MDHS Methods for the Determination of

Hazardous Substances
94
Pesticides in air and/or
on surfaces
Health and Safety Laboratory
Methods for the sampling and analysis of
pesticides in air and/or on surfaces, using
pumped filters/sorbent tubes and gas
chromatography

February 1999

Requirements of the COSHH Regulations details of pesticides which fall outside the scope of the
legislation is given in Regulation 3 of the Control of
1 The Control of Substances Hazardous to Health Pesticides Regulations 1986.3
(COSHH) Regulations1 require assessment of the health
risk created by work involving substances hazardous to Health effects
health, and to prevent or control exposure to such
substances. The COSHH Regulations also require that 5 Pesticides are substances hazardous to health,
persons who may be exposed to substances hazardous to designed to control pests, and should be treated as such.
health receive suitable and sufficient information, There are many possible complex symptoms resulting
instruction and training. Employers should therefore ensure from exposure. They may cause symptoms such as
that the requirements of the COSHH Regulations are fully headaches, dermatitis, muscle twitches, allergies,
satisfied before allowing employees to undertake any reproductive damage, cancer and even death. A recent
procedure described in this MDHS. Guidance is given in review has put pesticide poisoning in perspective: ‘The
the Approved Codes of Practices (ACOP) for the Control of primary hazard of pesticide exposure is the development
Substances Hazardous to Health, the General COSHH of acute toxic reactions as a result of dermal contact with,
ACOP, and the Control of Carcinogenic Substances, the or inhalation of, a relatively large dose’. 4 Over-exposure
Carcinogens ACOP, which are included in a single by skin contact or breathing in pesticides can lead to toxic
publication with the COSHH Regulations .2 This includes effects.
assessment of the risks in sampling pesticides.
6 It is a requirement under RIDDOR that any cases
Definition of poisoning by pesticides must be reported without delay
to the nearest office of the Health and Safety Executive
2 Unless otherwise stated, reference to ‘pesticides’ in (see Appendix 4).
this method includes compounds that can be present in
both agricultural and non-agricultural formulations. These First aid
species may be present as either a vapour or a mixture of
vapour and airborne particles. 7 Measures appropriate in cases of suspected
poisoning include:
Properties and uses
■ remove any protective or other contaminated
3 The term pesticides has a very broad definition clothing (taking care to avoid personal
which embraces herbicides, fungicides, insecticides, contamination);
rodenticides, soil-sterilants, wood preservatives and
surface biocides among others. It can also include ■ wash any contaminated areas carefully with water
substances like growth regulators, defoliants, desiccants, or with soap and water if available;
fumigants and repellents/attractants.
■ in cases of eye contamination, flush with plenty of
4 Pesticides are used to reduce crop loss from clean water for at least 15 minutes;
disease and pest (plant and insect) attack, both before and
after harvest. They are also used for public health to ■ lay the patient down, keep at rest and under
control various human pests and disease carriers. By the shelter. Cover with one clean blanket or coat etc;
very nature of these functions, pesticides are released into
occupied environments. A more complete definition and ■ avoid overheating;

1
■ monitor level of consciousness, breathing and other substances in their formulation, including solvents,
pulse-rate; which may have their own OES/MEL.

■ if consciousness is lost, place the casualty in the Analytical methods

recovery position (on their side, tilt the head back
to ensure the airway remains open). Ensure that 13 This is not a ‘reference’ method in the strict
the mouth is clear of obstructions such as false analytical sense of the word. There may be alternative
teeth, that the breathing passages are clear, and methods available for the determination of a particular
that tight clothing around the neck, chest and analyte. With the exception of a few cases, where an
waist has been loosened; exposure limit is linked to a specific method (eg rubber
fume or asbestos), the use of methods not included in the
■ DIAL 999 FOR AN AMBULANCE; MDHS series is acceptable provided that they have been
shown to have the accuracy and reliability appropriate to
■ monitor and record breathing and pulse every ten the application.
minutes until help arrives;
14 This method has been validated to demonstrate
■ if breathing ceases commence mouth to mouth that it is capable of meeting the stated performance
resuscitation immediately, placing the casualty on parameters for the method.
their back. If a poisonous chemical has been
swallowed, it is essential that the first aider is
protected by the use of a resuscitation device; PRINCIPLE

