FCC International is a network of
over 125 Non- Governmental Organizations (NGOs) in 56 countries
working to promote government and individual action to limit
human-induced climate change to ecologically sustainable levels.
eIEN South Asia scientists concerned of Global Climate Change issues
responded to the emerging challenge and threat of climate change by
establishing Forum for Climate Change Kashmir, in 2005 , to provide
advice on recognizing potential dangers and immediate threats of
Global Climate Change to the regional populace and strong advocacy
for economically depressed Himalayan communities who are minor
contributors to global warming.
Environmental Effects of Ozone Depletion (Interim
Report)
Ozone Layer
Depletion
Ozone ( O3 ) is the important species in the
stratosphere, acting as protective radiation shield for living
organisms in the earth .The maximum ozone concentration is around 10
ppm in the stratosphere at an altitude of 25-30 Km. Ozone simply
absorbs ultraviolet radiation in the region of 220-330 nm, only a
fraction of the ultraviolet light reaches the lower atmosphere and
the earth.
Ozone Chemistry:
Mechanism of normal Ozone formation:
O2 + hv ( 242 nm ) -› O + O
O + O2 + M ( N2 or O2 ) -› O3
+ M
Mechanism of normal Ozone removal :
O3 + HO* -› O2+ HOO*
O3 + NO -› NO2 + O2
How Ozone gets Depleted ?
In nature there exists a sort of equilibrium in the formation and
removal of ozone concentration in the stratosphere. However in the
recent past , due to anthropogenic activities due to excessive use
of certain chlorofluorocarbon compounds and volcanic injection (Cl2)
ozone layer is depleting at faster rate and is getting extremely
alarming because of its global importance .
CFC were first introduced in 1930’s as miracle chemicals because of
their non toxic , non inflammable and stable properties . Therefore
had find various uses, as coolant in refrigerators – air
conditioners, blowing plastic foams etc,. A Large hole in the ozone
layer over Antarctica has been discovered, where ozone is being
dropped by 30 % . Subsequently a similar hole was discovered over
the thickly populated northern hemisphere, dropped by 3 % and this
list may go on. The overall reduction in the ozone layer is now
estimated to be about 8 %. The troposphere carries the burden of air
pollution. Hardly any pollutant exists beyond 2000 feet above ground
level. Relatively small amounts of pollutants are found in the
stratosphere. However, in the troposphere the pollutants reside for
a few weeks only as they are quickly dispersed by the air movements
and also removed in precipitated rain. In contrast, stratosphere,
the residing time of pollutants is fairly long ranging from 1 to 3
years due to very little gaseous circulations and diffusion.
Unfortunately CFC finds its way to stratosphere, when transferred
from the troposphere; start accumulated for a longer period of time.
Furthermore, exposure to intense solar radiations in the
stratosphere favors photochemical activity.
Mechanism of O3 Depletion by CFC :
Chlorine from CFC :
CFCl3 + hv -› CFCl2 + Cl*
Cl* + O3 -› ClO* + O2
ClO* + O -› Cl* + O2
In a cyclic reaction each ClO*can initiate a series of chemical
reactions which lead to disturb of up to 1000,000 molecules of O3
without being destroyed itself in the process.
ENVIRONMENTAL EFFECTS OF OZONE DEPLETION (Interim
Report)
Executive Summary
Ozone and UV Changes
Reductions in stratospheric ozone are continuing, both in the
Antarctic with the re-appearance of the ozone "hole" each spring,
and at other locations and times in both hemispheres. High latitudes
of the northern hemisphere have experienced very low ozone in the
last two winters, apparently due to record-low temperatures in the
lower stratosphere, which favor the formation of polar stratospheric
clouds and thereby the activation of ozone-destroying chlorine. Mid-
latitude ozone levels in both hemispheres remain significantly lower
than during the 1980s. Record low ozone recently observed at some
lower latitude locations (e.g., Mauna Loa) during 1994/95 was
probably mainly due to stratospheric circulation changes rather than
to chemical causes. Re-analysis of ozone measurements from the Total
Ozone Mapping Spectrometer (TOMS) aboard the Nimbus-7 satellite has
been carried out recently. However, detailed comparisons between the
re-analyzed data and the earlier (version 6) TOMS data, the other
satellite data (e.g., SBUV and SBUV/2), and the ground-based ozone
measurements (Dobson instruments) are yet to be published.
Substantial progress has been made in the estimation of global
surface UV levels through the assimilation of satellite-derived data
into radiative transfer models. In contrast to earlier models, which
accounted only for variations in ozone, these new techniques appear
promising for including also the effects of clouds and possibly
aerosols on UV transmission. One study, based on 1979-1992 ozone and
cloud reflectivity data from TOMS (version 7), gives erythemal UV
trends that are smaller (by 10-50%, depending on latitude) than the
cloud-free trends previously estimated from TOMS version 6, SBUV and
SBUV/2 ozone data. However, clouds had only a minor impact on the
trends of the new study, and the discrepancies appear to result from
the lower ozone trends estimated from the new version 7 TOMS data.
The record of direct UV measurements is still too short for reliable
estimation of long-term trends. However, recent measurements at both
polar and middle latitudes show the expected relationship between
episodic ozone decreases and UV increases. Surface UV- monitoring
continues to expand, with international coordination under the
auspices of the World Meteorological Organization (WMO) and the
Network for Detection of Stratospheric Change (NDSC). Several
international comparisons of monitoring instruments have been
carried out, and confirm earlier estimates of usual agreement at the
5% level in the UV-A and 10% in the UV-B. Intercomparisons among UV
radiation models, and between models and measurements are also being
carried out or planned.
The effects of clouds on atmospheric and surface radiation have
received considerable theoretical and observational attention in the
last year. Topics of active research have included the spectral
dependence induced by clouds (showing more effective transmission of
UV-B than visible radiation), and the complex effects of non-
uniform and broken cloud fields.
