BINDURA UNIVERSITY OF SCIENCE EDUCATION

FACULTY OF AGRICULTURE AND ENVIRONMENTAL SCIENCE

DEPARTMENT OF ENVIRONMENTAL SCIENCE

An assessment of the level of occupational exposure to noxious gases (H2S, NH3

and HCl) at three different sewerage treatment plant stations in Harare.

Justice Gonde

(B1336415)

A DISSERTATION SUBMITTED IN PARTIAL FULFILMENT OF THE

REQUIREMENTS OF BACHELOR OF ENVIRONMENTAL SCIENCE
DEGREE HONOURS IN SAFETY HEALTH AND ENVIRONMENTAL
MANAGEMENT.

March 31, 2017

 DEDICATION
This research work is wholly dedicated to my father Mr M. Gonde, my brother Justin Gonde,
my late mother Mrs E. Gonde and all City of Harare sewer workers who lost their lives during
operations.

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 ACKNOWLEDGEMENTS
Firstly I would like to thank God who make all things possible

I would like to express my deepest appreciation to all those who provided me the possibility to
complete this research. Special thanks goes to City of Harare for allowing me to be attached at
their organization and to carry out my research. Through its supportive members of staff I have
found my stay quiet, enjoyable and enlightening in all areas related to my studies. Thanks for
the support, motivation and co-operation from my workplace mentors across all Departments,
may the Lord richly bless them.

A special gratitude goes to my immediate workplace supervisors Mr. A. Chikunya, Ms. L.

Taru, Mr. F. Tekedese, Mr. T. Verengai, Ms. C. Dube and Mr. J. Duve whose contribution in
stimulating suggestions and encouragement, helped me in carrying out my tasks with limited
to no supervision

Furthermore I would like to express my special gratitude to my dearest Father and family for
their continued support in my academic journey, where would I be without you. A special
thanks goes to my academic supervisor Mrs. L. Mabhungu, to her I say, your advice is priceless,
and may you continue to help me and other students in our academic endeavors. Tafadzwa
Piyo, may the good Lord I worship abundantly bless you and grant you what you deserve.
BES-SHEM class of 2013, thank you for your constructive criticism and moral support.

May God continue to guide and protect all the people even those I didn’t mention who helped
and continue to help me in this academic journey.

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 ABSTRACT
The study was carried out at three sewerage treatment plants for city of Harare. The city has
been facing serious health complications to its workers at the wastewater treatment plants. The
ultimate cause being sewer gases which have not been quantified before to determine
occupational exposure. A survey study was carried out at three Harare City Council wastewater
treatment plants (Workstations). The study aimed at quantifying occupational exposure levels
to hydrogen sulphide (H2S), hydrogen chloride (HCl) and ammonia (NH3) across three selected
wastewater treatment plants (Firle, Crowborough and Hatcliffe). The occupational gas
concentrations were monitored using the passive dosi-tubes for a period of six months, that is
three months for summer and winter seasons respectively. Samples were collected three times
a day, for four days a month (every Monday). Samples for each day were combined to form
a composite sample for that particular day. Data was analysed using the Statistical Package for
Social Sciences (SPSS) Version 20.0 One sample t-test was done to compare the
occupational exposure to noxious gases by employees with the threshold limit value for
National Social Security Authority guidelines of 1 May 2009. One way ANOVA was carried
to determine whether there is any significant variation in gas concentration at different
workstations, and on different seasons. Post-hoc comparison was performed for multiple
comparison.For all the gases, highest concentrations were recorded in summer and the least in
winter. It was concluded that gas concentrations was highly affected by variations in seasonal
temperature. With the exception of hydrogen chloride gas, all the mean gas concentrations
were significantly below the NSSA-TLV (p<0.05). Firle treatment plant recorded the highest
concentrations for all gases that were under study and Hatcliffe recorded the least.
Crowborough recorded figures which were slightly below those for Firle workstation. One way
ANOVA indicated a significant difference in gas concentration across all workstations
(p<0.05). It was concluded that the variations in concentration across workstations was affected
by the factor of differences in carrying capacity and also the sources of wastewater that is being
discharged into the sewerage system.

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 TABLE OF CONTENTS

Contents Page Number

DEDICATION ............................................................................................................................ i
ACKNOWLEDGEMENTS .......................................................................................................ii
ABSTRACT ............................................................................................................................. iii
TABLE OF CONTENTS .......................................................................................................... iv
LIST OF TABLES .................................................................................................................... vi
LIST OF FIGURES .................................................................................................................vii
ABREVIATIONS .................................................................................................................. viii
CHAPTER ONE: INTRODUCTION ........................................................................................ 1
1.1 BACKGROUND TO THE STUDY ............................................................................. 1
1.2 STATEMENT OF THE PROBLEM ............................................................................ 1
1.3 JUSTIFICATION ......................................................................................................... 2
1.4 AIM ............................................................................................................................... 2
1.5 OBJECTIVES ............................................................................................................... 2
1.6 RESEARCH HYPOTHESIS ........................................................................................ 2
CHAPTER 2: LITERATURE REVIEW ................................................................................... 4
2.1 CHARACTERISTICS OF SEWER GASES ................................................................ 4
2.2 EMPLOYEE EXPOSURE TO SEWER GASES ......................................................... 6
2.3 HEALTH EFFECTS OF EMPLOYEE EXPOSURE TO SEWER GAS ..................... 8
2.4 SEASONAL VARIATIONS OF SEWER GAS EXPOSURE ................................... 10
CHAPTER: 3 METHODOLOGY ........................................................................................... 12
3.1 SITE DESCRIPTION ................................................................................................. 12
3.2 RESEARCH DESIGN ................................................................................................ 13
3.3 POPULATION AND INDIVIDUAL SAMPLING.................................................... 13
3.4 DATA COLLECTION PROCEDURE....................................................................... 13
3.5 STATISTICAL ANALYSIS ...................................................................................... 14
CHAPTER 4: RESULTS ......................................................................................................... 15
4.1 VARIATION OF GAS CONCENTRATIONS AT THREE DIFFERENT
WORKSTATIONS. .......................................................................................................... 15

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 4.2 VARIATION OF SEWER GASES ACROSS SEASONS ......................................... 17
CHAPTER 5: DISCUSSION ................................................................................................... 19
5.1 VARIATION IN CONCENTRATION ACROSS WORKSTATIONS. .................... 19
5.2 SEASONAL VARIATION OF GASES CONCENTRATIONS ............................... 20
CHAPTER 6: CONCLUSIONS AND RECOMMENDATION ............................................. 22
6.1 CONCLUSION ........................................................................................................... 22
REFERENCES ........................................................................................................................ 23
Appendices ............................................................................................................................... 30
Appendix 1 ........................................................................................................................... 30
MEASUREMENT PROCEDURE FOR: ............................................................................. 30
Hydrogen sulphide ............................................................................................................ 30
Hydrogen Chloride............................................................................................................ 31
Ammonia........................................................................................................................... 32
Appendix 2a ......................................................................................................................... 33
Appendix 2b ......................................................................................................................... 34
Appendix 2c ......................................................................................................................... 35
Appendix 3 ........................................................................................................................... 36
One-Sample Statistics ....................................................................................................... 36

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 LIST OF TABLES
Table 4.1: Summary of mean values across seasons…………………………………..…….17

Table 4.2: Seasonal mean variations at different workstations against the NSSA threshold
limit values (TLV)…………………………………………………………………………...18

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 LIST OF FIGURES
Figure 4.1: Hydrogen Sulphide mean concentration across three workstations……....……15

Figure 4.2: Hydrogen Chloride mean concentration across three workstations……............16

Figure 4.3: Ammonia mean concentration across three workstations……………… ……..17

Figure 3.1: study area map………………………………………………………………….21

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 ABREVIATIONS
ACGIH : American Conference of Governmental Industrial Hygienists.

