Environmental Assignment 2

Pollution

The monitoring of Nitrogen Dioxide using diffusion tubes

INTRODUCTION
Adverse effects on health and the natural environment from air pollution have been recognised and reduced in the last century by effective legislation, and pollution control. However, there is emerging evidence that the toxic effects of new photochemical pollutants such as Nitrogen Dioxide are apparently related to respiratory infections, (Chauhan & Johnston, 2003) of which account for an estimated 4 million deaths worldwide from 1997 to 1999 (World Health Report, 1997). Current epidemiological evidence suggests that much of the morbidity and mortality, especially in young children is related to both sources of indoor and outdoor pollution (Hester and Harrison, 1998). In terms of outdoor pollution, recent evidence from monitoring data and research has inferred that NO2 emissions have increased, and are much higher than initially thought particularly due to one sector, road transport (e.g. AQEG, 2004). Furthermore, recent studies show that NO2 emissions are the main source of pollution in Bristol (Bristol City Council Air Quality Data, 2009). In particular NO2 concentrations are higher closer to motorways and decline with distance, perhaps elevating local vicinity background concentrations (Roorda-Knape, M.C., et al. 1999). In order to protect human health, outdoor concentrations of ambient NO2 have been regulated throughout Europe since 1985, with the EC Daughter Directive (1999/30/EC) setting Value Limits to be achieved by 2010 (European Council, 1999). In response to attempt to achieve these targets is the UK Governments National Air Quality

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Strategy (NAQS), providing objectives for ambient NO2 (DETR, 2000) concentrations as purposed in Table 1 below. As stated in LAQM. TG(03) the NAQS annual mean objective applies to air at locations which are situated outside of buildings or other natural or man-made structures, above and below ground, and where members of the public are regularly present. The particular site does accommodate regular members of the public. As the exposure period in the experiment was two weeks, results cannot be standardised with shorter averaging means (i.e. 1 hour mean) only annual means. However Air Quality Consultants state that if an annual mean concentration exceeds 60 g/m then it is likely that the NAQS 1-hour mean objective would have been exceeded (Air Quality Unit, 2008).
Table 1: NAQS objectives for NO2 to be completed by December 2005

(Source: Defra, 2000)

Background NO2 concentrations for the surveyed area on the Bristol, South Gloucester boundary for 2009, as estimated by Bristol City Council (2007) is ~ 16-40 g/m.
Figure 1 A) Regional annual mean of recorded NO2 in 2007 location B) Sampling site

(Source: Bristol City Council, 2007)

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To model roadside NO2 concentration from traffic related air pollution, passive diffusion tube samplers where located as in Figure 2 C), on the South Gloucester boundary near the M32 motorway. The M32, is the principal link between the National Motorways and the City network, carrying an annual average daily traffic (AADT) volume of ~ 85,000 vehicles per day including medium and heavy goods vehicles (Bristol City Council, 2006).
Figure 2 A) National geographical area B) Regional geographical area C) Sampling site location

B C A

(Source: Google Earth, 2009)

THEORETICAL TUBES

PRINCIPLE

OF

DIFFUSION

Since their introduction in the late 1970s by Palmes and Gunnison (Palmes et al., 1976) the method has been validated for outdoor use (Atkins et al., 1986) allowing passive diffusion tubes to be used for indicative measurements of time weighted average concentrations of nitrogen dioxide in ambient air (Gatrell & Lytnen 1998). At present it is undertaken on a wide scale in the UK for spatial and temporal measurements in the context of Local Air Quality Management (AEA, 2008). Typical components of a passive diffusion sampler are shown in Figure 3.
Figure 3: Typical components of a diffusion sampler, consisting of an acrylic or polypropylene tube (length 7.1cm and internal diameter of 1.1cm), two or three

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stainless steel inert meshes coated with triethanolamine and two polyethylene caps

(Source: AEA, 2009)

As the name suggests passive diffusion tubes absorb the pollutant to be monitored directly from the surrounding air, without the need of a power supply. It is designed and based on molecular diffusion along a fixed length tube into an efficient absorbing medium as depicted in Figure 4.
Figure 4: Palmes diffusion tube. Co is the NO2 concentration in ambient air, Cout is the NO2 concentration at the external interface of the membrane, Cin is the NO2 concentration at the internal interface of the membrane and Cfin is the NO2 concentration at the interface with the sorbet. S is the internal cross-area of the tube and Sout is the internal cross-area of the membrane cap.