■ if there is no pulse commence chest Air sampling

compressions immediately, placing the casualty
on their back. 15 A measured volume of air is drawn through a
25 mm GF/A filter contained in a sampling head. A glass
Exposure ‘NIOSH’ Tenax tube may be connected as a back-up, in
series, to collect any of the more volatile pesticides which
8 Exposure to pesticide concentrates (often in may pass through the filter (see paragraph 32). The
organic solvent) is a greater risk than is exposure to sampling efficiency for particulate matter may be
dilutions in water for application. Splashes of concentrate compromised if the filter/tube combination is employed,
on the skin should be avoided, whereas contamination because flow rates lower than 2 l/min must be used. After
by spray is of less concern. sampling, the filter and tube packing is desorbed in either
ethyl acetate or acetone for analysis. The resultant
Exposure limits solutions are analysed using gas chromatography with
mass spectrometric detection and quantified by
9 A fundamental requirement of the COSHH comparison with a range of standard solutions.
Regulations is that exposure of employees to substances
hazardous to health should be prevented or adequately Sampling potential dermal exposure
controlled. Exposure by inhalation is a hazard, and in
order to set standards for control of exposure by this 16 An estimate of dermal exposure is made by using
route, various substances have been assigned 10 cm x 10 cm cotton gauze swabs, set in seven positions
occupational exposure limits. on the worker’s outer clothing. The method used is
modified from a protocol for field surveys of exposure to
10 There are two types of occupational exposure pesticides developed by WHO in 1982.6
limits defined under COSHH: Occupational Exposure
Standards (OES) and Maximum Exposure Limits (MEL).
The key difference is that an OES is set at a level at
1
which there is no indication of risk to health; for an MEL
a residual risk may exist and the level takes socio-
economic factors into account. In practice, MELs have
been most often allocated to carcinogens and to other 7 2
substances for which no threshold of effect can be 3
identified and for which there is no doubt about the 4
seriousness of the effects of exposure.
5
11 OESs and MELs are set on the recommendations
of the Advisory Committee on Toxic Substances (ACTS).
Full details are published by HSE in EH 40/98
Occupational exposure limits 1998.5
6
12 As far as pesticides are concerned, OESs and
MELs have been set for relatively few active substances.
This is partly because pesticide products usually contain Back Front

2
Position 1 On the hat as close as practicable to the top Overall uncertainty
of the head
Position 2 Over sternum on outside of normal clothing 23 The overall uncertainty has been calculated using
the following CEN8 definition for each batch of samples:
Position 3 On sternum, on inside of normal clothing
Position 4 Upper surface of right forearm held with the Overall uncertainty = |Bias| + 2 x (precision)
elbow bent at right angles across the body,
midway between elbow and wrist. On For this method the bias was calculated as the possible
outside of normal clothing bias of the flow-meter (2%) and the average difference
between the stated and analysed concentration of a series
Position 5 Front of left leg, mid-thigh. On outside of
of pesticides of known concentrations (2%). The precision,
normal clothing
as a coefficient of variation, was calculated using the
Position 6 Front of left leg, above ankle. On outside of pump precision (5%) and the average precision of the
normal clothing analysis of a series of pesticides (8%). This gives an
Position 7 On back between shoulder blades. On overall uncertainty of 23%.
outside of normal clothing
Analytical recoveries
17 To determine hand and foot contamination, thin
cotton gloves and socks are worn under protective gloves 24 The pesticide mixture detailed at paragraph 28 was
and boots. used for this study. The carbaryl OES (from EH 40/98) of
0.1 mg/m3 was used as a benchmark for all the compounds in
the mixture. Spiking was carried out at five levels; 0.1
SCOPE AND FIELD OF APPLICATION (x OES), 0.5, 1.0, 2.0 and 10.0. The spiked sampling devices
were prepared for analysis using the method described in
18 The method described is for the determination of paragraphs 56 to 58. The only exception in this case was that
the time-weighted average inhalable concentrations of the spikes at 2.0 and 10.0 (x OES) were desorbed in 5 ml and
pesticides in workplace atmospheres. The method is 20 ml, respectively, instead of the standard 2 ml of desorbing
suitable for sampling over periods in the range 10 minutes solvent. The analytical range of these spikes was 50 to
to 8 hours, with a concentration range from approximately 500 ng/ml of each pesticide. At each analytical level, 6 GF/A
10 to 1000 µg/m3 for samples of 10 litres of air. filters and 6 Tenax tubes were loaded, desorbed and
subsequently analysed. The data showing the mean analytical
19 This procedure is compatible with low flow rate recoveries is shown in a back-up data report to this method.9
personal sampling pumps and can be used for personal
and fixed location sampling. It cannot be used to measure Storage stability tests
instantaneous or short-term fluctuations in concentration.
25 Laboratory tests on filters and tubes spiked with the
Interferences mixture detailed at paragraph 28 were used to monitor each
pesticide’s stability over a 14-day period. A single load level
20 Organic components which have the same or of 1.0 x OES was used for all devices, which were stored at
nearly the same retention time as the analyte of interest room temperature. The stabilities were monitored on day 0
during the gas chromatographic analysis will interfere. (the day of spiking), day 3, day 7 and day 14. The results
Interferences can be minimised by proper selection of are summarised in Appendix 1, Tables 1 and 2.
chromatographic columns and conditions.
REAGENTS AND STANDARDS
Quality control
26 The method is suitable for a range of organic
21 The procedure for spiked recoveries and storage pesticide compounds, either singly or in mixtures, and the
stability tests described in this document acts as an internal chromatograph should be calibrated with the compound or
quality control. This should be performed for every batch of compounds of interest. A mixture of 27 organic pesticides
filters and tubes. Analytical quality requirements, guidance is used as an example; these are arranged to give resolved
on the establishment of a quality assurance programme peaks on a HP-5MS gas chromatography column.
and details of internal quality control and external quality
assessment schemes are fully described in MDHS 71.7 Mixture solvents

Ethyl acetate and acetone

Detection limits
27 These should be of residue analysis quality and
22 The detection limit for each individual pesticide will must be free from compounds co-eluting with the
vary. A typical example would be that of carbaryl which compound or compounds of interest.
has an OES of 100 µg/m3 and a detection limit typically
around 0.13 mg per sample. For a 10 l (20 min) volume air Pesticide mixture
sample this corresponds to a detection limit of 13 µg/m3,
and for a 240 l (8 hour) volume air sample this 28 The representative mixture of pesticides (made up
corresponds to a detection limit of 0.54 µg/m3. in ethyl acetate) which can be analysed directly by GC is
shown over the page.