CO : Carbon Monoxide

GWESAC: Guide on the Workplace Exposure Standards for Airborne Contaminants.

H2S : Hydrogen Sulphide

HCL : Hydrogen Chloride

IARC : International Agency for Research Cancer.

NIOSH : National institute of Occupational Health and Safety.

NSSA : National Social Security Authority.

OEL : Occupational Exposure Limit.

OHS : Occupational Health and Safety

OSHA : Occupational Safety and Health Administration.

PEL : Permissible Exposure Limit.

PPE : Personal Protective Equipment.

PPM : Parts per million

TLV : Threshold Limit Value.

TWA : Time Weighted Average.

WHO : World Health Organisation.

WWTP : Wastewater Treatment Plant

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 CHAPTER ONE: INTRODUCTION
1.1 BACKGROUND TO THE STUDY
Sewerage is the used water of a community and can include domestic wastewater and industrial
wastewater (Barrasa et al., 2012). Combined sewer systems will include storm water such as
road runoff which carries oils, salts, acids, and pesticides from soil application. Zhang et al.,
(2001) reported that for many years work in the wastewater treatment field was considered the
most hazardous, especially due to the deaths involving suffocation in confined spaces. One
sewerage treatment plant may service a hundred or more industries therefore an enormous
range of chemicals may be present in the influent and sludge (Aneja et al., 2006). The presence
of toxic chemicals in sewerage, in sludge and in the air at specific sites in sewerage plants has
raised suspicions regarding their possible health effects on workers, (Aneja et al., 2006).

Teye et al. (2009), noted that 23 416 accidents related to noxious wastewater gases were
reported within the European Union. Zhang et al. (2013), reviewed treatment records for sewer
workers in Mumbai and these records indicated nausea, vomiting, indigestion, diarrhoea, and
flu-like complaints. Also studies of antibodies in the blood of workers have indicated that
disease exposure have occurred (Zhang et al., 2013). Richford, (2010) stated that four workers
died at Kennebunkport Sewer District from hydrogen sulphide toxicity in a confined space with
terminal inhalation of sewerage. Lamosa, (2013) stated that in Denmark, two workers, who
works in the municipality of Copenhagen died in confined spaces associated with sewer line
activity. In Denmark, fear has been expressed for the past years about the exposure of
wastewater treatment plant workers to sewer gases but little efforts has been made (Warneck,
2009).

In Zimbabwe, previous conducted researches had shown that concerns about the implications
of sewer gases are still little (Dozva. et al., 2009). Mutetwa et al. (2013), noted that there is
serious lack of a health and Safety Culture in all local authorities especially as it relates to
sewerage treatment works and sewer lines operations. In 2015, NSSA had recorded two fatal
accidents which they believed were caused by hydrogen gas inhalation (Workers
Compensation and Insurance Fund, 2015).

1.2 STATEMENT OF THE PROBLEM

City of Harare has reported two fatalities and other health complications of its employees
working at wastewater treatment plants (Workers Compensation and Insurance Fund Records,

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2016). There are currently no engineering controls or the issuance of proper protective
equipment to reduce employees’ exposure to noxious gases at wastewater treatment plants.
Little research effort has been focused towards quantification of inhalable gases at these sites.
Therefore, due to the incomplete understanding of sewer gases concentration and exposure,
this research seeks to quantify occupational exposure to determine exact concentration of
noxious gases the employees are exposed to.

1.3 JUSTIFICATION
Prior to the study there has been no assessment of workers’ occupational exposure to hydrogen
sulphide, hydrogen chloride and ammonia at City of Harare sewerage treatment plants. Unlike
earlier studies which characterized the gas exposure environmentally, this research will answer
whether occupational exposure levels are below or above maximum threshold limit value and
define the course of action. In case the obtained results are not desirable, the study will help
the organization to select the appropriate mechanisms and systems that reduce workers
exposure to noxious gases effectively and come up with realistic smart measures which can
reduce the cost of paying medical costs to the injured. The research can be of paramount
importance to the organization for continual improvement and compliance with local as well
as international standards. In Zimbabwe only 16. 7% of all sewerage treatment works had OSH
policies to guide implementation of OSH programmes (Dozva et al., 2011). By virtue of these
statistics at national level, the results of this research will act as a snapshot of the dangers
associated with wastewater treatment works to other local authorities across Zimbabwe

1.4 AIM
To assess workers’ exposure to sewer gases at Firle, Crowborough and Hatcliffe wastewater
treatment plants in Harare.

1.5 OBJECTIVES
 To determine the variation of occupational exposure to noxious gases (H2S, NH3, and HCl)
at Firle, Crowborough and Hatcliffe wastewater treatment sites.
 To determine the variation of employee exposure to hydrogen sulphide, ammonia and
hydrogen chloride with seasons.

1.6 RESEARCH HYPOTHESIS

 There is a significant difference in variation of gas concentration at different workstation
in cold and hot season

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 Occupational exposure to noxious gases by employees is significantly different to the
threshold limit values for National Social Security authority guidelines of 1 May 2009.

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 CHAPTER 2: LITERATURE REVIEW

2.1 CHARACTERISTICS OF SEWER GASES

Sewer gas is a generic name for a complex mixture of gases and airborne agents that result
from the natural process of the decomposition of organic materials in sewage. Gases produced
by domestic wastewater decomposition commonly include hydrogen sulfide (H2S), ammonia
(NH3), methane (CH4), carbon dioxide (CO2), and hydrogen chloride (HCl) (Zhang et al.,
2001). Of these gases, hydrogen sulfide, hydrogen chloride and ammonia are malodorous
(Hutter, 1993). Sewer gas also contains sulfur dioxide (SO2), nitrous oxides (NOx), biological
organisms, water vapor, and chemicals introduced into wastewater such as chlorine bleaches,
industrial solvents, and gasoline (Barrasa et al., 2012). The presence and concentration of these
components can vary with time, composition of the sewage, temperature, and pH (Hutter 1993;
WDHFS 2003). Also, the clinical effects of sewer gas depend on its chemical composition,
concentration and the duration of exposure.

Hydrogen sulfide is the most commonly known and prevalent odorous gas associated with
domestic wastewater. It is also the sewer gas component of greatest health concern (Woodall
et al., 2005). The conditions leading to hydrogen sulfide formation generally favor production
of other malodorous organic gases. Many of those are also sulfur-bearing compounds, such as
mercaptans and dimethyl disulfide. Because of this association, solving for hydrogen sulfide
odor problems can often resolve other odor problems (Li et al., 2007).

Hydrogen sulfide is a colorless, flammable, highly toxic gas with a characteristic of rotten egg
odor. The reported odor threshold for hydrogen sulfide gas varies greatly, but it is generally
less than 0.01 parts per million (ppm) (McGavran, 2001). Some people may be able to detect
the odor of hydrogen sulfide in air at concentrations as low as 0.0005 ppm (Legator, 2001).
Hydrogen sulfide is likely to remain in ambient air for less than one day, but it may persist for
as long as 42 days (Lambert et al., 2006). It is formed from the bio-chemical reduction reaction
of naturally occurring sulphate ions in water or from the decomposition of organic matter that
contains sulphur under aerobic conditions, and from the reaction of metal sulphides and strong
acids (Szabó, 2007).

