Comparison of UV and IR Laser Ablation ICP-MS on Silicate Reference Materials and Implementation of Normalisation Factors for Quantitative Measurements

Direct analysis of geological reference materials was performed by LA-ICP-MS using two Nd:YAG laser systems operating at 266 nm and 1064 nm. The aim of this work was to compare UV and IR laser ablation and to assess the potential of the technique for the quantitative bulk analysis of rocks, sediments and soils. The laser sampling process was investigated and the analytical performance of both systems was compared. The influence of the laser operating conditions and the nature of the matrix on ICP-MS response factors calculated for major, minor and trace elements was evaluated. Under consistent laser settings, the response factors appeared to be matrix dependent. For a given matrix, the response factors were also significantly different for the two lasers. Normalisation with a single matrix element was effective only for matrices with similar mineralogy. When operating at 266 nm instead of 1064 nm, matrix effects could be reduced but not overcome. However, variations of the response factors between the different matrices appeared to be similar within distinct groups of elements, reflecting geochemical associations. When using multiple internal standards, matrix effects but also effects of the laser wavelength, could be fully compensated.     

Effect of clouds on the photodissociation of NO2: Observations and modelling

The role of clouds in photodissociation is examined by both modelling and observations. It is emphasized that the photodissociation rate is proportional to the actinic flux rather than to the irradiance. The actinic flux concerns the energy that is incident on a molecule, irrespective of the direction of incidence. The irradiance concerns the energy that is incident on a plane.As far as the modelling aspect is concerned, a multi-layer delta-Eddington model is used to calculate irradiances, actinic fluxes, and photodissociation rates of nitrogen dioxide J(NO₂) as a function of height in inhomogeneous atmospheres. For the considered wavelength interval [290–420 nm], Rayleigh scattering, ozone absorption, and Mie scattering and absorption by cloud drops and aerosols should be taken into account.Further, a three-layer model is used to calculate the actinic flux above and below a cloud, relative to the incident flux, in terms of cloud albedo, zenith angle, and the albedo of the underlying and overlying atmosphere. Cloud albedo is mainly determined by cloud optical thickness. An expression for the incloud actinic flux is given as a function of in-cloud optical thickness. The three-layer model seems to be a useful model for the estimation of photodissociation rates in dispersion models.It is stressed that both models in their present form cannot handle partial cloudiness.It is shown that if no clouds are present, the actinic flux depends primarily on solar zenith angle. Further, the incident flux at the top of the atmosphere diminishes downward into the atmosphere due to the increasing effect of scattering. Therefore, the actinic flux usually increases with height, although above clouds the actinic flux sometimes decreases with height due to a large contribution of the upward scattered light.For cloudy atmospheres, another important parameter with respect to the actinic flux is added: cloud optical thickness. Cloud optical thickness determines cloud albedo. It can be shown that incloud characteristics and cloud height are less important while describing the effect of a cloud on the actinic flux (outside the cloud). The in-cloud values of the actinic flux can exceed the values outside the cloud.Finally, using the photostationary state relationship, a comparison is performed between model results and ground-based measurements as well as in-cloud air craft measurements.     

Measurements of chemically and biologically effective radiation reaching the ground

Solar ultraviolet radiation at the surface has been measured at Potsdam on cloudless days by spectrometer OL 752/10. The measurements are compared with broad-band filter measurements and with model calculations using a modified version of Green's model, which is independent of the measurements. Input data to the model such as atmospheric ozone and aerosol optical thicknesses were measured by a Dobson and Brewer spectrophotometer as well as a Linke Feussner pyrheliometer, respectively. Differences between the model and the measurements are discussed in terms of uncertainties in the calibration and errors of instruments as well as uncertainties in the model calculations including the errors of input data. It is demonstrated that different chemically and biologically effective radiances can be determined from only one set of measured spectral irradiance components, i.e. global radiation and diffuse downward and upward directed radiation. Examples of diurnal variations of the photochemical production of ozone and hydroxyl radicals as determined from spectral irradiance measurements and measured concentrations of relevant trace gases are given.It is shown from the measured irradiance that relations between different effects of radiation to the biosphere depend on solar zenith angle, and to a certain extent also on atmospheric ozone. This has to be taken into account when adverse effects of changing UV radiation are evaluated. Radiation Amplification Factors derived from measurements correspond to those determined from model calculations.     

Solar UV variability: Effects on stratospheric ozone,trace constituents and thermal structure

The effect of long-term (11-year solar cycle) solar UV variability on stratospheric chemical and thermal structure has been studied using a time-dependent one-dimensional model. Previous studies have suggested substantial variations in local and total ozone, and in stratospheric thermal structure from solar minimum to solar maximum. It is shown here that significant variations also occur in some of the trace constituents. Members of the HO _x family and N₂O exhibit the largest variations, and these changes, if detected, may provide additional means of verifying the presence of solar UV variability and its effects. Some of the species show large phase differences with the assumed solar flux variation. The role of chemical and transport time constants on the time variations of the trace species is examined. Comparisons with reported ozone and temperature data show reasonable agreement for the period 1960 to 1972.     

