Ultraviolet Spectrophotometers: Principles of operation

C.T. McElroy, David Wardle Environment Canada

11/17/200

MSC Brewer Optics, JBK, DIW, CTM

Beers Law -3
Phenomenological
stuff - equivalent thickness of a layer of gas at standard temperature and pressure e.g. total ozone or column ozone (same) constant - absorption coefficient I =I0 . exp(- x ) n cm - 2 cm 2 x cm at s.t.p. cm - 1 at s.t.p.

Physical

stuff - number of molecules per unit area constant - absorption cross-section per molecule I =I0 . exp(- n )

Given L = Lochsmidts number = 2.687 10 19 molecules per cm 3 at s.t.p. (s.t.p. 0 C and 1 atmosphere)

=
2

11/17/200

MSC Brewer Optics, JBK, DIW, CTM

Ozone absorption - general

1E+2

Ozone absorption coefficients (cm at stp)-1

HARTLEY

Dissociation if < 1.1m O3 % h 6 O2 % O Excited states if < 315nm ( O3 % h 6 O2 % O ( O O( ( O2 note : usually recombines with O2 may make OH may emit a 1.27m photon

1E+1

IR approximate, equivalent
BREWER OZONE MEASUREMENT RANGE

1E+0

HUGGINS
1E-1

CHAPPIUS
1E-2
2 4 6 8

Wavelength 0.2 to 20 micrometers

1.0

10.0

11/17/200

MSC Brewer Optics, JBK, DIW, CTM

Ozone absorption Brewer wavelengths

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Ozone Absorption Coefficients (cm at stp)-1

Showing the wavelengths of the six Brewer slits at the ozone-measuring setting. Also, the local minimum at 324 nm.

0.30

0.31

0.32

0.33
4

Wavelength - micrometers
11/17/200
MSC Brewer Optics, JBK, DIW, CTM

Rayleigh scattering
i.e. the scattering of radiation by air molecules (elastic no change in wavelength) Rayleigh scattering causes unidirectional, monochromatic radiation, when passing through the atmosphere, to be attenuated by a factor: exp(m ) where m is the air mass (

and is the Rayleigh scattering coefficient

pressure 313.44 .
1013
4

i .e. ' 1 when ' 313.4nm and pressure ' 1013 hPa
Thus for an atmosphere containg only air and ozone:

I = I0. exp( -

x m )

- the radiant energy originating from a small solid angle including the sun arriving at the earths surface (also in a small range of wavelength) I0 is the direct solar irradiance above the atmosphere

I is the direct solar irradiance in watts.m-2.nm-1

11/17/200

MSC Brewer Optics, JBK, DIW, CTM

Langley plot: single-wavelength determinations of ozone

A Langley plot is a graph of log I versus sec2 (or ) . Assuming that attenuation is due only to Rayleigh scattering and ozone absorption (and that m = ), the Langley plot should follow:

log I ' log I0& ( x % )

This same expression applies if I signifies the instrument readings provided they are known to be proportional to the radiation; I0 is then the reading the instrument would show if subjected to the radiation above the atmosphere. (Absolute irradiance calibration is not needed.) The long method (terminology of G.M.B. Dobson) derives the ozone x and the extraterrestrial reading I 0 from the slope and intercept of the Langley plot. It uses several measurements obtained during any morning or afternoon to obtain single values for x and I 0. Changes in the ozone during the the day can cause significant errors! The short method gives one ozone value for each measurement but requires a predetermined value for the extra-terrestrial reading. Long-term drift in the instrument responsivity contributes to error in I0 and, consequently, in x.

11/17/200

MSC Brewer Optics, JBK, DIW, CTM

Langley plot Short and Long Methods

log I0

Long Method

log I0 (given)

Short Method

Log I

0
--

1
0

2
60

3
70

4
75

2 }

intercept ' log I0 ; slope ' x % OZONE '

slope

&

OZONE '

log I0 & log I

&

In practice, both methods applied to single-wavelength measurements give large uncertainties due to sources of attenuation other than air and ozone. The uncertainties can be greatly reduced by using ratios of measurements at two or more wavelengths instead measurements at any single wavelength.

11/17/200

MSC Brewer Optics, JBK, DIW, CTM

Single wavelength attenuation expression log I = log I0 ! ( a x + m $ + sec2 + a y )

T (T) TT ? TT T ? T T ? where:

I I0

= = = = = = = = =

a
x

a
y

radiation as measured by Brewer radiation as would be measured by the Brewer above atmosphere solar zenith angle m sec slant path factors ozone absorption coefficient ozone amount Rayleigh scattering coefficient amount of other absorption SO2 absorption coefficient SO2 amount

11/17/200

MSC Brewer Optics, JBK, DIW, CTM

Brewer standard direct sun measurement

The Brewer measures the intensities in five wavebands when in the Direct Sun (ds) and several other routines. Using the index k to denote each of the five wavebands(1#k#5) the absorption expressions may be written as: logI k = logI0k - ( " k x + m $ k + sec2 * k + k y ) The Brewer signals are photocounts. They are corrected for the dark signal and for non-linearity and used in place of the irradiances I k in the above and following expressions. The wavebands are roughly triangular(see later), with FWHI=0.55 nm, centered on the following wavelengths (nm): k 8k 0 z* 1 306.3 2 310.1 3 313.5 4 316.7 5 320.0

( * z= 302.1 or 303.1, used mostly for calibration.)

11/17/200

MSC Brewer Optics, JBK, DIW, CTM

Brewer DS algorithm for ozone

There are several valid ways to derive ozone values from the five measurements. The standard method does not use the measurement at 306.3nm. It is expressed in terms of weighting factors using the following notation: Fk WC = = logI k + m $k j k wk k etc. with W = ( 0 1.0 -0.5 -2.2 1.7 ) ( F0k = logI0k )

The weighting factors wk are chosen so that the sulphur dioxide product WC"0 is zero and WC* is negligible* provided * only varies slowly with wavelength. Consequently the following equation applies: WC ( F0 - F ) = x WC" This allows a solution for the ozone amount (x) for each measurement of I 1<k<6 provided WCF0 is known, either by comparison with another Brewer on which WCF0 is known, or by extrapolation. *W is orthogonal to the wavelength 8k so any linear variation of * with k has minimal effect. ( c.f. Dobson double pair assumption).

11/17/200

MSC Brewer Optics, JBK, DIW, CTM

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Brewer SO2 algorithm and the ds sequence

The standard sulphur dioxide calculation is similar to that for ozone. It initially uses the vector V = (1 0 0 -4.2 3.2) and is equivalent to replacing W in the ozone algorithm with the vector U = V - W V / VC . During the standard ds measurement routine, the wavebands are sampled in 5 groups of 20 cycles each. The total duration is about 3 minutes during which each waveband is sampled 200 times. With 1#k#5 denoting each of the wavebands the sampling sequence is described by 5 x ( 20 x (1234554321) ). The counts are accumulated during each group and recorded. Thus there are five sets of data each of which gives a single value for ozone and sulphur dioxide. The overall result can be given as the mean and standard deviation of the five ozone and sulphur dioxide values.

11/17/200

MSC Brewer Optics, JBK, DIW, CTM

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