Hydrogen sulphide will generally not form if there is an abundance of available oxygen. Its
concentration in the gas phase is dependent upon its concentration in the liquid phase and
ambient equilibrium conditions. Davison, (2003), states in reference to the Phoenix
metropolitan area that “Sulphide production is highly sensitive to wastewater temperature, and

4
therefore, sulphide and H2S production are typically at least 4 times higher in the summer than
in the winter .Due to its relatively high toxic level while at dilute concentration, and normally
expected air currents, molecular gas density of H2S gas is also flammable at concentration
which are well above toxic levels (Lower Explosive Limit 4.35%, Upper Explosive Limit
46%).

Apart from H2S, hydrogen chloride (HCl) is another sewer gas which is a colourless, corrosive
gas with a pungent, suffocating odour. It is highly soluble in water, forming hydrochloric acid.
HCl can occur in gaseous and aerosol forms in the atmosphere, and its partitioning depends on
temperature and humidity (Sebacher et al., 1996). Inhaled HCl in contact with moisture in the
upper respiratory tract is expected to rapidly disassociate because of its high water solubility.

It is readily in polar organic solvents such as methanol, ethanol or acetic acid. It is a strong acid
and it reacts with most metals producing explosive hydrogen gas. Today wastewater
chlorination is widely practised to reduce microbial contamination and potential disease risks
to exposed populations. This chlorine enters the water through the process of chlorination,
chlorine is the most used disinfectant for municipal wastewater because it destroys targeted
organisms by oxidising cellular material (Li et al., 2007). Also chlorine reaches wastewater
through household laundry bleach to which the chlorine bleach is made by mixing chlorine and
caustic soda (sodium hydroxide). The chemical equation for HCl is as follows.

H2 + Cl2=2HCl

Ammonia is a chemical that is made both by humans and by nature. It is made up of one part
nitrogen (N) and three parts hydrogen (H3). It is a colourless gas with a sharp odour. Ammonia
in this form is known as ammonia gas or anhydrous (without water) ammonia (Li et al., 2007).
The amount of ammonia manufactured by humans is almost equal to the amount of produced
by nature every year (Close et al., 1980). Ammonia easily dissolves with water. In this form,
it is known as liquid ammonia, aqueous ammonia, or ammonia solution. In water, most of the
ammonia changes to the ionic form of ammonia, known as ammonium ions which are
represented by the formula NH4+ (Close et al.,1980). Ammonia volatilization occurs because
ammonium-N in manure or solution is converted to dissolve ammonia gas, by the reaction:

NH4+ - N ↔NH3g + H+

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The reaction produces more NH3g as pH or temperature increases, and as the NH4-N
concentration increases. The rate of ammonia release to the atmosphere is a function of the
difference in NH3g concentration in the manure and the air (Zhang et al., 2012).

2.2 EMPLOYEE EXPOSURE TO SEWER GASES

The primary route for sewer gas exposure is through inhalation. It is the easiest and fastest
mode of exposure to noxious gases because toxic substances are readily absorbed in the
respiratory system (Watt et al., 2005). The lining of the respiratory tract is not effective in
preventing absorption of sewer gases into the body. Some of the factors which affect inhalation
of toxic gases include, concentration of toxic gas in the air, respiration rate, length of exposure,
condition of respiratory tract, and size of toxic particle (Bannert et al., 1997).

Inhalation of toxic gases can produce poisoning by absorption through the mucous membrane
of the mouth, throat and lungs, and can seriously damage these tissues by local action (Barrasa
et al., 2012). Inhaled gases may pass rapidly through the capillaries of the lungs and enter the
circulatory system (Teye et al., 2001).

The eye is a common point of contact for toxic gases. The primary point of contact for toxic
substances is the cornea. Exposure to high gas concentrations can result in eye irritations.
Acidic and basic compounds are the most common types of exposures that do damage (de la
Hoz et al., 1998). Depending on the amount of damage, the cornea may be able to repair itself.
All nutrients and oxygen must diffuse through the aqueous humour in the back to the cornea to
repair the damaged tissue (de la Hoz et al., 1998).

A study in Canada indicated 221 cases of H2S exposure from 1979 to 1983, and 173 patients
were transported to the hospital; 14 victims (6%) were dead on arrival (Bannert et al., 1997).
Another research by Watt et al. studied 26 sewer workers exposed to smell and found that
53.8% developed sub-acute symptoms including sore throat, cough, chest tightness,
breathlessness, thirst, sweating, irritability and loss of libido.

To avoid these incidents, sources of exposure must be determined. For a sewer gas to be
detected, it must first transfer from the liquid to the gas phase (Legator, 2005). The main sewer
gas sources at a sewage treatment works tend to be towards the inlet, if the incoming sewage
is septic, or associated with sludge processing where anaerobic conditions result in the
formation of new odorants (Friis, 2001). In some cases, both conditions are satisfied. In long
gravity trunk sewers the air emanating from the inlet sewer at treatment plants can be highly
odorous having been in contact with sewage for many hours.(U.S. EPA, 2007) stated that

6
influent wastewater entering the treatment facility from the collection system may contain high
concentrations of sulphide and volatile organic compounds (VOCs). In general, the preliminary
and primary treatment processes are often major sources of emissions.

Aneja et al, (2002) stated that primary tanks promote the emission of noxious gases formed in
the sewerage system by virtue of the large area of sewage which is contacted with the
atmosphere, and also by means of the turbulence generated at inlet or outlet weirs. Where
desludging is infrequent, large volumes of sludge accumulate and anaerobic conditions develop
within the stored sludge. This can lead to the formation of new odorants. Primary tanks have
been identified as major sources of odour at many works, especially where the influent sewage
is septic and where desludging is infrequent (Hobson, 1995; Vincent and Hobson, 1998).

Primary clarifiers can be a major source of odour emissions, particularly if the influent
wastewater contains significant levels of dissolved sulphide (Vincent and Hobson, 1998)
Primary clarifiers represent a large sewer gas-emitting surface area, and the character of the
odour is often considered objectionable. The turbulent effluent launders often represent a
significant portion of the total clarifier odorous emissions (Vincent and Hobson, 1998). The
greater the free fall over the effluent weirs, the greater the release of odorants. Covering the
entire basin and treating in an odour control system can reduce off-site odour impacts of
primary clarifiers.

Accumulations of scum on the tank water surface and of organic matter on the effluent weirs
can generate odours (Legator, 2005). Primary sludge odours will also result if settled solids
remain for long periods on the tank floor or in the sludge collection area. Therefore, frequent
sludge removal from operating tanks is necessary to prevent the production of gases that could
cause the sludge to rise to the surface, releasing odours and inhibiting solids settling.

Biological trickling filters can be a source of sewer gases. This wastewater treatment
mechanism is considered effective and efficiency by many researchers only if properly
designed and maintained. However, there are periods which there is little or no air flow through
the filter, in either directions (Barrasa et al., 2012). It has been estimated that when the
temperature differences between the ambient air and the wastewater is less than 12 to 16F, an
inadequate air supply through the filter results, and anaerobic conditions within the filter can
occur.

In addition to generating odours, period of inadequate air flow can result in loss of process
efficiency (Leduc et al., 1992). When air movement resumes, either upward or downward,

7
odorous gases may be released to the atmosphere. Biological filters can be a source of odour
generation if they are overloaded, or if the media have deteriorated and also if the feed sewerage
is odorous (Legator, 2005). .