Determination of dissolved organic matter in streamwater using visible spectrophotometry: A comment

A discussion querying the need (Grieve, 1985) for further studies on the use of the technique, which is already well established. The use of chemical oxygen demand is also questioned.     

Photochemical Degradation of Hydrophilic Xenobiotics in the UV/H2O2-process. Influence of Humic Matter on the Degradation Rate of 2-Amino-1-naphthalenesulfonate and Ethylenediaminetetraacetate

Photochemical oxidation methods are able to eliminate hydrophilic xenobiotics with a high efficiency. In waters with high DOC values caused by humic substances (HS) which are able to absorb UV light, problems can result. The degradation rates of the micropollutants using irradiation wavelengths in the range between λ = 200 nm to λ = 260 nm are significantly influenced by HS. This is mainly caused by the high absorption of the HS at shorter wavelength. In the presence of HS, the photolytic degradation of EDTA and FeEDTA was slowed down by an inner filter effect. A similar tendency could be seen for the photolytic degradation of 2-amino-1-naphthalenesulfonate where additional effects to the inner filter effect were also operating. In the UV/H₂O₂-process, the decrease of the degradation rate could be assigned to the ability of the HS to scavenge HO radicals.     

Out-of-Range Stray Light Characterization of Single-Monochromator Brewer Spectrophotometers

Stray light in single-monochromator Brewer instruments increases the uncertainty of solar ultraviolet spectral irradiance measurements and ozone retrievals. To study how spectral irradiance within and outside the measurement ranges of the instruments affects stray light, two Brewer MKII instruments were characterized for the level of in- and out-of-range stray light at multiple laser wavelengths. In addition, several solar-blind filters utilized in single-monochromator Brewers to limit out-of-range stray light were characterized for spectral and spatial transmittances. Finally, the measurement results were used to simulate the effect of stray light and stray light correction on spectral irradiance and ozone measurements at different wavelength regions. The effect of stray light from wavelengths above 340?nm was found to be negligible compared with other sources of uncertainty. On the other hand, contributions from wavelengths between 325 and 340?nm can form a significant portion of the overall stray light of the instrument, with 325?nm being the upper limit of the nominal measurement range of the instrument.     

Hubble Space Telescope observations of magellanic cloud planetary nebulae: Stellar winds

Narrow-band [OIII] 500.7 nm images and ultraviolet spectrophotometry are obtained for 20 planetary nebulae (PNe) in the Magellanic Clouds using the Hubble Space Telescope (HST). Four objects show P Cygni-like features in the ultraviolet HST data, and/or broad emission complexes near the HeII 468.6 nm and CIV 580.6 nm lines in ground-based spectra. All objects are of excitation class four or lower, and all are compact and dense compared to other objects in the sample. The likelihood of detecting ultraviolet P Cygni-like profiles in future HST spectroscopy of other objects is discussed.     

Modelling the formation of H2SO4–H2O particles in rural, urban and marine conditions

The factors which affect the formation of new sulphuric acid particles in different atmospheric conditions are investigated. An atmospheric chemistry gas phase box model coupled to a three mode integral aerosol dynamics model is used. The simulations show the dependence of the concentration of nucleation mode particles on initial pre-existing particles, the intensity of UV radiation, the emissions of dimethylsulphide (DMS) and the ratio of emissions of hydrocarbons (HC) and NO_x present in the atmosphere. Eight different basic cases are simulated in urban, rural and marine conditions. The effects of pre-existing particles as a sink of sulphuric acid are clearly seen. The increased UV radiation is also seen to enhance particle formation via sulphuric acid route significantly.     

A simplified resorcinol method for direct spectrophotometric determination of nitrate in seawater

A direct, spectrophotometric method has been adapted for quantitative determination of nitrate concentrations in seawater. The method is based on nitration of resorcinol in acidified seawater, resulting in a color product. The absorption spectrum obtained for the reaction product shows a maximum absorption at 505 nm, with a molar absorptivity of 1.7 × 10⁴ L mol^− 1 cm^− 1. This method has a detection limit of 0.5 μM and is linear up to 400 μM for nitrate. The advantage of this method is that all reagents are in aqueous solutions without involving cadmium granules as a heterogeneous reactant, as in conventional methods, and therefore is simple to implement. Application of the resorcinol to seawater analysis demonstrated that the results obtained are in good agreement with the conventional approach involving the reduction of nitrate by cadmium followed by diazotization.