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(Source: Gerboles et al., 2005)

The gas molecules undergo what is deemed molecular diffusion, with regards to the molecules diffusing from a region of high concentration (open end) to a region of low concentration (absorbent end) along the tube, (which stops particulate material accumulation due to a lower rate of diffusion) until collection onto an impregnated filter or an absorbent material. The diffusion barrier is believed to maintain the sampling rate. Additionally the fine mesh minimises convective transport of gas to the filter. In terms of monitoring nitrogen dioxide the filter is usually coated with triethanolamine that retains NO2 as a stable nitrite analyte, as shown in the following reaction.

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2NO2 (g) + N(Et OH)3 (l) + 2OH H2O (l)

2NO2

- + O- N(Et OH)3 +

TEA is frequently used because it captures NO2 very effectively and ion chromatograph (IC) can be used to conduct analysis at low detection limit (Gair et al., 1991). The diffusion rate is governed by Ficks first law as given in Equation 1, which is proportional to the concentration gradient along the diffusion path. In other words the diffusion rate is proportional to the concentration of nitrogen dioxide in the atmosphere (Fifield & Haines, 2000). Therefore after a specific exposure time, the retained concentration of nitrite can be used in combination with Ficks second law (Figure 5) to estimate the ambient NO2 concentration. This is quantified using the Griess-Saltzman colorimetrical method measured at 543nm using a spectrophotometer with the aid of a nitrite standard calibration curve.
Equation 1: Ficks first law of diffusion describes the unidirectional diffusion of gas (a) through a mixture of gases (b) under conditions of constant temperature. The negative value sign of D12 arises from the measurement of flux in the direction of decreasing concentrations of (a).

F1 = -D12 (dc1/dz)
F1 = Flux of a (moles cm-2 s-1) D12 = molecular diffusion coefficient of (a) through (b) 2 -1 [cm s ] C1 Z = concentration of (a) in (b)[moles cm-3] = distance, in the direction of diffusion (cm)

The principles of passive diffusion are summarised in Figure 5.

Figure 5: Summary of passive diffusion principle

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(Source: Hangartner, 2007)

LIMITATIONS OF TECHNIQUE
The diffusion tube technique has two main limitations. Firstly it is an indicative monitoring technique. Therefore, suitable for screening surveys, or identifying locations of high NO2 concentrations, however it doesnt provide the same level of accuracy as automatic monitoring techniques. Secondly, the method only provides a concentration that is averaged over the exposure period (typically 1-4 weeks) reducing temporal resolution as it is not possible to measure short-term (e.g. hourly) concentrations (Bush et at., 2001). This also means that results cannot be compared with air quality standards and objectives based on shorter averaging periods i.e. 1 hour means (AEA, 2008). Process is reliant on the following underlining assumptions in determining sample rate; 1.) Molecular diffusion coefficient is known for NO2 in air, along with its dependence on temperature, pressure, humidity (i.e. presence of water vapour) 2.) The absorber is perfect.

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3.) The absorbed gas can be measured quantitatively. 4.) There is no absorption or adsorption by the tube walls. 5.) No chemical reactions occur in the tube during sampling that would affect the NO2the concentrations. 6). The concentration is maintained constant at the entrance of the tube (Cape, 2005). General consensus is that most of the original assumptions are met in practice, with inaccuracies minimised except under certain well-defined conditions. However these limitations still remain. Other possible limitations are summarised in Table below.
Table 2: Possible limitations of the passive diffusion technique

