Skin Cancer and UV Protection

Abstract

The incidence of skin cancer is increasing by epidemic proportions. Basal cell cancer remains the most common skin neoplasm, and simple excision is generally curative. On the other hand, aggressive local growth and metastasis are common features of malignant melanoma, which accounts for 75% of all deaths associated with skin cancer. The primary cause of skin cancer is long exposure to solar ultraviolet radiation (UV-R) crossed with the amount of skin pigmentation and family genetics. It is believed that in childhood and adolescence, 80% of UV-R gets absorbed while in the remaining, 20 % gets absorbed later in the lifetime. This suggests that proper and early photoprotection may reduce the risk of subsequent occurrence of skin cancer. Reducing the exposure time to sunlight, using sunscreens and protective textiles are the three ways of UV protection. Most people think that all the clothing will protect them, but it does not provide full sun screening properties. Literature sources claim that only 1/3 of the spring and summer collections tested give off proper UV protection. This is very important during the summer months, when UV index is the highest. Fabric UV protection ability highly depends on large number of factors such as type of fiber, fabric surface, construction, porosity, density, moisture content, type and concentration of dyestuff, fluorescent whitening agents, UV-B protective agents (UV absorbers), as well as nanoparticles, if applied. For all of these reasons, in the present paper, the results of UV protecting ability according to AS/NZS 4399:1996 will be discussed to show that standard clothing materials are not always adequate to prevent effect of UV-R to the human skin; and to suggest the possibilities for its improvement for this purpose enhancing light conversion and scattering. Additionally, the discrepancy in UV protection was investigated in distilled water as well as Adriatic Sea water.

Full text

SKIN CANCER AND UV PROTECTION
Anita Tarbuk1, Ana Marija Grancarić1, Mirna Šitum2
1 University of Zagreb Faculty of Textile Technology, Department for Textile Chemistry and Ecology, Prilaz baruna Filipovića 28a, HR-10000 Zagreb, Croatia,
2 University Hospital “Sestre milosrdnice”, Department of Dermatology and Venereology, Vinogradska cesta 29, HR-10000 Zagreb, Croatia
Corresponding author e-mail: anita.tarbuk@ttf.hr
1. Introduction
The incidence of skin cancer is increasing by epidemic
proportions. One person dies of melanoma skin cancer every
hour; between 2 and 3 million non-melanoma skin cancers
and 132,000 melanoma skin cancers occur globally each year
according to World Health Organization (WHO) [1]. Because
of highly visible location, it is more easily diagnosed and
treated than other types of cancer. Basal cell carcinoma (BCC)
and squamous cell carcinoma (SCC), referred to as non-
melanoma skin cancers (NMSC) [2]. These skin tumors are the
most common tumors in human population, but due to very
low mortality rate, until recently, there was no systematically
collected data in the National Cancer Registries. On the other
hand, most of the studies were focused on white populations in
Australia, the U.S.A. and Europe; while limited data is available
for other skin types as naturally brown and black people. The
incidence and mortality are usually expressed as a rate per
100,000 persons per year. Worldwide, the incidence for NMSC
varies widely; with the highest rates for BCC in Australia >
1000 and the lowest rates in parts of Africa < 1 person [2]. The
average incidence rates for BCC in the U.K. were 76.21, what
appears a greater rate when compared with the rest of Europe,
for example, Italy and Switzerland 70, Slovakia 38, Croatia only
33.6 for BCC [2, 3]. In USA, south west states like Arizona and
New Mexico reported 935.9, while northern states reported only
170 incidence rate for BCC. SCC have much lower rates, for
example, in Europe, for males in UK 22.65, in Switzerland 14.2,
the highest rate is reported in Sweden 34.4 and the lowest in
Croatia 8.9. In the USA, rate for SCC in southern states is 290,
and in northern less than 60. In Australia, rates are signicantly
higher, > 500 [2–4]. BCC remains the most common skin
neoplasm, and simple excision is generally curative. SCC
detected at an early stage and removed promptly are almost
always curable and cause minimal damage. However, in most
cases, SCC recurs, especially in the same skin area or nearby
within the rst 2 years after surgery. If left untreated, it can
penetrate the underlying tissues and even metastasize to local
lymph nodes, distant tissues, and organs and can become
fatal.
On the other hand, aggressive local growth and metastasis
are common features of malignant melanoma, which accounts
for 75% of all deaths associated with skin cancer [5–9]. The
reason for that is most likely that in most cases, melanoma was
diagnosed in an advanced stage. The world’s highest incidence
of melanoma is in Australia and New Zealand, more than twice
as high as in North America, or 5 times higher than Europe.
