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Diffusive Sampler
Diffusive or passive samplers are known as the cheapest method of monitoring air quality and can give a good overall picture of average pollutant levels in an area. The low cost per tube permits sampling at a number of points in the area of interest. Although results from single point passive samplers are not as precise as those from automatic point monitors, the accuracy and reproducibility of the measurements has increased over recent years. Diffusive samplers are typically clear plastic tubes open, or with a membrane screen, at one end and a pollutant-absorbing chemical matrix or gel at the closed end. The diffusion tube collects the pollutant during the exposure period (one week or more), at the end of which the tube is returned to an analytical laboratory. The time resolution of this technique is limited, as it can only provide information on integrated average pollutant concentration over the exposure period. They have been widely used for many years in personal monitoring and occupational health assessments (Dore and McGinlay, 1997). These kind of devices are very appropriate for gas flux emission measurement, they do not require another measurement and can be applied over a wide area, because of their low cost. One disadvantage of these devices are that they still require further analysis in laboratory. Theoretical understanding of gas movement in diffusive samplers have been introduced by Palmes, et.al in 1976. For the axial tube type diffusive sampler, the rate of mass transfer down the concentration gradient induced in the air gap, can be derived from the Ficks first law (Bates, et.al, 1997):

dm dC = DA dt dx
where: dm/dt = rate of mass transfer d = diffusion coefficient of gas dc/dx = concentration gradient along the axis Integration of the above equation gives:

mt DA = (C 0 Ca ) t l
where: mt = mass transferred in time t t = sampling duration l = diffusion path-length C0 = ambient concentration Ca = concentration just above adsorbent surface By using a suitable absorbent or adsorbent at one end of the tube, with the other end being exposed to the environment to be measured, it can be assumed that the concentration of gas in the surface of adsorbent or absorbent layer is maintained at zero and the gradient concentration of gas becomes numerically equal to the ambient concentration of the gas to be measured C0.

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Besides the axial tube type sampler described above, to increase the uptake rate of gases, the radial type sampler has been introduced. Again Ficks first law may be used to describe the transfer across the still air zone. In cylindrical coordinates the equation becomes:

dm dC = D 2 rh dt dr
where r = radius h = length of the cylinder dC/dr = concentration gradient along the radius The integrated form is follows:

mt C Ca = D 2h 0 r t ln 0 ra
Several types of diffusive sampler now commercially available. They can be tube or badge type, pollutant can be chemically bound by appropriate reagent or physically adsorbed by inert media. For further analysis the pollutant may be extracted by thermal desorption or solvent extraction. Various types of diffusive sampler can be seen in appendix 2.

Adsorbent For Gases Silica gel

Silica gel is one of the synthetic amorphous silicas, It is rigid and forms a continuous network of spherical particle of colloidal silica. It is synthesised by following reaction: Na2SiO3 + 2HCl + nH2O 2NaCl + SiO2.nH2O + H2O

Its properties e.g. surface area, pore volume and strength can be varied by varying the silica concentration, temperature, pH and activation temperature. Silica gel (along with activated alumina) is a desirable sorbent for drying because of its high surface areas and unique surface properties. At low surface coverage, the water molecule is bound to the silanol group oxygen donor. At higher coverage, hydrogen bonding becomes predominant, with a bound strength or heat of adsorption 10.8 kcal/mole. Thus the heat of adsorption of water vapour on silica gel is approximately 11 kcal/mole. This property causes regeneration of silica gel is achieved by heating to approximately 150oC, lower than zeolite (350oC). Its adsorption properties to organic pollutant have been studied extensively, particularly for the following compound: - alcohol - aromatic hydrocarbon - chlorinated hydrocarbon
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aldehyde

Activated carbon
The surface properties of activated carbon is non-polar or only slightly polar as a result of the surface oxide groups and inorganic impurities. This properties give the following advantages: - can be used to perform separation and purification processes without prior stringent moisture removal. - it adsorb more non-polar and weakly polar organic molecules than other sorbents do - the heat of adsorption is generally lower than other sorbents so that stripping of the adsorbed molecules is easier. It has a large surface area 300-2500 m2/g which is the largest among all sorbents. For application in liquid phases, it should have pore size near or larger than 30 A, whereas for gas phases the pore diameter in the range from 10 A to 25 A. According to IUPAC, the pores are subdivided by diameter (d) - macropores (d>500 A) - mesopores (20 A <d< 500 A) - micropores (d< 20 A) Activated carbon has been used extensively for industrial gas cleaning and indoor air cleaning. Based on the adsorption systems it has been used to control organic vapour in the workplace. It has the greatest affinity for organic molecule because of the nonpolar nature of its surface as compared to other solid adsorbent. Below 40% RH, water vapour does not interfere with the adsorption process of organic and other compound on activated carbon.