3
Pesticide name Formulae Chemical group Use

Bifenthrin C23H22ClF3O2 Pyrethroid Insecticide

Bromopropylate C17H16Br2O3 Benzilate Acaricide
Bupirimate C13H24N4O3S Pyrimidine Fungicide
Captan C9H8Cl3NO2S Dicarboximide Fungicide
Carbaryl C12H11NO2 Carbamate Insecticide
Chlorfenvinphos C12H14Cl3O4P Organophosphate Insecticide
Chlorothalonil C8Cl4N2 Organochlorine Fungicide
Chlorpyriphos C9H11Cl3NO3PS Organophosphate Insecticide
Chlorpyriphos-Methyl C7H7Cl3NO3PS Organophosphate Insecticide
Cypermethrin C22H19Cl2NO3 Pyrethroid Insecticide
Deltamethrin C22H19Br2NO3 Pyrethroid Insecticide
Dichlofluanid C9H11Cl2FN2O2S2 Sulfamide Fungicide
Dimethoate C5H12NO3PS2 Organophosphate Insecticide
α−Endosulfan C9H6Cl6O3S Organochlorine Insecticide
β−Endosulfan C9H6Cl6O3S Organochlorine Insecticide
Endosulfan-Sulphate C9H6Cl6O4S Organochlorine Insecticide
Fenoxycarb C17H19NO4 Carbamate Insecticide
Iprodione C13H13Cl2N3O3 Dicarboximide Fungicide
Lindane C6H6Cl6 Organochlorine Insecticide
Metalaxyl C15H21NO4 Acylalanine Fungicide
Omethoate C5H12NO4PS Organophosphate Insecticide
Permethrin C21H20Cl2O3 Pyrethroid Insecticide
Phosalone C12H15ClNO4PS2 Organophosphate Insecticide
Pirimiphos-Methyl C11H20N3O3PS Organophosphate Insecticide
Tetradiphon C12H6Cl4O2S Organochlorine Acaricide
Tolylfluanid C10H13Cl2FN2O2S2 Sulfamide Fungicide
Triazophos C12H16N3O3PS Organophosphate Insecticide

SAMPLING EQUIPMENT Pumped tubes

Swabs, gloves and socks 31 NIOSH-style Tenax tubes may be used. These
consist of a glass tube with both ends flame sealed,
29 Cotton is the preferred fabric for all dermal 70 mm in length with 6 mm OD and 4 mm ID, containing
sampling devices. If dermal sampling is to be used, all two sections of 0.4-0.8 mm Tenax separated by a 2 mm
devices should be initially treated to a thorough cleaning portion of urethane foam. The sorbing section contains
process involving ultra-sonication in residue analysis 30 mg of Tenax, and the back-up section contains 15 mg.
grade acetone, and subsequent drying before undertaking A 3 mm portion of silylated glass wool is placed in front of
any sampling strategy. the sorbing section. The pressure drop across the tube
should be less than 3 kPa (25 mm of mercury) at an
Filters airflow of 0.5 l/min. The OSHA ‘Versatile Sampler’ (OVS)
tube may also be suitable, but has not been evaluated by
30 Whatman 25 mm GF/A filters are used for this HSE for the present method. The tube is capable of
application. Care must be taken when handling these sampling at a higher flow-rate than the Tenax tube, so
fragile filters. It is recommended that tweezers are used at may produce some improvement in sampling efficiency.
all times when filters are to be transferred, eg between
filter tin and sampling assembly.

Connector for 'UKAEA' filter holder 'NIOSH' Tenax tube 'O' rings Connector for pump