Health Effects
The principal impacts of UV on health are mediated through two organ
systems, the skin and the eyes, which receive all of the exposure.
These systems are generally either well adapted to (the skin) or
well protected from (the eyes) such exposures; humans benefit from
UV exposures through the initiation of Vitamin D3 production, and
even detrimental effects such as DNA damage, are normally corrected
by efficient repair mechanisms. Our average day-to-day exposure to
UV is generally sufficient to ensure appropriate levels of Vitamin
D. There is some evidence in tissue culture that Vitamin D has
inhibitory effects on tumor cell growth. Such effects have been
suggested as the mechanism underlying an observed increase in breast
and colon cancers at higher latitudes (where solar exposures are
less). This linkage is still conjectural, however. The production of
the biologically active vitamin is self- limiting so that excessive
exposures are not likely to be associated with any benefit.
New findings with regard to the molecular events underlying UV-
induced nonmelanoma skin cancer extend the earlier observations that
these tumors often have alterations (mutations) in a particular
tumor suppressor gene that are typical of UV-B radiation. The recent
findings indicate that similar UV-B alterations in a second tumor
suppressor gene (ptc) are associated with spontaneous (non-
hereditary) basal cell carcinomas (BCC). These data provide the most
direct evidence that UV-B radiation contributes to the development
of these skin tumors.
Additional studies on the involvement of p53 indicate that the
frequency of such typical UV-B alterations in the skin tumors may
decrease with lower dose levels and spectral shifts toward the
longwave UV-A. An additional finding in UV-induced carcinogenesis
comes from recent epidemiologic studies, which indicate that BCC is
not principally related to cumulative UV dose, but as with melanoma,
appears to be more related to childhood and intermittent over-
exposures.
New epidemiologic studies on melanoma for the most part confirm
earlier work. Several studies have suggested that sunscreen use may
not be protective for melanoma and may even be associated with
increased risk. A possible explanation offered to explain these
observations is that wearing sunscreens, while reducing UV-B
exposure, provides little protection from UV-A exposures and that
such exposures are important to melanoma risk. Although such an
interpretation is in line with the spectral response of melanoma
induction in a fish model, such epidemiologic findings may be biased
by linkages among susceptibility, exposure and sunscreen use. New
work in the opossum model for melanoma has shown that short-term
neonatal exposures to broadband UV-B/UV-A radiation (of
approximately a week) result in highly aggressive (metastatic)
melanomas.
It is now clear that there are at least three mechanisms by which
UV-B exposures may suppress cellular immunity: DNA damage,
isomerization of urocanic acid, and through the active metabolite of
vitamin D. Immune effects can occur both locally at the skin and
systemically throughout the body. The local effects have long been
considered important to the development of skin cancer, but there
has been little evidence found with regard to the importance of
systemic effects. Recent observations of an increase in non-
Hodgkin's lymphoma with increasing solar radiation have led to the
suggestion that UV-B-induced systemic immunosuppression contributes
to cancer development in this system. The implications of either
local or systemic immune effects for human infectious diseases are
still unknown. Epidemiological studies are still required to explore
these issues. There is very little new information on UV effects on
the eye. A critical lack is an action spectrum for eye effects
associated with chronic exposures, e.g., cataract.
Effects on Terrestrial Ecosystems
Since the last report in 1994, there has been progress on
understanding the mechanisms of UV action on organisms. There has
also been an increasing emphasis on outdoor studies of
nonagricultural vegetation. In such experimentation, the importance
of maintaining a realistic spectral balance between UV and longer
wavelength radiation during experiments has received more attention.
This is important because longer wavelength radiation may have
ameliorating effects. The UV-A can also have effects in some
respects similar to that of UV-B. In addition to UV-B
supplementation studies designed to simulate the consequences of
ozone reduction on sunlight, other research of late has involved
manipulation of natural solar radiation with filters to show the
effectiveness of both UV-B and UV-A on organisms.
Many of the effects of UV-B may not involve damage, per se, but
instead be a matter of the plant using this type of radiation as a
signal for altering growth form and some physiological processes.
One example of such a change is the commonly observed increase in
UV-absorbing protective compounds in plant leaves following exposure
to UV-B. This may explain, at least in part, many of the seemingly
paradoxical results of recent and earlier studies suggesting
stimulating effects in plants by UV-B. The UV-B responsiveness is
often very specific to species, or even races of a given species,
and depends on other environmental factors such as mineral
nutrition, drought, local air pollutants, etc. These differential
effects on species will likely lead to changes in species
interactions and on ecosystem dynamics. Various indirect effects of
elevated UV-B radiation are receiving attention, including effects
of UV-B on decomposition of plant litter, which may influence
cycling of nutrients. Other indirect effects include influence on
plant pathogen susceptibility and plant attractiveness to herbivores
and pollinators. Many of these indirect effects may be UV-B action
mediated through changes in plant structure, secondary chemistry and
timing of life cycle events. Nevertheless, these effects may
ultimately be the most important on ecosystems. This is not to
dismiss more direct, apparently detrimental effects of UV-B on
organisms, including microbes and lower plants such as mosses. The
peat-forming moss, Sphagnum, appears to be sensitive which has
implications for some processes in biogeochemical cycles such as
decreased carbon storage. Trace gas emission from vegetation is also
potentially important. One recent study, however, showed no effect
of elevated UV-B on emission of isoprene, an important precursor
compound for tropospheric ozone formation.
Recent studies suggest that potentially detrimental effects of UV-B
radiation in evergreen woody plants may accumulate from year to year
as had been indicated in earlier work. Another example of
accumulating effects has recently been shown for subsequent
generations of native annual plants. With exposure of each
generation, the manifestations of adverse effects were intensified.