Zeolite
Zeolites are crystalline aluminosilicates of alkali or alkali earth element such as

[( AlO 2 ) x ( SiO 2 ) y ] zH 2 O

sodium, potassium and calcium, represented by the stoichiometry: where: x, y : integer with y/x equal or greater than 1 n : valence of cation M z : number of water molecules in each unit cell Presence of cations are necessary to balance the electrical charge of the aluminium atom, each having a net charge of 1. The water molecule can be removed with ease upon heat and evacuation, leaving an almost unaltered alumino silicate skeleton with a void fraction between 0.2 and 0.5. There are a regular structure of cages in the skeleton, interconnected by six windows in each cage. The cages can bind or occlude large amount of guest molecules in place of water. The size of the window aperture (can be controlled by fixing the type and number of cations), range from 3-10 A. The sorption may occur with great selectivity because of the size of the aperture, hence it is called molecule sieve (Yang, 1997).

Activated Alumina
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Activated alumina is a dehydrated (or partially) alumina hydrates, both crystalline and amorphous with high surface area. It has the greatest affinity for water, and is applied in drying of gases and liquids because of its hydrophilic property and large surface area. It has been applied as a sorbent for drying gases: Ar, He, H2, alkanes (C1-C3), hydrocarbon, Cl2, HCl, SO2, and NH3. It also may be used for the removal of various contaminants from gases, such as trace fluorides, cloride, H2S, alcohol and ethers.

Molecular sieve carbon

Molecular sieve carbon (MSC) is less hydrophilic than zeolites, so can be used more efficient in separation process involving wet-gas streams. It has been used for the production of nitrogen from air. In the preparation and sieving properties study, three approaches were taken: a. Carbonization of polymers such as poly vinylidene chloride (PVDC); saran (90/10 mixture of vinylidene chloride and vinyl chloride); and cellulose, sugar and coconut shell. b. Slightly carbonizing coals, especially anthracites c. Coating of the pore mouth of the commercial activated carbon with a carbonised or coked thermosetting polymer.

Direct Reading Colorimetry Detector Tube

Colorimetry detector tube or direct reading diffusive sampler is a simple device that capable to analyse the airborne contaminant quantitatively based on coloration of indicating layer. When the molecule of airborne contaminant reach the reagent layer they react chemically with the filling material causing a colorimetric stain. The residual stain length is a measure of the dosage of the contaminant to be measured, i.e. the product of concentration and time. Molecules of air contaminants migrate into a diffusive sampler according to the laws of gaseous diffusion. When the sampler is exposed in air a concentration gradient is developed between the ambient air and the air inside the sampler.This phenomenon can be described by Ficks first law of diffusion as described previously. Because of a gas molecule react with the impregnated chemicals, there are virtually no free gas molecule in the air inside the sampler. The full concentration difference is thus available as a driving force for diffusive sampling. However the diffusion pathway for the gas molecule becomes longer as the stain gets longer. It is mean, according to Ficks law, that the mass flow decreases with increasing stain length. The increase of the stain length (dl) can be formulated by

dl =

dm ki A

ki = adsorption capacity of a discrete layer element. Its combination with Ficks law of diffusion gives:

ldl =

Dc dt ki

and the integrated form and further arrangement of this formula is:

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2 D ct l= k i

1/ 2

The validity of above relationship can be demonstrated by the calibration curve of the direct-reading diffusive sampler using scale figures for the dosage of the contaminant to be measured (May, 1989). Due to the air movement only depending on diffusion of gases, then a passive detector tube can be imagined as long term sampler. The problem associated with this kind of device is the flow rate of gas can be too low for the reagent system used because side reactions can occur on long contact of the gas with the indicating layer. For satisfactory function, the reagent must fullfil the following requirements ((Leichnitz, 1976): 1. the indication color must be a measure of the absolute amount (mass) of gas (product of concentration and air sample volume must be constant). 2. the absorption capacity of the reagent must not be affected by humidity changes and must remain constant during the measuring process. 3. The rate of reaction of the gas with the reagent system must be much higher than the rate of any side reaction with may take place on the surface of the reagent carrier In many detector tubes, the calibration curve can be represented by the following equation:

l=

m v + (1 e1A/ v ) C A

where: l = length of the discoloration m = mass of gas which has reacted in the tube, A = constant with the dimension of reciprocal time C = sorption capacity of the indicating preparation v = flow by volume of air sample in the tube.