PTPE parts PTPE parts PTPE parts

Figure 1 PTPE holder for Tenax back-up tube

4
Sampling assembly flasks, all class A, complying with the requirements of
BS 1792.11
32 A suitable assembly for air sampling is illustrated in
Figure 1. It utilises a 25 mm filter held within a sampling 37 As a precautionary measure it is recommended
head (not shown), backed up by a PTFE tube holder that all glassware should be pre-silanised.12 An
containing the Tenax sorbent tube. This assembly is alternative to this is to use Nalgene synthetic labware
employed when sampling airborne mixtures of both vapours where appropriate. All laboratory glassware should be
and aerosols. A 25 mm filter can also be used independently prewashed with residue analysis grade acetone prior to
by mounting it in a multi-orifice sampling head with seven commencing experimental work.
equispaced inlet holes. Other equivalent sampling heads
may be used10 (criteria for judging equivalence of other Micropipettes
samplers is under discussion by standards organisations; on
present information the IOM dust sampler will meet those 38 A set of adjustable positive displacement
requirements if pumped at 2 l/min). micropipettes, calibrated against a primary standard, for
preparation of calibration and sample solutions.13
Sampling pump
Balance
33 The pump should be suitable to be worn by a
person carrying out normal work, and should be capable 39 A balance, calibrated against a primary standard,
of running continuously for 8 hours at the recommended for the preparation of the calibration solutions. The
flow rate (0.5 to 2 l/min). The total volume of air sampled balance should be capable of weighing to ±0.1 mg over
by the pump over the sampling period should be within the range 0 to 100 g.
±5% of the calculated volume. A flow-stabilised pump,
capable of continuous low-flow, may be necessary to Disposable gloves
achieve this. It is also recommended that a pump with a
flow interruption indicator is used. 40 Disposable gloves, impermeable, to avoid the
possibility of contamination from the hands and to protect
Flow-meter them from harmful substances. Vinyl or nitrile gloves are
suitable.
34 Flow-meter, portable, capable of measuring the
appropriate flow rate (see paragraph 33) to within ±2%, Miscellaneous
and calibrated against a primary standard.10
41 Other equipment needed for this analysis is:
Note 1: The flow-meter incorporated into the pump may
be used provided that it has adequate sensitivity, that it ■ ultrasonic bath;
has been calibrated against a primary standard with a
loaded sampler in line, and that it is read in a vertical ■ sample concentration unit;
direction if it is the supported float type. However, it is ■ a range of micro-syringes in the range 1 µl to 500 µl;
important to ensure that there are no leaks in the ■ glass sample vials.
sampling train between the sampling head and the flow-
meter, since in this event a flow-meter in the pump or Gas chromatograph
elsewhere in line will give an erroneous flow rate.
42 A gas chromatograph (GC) fitted with a mass
Note 2: A soap bubble flow-meter may be used as a
spectrometric detector is the preferred method of
primary standard, provided its accuracy is traceable to
analysis, as this gives the highest amount of selectivity.
national standards (see Appendix 2).
Alternatively, a GC fitted with electron capture/nitrogen
phosphorous detection can be used.
Ancillary equipment

35 Flexible plastic tubing, of a diameter suitable for 43 The selection of a GC column capable of
making a leakproof connection from the sampler to the separating the analytes of interest from other
sampling pump; belts or harnesses to which the sampling components is most important. A 30 m HP-5MS (low
pump can conveniently be fixed, unless the pump is bleed (5%)-diphenyl-(95%)-dimethylsiloxane copolymer)
sufficiently small to fit in the worker’s pocket; flat-tipped with internal diameter of 0.25 mm and a film thickness of
tweezers for loading and unloading the filters into 0.25 µm, has been found suitable for this analysis.
samplers; tube breakers to open the Tenax sampling
tubes; containers to hold filters while being transported.
SAMPLING PROCEDURE

LABORATORY APPARATUS Calibration of sampling pumps

Glassware 44 Measurement of the volume of air sampled may

be a significant source of error in the final calculation of
36 A selection of laboratory glassware, including pesticide concentrations. About 15 minutes before
pipettes, beakers, measuring cylinders and volumetric sampling is to begin, connect the pump to a filter holder

5
(with a filter in place) by means of a flexible tube, and sampling period. Reseal the sampler with its protective
adjust the flow rate to the desired value by attaching a cover and disconnect it from the sampling pump.
suitable calibrated airflow meter to the front of the filter
holder. The pump should then be allowed to run for 15 49 Carefully record the sample identity using a
minutes to stabilise the flow rate. Before taking the actual unique sample number and all relevant sampling data
sample, a filter holder with a clean filter is fitted, with a (see Appendix 3). Calculate the mean flow rate by
Tenax tube in line if required, and the flow rate readjusted averaging the flow rate measurements throughout the
to its original value. The meter should also be used to sampling period and calculate the volume of air
check the flow rate at the end of the sampling period. sampled, in litres, by multiplying the flow rate in l/min by
the sampling time in minutes.
Collection of samples
Blanks
Air samples
50 With each batch of ten samples, submit for
45 Connect the sampling assembly to the pump as analysis at least two unused filters/tubes from the same
described above. The filters should be handled with lot of sampling devices used for sample collection.
tweezers, and the ends broken from the Tenax tubes
carefully, to avoid damage to the ‘O’ ring seals. When 51 Sample blanks should be prepared by using
used for personal sampling, the sampler should be filters, tubes and dermal samplers identical to those
mounted in the worker’s breathing zone (within 30 cm of used for sampling and subjecting them to the same
the nose/mouth region), for example on the lapel, with handling procedure except for the actual period of
the filter surface approximately vertical. The pump is sampling. Label these as blanks.
attached to the worker as appropriate to minimise
inconvenience. When used for fixed location sampling, a 52 For transport back to the laboratory, seal the filters
suitable sampling site is chosen. in individual tins and replace the end-caps on the tenax
tubes. Any dermal samplers should be sealed in individual
46 When ready to begin sampling, remove the polythene bags. Samples should be kept cool (dry ice
protective cover from the sampling head and switch on containment if possible) during transport, stored in a
the pump. Record the time at the start of the sampling freezer and analysed within 1 week.
period, and if the pump is equipped with an elapsed time
indicator, ensure that it is set to zero. Draw a measured
volume of air through the GF/A filter paper. The ANALYSIS
recommended air sample volume is 200 l, and the
sampling rate 2 l/min. Take a separate sample for each Preparation of samples for analysis
100-minute period. If Tenax tubes are connected in
series, the maximum achievable flow rate is 0.5 l/min, or Air samplers
1 l/min if OVS tubes are used.
53 GFA filters - Desorb each filter in a sealed glass
47 Since it is possible for a filter to become clogged, bottle containing 2 ml of the desorbing solution (see
monitor the performance of the sampler periodically, a paragraph 27) for 2 hours under sonication.
minimum of every two hours (or more frequently if heavy
filter loadings are suspected). Measure the flow rate with 54 Tenax tubes - Carefully empty the packing (omit
the calibrated flow-meter and record the measured the glass wool and urethane pads) from each Tenax
value. Terminate sampling and consider the sample to tube into glass bottles which contain 2 ml of the
be invalid if the flow rate is not maintained to within ±5% desorbing solution. Desorb as per filter.
of the nominal value throughout the sampling period.10
55 After desorption, carefully filter the extracts with
Note 3: If a flow fault indicator is fitted to the pump, 0.45 µm PTFE filters and place into amber glass GC
regular observation of this indicator is an acceptable vials for analysis.
means of ensuring that the flow rate of flow-stabilised
pumps is maintained satisfactorily, provided that the flow Dermal samplers
fault indicator indicates malfunction when the flow rate is
outside ±5% of the nominal value. 56 Desorb each swab, glove and sock in sealed glass
bottles containing 25 ml, 100 ml and 250 ml respectively
48 At the end of the sampling period, measure the of the desorbing solution for 2 hours under sonication.
flow rate with an accuracy of ±5% using the calibrated
flow-meter (paragraph 34), switch off the sampling pump, 57 After desorption, take 1 ml of each of the resulting
and record the flow time and the time. Also observe the extracts and filter using 0.45 µm PTFE filters. The clean
reading on the elapsed time indicator, where fitted, and solutions can be placed directly into amber glass GC
consider the sample to be invalid if the reading on the vials and analysed.
elapsed time indicator and the timed interval between
switching on and switching off the sampling pump do not 58 If the samples initially prove to be lower than the
agree to within ±5%, since this may suggest that the calibration range, a method of sample concentration can
sampling pump has not been operating throughout the be used. This would normally involve taking 10 ml of