The interacting effects of elevated UV-B with other factors
important in global change such as elevated CO2 and
temperature are receiving more attention. While elevated CO2
and temperature usually have more pronounced effects than elevated
UV-B, there are often interactions among these factors such that the
effects may counteract each other or sometimes they may be additive.
Effects on Aquatic Ecosystems
In the recent past, scientific and public interest has focused on
marine primary producers and aquatic ecosystems, which resulted in a
multitude of studies indicating mostly detrimental effects of UV-B
radiation on aquatic organisms. The interest has expanded to include
effects in individual species as well as specific responses and has
concentrated on ecologically significant groups and major biomass
producers using mesocosm studies, emphasizing species interactions.
In addition, light penetration into the water column was
investigated by several research groups. Macroalgae and seagrasses
are major biomass producers in aquatic ecosystems. In contrast to
phytoplankton most of these organisms are sessile and can thus not
avoid the exposure to solar radiation at their growth site. Recent
investigations showed a pronounced sensitivity to solar UV-B, and
effects have been found throughout the top 10 - 15 m of the water
column. Mechanisms of protection and repair are being investigated.
Controversy still exists regarding the interpretation of data on
UV-B effects in Antarctic phytoplankton. Estimates of the decreases
in overall biomass productivity by different authors range from 0 -
12 %. Most recently, shifts in phytoplankton community structure
have been demonstrated, which may have consequences for the food
web. Bacteria play a vital role in mineralization of organic matter
and provide a trophic link to higher organisms. Recently, the
mechanism of nitrogen fixation by cyanobacteria has been shown to be
affected by UV-B stress. Wetlands constitute important ecosystems
both in the tropics and at temperate latitudes. In these areas
cyanobacteria form major constituents in microbial mats. The
organisms optimize their position in the community by vertical
migration in the mat which is controlled by both visible radiation
and UV-B. Cyanobacteria are also important in tropical and
subtropical rice paddy fields where they contribute significantly to
the availability of nitrogen. Growth, development and several
physiological responses of these organisms are affected by solar UV.
Dissolved organic carbon (DOC) and particulate organic carbon (POC)
are degradation products of living organisms. These substances are
of importance in the cycling of carbon in aquatic ecosystems. UV-B
radiation has been found to break down high molecular weight
substances and make them available to bacterial degradation. In
addition, DOC is responsible for short wavelength absorption in the
water column. Especially in coastal areas and freshwater ecosystems,
penetration of solar radiation is limited by high concentrations of
dissolved and particulate matter. On the other hand, climate warming
and acidification result in faster degradation of these substances
and thus enhance the penetration of UV radiation into the water
column. UV effects on aquatic animals have found increased interest.
In addition to effects on larval stages in amphibia, sea urchins
were found to be affected by solar UV-B radiation despite the fact
that they have partial protection from mycosporine amino acids,
which they take up with their food. Corals have been known to be
directly affected by solar UV; in addition, photosynthesis in their
symbiotic algae is impaired, resulting in reduced organic carbon
supply.
All of the previous studies on UV penetration into the water column
were based on occasional measurements. This will be corrected by a
recent project involving the development of a monitoring system (ELDONET)
for solar radiation in Europe using three-channel dosimeters (UV-A,
UV-B, PAR), which are being installed from Abisko (North Sweden, 68°
N, 19° E) to Tenerife (Canary Islands, 27° N, 17° W). Some of the
instruments will be installed in the water column (North Sea, Baltic
Sea, Kattegat, East and Western Mediterranean, North Atlantic),
establishing the first network of underwater dosimeters for
continuous monitoring.
Effects on Biogeochemical Cycles
Terrestrial studies are continuing to examine the influence of
enhanced UV-B radiation on microbial decomposition of plant litter
to carbon dioxide and nutrients. Additional studies have confirmed
that litter from plants grown under enhanced UV-B is enriched in
lignin and decomposed to CO2 more slowly by soil
microorganisms. The fate and transport of trifluoroacetate (TFA), a
persistent substance derived from the oxidation of certain CFC
replacements (HFC-123, HFC-124, HFC-134a), was investigated in a
temperate forest of North America. The study indicates that the
added TFA was retained in vegetation and soil, especially in the
case of wetlands with organic soils. In addition, biological
accumulation was observed as was a lack of microbial consumption.
Studies of photodegradation of dissolved organic carbon (DOC) by UV
radiation are continuing and expanding. Several studies published
over the past year have provided additional evidence that exposure
to UV radiation enhances the degradation of DOC to CO2
and ammonium. In addition, low-molecular-weight organic products are
produced and are readily assimilated by microorganisms. Volatile
compounds are produced by aquatic DOC photodegradation and
additional studies of the photoproduction of carbon monoxide have
appeared. CO is an important trace gas that strongly influences
biogeochemical cycles through its effects on chemical reactions in
the atmosphere. Two new studies of marine CO photoproduction have
resulted in disparate estimates of global oceanic sea-to-air
emissions. These two global flux estimates are two orders of
magnitude apart: 10-15 Tg CO year-1 and 1000 Tg year-1 (1 Tg = 1012
g). Total annual emissions of CO from all sources, by comparison,
are about 2000-2500 Tg year-1 primarily from fossil fuel combustion
and CH4 oxidation.
New modeling approaches are being developed to predict the
interactions and feedbacks between climate change and UV-B induced
changes in marine biogeochemical cycles. Important links exist
between oceanic dimethylsulfide (DMS) production, sea-to-air DMS
flux and subsequent changes in the sulfate aerosol-related
atmospheric radiation balance. These alterations indicate possible
consequences with regard to climate and climate prediction, because
DMS is an important source of cloud condensation nuclei over parts
of the ocean.
Effects on Air Quality
The photo-dissociation of ozone by atmospheric UV-B radiation is a
key reaction that controls urban and regional oxidants, the self-
cleaning capacity of the troposphere, and the atmospheric lifetimes
of many natural and anthropogenic gases. In the last year, published
evidence from theoretical, laboratory, and field studies shows that
UV-A wavelengths also contribute to this reaction, and therefore
some revision of current tropospheric chemistry models is required.
