71

MAPPING MATERIAL DAMAGES OF LIMESTONE AND SANDSTONE ON THE TERRITORY OF THE EUROPEAN PART OF RUSSIA

MIKHAILOV, A.A. AND SULOEVA, M.N.

Institute of Physical Chemistry, Russian Academy of Sciences, Leninski Prospekt 31, 117915 Moscow, Russian Federation

KEYWORDS: limestone, sandstone, climatological influences, air pollution, dose-response function, dry&wet deposition, mapping.

SUMMARY

The results of the estimate of the material damages of limestone and sandstone on the territory of the European part of Russia are reported. This estimate is made using dose-response functions obtained under the UN/ECE International Co-operative Programme on Effects on Materials, including Historic and Cultural Monuments. The average annual temperature, relative air humidity and precipitation data for many years are used for calculations. The SOrdata are used for the period 1991 : for low polluted areas - the S02 UNEP/WMO data prepared by the EMEP Meteorological Synthesizing Center-East and the World Meteorological Organization, for towns and industrial centres - the maximum measured annual values obtained by the Governmental network of observation and air pollution control stations. The effect of dry (in terms of [S02]x[time of wetness]) and wet (the total amount of deposit H+ in rain) deposition on these stone materials are considered. It is concluded that almost on all territory of the European part of Russia the effects of wet deposition are small because of neutral pH values. The mapping are made using EMEP scale (150x150 km). The maps alloy us to divide the regions according to the environmental parameters and material damages of the limestone and sandstone, as a first approximation, and to distinguish regions with large damages for future more detailed mapping.

1. INTRODUCTION

Limestone and sandstone as an important building materials has been included in the list of materials for investigation within the UN ECE International Co-operative Programme on Effects on Materials including Historic and Cultural Monuments. This Programme involves 39 exposure sites in 12 European countries together with the United States and Canada. The major objective of this programme is the development of the dose-response functions for the calculation of the rates of the material deterioration including the estimate of the dry and wet deposition (UN/ECE ICP, 1988). The results obtained are recommended for the assessment of material damages, so called acceptable levels of pollutants for different materials and geographical are as where they are exceeded at different pollution scenarious, as well as for calculation of economic damage, and related mapping (Kucera et.al. , 1995; Kucera and

Fitz, 1995; Manual, 1996). This paper presents the results of mapping the European part of Russia in terms of the environmental

parameters and material damages of the limestone and sandstone.

2. DOSE-RESPONSE FUNCTIONS

The dose-response functions were obtained on the basis of the results of 4-year exposure of specimens of Portland limestone and White Mansfield dolomitic sandstone. Stone tablets 50x50x8mm+2mm) were prepared before and analysed after exposure by sub-centre responsible for them - Building Research Establishment, Watford, UK (Coote et al., 1991; Coote et al., 1993). At the sites stone tablets were fixed, to hand vertically, from the arms of carousels that were free to rotate about a vertical axis in

order to eliminate directional bias. For an unsheltered exposure the dose-response functions can be

written as (V.Kuceraet.al., 1995; Kucera and Fitz, 1995; Manual, 1996):

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Limestone ML= 34.4 + 5.96*TOW*[S02] + 388*Rain*[H•]

Sandstone ML = 29.2 + 6 .24*TOW*[S02] + 480*Rain*[H+]

where ML - mass loss, g/m2;

TOW - time of wetness (Rh>80%, T>0° C), time fraction ;

S02 - yearly average concentration, ug/m3

;

Rain - amount of precipitation , m/year;

H• - yearly concentration, mg/I;

R2

0.66

0.63

(1)

(2)

Time of wetness may be represented by regression equation on the basis of average annual relative

air humidity (Rh) and temperature (T) data (Mikhailov et.al , 1994)

R2

TOW = -10700 + 176*Rh + 120*T 0.74 (3)

where TOW - hours/year; Rh - %; T - ° C.

