Measurement &Sampling
Part 1 Introduction to Sampling
What to sample ? - Hazard Recognition
Raw Material Finished product By product Exposure standards Length of shift Physical environment
Hazards Recognition
To Determine
Level of exposure The effectiveness of control measures Investigate complaints Compliance with regulations Locate existing hazards Review process See, smell, feel Control measures
Walk through Survey
Field Survey
More detail observation, Monitoring Normal and abnormal conditions
Types of Sampling
Grab or Instantaneous Samples
Concentration GRAB SAMPLES
Source; BP International
Time
Types of Sampling
Short Term Samples
SHORT TERM Concentration TIME WEIGHTED AVERAGE
Source; BP International
Time
Types of Sampling
Long Term Samples
LONG TERM TIME WEIGHTED AVERAGE
Concentration
Source; BP International
Time
Types of Sampling
Continuous Monitoring
CONTINUOUS MONITORING
Concentration
Source; BP International
Time
Sampling of Gases and Vapours
1. Whole of Air or Grab Sampling 2. Active sampling Absorption Adsorption
3. Diffusion or passive samplers
4. Direct reading instruments
5. Detector tubes
Grab Sampling
Whole of Air or Grab Sampling
Collected
Passively-evacuated prior to sampling Actively-by using a pump
Evacuated containers
Canisters Gas bottles Syringes
Used when
Concentration constant To measure peaks Short periods
Whole of Air or Grab Sampling (cont)
Container preparation
Cleaned Passivation (e.g. Summa process)
Compounds ideally
Stable Recoveries dependent on humidity, chemical reactivity & inertness of container Down to ppb levels Landfill sampling
Whole of Air or Grab Sampling (cont)
Gas bags e.g. Tedlar or other polymers Filled in seconds or trickle filled ppm levels
Source: Airmet Scientific reproduced with permission
Whole of Air or Grab Sampling (cont)
Sample loss issues:
Permeation Adsorption onto bag Bag preparation Bag filling
Whole of Air or Grab Sampling (cont)
Gas bags (cont) Single use cheap enough, but ?? If reuse purge x 3 at least Run blanks Dont overfill bag will take 3 times stated volume
Active Sampling
Active Sampling
Pump Absorption Adsorption sorbent tubes eg Charcoal Silica gel Porous polymers Tenax, Poropaks etc TD Mixed phase sampling
Active Sampling (cont)
Source: 3M Australia reproduced with permission
Source: Airmet Scientific-reproduced with permission
Low volume pump 50 200 ml/min
Sample train Calibration
Source: Airmet Scientific-reproduced with permission
Active Sampling (cont)
Tube Holder
Source University of Wollongong
Active Sampling (cont)
Gas/Vapour Sampling Train
Break off both ends of a sorbent tube (2mm dia, or dia of body) Put tube in low flow adapter/tube holder
Make sure tube is in correct way around
Source: Airmet Scientific reproduced with permission
Taking the Sample
Place sample train on person:
Start pump Note start time At end of sample: Note stop time
Source :Airmet Scientific reproduced with permission
Active Sampling (cont)
Multi Tube sampling
Universal type pumps allow: Up to 4 tubes at the same time either running at different flow rates or with different tubes
3 way adaptor shown
Source :Airmet Scientific reproduced with permission
To sample pump
Absorption
Absorption gas or vapour collected by passing it through a liquid where it is collected by dissolution in the liquid
Impingers
Source: University of Wollongong
Absorption - Impinger Sampling Train
Source :Airmet Scientific reproduced with permission
Absorption (cont)
Collection efficiencies
Size and number of bubbles Volume of liquid Sampling rate typically up to 1 L/min Reaction rate Liquid carry over or liquid loss Connect in series
Need to keep samplers upright Personal sampling awkward & difficult
Absorption (cont)
Absorption derivatisation often used for:
Formaldehyde collected in water or bisulphite Oxides of nitrogen sulphanilic acid Ozone potassium iodine Toluene diisocyanate 1-(2- methoxy phenyl) piperazine in toluene
Adsorption
Gas or vapour is collected by passing it over and retained on the surface of the solid sorbent media
Direction of sample flow
Back up sorbent bed Main sorbent bed
Source :Airmet Scientific reproduced with permission
Adsorption (cont)
Breakthrough:
Source :Airmet Scientific reproduced with permission
Adsorption (cont)
After sampling:
- remove
tube - cap the
tube
- store, submit for analysis with details of sample
Dont forget to send a blank with samples to laboratory
Source :Airmet Scientific reproduced with permission
Activated Charcoal
Extensive network of internal pores with very large surface area Is non polar and preferentially absorbs organics rather than polar compounds Typically CS2 for desorption
Activated Charcoal (cont)
Limitations
Poor recovery for reactive compounds, polar compounds such as amines & phenols, aldehydes, low molecular weight alcohols & low boiling point compounds such as ammonia, ethylene and methylene chloride
