CHAPTER 9

SOLUTIONS TO END-OF-CHAPTER EXERCISES

9.1.

To protect the firm from liability for pre-employment health conditions

or pre-existing injuries or damage to tissues, such as lungs.

9.2.

The term "toxic substances" generally refers to agents that cause harm
to the body. Examples would be irritants, systemic poisons, depressants,
asphyxiants, carcinogens, teratogens, and mutagens. "Hazardous materials"
are more likely to be associated with safety hazards, such as fire and
explosion hazards. Admittedly, toxic substances are also hazardous, but
the terminology used by OSHA and practicing professionals is to make the
above-described distinction between the two terms.

9.3.

Irritants, systemic poisons, depressants, asphyxiants, carcinogens,

teratogens, and mutagens.

9.4.

Ethyl alcohol or "ethanol." Its principal hazard is as a depressant.

9.5.

Inhalation, (skin) absorption, and ingestion.

9.6.

Dentistry

9.7.

For most toxic substances, OSHA has taken a general approach and has
published "national consensus" PELs, based upon existing TLVs published
by the American Conference of Governmental Industrial Hygienists (ACGIH).
However, for some substances OSHA has gone much further and written
"completed" standards, each addressing a particular substance. Prominent
examples of such substances are asbestos and lead. Other prominent
examples include benzene, vinyl chloride, cadmium, and arsenic. (See
Table 9.1 of the text).

9.8.

Odorless gases include carbon monoxide, carbon dioxide, methane, and

nitrogen. Carbon monoxide is more dangerous than the others, but the
others can be dangers as simple asphyxiants, crowding out life-giving
oxygen. Methane is listed here as odorless, but usually, for safety
reasons, the gas utility company adds a stanching agent, such as ethyl
mercaptan, to make the methane have the characteristic "natural gas"
odor.

9.9.

Hydrogen sulfide, commonly known as "rotten-egg gas." The term

"olfactory" refers to the sense of smell.

9.10.

AL represents the "Action Level," and PEL represents the "Permissible

Exposure Level." The AL is usually 1/2 of the level of the PEL and is
intended to be a warning level so that controls can be instigated before
employee exposures exceed the legal limit prescribed by the PEL.

9.11.

"Solid" particles that are generally too fine to be called dusts. Fumes
are typically formed by the resolidification of vapors from very hot
processes such as welding.

9.12.

0.033% is equivalent to 0.00033 x 106 = 330

The PELs (TWAs) are found in Appendix A.1:
PELs (ppm)
Carbon
Monoxide
50
Em =

Carbon
Dioxide
5,000

Ci
330
x
-- = ------- + ---- < 1

Li

5000

50

x < 1 - 330
50
5000
x < 9670
50
5000
x < 9670(50)
5000
x < 96.7 ppm carbon monoxide
9.13.

Concentration Length of Time

.00001
4 hr
.00015
4 hr
Total

C x Ti

8 hr

.00004
.00060
.00064

CiTi
.00064
E = --------- = ------- = .00008
8
8
TWA
.00008 = ---106
TWA = 80 ppm
The PEL for methyl styrene (from Appendix A.1) is 100 ppm and is
preceded by the letter C, which identifies it as a "ceiling"
concentration, not a TWA. The AL, at one-half the PEL, would be 50 ppm,
also a "ceiling" concentration. Since the afternoon concentration, at .
00015 = 150 ppm, exceeds both PEL and AL ceilings, both PEL and AL are
exceeded, even though the TWA at 80 ppm is lower than the PEL.
9.14.

NOTE: This problem has been complicated by a change in nomenclature as

used in the OSHA standards. The organic chemical names
"trifluoromonobromomethane" and "trifluorobromomethane"
are synonyms. OSHA PEL tables have dropped the "mono" from the name and
Appendix A.1 lists the PEL for "trifluorobromomethane." Students should
be advised to use this entry in solving this problem.
(a)

Concentration

Duratio

n
trifluorobromomethane

.001

propane

.0005

phosgene

1 x 10-6

1/4

hrs
hrs
hr
TWA

= .001 x 3 (106) = 375 ppm

8

(trifluorobromomethane)

TWA

= .0005(8) (106) = 500 ppm

8

(propane)

TWA = 1/10-6 x 1/4 (106) = .03125 ppm

8

(phosgene)