Equation (3) is valid for the range of annual temperature 0 < T < 16° C. An analogous equation we

obtained for the assessment of TOW for the range of negative annual temperatures (-17 < T < 0° C) on

the basis of the results of the I PS/RAS Programme in the Far East:

TOW= -1016 + 45*Rh - 92'1 T I 0.63 (4)

The results shows that the mass loss of these stone materials depends both on dry deposition of S02

(in terms of [S02]*[TOW]) and wet deposition (the total amount of deposit H+ in rain) . In according with

the dose-response functions (1-2) dry deposition of S02 has the dominating effect on the damage of

these calcereous stone materials, especially in urban and industrial regions. It is obvious that the effect

of wet deposition may be significant in background acidifying regions.

3. MAPPING OF THE ENVIRONMENTAL PARAMETERS

In our work we used the climetic data collected during many years (Sci.-Appl. Ref. Book, 1988;

Mikhailov et al. , 1993). Fig. 1-4 shows the results of the mapping of the European part of Russia in terms

of averade annual temperature and relative air humidity, yearly amount of precipitation and time of

wetness. The mapping are made using EMEP scale(150x150 km). For the mapping, each square of

the grid was given the parameters of a city with the largest population or (in the absence of such a city) the maximum values (Mikhailov et al. , 1995).

The average annual temperature in the European part of Russia changes from -8° C in the north

eastern part to +15° C in the south. The range of the changes in the relative air humidity is from 65 to 89

%. Accordingly, the TOW in this part of Russia changes over a wide range from 0.15 to 0 .54 part of year or approximatelly from 1300 to 5000 h/year.

In the north eastern part, relatively low TOW values are mainly due to temperature factor, whatever

high the relative humidity (up to 80-89 %). In the south eastern part, low TOW values associated with

low air humidity. In the central , western and southern part (on the 46% of the territory), increased TOW contribute to deterioration processes.

The amount of precipitation is moderate (0.18 - 0.60 m/year) on the most part (79 %) of the territory and

increase in the piedmont regions (the Caucasus, the Ural) and on the Middle Russian Height. In

mountain regions the value of parameters within one square may vary over a wide range.

Fig. 5 shows the results of the mapping of the territory in terms of the pH values of precipitation. It is

necessary to note that this map is obtained on the basis of available pH data and tentative map of

73

distribution of the pH values on the territory of Russia prepared by Main Geophysical Observatory, Sankt-Petersburg. The pH values of precipitation are neitral almost on all territory of the European part of Russia.

The SOrdata are used for the period 1991 . Taking into account that materials are concentrated mainly in a cities, for the mapping each square of the grid was given the maximum annual values of S02 in a city of industrial centre (SOr data of the Governmental network of observation and air pollution control stations). In absence of such acity or industrial centre (for low polluted areas) are used the calculated S02 UNEP/WMO data prepared by the EMEP Meteorological Synthesizing Centre-East and the World Meteorological Organization (UNEP/WMO, 1994). Fig. 6 shows the assistante map [S02]*[TOW].

4. MAPPING OF THE LIMESTONE AND SANDSTONE DAMAGES

Fig. 7-8 shows the results of mapping of the 4 year material damages of limestone and sandstone. In according with methodologies of the mapping of material damages and acceptable levels of pollutants (V.Kucera et.al. , 1995; Kucera and Fitz, 1995; Manual, 1996) the background defined as a constant, for each exposure period, using 10-percentile of the corrosion attack at the 39 test sites. The preferably recommended values of the background daterioration rate (BDR) after 4 year of exposure for limestone is 44 and for sandstone is 40 g/m2 in regions with time of wetness 2000-6000 hours/year or time fraction interval of 0.23-0.68 (the interval covered by ICP Materials Programme). Therefore the intervals of the range of mass loss of these stone materials on fig. 7-8 correspond to the intervals of< BDR, 1-1 .5, 1.5-2, 2-3 and 3-4 BDR. It seems that the dose-response functions obtained are hardly applicable to the square 31-37. In this square the maximum S02 level in Mednogorsk in 1991 is significantly higher (more than two times) that upper limit of S02 interval (1-80 uglm3) covered by the ICP Programme. The maps alloy us to divide the regions according to the environmental parameters and material damages of the limestone and sandstone, as a first approximation, and to distinguish regions with large damages for future more detailed mapping. Obtained results are certainly preliminary. The maps of material damages of the limestone and sandstone will be revised as new experimental input data become available and as new UN/ECE ICP dose-response functions will be obtained on the basis of the results of 8-years of exposure.

