Safety and Health at Work 9 (2018) 360e364

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Short Communication

Types and Health Hazards of Fibrous Materials Used as Asbestos

Substitutes
Seung-Hyun Park
Occupational Safety and Health Research Institute (OSHRI), Korea Occupational Safety and Health Agency (KOSHA), #400, Jongga-ro, Jung-gu, Ulsan, 44429,
Republic of Korea

a r t i c l e i n f o a b s t r a c t

Article history: Asbestos has been banned in many countries but many countries, including developing countries, are still
Received 5 August 2015 using asbestos or materials containing asbestos. Substitute materials have been studied and developed
Received in revised form over a long period of time because of the hazards of asbestos, and many people have recently shown
12 March 2018
interest in the hazards of substitute materials. However, comprehensive information about the types of
Accepted 4 May 2018
Available online 11 May 2018
asbestos substitutes, their use and health hazards, and references for the protection for the health of
workers is limited. The purpose of this study is to provide people in the related industries with infor-
mation on the types and health hazards of fibrous materials that can be used as asbestos substitutes.
Keywords:
Asbestos According to the patent resources from the United States and Europe, fibrous materials have been used to
Asbestos-free products develop asbestos-free products since before 1980. Recently, the health hazards of asbestos substitutes
Asbestos substitutes have been assessed and many additional researches are required. However, only some of the substitute
Fibrous materials materials have been assessed for health hazards, and health hazard data has not been sufficient in many
cases. Therefore, efforts should be made to minimize workers’ exposure to substitute materials that do
not contain asbestos.
Ó 2018 Occupational Safety and Health Research Institute, Published by Elsevier Korea LLC. This is an
open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

1. Introduction According to patent resources in the United States and Europe,

asbestos substitutes have constantly been developed since before
The World Health Organization (WHO) estimates that about 125 1980 [3e31]. An asbestos-free drywall joint compound was
million people are exposed to asbestos at worksites around the developed in 1975 [3], an asbestos-free tape sealant was developed
world, and more than 107,000 people die of asbestos-related dis- in 1979 [4], and an asbestos-free friction material was developed in
eases, including lung cancer, mesothelioma, or asbestosis, due to 1980 [5]. An asbestos-free gasket was developed in 1982 [7] and a
occupational exposure to asbestos [1]. Substitute materials have method of manufacturing an asbestos-free glass fiber reinforced
been studied and developed over a long period of time because of product was developed in 1983 [10]. Flexible sheet material suit-
the hazards of asbestos, and many people have recently shown able for use in the manufacture of asbestos-free gaskets was
interest in the hazards related to such substitute materials. developed in 1985 [15] and a method of manufacturing aramid-
Fibrous materials may be considered as an alternative to containing friction materials in 1986 [16]. In 1996, a fiber-rein-
asbestos. There are many kinds of fibrous materials, which can be forced building material was developed using sepiolite [26]; in
largely classified into synthetic fibers and natural fibers. Synthetic 2002, a press pad composed of an asbestos-free material was
fibers can be classified into organic and inorganic fibers; synthetic developed [29].
organic fibers include polyamide fiber, polyolefins fiber, polyester The International Social Security Association provides informa-
fiber, polyurethane fiber, and polyvinyl fiber, and synthetic inor- tion on asbestos substitute materials through a technical report
ganic fibers include glass filaments, glass wool, refractory ceramic [32]. The report classifies types of asbestos use into eight categories
fibers, rock wool, and slag wool fiber. Natural fibers include natural which are raw asbestos in bulk, asbestos in powder, asbestos in
organic fibers such as cotton and hemp and natural inorganic fibers liquid or pastes, asbestos in sheet or board, asbestos in woven or
such as attapulgite, erionite (zeolite), nemalite (fibrous brucite), braided goods, asbestos in a resin or plastic matric, asbestos in
sepiolite, and wollastonite [2]. cement, and asbestos in asphalt or bitumen. According to the report

E-mail address: parksh903@gmail.com (S.-H. Park).