For instance, in Australia, in 2012, ASR was 62.7 for men and
39.9 for women with mortality of 8.9 for men and 3.5 for female
Abstract:
The incidence of skin cancer is increasing by epidemic proportions. Basal cell cancer remains the most common
skin neoplasm, and simple excision is generally curative. On the other hand, aggressive local growth and metastasis
are common features of malignant melanoma, which accounts for 75% of all deaths associated with skin cancer.
The primary cause of skin cancer is long exposure to solar ultraviolet radiation (UV-R) crossed with the amount
of skin pigmentation and family genetics. It is believed that in childhood and adolescence, 80% of UV-R gets
absorbed while in the remaining, 20 % gets absorbed later in the lifetime. This suggests that proper and early
photoprotection may reduce the risk of subsequent occurrence of skin cancer. Reducing the exposure time to
sunlight, using sunscreens and protective textiles are the three ways of UV protection. Most people think that all the
clothing will protect them, but it does not provide full sun screening properties. Literature sources claim that only 1/3
of the spring and summer collections tested give off proper UV protection. This is very important during the summer
months, when UV index is the highest. Fabric UV protection ability highly depends on large number of factors such
as type of ber, fabric surface, construction, porosity, density, moisture content, type and concentration of dyestuff,
uorescent whitening agents, UV-B protective agents (UV absorbers), as well as nanoparticles, if applied. For all
of these reasons, in the present paper, the results of UV protecting ability according to AS/NZS 4399:1996 will be
discussed to show that standard clothing materials are not always adequate to prevent effect of UV-R to the human
skin; and to suggest the possibilities for its improvement for this purpose enhancing light conversion and scattering.
Additionally, the discrepancy in UV protection was investigated in distilled water as well as Adriatic Sea water.
Keywords:
UV protection, skin cancer, cotton, textiles, uorescence, natural zeolite
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both Mediterranean and Eastern European populations [6].
On the other hand, European Union supported research of UV
protective textiles for the sunshade constructions, umbrella
covers, hats, knitted and woven fabrics in Eastern European
and Mediterranean countries of high UV index. The primary
cause of skin cancer is long exposure to solar UV-R crossed
with the amount of skin pigmentation and family genetics. UV
as a whole does not exceed 5% of the total energy emitted
by the sun, but their impact on the organic molecules is very
important and it induces signicant physiological responses in
all areas of life. It is known that, beside the UV-B radiation with
biochemical reactions, the UV-A can also initiate deleterious
biochemical reactions [5–11]. Dangerous UV-B (l = 280–320
nm) rays, can cause acute and chronic reactions and damages
such as erythema (sunburn), sun tanning, “photoaging,”
DNA and eye damage, photokeratitis and cataract, and
photocarcinogenesis; increase risk factor for melanoma, or
cause various skin cancers [3–33]. Experts estimate about
90% of melanomas are associated with severe UV exposure
and sunburns over a lifetime. Intermittent sun exposure,
especially in childhood and adolescence is considered to be
a stronger risk factor for melanoma than continuous exposure.
It is believed that in these periods of life, 80% of UV-R gets
absorbed, while in the remaining, 20% gets absorbed later in
the lifetime [7,10]. That is the main reason why the melanoma
is the most common form of cancer for young adults 25–29
years old and the second most common form of cancer for
young people 15–29 years old [34].
This suggests that proper and early photoprotection may reduce
the risk of subsequent occurrence of skin cancer. Reducing the
exposure time to sunlight, using sunscreens and protective
textiles are the three ways of UV protection. Designing and
engineering of UV protective fabrics, that are mostly clothing
and accessories made of textiles, for example, hats, shoes,
shade structures such as umbrellas, awnings, and baby carrier
covers, etc, can be accomplished by chemical approach. UV
clothing can show UV protection, but in most cases, it does
not provide full sun screening properties. Literature sources
claim that only 1/3 of the spring and summer collections tested
give off proper UV protection [13]. This is very important during
summer months when UV index is the highest. In contact with
textile fabric, UV radiation can be reected and/or scattered
from fabric surface, or get absorbed or transmitted [18]. Most
people think all clothing will protect them, but that is not the
case. For instance, jeans offer a very good level of protection,
as do garments made from other tightly woven, dark fabrics.