6
filtered solution and concentrating down to 0.5 ml. This 63 By carrying out spiked recoveries (paragraph 24)
allows the sample to be made up to 1 ml, giving a 10-fold of individual pesticides on each sample type, a profile
concentration from the initial solution. can be made as to how much adjustment is necessary to
results which carry a low percentage recovery. This is
Blank samples also true of the air samples.

59 Blank samples are subjected to the same Volume of air sample

analytical procedure as the other samples in the set
(paragraphs 53 to 58). 64 Calculate the volume, V, in litres, of each air
sample (paragraph 49).
Preparation of calibration standards
Pesticide concentrations on air samples
60 At least four standard solutions of each pesticide,
spanning the analytical range, should be prepared by 65 Calculate the concentration of pesticide found on
dissolving a known amount of a certified standard in the air sampler by comparison with the graph of the
solvent and diluting as appropriate. calibration standards. This will give an analytical result
for the sample in µg/ml. This result can then be adjusted
Chromatography for each sample to take into account the air volume
sampled, eg:
61 Gas chromatographic conditions that have been
A x S x 1000
found to be suitable for analysis are: C=
V
Column dimensions 30 m x 0.25 mm ID (0.25 µm
film thickness) where C = Pesticide concentration (µg/m3)
A = Analytical result (µg/ml)
Column packing HP-5MS (5%-Diphenyl / 95%- S = Volume of desorbing solvent (ml)
dimethylsiloxane copolymer) V = Volume of air sampled (l)

Temperature programme Injector: 250°C

Detector: 280°C TEST REPORT
Initial temp: 60°C for 1 min
Ramp at 10°C/min to 295°C; 66 Appendix 3 gives recommendations for
hold for 3.5 min information to be included in the test report.

Carrier gas Helium

ADVICE
Flow rate 1 ml/min
Advice on this method and the equipment used can be
obtained from the Health and Safety Executive, Health
CALCULATIONS and Safety Laboratory, Broad Lane, Sheffield, S3 7HQ
(telephone 0114 289 2000, fax 0114 289 2500, email
Pesticide concentrations on dermal samples info@hsl.gov.uk).
62 Calculate the concentration of pesticide found on
The Health and Safety Executive wishes, wherever
the dermal sampler by comparison with the graph of the
calibration standards. This will give an analytical result possible, to improve the methods described in this
for the sample in µg/ml or ppm. This result can then be series. Any comments that might lead to improvements
adjusted for each sample volume, eg: would therefore be welcome and should be sent to the
above address.
Ai Analytical result (µg/ml) x 25 (ml) = µg on
swab sample

Aii Analytical result (µg/ml) x 2.5 (ml) = µg on

swab sample (if concentrated)

Bi Analytical result (µg/ml) x 100 (ml) = µg on

glove sample

Bii Analytical result (µg/ml) x 10 (ml) = µg on

glove sample (if concentrated)

Ci Analytical result (µg/ml) x 250 (ml) = µg on

sock sample

Cii Analytical result (µg/ml) x 25 (ml) = µg on

sock sample (if concentrated)