Influence of meterological factors on NO2 sampling rates, i.e. changes in temperature and relative humidity can impact on performance (Plaisance et al., 2004). Furthermore studies have found that a temperature reduction has a strong effect on NO2 calibration factors (sampling rates) (Sickles and Mitchle, 1984). Tubes usually manufactured from either acrylic or polypropylene have the disadvantage of being almost opaque to UV light. This blocking of UV light is thought to result in reduced NO2 photolysis in the tube. Slight possibility of secondary reactions or chemical changes in the trapped material during sampling and/or storage i.e. NO and O3 to give NO2 effecting sampling rate Possible interference from other gases Interfering effects of peroxyacetyl nitrate (PAN) a pollutant associated with vehicle emissions (Campbell et al., 1994) Insufficient extraction of nitrite from grids (Heal et al., 2000) Require two consecutive exposure periods to improve systematic error, reducing turnaround time of results. Colour development determination in methodology subjective. Risk of losses of sampled material due to back-diffusion (reverse diffusion), especially for longer sampling times. Lack of specificity compared to chemiluminescent detectors.

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No standard operating procedures exist Relatively limited shelf life (1+ year). Laboratory analysis required.

RESULTS
Nitrogen dioxide was measured at sample site (Figure 2C) between the 3rd and the 17th of February, using Palmes diffusion tubes. As described in the principles section, TEA retains NO2 as a stable NO2 (nitrite) analyte. NO2 concentrations can then be inferred from this estimation, as the quantity of nitrite in the tubes is directly related to the average concentration of NO2 in the air. Therefore by using prepared known standard nitrite solutions, a calibration curve can be plotted of of absorbance of standards against NO2(Table 3). The indicative mean absorbance of nitrite in the sampled tubes (Table 4) can then be used to estimate the concentration directly from the curve (Figure 6). This estimation can be improved by rearranging the linear regression formula y = ax + b to make x (i.e. estimated nitrite concentration) the subject.
Table 3: Mean absorbance of nitrite standard solutions with statistical evaluation

Concentration Nitrite Standard Solution(s) [mg/dm3] 0.0 0.2 0.4 0.6 0.8 1.0 X
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Mean Spectrophotometer Response at 543nm wavelength 0.000 0.090 0.184 0.352 0.460 0.572 0.457
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Statistical Evaluation

Y A B r-squared

0.251 -0.0192 0.5911 0.992

Figure 6 Calibration curve of nitrite standards

Calibration Curve of Nitrite Standrds

0.700 Nitrite absorbance [543nm wavelength] 0.600 0.500 0.400 0.300 0.200 0.100 0.000 -0.100 0.0 0.2 0.4 0.6 0.8 1.0 1.2

y = 0.5911x - 0.0192 r-squared = 0.992

Nitrite concentration [mg / dm3]

Table 4: Estimated absorbance of nitrite from sampled site including field blanks

Sampled diffusion tubes Mean absorption at 453nm replicates wavelength 1 0.260 2 0.268 3 0.243 4 0.241 5 0.261 6 0.226 7 0.261 Mean 0.251 Standard deviation 0.015 Coefficient of variance 5.98 Field blanks Mean absorption at 453nm wavelength

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1 2 3 Control blank 1

0.000 0.002 0.000 Mean absorption at 453nm wavelength 0.001

Figure 7: Estimated absorbance of nitrite from sample site with mean

Estimated mean absorbance of nitrite from sampled site

Absorbance at 453nm 0.280 0.270 0.260 0.250 0.240 0.230 0.220 0.210 0.200 1 2 3 4 5 6 7 Diffusion tube sample

Mean

Field blanks where used and analysed simultaneously with the exposed samples to check for any possible contamination i.e. passive diffusion into sealed tube. The control blank was placed in the fridge to determine any absorption or adsorption by the tube walls under controlled conditions. The mean nitrite concentration from the sample site is estimated at 0.457 mg/dm3. Rearranging Ficks second law (Figure 5) allows ambient nitrogen dioxide concentrations (in mass per volume or air and volume per volume of air) to be estimated to two decimal places as follows;
Equation 2: Ficks second law, prediction of how diffusion causes the concentration field to change with time

C = (Q x Z) (D x r2 x t)

C = average concentration NO2 in air (g m3)

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Q = quantity of analyte, Q= 2G g as analysis on 2 cm3 (g /cm3) Z = diffusion path (m) D = diffusion coefficient (m2/sec) r2 = cross section (mm2) t =exposure time (s)