Em = Ci =
LI

375 +
1000

500 + .03125
1000
.1

= .375 + .5 + .3125
Em = 1.1875
Since Em > 1, the mixture exceeds the OSHA PEL (and the AL, too).
(b)

The given exposure levels of the trifluorobromomethane and

propane (without any phosgene exposure) already exceed
the AL (.375 + .5 = .875 > .5). To determine the allowable
exposure to phosgene to keep the total mixture below the PEL, we
subtract the other exposures from "1" to find the allowable time
of concentration permissible for phosgene:
1 - [.375 + .5] = .125 allowed for phosgene
Time of exposure x concentration < .125
8 hrs x PEL (phosgene)
Time x 1/106 < .125
8 x .1/106
Time < .125 x 8 hrs x .1
< .1 hr = 6 min

Therefore, to meet the OSHA PEL a total of 6 minutes exposure of

phosgene (at one part per million) is permissible given the other
contaminants. This represents a decrease in exposure of 9 minutes (15
min. - 6 min. = 9 min.).
9.15.

Tube A provides greater precision. Note that Tube A measures a more

precise range (0.5 to 10 ppm) using the same number of pump strokes (5)
that for Tube B will measure a much broader range (5 to 100 ppm). Tube B
would be better for gross concentrations, but for a precise measurement
within its range Tube A is better.
The PEL for nitrogen dioxide can be found in Appendix A.1 to be 5 ppm.
Tube A provides better precision and has the capability of measuring
concentrations both below and above 5 ppm. Tube B would be better for
much higher concentrations.
The AL for nitrogen dioxide is 2.5 ppm (1/2 PEL). Tube A again would be
better for checking concentrations at close to the AL because it is more
precise and its sensing range encompasses 2.5 ppm. Tube B is barely able
to detect concentrations at 2.5 ppm because its lower detection limit is
2 ppm, using 10 pump strokes.

9.16.
Conc.
10

CO
Length C x L
2
20

Conc.
1

Iron Oxide
Manganese
Length C x L Conc. Length C x L
2
2
1
2

2
20

40

25

25

30
Total

9
21

1
Total

2
0
90
175

7
TWA CO = 175/8 = 21.875 ppm

3
Total

TWA CO2 = 1000 ppm

TWA Iron Oxide = 21/8 = 2.625 mg/m3
TWA Manganese = 7/8 = .875 mg/m3
Substance
CO
CO2
Iron Oxide
Manganese

PELs
50
5000
10
(C)5

from Appen A.1

ppm
ppm
mg/m3
mg/m3

Since the PEL for manganese is shown as a C (Ceiling) concentration, the

ceiling observed during the shift must be used in the Em equivalent
mixture calculation. Thus, for the manganese term in the summation, the
ratio is 1/5 for the ceiling concentration, not the TWA ratio of .875/5.
Em = Ci = TWA
Li
PEL
= 21.875
50

1000
5000

2.625
10

1
5

= .4375 + .2 + .2625 + .2
Em = 1.050
Since Em = 1.050 > 1, the mixture exceeds the PEL.
9.17.
9.18.

Most dangerous: asbestosis, silicosis

Others: siderosis, stannosis, byssinosis, aluminosis
Fibrosis is a more serious condition which includes the development of
scar tissue in the lungs.

9.19.

Simple asphyxiants: methane, nitrogen, carbon dioxide

Chemical asphyxiants: carbon monoxide, hydrogen cyanide

9.20.

(a) mutagens--substances that are harmful to chromosomes (species)

(b) carcinogens--substances that are know to cause or are suspected to
cause cancer
(c) teratogens--substances that are harmful to the fetus

9.21.

At home, ingestion, skin contact, then inhalation are the order of most
frequent occurrences of poisoning. At work, the order is reversed.

9.22.

Vapors are gases that come from substances that are normally in a liquid
or solid state. Fumes are solid particles which are too fine to be
considered as dust. Fumes are usually formed by the resolidification of
vapors from very hot processes such as welding.

9.23.

9.24.

(a)
(b)
(c)
(d)

zinc oxide fumes

tobacco smoke
diameter of human hair
bacteria

.01 to

0.3 micrometers
.01 to 0.4 micrometers
500 to 700 micrometers
.2 to 20 micrometers

(a) TLV--"threshold limit value": that level of concentration to which

the worker could be exposed during the entire workday without significant
harm.
(b) PEL--"permissible exposure level": prescribed by OSHA or other
enforcement agency. Many PELs are numerically the same as the
corresponding TLV.