7
APPENDIX 1

Table 1 The stability of various pesticides over a 14-day period after being spiked onto GF/A filters

Pesticide Day 0 Day 3 Day 7 Day 14 Vapour pressure

% % % % mPa
remaining remaining remaining remaining
Bifenthrin 83.1 92.2 92.6 82.2 0.024 (25oC)
Bromopropylate 87.9 92.2 91.5 84.2 0.011 (20oC)
Bupirimate 86.6 91.8 90.7 83.8 0.100 (25oC)
Captan 92.5 85 82.3 75.2 <1.30 (25oC)
Carbaryl 106.4 88.3 68.2 59.5 0.041 (23.5oC)
Chlorfenvinphos 88.6 85.5 84.4 70 0.530 (20oC)
Chlorothalonil 89.7 81.9 70 45.9 0.076 (25oC)
Chlorpyriphos 87.6 59 36.9 < 10 2.700 (25oC)
Chlorpyriphos-Methyl 88.8 19.7 < 10 < 10 3.000 (25oC)
Cypermethrin 96.9 92.9 93.8 74.9 1.8x10-4 to 0.023 (20oC)
Deltamethrin 98.2 92.4 96.3 79.1 1.24x10-5 (25oC)
Dichlofluanid 83.7 20 < 10 < 10 0.015 (20oC)
Dimethoate 102.6 94 83.7 70.7 0.250 (25oC)
α - Endosulfan 88.5 62.3 49.9 32.2 0.830 (20oC)
β - Endosulfan 89.8 88.7 86.2 68.1 0.830 (20oC)
Endosulfan-sulphate 87.1 93.5 92.2 81.1 —
Fenoxycarb 98.3 88.5 83.1 76.3 8.67x10-4 (25oC)
Iprodione 95 85.3 81.4 72.6 5.00x10-4 (25oC)
Lindane 91 22.5 11.9 < 10 5.600 (20oC)
Metalaxyl 85.6 87.2 85.8 74.7 0.750 (25oC)
Omethoate 100.5 86 76 72.2 3.300 (20oC)
Permethrin 85.8 90.4 90.9 80.1 0.070 (20oC)
Phosalone 90.4 93.9 92.6 85.3 <0.06 (25oC)
Pirimiphos-Methyl 89.8 71.4 46 12.6 2.000 (30oC)
Tetradifon 87.2 97 92.2 88.1 3.20x10-5 (20oC)
Tolylfluanid 81.6 45.6 13.1 < 10 0.020 (20oC)
Triazophos 90.6 88 80.2 68.9 0.390 (30oC)

8
Table 2 The stability of various pesticides over a 14-day period after being spiked onto NIOSH Tenax tubes

Pesticide Day 0 Day 3 Day 7 Day 14 Vapour pressure

% % % % mPa
remaining remaining remaining remaining
Bifenthrin 86.8 86.9 83.2 80 0.024 (25oC)
Bromopropylate 81.4 92.5 90.1 87 0.011 (20oC)
Bupirimate 93.5 94.3 94.3 94.4 0.100 (25oC)
Captan 93.7 76.4 75.1 69.3 <1.30 (25oC)
Carbaryl 113.4 108.5 93.7 88.9 0.041 (23.5oC)
Chlorfenvinphos 87.6 85.1 81.5 76.7 0.530 (20oC)
Chlorothalonil 87.3 78.5 77.5 63.4 0.076 (25oC)
Chlorpyriphos 88.7 85.9 81.5 66.3 2.700 (25oC)
Chlorpyriphos-Methyl 91.2 85.6 83.3 61.6 3.000 (25oC)
Cypermethrin 110 97.5 90.2 80.3 1.8x10-4 to 0.023 (20oC)
Deltamethrin 109.1 91.7 92.7 75.5 1.24x10-5 (25oC)
Dichlofluanid 93.8 80.4 80.8 75.2 0.015 (20oC)
Dimethoate — — — — 0.250 (25oC)
α - Endosulfan 90.9 93 92.4 82 0.830 (20oC)
β - Endosulfan 88.9 87 86.8 75.9 0.830 (20oC)
Endosulfan-sulphate 90.4 92.9 92.3 85.2 —
Fenoxycarb 84.9 81.4 78.1 65.2 8.67x10-4 (25oC)
Iprodione 98.8 86.8 79.2 68.4 5.00x10-4 (25oC)
Lindane 87.6 91.1 86.5 61.2 5.600 (20oC)
Metalaxyl 86.1 89 83 74.2 0.750 (25oC)
Omethoate — — — — 3.300 (20oC)
Permethrin 88.1 88.3 85 77.8 0.070 (20oC)
Phosalone 98.3 89.8 88.4 80.8 <0.06 (25oC)
Pirimiphos-Methyl 89.7 86 85 59.8 2.000 (30oC)
Tetradifon 90.3 92.3 88.5 83.8 3.20x10-5 (20oC)
Tolylfluanid 92.1 81.7 81.5 58.7 0.020 (20oC)
Triazophos 97.7 93.8 80.8 73.1 0.390 (30oC)

9
APPENDIX 2 APPENDIX 4

Primary standard for calibration of portable flow-meter Alphabetical list of HSE field offices