However, on a hot summer day, those are not the kinds of
clothing people usually reach for. More often, when they are
[4]. In 2008, Croatia had an intermediate melanoma incidence,
with the ASR of 8.7 for men and 7.0 for women. However, with
the ASR of 3.5 for men and 1.8 for women, Croatia had the
third highest male and fourth highest female mortality [5].
There are four basic types of melanoma (Figure 1). Supercial
spreading melanoma (SSM) is the most common type,
accounting 60–70% of all cases. This is the one most often
seen in young people. It can be found almost anywhere on the
body, but is most likely to occur on the trunk in men, the legs
in women, and the upper back in both. Nodular melanoma
(NM) is usually invasive at the time it is rst diagnosed. The
malignancy is recognized when it becomes a bump. The most
frequent locations are the trunk, legs, and arms, mainly of
elderly people, as well as the scalp in men. This is the most
aggressive of the melanomas, and is found in 15–30% of all
cases. Lentigo maligna melanoma (LMM) usually appears
in the elderly, arising on chronically sun-exposed, damaged
skin on the face, ears, arms, and upper trunk accounting
5–15% of all cases. Acral lentiginous melanoma (ALM) also
spreads supercially before penetrating more deeply. It is
quite different from the others, though, as it usually appears
as a black or brown discoloration under the nails or on the
soles of the feet or palms of the hands, accounting 2–8% of
all cases. This type of melanoma is sometimes found on dark-
skinned people, and can often advance more quickly than
supercial spreading melanoma and lentigo maligna. It is the
most common melanoma in African-Americans and Asians,
and the least common among Caucasians. The rare types
melanomas are: Salivary gland melanoma, which occurs in
< 1% of all cases; Amelanotic melanoma, usually pink, red,
purple, or of normal skin color; Desmoplastic (Neurotropic)
melanoma, a rare cutaneous condition (< 4%) which is deeply
inltrating type with an abundance of brous matrix on the
head and neck region; “Nevoid” or “spitzoid” melanoma,
which is < 1% of all cases, usually in young people. The
common treatment for localized (early stage) melanoma is
surgery, and in the majority of cases, this is the only treatment
required. If it spreads, it is usually fatal. Therefore, the most
important is early melanoma diagnostics-ABCDEFG rule:
A-asymmetry, B-border, C-color, D-diameter, E-elevation,
evolution, F-feeling, G-growth [7].
In general, melanoma incidence rates in white populations
increase with proximity to the Equator, and vary across Europe,
with the highest rates for both sexes in Switzerland, Denmark,
Norway, Sweden, and the Netherlands and the lowest rates
in Central and Southeastern Europe. Recent trends in
melanoma incidence and mortality have been less studied in
SSM NM LMM ALM
Figure 1. The four basic types of melanoma [7]
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in white, black, and skin color available in the market were
selected for the research. Cotton knitted fabric was pretreated,
modied, and nished-scoured with alkali, and with pectinase,
bleached, mercerized, cationized and treated with FWA and
UV absorber. It was dyed in black, navy blue, purple, and beige
color in industrial conditions. The labels and treatments are
listed in Table 1.
The fabric UV protection was determined according to AS/
NZS 4399:1996 Sun Protective Clothing: evaluation and
classication. UVA and UVB transmission through fabric
were measured on Varian Cary 50 Spectrophotometer. This
instrument measures sunlight transmission in the range from
280 to 400 nm. The irradiation applied is a simulation of a part of
sunlight spectrum, as measured at noon on January 17th 1990
in Melbourne, Australia, while the results obtained indicate the
degree of protection offered by the fabric when worn directly on
the skin. The ultraviolet protection factor (UPF), which indicate
the ability of fabrics to protect the skin against sun burning
saying how much longer a person can stay in the sun with the
fabric covering the skin as compared with the uncovered skin to
obtain same erythemal response, was calculated automatically.
According to the standards, excellent protection is when UPF
is higher than 40 (Table 2). However, for the countries with UV
index 7–10 as Mediterranean countries, Australia, and USA,
the UPF should be 15 times higher than UV index [18].
on the beach, they wear T-shirt, as well during swimming in the
sea, thinking that it will protect them from harmful UV-R.
The UV protection highly depends on large number of factors
such as type of ber, fabric surface, construction, porosity,
density, moisture content, type and concentration of dyestuff,
uorescent whitening agents (FWA), UV-B protective agents
(UV absorbers), as well as nanoparticles, if applied [11]. Since
the back sides in men and women, as well as the lower limbs
in women, are the most common site for melanomas, fabric
UV protection in this paper was researched on the pretreated,
nished and modied knitted fabrics for T-shirts, and ladies
pantyhoses. The possibilities for its improvement enhancing
light conversion and scattering are shown. Additionally, the
discrepancy in whiteness and UV protection was investigated
in distilled water as well as Adriatic Sea water.