0.914 x 0.07 1.46 x 10 x 9.5 x 10-5 x 1188600

-5

C = 38.8 g/m3 (over two week duration)

Air quality standards require concentration measurements in units of volume of nitrogen dioxide per volume of air. This calculation takes into account the variation of temperature and pressure on molar volume (Figure 5). In addition mean wind velocity was estimated at 3.6 mph or 1.61 m/s.
Table 5: Daily mean temperature and pressure

Date(s) 03.02.09 04.02.10 05.02.11 06.02.12 07.02.13 08.02.14 09.02.15 10.02.16 11.02.17 12.02.18 13.02.19 14.02.20 15.02.21 16.02.22 17.02.23 Mean

Mean [C] 0.3 1.9 0.2 0.5 1.1 1.7 2.5 3.3 3.4 2.4 4.9 4.6 6.2 7.1 8.6 3.2

temperature Mean pressure [mb] 992.9 991.7 988.6 991.4 998 1001.6 991.9 1003.3 1018.2 1024.9 1023.3 1028.2 1027.8 1026.7 1027 1009

(Source: Prodata Weather systems, 2009)

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This means the results must be converted as follows;

Molar volume = 22.41 x 276.2 x 1009 273 1013 = 22.57 ppb = C x MV RMM Relative molecular mass of NO2 = 46 ppb = 33.8 x 22.57 46 ppb = 16.6 (over two week duration)
DATA ANALYSIS
Data validity requires comprehensive intraspecific analysis of both systematic and random errors. In terms of systematic errors it is important to appreciate that the results of the measurements are only as good as the instrument, which in turn will only give accurate results if properly calibrated (Pepper et al., 1996). Therefore the greatest source of systematic error in the assignment is most likely attributable to the nitrite standard calibration especially at lower concentrations, as shown by high coefficient of variance in previous classroom experiments. It must be appreciated that for complete statistical evaluation, a comparison of laboratory results against certified reference standards would be required. Therefore this absence significantly reduces data validity, as analyte quality and methodology cannot be accessed. The statistical analyse of estimated calibration data (Figure 6) did however produce a high r-squared value (correlation coefficient) for linearity. This result is equal to the percent of the variation in one variable that is related to the variation in the other. This strong correlation suggests
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that the equipment response is universally sensitive and that no apparent anomies occurred during the procedure. In terms of sample site data validity, both standard deviation and coefficient of variance statistics have been implemented. These can be used to assess random error or precision as a measure of reproducibility. The average amount data deviates from the mean abundance is 0.251 0.015. This low standard deviation suggests great precision of reproducibility. Consequently the precision in measurements is good, as there is only an estimated 5.98%, variation in the data set, with no apparent outliners. There is however an important caveat in using this statistic for data interpretation. Comparison of sampled data to quality control data is required to calculate percentage deviation. Without this standardised benchmark, data could have a desirable coefficient of variance but operators could repeatedly make the same mistakes gaining similar but inaccurate results. Reiterated by Cape (2005), the largest source of error in using diffusion tubes for monitoring nitrogen dioxide is interlaboratory variation. This apparent lack of standardisation in methodology seriously reduces data validity. Field blanks and control blanks used in the preparation of the calibration curve and in-situ seem to suggest that there is no evidence of trace sources of artificially introduced contamination causing bias. Therefore values did not require subtracting from masses of exposed samplers. However in QC analysis laboratory equipment should be calibrated against blank control diffusion tubes from a certified laboratory. The validity of data is influenced not only by methodology (Bush et al., 2001) but, meterological factors. (Plaisance et al., 2004) Of which the strongest bias on sampling rate is created by the effect of wind velocity, causing a reduction in molecular diffusion length (Glair & Penkett, 1995). The study quantified this as a 47% reduction in diffusion length for air velocities close to 2m/s. Consequently, with a calculated mean air velocity of 1.6 m/s during the two

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week sampling period (Prodata Weather Systems, 2009) then a plausible diffusion reduction is 38%.