2093-7911/$ e see front matter Ó 2018 Occupational Safety and Health Research Institute, Published by Elsevier Korea LLC. This is an open access article under the CC BY-NC-
ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
https://doi.org/10.1016/j.shaw.2018.05.001
 S.-H. Park / Asbestos Substitutes and Health Hazards 361

of the International Social Security Association, mineral wool and materials [33,34,39], and ACGIH’s resources on threshold limit
ceramic fibers can be used as an asbestos fiber substitute for values (TLVs) [41]. The participants in the WHO workshop evalu-
insulation or soundproofing, while sheets and boards containing ated the health hazards and carcinogenicity of asbestos substitutes
asbestos can be substituted with synthetic vitreous fibers or clay based on epidemiological evidence, studies in experimental ani-
instead of asbestos, and textile containing asbestos can use poly- mals, in vitro short-term tests, physicochemical properties, and
ethylene fiber, polypropylene fiber, polyamide fiber, carbon fiber, biopersistence. The workshop decided to group asbestos sub-
and glass fiber instead of asbestos. Asbestos cement products can stitutes roughly into hazard groupings of high, medium, and low.
use cellulose, polypropylene fiber, polyvinyl alcohol fiber, aramid, These hazard groups should be considered in relation to each
and glass fibers instead of asbestos. Cellulose, polypropylene fiber, other and did not have reference to formal criteria or definitions,
polyvinyl alcohol fiber, aramid, and glass fibers can be used as an as such. The IARC evaluated the carcinogenicity of some silicates
asbestos fiber substitute for asbestos cement products. and synthetic vitreous fibers based on studies of cancer in human,
In addition to the development of asbestos substitute materials, studies of cancer in experimental animals, physicochemical
a series of studies have also been conducted in regard to the haz- properties, persistence and biodegradability, other data relevant to
ards of fibrous materials. Erionite fiber, which is a mineral fiber, evaluation of carcinogenicity and its mechanism. ACGIH evaluated
causes malignant mesothelioma and has been classified into Group the carcinogenicity of synthetic vitreous fibers based on studies of
1 (carcinogenic to humans) by the International Agency for cancer in humans, studies of cancer in experimental animals,
Research on Cancer (IARC) [33]. Also, refractory ceramic fibers are physicochemical properties, and other data relevant to evaluation
classified into Group 2B (possibly carcinogenic to humans) by the of carcinogenicity.
IARC [34] and Group A2 (suspected human carcinogen) by the
American Conference of Governmental Industrial Hygienists 3. Results
(ACGIH) as it can cause lung fibrosis [35]. The WHO has assessed
the hazards of 14 types of asbestos substitute materials, including 3.1. Types and characteristics of fibrous materials
para-aramid, attapulgite, and carbon fiber [36]. Also, Harrison et al
[37] has discussed the health hazards of para-aramid, polyvinyl The asbestos substitute materials known so far include syn-
alcohol, and cellulose in comparison to chrysotile. According to this thetic fibers such as man-made vitreous fibers (synthetic vitreous
literature, the major characteristics related to the health hazards of fibers) and para-aramid and natural inorganic fibers such as
fiber are its dose, dimensions (especially diameter), and durability. attapulgite, sepiolite, and wollastonite. Man-made vitreous fibers
National Institute for Occupational Safety and Health has recently refer to inorganic fibrous materials made with glass, rocks, min-
presented a research roadmap for a broad understanding of the erals, slag, or processed inorganic oxides [34]. Para-aramid, which
health hazards of asbestos fiber and other elongate mineral parti- is a widely known asbestos substitute material, is a type of
cles [38]. This roadmap suggests that studies related to the toxic polyamide fiber similar to nylon fibers. This material is mostly