(c) TWA--"time-weighted average": exposure level averaged over an 8 hour

time period.
(d) MAC--"maximum acceptable ceiling": PEL should never be
exceeded. TWA is not applicable when a MAC is set. Substances for which
a MAC applies are identified by "C" (ceiling) in the OSHA PEL tables.
(e) STEL--"short-term exposure limit": STEL states a maximum
concentration permitted for a specified duration.
(f) AL--"action level": usually set at 1/2 of the PEL.
9.25.

(1) Smell--convenient but unreliable.

(2) Examining technical literature to determine what industries might
release what substances--good way to find some agents to check for.
(3) Analyzing the processes in the plant to determine potential leaks to
the atmosphere; this can be very effective if it is done thoroughly; a
chemical engineer may need to be consulted.

9.26.

(1) Direct-reading instruments

(2) Sampling and subsequent laboratory analysis
(3) Dosimeters

9.27.

Methanol is a synonym for methyl alcohol.

Nitric
Period
Methanol
Oxide
Time
Ti
Ci
CiTi
Ci
8:00-10:00
10:00-11:00
11:00- 1:00
1:00- 4:00
Total
TWA
PEL

2
1
2
3
8

hrs
hr
hrs
hrs
hrs

50
150
100
200

1050/8 = 131.25
200

100
150
200
600
1050

Sulfur
Total
Dioxide (Mixture)
CiTi
Ci
CiTi
5
10
5
10

60/8 = 7.5
25

Ratio TWA/PEL 131.25/200 = .65625

7.5/25 = .3
.75/5 = .15
1.10625

10
10
10
30
60

0
1
1
1

1
2
3
6
6/8 = .75
5

> 1.0; mixture exceeds the

PEL.
(Also exceeds the AL, of course)
9.28.

PEL for ethanol (ethyl alcohol) = 1000 ppm

Since the PEL for ethanol (1000 ppm) is 5 times the PEL for methanol
(200 ppm), and the new concentration (of ethyl alcohol) would be only
double the old concentration (of methyl alcohol), the process change
would help to reduce the health hazard. The new concentration would have
a smaller ratio to its PEL and would thus improve matters. The advantage
of this improvement could be shown numerically by recalculating the total
equivalent mixture ratio sum. (The result is a reduction from 1.10625 to
0.7125, which is less than 1 and thus within the PEL for mixtures.)

9.29.

OSHA recognizes both solvents as hazards. Chlorobenzene is listed in

Table A.1 as having a PEL (TWA) of 75 ppm. Benzene is much worse, being
recognized as a depressant on the central nervous system, an irritant, a
systemic poison, and a carcinogen (in its role as a cause of
leukemia). In addition, benzene is a dangerous fire and explosion
hazard. So hazardous is benzene that OSHA has issued a separate standard
for it (29 CFR 1910.1029) as a part of the "standards completion
project." In addition it is listed in Table A.2 as having a PEL (TWA) of
10 ppm. If there are only two choices, and other factors are equal,
chlorobenzene should be selected.

9.30.

Volume of room = 600 ft2 x 8 ft = 4800 ft3

5 ft3
Concentration (initial) = ------- = .001042 = 1042 ppm
4800 ft3
Assuming a steady dilution due to the open window, the average
concentration for the 8-hour all-night period is:
1042 + 500
1542
--------------- = ------ = 771 ppm
2
2
PEL for ethyl alcohol = 1000 ppm
Since 771 ppm < 1000 ppm. PEL is not exceeded.

9.31.

(The AL is exceeded.)

With the hot oven adding an additional 25 ft3 of alcohol vapor to the
room, the total would be 5 ft3 + 25 ft3 = 30 ft3. Under these new
conditions, six times as much vapor has been introduced into the
apartment's air. If it is assumed that the initial and average
concentrations are also six times as great as in Exercise 9.30, then:
Concentration initial = 6 x 1042 ppm = 6252 ppm
Average concentration 6 x 771 ppm = 4626 ppm
Since 4626 ppm > 1000 ppm, PEL is exceeded.

9.32.

Range
Tube 5H
Percent
PPM

Lower
.05%
500

Tube 5M
Upper
8.0%
80000

Lower
.002%
20

Upper
.36%
3600

Tube 5M is more sensitive.

9.33.

