Health Hazar

Evaluation 

Report 

d HETA 83-376-1556

PORTSMOUTH -NAVAL SHIPYARD 

PORTSt10lJTHJ NEW HMPSHIRE
PREFACE 


The Hazard Evaluations and Technical Assistance Branch of ~JOSH conducts fi eld 

investigations of possible health haza~ds in the workplace. T~ese 

investigations are conducted under the authority of Section 20(a)(€) of t he 

Occupational Safety and Health Act of 1~7C, 2~ U.S.C. 6~(a ) (6) which 

authorizes the Secretary of Hea· h and Human Services, following a written 

request from any employer or authorized representative of employees, to 

determine whether any substance normally found in the place.of employment ha s 

potentially toxic effects in such concentrations as used or found. 

The Hazard Evaluations and Technical Assistance Branch also provides, upon 

request, medical, nursing, and industrial hygiene technical and consultative 

assistance {TA) to Federal, state, and local agencie~; labor; industry and 

other groups or individuals to control occupational health hazards and to 

prevent related trauma and disease. 

I 


Mention of company na~es or products does not constitute endorsement by the 

National Institute for Occupational Safety and Health. 
HETA 83-376-1556 NIOSH INVESTIGATORS: 

April 1985 

PORTSMOUTH NAVAL SHIPYARD 

Dawn Gilles Tharr 

Mitchell Sirigal 

PORTSMOUTH, NEW HAMPSHIRE 

I. SUMMARY 

In August 1983, the National Institute for Occupational Safety and Health 

(N IOSH) received a request to evaluate occupational exposures during the 

system testing conducted as part of a submarine overhaul at Portsmouth Naval 

Shipyard, Portsmouth, New Hampshire. Employees reported experiencing 

headache, nausea, and eye, skin and mucous membrane irritation during this 

operation and believed these symptoms were due to exposures to substances 

released as a result of the heat produced by the operation. 

In No vember and December 1983, NIOSH performed laboratory tests on numerous 

materials used during the submarine overhaul to identify possible substances 

released from the heating of the se materials. As a result of these tests 

and information on the composition of the ireterials used, the following 

substances were chosen to be evaluated both prior to and during an actual 

system testing: acrolein, aldehydes, organics, acids and phthalates. 

Area ai r samp les for acrolein , alde hydes, acids and organic vapors were 

collected on December 14, 1983 in the affected conpartment of the submarine 

USS Jack (SSN 605). These samples were collected to determine background 

concentrations of en vironmental contaminants prior to system testing. On 

December 30 , 1983, approximately 8 hours after the maximum test temperature 

was reached and with ventilation to the affected areas isolated to maximize 

the concentration of vapors, samples were again collected. 

Onl y low concentrations of three organic solvents were measured during 

background sampling. tl umerous other compounds were detected during system testing. Acrolein level s ranged from 0.057 ppm to 0.085 ppm. Five 

different aldehydes were identified; acetaldehyde (range 1.1 ppm to 1.2 

ppm), formaldehyde (range 0.21 ppm - .23 ppm), proprionaldehyde (0 .07 ppm), 

butyraldehyde {0 .07 ppm - 0.08 ppm) and valeraldehyde {0.04 ppm). Organic 

materials included butanol (0.24 ppm - 0.33 ppm), benzene (0.24 ppm - 0.29 

ppm), toluene {0 .09 ppm - 0.11 ppm), xylene (0.39 ppm - 0.44 ppm) and 

naphtha (12 mg/M3 - 148 mg/M3). Low levels of acetic acid (0.02 ppm ­

0.11 ppm) and formic acid {0.02 ppm) were also measured. 

Of nine workers involved in previous system tests, eight reported eye 

irritation. Five workers also reported throat irritation and four of them 

nasal irritation . Only two workers reported cough, hut five reported other 

chest symptoms. Five reported headache and three nausea. All ei ght 

symptomatic workers sa i r that irritative symptoms began within half an hour 

of entering the affected shipboard areas. 

The NIOSH investigation concludes that the health effects experienced by 

workers during submarine system testing were a result of the combined 

effects of exposures to acrolein and other aldehydes. Considering the 

relatively low concentration of these substances measured and the episodic 

exposures during system tests, the risk of chronic health effects from these 

exposures is bel ieved slight. 