2.3 HEALTH EFFECTS OF EMPLOYEE EXPOSURE TO SEWER GAS

The health effects of sewer gases differ with the concentration and the type of the gas one is
exposed to. The toxicology of hydrogen sulphide has been well revised recently by Reiffenstein
et al., (1999) and Glass, (2001). The acute effects of exposure to H2S are well recognised but
accurate exposure-response data are limited to lethal effects, even in animal studies. Odour
followed by olfactory paralysis and kerato-conjuctivitis are the typical effects of H2S at lower
concentrations (Reiffenstein et al., 1999). The effects depends on how much hydrogen sulphide
you breathe and for how long. At concentration between 1-5ppm, the effects include prolonged
exposure which may cause nausea, tearing of the eyes, headaches or loss of sleep (Legator,
2005). Possible fatigue, loss of appetite, headache, irritability and dizziness can also result from
concentrations in the range of 20 ppm. Any concentration above 50ppm – 100ppm can cause
death within 48 hours if not attended to. Instant death can result from any concentration above
500ppm (Zhang et al., 2001).

Long-term H2S exposure has mainly been associated with nervous and respiratory system and
eye effects. However, controversy exists as to whether or not long term exposure to H2S causes
significant health effects. The disagreement centres on the quality of the research and the nature
of some reported symptoms which include headaches, dizziness, loss of appetite and irritability.

There are few studies that have evaluated and concluded the long term effects of H2S (Sobonya
et al, 2002). Aneja et al. (2006) conducted a research of two groups of workers, the first group
(459 men) were exposed to H2S in their day work, often at concentrations exceeding 20ppm.
Group two (384 men) were generally not exposed. Concluded results were that, group 1 more
frequently reported symptoms such as fatigue, loss of appetite, frequent headaches, dizziness
and itching. However, Matt, (2008) clashed the results accusing the limitations of the study in
areas which include the lack of statistical analysis, possible self-reporting biases and lack of
control over potential confounding factors.

The US National Toxicology Board (NTB) had claimed that chronic exposure to H2S gas have
health complications on the respiratory and circulatory systems due to the deaths, especially
cardiovascular deaths, was observed in sewerage treatment works in India( Legator, 2011).

8
The National Research Council reviewed the toxicological effects of HCl in Humans (NRC
1987, 1991). The report concluded that exposure to irritating concentrations of HCl can result
in coughing, pain, inflammation, edema, and desquamation in the upper respiratory tract. Acute
exposure to high concentrations might produce constrictions of the larynx and bronchi and
closure of the glottis (Matt, 2008). Hydrogen chloride is irritating and corrosive to any tissue
with which it comes into contact. On exposure to air, hydrogen chloride forms dense white
vapour due to condensation with moisture in the air (Legator, 2011). It dissolves rapidly in
water to form hydrochloric acid affecting moist areas, for example, mucus membranes.
Because HCl is highly irritating to the mucosal surfaces of the respiratory tract and the eyes.

Matt, (1989) in his doctoral dissertation included only two individuals and three exposure
concentrations. Each individual was exposed once to HCl at 10ppm (10mins), 70ppm (15mins)
and 100ppm (15mins). When exposed to 70ppm, the individuals left the exposure chamber
once briefly during the 15min period, and when exposed at 100ppm, they left several times
because of their discomfort. During exposure at the high concentrations, the individuals
experienced coughing, increased breathing frequency and strong irritation of the throat and
respiratory tract.

Chronic exposure to hydrogen chloride gas or mist may result in decreased pulmonary function,
inflammation of the bronchi, dermatitis, conjunctivitis, upper respiratory tract abnormalities
and nasal ulcerations. (Woodall et al., 1994) Symptoms may be delayed for 1-2days and they
are similar to those of acute viral infections of the upper respiratory tract may also occur.
Inhalation also causes a transitory constriction of the respiratory tract, which lessens on
prolonged exposure.

Woodall et al., (1994) have reviewed the results of several studies of long-term occupational
exposure. In the majority of those studies, the occupational exposures were to mixed mineral-
acid vapours. Prolonged occupational exposure in which HCl concentrations repeatedly
exceeded 5ppm for 5mins or more have been associated with dental erosion and tooth decay,
bleeding mucus membranes in the nose and gums, and ulcerations of the nasal and oral mucosa
(Teye et al., 2009)

Water-soluble, ammonia is rapidly absorbed in the upper airways, with the result of damaging
upper airway epithelia (Close et al., 1980). Severe cough and mucous production can result
from moderate concentrations (50-150 ppm), higher concentrations which are greater than
150ppm may cause scarring of the upper and lower airways (Close et al., 1980; Leduc et al.,

9
1992). A consequence of these inflammatory responses, in some cases, is reactive airways
dysfunction syndrome (RADS) and associated persistent airway hyper-responsiveness
(Bernstein and Bernstein, 1989; Flury et al., 1983). At higher concentrations, sufficient
ammonia may move through the upper airways to cause lower lung inflammation and
pulmonary edema (Close et al., 1980; Sobonya, 1977). Massive exposure to ammonia can be
fatal, including in the agricultural sector, a consequence to disruption of tanks of anhydrous
ammonia (Sobonya, 1977). These fatalities, as well as the chronic lung disease seen following
as little as two minutes of exposure to high concentrations of ammonia gas may result in the
development of bronchiolitis obliterans (de la Hoz et al., 1996; Kass et al., 1972; Sobonya,
1977), restrictive lung disease (de la Hoz et al., 1996), and bronchiectasis (Leduc et al., 1992).

In addition to pulmonary diseases, exposure to ammonia may also result in irritation of the
eyes, sinuses, and skin. Exposure to 100 ppm ammonia for short (30 second) period can result
to nasal irritation (McLean et al., 1979). Clinical sinusitis has been reported following
accidental exposure to ammonia as well (Kass et al., 1986). Chemical burns to the skin and
eyes are also commonly seen following high-concentration ammonia exposures (Kiplinger et
al., 1973).

Inhaled ammonia is retained by the mucosal membranes of the upper respiratory tract, therefore
effects on the lower respiratory tracts are less common (Leduc, 2007). However there are few
cases reported of interstitial lung disease associated with chronic level exposure to ammonia

Acclimatisation to the irritant effects of ammonia at concentrations up to 70mg/m 3 (100ppm)

has been demonstrated after repeated exposure for 6 hours a day for 2 months (Kass et al.,
1986).

2.4 SEASONAL VARIATIONS OF SEWER GAS EXPOSURE

Literature on seasonal variation of sewer gases is very little. Blunden et al. (2008) conducted a
study on emissions of atmospheric NH3 and H2S from an anaerobic swine waste treatment pond
over a one year period during four different seasons. The main aim was to examine diurnal and
seasonal variations and the respective relationships of (atmospheric ammonia-nitrogen) NH3-
N and H2S discharges to pond physicochemical properties and meteorological parameters
(Blunden et al., 2008). For NH3-N, the largest fluxes were observed during the summer (44200
mgNm_2 min_1). The lowest fluxes for H2S were also observed during the winter season and
were considered to be insignificant since concentration quantities were generally below the
detection limit of the instrument which was used. Average fluxes increased during the fall

10
(0.370.1 mgm_2 min_1) and spring (0.571.0 mgm_2 min_1) and were observed at highest flux
values during the summer (5.37 3.2 mgm_2 min_1) (Blunden et al., 2008). Generally, the pond
emissions for H2S were 3–4 orders of magnitude less than NH3-N during all four measurement
periods. Hydrogen sulphide emissions were well correlated with lagoon aqueous H2S
concentration, lagoon temperature, and pH.