Indicating Layer Material for Detector Tube

The supporting material for the indicating layer in the tube may be silica gel, alumina, ground glass, pumice, or resin (Jungreis, 1985). The indicating layer or the reagent system comprises of one or more chemical compound which can produce a colour change when react with target contaminant. Nitrogen Dioxide (NO2) A drying agent and pale gray diphenyl benzidine can be used as the indicating layer. Nitrogen dioxide oxidises the diphenylbenzidine to the bluish-gray quinoidal reaction product NO2 + Diphenylbenzidine Diphenylbenzidine blue + NO + H2O The other gaseseous compounds that can oxidise diphenylbenzidine are ozone and clorine with the cross-sensitivities of 0.5 relative to nitrogen oxide.

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Ozone (O3) The indicating layer contains indigo compound which changes colour from blue to colourless due to oxidation by ozone. O3 + Indigo (blue) Isatine (colourless) Chlorine and nitrogen dioxide also discharge the color of indigo when present in concentration higher than 5 ppm. Sulphur dioxide (SO2) The indicating reaction for measurement of sulphur dioxide in the various detector tube may involve formation of the extremely stable anion complex [Hg(SO3)2]2-. The indicating reagent is composed of disodium tetra chloromercuriate and methyl red. Hydrochloric acid liberated during the reaction changes the indicator color. 2SO2 + Na2[HgCl2] + 2H2O Na2[Hg(SO3)2] + 4 HCl The second principle that can be used for sulphur dioxide detection is reaction of free iodine with sulphur dioxide (decolorizing the blue iodine-starch complex) SO2 + I2 + H2O SO42- + 2I- + 4H+ Hydrogen sulphide become serious interferen if use the detector tube without a cupriccontaining precleansing layer.

Reactions in Colorimetric Detector Tube

Several types of chemical reaction that used to generate colour change are: Oxidation-reduction Acid-base Substitution-addition and others

Oxidation-reduction Example of this type is CO detector tube that created by using reagent a mixture of iodine pentoxide and fuming sulphuric acid. The iodine is reduced and the carbon monoxide is oxidised: H2S2O7 5CO2 + I2

I2O5 + 5CO

The colour change is from white to brown/green. Another oxidant that commonly used is dichromate. The iodine pentoxide and dichromate oxidation-reduction reactions are nonspecific. This property is a common problem in designing detector tubes and it happens in other reactions. Oxidation-reduction used in detector tube
Reaction
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Colour change

Used for
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ANALISIS PENCEMAR LINGKUNGAN SeO2 I2O5 + H2 S2O7 I2+ Ox.Pr I2O5 + H2 S2O7 I2+ Ox.Pr I2O5 + H2 SO4 I2+ Ox.Pr Cr2O7+H2SO4 Cr3+ + Ox.Pr Cr2O7+H3PO4 Cr3+ + Ox.Pr

White/Brown-green White/Brown-green White/Brown-green Orange/Green Orange/Green Yellow/Green Yellow/blue

CO, many organics CO, many organics Aromatic hydrocarbon Alyphatic Hydrocarbon Alcohol CO specific Unsaturated hydrocarbon

CO + K2Pd(SO3)2 CO2+SO2+K2SO3+Pd
R1C=CR2 + Mo6+ Mo

+ Ox.Pr (splitting of double bond)

3+

Acid-Base Reactions Many detector tubes use acid-base indicators impregnated on a neutral or buffered substrate to measure gaseous substance that have acidic or basic properties. Such compounds are acetic acid, ammonia and amines, carbon dioxide, hydrazine, hydrogen chloride, hydrogen fluoride, nitric acid and sulphur dioxide. As can be seen, these reactions are not specific, other acids and bases will interfere, particularly strong acids and bases. Acid-base indicator used in detector tube
Gas/vapour
Acetic acid Ammonia Carbon dioxide Hydrazine Hydrogen chloride Sulphur dioxide

Indicator
Phenol red Bromophenol blue or thymol blue Thymol blue Bromophenol blue Bromophenol blue or congo red Phenol red or bromocresol green

Colour change
Pink/white Orange/blue green; Lavender/pale yellow Blue/pale yellow Yellow/blue Blue/white; pink/blue Pink/white; blue/yellow

Other types of reactions These reactions included addition, substitution or mixtures of these. Some types are fairly specific for one compound. For example, the substitution reaction of carbonyl compounds with dinitrophenyl hydrazine, addition reaction of chlorine with tetraphenylbenzindine. The reaction can be simply one stage reaction or two stages or more. For some gases, because of their stability, it is not possible to obtain directly a colour indication with detector tube reagent systems. In many cases a solution is found by chemically or thermally breaking down the compound into a detectable substance. More drastic treatment sometimes is needed for more stable compound to break them into a detectable substance. This can be pyrolizing treatment, which heating the compounds in air to 400-500oC.