However, due to irritative effects and the potential for chronic effects at 

higher levels, steps should be taken to reduce expo sures. Recommendations 

are presented in Section VII. 

KEYWORDS: SIC 3731 (ship building and repairing), acrolein, aldehydes, 

.&--r•., i~"h" rio hon 7o n o ovo irrit;:itinn 
Page 2 - Health Hazard Evaluation Report No. 83-376 

II. INTRODUCTION 

In August 1983, NIOSH received a request for a health hazard evaluation 

at the Portsmouth, Naval Shipyard, Portsmouth, New Hampshire. The 

Portsmouth Federal Employees Metal Trades Council (AFL-CIO) requested 

that NIOSH evaluate workers' exposures during system testing performed 

during overhaul. Concern was expressed about the possible substances 

released into the working environment by the heat produced during the 

testing as workers reported experiencing a variety of symptoms 

including headache, nausea and eye, skin and mucous membrane irritation. 

On December 14, 1983 an initial environmental and medical survey was 

conducted to collect background data. NIOSH investigators returned on 

December 30, 1983 to conduct environmental sampling and collect medical 

information during the initial phases of system testing. 

Findings of these evaluations were reported in the letter of March 9, 1984 to the requestors and the Navy. 

111. BACKGROUND 

The Portsmouth Naval Shipyard was established in 1800 for designing, 

constructing and repairing ships. The Portsmouth Naval Shipyard was 

officially designated a submarine yard in 1923 and at present is 

exclusively dedicated to overhauling, repairing and refueling nuclear 

powered submarines. 

The operation evaluated in this study is the testing of shipboard 

systems performed near the end of a submarine overhaul. During the 

tgst period the shipboard systems are heated and are exercised to 

demonstrate proper operation. The heat was believed by workers to 

cause the release of irritant vapors from paints, adhesives, insulati on 

materials and other products installed during the earlier phases of the 

overhaul. These 11 unknown 11 substances were reportedly causing symptoms 

among workers present during this operation. The request for 

evaluation asked specifically for the identification of the substances 

causing these health effects and for an evaluation of the potential for 

chronic health problems. 

IV. EVALUATION DESIGN AND METHODS 

A. Environmental 

1. Laboratory Evaluation 

In November and December, 1983, NIOSH performed laboratory 

tests on twelve bulk materials of construction used during the 

submarine overhaul to determine possible substances released as 

a result of exposure to heat. The samples were handled in the 

following manner: 
Page 3 - Health Hazard Evaluation Report No. 83-376 

a. 	 Experimental-Sampling 

Small amounts (less than 1 ml) of each of the bulks were 

coated on the inside of disposable glass pipettes, and 

allowed to air dry 2-4 days prior to any analyses. A tube 

furnace equipped with quartz tubing was set up to heat the 

samples . Nitrogen was used as the purge gas for the 

system. Although sampling conditions such as temperatures and times varied somewhat, the general procedure used for 

heating the materials and collecting samples was as follows: 

1) 	 With the oven temperature cool (20-4o·c), a sample 

coated pipette from one of the bulks was placed in the 

oven tubing. A charcoal tube followed by a porous polymer tube in series was placed at the outlet of the 

oven tubing to collect the effluent. The oven 

temperature was turned up and the heated paint sampled for 30-45 minutes. Nitrogen purge flow was about 

150-250 cc/min. The final temperature of the oven at 

this time was 140-160°C. 

2) 	 The sampling tubes described above were removed and 

replaced with a new series of sorbent tubes - a 

benzylethanol amine (BEA) coated Chromosorb 102 tube 

used to sample for formaldehyde, another charcoal tube, 

and a hydrogen chloride (HCl) detector tube. The oven 

temperature was again increased and another 30-45 

minute sample collected. Final oven temperatures after 

this set ranged from 260-280°C. 

b. 	 Analyses 

All 	 charcoal tube samples were desorbed with carbon 

disulfide and screened by gas chromatography (FID) using 30 

meter DB-1 bonded phase fused silica capillary columns 

(splitless mode). Selective samples were further analyzed by GC/MS to identify components. Both the front and 

back-up sections of the charcoal tubes were desorbed 

together for these analyses. 