2. Experimental
Knitted fabrics for T-shirts, a circular weft single jersey, of mass
per surface area of 130 g/m2 were made in 56 cm (22 inch)
width in tubular form, having 11 whales/cm and 12 courses/
cm. The yarn used was polyester (PES) of 25 tex, and of 100%
cotton of 17 tex, 20 tex, and 25 tex. The cotton/PES blend was
made as well. Ladies pantyhoses of 100% PA 6.6 of 40 den
Table 1. Labels and treatments of cotton knitted fabrics
Label Treatment
R Raw-untreated
S
Traditional scouring with NaOH-3% NaOH and 2 g/l nonionic surfactant Kemonecer NI (Kemo), t = 2h, T = 100°C in
autoclave (Scholl)
Enzymatic scouring with neutral pectinase-3 g/l Beisol PRO (Bezema), 1 g/l Felosan NOG (Bezema); pH 7, t = 50
min, T = 80°C, LR 1:10
B Chemical bleaching (HP)-in industrial conditions in peroxide baths
BM Mercerization in 24% NaOH, 8 g/l Subitol MLF
BMC Cationization with 3-chloro-2-hydroxypropyl-trimetyl ammonium chloride (CHPTAC) (Fluka), during the
mercerization process [35,36]
FWA
FWA treatment by exhaustion method in Turbomat (Mathis), t = 30 min, T = 90°C, LR 1:30
Uvitex BHT (Ciba-Geigy AG)-derivative of stilbene disulphonic acid in optimal conc. of 0.6% (owf)
Uvitex BAM (Ciba-Geigy AG)-bis (4,4’-triazinylamino)-stilbene-2,2’-disulfonic acid derivative
in wide concentration range
UV
UV absorber treatment by exhaustion method in Turbomat (Mathis), t = 30 min, T = 90°C, LR 1:30
Tinofast CEL (Ciba) on the base of oxalanilide
Tinosorb FD (Ciba-Geigy AG) -stilbene disulphonic acid triazine derivative in wide concentration range by
exhaustion method
Z Natural zeolite treatment by impregnation or during the mercerization process [37]
Table 2. UV protection rating according to AS/NZS 4399:1996
UPF range UPF rating UV-R protection category UV-R blocking [%]
< 14 0, 5, 10 non-rateable < 93.3
15–24 15, 20 good 93.3–95.8
25–39 25, 30, 35 very good 95.9–97.4
> 40 40, 45, 50, 50+ excellent > 97.5
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Dyeing in darker shades signicantly improves UV protection as
dyes are selective absorbers. All dyes absorb visible light, but
some of them also absorb light in the near UV region. On textiles,
dyes often provide tangible UV blocking with the structure of dye
molecules playing an important role. Other important factors are
including type of dye or pigment, present absorptive groups,
depth of dyeing, and the uniformity [11, 13]. According to the
color physic principles, results of dyed cotton T-shirts conrm
that darker colors (e.g. black, navy blue, and dark red) absorb
UV-R much more strongly than light pastel colors resulting in
excellent UV protection, while beige one gives off only good.
For the polyamide ladies pantyhoses dyed in lighter shades, for
example, white and skin color, it can be seen that there is no UV
protection, while black one gives good protection.
The evaluation of the cotton fabric protection against UV-R
regarding the fabric surface construction, porosity, and yarn
density is shown in Figure 3b, while the results of UV protection
and whiteness of pretreated cotton knitted fabrics, additionally
modied by mercerization, cationization and/or zeolite addition,
and optically brightened with Uvitex BHT and UV reactive
absorber on the base of oxalanilide Tinofast CEL (Ciba) are
shown in Figure 3a and in Table 3.
UPF directly depends upon transmission of UV-A and UV-B
radiation through fabric. On the other hand, these transmissions
Remission spectrophotometer SF 600 PLUS CT (Datacolor)
was used for measuring spectral characteristics of cotton
and PES/cotton blend fabrics. CIE whiteness degree (WCIE)
was calculated automatically according to ISO 105-J02:1997
Textiles - Tests for color fastness - Part J02: Instrumental
assessment of relative whiteness. The discrepancy of color,
dE*, in wet state was determined through color differences of
color coordinates automatically.