Although quantitative estimates of the implications of this new
finding have not been carried out yet, impacts are likely for
predicted geographical and seasonal distributions of gases such as
methane (CH4) and carbon monoxide (CO), and the
sensitivity of tropospheric chemistry to stratospheric ozone
depletion. Further evidence for the linkage between stratospheric UV
transmission and tropospheric composition was found in the records
of surface CH4 and CO concentrations. Temporary increases
in tropical CH4 and CO concentrations were observed in
the second half of 1991, in phase with high levels of stratospheric
sulfur dioxide and sulfate aerosols that resulted from the June 1991
eruption of Mt. Pinatubo. The reduced stratospheric UV transmission
is believed to have lowered the rate of CH4 and CO removal, due to
decreased photo-dissociation of tropospheric ozone, and therefore
decreased hydroxyl radical (OH) production.
The atmospheric chemistry of CFC substitutes and the possible build-
up of their breakdown products (particularly trifluoroacetic acid,
or TFA) has attracted more attention. The background atmospheric
concentrations of HFC-134a (a principal precursor of TFA) are
increasing rapidly, according to measurements at Cape Grim, Tasmania
(41° S) between 1978 and 1995, and Mace Head, Ireland (53° N)
between July 1994 and May 1995. Model estimates suggest that
HFC-134a emissions have risen rapidly from ca 0.25x106 kg in 1991 to
ca 8x106 kg in 1994. TFA concentrations in air and water samples
collected in Germany, Switzerland and Israel in 1995 contained
surprisingly high levels of TFA, comparable to concentrations
predicted by models for the year 2010. This suggests that an
additional yet unknown source of TFA may be present.
Modeling studies give different estimates for future concentrations
of TFA in rainwater, e.g., tropical maxima of 0.114 µg l-1 predicted
for the year 2020, and a global mean of 0.160 µg l- 1 by the year
2010 predicted by another study. However, other modeling studies
have concluded that a number of factors can enhance local
concentrations of TFA. The TFA concentrations in the precipitation
of arid and semi-arid regions may be 2-4 times greater than the
global mean. Furthermore, in urban air where high OH and HFC levels
are present, the rate of formation of TFA may be enhanced by an
order-of-magnitude or more. Therefore, local TFA concentration in
rainwater as high as 2-20 µg l-1 or more appears plausible. Water
bodies characterized by little or no outflow and which have high
evaporation rates may be susceptible to accumulation of rain-borne
TFA, leading to significant concentration enhancements. Model
calculations predict that such wetlands could experience
concentrations of up to 100 µg l-1 within 30 years, even when
seepage is as much as 10%.
Materials Damage
Efforts to refine the wavelength sensitivity data for common
polymers have continued, with the commodity polymers polyethylene
and polypropylene receiving the most attention. Results from several
research groups include data on the relative photodamage to
polyolefins, acrylics, polystyrene, and other polymers, caused by
exposure to different regions of a solar- simulated source spectrum.
With polyethylene, the wavelength range 300-330 nm in simulated
sunlight was reported to be most effective in reducing the tensile
extensibility of the material, a result in agreement with previous
findings. These types of data, referred to here as activation
spectra, are useful in the estimation of damage to polymers exposed
to UV-enhanced solar radiation that results from ozone depletion.
Recent findings have shown that while solar radiation is principally
responsible for outdoor degradation of polymers including
polyethylene, factors such as temperature and exposure to moisture
also have an impact on the useful lifetime of materials outdoors.
Several studies have reported on the acceleration of weathering of
polyethylene films under harsh desert conditions, where the
radiation dose and the temperatures are particularly high.
Research was recently carried out on polycarbonate photodegradation
aimed at generating action spectra for the yellowing and
molecular-level breakdown of this polymer used in glazing
applications. This research also studied the irradiance dependency
of the degradation process, an important consideration, since the
construction of action spectra and their derivation from
polychromatic exposure experiments assume the damage process to be
irradiance-independent within the range of irradiance encountered in
the experiments. The findings facilitate the intercomparison of
previously reported wavelength sensitivity data for polycarbonate
polymers. An on-going study is aimed at separating out the
contributions of solar radiation and temperature, to the damage
suffered by polyethylene polymers during outdoor exposure. The data
will allow a better understanding of the role of temperature in
modifying the UV-induced photodegradation of polymers exposed to
UV-enhanced sunlight resulting from ozone depletion.
Future Effects Studies
The global environment is experiencing a wide range of
perturbations. Increased greenhouse gases, sulfate and dust aerosols
and increased UV-B from ozone depletion are all occurring
simultaneously. Assessment of the potential risks from such changes
needs to consider the full context in which these changes are taking
place and must take into account the many interactions that may
occur. This will require a long-term integrated, interdisciplinary
research program designed to include studies which evaluate not only
UV-B but also the other processes which are contributing to global
environmental change.
Health: Each 1 % reduction in ozone may cause as much as 6 %
increase in skin cancer cases annually from exposure to UV
radiation. The principal impacts of UV on health are mediated
through two organ systems, the skin and the eyes, which receive all
of the exposure; humans do benefit from UV exposures through the
initiation of Vitamin D3 production, and even detrimental effects
such as DNA damage, are normally corrected by efficient repair
mechanisms. Our average day-to-day exposure to UV is generally
sufficient to ensure appropriate levels of Vitamin D. The production
of the biologically active vitamin is self- limiting so that
excessive exposures are not likely to be associated with any
benefit. There are at least three mechanisms by which UV-B exposures
may suppress cellular immunity: DNA damage, isomerization of
urocanic acid, and through the active metabolite of vitamin D.