effect, occupational exposure, and development of methods of used to improve the strength, durability, and heat resistance of
measurement and analysis of asbestos fibers and elongate mineral synthetic materials. It is light enough to be used within the
particles are required. aviation and sports industries, and it is also used to reinforce fiber
This study discusses the types of fibrous materials that can be for synthetic materials, thermoplastic materials, tires, and rubber
used as asbestos substitute materials, the development of asbestos- products. It is used as an asbestos substitute material for auto-
free products, and the health hazards of fibrous materials to pro- motive friction materials and gaskets [39]. Natural inorganic fibers
vide information for the protection of health of workers in the such as attapulgite, sepiolite, and wollastonite have been used as a
related industries. substitute for asbestos in building materials and friction materials
[3,11,13,26,31].
2. Materials and methods Attapulgite is a hydrated magnesium aluminum silicate mineral
[40]. Attapulgite is elongated in structure and similar to the mineral
Literature on the types and characteristics of asbestos sub- structure of amphibole group. It is known as “palygorskite” in
stitutes, the development status of asbestos-free materials, and the mineralogy, but it is more widely known as “attapulgite” [39].
health hazards of asbestos substitutes was reviewed for this study. Attapulgite has been used as an asbestos substitute material for
To examine the types and characteristics of asbestos substitutes, building materials and friction materials as asbestos has been found
this study referenced literature on chemical and physical to be hazardous [3,13].
properties and morphology [2,3,11,13,26,31,33,34,39e41]. The re- Sepiolite is a clay mineral composed of hydrated magnesium
sources on the development of asbestos substitutes referred to the silicate. Structurally, it is similar to attapulgite, but it has one more
cases of asbestos substitutes that have been certified internation- SiO4 tetrahedron when compared to attapulgite. Sepiolite is an
ally based on patent resources from the United States and Europe. elongated and lath-like structure of crystals. The length of fibers
According to the United States Geological Survey report on the varies according to the location of sepiolite sediments [39]. The
worldwide asbestos supply and consumption, the United States elongated particles of sepiolite improve its usability as a viscosity
and Europe imported more than 80% of worldwide asbestos pro- improver and sedimentation preventer.
duction during 1920w1960 [42], which caused high levels of Wollastonite is a calcium silicate mineral that is chemically
asbestos-related disease in the United States and Europe [43,44]. inert, but it can be decomposed in concentrated hydrochloric acid.
As a result of searches on the patent site (Google patents, https:// With its unique cleavage property, it breaks into thin lath-like
patents.google.com), there were many patents for asbestos sub- shapes or needle-like particles. Wollastonite is mostly used for
stitutes in the United States and Europe. The development status ceramic, plastic, rubber, asbestos substitute, paint, and coating
of building materials, friction materials, gaskets, joint sheets, and products, and wollastonite with a high aspect ratio (10: 1 to 20: 1) is
fabrics that are free of asbestos was identified by patent resources used to reinforce plastic and rubber and as a functional filler and an
[3e31]. Literature on the hazard assessment of asbestos sub- asbestos substitute material [39].
stitutes has referenced hazard assessment report of asbestos Erionite is a fibrous hydrated aluminosilicate mineral in the
substitutes prepared by the WHO through an workshop of expert zeolite group. Erionite is similar to amphibole in shape, but it has
group [36], IARC’s carcinogen assessment resources on fibrous different physicochemical structures. Erionite exists in the form of a
362 Saf Health Work 2018;9:360e364

