reported by measurements or models that assume horizontal incidence (e.g., UV index). On cloudy days the normal-incidence UV can be less than 50% of the horizontal-incidence UV. Averaged over a day, any enhancements in normal-incidence UV over horizontal-incidence UV are smaller. The effects were strongly dependent on cloud conditions. Under clear skies the enhancements are generally less than 10%, and the integrated excess over horizontal-incidence UV is usually less than 5%. However, under cloudy skies the reductions can still be large.

A research-grade scanning UV spectroradiometer was installed at Mauna Loa Observatory (MLO), Hawaii, in July 1995. This instrument, built around a commercially available double monochromator, is interfaced with a PC to provide auto- matic control and data acquisition. The spectral range sampled by the instrument is 290-450 nm, and ,the bandpass is about 1 nm. A complete scan requires about 200 seconds and is per- formed every 5 degrees of solar zenith angle (SZA) during day- light hours. Calibration is performed On site at 6-month intervals using a 1000-W standard quartz-halogen FEL lamp with calibration traceable to NIST. TheUV irradiances meas- ured at MLO are much more intense than at low altitude mid- latitudelocations. For observations at a SZA of 45 o, the erythemally weighted UV can ,excee d t 8 tW cm -2, which is ap- proximately 15-20% greater than the maxima seen at Laude,r, NeW Zealand, for similar ozone amounts. The difference is pri- marily due to the higher altitude at MLO. For overhead sun conditions at MLO, erythemal UV can exceed 45 gW cm -2, which to our knowledge is the highest recordedanywhere at the Earth's surface. UV irradiance is strongly correlated (inversely) with Dobson spectrophotometer total ozone measurements at MLO, with higher correlations at shorter wavelengths. The ra- diative amplification factor (RAP) for erythema at MLO is about 1.44 n 0.46 at SZA 45 o. Using ozone retrievals from the UV spectra themselves, the deduced RAF for erythema is 1.26 s 0.38. The RAPs for e,rythema at SZA 60 o are similar, and in agreement with other determinations within the limits of experi- mental uncertainty.

Simultaneous measurements of upwelling and downwelling ultraviolet (UV) spectral irradiance were used to deduce the wavelength dependence and the solar zenith angle dependence of the albedo of the ground surface (long grass) at Lauder, New Zealand (45.05°S, 169.68°E). In the UVB region the deduced albedos are approximately 1%. At longer wavelengths the albedo increases to approximately 2% at 400 nm, and 4.5% at 450 nm. These albedos are significantly smaller than those generally quoted for the visible region. The deduced albedos tend to increase at larger solar zenith angles, demonstrating that the surface is not strictly Lambertian.

Three UV spectroradiometers from the National Institute of Water and Atmospheric Research (NIWA) New Zealand, the Fraunhofer Institute (IFU) Germany, and the Australian Radiation Laboratory (ARL) Australia were intercompared at Lauder NZ on 23 February 1993. Over the spectral range 290–400 nm, the agreement between the IFU and NIWA instruments was better than 5%. At noon on this day, the irradiances measured by all three instruments agreed within ±10%, except at wavelengths shorter than 300 nm, where the ARL instrument gave higher readings. At larger solar zenith angles (SZA) the differences at short wavelengths were more pronounced, and at wavelengths above 300 nm the ARL measurements were systematically lower. The reasons for these differences are discussed. Having established the differences between the sets of instrumentation, spectra of maximum clear sky UV irradiances observed by these groups in New Zealand, Australia, and Europe are compared. The erythemally weighted irradiance observed in Melbourne Australia was the highest (0.35 W m−2). Respective maxima for Lauder NZ and for Neuherberg Germany were 85% and 66% of that in Australia. Differences are larger for DNA-weighted UV.

In 1988 the New Zealand Department of Scientific and Industrial Research initiated a program to characterize the spectrum of solar ultraviolet radiation reaching the ground in New Zealand and to identify the extent and causes of its variability. Routine measurements began at Lauder (45 degrees S 170 degrees E) in December 1989. The instrumentation, measurement strategy, and calibration procedures are discussed and uncertainties in the measurements are analyzed. With the present system useful measurements at 1-nm resolution are limited to irradiances greater than 10(-3) microW cm(-2) nm(-1), which corresponds to a lower limit in wavelength in the region 290-295 nm (depending on the Sun angle and ozone amount). This is a useful lower limit for many applications of relevance to the biosphere. Results from the first year of operation are presented and discussed.

[1] Solar ultraviolet irradiance has been monitored in Antarctica for almost two decades by a network of spectroradiometers established by the National Science Foundation. Data have been used for investigating increases in ultraviolet radiation in response to ozone depletion, validation of satellite observations, and the establishment of ultraviolet radiation climatologies and trends. To assess the quality of data collected, measurements of the monitoring spectroradiometer installed at Arrival Heights (78°S, 167°E) were compared with an independently calibrated, state-of-the art instrument, which was installed next to the monitoring system for a three-month campaign. Measurements of the two instruments differed by 5–7% on average. The discrepancy is quantitatively explained by the different irradiance scales used by the two systems, a bias in determining the reference plane of fore-optics, drifts of calibration standards, some temperature-dependence in the transmission of the entrance optics, and nonlinearity of one of the systems. The wavelength accuracy of data from both instruments was also tested with two commonly used correlation methods. Wavelength shifts determined with the two methods agreed to within 0.003–0.006 nm. Results of the campaign suggest that data collected by the monitoring instrument are of adequate quality for submission to the Network for the Detection of Atmospheric Composition Change.