All 	 the BEA coated tubes for formaldehyde were desorbed 

with isooctane and screened by gas chromatography (method

P&CA 354) for formaldehyde. A 25 meter fused silica 

carbowax 20M capillary column was used. These samples were 

also screened on the 30M DB-1 column and selective ones 

reanalyzed by GC/MS. 
Page 4 - Health Hazard Evaluation Report ~o. 83-376 

Portions of the bulks were extracted directly (no heating 

or drying first) with carbon disulfide and screened by GC. 

A couple of these CS2 extracts were further analyzed by

GC/MS. 

2. Initial Survey 

Environmental air samples for acrolein, aldehydes, acids and 

organic vapors were collected on December 14, 1983 in the two 

affected areas aboard the submarine USS Jack (SSN 605). These 

samples were collected to determine background concentrations 

of environmental contaminants prior to system testing. Sampling and analytical methods are presented in Table 1. 

3. Follow-up Survey 

On December 30, 1983, approximately 8 hours after the maximum 

temperature was reached, environmental air samples were again collected for acrolein, aldehydes, acids and organic vapors in 

both of the affected areas. Sampling for phthalates was also 

conducted. Sampling duration was approximately 7 1/2 hours. 

Samples, for several of the substances being evaluated, were 

collected by two or more methods to eliminate data loss due to 

possible presence of interfering compounds (Methods - Table 1). 

4. Medical 

The NIOSH medical officer interviewed (a) the four workers 

identified by the requester as having had symptoms during 

system testing, and (b) workers identified on ship access logs 

as working in or near affected areas during the first 48 hours 

in September 1982 aboard the USS James K. Polk (SSBN 645) or in 

May 1983 aboard the USS Billfish (SSN 676). He also reviewed 

the medical records of those interviewed workers who sought medical attention for their symptoms. (All interviews were 

private, except in the case of one worker who, despite his 

union steward's efforts to encourage him to have the interview 

privately, insisted that the steward be present.) 

In addition to the four requester-identified workers, five of 

the seven NIOSH-selected workers were interviewed. (One of the 

remaining two was on vacation, and the other no longer worked 

at the shipyard). 
Page 5 - Health Hazard Evaluation Report No. 83-376 

V. EVALUATION CRITERIA 

A. Environmental Criteria 

As a guide to the evaluation of the hazards posed by workplace 

exposures, NIOSH field staff employ environmental evaluation 

criteria for assessment of a number of chemical and physical 

agents. These criteria are intended to suggest levels of exposure 

to which most workers may be exposed up to 10 hours per day, 40 

hours per week for a working lifetime without experiencing adverse 

health effects. It is, however, important to note that not all 

workers will be protected from adverse health effects if their 

exposures are maintained below these levels. A small percentage 

may experience adverse health effects because of individual 

susceptibility, a pre-existing medical condition, and/or a 

hypersensitivity (allergy). 

In addition, some hazardous substances may act in combination with 

other workplace exposures, the general environment, or with 

medications or personal habits of the worker to produce health 

effects even if the occupational exposures are controlled at the 

level set by the evaluation criterion. These combined effects are 

often not considered in the evaluation criteria. Also, some 

substances are absorbed by direct contact with the skin and mucous 

membranes, and thus potentially increase the overall exposure. Finally, evaluation criteria may change over the years as new 

information on the toxic effects of an agent become available. 

The primary sources of environmental evaluation criteria for the 

workplace are: 1) NIOSH Criteria Documents and recorrmendations, 2) 

the American Conference of Governmental Industrial Hygienists'

(ACGIH) Threshold Limit Values (TLV's), and 3) the U.S. Department 

of Labor (OSHA) occupational health standards. Often, the NIOSH 

recommendations and ACGIH TLV's are lower than the corresponding 

OSHA standards. Both NIOSH recommendations and ACGIH TLV's usually 

are based on more recent information than are the OSHA standards. 

The OSHA standards also may be required to take into account the 

feasibility of controlling exposures in various industries where 

the agents are used; the NIOSH-recommended standards, by contrast, 

are based primarily on concerns relating to the prevention of 

occupational disease. In evaluating the exposure levels and the 

recommendations for reducing these levels found in this report, it 

should be noted that industry is legally required to meet only 

those levels specified by an OSHA standard. 
Page 6 - Health Hazard Evaluation Report No. 83-376 

A time-weighted average (T\~A) exposure refers to the average 

airborne concentration of a substance during a normal 8- to 10-hour 

workday. Some substances have recommended short-term exposure 

limits or ceiling values which are intended to supplement the TWA 

where there are recognized toxic effects from high short-term 

exposures. 