3. Results and discussion
The obtained results according to AS/NZS 4399:1996 are
summarized in Figures 2–4 showing mean UPF value of
differently pretreated, modied, and nished knitted fabrics
cotton and PES for T-shirts, and polyamide pantyhoses.
Considering the results of mean UPF value of T-shirts and
pantyhoses shown in Figure 1, it can be seen that PES fabric
gives off better UV protection than cotton one, due to the
PES benzene rings [18, 26]. White PES T-shirt offers good
UV protection (UPF = 33.92), but on the other hand, it is not
comfortable due to its low water adsorption. Bleached cotton
fabrics is non-rateable for UV protection (UPF = 5.24). Blending
with PES increases UPF to 11.35, resulting in UV rating 10, but
still it is non-rateable for this purpose.
CB PES CB/PES PA 6.6 PA-Skin
color PA-Black C-black C-Navy
blue C-purpur C- beige
-5,242 33,92 11,35 4,686 4,944 27,319 1000,00 1000,00 399,652 22,974
0
100
200
300
400
500
600
700
800
900
1.000
Mean UPF
Figure 2. Mean UPF of knitted fabrics for T-shirts— C = cotton, PES = polyester (25 tex); and PA 6.6 (40 den) for pantyhoses
Table 3. CIE whiteness (WCIE) of knitted cotton fabrics after pretreatment, modication and treatment with FWA (Uvitex BHT) and UV absorber
Tinofast CEL
Fabric NaOH Enzyme FWA (0.9 %
Uvitex BHT)
UV (Tinofast
CEL) FWA+UV
R 9.88 9.88 90.23 30.56 80.32
S 37.71 17.51 85.55 33.11 83.60
B 69.87 69.42 125.36 88.61 117.26
BM 51.38 51.48 129.08 94.05 118.54
BMC 47.32 48.15 122.13 92.37 116.93
BMZ 60.22 59.78 120.27 87.82 110.13
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Raw cotton bers contain around 95% of pure cellulose
balanced by the non-cellulosic impurities of proteins, oils, waxes,
proteins, pectins, carbohydrates, and inorganic materials
[36, 38]. Pectin and waxes absorb small quantities of UV-R;
therefore, raw fabric has small sun screening properties, but for
UV protection, it is still non-rateable (UPF rating 10). Removing
impurities like pectin and waxes, etc., during scouring and
pigments in chemical bleaching results in lower UV protection
even though fabric shrunk. On the other hand, textile cleaning
of genetic and added impurities leads to cotton whitening
(Table 3). Conventional alkali scouring, which is performed at
high temperatures, removes non-cellulosic genetic and added
impurities from the cuticles of the cotton bers, while pectinase
scouring degrades only pectin [38]. Therefore, whiteness of
depend upon fabric cover factor [20, 21]. It is well known that in
every wet treatment, cotton swells, which leads to shrinkage of
fabric, lowering the UV-R transmission, resulting in higher UV
protection [21, 38]. Shrinkage of knitted fabric in wet condition
is affected by stresses accumulated during the production
so that relaxation in wet conditions is inevitable. Yarn linear
mass density has the same inuence on UV protection. The
increment of yarn linear mass density lowers fabric porosity and
transmission of UV-R, resulting in higher UPF values. Results
of UPF in Figure 3b for cotton of 17 tex, 20 tex and 25 tex
yarns, regardless of pretreatment, conrm that. For example,
for HP bleached fabrics, UPFB 17 tex = 3.48 is increasing to UPFB
25 tex = 5.24.
a.
R S B BM BMC BMZ
Enzyme 13,24 7,38 5,24 12,41 20,15 15,12
NaOH 13,24 7,93 5,83 11,24 22,14 14,53
FWA 27,34 30,16 113,45 1000,00 1000,00 1000,00
UV 17,35 21,93 197,47 537,02 451,09 419,91
FWA+UV 28,54 63,67 211,01 1000,00 1000,00 1000,00
0
100
200
300
400
500
600
700
800
900
1000
Mean UPF
b)
R S B BZ RM RZ RMZ RZM
17 tex 3,918 7,537 3,485 6,577 13,593 13,698 24,429 23,734
20 tex 8,852 5,154 4,401 8,197 18,231 24,045 50,264 30,778
25 tex 13,237 7,304 5,242 10,431 65,273 27,514 85,078 76,168
0
10
20
30
40
50
60
70
80
90
100
Mean UPF
Figure 3. UV protection expressed via Ultraviolet protection factor (UPF) of pre-treated and modied knitted cotton fabrics after a. treatment with
FWA (Uvitex BHT) and UV absorber Tinofast CEL; b. different yarn density
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the damaging UV-R range of 290 to 360 nm, and convert it
into harmless heat energy. Latest research declares that
FWAs and UV absorbers can be applied in washing process
and in detergent formulations [26, 27]. After treatment with UV
reactive absorber on the base of oxalanilide fabric, whiteness
increased a little bit due to its chemical constitution.