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Reaction

Colour change

Specificity

Substitution
H2S + PbAc2 PbS + 2Hac R1R2C=O + H2NNHC6H3(NO2)2 R1R2C=NNHC6H3(NO2)2 + H2O Dinitrophenylhydrazine hydrazone White/black Pale-yellow/ yellow Specific

Specific for carbonyls

Addition
Cl2 + TPB Cl-TPB-Cl Tetraphenylbenzidine quinoidimonium salt White/blue Fairly specific

Combination
2C6H6 + CH2O C6H5CH2C6H5 + H2O + 2H2SO4 White/brown 3H2O + SO2 + C6H5CH= =O

Specific for aromatics (or aldehydes)

paraquinoid compound

Using strong oxidant

Chlorinated hydrocarbons + KMnO4 + H2SO4 (conc) Cl2 Cl2 + TPB Cl-TPB-Cl White/blue Nonspecific

Using heat to break down compound

CCl4 + heat Cl2 CH3CN + heat NO2 CF2Cl2 + heat Cl2 White/blue nonspecific

From the literature review, the first task identified was to prepare a sensitive detector system for nitrogen dioxide (NO2).

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Appendix 1

Various types of diffusive samplers

a. Thermal desorption passive sampler
This sampler is usually used for organic vapour and un-reactive pollutants. The sampler can be radial or axial type. The filling material for trapping the gases may be molecular sieve, activated charcoal, graphitized carbon black etc.

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b. Solvent desorption passive sampler.

This type of sampler commonly uses for inorganic gases: NO, NO2, NOx , SO2, O3, NH3 etc. Reagent used depends on the target gases. The support material can be paper, glass fibre, etc.

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Appendix 3
Various type colorimetric detector tube

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Appendix 4

Diffusive sampler for greenhouse gases

NITROGEN DIOXIDE PASSIVE SAMPLER (NO2)
No 1 Type Badge (Ferm) Dimension D: 24 Chemistry of active material Whatman filter paper coated with a solution of NaOH and NaI in methanol Whatman GF-A glass fibre filter impregnated with a solution of triethanolamine-acetone. Method of analysis Spectrophotometry (540nm: nitrite) after mixing with diazotizing reagent. FIA_ Spectrophotometry (540nm: nitrite) after mixing with diazotizing reagent (Saltzman method) FIA-Spectrofotometry (545nm: nitrite) Ref 8

Badge (Willems)

D: 28

Badge (Ogawa)

D: unknown

Impregnated-cellulose fibre filter (unknown chemicals)

10

NITROUS OXIDE PASSIVE SAMPLER

No 1 2 Type Badge (RS Landauer) Tube with stainless screen Dimension Unknown L:55; D:4 Chemistry of active material Molecular sieve Molecular sieve 5A (60/80 mesh, Supelco) in glass tube Method of analysis Thermal desorption and than analysed by IR Partially desorption in vial, measurement head space by GC with EC detector Ref 11 12

SULPHUR DIOXIDE PASSIVE SAMPLER

No 1 Type Badge (Toyo Roshi Kaisha) Badge (Ferm) Dimension Unknown Chemistry of active material Filter paper impregnated with tetraethanolamine (TEA) Method of analysis SO2 absorbed was oxidized to SO4 by H2O2; SO4 was analyzed spectrophotome-trically (662) Ion chromatography Ref 13
8

D: 24

Whatman filter paper coated with a solution of NaOH (dissolved in

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3 4

Badge Badge (Ogawa)

Unknown D: unknown

small water) in methanol Potassium Carbonate Impregnated-cellulose fibre filter (unknown chemicals)

Ion chromatography Ion Chromatography

14,15
10

OZONE PASSIVE SAMPLER

No 1 Type Diffusion tube in protective box Indigo papers under shelter Diffusion tube Badge under shelter (poor correlation) Petridisk under shelter (poor correlation) Badge sampler (Ogawa & Co) Badge sampler (CSIRO Australia) Dimension L:74; D:10 Chemistry of active material Glass fibre filter coated with a solution of 1,2-di(4-pyridyl)ethylene (6%m/v) in acetic acid (75%), ethylene glycol (15%); reaction with methylbenzothiazoline hydrazone (MBTH) Indigo on filter paper buffered to pH 2.2; extraction of isatin with ethanol Indigo on filter paper unbuffered; extraction of isatin with ethanol Potassium Iodide on filter paper; Potassium Iodide-starch solution on filter paper; Method of analysis Spectrophotometry (442 nm) Ref 16
16