Spectral measurements of UV irradiances at Tokyo are compared with corresponding measurements at a pristine site (Lauder New Zealand) to identify the causes of the reductions in urban UV irradiances, and to quantify their effects. Tropospheric extinctions in Tokyo were found to be up to ~40% greater than at Lauder. Most of these differences can be explained by differences in cloud and aerosols, but ozone differences are also important in the summer. Examining spectral signatures of tropospheric transmission of both sites shows that reductions due to mean NO2 and SO2 amounts are generally small. However, at times the amount of NO2 can be 10 times higher than the mean amount, and on these days it can decrease the UVA irradiance up to 40%. If SO2 shows comparable day to day variability, it would contribute to significant reductions in UVB irradiances. The results indicate that at Tokyo, interactions between the larger burden of tropospheric ozone and aerosols also have a significant effect. These results have important implications for our ability to accurately retrieve surface UV irradiances at polluted sites from satellites that use backscattered UV. Supplementary data characterising these boundary layer effects are probably needed.

The purpose of this work is determine the extent of closure between measurements and models of UV irradiances at diverse sites using state of the art instruments, models, and the best available data as inputs to the models. These include information about aerosol optical depth (unfortunately not extending down as far into the UVB region as desirable because such information is not generally available), ozone column amounts, as well as vertical profiles of temperature. We concentrate on clear-sky irradiances, and report the results in terms of UV Index (UVI). Clear-sky data from one year of measurements at each of four diverse sites (Lauder – New Zealand, Mauna Loa Observatory – Hawaii, Boulder – Colorado, and Melbourne – Australia) have been analysed in detail, also taking account of different measurements of ozone, including satellite-derived values, as well as ground measured values, both from Dobson instruments and as retrieved from the UV spectra under study. Previous studies have generally focussed on data from a single site, and for shorter periods. As such, it is the most comprehensive study of its kind to date. At Lauder, which is the cleanest low altitude site, we obtained agreement between measurement and model at 5% level, which is consistent with the best agreement found previously. At Mauna Loa Observatory, similar agreement was achieved, but model calculations need to allow for reflections from cloud that are present below the observatory. At this site, there are occasional problems with using satellite-derived ozone. At Boulder, mean agreements were similar but the dispersion around the mean was slightly larger, corresponding to larger uncertainties in the aerosol inputs to the model. However, at Melbourne, which is the only non-NDACC (Network for the Detection of Atmospheric Composition Change) site, there remain unexplained discrepancies. The measured values are significantly lower than the calculated values. We investigate the extent to which this discrepancy can be explained by incomplete knowledge of aerosol extinctions in the UV at this site. We conclude that further information about aerosol optical depth and single scattering albedo in the UVB region is needed to resolve the issues. For more polluted sites (the four considered locations show in general small aerosol load), the uncertainties in the aerosol input parameters would lead to less confidence on the modelling approach. At the three NDACC sites, the closure provided by the study gives confidence in both the measurements and our ability to model them. This study revealed a limitation in the use of PTFE diffusers when temperatures are lower than approximately 20°C. It also documents the range of clear sky UVI values expected at these diverse sites.

[1] The effect of temperature-dependences on the transmission of PTFE diffusers used in NIWA UV spectrometers is quantified through laboratory and field measurements. It is shown that data taken at temperatures less than 15°C typically require an upward correction of ∼2%.

We discuss the move from reporting damaging UV radiation in terms of UVB to the now widely accepted erythemally weighted UV radiation (UV(Ery)) and the UV Index (UVI). The relationship between these quantities is given: to a good approximation, it is found that UVB(280-315 nm)= 7.55 [times] UV(Ery). In terms of the UV Index, the estimated UVB(280-315 nm) in units of W m(-2) is 18.9 times the UVI. These approximations generally hold to within approximately 10% for all solar zenith angles (sza) less than 70 degrees. For most practical purposes, this is a sufficient range, since for larger sza, the intensity of UVB is less than 10% of that for overhead sun conditions. The simple relationship above is verified using spectral measurements. However, tables are provided to enable calculation of the conversion with greater accuracy under such conditions. Similar model calculations are provided to estimate UVB(280-320 nm). Correction tables to convert erythemally weighted UV to other biological weightings are also presented.

High-precision micrometeorological measurement with tunable diode laser (TDL)-based trace gas analysers provides a continuous spatially integrating and non-intrusive measurement technique that is capable of detecting and quantifying episodic N2O emission at the paddock scale. Results are presented from the FarmGas2006 measurement campaign conducted on a commercial dairy farm in North Canterbury, New Zealand, over 3 weeks in October 2006. This was the first field deployment of a TDL instrument for paddock-based N2O flux measurement in New Zealand. A goal of this campaign was assessment of a range of atmospheric N2O sensing technologies and micrometeorological approaches. In this paper the capabilities of TDL technology are compared with gas chromatography (GC) in flux-gradient measurements. Baseline emission was