Sharma et al. (2015) noted that studies addressing H2S formation also show significant
variability. Hydrogen sulphide is well known to be released in areas with slow flow rates,
insufficient re-aeration (low oxygen water transfer), relatively high temperature, low pH, and
high turbulence (Sharma et al., 2008). Yang et al. (2015) did an investigation of information
available on factors affecting gas production in sanitary sewerage. It was found that, in general,
the principles developed from the study of gas production in other media were applicable to
the wastewater treatment plant environment. It was found that gas production increases with
increased moisture (Yang et al., 2015). There appears to exist a typical pattern of temperature
variation within the wastewater treatment plant with a peak temperature being reached during
the initial phase of anaerobic decomposition. The magnitude of this peak is related to the
wastewater temperature at placement (Yang et al., 2015). Subsequent temperatures are lower
and tend to fluctuate with season. Optimum temperatures for gas production are in the range
of from 30°C to 35°C, however, wastewater temperatures are often lower than this. Optimum
levels of pH and alkalinity exist which maximize gas production rates. The types and amounts
of gas produced are influenced by wastewater composition (Yang et al., 2015).

11
 CHAPTER: 3 METHODOLOGY

3.1 SITE DESCRIPTION

The study was conducted at three sewerage treatment plants in Harare city council namely
Firle, 17º 91' 69 South and 30º 92’ 525 East; Crowborough, 17º 85' 02 South and 30º 91' 645
East; and Hatcliffe, 17 º 66' 88 South and 31 º 09' 105 East. The average annual rainfall for
Harare is 825mm and the average temperature of 19.98ºC (Lorenc et al, 2014). Firle and
Crowborough wastewater treatment plants in Harare were commissioned to cater for 250 000
people (Muzondi, 2014). Hatcliffe treatment plant was later commissioned in the late 90s. Firle
has the highest carrying capacity of 144ML/day and it receive industrial wastewater mainly
from Lyton, Graniteside and waterfalls as well as domestic sewer from Glenview and other
surrounding residential areas. It is followed by Crowborough with 54ML/day which received
wastewater mainly from Southerton and Lochivale industrial sites. Hatcliffe has the carrying
capacity of 2,5ML/day, receiving its main effluent from Hatcliffe residential location and some
parts of Borrowdale (Muzondi, 2014). Fig 3.1 shows the map of the study area.

Study area

Figure 3.1: Study area map.

12
3.2 RESEARCH DESIGN
A random block design was used. Employees from three blocks namely, Firle, Crowborough
and Hatcliffe were selected. From each block, employees were divided into homogenous sub-
group in which individuals were selected. The research covered a period of six months,
(October, November, and December) for hot and (April, May and June) cold seasons
respectively. Sewer gas samples for occupational exposure were replicated three times per day
at different intervals and four times per month.

3.3 POPULATION AND INDIVIDUAL SAMPLING

Stratified random sampling was used during this research to select individuals for personal gas
sampling. It involved dividing the population into homogeneous subgroup and then taking
simple random samples in each subgroup. Out of our 3 blocks (Hatcliffe, Firle and
Crowborough), 4 subgroups were formed from each block which included workers at the
screening intake, operators who clean the settling tanks, operators who monitors the biological
filters and those near the fermentation basins. From the total block population of 26 employees
(Hatcliffe), 34 (Crowborough) and 41 (Firle), two sewer operators were selected randomly
from each subgroup to come up with 8 samples for each block.

3.4 DATA COLLECTION PROCEDURE

Multi-Gastec tubes (passive dositubes) were used for collecting gas samples. These tubes are
capable of measuring both occupational and environmental exposure concentrations. They use
the principle of the natural gas diffusion. The diameter of a passive dosi-tube was filled with a
diffuser and chemical reagent in parallel that enable gas to disperse at a constant rate resulting
in a longer discolouration and better demarcation. Air diffuses through the tube and reacts, like
the standard detector tube system, with a detecting reagent within a tube producing a strain
depending with the gas being measured. Passive dositubes differs with the type of gas being
sampled. For hydrogen sulphide, tube number 4d was used with the range of 0.2ppm-200ppm
and measuring time of up to 48hours. Hydrogen chloride, 14d tube was used with a range of
0.1ppm-100ppm with a measuring time of 10hours and for ammonia, 3dL tube was used with
a measuring range of 1.2ppm-200pppm and a measuring time of 0.5-48hours. Gas samples
were collected three times a day, early in the morning (8-1000hrs), mid-morning (11-1300hrs)
and afternoon (14-1600hrs) respectively. Personal gas samples for all gases were measured
simultaneously at each interval. Each site was sampled once per week (every Monday), for six
months as indicated above. The tubes were first checked if there were any cracks before used.
Tube holders were clipped on workers within a 10cm breathing zone. Thermometer and

13
hygrometer were used to measure temperature and humidity respectively and correction tables
were used for extreme changes in temperature, humidity and pressure whenever necessary (See
appendix 1). Colour changes were monitored for all the gases under study at each interval to
detect if there were any interferences. Since the samples were replicated three times per day, a
composite sample was obtained for each gas using the TWA compliance formula (See
Appendix 1).

3.5 STATISTICAL ANALYSIS

After all the gas recordings, data were entered into the Statistical Package for Social Sciences
(SPSS) Version 20.0 for analysis. One sample t- test was done so as to compare the
occupational exposure to noxious gases by employees with the threshold limit value for
National Social Security authority guidelines of 1 May 2009. One way ANOVA was carried to
determine whether there is a significant variation in gas concentration at different workstations,
and on different seasons. Post-hoc comparison was performed for multiple comparison. Data
were presented using tables and bar graphs for interpretation and discussion of results.

14
 CHAPTER 4: RESULTS

4.1 VARIATION OF GAS CONCENTRATIONS AT THREE DIFFERENT

WORKSTATIONS.
Lowest H2S gas concentration (3.9±0.42ppm) was recorded at Hatcliffe wastewater
workstation whilst the highest gas concentration (8.5±2.15ppm) was recorded at Firle
workstation (Fig. 4.1). Crowborough workstation recorded the concentration which was
slightly below Firle treatment plant (7.5±0.23ppm). The test (One way ANOVA) indicated that
there was a significant difference in H2S gas concentration across all workstations (F= 67.711,
p< 0.05). Post hoc (LSD) also revealed a significant difference in H2S gas concentration for
all workstations that were under study. Total mean concentration of hydrogen sulphide gas was
below the NSSA threshold limit value (TLV) of 10ppm.

10
b
9
H2S Concentration (ppm)

8 a
7
6
5
c
4
3
2
1
0
Crowborough Firle Hatcliffe
Workstations

Figure 4.1: Hydrogen Sulphide total mean concentration across three workstations.
[Different letters indicate significant differences (P<0.05).]

For hydrogen chloride gas, the highest and lowest concentration was recorded at Crowborough
(2.4±0.23ppm) and Hatcliffe (1.3±0.32ppm) respectively (Fig. 4.2). Firle workstation recorded
total mean concentration of (2.4±0.34ppm). The computed test (One way ANOVA) indicated
that there was no significant difference in the concentration of HCl across all workstations
(F= 2.296; p<0.05). Post hoc tests for multiple comparison, correspondingly indicated no
significant difference in hydrogen chloride concentration across all workstations. The total
mean concentration of hydrogen chloride was above the NSSA- TLV of 1ppm.

15
 3.0
a

HCl Concentration (ppm)

2.5 a

2.0

a
1.5

1.0

0.5

0.0
Crowborough Firle Hatcliffe
Workstations

Figure 4.2: Hydrogen Chloride mean concentration across three workstations.

[Different letters indicate significant differences (P<0.05).]