The primary standard must be a flow-meter whose

accuracy is traceable to national standards, used with Office name HSE region Telephone no
careful attention to the conditions of the calibration Aberdeen Scotland 01224 252500
certificate. A bubble flow-meter may also be used. This is
Ashford London & SE 01233 624658
an arrangement whereby the pump under test draws a
soap film up a calibrated tube. The passage of the film is Basingstoke Home Counties 01256 404000
accurately timed between two marks whose separation
Birmingham * Midlands 0121 607 6200
defines a known volume. The volume between the marks
can be checked by filling the burette with water, allowing Bootle North West 0151 479 2200
temperatures to stabilise, drawing off a known volume and Bristol Wales & West 0117 988 6000
weighing the water, making allowance for the dependence
of volume on temperature. A suitable bubble solution can Cardiff * Wales & West 01222 263000
be made by mixing one part of concentrated washing-up Carlisle North West 01228 539321
liquid, two parts glycerol and four parts water. The burette
must be thoroughly wetted with the solution and several Carmarthen Wales & West 01267 232823
attempts at drawing the film up the tube may be necessary Chelmsford Home Counties 01245 706200
before the tube is wet enough for this to be achieved
consistently. Traceability of the calibration will require East Grinstead London & SE 01342 334200
checking of the clocks and use of certificated weights. Edinburgh * Scotland 0131 247 2000
Glasgow Scotland 0141 275 3000
APPENDIX 3 Horsforth * Yorkshire & NE 0113 283 4200

Recommendations for the test report Hull Yorkshire & NE 01482 223487
Inverness Scotland 01463 718101
It is recommended that the test report should include the
following information: Leeds Yorkshire & NE 0113 283 4200
Luton * Home Counties 01582 444200
■ a complete identification of the air sample using a
unique sample number, the date of sampling, the Manchester * North West 0161 952 8200
place of sampling, and the identity of the individual
Newcastle-U-Lyme Wales & West 01782 602300
whose breathing zone was sampled;
Newcastle-U-Tyne Yorkshire & NE 0191 202 6200
■ a reference to this MDHS and a description of any
deviation from the procedures described; Northampton Midlands 01604 738300

■ the type and diameter of filter used, and the type of Norwich Home Counties 01603 615711
sampling head; Nottingham Midlands 0115 971 2800
■ the type of sampling pump and flow-meter used, Plymouth Wales & West 01752 668481
the primary standard against which it was
Poole Home Counties 01202 667219
calibrated, and the range of flow rates for which the
flow-meter was calibrated; Preston North West 01772 836200
■ the duration of the sampling period in minutes Sheffield Yorkshire & NE 0114 291 2300
and/or the time at the start and at the end of the Southwark * London & SE 0171 556 2100
sampling period;
Stoneleigh Midlands 01203 696518
■ the volume of air sampled, in litres;
Worcester Wales & West 01905 723406
■ the name of the person who collected the samples;
Wrexham Wales & West 01978 290500
■ the time-weighted average sample concentration
found in the air sample, in milligrams per cubic
* Also Regional HQ
metre and/or the mass collected on the filter, in
milligrams;
■ the overall uncertainty of the method;
■ the name of the analyst;
■ the date of the analysis;

■ any unusual features with the analysis;

■ recovery data.

10
REFERENCES 9 Douglas N Validation of a method for the sampling
and analysis of pesticides in air, using pumped
1 Health and Safety Commission Control of filters/sorbent tubes and gas chromatography
Substances Hazardous to Health Regulations, 1994 HSE internal report IR/L/IAC/97/10 1997
(SI 1994/3246) as amended by the Control of Substances
Hazardous to Health (Amendment) Regulations 1997 10 Health and Safety Executive Methods for the
(SI 1997/11) HMSO Determination of Hazardous Substances General
methods for sampling and gravimetric analysis of
2 Health and Safety Executive General COSHH respirable and total inhalable dust MDHS 14/2
ACOP (Control of Substances Hazardous to Health). HSE Books 1997 ISBN 0 7176 1295 3
Control of Substances Hazardous to Health Regulations:
Approved Codes of Practice (6th edition) HSE Books 11 British Standards Institution Specification for one-
ISBN 0 7176 1308 9 mark volumetric flasks BS 1792 BSI 1993
ISBN 0 5801 2754 0
3 Ministry of Agriculture, Fisheries and Food/Health
and Safety Commission Control of Pesticides Regulations 12 Rimmer D A, Johnson P D and Brown R H
1986 SI 1986/1510 HMSO ISBN 0 11 067510 X Determination of phenoxy acid herbicides in vegetation,
utilising gel chromatographic clean-up and methylation
4 American Medical Association Council on with trimethylsilyldiazomethane prior to gas
Scientific Affairs Cancer risk of pesticides in agricultural chromatographic analysis with mass selective detection
workers JAMA 1988 vol 260 no 7 959-66 Journal of Chromatography A 755 (1996) 245-50

5 Health and Safety Executive Environmental 13 British Standards Institution Piston and/or plunger
Hygiene Guidance Note Occupational exposure limits operated volumetric apparatus (POVA) Part 3: Methods of
EH40 1998 HSE Books ISBN 0 7176 1474 3 test BS 7653-3 BSI 1993 ISBN 0 580 2215 3