Based on electronically excited state by energy of UV-R (usually
340– 370 nm), the molecules of FWAs or optical brightening
agents (OBAs) show the phenomenon of uorescence giving
to white textiles the high whiteness of outstanding brightness
by re-emitting the energy at the blue region (typically 420–
470 nm) of the spectrum. By absorbing UV-A radiation optical
brightened fabrics transform this radiation to blue uorescence,
which leads to the better UV protection [10, 11, 17, 18, 24–27].
From Table 1, it is evident that FWAs increase UPF values from
UPFEB = 4.24 to UPFEB-FWA = 113.81 for bleached cotton; and
from UPFEBM = 12.41 to UPFEBM-FWA = 1000 for mercerized cotton
knitted fabrics. It can be seen that maximum UV protection can
be accomplished without UV absorber.
Recently, the new uorescent agents on the base of stilbene
derivative were developed for UV-B protection as well.
Therefore, FWA and such UV absorber were applied in wide
concentration range and the discrepancy in whiteness and UV
protection was research in distilled water as well as Adriatic
Sea water. Results are presented in Figure 4 and Table 4. It
can be seen that FWA applied even in small concentration
leads to higher UPF and whiteness. From Table 4, it can
be seen that FWA concentration of 0.25% (up to 1%) over
weight of fabric is the optimal concentration for this optical
brightener. That is the concentration of uorescent agent at
which the maximum of Φrel or WCIE are observed [17]. Since
this UV absorber has similar chemical composition (stilbene
disulphonic acid derivative) as FWA, its optimum concentration
is 0.25% owf. Applied in the higher concentration then optimal
one, as a consequence of bathochromic shift of the remission
spectrum, comes to a reduction of remission intensity with FWA
and/or UV absorber’s concentrations causing the extinction of
uorescence by quenching phenomenon what leads to fabric
yellowing. On the other hand, absorption of UV-A radiation
leads to excellent UV protection in the higher concentration
(UPFFWA5% = 47.68, UPFFWA25% = 93.89). Therefore, cotton fabrics
of the highest FWAs concentration have the highest UPF in
dry state. By treating cotton fabric with an UV absorber in the
wide concentration range, protective effect is more enhanced.
Application of small amount of UV absorber results in good,
while in optimal concentration or higher, it offers excellent UV
protection in dry state. For difference of FWAs, UV absorbers
offer UV-B protection as well. However, the fabrics with the
highest intensity of uorescence do not show the highest UPF
values. In dry state, UV protection increases with uorescent
agent concentration, regardless of quenching phenomenon.
Considering the results of discrepancy of whiteness, it can be
observed that all fabrics get darker when wet and in general,
bluer and redder. The reason for that is lower reection of
light from the fabric. In dry fabric, some of the photons of light
are absorbed, but some are reected and land on the eye’s
retina, which gives the sensation of seeing a certain level of
pectinase-scoured cotton is a little bit lower than alkali-scoured
ones (Figure 3a). Bleaching in peroxide baths removes
pigments [36, 38] resulting in white cotton, but the UPF values
are low, and non-rateable for UV protection. Therefore, it is
necessary to modify and/or treat knitted fabric for better UV
protection. In mercerization, fabrics highly shrink, resulting
in lower transmission of UV-R through a more tightly knitted
fabric. Therefore, UV protection of mercerized cotton is good
(UPF > 15). Cationization during mercerization results in good
UV protection while treatment with UV absorber leads to very
good UV protection. Mercerization and cationization leeds to
small lost of fabric whiteness and small yellowing occurs.