Acrolein 

Acrolein produces intense irritation to the eyes and mucous membrance 

of the respiratory tract. Because of acrolein's pungent, offensive 

odor and the intense irritation of the conjunctiva and upper 

respiratory tract, severe toxic effects from acute exposure are rare as 

workers will not tolerate the vapor even in minimal concentration. 

Acute exposure to acrolein may cause bronchial 

in bronchitis or pulmonary edema. The Federal 

exposure to acrolein is 0.1 ppm. 

inflammation, resulting 

OSHA standard for 

A1dehydes 

The effects of acute exposure to aldehydes are primarily mucous 

membrane irritation (burning, tearing eyes, nose and throat 

irritation). These symptoms can occur with exposures as low as about 

0.1 ppm. 

At the present time there are no exposure criteria for either 

proprionaldehyde or butyraldehyde. The American Conference of 

Governmental Industrial Hygienists (ACGIH) Threshold Limit Value (TLV ) 

for acetaldehyde is 100 ppm and for valeraldehyde 50 ppm. The current 

OSHA standard for formaldehyde is 3 ppm as an 8-hr TWA. However, a 

study conducted by the Chemical Industry Institute of Toxicology

(CIIT), in which mice and rats exposed to formaldehyde vapors developed 

nasal cancer, has raised concerns about its carcinogenic potential in 

humans. On the basis of the CIIT study findings, ACGIH and NIOSH 

currently recommend that formaldehyde be treated as a potential human 

carcinogen. NIOSH recommends that exposures be reduced to the lowest 

feasible level. 

Benzene 

Acute exposure to benzene can cause central nervous system depression 

resulting in such symptoms as headache, vertigo (dizziness), 

lightheadedness, drowsiness, confusion and incoordination. Chronic 

exposure to benzene can cause decreased production of red blood cells, 

white blood cells and platelets, resulting in pallor and shortness of 

breath, impaired ability to fight infections and bleeding problems. 

Benzene can also cause leukemia. In order to reduce the risk of 

leukemia, NIOSH recommended in 1977 that exposure to benzene not exceed 
Page 7 - Hea lth Hazard Evalua tion Report No . 83- 376 

1 ppm. Th is criterion, initially a 2-hour TWA, then l ater a 1-hour TW A 

as analytical sensitivity improved, was chosen because it represented 

the limit of analytical reliability. As with other carcinogens, NIOSH 

recommends that employee exposure to benzene be reduced to the lowest 

feasible level. 

VI. RESULTS 

A. En vironmental 

1. Bul k Sample Testing 

Volatil e materials identified in the bulk materials tested 

included mineral spirit-type naphthas (composed main ly of 

C9-C12 aliphatics and some alkyl substitued benzenes),

toluene, xylene, cellosolves, butyl cellosolve, butanol, methyl ethyl ke tone, alkyl substituted dioxan and methyl pentanediol. 

Although the BEA coated Chromosorb 102 tubes have been 

evaluated only for formaldehyde, they were used i n this study 

as indicators of other aldehydes present based on the reaction 

products observed by GC/MS. Formaldehyde was detected in ten 

of the twelve heated bulk material samples. In addition to 

formaldehyde, various other aldehydes were also indicated in 

the samples, some in fairly large amounts. The largest single

aldehyde present in most of the samples was suspected to be 

acetaldehyde based on the m/e 176 ion detected by GC/MS. The 

aldehydes possibly present were propionaldehyde, butyra ldehyde, valeraldehyde and furfural. 

One of the paint sampl es also gave a positive indi ca tion on the 

HCl de tector tube (e ntire indicating layer changed to positive 

yellow color). Other materials identified on the sample bulk 

included butyl acetate, 2-chloroethylacetate and other 

acetate-type compounds such as acetol acetate, butenes, butanol 

and benzene. 