Immune effects can occur both locally at the skin and systemically
throughout the body. The local effects have long been considered
important to the development of skin cancer, but there has been
little evidence found with regard to the importance of systemic
effects.
eIEN South Asia
Western Himalaya Kashmir
FCC KASHMIR
A cause supported by 125 non-governmental organizations in 56 countries.
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FCC
eIEN South Asia
Western Himalaya Kashmir
FCC International is a network of over 125 Non- Governmental Organizations (NGOs) in 56 countries working to promote government and individual action to limit human-induced climate change to ecologically sustainable levels. eIEN South Asia scientists concerned of Global Climate Change issues responded to the emerging challenge and threat of climate change by establishing Forum for Climate Change Kashmir, in 2005 , to provide advice on recognizing potential dangers and immediate threats of Global Climate Change to the regional populace and strong advocacy for economically depressed Himalayan communities who are minor contributors to global warming.
FCC KASHMIR Reports
Glaciers in the Himalayas melting at rapid rate
Global Warming : We have a role
Environmental Effects of Ozone Depletion (Interim Report)
Key Findings: Climate Change Impacts, Adaptation and Vulnerability
The Economist vs the Green Mantra
Status of the Glacier Research in HKH Region
Environmental Effects of Ozone Depletion (Interim Report)
Ozone Layer Depletion
Ozone ( O3 ) is the important species in the stratosphere, acting as protective radiation shield for living organisms in the earth .The maximum ozone concentration is around 10 ppm in the stratosphere at an altitude of 25-30 Km. Ozone simply absorbs ultraviolet radiation in the region of 220-330 nm, only a fraction of the ultraviolet light reaches the lower atmosphere and the earth.
Ozone Chemistry:
Mechanism of normal Ozone formation:
O2 + hv ( 242 nm ) -› O + O
O + O2 + M ( N2 or O2 ) -› O3 + M
Mechanism of normal Ozone removal :
O3 + HO* -› O2+ HOO*
O3 + NO -› NO2 + O2
How Ozone gets Depleted ?
In nature there exists a sort of equilibrium in the formation and removal of ozone concentration in the stratosphere. However in the recent past , due to anthropogenic activities due to excessive use of certain chlorofluorocarbon compounds and volcanic injection (Cl2) ozone layer is depleting at faster rate and is getting extremely alarming because of its global importance .
CFC were first introduced in 1930’s as miracle chemicals because of their non toxic , non inflammable and stable properties . Therefore had find various uses, as coolant in refrigerators – air conditioners, blowing plastic foams etc,. A Large hole in the ozone layer over Antarctica has been discovered, where ozone is being dropped by 30 % . Subsequently a similar hole was discovered over the thickly populated northern hemisphere, dropped by 3 % and this list may go on. The overall reduction in the ozone layer is now estimated to be about 8 %. The troposphere carries the burden of air pollution. Hardly any pollutant exists beyond 2000 feet above ground level. Relatively small amounts of pollutants are found in the stratosphere. However, in the troposphere the pollutants reside for a few weeks only as they are quickly dispersed by the air movements and also removed in precipitated rain. In contrast, stratosphere, the residing time of pollutants is fairly long ranging from 1 to 3 years due to very little gaseous circulations and diffusion. Unfortunately CFC finds its way to stratosphere, when transferred from the troposphere; start accumulated for a longer period of time. Furthermore, exposure to intense solar radiations in the stratosphere favors photochemical activity.
Mechanism of O3 Depletion by CFC :
Chlorine from CFC :
CFCl3 + hv -› CFCl2 + Cl*
Cl* + O3 -› ClO* + O2
ClO* + O -› Cl* + O2
Chlorine from Volcanoes :
Cl + O3 -› ClO* + O2
ClO* + O -›Cl + O2
Cl* + CH4 -›CH3* + HCl
ClO* + NO2-›ClONO2
In a cyclic reaction each ClO*can initiate a series of chemical reactions which lead to disturb of up to 1000,000 molecules of O3 without being destroyed itself in the process.
ENVIRONMENTAL EFFECTS OF OZONE DEPLETION (Interim Report)
Executive Summary
Ozone and UV Changes
Reductions in stratospheric ozone are continuing, both in the Antarctic with the re-appearance of the ozone "hole" each spring, and at other locations and times in both hemispheres. High latitudes of the northern hemisphere have experienced very low ozone in the last two winters, apparently due to record-low temperatures in the lower stratosphere, which favor the formation of polar stratospheric clouds and thereby the activation of ozone-destroying chlorine. Mid- latitude ozone levels in both hemispheres remain significantly lower than during the 1980s. Record low ozone recently observed at some lower latitude locations (e.g., Mauna Loa) during 1994/95 was probably mainly due to stratospheric circulation changes rather than to chemical causes. Re-analysis of ozone measurements from the Total Ozone Mapping Spectrometer (TOMS) aboard the Nimbus-7 satellite has been carried out recently. However, detailed comparisons between the re-analyzed data and the earlier (version 6) TOMS data, the other satellite data (e.g., SBUV and SBUV/2), and the ground-based ozone measurements (Dobson instruments) are yet to be published.
Substantial progress has been made in the estimation of global surface UV levels through the assimilation of satellite-derived data into radiative transfer models. In contrast to earlier models, which accounted only for variations in ozone, these new techniques appear promising for including also the effects of clouds and possibly aerosols on UV transmission. One study, based on 1979-1992 ozone and cloud reflectivity data from TOMS (version 7), gives erythemal UV trends that are smaller (by 10-50%, depending on latitude) than the cloud-free trends previously estimated from TOMS version 6, SBUV and SBUV/2 ozone data. However, clouds had only a minor impact on the trends of the new study, and the discrepancies appear to result from the lower ozone trends estimated from the new version 7 TOMS data.