bundle of fibers [33]. Natural erionite has not been mined or Other aramid fiber, polytetrafluoroethylene fiber, carbon fiber,
distributed for commercial purposes since the late 1980s and has and metallic alloy fiber have been used to develop asbestos-free
been substituted with nonfibrous synthetic zeolite. sealing materials, diaphragms, electroconductive substrates, and
valve packing [19,22,23,27,28].
3.2. Development of asbestos-free materials
3.3. Health hazards of fibrous materials
Asbestos has been widely used for building materials, automo-
tive and industrial friction materials, gaskets and joint sheets, and The major factors of toxicity of fibers are in the fiber sizes, fiber
asbestos fabrics [45]. For building materials, 10e20% asbestos is durability, and fiber types [46]. In terms of the size of a fiber, fibers
mixed with cement, pulp, sand, plaster, etc. to make cement thinner than 3 mm can reach lower airways, while fibers longer
corrugated sheets, cement flat boards, cement gypsum boards, and than 5e10 mm can stay in the lungs longer than other shorter fi-
autoclaved cement extrusion panels. For automotive and industrial bers. Also, the length of fibers which macrophage can remove is
friction materials, 10e20% chrysotile is mixed with synthetic resin, about 16e17 mm. Considering the durability of fibers, a fiber
metal powder, etc. to make brake lining, brake pads, clutch lining, generally undergoes the process of fragmentation (latitudinal
clutch facing, and special brakes for railroads or cranes. In the case breakage) or splitting (longitudinal breakage) in the human body.
of gaskets and joint sheets, 30e40% chrysotile is mixed with syn- Both fragmentation and splitting can increase the number and
thetic resin, fiber, etc. For asbestos fabrics, asbestos is the main surface area of fibers, but shorter fibers resulting from fragmen-
component (90% or greater asbestos content) to make asbestos tation are easily removed by macrophage. In the case of splitting, it
yarns, asbestos ropes, asbestos tapes, asbestos packing, asbestos does not affect the removal by macrophage. When considering the
cloths, and asbestos gloves. types of fibers, it is known that amphibole asbestos stays in the
As the hazards of asbestos have been known since before 1980, lungs longer than the serpentine chrysotile.
products using asbestos substitute materials have been consistently Considering the health hazard of asbestos fibers by size, asbes-
developed. Table 1 lists the development of asbestos-free products tosis is most closely related to the size of fibers that are 2 mm or
using asbestos substitute materials based on the patent resources longer and 0.15 mm or thicker in diameter, while malignant meso-
from the United States and Europe. thelioma is most closely related to the number of fibers that are
With regard to building materials, attapulgite, cotton, mineral 5 mm or longer and 0.1 mm or thinner in diameter. In the case of lung
fiber, polyacrylamide, polypropylene, polyvinyl alcohol fiber, cancer, it is most closely related to the number of fibers that are
sepiolite, and slag wool have been used to develop asbestos-free 10 mm or longer and 0.15 mm or thicker in diameter [47].
building materials such as boards and sheets, drywall joints, The WHO assessed the hazards of 14 kinds of asbestos substitute
fiber reinforced products, inorganic sheets, and joint compounds materials, including para-aramid, through a workshop conducted
[3,6,10,11,18,21,26,31]. by experts in the field [36]. This workshop classified the hazards of
Friction material area is one of the areas that has actively asbestos substitute materials into three stepsdhigh, medium, and
developed substitutes as asbestos was widely used for automo- lowdand the major factors of hazards were health hazards related
tive brake lining, mechanical clutches, and brake pads for ma- to lung cancer, malignant mesothelioma, and asbestosis.
chine tools. In the realm of friction materials, aramid, aromatic Table 2 lists the results of hazard assessment of asbestos substi-
polyamide, attapulgite, carbon fiber, ceramic fiber, cotton, glass tute materials by the WHO and the classification of carcinogens by
fiber, mineral wools, and silica fiber have been used to develop IARC and ACGIH. According to the assessment results of the WHO, p-
asbestos-free friction materials such as brake lining and pads, aramid fibers have respirable fibers with similar dimensions as
brake shoes, clutch facing, clutch lining, clutch surfaces, and press carcinogenic fibers and had effects on the lungs in an animal testing.
pads [5,9,13,16,29,30]. As it also has biopersistence, its hazards were rated medium.
For gaskets and joint sheets, aramid fiber, aromatic polyamide Respirable attapulgite fiber is highly hazardous when it contains
fiber, cellulose fiber, ceramic fiber, nylon fiber, and vitreous fiber long fibers, but shorter fibers are less hazardous. In the respiratory
have been used to develop asbestos-free gaskets or joint sheets testing on animals, longer fibers caused tumors, whereas shorter
[7,12,14,15,24,25]. fibers did not. Carbon fibers were 5e15 mm in diameter and mostly
For fabrics, cotton fiber, glass fiber, ceramic fiber-containing nonrespirable in the industrial sites with low hazards, and cellulose
paper (strand), texturized fiber glass roving or yarn, and acrylic was also mostly nonrespirable and not hazardous. However, respi-
fiber have been used to develop asbestos-free fabrics such as tape rable cellulose fibers were found to be indeterminate due to insuf-
sealants, rope packing, yarns, and other fabrics [4,8,17,20]. ficient data.