Results showed highest and lowest concentration of ammonia at Firle workstation

(7.3±0.21ppm) and Hatcliffe (5.5±0.77ppm) respectively. One way ANOVA was performed
and it revealed that there was a significant difference in the concentration of ammonia gas
across workstations (F=7.441; p<0.05). However, the post hoc tests for multiple comparison
indicated that there was no significant difference between Crowborough and Firle. Monthly
mean for ammonia was far below the NSSA-TLV of 25ppm for all months (p< 0.05).

8.0
a a
7.0
NH3 Concentration (ppm)

6.0 b

5.0

4.0

3.0

2.0

1.0

0.0
Crowborough Firle Hatcliffe
Workstations

Figure 4.3: Ammonia mean concentration across three workstations. [Different letters
indicate significant differences (P<0.05).]

16
From the results obtained by the test (One way ANOVA), we accept the H0 and conclude that
there is a significant difference in concentration of gas concentration at different workstations.

4.2 VARIATION OF SEWER GASES ACROSS SEASONS

The results showed highest and lowest concentration of all sewer gases which were under study
in summer and winter period respectively. H2S recorded the highest figures in both summer
and winter, followed by NH3 and HCl respectively (Fig: 4.1). However, the concentration of
HCl in both seasons were above the NSSA threshold limit values of 1ppm

Table 4.1: Summary of mean values across seasons.

SUMMER WINTER
SITE H2 S HCl NH3 H2 S HCl NH3
(mean±SE) (mean±SE) (mean±SE) (mean±SE) (mean±SE) (mean±SE)
1 9.1±0.42 3.3±1.26 7.8±0.36 5.9±0.26 1.37±0.87 6.0±0.29
2 9.7±0.33 2.9±0.41 8.5±0.25 7.3±0.51 1.6 ±0.76 5.9±0.38
3 4.4±0.46 1.3±0.10 7.1±0.64 3.3±0.38 1.37±0.61 3.8±0.34

17
Table 4.2: Seasonal mean variations at different workstations against the NSSA threshold limit
values (TLV)

Workstation Gases Season Mean ± S.E Sig SI-TLV Result Decision

Crowborough H2S Summer 9.1 ± 0.62 0.177 10 Below TLV

Winter 5.9 ± 0.63 0.000 10 Below TLV
NH3 Summer 7.8 ± 0.45 0.000 25 Below TLV
Winter 6 ± 0.62 0.000 25 Below TLV
HCl Summer 3.34 ± 1.14 0.065 1 Above TLV
Winter 1.37 ± 0.12 0.013 1 Above TLV
Firle H2S Summer 9.7 ± 0.98 0.822 10 Below TLV
Winter 7.3 ± 0.63 0.002 10 Below TLV
NH3 Summer 8.6 ± 0.34 0.000 25 Below TLV
Winter 5.9 ± 0.42 0.000 25 Below TLV
HCl Summer 2.9 ± 0.56 0.007 1 Above TLV
Winter 1.6 ± 0.25 0.037 1 Above TLV
Hatcliffe H2S Summer 4.4 ± 0.35 0.000 10 Below TLV
Winter 3.3 ± 0.39 0.000 10 Below TLV
NH3 Summer 7.1 ± 0.38 0.000 25 Below TLV
Winter 3.8 ± 0.4 0.000 25 Below TLV
HCl Summer 1.3 ± 0.11 0.018 1 Above TLV
Winter 1.4 ± 0.14 0.370 1 Above TLV

The results indicated that Hydrogen sulphide and Ammonia concentration were below (p<0.05)
the NSSA threshold limit values of 10ppm and 25ppm respectively across all workstations
(Table 4.2). However HCl results were far above the NSSA threshold limit value of 1ppm
across all workstations. As a result, we accept the null hypothesis to conclude that occupational
exposure to noxious gases by employees is significantly different with the threshold limit value
for National Social Security authority guidelines of 1 May 2009. T-test reviewed that there is
a significant difference between the measured mean of hydrogen sulphide and the NSSA
occupational exposure limit (NSSA-OEL) for all workstations except in the summer periods at
Firle and Crowborough. Hydrogen chloride and ammonia reviewed a significant difference
(p<0.05) between the measured mean and the NSSA- OEL for all workstations in both summer
and winter seasons.
18
 CHAPTER 5: DISCUSSION
5.1 VARIATION IN CONCENTRATION ACROSS WORKSTATIONS.
Another objective of the study was to determine variation of sewer gas exposure across
workstations. The major reasons behind the results obtained was possibly related to differences
in carrying capacity and type of wastewater received by each plant. On average, Firle treatment
site recorded the highest concentrations in both summer and winter periods for all the gases
under study whilst Crowborough and Hatcliffe followed respectively. These results are
associated with the carrying capacity of these treatment plants respectively. Normally, Firle
has the highest carrying capacity of 144ML/day, followed by Crowborough with 54ML/day
and Hatcliffe 2,5ML/day (Muzondi, 2014). Wastewater treatment plants in Harare were
initially commissioned to cater for 250 000 people which is a tenth of the current population
which stand at 1.56 million in 2012 (ZIMSTATS 2012). The total design capacity of these
plants is 198,000 m3/day compared to total current inflows of about 300,000 m3/day. Harare
now pumps about over 190 mega litres of waste water per day to Firle treatment plant which is
reportedly now able to process about 90 mega litres a figure which is now less than its normal
carrying capacity due to ageing dysfunctional plant (Madyiwa, 2006). This overally results in
44 % overloading (Tsiko and Togarepi 2012). This indicates that the plants are no longer able
to treat the wastewater efficiently and effectively which is likely to result in sludge bulking and
other anaerobic processes promoting sewer gas formation.

In line with the above argument, Howe (2009) noted that, foul odours at treatment plants
originate from the anaerobic decomposition of organic compounds. A natural by-product of
anaerobic digestion is hydrogen sulphide (H2S), which gives off a strong, nauseating smell.
Due to its low solubility in wastewater, it is released into the atmosphere, producing an
offensive odour. Similarly, Mudungwe, (2009) states that when the plant is overloaded, odour
is produced, this occurs as a result of pH drop and formation of hydrogen sulphide gas due to
sulphate reduction. In low pH, hydrogen sulphide is formed and smells. In high pH, ammonia
is produced and smells too. Hatcliffe treatment plant recorded the lowest concentrations since
it receives wastewater from few locations which include Hatcliffe, Vainona and some parts of
Borrowdale. It is also not connected to any industrial sewer line.

Wastewater composition is the other aspect which resulted in variation of gas concentration
across the three workstations. The materials responsible for the diffusion of odours into the
atmosphere in the vicinity of treatment plants are generally gaseous inorganic products or

19
highly volatile organic compounds. Domestic waste which constitutes the highest percentage
of sewer water consists mainly of organic matter which takes part in the formation of hydrogen
sulphide (Friss, 2001). This explains why high concentration of hydrogen sulphide was
recorded at Crowborough since most of its effluent is from the household areas, containing
many cleaning detergents. Crowborough plant also has the high concentration of hydrogen
chloride which is due to the fact that it receive influent from Southerton as well as Lochivale
industrial site where there are a number of companies that deal with chlorine. Industrial
activities have an effect to gas concentration (Caro et al., 2009). The highest concentrations at
Firle was due to the fact that it receives the highest number of mega-litres of combined
wastewater from main industries which include Lyton, Graniteside and Waterfalls as well as
domestic wastewater from Glenview and other residential sites. In line with the above assertion,
Caro et al. (2001) supported the findings by mentioning that industrial wastewater is
characterized with several dangerous organic pollutants and these are volatile because of their
low solubility, more molecular weight and high vapour pressure. Therefore they may be
transferred to the atmosphere in open units of the WWTPs such as aeration tanks. If adequate
means are not taken, their volatilization represents a potential health risk to the population and
workers who are frequently exposed to it (Caro et al., 2001).