CONCLUSION
In comparison to Defras NAQS for the UK (Table 1) the roadside sampling site analysed was 3% below the objective for protection of human health at 38.8g/m3. More specifically for kerbside locations (1-5m from the kerb of a busy road) it is 28% below the annual UK average concentration determined by the NO2 diffusion tube network in 1997 (Stevenson et al. 2001). Moreover the results reflect ambient findings published by Bristol City Council in 2007 (Figure 1). Hence it seems that in the light of scientific understanding about the effects of nitrogen dioxide on health, levels at that particular sample site levels are acceptable. However despite this, concentrations are above new legislation introduced in 2007 for protection of vegetation and ecosystems (Defra, 2007). Finally, as an indicative method for screening nitrogen dioxide in potential problematic locations, evidence strongly suggests (Gerboles et al, 2005 & Bush et al. 2001) that the accuracy of measurement accomplishes the Data Quality Objective (DQO) laid down in the European Directive, justifying their continued use. Being cost effective and convenient in mapping spatial distributions and investigating long-term trends. However data must be interpretated carefully, with regards to appreciating potential systematic and random error that could cause either positive or negative bias. Additional research and method standardisation is required to fully validate and clarify these internal and external impacts.

REFERENCES
AEA Energy & Environment, 2008. Diffusion Tubes for Ambient NO2 monitoring: Practical Guidance for Laboratories and Users. Report to Defra and the Devolved Administrations. Available from http://www.airquality.co.uk/archive/reports/cat05/0802141
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004_NO2_WG_PracticalGuidance_Issue1a.pdf [accessed 7th March 2009]. Air Quality Expert Group, 2004. Nitrogen dioxide in the United Kingdom. First report of the Air Quality Expert Group. Defra, London. Available from http://www.defra.gov.uk/environment/airquality/aqeg/nitro gen-dioxide/index.thm [accessed 7th March 2009] Air Quality Unit, 2008. North Cornwall District Council. Report on the nitrogen dioxide diffusion tube and continuous monitoring in Dennison Road, Bodmin. Available from http://www.cornwallairquality.org.uk/Reports/North_Cornwall/Bodmin.p df [accessed accessed 7th March 2009]. Atkins, D.H.F., Sandalls, J., Law, D.V., Hough, A.M., Stevenson, K., 1986. The measurement of nitrogen dioxide in the outdoor environment using passive diffusion tube samplers. United Kingdom Atomic Energy Authority, Harwell Laboratory, Oxfordshire (UK), Report, AERE R 12133 Bristol City Council, Air Quality Data, 2009. Local air quality and emission readings. Frequently asked questions. Available from http://www.bristol.airqualitydata.com/cgi-bin/faqs.cgi? 1008 [accessed 7th March 2009]. Bristol City Council Air Quality Data, 2009. Local air quality and emission readings. Available from http://www.bristol.airqualitydata.com/cgi-bin/faqs.cgi? 1008 [accessed 6th March 2009] Bristol City Council, Environment and Planning, 2007. Google Earth layer of NO2 diffusion tubes in Bristol. Available from http://www.bristol.gov.uk/ccm/navigation/environmentand-planning/pollution/pollution-control---air-quality/ [accessed 7th March 2009].

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Bristol City Council, 2006. Environmental Act 1995. Local Air Quality Management. Updating and Screening Assessment. Available from http://www.bristol.gov.uk/ccm/cms-service/stream/asset/? asset_id=25473032 [accessed 7th March 2009]. Bush, T., Smith, S., Stevenson, K., Moorcroft, S., 2001. Validation of nitrogen dioxide diffusion tube methodology in the UK. Atmospheric Environment. 35, 289-296. Campbell, G.W., Stedman, J.R., Stevenson, K.J., 1994. A survey of nitrogen dioxide concentration in the UK using diffusion tubes. Atmospheric environment. 28, 477-486 Cape J.N., 2005. Review of the use of passive diffusion tubes for measuring concentration of nitrogen dioxide in air. Available from http://www.airquality.co.uk/archive/reports/cat05/0810141 025_NO2_review.pdf [accessed March 14 th 2009] Chauhan, A.J, and Johnston, S.L., 2003. Air pollution and infection in respiratory illness. British Medical Bulletin. 68, 95-112 Defra, 2007. UK Air Quality Objectives for protection of vegetation and ecosystems. Available from http://www.airquality.co.uk/archive/standards.php [accessed 14th March 2009] Department of the Environment, Transport and the Regions, 2000. The Scottish Executive, The National Assembly for Wales and The Department of the Environment Northern Ireland. The Air Quality Strategy for England, Scotland, Wales and Northern Ireland. January 2000. Avaible from http://www.environment.detr.gov.uk/airquality/inde x.htm [accessed 6 th March] European Council Directive, 1999. Official Journal of European Communities 1990/30/CE, L 163/41.