Table 1
Examples of asbestos substitutes used in development of asbestos-free materials.

Type of materials Use Asbestos substitutes

Building materials Boards & sheets, drywall joint, fiber reinforced Attapulgite, cellulose pulp, cotton, mineral fiber, hydroxypropyl methyl
product, inorganic sheet, and joint compound cellulose, polyacrylamide, polypropylene, polyvinyl alcohol fiber, sepiolite,
silica fume pulp, and slag wool
Friction materials Brake lining & pad, brake shoe, clutch facing, Aramid, aromatic polyamide, attapulgite, carbon fiber, ceramic fiber,
clutch lining, clutch surface, and press pad cotton, glass fiber, metal fiber, mineral wools, silica fiber, steel wool,
wood pulp, and woven fabric (heat-resistant yarn)
Gasket & joint sheet Gasket and joint sheet Aramid fiber, aromatic polyamide fiber, cellulose fiber, ceramic fiber,
nylon fiber, phenolic fiber, and vitreous fiber
Fabrics Tape sealant, rope packing, yarn, and other fabrics Cotton fiber, glass fiber, ceramic fiber-containing paper (strand),
texturized fiber glass roving or yarn, and acrylic fiber
Others Sealing, damping, and separating Aramid fibers and polyaramide
Diaphragms (fibrous sheet) Polytetrafluoroethylene (PTFE) fiber and inorganic fiber,
Electroconductive substrate Carbon fiber (or graphite fiber), inert mineral fiber and PTFE fiber
Valve packing Carbon and metallic alloy fiber
 S.-H. Park / Asbestos Substitutes and Health Hazards 363