5. CONCLUSION

Damages of the limestone and sandstone has been modelled for the first time for the territory of the European part of Russia according to the UN/ECE ICP dose-response functions obtained after 4 year of exposure and based on the available environmental data. The dry deposition of S02 has the dominating effect on the damage of these calcareous stone materials almost on all territory of the European part of Russia. The maps on a 150 km square grid allow us to divide the regions according to the environmental parameters and material damages of the limestone and sandstone and to distinguish regions with large

damage for future more detailed mapping.

ACKNOWLEDGMENTS

This study was supported by the Programme "Ecological Safety of Russia".

REFERENCES

Coote A.T., Yates T.J.S., Chakrabarti S., Bidland D.J., Ridal J.P., Butlin RN.: UN/ECE ICP on Effects on Materials. Evaluation of decay to stone tablets: Part 1 . After exposure for 1 year and 2 years. Report No.4. 1991. Building Research Establishment, Garston, Watford, UK.

74

Coote A.T., Yaites T.J.S., Chakrabarti S., Murray M.J., Butlin R.N.:UN/ECE ICP on Effects on Materials. Evaluation of decay to stone tablets: Part 2. After exposure for 4 years. Report No.13. 1993. BuildingResearch Establishment, Garston, Watford, UK. Kucera V., Tidblad J., Henriksen J., Bartonova A., Mikhailov A.A. :UN/ECE ICP on Effects on Materials. Statistical analysis of 4 year materials exposure and acceptable deterioration and pollution levels. Report No.18. 1995, Swedish Corrosion Institute, Stockholm, Sweden. Kucera V., Fitz S.: Direct and indirect air pollution effects on materials including cultural monuments. Acid Reign'95, 5th International Conference on Acidic Deposition, Goteborg, 1995. Water, Air and Soil Pollution 1995, 85, P. 153 - 165. Manual on Methodologies for Mapping Critical Loads/Levels and Geographical Areaswhere they are exceeded. Final Draft prepared by the Task Force on Mapping with the assistance of the Coordination Center for Effects (CCE). 1996, Budapest, Hungary. Mikhailov A.A. , Suloeva M.N., Vasil'eva E.G.: Data base on atmospheric corrosivity in towns and industrial centres on the territory of the former USSR. Workshop on Critical Levels for Buildings Materials, including Cultural Heritage. 1993. Bath, UK. Mikhailov A.A. , Suloeva M.N .. Vasil'eva E.G.: 1994, Propection of Metals, 30, P. 329 - 335. Mikhailov A.A. , Suloeva M.N., Vasil'eva E.G.: Environmental aspects of atmospheric corrosion. Acid Reign'95, 5th International Conference on Acidic Deposition, Goteborg, 1995. Water, Air and Soil Pollution 1995, 85, P. 2673-2678.

Scientific-Applied Reference Book on the climate of the USSR. Series 3. Many years data. 1988, Gidrometeoizdat, Leningrad (in Rissian). UN/ECE ICP on Effects on Materials. Technical manual. Report No.1. 1988, Swedish Corrosion Institute, Stockholm, Sweden.UNEP/WMO: MAP Technical Reports Series No. 85. Erdman I., Sofiev M.,Subbotin S., Dedkova I. et al,. - EMEP MSC-E, Moscow, and Soudine A., WMO, Geneva. 1994, UNEP, Athens.