Ceiling (MAC) concentration for hydrogen sulfide (H2S) is 20 ppm (from

Appendix A.2 of the text).
Four tubes in the table encompass the 20 ppm MAC. They are 4H, 4M, 4L,
and 4LL. Tube 4LL covers the narrowest range (.25 ppm - 60 ppm).

9.34.

From Table A.1 of the text, the PEL (TWA) for isopropyl acetate is 250
ppm. The AL = 1/2 PEL = 125 ppm
Detector tube range: 0.05% to 0.75%
converted to ppm:
Detector tube range: 500 ppm to 7500 ppm
The detector tube is of insufficient sensitivity to be useful as a
detector of concentrations near the PEL or AL.

9.35.

1 micrometer = 10-6 meters; 1 cm = 10-2 meters; 1 cm = 10-4 micrometers

Diameter in centimeters = 17 x 10-4 = 0.0017 cm
Diameter in inches = .0017cm/2.54 cm/in = .00067 in.
The particle would be classified as dust.

9.36.

Contaminant

Conc

PEL

AL

Isopropyl ether
Ethyl benzene
Chlorobenzene

200
40
25

500
100
75

250
50
37.5

Chlorobromomethane

50

200

100

Taken separately none of the contaminants exceed either their respective

PEL's or AL's. When considered together, however, the following formula
is used for mixtures:
Em = (200/500) + (40/100) + (25/75) + (50/200)
= .4 + .4 + .33 + .25 = 1.38
Since 1.38 > 1 and 1.38 > 0.5, the concentrations exceed both the PEL
and the AL, respectively.
9.37.

On the surface it appears that the new solvent will help matters by
reducing the solvent vapor release by 20%. However, 20% is only a modest
improvement, and a more knowledgeable assessment would include a
comparison of the PELs for the two solvents under consideration. The old
solvent, Stoddard solvent, is listed in the OSHA list for air contaminant
PELs as a TWA of 500 ppm (see Appendix A.1). The new solvent,
perchloroethylene is listed in Appendix A.1 with a reference to Appendix
A.2. Earlier editions of the Appendix have recognized "perchloroehtylene"
and "tetrachloroethylene" as synonyms. Tetrachloroethylene is found in
Appendix A.2 to have a TWA PEL of 100 ppm and a MAC of 200
ppm. Therefore perchloroethylene is much more tightly controlled as a
more hazardous substance than Stoddard solvent. The advantage of the
modest reduction in solvent vapors is more than offset by the fact that
the new solvent is much more dangerous, five times as dangerous as
indicated by the ratio of PELs. It would be more difficult to control
the new solvent to levels within the PEL and AL. The consultant should
point this out to the process engineer and caution against making the
process change.

9.38.

Morning
Exposure

Ci/Li

Substance
TWA

hrs)
ppm

.15

mg/m3

.125

ppm
ppm
ppm

.25

mg/m3
mg/m3

(4 hrs)

Li
OSHA

(4

PEL*
.5 ppm

1 ppm

Sodium hydroxide

.2 mg/m3

.3 mg/m3

Ammonium sulfide
none
0
Calcium bisulfide
none
0
Carbon disulfide

3 ppm

4 ppm

3.5

5 ppm

8 ppm

6.5

4 ppm

6 ppm

Sodium sulfide
none
0
Sodium sulfite
none
0

.7 mg/m3

.8 mg/m3

.75

.5 mg/m3

.5 mg/m3

.5

Total Em =

i=1

9.39.

Ci
----- = .525
Li
Morning
Exposure

Substance
TWA

hrs)

Ci
8-hr

Acetic anhydride

.525

Ci/Li

Afternoon
Exposure

(4 hrs)

.75 ppm

.25 mg/m3

5 ppm

20

< 1 so PEL is not exceeded.

> .5 so AL is exceeded.
Afternoon
Exposure

Ci
8-hr

Li

OSHA

(4

PEL*

Mixture from Ex.

9.38

.525
Formaldehyde

ppm

.333*

1 ppm

1 ppm

1 ppm

.858
*Appendix A.2

Total Em =

i=1

Ci
----- = .858
Li

The addition of 1 ppm formaldehyde to the other contaminants pushes up

the Em dangerously close to unity, at which point the PEL would be
exceeded. An error of only 1 ppm in the expected concentration would
push the Em over 1.0. Recommendations to the design engineers should
include cautions against the use of formaldehyde unless releases to the
atmosphere are closely controlled. Formaldehyde is so hazardous that
OSHA has promulgated a separate standard (29 CFR 1910.1048) for its
control under the "standards completion project." The tight PEL limits
and other contaminants already present in the plant atmosphere warrant
serious consideration and "back to the drawing board" process changes.
RESEARCH EXERCISES
9.40.