2. Survey Re sults 

As a result of the bulk material tests and general knowledge of 

the composition of the materials used, the following classes of 

compounds or substances were chosen to be evaluated both prior 

to and during system testing: acrolein, aldehydes, organics,

acids and phthalates. 
Page 8 - Health Hazard Evaluation Report No. 83-376 

Table II contains the environmental results from the air 

samples collected for background determination and those 

collected during system testing. A review of the data shows 

that only low concentrations of three organic solvents were 

measured during background sampling. The substances identified 

were toluene, xylene, and naphtha. These substances are all 

common solvents used in paints, adhesives, etc. and their 

presence under the above described construction condition would 

be predictable. 

A review of the data collected during system testing shows the 

presence of numerous other compounds not detected during the 

background monitoring. Acrolein levels ranged from 0.057 ppm 

to 0.085 ppm. Five different aldehydes were identified as 

being present in measurable concentrations: acetaldehyde (1.1 

ppm to 1.2 ppm), formaldehyde (0.21 ppm to 0.23 ppm), 

proprionaldehyde (0.07 ppm), butyraldehyde (0.07 ppm to 0.08 

ppm) and valeraldehyde (0.04 ppm). Organic materials present 

included butanol (0.24 ppm - 0.33 ppm), benzene (0.24 ppm ­ 0.29 ppm}, toluene (0.09 ppm - 0.11 ppm), xylene (0.39 ppm ­ 0.44 ppm), and naphtha (12 mg/m3 - 14.8 mg/m3). Low 

concentration of acetic acid (0.02-0.11 ppm) and formic acid 

(0.02 ppm) were measured. No hydrochloric acid or phthalates 

were found. 

3. Medical 

All but one of the interviewees reported eye irritation during 

system testing. Five workers also reported throat irritation, 

and four of them nasal irritation. Two persons reported facial 

skin irritation. Only two workers reported cough, but five 

(including the two with cough) reported other chest symptons 

(tightness, soreness, shortness of breath). Five persons 

reported headache, and two of them reported addition neurologic 

symptoms (lightheadedness, dizziness, confusion). Three 

workers reported nausea; none had vomiting. The 

requester-referred workers, as a group, were no more likely to 

report multiple, non-irritative symptoms than the 

NIOSH-selected interviewees. 

All eight symptomatic workers said that irritative symptoms 

began within half an hour of entering the affected areas; four 

of them said that the onset occurred within a few minutes. 

Four of the affected workers said that recovery from the 

irritative symptoms took only a few minutes. Two others said 

that recovery took an hour or two, and the remaining two said 

that it took until the next day. Respiratory symtpoms tended 

to last an hour or so after exposure ended. One worker claimed 

residual respiratory impairment. 
Page 9 - Health Hazard Evaluation Report No. 83-376 

Two workers sought medical attention for symptoms related to 

system testing; they were working on the USS James K. Polk, 

(SSBN 645) at the time. Their medical records indicated eye, 

nose, throat, and/or chest symptoms, and noted redness of the 

nose or throat on examination. 

All six symptomatic workers who recalled working during system testing both on the USS James K. Polk (SSBN 645) and on other 

submarines said that symptoms were more severe or occurred only 

on USS James K. Polk (SSBN 645). Three workers recalled 

symptoms recurring over at least several days; the others 

either could itot remember or were not assigned to system 

testing long enough to know. 

VII. DISCUSSION AND RECOMMENDATIONS 

The irritative symptoms reported from previous system testing 

operations are compatible with the effects of exposure to aldehydes and 

acrolein. NIOSH's environmental measurements cannot determine whether 

concentrations of air contaminants were higher earlier (as suggested by the Naval Research Laboratory data) or later in the testing, nor 

whether they were higher during previous system tests. The headaches 

and neurologic symptoms reported during previous system tests are 

compatible with the effects of exposure to aldehydes, and the 

respiratory symptoms and nausea are compatible with the effects of 

exposure to acrolein. While none of these effects, with the exception 

of mild irritation, would be expected at the concentrations measured by NIOSH, even when the substances are considered in combination, they 

suggest the possibility of exposure to higher concentrations during 

previous system tests. 

Except for acrolein, benzene, and formaldehyde, none of the substances 

measured by NIOSH are known to cause chronic health effects, even at 

concentrations much higher than NIOSH found. Benzene is a known human 

carcinogen, and formaldehyde is an animal carcinogen and therefore a 

suspect human carcinogen. Considering the relatively low 

concentrations of these compounds at the time of the NIOSH study, though, the health risk from the episodic exposures during system 

testing is believed slight. 