The record of direct UV measurements is still too short for reliable estimation of long-term trends. However, recent measurements at both polar and middle latitudes show the expected relationship between episodic ozone decreases and UV increases. Surface UV- monitoring continues to expand, with international coordination under the auspices of the World Meteorological Organization (WMO) and the Network for Detection of Stratospheric Change (NDSC). Several international comparisons of monitoring instruments have been carried out, and confirm earlier estimates of usual agreement at the 5% level in the UV-A and 10% in the UV-B. Intercomparisons among UV radiation models, and between models and measurements are also being carried out or planned.
The effects of clouds on atmospheric and surface radiation have received considerable theoretical and observational attention in the last year. Topics of active research have included the spectral dependence induced by clouds (showing more effective transmission of UV-B than visible radiation), and the complex effects of non- uniform and broken cloud fields.
Health Effects
The principal impacts of UV on health are mediated through two organ systems, the skin and the eyes, which receive all of the exposure. These systems are generally either well adapted to (the skin) or well protected from (the eyes) such exposures; humans benefit from UV exposures through the initiation of Vitamin D3 production, and even detrimental effects such as DNA damage, are normally corrected by efficient repair mechanisms. Our average day-to-day exposure to UV is generally sufficient to ensure appropriate levels of Vitamin D. There is some evidence in tissue culture that Vitamin D has inhibitory effects on tumor cell growth. Such effects have been suggested as the mechanism underlying an observed increase in breast and colon cancers at higher latitudes (where solar exposures are less). This linkage is still conjectural, however. The production of the biologically active vitamin is self- limiting so that excessive exposures are not likely to be associated with any benefit.
New findings with regard to the molecular events underlying UV- induced nonmelanoma skin cancer extend the earlier observations that these tumors often have alterations (mutations) in a particular tumor suppressor gene that are typical of UV-B radiation. The recent findings indicate that similar UV-B alterations in a second tumor suppressor gene (ptc) are associated with spontaneous (non- hereditary) basal cell carcinomas (BCC). These data provide the most direct evidence that UV-B radiation contributes to the development of these skin tumors.
Additional studies on the involvement of p53 indicate that the frequency of such typical UV-B alterations in the skin tumors may decrease with lower dose levels and spectral shifts toward the longwave UV-A. An additional finding in UV-induced carcinogenesis comes from recent epidemiologic studies, which indicate that BCC is not principally related to cumulative UV dose, but as with melanoma, appears to be more related to childhood and intermittent over- exposures.
New epidemiologic studies on melanoma for the most part confirm earlier work. Several studies have suggested that sunscreen use may not be protective for melanoma and may even be associated with increased risk. A possible explanation offered to explain these observations is that wearing sunscreens, while reducing UV-B exposure, provides little protection from UV-A exposures and that such exposures are important to melanoma risk. Although such an interpretation is in line with the spectral response of melanoma induction in a fish model, such epidemiologic findings may be biased by linkages among susceptibility, exposure and sunscreen use. New work in the opossum model for melanoma has shown that short-term neonatal exposures to broadband UV-B/UV-A radiation (of approximately a week) result in highly aggressive (metastatic) melanomas.
It is now clear that there are at least three mechanisms by which UV-B exposures may suppress cellular immunity: DNA damage, isomerization of urocanic acid, and through the active metabolite of vitamin D. Immune effects can occur both locally at the skin and systemically throughout the body. The local effects have long been considered important to the development of skin cancer, but there has been little evidence found with regard to the importance of systemic effects. Recent observations of an increase in non- Hodgkin's lymphoma with increasing solar radiation have led to the suggestion that UV-B-induced systemic immunosuppression contributes to cancer development in this system. The implications of either local or systemic immune effects for human infectious diseases are still unknown. Epidemiological studies are still required to explore these issues. There is very little new information on UV effects on the eye. A critical lack is an action spectrum for eye effects associated with chronic exposures, e.g., cataract.
Effects on Terrestrial Ecosystems
Since the last report in 1994, there has been progress on understanding the mechanisms of UV action on organisms. There has also been an increasing emphasis on outdoor studies of nonagricultural vegetation. In such experimentation, the importance of maintaining a realistic spectral balance between UV and longer wavelength radiation during experiments has received more attention. This is important because longer wavelength radiation may have ameliorating effects. The UV-A can also have effects in some respects similar to that of UV-B. In addition to UV-B supplementation studies designed to simulate the consequences of ozone reduction on sunlight, other research of late has involved manipulation of natural solar radiation with filters to show the effectiveness of both UV-B and UV-A on organisms.
Many of the effects of UV-B may not involve damage, per se, but instead be a matter of the plant using this type of radiation as a signal for altering growth form and some physiological processes. One example of such a change is the commonly observed increase in UV-absorbing protective compounds in plant leaves following exposure to UV-B. This may explain, at least in part, many of the seemingly paradoxical results of recent and earlier studies suggesting stimulating effects in plants by UV-B. The UV-B responsiveness is often very specific to species, or even races of a given species, and depends on other environmental factors such as mineral nutrition, drought, local air pollutants, etc. These differential effects on species will likely lead to changes in species interactions and on ecosystem dynamics. Various indirect effects of elevated UV-B radiation are receiving attention, including effects of UV-B on decomposition of plant litter, which may influence cycling of nutrients. Other indirect effects include influence on plant pathogen susceptibility and plant attractiveness to herbivores and pollinators. Many of these indirect effects may be UV-B action mediated through changes in plant structure, secondary chemistry and timing of life cycle events. Nevertheless, these effects may ultimately be the most important on ecosystems. This is not to dismiss more direct, apparently detrimental effects of UV-B on organisms, including microbes and lower plants such as mosses. The peat-forming moss, Sphagnum, appears to be sensitive which has implications for some processes in biogeochemical cycles such as decreased carbon storage. Trace gas emission from vegetation is also potentially important. One recent study, however, showed no effect of elevated UV-B on emission of isoprene, an important precursor compound for tropospheric ozone formation.