The accident occurred on January 30, 1995. The Arkhangelsk Pulp and
Paper Combine of Novodvinsk, Russia emitted up to 16 tons of mercury
compounds into the Svernaya Dvina River. The emission of toxic mercury
compounds into the river were, and still are, a health threat to the
people of the area, and are a threat to the ecological health of the
river itself. The contamination of the Svernaya Dvina River at this point
was as high as 740 and 640 critical contamination concentrations (cac),
on each side of the river. In laymens terms, this represents a
contamination 20 times greater than the acceptable level for the Svernaya
Dvina River at this geographical point. There is danger that the
accidental release and the continued release of mercury compounds into
the river will result in the death of the river. The Svernaya Dvina
River empties into the White Sea and ultimately into the Arctic
Ocean. While the much larger body of water represented by the Arctic
Ocean will disperse the concentration rather quickly, the Arctic Ocean,
because of the low water temperatures is a much more fragile environment
than the waters of more temperate oceans. The Arctic Region is much more
sensitive to this type of pollution due to the lack of microscopic
organisms that help to neutralize this type of contamination in more
temperate regions. Source:
Internet
http://gurukul.ucc.american.edu/TED.MERCURY.HTM

9.41.

(a) 1910.1052
(b) April 10, 1997
(c) The rate of implementation of the start-up phase depends upon the
size of the company and upon the section of the standard, as follows:
COMPANY SIZE: <20 employees 20<employees<99

>99 employees

Initial monitoring

300 days

210 days

Engineering controls

3 years

2 years

120

days
1

year
All other requirements
days

1 year

270 days

180

The longest implementation phase in the above table is 3

years. Therefore the date of the end of the implementation phase is
April 10, 2000.
(d) 25 ppm
(e) 125 ppm over a period of 15 minutes
(f) 30 years
9.42.

By searching the OSHA website for the keyword "methylene chloride" the
Internet surfer can be directed to the preamble to the standard that
appeared in the Federal Register when the methylene chloride standard was
promulgated (January 10, 1997). The summary to the preamble claimed that
the standard would result in a savings of 31 cancer deaths per year plus
3 deaths per year from central nervous system disorders and
carboxyhemoglobinemic effects (carbon monoxide poisoning complications).
The cost of compliance was estimated to be $101 million/year. Searching
the archived News Releases on the OSHA website, OSHA News Release 97-06,
dated January 9, 1997, can be found. In this release, then OSHA Director
Joseph Dear stated that a total of 34 lives per year would be saved, 31
from long-term effects and 3 from short-term effects. The news release
also reported an estimated 237,500 workers are exposed to methylene
chloride.

9.43.

On the OSHA website, going to the archived news releases, search for the
term "butadiene." This will display OSHA News Release 96-147, dated
October 24, 1996. According to the News Release, the PEL was reduced from
1,000 ppm to 1 ppm. (This represents a thousand-fold reduction.) The
estimated cost of compliance with the standard was $2.9 million per year.
The more stringent standard is expected to prevent at least 79 cancer
deaths over a 45-year working lifetime.

9.44.

The top on the list of frequently cited standards among the standards
completion project substances was Lead, which accounted for
approximately one-third of all citations for standards completion
project substances. Following is a listing of the top three, with
frequency of citation for each:
29CFR1910.1025 Lead: 1137 citations
29CFR1910.1052 Methylene Chloride: 769 citations
29CFR1910.1048 Formaldehyde: 308 citations
Source: NCM database

9.45.

From the OSHA website it can be determined that the general OSHA
standard for air contaminants is 29CFR1910.1000. The specific provisions
that require air contaminants to be held within their respective PELs are
presented with their respective enforcement statistics, as determined
from the NCM database:

Standard Provision

Coverage

1000(a)
1000(b)
1000(c)
All of the above

Table Z.1
Table Z.2
Table Z.3

Citation
Frequency
150
21
97
268

Total
$ Penalty
$168,000
$79,425
$145,950
$393,375

Average
$ Penalty
$1,123
$3,782
$1,505
$1,468
Source NCM database

9.46.

From the OSHA website, the appropriate standard is OSHA standard

29CFR1910.1000(d)(2)(i). The formula is the same as shown in the text.