Table 2 Its chemical components are similar to those of wollastonite, but it

Health hazard and carcinogenicity of some fibrous materials. is more quickly removed from the lungs.
Materials Health hazard & carcinogenicity According to IARC’s classification of carcinogens, p-aramid
WHO IARC (ACGIH)
fibers are classified into Group 3 which is not classifiable because it
is carcinogenic to humans. Attapulgite has insufficient evidence of
p-Aramid fibers Medium Group 3
carcinogenicity in humans, but a study of samples containing
Attapulgite fibers
Long fibers, >5 mm High for long fibers Group 2B fibers that are 5 mm or longer showed occurrence of malignant
Short fibers, <5 mm Low for short fibers Group 3 tumors and mesothelioma in animal testing; however, no signifi-
Carbon fiber Low d cant increase in the occurrence of tumors was observed for fibers
Cellulose fibers Low for not respirable, that are shorter. IARC classifies attapulgite fibers that are 5 mm or
indeterminate for respirable longer into Group 2B (possibly carcinogenic to humans) and
Continuous filament Refer to synthetic Group 3 (A4) shorter fibers into Group 3 (not classifiable as to its carcinogenicity
glass fibers vitreous fibers
in humans) [39]. Also, erionite fibers that cause malignant meso-
Erionite fibers Group 1
thelioma and are carcinogenic to human are classified into Group 1
Glass wool fibers Refer to synthetic Group 3 (A3)
vitreous fibers
[33]. With respect to fire-resistant ceramic fibers, there is insuffi-
Graphite whiskers Indeterminate d
cient evidence of carcinogenicity in humans, but there is signifi-
Magnesium sulfate whiskers Low or indeterminate d cant evidence of lung cancer and malignant mesothelioma in the
Polyethylene fibers Indeterminate d long-term inhalation test of mouse. Therefore, fire-resistant
Polypropylene fibers Indeterminate d ceramic fibers are classified into Group 2B (possibly carcinogenic
Polyvinyl alcohol fibers Indeterminate d to humans) [34].
Polyvinyl chloride fibers Indeterminate d ACGIH classifies some synthetic vitreous fibers according to
Potassium octatitanate fibers High d their carcinogenicity and recommends the TLV. Fire-resistant
Refractory ceramic fibers Refer to synthetic Group 2B (A2) ceramic fibers are classified into the A2 group (suspected human
vitreous fibers carcinogen), and the recommended TLV is 0.2 f/cc. Also, glass wool
Rock wool fibers Refer to synthetic Group 3 (A3) fibers, rock wool fibers, and slag wool fibers are classified into the
vitreous fibers A3 group (confirmed animal carcinogen with unknown relevance
Sepiolite fibers d Group 3 to human), and the recommended TLV is 1 f/cc [35].
Slag wool fibers Refer to synthetic Group 3 (A3)
vitreous fibers
4. Discussion
Synthetic vitreous fibers High for biopersistent, d
low for nonbiopersistent
As the hazards of asbestos have been known to many people,
Wollastonite fibers Low Group 3
substitute materials have been studied and developed over a long
Xonotlite fibers Low d
period of time, and many people are also concerned about the
ACGIH, American Conference of Governmental Industrial Hygienists; IARC, Inter-
hazards of substitute materials. Some fibrous materials have been
national Agency for Research on Cancer; WHO, World Health Organization.
assessed for health hazards, but there are some materials that may
be carcinogenic to humans or may affect the health of humans.
IARC classifies erionite fibers into Group 1 (carcinogenic to
Graphite whiskers, in terms of dimensions, are highly respirable humans) and fire-resistant ceramic fibers and attapulgite fibers
with a long half-life in the lungs but findings were indeterminate that are 5 mm or longer into Group 2B (possibly carcinogenic to
due to insufficient data. Magnesium sulfate whiskers did not cause humans). Recently, the WHO assessed the hazards of 14 kinds of
tumors in limited studies and they are very quickly removed from asbestos substitute materials, including attapulgite and potassium
the lungs. Overall, the hazard was assessed as low or indetermi- octatitanate fibers. As a result of the assessment, attapulgite was
nate. Polyethylene, polyvinyl chloride, and polyvinyl alcohol fibers classified as highly hazardous as it can cause tumors when the fi-
were also found to be indeterminate due to insufficient data. In the bers are long. Potassium octatitanate fibers were also classified as
case of polypropylene fibers, they could be respirable in the pro- highly hazardous. They can be exposed as respirable fibers at in-
duction process and respirable polypropylene fibers showed high dustrial sites and cause mesothelioma when injected into intra-
biopersistence after intratracheal administration, but did not show peritoneal organs, and there is evidence of genetic toxicity and
fibrosis in the subchronic test. Overall, polypropylene fibers were biopersistence. In the case of synthetic vitreous fibers , bio-
found to be indeterminate due to insufficient data. In the case of persistence fibers were classified as highly hazardous, while non-
potassium octatitanate fibers, they were found to be highly haz- biopersistence fibers were classified as low hazard. para-Aramid
ardous. They are exposed as a respirable fiber at industrial sites, has a medium level of hazard as it is similar in the size of fibers
cause mesothelioma when injected into intraperitoneal organs, that are known to be carcinogenic and may be exposed as respi-
and show evidence of genetic toxicity and biopersistence. In rable fibers. Also, carbon fibers, wollastonite, xonotlite, and short
Table 2, synthetic vitreous fibers include continuous filament glass attapulgite fibers have low hazard. Polyethylene fibers, polyvinyl
fibers, glass wool fibers, refractory ceramic fibers, rock wool fibers, chloride fibers, polypropylene fibers, and graphite whiskers were
and slag wool fibers. The major factors that determine the hazards not assessed due to insufficient data. Assessment of these asbestos
of synthetic vitreous fibers are the dimensions, biopersistence, and substitute materials has been limited and further studies are
physicochemical properties of fiber. The hazards of synthetic vit- needed in the future. It is necessary to develop building materials
reous fibers vary from high to low; the materials with bio- and friction materials using substitute materials that can replace
persistence were found highly hazardous, while other materials the carcinogenic asbestos. However, fibrous materials include
were found less hazardous. Natural wollastonite contains respi- materials that may be carcinogenic and may affect health. Only
rable fibers but found to be less hazardous because workers are some substitute materials have been assessed for health hazards,
mostly exposed to short fibers occupationally, and it did not cause and there are materials that do not have sufficient assessment data.
tumors in chronic toxicity assessment. In the case of xonotlite, it For this reason, there are still many materials for which occupa-
did not cause tumors in an intraperitoneal implantation research. tional exposure limits have not been established yet. Therefore,
364 Saf Health Work 2018;9:360e364

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