Recent studies suggest that potentially detrimental effects of UV-B radiation in evergreen woody plants may accumulate from year to year as had been indicated in earlier work. Another example of accumulating effects has recently been shown for subsequent generations of native annual plants. With exposure of each generation, the manifestations of adverse effects were intensified. The interacting effects of elevated UV-B with other factors important in global change such as elevated CO2 and temperature are receiving more attention. While elevated CO2 and temperature usually have more pronounced effects than elevated UV-B, there are often interactions among these factors such that the effects may counteract each other or sometimes they may be additive.
Effects on Aquatic Ecosystems
In the recent past, scientific and public interest has focused on marine primary producers and aquatic ecosystems, which resulted in a multitude of studies indicating mostly detrimental effects of UV-B radiation on aquatic organisms. The interest has expanded to include effects in individual species as well as specific responses and has concentrated on ecologically significant groups and major biomass producers using mesocosm studies, emphasizing species interactions. In addition, light penetration into the water column was investigated by several research groups. Macroalgae and seagrasses are major biomass producers in aquatic ecosystems. In contrast to phytoplankton most of these organisms are sessile and can thus not avoid the exposure to solar radiation at their growth site. Recent investigations showed a pronounced sensitivity to solar UV-B, and effects have been found throughout the top 10 - 15 m of the water column. Mechanisms of protection and repair are being investigated.
Controversy still exists regarding the interpretation of data on UV-B effects in Antarctic phytoplankton. Estimates of the decreases in overall biomass productivity by different authors range from 0 - 12 %. Most recently, shifts in phytoplankton community structure have been demonstrated, which may have consequences for the food web. Bacteria play a vital role in mineralization of organic matter and provide a trophic link to higher organisms. Recently, the mechanism of nitrogen fixation by cyanobacteria has been shown to be affected by UV-B stress. Wetlands constitute important ecosystems both in the tropics and at temperate latitudes. In these areas cyanobacteria form major constituents in microbial mats. The organisms optimize their position in the community by vertical migration in the mat which is controlled by both visible radiation and UV-B. Cyanobacteria are also important in tropical and subtropical rice paddy fields where they contribute significantly to the availability of nitrogen. Growth, development and several physiological responses of these organisms are affected by solar UV.
Dissolved organic carbon (DOC) and particulate organic carbon (POC) are degradation products of living organisms. These substances are of importance in the cycling of carbon in aquatic ecosystems. UV-B radiation has been found to break down high molecular weight substances and make them available to bacterial degradation. In addition, DOC is responsible for short wavelength absorption in the water column. Especially in coastal areas and freshwater ecosystems, penetration of solar radiation is limited by high concentrations of dissolved and particulate matter. On the other hand, climate warming and acidification result in faster degradation of these substances and thus enhance the penetration of UV radiation into the water column. UV effects on aquatic animals have found increased interest. In addition to effects on larval stages in amphibia, sea urchins were found to be affected by solar UV-B radiation despite the fact that they have partial protection from mycosporine amino acids, which they take up with their food. Corals have been known to be directly affected by solar UV; in addition, photosynthesis in their symbiotic algae is impaired, resulting in reduced organic carbon supply.
All of the previous studies on UV penetration into the water column were based on occasional measurements. This will be corrected by a recent project involving the development of a monitoring system (ELDONET) for solar radiation in Europe using three-channel dosimeters (UV-A, UV-B, PAR), which are being installed from Abisko (North Sweden, 68° N, 19° E) to Tenerife (Canary Islands, 27° N, 17° W). Some of the instruments will be installed in the water column (North Sea, Baltic Sea, Kattegat, East and Western Mediterranean, North Atlantic), establishing the first network of underwater dosimeters for continuous monitoring.
Effects on Biogeochemical Cycles
Terrestrial studies are continuing to examine the influence of enhanced UV-B radiation on microbial decomposition of plant litter to carbon dioxide and nutrients. Additional studies have confirmed that litter from plants grown under enhanced UV-B is enriched in lignin and decomposed to CO2 more slowly by soil microorganisms. The fate and transport of trifluoroacetate (TFA), a persistent substance derived from the oxidation of certain CFC replacements (HFC-123, HFC-124, HFC-134a), was investigated in a temperate forest of North America. The study indicates that the added TFA was retained in vegetation and soil, especially in the case of wetlands with organic soils. In addition, biological accumulation was observed as was a lack of microbial consumption.
Studies of photodegradation of dissolved organic carbon (DOC) by UV radiation are continuing and expanding. Several studies published over the past year have provided additional evidence that exposure to UV radiation enhances the degradation of DOC to CO2 and ammonium. In addition, low-molecular-weight organic products are produced and are readily assimilated by microorganisms. Volatile compounds are produced by aquatic DOC photodegradation and additional studies of the photoproduction of carbon monoxide have appeared. CO is an important trace gas that strongly influences biogeochemical cycles through its effects on chemical reactions in the atmosphere. Two new studies of marine CO photoproduction have resulted in disparate estimates of global oceanic sea-to-air emissions. These two global flux estimates are two orders of magnitude apart: 10-15 Tg CO year-1 and 1000 Tg year-1 (1 Tg = 1012 g). Total annual emissions of CO from all sources, by comparison, are about 2000-2500 Tg year-1 primarily from fossil fuel combustion and CH4 oxidation.
New modeling approaches are being developed to predict the interactions and feedbacks between climate change and UV-B induced changes in marine biogeochemical cycles. Important links exist between oceanic dimethylsulfide (DMS) production, sea-to-air DMS flux and subsequent changes in the sulfate aerosol-related atmospheric radiation balance. These alterations indicate possible consequences with regard to climate and climate prediction, because DMS is an important source of cloud condensation nuclei over parts of the ocean.