Textile nishing agents for UV protection can be incorporated
into the ber matrix, or it can be applied to the surface of the
fabric [28–31]. The presence of inorganic pigments in the bers
also allows better scattering of light from the substrate, thus
providing better protection. Titanium dioxide (TiO2), which is
used as a delustering agent and other ceramic materials have
an absorption capacity in the UV region of 280 to 400 nm
reecting visible and infrared rays. Incorporation of TiO2 in ber
matrix improves the UV blocking capacity of the ber. Good
skin protection thereby can be achieved by the textile itself, if
the fabric is sufciently dense. Introducing the nanoparticles
in textile nishing, led to UV protection by coating the surface
of textiles and clothing with nanoparticles of TiO2 titanium,
and zinc oxide [28–30], and nowadays, of natural zeolite
clinoptilolite [22, 32, 33].
Natural zeolites are rock-forming, micro porous silicate
minerals that act as strong adsorbents and ion-exchangers,
having multiple uses in medicine and industry, agriculture,
water purication, and detergents. Zeolites are nontoxic
substance, excellent for proteins and small molecules such
as glucose adsorption; even absorbs toxins, mould, and
caesium. It has positive effect on the metabolism of living
organisms and its anticancerogenic, antiviral, antimetastatic,
and antioxidant effect. Clinoptilolite can be ground by a certain
tribomechanical processing in a patented machine (Patent:
PCT/1B99/00757) yielding particles on a submicron level
(micro and nanoparticles) yielding all the above-mentioned
properties. When applied externally in powder form, it has been
found to quicken the healing of wounds and surgical incisions,
and act as proven bactericides and fungicides as well [32, 37].
Applied as nanoparticles to textile surface (Figure 3), it scatters
the UV-R, resulting in lower UV-A and UV-B transmission.
Addition of micronized and nanoparticles of natural zeolite to
the bath increases signicantly UV protection, regardless of the
applying method (BZ, RZ). If applied during the mercerization
process (RZM), synergistic effect occurs. Application after
mercerization (BMZ, RMZ) results in excellent UV protection
because more nanoparticles remain on fabric surface and UV-R
scattering is higher. Considering the yarn linear density (Fig.
3b) fabrics of higher yarn linear density, 20 and 25 tex, give
off excellent UV protection. If applied with other UV absorbing
agents, for example, FWAs, synergistic effect occurs.
Usually, sun protection effect is achieved through the use of
UV absorbers [10,15–19]. Molecules of UV absorbers such
as benzotriazole and phenyl benzotriazole, are able to absorb
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enhanced for sea water, since the refractive index increases
with salinity increment and decrease in temperature. That
can be explained by that some of the Sun’s radiant energy
is reected from the water surface; it is not absorbed, but
additionally scattered by molecules suspended in the water,
whilst the other part penetrates the water’s surface, absorb and
converse to other forms of energy such as heat that warms or
evaporates water, or is used by plants to fuel photosynthesis.
Considering the applied concentrations, in general, it can be
said that higher concentration of uorescent agent applied,
better UV protection was achieved in wet state. The only
exception is the highest concentration of UV absorber. From
Figure 3b, it can be seen that the UV protection in wet state is
lower if applied 25% owf than 5% owf of UV absorber. As it was
observed for the CIE whiteness, which signicantly decreased,
brightness. But when the fabric gets wet, the water lls the
interyarn spacing. When the light falls on the wet fabric, some
of it enters the water at one angle and refracts at other because
the light waves travel at a slower speed in water than it does in
air. Fewer photons of light get back to the eyeball, and therefore
the wet fabric “appears” darker than the dry one. The amount of
refraction, referred to as the refractive index, is affected by both
the salinity and temperature of the water, and therefore there is
a difference between fabrics treated with sea and distilled water.
It is to point out that the salts in sea water act as quenchers
of uorescence as well, resulting in decreased whiteness. As
for the UV protection, it can be said that in wet state, cotton
knit fabrics treated with uorescent agents give off better UV
protection than in dry state regardless of the concentration and
type of uorescent agent applied. This phenomenon is more
a.
00,01% 0,05% 0,25% 1% 5% 25%
FWA-Dry 5,24 10,77 20,13 23,04 36,01 47,68 93,89
FWA-SW 16,62 21,55 27,89 36,82 112,23 117,52 189,68
FWA-DW 16,92 21,30 34,79 54,66 65,27 105,57 125,14
0
50
100
150
200
250
300
Mean UPF
b.
00,01% 0,05% 0,25% 1% 5% 25%
UV-Dry 5,24 12,53 28,19 41,25 53,24 70,68 194,29
UV-SW 16,62 28,39 50,65 82,74 123,12 297,16 198,01
UV-DW 16,92 22,19 48,44 111,66 171,42 243,07 192,60
0
50
100
150
200
250
300
Mean UPF
Figure 4. UV protection expressed via Ultraviolet protection factor (UPF) of cotton fabrics in dry and wet state treated with stilbene type-a.