5.2 SEASONAL VARIATION OF GASES CONCENTRATIONS

From the obtained results above, seasonal variation of sewer gases was affected by temperature
fluctuations between the two seasons. The reason why summer recorded higher levels was
because of high temperature during summer period and low temperatures in winter. This is by
the virtue of the fact that temperature is a catalyst for biochemical reduction of sulphides into
the environment. This process depletes oxygen causing sewer gas build-up in the atmosphere.
These results are supported with the research conducted by Pennell, (2013) which have
suggested that, in general, sewer gas production is greatest during the summer months.
Similarly, Davison, (2003), states in reference to the Phoenix metropolitan area that “Sulphide
production is highly sensitive to wastewater temperature, and therefore, sulphide and H2S
production are typically at least 4 times higher in the summer than in the winter. The trend
observed in the current research also coincides with those obtained by Marleni et al. (2015)
which pointed out that, the major factor that affects sewer odour production especially
hydrogen sulphide gas generation is sewer temperature.

Temperature is the key factor in causing an increase in sewer gas concentration. This is valid
because of the fact that, high temperatures affect other wastewater parameters like biological

20
oxygen demand and chemical oxygen demand. Correspondingly, Jeppsson, (2002)
experimented that the increase in NH3 emissions with air temperature followed an exponential
pattern, and found correlations between CO2 emissions and temperature in an uninsulated
experimental building with pigs. He also stated that, there is a correlation between temperature
and biological oxygen demand. Alike, a study by Liang et al. (2003) observed that NH3
emission rates were higher in summer than in winter, although NH3 concentration might be
much lower in summer. High temperature triggers more release of hydrogen sulphide to sewer
atmosphere. Alani et al. (2014) noted that the rate changes with temperature on chemical
reactions is accelerated in higher temperatures, the rate of gas build-up increases with increase
of temperature.

However, the research conducted by Jeon et al. (2009) is in contrary with the current research
in such a way that despite the ambient air and sewage temperature during the summer season
falls between 29.5 - 32.4, (Average 31.3 °C) and 22.0 - 24.2 (average 24.2 °C) and for Winter’s
average temperatures being 9.6 °C and 12.4 °C for both the ambient air and sewage
respectively. In summer, Ammonia and Hydrogen sulphide recorded average concentrations of
506 ppb and 22.04ppb respectively and 967ppb and 54.8ppb in winter correspondingly. This
might have been due to fluctuating temperatures or changes in wind speed.

21
 CHAPTER 6: CONCLUSIONS AND RECOMMENDATION

6.1 CONCLUSION
The findings from the study concluded that occupational exposure to sewerage gases vary from
one wastewater treatment plant to the other due to differences in wastewater sources and
carrying capacity size. Summer period recorded higher concentration than winter suggesting
that temperature was a highly influential parameter. However, the performed test indicated a
significant difference (p >0.05) in gas concentration at different workstation between cold and
hot season. The results for occupational exposure to sewer gases were below the NSSA-TLV
except for hydrogen chloride gas which recorded concentrations which were above the standard
threshold limit values for NSSA guidelines of 2009.However, even though H2S gas recoded
values that were below the TLV, statistically, they were likely to cause harm since there was
no significant difference between the measured mean and the occupational exposure limit for
the summer periods recorded at Firle and Crowborough. Hatcliffe treatment site recorded
concentrations which were below the TLV for NSSA guidelines except for HCl, employees
who work at this treatment plant should continue to use gas respirators so as to prevent the
effects of chronic exposure.

6.2 RECOMMENDATION

 The study recommends all workers under City of Harare to undergo periodical medical
examinations and initial examinations at pre-employment stage
 The researcher also recommends the organization for continual sewer gas monitoring
at each workplace to ensure employees’ exposure is controlled and as a part of ongoing
evaluation process of control measures.
 Trainings should be conducted on the importance of wearing personal protective
equipment properly although it is the last line of defence.
 Use of gas detectors before opening manholes and keeping it open for not less than
30min before any maintenance work is carried out.
 The organization should rehabilitate the treatment plants so that they can cope with an
increasing population to ensure efficiency and effectiveness.

22
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 Appendices

Appendix 1

MEASUREMENT PROCEDURE FOR:

Hydrogen sulphide
 Reaction principle- Hydrogen Sulphide react with Lead Acetate to produce Lead
Sulphide (brown in colour)

H2S + Pb (CH3 +COO) 2 PbS+ 2CH3COOH

 Break the tube at the score of the tube with Gastec Passive Dosi-tube holder No 710

 Set the Dosi-tube No 4D in the tube holder firmly inside the holder so the broken part
is not appeared from the edge of the holder

 Record the measurement starting time on the peel off numbered label in each box of
the tube and put the label on the tube

 Put the dositube holder to the shirt collar of the person and support the tube holder with
a string through a small hole of the tube holder

 Monitor colour changes (from white to brownish)

 When the sampling is finished record the time, record the time on the label of the tube.
i.e. sampling time = finishing time – starting time

 Obtain the average concentration (TWA) by using the compliance formula:

T1C1 + T2 C2 +⋯Tn Cn
8hr TWA = 8ℎ𝑟

Where T= time

C= concentration

 Correction for temperature, humidity and pressure are not required

30
 Hydrogen Chloride
 Reaction Principle – Hydrogen Chloride reacts with base to discolour the indicator to
purple

HCl + Indicator Purple reaction product

 Break the tube at the score of the tube with Gastec Passive Dosi-tube holder No 710

 Set the Dosi-tube No 14D in the tube holder firmly inside the holder so the broken part
is not appeared from the edge of the holder

 Record the measurement starting time on the peel off numbered label in each box of
the tube and put the label on the tube

 Put the dositube holder to the shirt collar of the person and support the tube holder with
a string through a small hole of the tube holder

 Thermometer and Hygrometer to be used to measure temperature and humidity

respectively

 Monitor colour changes (from yellow to purple)

 When the sampling is finished record the time, record the time on the label of the tube.
i.e. sampling time = finishing time – starting time

 Obtain the average concentration (TWA) by using the compliance formula:

T1C1 + T2 C2 +⋯Tn Cn
8hr TWA = 8ℎ𝑟

Where T= time

C= concentration

 Correction for temperature and humidity are necessary. Calibration of the Gastec
passive tube No 14d is based on a tube temperature of 20ºC (68ºF) and approximately
50% relatively humidity and normal atmospheric pressure. To correct for temperature
of 0-40ºC (32-104ºF) and relative humidity range of 30-80%, the following table is to
be applied.

Temperature and humidity Correction Table

31
 Temperature 0ºC 10ºC 20ºC 30ºC 40ºC

Relative 32ºC 50ºC 68ºC 86ºC 104ºC

humidity

30% 0.7 0.6 0.5 0.45 0.45

40% 0.9 0.8 0.7 0.65 0.6

50% 1.2 1.1 1.0 0.9 0.8

60% 1.6 1.5 1.3 1.2 1.1

70% 1.9 1.8 1.7 1.6 1.4

80% 2.4 2.3 2.2 2.0 1.7

Ammonia
 Reaction principle: Ammonia reacts with sulfuric Acid to produce yellow discoloration
on colour indicator

2NH3 + H2SO4 (NH4)2SO4

 Passive dositube No 3DL to be used

 No correction factor for pressure and humidity for relative humidity range of 20 -90%

 The correction factor for temperature is necessary wherever it exceeds 20ºC. The
following table is to be applied.