2 3 4 5

D: 50 L:240 D:30 D:50 D:50

Spectrophotometry (408 nm) Spectrophotometry (408 nm) Ion Chromatography Spectrophotometry (575 nm)

16 16

16

6 7

Filter coated with a nitrite-based solution D:25 Impregnated filter (unidentified)

Ion Chromatography Ion Chromatography

17 18

AMMONIA PASSIVE SAMPLER

No 1 2 Type Open Tube Tube with a stainless steel grid in the inlet Tube with permeable membra-ne in the inlet Badge, with a Dimension D: 10.9 L:71.2 D: 10.9 L:71.2 Chemistry of active material Unknown Unknown Method of analysis FIA- Conductometric detection FIA- Conductometric detection Ref 19
19

D:10.9 L:35.6

Unknown

FIA- Conductometric detection

19

D:28

Tartaric acid applied to a glass fibre filter disc

FIA- Conductometric detection

19, 20

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5 6 7

Teflon filter Badge, with a membrane inlet Badge with teflon filter (5um) Badge with membran inlet Badge with teflon filter Palmes type with membran

Unknown Unknown Unknown Unknown Unknown

Impregnated filter with citric acid Stainless steel grid with phosporic acid Impregnated filter with phosporic acid Impregnated glass surface with Phosphoric acid Stainless steel grid with sulphuric acid

FIA/Indophenol Ion chromatography Indophenol Ion Chromatography Conductance

21
21

21

21

21

References:
1. K Leichnitz, Ann.Occup. Hyg., 19, 1976, pp 159-161 2. ED Palmes, AF Gunnison, J DiMattion, and C Tomczyk, AIHA Journal, 37, 1976, pp 570-577 3. E Jungreis, Spot Test Analysis: Clinical, Environmental, Forensic and Geochemical Applications, John Wiley & Sons, New York, 1985 4. CJ Dore and J McGinlay, In: Air Pollution in The United Kingdom, edited by G Davison and CN Hewitt, Royal Society of Chemistry, 1997 5. WJ May, Ann.Occup.Hyg., 33, 1, 1989, pp 69-78 6. M Bates, N Gonzales-Flesca, V Cocheo and R Sokhi, Analyst, 122, 1997, pp1481-1484 7. DA Skoog, DM West and FJ Holler, Fundamental of Analytical Chemistry, 7nd Ed, 1996, Saunders College Publishing, London 8. GP Ayers, MD Keywood, R Gillett, PC Manins, H Malfroy and T Bardsley, Atmospheric Environment, 1998, 32, 20, pp 3587-3592 9. AH Gustafsson, R Lindahl, JO Levin and D Karlsson, J. Environ. Monit, 1999, 1, pp 349-352 10. Ogawa & Co., NO, NO2, Nox and SO2 sampling protocol using Ogawa sampler, 4th Ed., 1998 11. OSHA, Nitrous oxide in workplace atmosphere (passive monitor), 1994, OSHA Salt Lake Technical Center, Salt Lake City USA 12. S Kumagai and S Koda, Am. Ind. Hyg. Ass. J, 1999, 60, 4, pp 458-462 13. Y Yang, XX Zhang, T Korenaga, K Higuchi, Talanta, 1997, 45, pp 445-450

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14. M Ferm, A sensitive diffusional sample, 1991, IVL-Report B-1020, Gothenburg 15. M Hangartner, Diffusive sampling as an alternative approach for developing country, World Conggres on Air Pollution in Developing Countries, 1996, Costa Rica 16. M Hangartner, M Kirchner and H Werner, Analyst, 1996, 121, pp 1269-1272 17. Anonymous, Protocol for Ozone Measurement Using The Ozone Passive Sampler Badge, 1994, Rev.2, Harvard School of Public Health, Dept. of Environmental Health, USA 18. CSRIO Website, Atmospheric Research, http://www.csrio.edu.au 19. Th R Thijsse, JH Duyzer, HLM Verhagen, GP Wyers, A Wayers and JJ Mols, Atmospheric Environment, 1998, 32, 3, pp 333-337 20. JJ Willems, P Hofschreuder, In Air Pollution Research Report 37, Eds. I Allegrini, A Febo, and C Perrino, 1990, pp 113-118 21. M Kirchner, S Braeutigam, M Ferm, M Haas, M Hangartner, P Hofschreuder, A Kasper-Giebl, H Rommelt, J Stiedner, W Terzer, L Thoni, H Werner, and R Zimmerling, J Environ. Monit, 1999, 1, pp 259-265 22. RT Yang, Gas separation by adsorption processes, Imperial College Press, 1997 London

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