Acrolein can cause permanent pulmonary damage, but this ordinarily 

requires exposure to a concentration higher than that which usually 

causes intolerable eye irritation. Thus, the circumstances of such an 

exposure would generally involve an inability to remain in an area 

where the acrolein concentration has suddenly increased, as from a 

spill or leak, for example. These conditions apparently would not 

normally occur during system testing, but NIOSH has no way of 

determining whether individual cases of excessive exposure to acrolein 

occurred in the past. 
Page 10 - Health Hazard Evaluation Report No. 83-376 

NIOSH investigators believe that the health effects being experienced by workers during system testing are a result of the combined effects 

of exposures to acrolein and other aldehydes. Based on the laboratory 

testing of the construction materials. the majority of them release one 

or more of the aldehydes when heated, thus making elimination and 

substitution a difficult or impossible task. It is therefore 

recommended that during system testing, affected areas be properly 

ventilated to reduce acrolein, aldehyde and benzene levels or 

appropriate eye and respiratory personal protective equipment be 

provided to all individuals entering the affected areas . Additional 

monitoring for these substances should be performed to determine 

duration of release and also the effectiveness of the control measures 

used in reducing exposures. 

IX. AUTHORSHIP AND ACKNOWLEDGEMENTS 

Report Prepared by: 	 Dawn Gilles Tharr 


Industrial Hygienist
 Industrial Hygiene Section 


Mitchell Singal 

Medical Officer 

Medical Section 

Environmental Evaluation: 	 Kevin McManus 


Industrial Hygienist
 Region I 


Originating Office: Hazard Evaluations and Technical 

Assistance Branch 

Division of Surveillance, Hazard 

Evaluations, and Field Studies 

Report Typed By: 	 Sharon Jenkins 


Clerk Typist 


Industri a 1 Hygiene Section 


Lynette K. Jolliffe 

Secretary 

Industrial Hygiene Section 
Page 11 - Health Hazard Evaluation Report No. 83-376 

X. DISTRIBUTION AND AVAILABILITY OF REPORT 

Copies of this report are currently available upon request from NIOSH, 

Division of Standards Development and Technology Transfer, Publications 

Dissemination Section, 4676 Columbia Parkway, Cincinnati, Ohio 45226. 

After 90 days, the report will be available through the National 

Technical Information Service (NTIS), 5285 Port Royal, Springfield, 

Virginia 22161. Information regarding its availability through NTIS 

ca n be obtained from NIOSH Publications Office at the Cincinnati 

address. Copies of this report have been sent to: 

1. Department of the Navy, Portsmouth Naval Shipyard, Portsmouth, N.H. 

2. Portsmouth Federal Employee Metal Trades Council, Portsmouth, N.H. 

3. NIOSH, Region I 

4. OSHA, Region I 

5. Commander, Naval Sea Systems Command, Washington, D.C. 

For the purpose of informing affected employees, copies of this report sh~ll be posted by the employer in a prominent place accessible to the 

employees for a period of 30 calendar days. 
Table I 

Sampling and Analytical Methods 

Portsmouth Naval Shipyard 

Portsmouth. New Hampshire 

Sul>stance Sampling ~1edia Flow Rate Ana ly t1ca1 t1ethod Reference 

Acrolein 2-(hydroxymethyl)Piperidine 100 cc/min GC (FIO) N IOSll Method 2501 

coated XA0-2 tubes 

Aldehydes ~-benzylethanolamine 50 cc/min GC ( tlPO) PtCAH 354 

coated XAD-2 tub~s 

2.4-dini trophenylhydrozine 200 cc/min I C: Ana1. Chem (1900) g. l 110-)) 14 

coated silica gel tubes 

Organics f ha r coal tul>e JOO cc/min GC (FIO) P&f.AM 127 

Acids Si1i ca ge 1 tube 200 cc'min IC P&CAH 339 

Chrornosort' 103 tuhes 200 cc/nil n If. tlethod fleveloprnent 

Phthalates Teflon Filter J.5 liters/min GC (F IO) S-33 (Modified) 
DEPARTMENT OF HEALTH ANO HUMAN SERVICES 

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