=~ 2 ~ :~ :;. _ _ :s 20 ... ~ ze 29

Ranges: [Zl-8 . o ~0 1 . 3

831 3 1 ·6

~6 1 . 9

. 9.1 . 15

Unit s: C

Dalo: AVERAGE ANNUAL TEMPERATURE

&.33 32

roster . EMEP

pro1ecl 1on: Polar Stereogroph1c

Dote·

ECOPOLL 250 km MAG

Fig . 1. Map of the average annual temperature for the European part of Russ ia

: : : . 2:

1 1:; I_...&_ ~

~ Ii 1

'o

:9 I (I I J)_ !f ; I, . I I I (

Ranges: tzj 65 -71

Dalo: AVER AGE ANNUAL RELATIVE AIR HUMIDITY

[Jn-1" m1s-11 ~78-80 . 81-89

Units:%

39 rosier: EMEP

~ pro1ecl1on: Polar Stereographic

Dole· 1

ECOPOLL 250 km MAG

Fig. 2. Map of the average annual r elative ai r humid i t y for the European part of Russia

-.....! 01

:~ 21

Jl

J2

JJ

JG

JS

J6

J7

38

J3

Ranges: Dalo:

IZl 0.15 - 0.22

~023-0.30 mo.31 - 0.37

~0. 38 - 0.44

. 0.45 - 0.54

Unil s: PART OF YEAR

T !ME OF WETNESS

30 32- rosier: EMEP

..

pra1ec lion: Polar Slereogrophoc

Dole:

ECOPOLL Z50 km MAG

Fig . 3. Map of the time of wetness for the European part of Russia

't >>-~ ,,.:

2?

2 3

2 "

25

26

27

JI

J2

JJ

JG

J7

38

i ~l

39

: :: 2i: ~ - .: ~ .: ;

r J

Ranges: Da lo: AMOUNT OF PRECIPITA TION IZJo.18 - o.30

[J0.31 - 0.45

mo.1. 6 - 0.60

~061 -1.00

. 1.01 - 1.80

Un1ls: m

48

32 -" 3- :o 3o 3-1 I.

jl

rosier : EMEP

pro1ec l1on: Polar Slereogrophoc

Dote·

ECOPOLL Z50 km \ MAG

Fig . 4. Map of the amount of precipitation for the European part of Russia

......, (j)

Ranges: Dalo: 01. 6. 5.0

~5. 1 . 6.0

8316 1 . 7 0

11nil s· pH VALUE

pH OF PRECIPIT ATION

68

Ji ros ier. EMEP

pro1ec lion: Polar Slereograph1c

Dole:

ECOPOLL Z50 km MAG

Fig . 5. Map of the pH of precipitation for the European part of Russia

2~ 21 z 2 z 3

.s~l

37

38

39

Ranges: Dalo: IS02lx1TIME OF WETNESS! 00 ~ I.I . 5

831 5 1 . 10

~ 10 . 1. 20

• ) 20

Unil s: ug/ m3 · 1PART OF YEAR)

51

L rosier: EMEP

projection. Polar Slereogroph1c

Dole

ECOPOLL 2so km MAG

Fig. 6. Assistante map of [so2 ]x[time of wetness) for the Eu ­ropean part of Russia

........

........

.. <,.-~ ... ~

J·~J I l~iil 111 JS

JG

J7

38

Ranges: Da lo: MASS LOSS OF LIMESTONE D < l.l.

~ G5 - 66

m 67 _ 88

~ 89 - 132

. 132 - 176

Unds: g/m2•1G yeorsl

61 ro sier: EMEP

pro1ecl1on: Polar Slereogroph1c

Dole

1 6 ECOPOLL t:<'.'.'.1;'._21fI;j;jtE:J!!L.:1~ zsokm MAG

F i g . 7. Map of the predicted deterioration rate of limestone for the European pa rt of Russia

Ranges: Dalo: MASS LOSS OF SANDSTONE IZJ < GO

~ Gl - 60 m 61 _ 80

~ 81 - 120

. 120 - 160

Uni ts: g/ m2,(G yeorsl

63 roster: EMEP

L pr o1ec l1on: Polar Slereogroph1c

Da:e·

ECOPOLL 2so km MAG

Fig . 8. Map of the predicted deterioration rate of sandstone for the European part of Russia

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