Effects on Air Quality
The photo-dissociation of ozone by atmospheric UV-B radiation is a key reaction that controls urban and regional oxidants, the self- cleaning capacity of the troposphere, and the atmospheric lifetimes of many natural and anthropogenic gases. In the last year, published evidence from theoretical, laboratory, and field studies shows that UV-A wavelengths also contribute to this reaction, and therefore some revision of current tropospheric chemistry models is required. Although quantitative estimates of the implications of this new finding have not been carried out yet, impacts are likely for predicted geographical and seasonal distributions of gases such as methane (CH4) and carbon monoxide (CO), and the sensitivity of tropospheric chemistry to stratospheric ozone depletion. Further evidence for the linkage between stratospheric UV transmission and tropospheric composition was found in the records of surface CH4 and CO concentrations. Temporary increases in tropical CH4 and CO concentrations were observed in the second half of 1991, in phase with high levels of stratospheric sulfur dioxide and sulfate aerosols that resulted from the June 1991 eruption of Mt. Pinatubo. The reduced stratospheric UV transmission is believed to have lowered the rate of CH4 and CO removal, due to decreased photo-dissociation of tropospheric ozone, and therefore decreased hydroxyl radical (OH) production.
The atmospheric chemistry of CFC substitutes and the possible build- up of their breakdown products (particularly trifluoroacetic acid, or TFA) has attracted more attention. The background atmospheric concentrations of HFC-134a (a principal precursor of TFA) are increasing rapidly, according to measurements at Cape Grim, Tasmania (41° S) between 1978 and 1995, and Mace Head, Ireland (53° N) between July 1994 and May 1995. Model estimates suggest that HFC-134a emissions have risen rapidly from ca 0.25x106 kg in 1991 to ca 8x106 kg in 1994. TFA concentrations in air and water samples collected in Germany, Switzerland and Israel in 1995 contained surprisingly high levels of TFA, comparable to concentrations predicted by models for the year 2010. This suggests that an additional yet unknown source of TFA may be present.
Modeling studies give different estimates for future concentrations of TFA in rainwater, e.g., tropical maxima of 0.114 µg l-1 predicted for the year 2020, and a global mean of 0.160 µg l- 1 by the year 2010 predicted by another study. However, other modeling studies have concluded that a number of factors can enhance local concentrations of TFA. The TFA concentrations in the precipitation of arid and semi-arid regions may be 2-4 times greater than the global mean. Furthermore, in urban air where high OH and HFC levels are present, the rate of formation of TFA may be enhanced by an order-of-magnitude or more. Therefore, local TFA concentration in rainwater as high as 2-20 µg l-1 or more appears plausible. Water bodies characterized by little or no outflow and which have high evaporation rates may be susceptible to accumulation of rain-borne TFA, leading to significant concentration enhancements. Model calculations predict that such wetlands could experience concentrations of up to 100 µg l-1 within 30 years, even when seepage is as much as 10%.
Materials Damage
Efforts to refine the wavelength sensitivity data for common polymers have continued, with the commodity polymers polyethylene and polypropylene receiving the most attention. Results from several research groups include data on the relative photodamage to polyolefins, acrylics, polystyrene, and other polymers, caused by exposure to different regions of a solar- simulated source spectrum. With polyethylene, the wavelength range 300-330 nm in simulated sunlight was reported to be most effective in reducing the tensile extensibility of the material, a result in agreement with previous findings. These types of data, referred to here as activation spectra, are useful in the estimation of damage to polymers exposed to UV-enhanced solar radiation that results from ozone depletion. Recent findings have shown that while solar radiation is principally responsible for outdoor degradation of polymers including polyethylene, factors such as temperature and exposure to moisture also have an impact on the useful lifetime of materials outdoors. Several studies have reported on the acceleration of weathering of polyethylene films under harsh desert conditions, where the radiation dose and the temperatures are particularly high.
Research was recently carried out on polycarbonate photodegradation aimed at generating action spectra for the yellowing and molecular-level breakdown of this polymer used in glazing applications. This research also studied the irradiance dependency of the degradation process, an important consideration, since the construction of action spectra and their derivation from polychromatic exposure experiments assume the damage process to be irradiance-independent within the range of irradiance encountered in the experiments. The findings facilitate the intercomparison of previously reported wavelength sensitivity data for polycarbonate polymers. An on-going study is aimed at separating out the contributions of solar radiation and temperature, to the damage suffered by polyethylene polymers during outdoor exposure. The data will allow a better understanding of the role of temperature in modifying the UV-induced photodegradation of polymers exposed to UV-enhanced sunlight resulting from ozone depletion.
Future Effects Studies
The global environment is experiencing a wide range of perturbations. Increased greenhouse gases, sulfate and dust aerosols and increased UV-B from ozone depletion are all occurring simultaneously. Assessment of the potential risks from such changes needs to consider the full context in which these changes are taking place and must take into account the many interactions that may occur. This will require a long-term integrated, interdisciplinary research program designed to include studies which evaluate not only UV-B but also the other processes which are contributing to global environmental change. Health: Each 1 % reduction in ozone may cause as much as 6 % increase in skin cancer cases annually from exposure to UV radiation. The principal impacts of UV on health are mediated through two organ systems, the skin and the eyes, which receive all of the exposure; humans do benefit from UV exposures through the initiation of Vitamin D3 production, and even detrimental effects such as DNA damage, are normally corrected by efficient repair mechanisms. Our average day-to-day exposure to UV is generally sufficient to ensure appropriate levels of Vitamin D. The production of the biologically active vitamin is self- limiting so that excessive exposures are not likely to be associated with any benefit. There are at least three mechanisms by which UV-B exposures may suppress cellular immunity: DNA damage, isomerization of urocanic acid, and through the active metabolite of vitamin D. Immune effects can occur both locally at the skin and systemically throughout the body. The local effects have long been considered important to the development of skin cancer, but there has been little evidence found with regard to the importance of systemic effects.