6 World Health Organisation Field surveys of HSL internal reports are available from the HSL
exposure to pesticides WHO 1982 Standard Protocol Information Centre, tel: 0114 289 2330.
Ref VBC/82.1

7 Health and Safety Executive Methods for the

Determination of Hazardous Substances Analytical quality
in workplace air monitoring MDHS 71 HSE Books 1991
ISBN 0 7176 0266 0

8 Comité Européen de Normalisation (CEN)

Workplace atmospheres: general requirements for the
performance of procedures for the measurement of
chemical agents prEN 482 CEN 1992

11
TITLES IN THE MDHS SERIES 53 1,3 Butadiene thermal desorption/GC
54 Protocol for assessing the performance of a pumped
1 Acrylonitrile charcoal tube/gas chromatography (GC) sampler for gases and vapours
2 Acrylonitrile pumped thermal desorption/GC 55 Acrylonitrile diffusive/thermal desorption/GC
3 Standard atmospheres syringe injection 56/2 Hydrogen cyanide ion-selective electrode
4 Standard atmospheres permeation tube 57 Acrylamide liquid chromatography
5 On-site validation of methods 59 Manmade mineral fibres
6/3 Lead atomic absorption (AA) 60 Mixed hydrocarbons
10/2 Cadmium AA 61 Total hexavalent chromium compounds in air colorimetric
12/2 Chromium AA 62 Aromatic carboxylic acid anhydrides
14 Total inhalable and respirable dust gravimetric 63 Butadiene diffusive/thermal desorption/GC
15 Carbon disulphide charcoal tube/GC 64 Toluene charcoal diffusive/solvent desorption/GC
16 Mercury adsorbent tube (Hydrar) AA 65 Mine road dust: determination of incombustible matter
17 Benzene charcoal tube/GC 66 Mixed hydrocarbons (C5 to C10) in air diffusive/
18 Tetra alkyl lead continuous monitoring thermal desorption/GC
19 Formaldehyde colorimetric (Chromotropic acid) 67 Total (and speciated) chromium in chromium plating mists
20 Styrene pumped charcoal tube/GC colorimetric (1,5-diphenylcarbazide)
21 Glycol ethers charcoal tube/GC 68 Coal tar pitch volatiles
22 Benzene thermal desorption/GC 69 Toluene diffusive/solvent desorption/GC
23 Glycol ethers thermal desorption/GC 70 General methods for sampling airborne gases and vapours
24 Vinyl chloride charcoal tube/GC 71 Analytical quality in workplace air monitoring
25/2 Organic isocyanates reagent bubbler/HPLC 72 Volatile organic compounds in air
26 Ethylene oxide charcoal tube/GC 73 Measurement of air change in factories and offices
27 Diffusive sampler evaluation protocol 74 n-Hexane in air diffusive/solvent desorption/GC
28 Chlorinated hydrocarbons charcoal tube/GC 75 Aromatic amines solid sorbent/thermal desorption/GC
29/2 Beryllium AA 76 Cristobalite in respirable dusts X-ray diffraction
30/2 Cobalt AA (direct method)
31 Styrene pumped thermal desorption/GC 77 Asbestos in bulk materials
32 Phthalate esters solvent desorption/GC 78 Formaldehyde diffusive/solvent desorption/liquid
33 Adsorbent tube standards chromatography
35/2 HF and fluorides ion-selective electrode 79 Peroxodisulphate salts mobile phase ion chromatography
36 Toluene charcoal tube/GC 80 Volatile organic compounds diffusive/thermal desorption/GC
37 Quartz in respirable airborne dust direct infra-red 81 Dustiness of powders and materials
38 Quartz in respirable airborne dust KBr disc technique 82 The dust lamp
39/4 Asbestos fibres light microscopy (European reference 83 Resin acids GC
version) 84 Oil mist from mineral oil-based metalworking fluids
40 Toluene thermal desorption/GC 85 Triglycidyl isocyanurate in air pumped filter/
41/2 Arsenic AA desorption/liquid chromatography
42/2 Nickel AA 86 Hydrazine in air
43 Styrene diffusive/thermal desorption/GC 87 Fibres in air
44 Styrene diffusive/solvent desorption/GC 88 Volatile organic compounds in air diffusive/solvent
45 Ethylene dibromide solvent desorption/GC desorption/GC
46/2 Platinum AA 89 Dimethyl sulphate and diethyl sulphate thermal
47 Rubber fume in air measured as total particulates desorption/GC-mass spectrometry
and cyclohexane soluble material 90 Alkyl 2-cyanoacrylates liquid chromatography
48 Newspaper print rooms: measurements of total 91 Metals and metalloids XRF
particulates and cyclohexane soluble material in air 92 Azodicarbonamide high performance liquid chromatography
49 Aromatic isocyanates acid hydrolysis/ diazotisation (HPLC)
50 Benzene diffusive/thermal desorption/GC 93 Glutaraldehyde HPLC
51/2 Quartz in respirable dusts X-ray diffraction (direct method) 94 Pesticides pumped filters/sorbent tubes/GC
52/3 Hexavalent chromium in chromium plating mists
colorimetric (1,5-diphenylcarbazide)

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