Average Temperature Correction Factor

0 1.25

10 1.1

20 1.0

30 0.92

40 0.84

32
 Appendix 2a

Descriptives
H2S
N Mean Std. Std. Error 95% Confidence Interval for Minimum Maximum
Deviation Mean

Lower Bound Upper Bound

1 4 7.500 .3464 .1732 6.949 8.051 7.2 7.8

2 4 8.575 .7848 .3924 7.326 9.824 7.8 9.3
3 4 3.900 .5715 .2858 2.991 4.809 3.2 4.5
Total 12 6.658 2.1564 .6225 5.288 8.028 3.2 9.3

ANOVA
H2S
Sum of Squares Df Mean Square F Sig.

Between Groups 47.962 2 23.981 67.711 .000

Within Groups 3.188 9 .354
Total 51.149 11

Multiple Comparisons
Dependent Variable: H2S
LSD
(I) SITE ID (J) SITE ID Mean Difference Std. Error Sig. 95% Confidence Interval
(I-J) Lower Bound Upper Bound

2 -1.0750* .4208 .031 -2.027 -.123

1
3 3.6000* .4208 .000 2.648 4.552
1 1.0750* .4208 .031 .123 2.027
2
3 4.6750* .4208 .000 3.723 5.627
1 -3.6000* .4208 .000 -4.552 -2.648
3
2 -4.6750* .4208 .000 -5.627 -3.723

*. The mean difference is significant at the 0.05 level.

33
Appendix 2b
Descriptives
HCl
N Mean Std. Std. Error 95% Confidence Interval for Minimum Maximum
Deviation Mean

Lower Bound Upper Bound

1 4 2.350 1.1619 .5809 .501 4.199 1.3 4.0

2 4 2.250 .4655 .2327 1.509 2.991 1.8 2.9
3 4 1.325 .3202 .1601 .816 1.834 1.0 1.6
Total 12 1.975 .8292 .2394 1.448 2.502 1.0 4.0

ANOVA
HCl
Sum of Squares df Mean Square F Sig.

Between Groups 2.555 2 1.277 2.296 .156

Within Groups 5.008 9 .556
Total 7.563 11

Multiple Comparisons
Dependent Variable: HCl
LSD

(I) SITE ID (J) SITE ID Mean Difference Std. Error Sig. 95% Confidence Interval
(I-J) Lower Bound Upper Bound

2 .1000 .5274 .854 -1.093 1.293

1
3 1.0250 .5274 .084 -.168 2.218
1 -.1000 .5274 .854 -1.293 1.093
2
3 .9250 .5274 .113 -.268 2.118
1 -1.0250 .5274 .084 -2.218 .168
3
2 -.9250 .5274 .113 -2.118 .268

34
 Appendix 2c
Descriptives
Ammonia
N Mean Std. Std. 95% Confidence Interval for Minimum Maximum
Deviation Error Mean

Lower Bound Upper Bound

1 4 6.925 .6185 .3092 5.941 7.909 6.1 7.4

2 4 7.250 .1732 .0866 6.974 7.526 7.0 7.4
3 4 5.525 .9708 .4854 3.980 7.070 4.4 6.7
Total 12 6.567 .9903 .2859 5.937 7.196 4.4 7.4

ANOVA
Ammonia
Sum of Squares df Mean Square F Sig.

Between Groups 6.722 2 3.361 7.441 .012

Within Groups 4.065 9 .452
Total 10.787 11

Multiple Comparisons
Dependent Variable: Ammonia
LSD

(I) SITE ID (J) SITE ID Mean Difference Std. Error Sig. 95% Confidence Interval
(I-J) Lower Bound Upper Bound

2 -.3250 .4752 .511 -1.400 .750

1
3 1.4000* .4752 .016 .325 2.475
1 .3250 .4752 .511 -.750 1.400
2
3 1.7250* .4752 .005 .650 2.800
1 -1.4000* .4752 .016 -2.475 -.325
3
2 -1.7250* .4752 .005 -2.800 -.650

*. The mean difference is significant at the 0.05 level.

35
 Appendix 3

One-Sample Statistics

N Mean Std. Deviation Std. Error Mean

Site 1-H2S(Summer) 12 9.100 2.1595 .6234

Site 1-H2S(Winter) 12 5.900 2.1746 .6278
Site 2-H2S(Summer) 12 9.775 3.3788 .9754
Site 2-H2S(Winter) 12 7.367 2.1881 .6317
Site 3-H2S(Summer) 12 4.433 1.2025 .3471
Site 3-H2S(Winter) 12 3.350 1.3635 .3936

One-Sample Test

Test Value = 10

t df Sig. (2-tailed) Mean Difference 95% Confidence Interval of the

Difference

Lower Upper

Site 1-H2S(Summer) -1.444 11 .177 -.9000 -2.272 .472

Site 1-H2S(Winter) -6.531 11 .000 -4.1000 -5.482 -2.718
Site 2-H2S(Summer) -.231 11 .822 -.2250 -2.372 1.922
Site 2-H2S(Winter) -4.169 11 .002 -2.6333 -4.024 -1.243
Site 3-H2S(Summer) -16.036 11 .000 -5.5667 -6.331 -4.803
Site 3-H2S(Winter) -16.895 11 .000 -6.6500 -7.516 -5.784

One-Sample Statistics

N Mean Std. Deviation Std. Error Mean

Site 1-HCl(Summer) 12 3.342 3.9500 1.1403

Site 1-HCl(Winter) 12 1.375 .4413 .1274
Site 2-HCl(Summer) 12 2.900 1.9688 .5684
Site 2-HCl( Winter) 12 1.617 .8993 .2596
Site 3-HCl(Summer) 12 1.317 .3950 .1140
Site 3-HCl (Winter) 12 1.350 .5108 .1475

36
One-Sample Test

Test Value = 1

t df Sig. (2-tailed) Mean Difference 95% Confidence Interval of the

Difference

Lower Upper

Site 1-HCl(Summer) 2.054 11 .065 2.3417 -.168 4.851

Site 1-HCl(Winter) 2.943 11 .013 .3750 .095 .655
Site 2-HCl(Summer) 3.343 11 .007 1.9000 .649 3.151
Site 2-HCl( Winter) 2.375 11 .037 .6167 .045 1.188
Site 3-HCl(Summer) 2.777 11 .018 .3167 .066 .568
Site 3-HCl (Winter) 2.374 11 .037 .3500 .025 .675

One-Sample Statistics

N Mean Std. Deviation Std. Error Mean

Site 1-NH3(Summer) 12 7.800 1.5754 .4548

Site 1-NH3(Winter) 12 6.058 2.1360 .6166
Site 2-NH3(Summer) 12 8.600 1.1654 .3364
Site 2-NH3(Winter) 12 5.942 1.4463 .4175
Site 3-NH3(Summer) 12 7.150 1.6462 .4752
Site 3-NH3(winter) 12 3.850 1.3814 .3988

One-Sample Test

Test Value = 25

t df Sig. (2-tailed) Mean Difference 95% Confidence Interval of the

Difference

Lower Upper

Site 1-NH3(Summer) -37.821 11 .000 -17.2000 -18.201 -16.199

Site 1-NH3(Winter) -30.719 11 .000 -18.9417 -20.299 -17.584
Site 2-NH3(Summer) -48.748 11 .000 -16.4000 -17.140 -15.660
Site 2-NH3(Winter) -45.648 11 .000 -19.0583 -19.977 -18.139
Site 3-NH3(Summer) -37.562 11 .000 -17.8500 -18.896 -16.804
Site 3-NH3(winter) -53.038 11 .000 -21.1500 -22.028 -20.272

37
38