FWAUvitex BAM, b. UV absorber Tinosorb FD
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as scouring and chemically bleaching, lower the UV protection.
Therefore, for summer clothing, additional fabric protection is
necessary. Yarn linear density increment results in higher UV
protection regardless of fabric treatment. Mercerization and
cationization lower UV-A and UV-B transmission, which leads
to good UV protection. Natural zeolite treatment increases
signicantly UV protection, regardless of the applying method. It
scatters the UV-R resulting in lower UV-A and UV-B transmission.
If applied after or during the mercerization process, synergistic
effect occurs. Treatment with uorescent agents, FWA and UV
absorber leads to multifunctionality, which is high whiteness,
neutralizing yellowness, giving the fabric high luminosity and
protection against UV-R. In wet state, regardless of applied
water—sea or distilled, fabrics get darker, lowering its whiteness.
UV light is not absorbed, but reected from the water, resulting
in better UV protection. This phenomenon is more evident for
sea water because of additional light scattering since it contains
about 40% of inorganic salts. Having in mind that uorescent
agents are present in laundry detergents and their accumulation
during washing process leads to even better UV protection [27],
application of these agents to protective clothing for prevention
of skin cancer incidence is suggested.
it can be assumed that this drop of UPF in wet state can be the
result of quenching of uorescence as well. However, achieved
UV protection is excellent regardless of its decrease and can
even obey that request regarding UV index during the summer
time in Mediterranean countries, as well as Australia and USA.
4. Conclusions
Primary prevention and early detection are essential for
decreasing melanoma incidence. Considering prevention,
especially in childhood and adolescence, it is necessary to
apply sun screening lotions and wear adequate clothing, not
forgetting that UV-A does not lead to vitamin D synthesis.
Blocking all UV-R can lead to vitamin D deciency, which is
estimated to affect 1/3 of Australians. Skin needs to be exposed
for around half the time it takes to get erythema. How much
vitamin D is produced from sunlight depends on the time of day,
location on Earth, phototype, and the size of exposed area.
Raw cotton fabric contains pectin and waxes that give it some sun
screening properties, but it still is non-rateable. Pre-treatments,
Table 4. CIE whiteness (WCIE), and the discrepancy of whiteness in wet state of cotton fabrics treated with stilbene type FWA (Uvitex BAM) and
UV absorber (Tinosorb FD)
Fabric
FWA UV
WCIE dE* Discrepancy WCIE dE* Discrepancy
B69.4 - - 69.4 - -
B-DW 65.6 1.989 Darker greener less yellow 65.6 1.989 Darker greener less yellow
B-SW 67.3 1.528 Darker greener 67.3 1.528 Darker greener less yellow
B-0.01 100.5 - - 116.3 - -
B-0.01-SW 97.7 1.610 Darker redder bluer 110.0 2.727 Darker redder less blue
B-0.01-DW 102.9 1.227 Darker redder bluer 110.1 2.181 Darker less blue
B-0.05 138.6 - - 139.4 - -
B-0.05-SW 134.8 1.981 Darker redder less blue 137.1 1.699 Darker bluer
B-0.05-DW 136.4 1.639 Darker redder bluer 139.5 1.481 Darker redder bluer
B-0.25 144.8 - - 145.1 - -
B-0.25-SW 145.5 1.987 Darker redder bluer 144.2 1.084 Darker less red bluer
B-0.25-DW 147.1 2.160 Darker redder bluer 143.6 1.127 Darker less red
B-1 143.2 - - 132.7 - -
B-1-SW 144.8 2.145 Darker redder bluer 133.0 1.356 Darker bluer
B-1-DW 146.6 2.374 Darker redder bluer 130.1 1.136 Darker less red less blue
B-5 133.4 - - 84.9 - -
B-5-SW 137.8 2.272 Darker redder bluer 77.9 1.715 Darker greener less blue
B-5-DW 138.0 2.038 Darker redder bluer 83.8 0.928 Darker greener bluer
B-25 115.4 - - 51.5 - -
B-25-SW 107.2 1.913 Darker greener less blue 13.9 7.014 Darker greener yellow
B-25-DW 104.1 2.419 Darker greener less blue 28.9 4.448 Darker greener yellow
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ACKNOWLEDGEMENTS
The work has been supported by Croatian Science Foundation
under the project 9967 Advanced textile materials by targeted
surface modication.
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