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Fifield, F.W., Haines, P.J., 2000. Environmental Analytical Chemistry. Blackwell publishing, 337-338. Gair, A.J., Penkett, S.A., 1995. The effect of wind speed and turbulence on the performance of diffusion tube samplers. Atmospheric Environment. 29, 2529-2533 Gair, A.J., Penkett, S.A., Ovola, P., 1991. Development of a simple passive technology for the determination of nitrogen dioxide in remote continental locations. Atmospheric Environment. 25, 1927-1939. Gatrell, A.C., Lytnen, M., 1998. Houghton Mifflin Harcourt, 83-84 GIS and Health.

Gerboles, M., Buzica, D., Amantini, L., 2005. Modification of the Palmes diffusion tube and semi-empirical modelling of the uptake rate for monitoring nitrogen dioxide. Atmospheric Environment: 39, 2579-2592 Google Earth, 2009. Available from th http://maps.google.co.uk/ [accessed 7 March 2009].

Hangartner M., 2007. Diffusion tube methods for sampling NO3 NO2 and O3. Available from http://rscaamg.org/Documents/Papers/Prague/MarkusHangartner.p df [accessed 6 th March 2009] Heal, M.R., Kirby, C., Cape, J.N., 2000. Systematic biases in measurement of urban nitrogen dioxide using passive diffusion samplers. Environment: Monitoring and Assessment: 62, 39-54. Heal, M.R., Cape, J.N., 1997. A numerical evaluation of chemical interferences in the measurement if ambient nitrogen dioxide by passive diffusion samplers. Atmospheric Environment: 31, 1911-1923.

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Hester, R.E., Harrison, R.M., 1998. Royal Society of Chemistry (Great Britain). Air pollution and health. Royal Society of Chemistry, 1-2 Palmes, E.D., Gunnison, A.F., Dimattio, J., Tomczyk C., 1976. Personal sampler for nitrogen dioxide. American Industrial Hygiene Association Journal: 37, 570-577 Palmes, E.D., Gunnison, A.F., 1973. Personal monitoring device for gaseous contaminants. American Industrial Hygiene Association Journal : 34, 78-80 Pepper, I.L., Gerba, C.P., Brusseau, M.L., (1996). Pollution Science. Academic Press. UK. Plaisance, H. Piechocki-Minguy, A., Garcia-Fouque, S., Galloo, J.C., 2004. Influence of meterological factors on the NO2 measurements by passive diffusion tube. Atmospheric Environment: 38, 573-580 Prodata Weather Systems, 2009. Data from a Davis VP2 Plus automatic weather station, Horfield Bristol. Available from http://www.martynhicks.co.uk/weather/data.php? page=022009 [accessed 14th March 2009] Roorda-Knape, M.C., Janssen, N.A.H., Hartog, J.D., Van Vliet, P.H.N., Harssema, H., and Brunekreef B., 1999. Traffic related air pollution in city districts near motorways. The Science of the Total Environment: 235, 339-341 Sickles J.E., Mitchle R.M.,1984. Investigation of the performance of sulphation search Triangle Park. NTIS Report No. PB84-211184 Stevenson, K., Bush, T., Mooney, D., 2001. Five years of nitrogen dioxide measurement with diffusion tube samplers at over 1000 sites in the UK. Atmospheric Environment: 35, 281-287 World Health Report, 1997. Nitrogen oxides (2nd edition), environmental health criteria 188. Geneva (Switzerland):

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World Health Organisation, Chemical Safety.

Internal

Programme

on

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