Silica Gel
Used for polar substances such as
Glutaraldehyde Amines Inorganics which are hard to desorb from charcoal
Disadvantage
Affinity for water
Desorption
Polar solvent such as water and methanol
Porous Polymers & Other Adsorbents
Where gas & vapour not collected effectively with charcoal or poor recoveries Tenax low level pesticides XAD 2 for pesticides Chromosorb pesticides Porapaks polar characteristics Others: Molecular sieves Florisil for PCBs Polyurethane foam for pesticides, PNAs
Thermal Desorption
Superseding CS2 desorption especially in Europe Sensitivity
Desorption efficiency
Reproducibility Analytical performance
Thermal Desorption (cont)
Thermal desorption tubes:
inch OD x 3 long stainless steel Pre packed with sorbent of choice SwageLok storage cap Diffusion cap Conditioning of tubes prior / after use
Sources: Markes International reproduced with permission
Thermal Desorption Unit with GC/MS
Sources: Markes International reproduced with permission
Collection Efficiencies of Adsorption Tubes
Temperature Adsorption reduced at higher temperatures Some compounds can migrate through bed Store cool box, fridge or freezer Humidity Charcoal has great affinity for water vapour
Collection Efficiencies (cont)
Sampling flow rate If too high insufficient residence time Channeling If incorrectly packed Overloading If concentrations / sampling times too long or other contaminants inc water vapour are present
Mixed Phase Sampling
Solid, liquid, aerosol and gas and vapour phases.
Benzene Soluble Fraction of the Total Particulate Matter for Coke Oven Emissions Impingers used for sampling of two pack isocyanate paints Aluminium industry fluorides as particulate, or hydrofluoric acid as a mist or as gas.
Treated Filters
Chemical impregnation including use for: Mercury Sulphur dioxide Isocyanates MOCA Fluorides Hydrazine
Passive Sampling
Diffusion or Passive Sampling
Ficks Law m t
where m t A D = = = =
AD (c0 c) L
L c c0
= = =
mass of adsorbate collected in grams sampling time in seconds cross sectional area of the diffusion path in square cm diffusion coefficient for the adsorbate in air in square cm per second available from manufacturer of the sampler for a given chemical length of the diffusion path in cm (from porous membrane to sampler) concentration of contaminant in ambient air in gram per cubic cm concentration of contaminant just above the adsorbent surface in gram per cubic cm
Diffusion or Passive Sampling (cont)
Source: HSE reproduced with permission
Diffusion or Passive Sampling (cont)
Source: 3M Australia reproduced with permission
Every contaminant on every brand of monitor has its own
unique, fixed sampling rate
Diffusion or Passive Sampling (cont)
Advantages
Easy to use No pump, batteries or tubing & no calibration Light weight Less expensive TWA & STEL Accuracy 25% @ 95% confidence
Diffusion or Passive Sampling (cont)
Limitations
Need air movement 25 ft/min or 0.13m/sec Cannot be used for Low vapour pressure organics eg glutaraldehyde Reactive compounds such as phenols & amines Humidity Sampling rate needs to be supplied by manufacturer
Diffusion or Passive Sampling (cont)
After sampling diffusion badges or tubes must be sealed and stored correctly prior to analysis
For example with the 3M Organic Vapour Monitors: Single charcoal layer: Fig 1- remove white film & retaining ring. Fig 2 - Snap elution cap with plugs closed onto main body & store prior to analysis
Source: 3M Australia reproduced with permission
Fig 1
Fig 2
Diffusion or Passive Sampling (cont)
Those with the additional back up charcoal layer remove white film & snap on elution cap as above (Fig 3) Separate top & bottom sections & snap bottom cup into base of primary section (Fig 4) and snap the second elution cap with plugs closed onto the back up section
Source: 3M Australia reproduced with permission
Fig 3
Fig 4
Diffusion or Passive Sampling (cont)
What can be typically sampled ? Extensive range of organics
Monitors with back up sections also available
Chemically impregnated sorbents allows
Formaldehyde Ethylene oxide TDI Phosphine Phosgene Inorganic mercury Amines
Calculation of Results
Active Sampling
Conc mg/m3 = mf + mr mb x 1000 DxV where mf is mass analyte in front section in mg mr is mass analyte in rear or back up section in mg mb is mass of analyte in blank in mg D is the desorption efficiency V is the volume in litres
Calculation of results
Diffusion sampling: Conc (mg/m3) = W (g) x A rxt
where W = contaminant weight (g) A calculation constant = 1000 / Sampling rate r = recovery coefficient t = sampling time in minutes
Conc (ppm) = W (g) x B rxt
where W = contaminant weight (g) B = calculation constant = 1000 x 24.45 / Sampling rate x mol wt r = recovery coefficient t = sampling time in minutes
End of Part 1
