Atmospheric Environment Vol. 26B~ No. 2, pp. 24l 247, 1992, 0957 1272/92 $5.00+0.

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Printed in Great Britain. © 1992 Pergamon Press Ltd

ACID RAIN A N D DETERIORATION OF MONUMENTS:

HOW OLD IS THE P H E N O M E N O N ?
DARIO CAMUFFO
Consiglio Nazionale Ricerche-ICTR, Corso Stati Uniti 4, 1-35020 Padova, Italy

(First received 10 March 1991 and in final form 20 December 1991)

Abstract The first known articles on acid rain appeared when atmospheric pollution reached high levelsin
the industrial towns of England. Research was carried out to ascertain and interpret earlier documentation,
mainly written or printed in Italy, that could throw new light on both the environmental history and the
relationship between present-day pollution and weathering of monuments. Very important discussions on
dispersion and transport of airborne pollutants, atmospheric scavenging,acid rain, as wellas descriptions of
effects on fruit, monuments and people, were found in scientifictreatises of the 1600sand 1700s.The cause of
acidification can be found in volcanic activity, especially that of Stromboli, Vulcano, Vesuvius and Etna,
which increased in the 17th and 18th century. Although in the past some pollutants may have reached higher
concentrations locally than at present, nowadays air pollution has become a global problem; there are many
new species of pollutants and catalysts, and their combined action has increased impressively the
environmental risk and the deterioration rate of historic buildings and monuments.

Key word index: Air pollution, acid rain, volcanic activity, monument weathering

1. INTRODUCTION seen today on our monuments, then certain proverbial

phrases, such as the following, could be considered
Today, acid rain and the deterioration rate of historic under a new light: "What is harder than rock? and
buildings and monuments has reached alarming lev- what is softer than water? And yet, the hard rock is
els, although this phenomenon is as old as pollution made hollow by the soft water" (Ovid, Ars Amatoria 1,
itself, being either natural or of an anthropic nature. 475-476) or "The dripping of droplets hollows out
The question is, whether it is really true that the stones" (Lucretius, De Rerum Natura 1,314), where the
threshold has only been reached recently, in terms of acidity of the water may possibly have made the
environmental risk. dissolution of stones easier.
It is clearly impossible to find precise indications The extensive damage to the environment and
about acid rain in the very distant past, i.e. the Greek monuments, raises today new and urgent problems to
or Latin epochs, even in treatises which specifically be faced and resolved. It is necessary to know whether
deal with the salubrity of the air, such as Hippocrates' atmospheric pollution and acid rain are a recent
treatise, "Air, Water, Sites", in that the quality of the phenomenon, or whether we have only recently be-
air was judged on the basis of humidity and odours, come conscious of it, i.e. whether the damage has
especially if these smells were due to the putrification progressed slowly over a long time or has it increased
of organic material. In practice, the only polluting dramatically?
agents that the ancient scholars were capable of A study on the trend of the nitrate component in
recognizing were odours and smoke. Moreover, the acid rain by Brimblecombe and Stedman (1982) has
effects of these agents seemed quite clear to them, shown that this has increased alarmingly over the last
judging from this observation by Seneca: "The higher century. This would lead to lhe assumption that the
one climbs and the further away one is from the filth of nitrate has played a modest role in the acidification of
the ground, the purer and less contaminated is the air" rain in the past. Sulphur dioxide is considered the
(Nat. Quaest. IVB, 10, 1). Seneca also mentions water main precursor in the acidification of rain (Schneider,
pollution: "Why does water taste differently in differ- 1986) and great attention should be paid to this.
ent places? For four reasons. The first is the type of soil In literature, the history of air pollution (Stern,
from where it comes. The second depends on the soil, 1968; Perkins, 1974; Brimblecombe, 1987) begins in
whether it arises from its transformation [they be- Britain, with complaints about the smoke because of
lieved that the springs were the result of a direct the extensive burning of coal and, in modern times, it
transformation of the soil into water]. The third from is essentially related to the industrial development.
the air which is transformed into water. The fourth due There are no large-scale, detailed evaluations about
to the corruption of the water when it is contaminated the concentration of SO2 in the past, although one
by pollution agents" (Nat. Quaest. III, 20, 1). study, starting in 1700 (Brimblecombe, 1987), has
Moreover, if the acidity of the rain is to be judged on shown that in London, the maximum sulphate content
the basis of its capacity to dissolve stone, as can be in the emissions occurred near the end of the 1800s.

241
242 D. CAMUFFO

Thus, the most intense washout should have occurred part, attenuated by the strength of the flames, is
in London, Manchester and other industrial towns transformed into a black sooty vapour. It is certain
during that period. that only a very small part of this remains on the
Two famous papers by Angus Smith (1852, 1872), at ground. The same sulphur, if it is alone, is transported
present considered the earliest documents about acid away by the air, once it has been transformed by heat
rain, appeared in 1852 and 1872 and concerned obser- into minute particles" (p. 245).
vations made in urban Manchester where the rural "Also the winds themselves, when they transport the
pollution by ammonia was overcome by urban emis- air with all it contains from place to place, always
sions of sulphur compounds: "All the rain was found move materials from the places where they originated,
to contain sulphuric acid in greater proportion as it and gradually change the composition of the air,
approached the town, and with the increase in acid continually removing substances belonging to one
there was also an increase in organic m a t t e r . . . W e place and giving back always those which have been
may, therefore, easily find three kinds of air: that with taken up a short time before" (p. 248).
carbonate of ammonia in the fields at a distance, that Rainfall was described as scavenging the atmo-
with sulphate of ammonia in the suburbs, and that sphere, in very correct terms; the long-range transport
with sulphuric acid, or acid sulphate in the town." In of pollutants and the negative effects of acid rain were
the second half of the 1800s, atmospheric pollution well known: "From the first we will speak of rain. This
had reached such levels in the industrial towns of could be called a real and proper agent that washes the
Britain that people and scientists of the day were atmosphere, and that collects all types of bodies that
aware of them. Therefore, the beginning of the acidity are suspended in the air. Which and how many these
in rain should be moved back in time and it may be are, the treatise on the atmosphere quoted above
reasonable to expect that some information about the makes clear . . . . The bodies are volatilized spontan-
diffusion of sulphur and nitrogen compounds in the eously or by fire, fermentation, putrification, separa-
atmosphere can be found and, possibly, about acid tion or effervescence. Thus, the salts, spirits, oils,
rain too. The present work is aimed at seeking and soaps, the earth, the metals themselves can sometimes
interpreting early documentation, mainly written or reach the same state. But all these materials are
printed in Italy, that may throw new light on both the volatilized in different ways depending on the causat-
environmental history and the relationship between ive agent, which may be the heat of the sun, under-
present-day pollution and the deterioration rate of ground fire, household fire or the heat mechanically
historic buildings and monuments. generated by workers" (p. 299).
"These substances which were initially held in the
2. EVIDENCE F O R A T M O S P H E R I C P O L L U T I O N IN THE ground linked to other bodies by the cold, are liber-
1600S AND 1700S ated by the heat, dispersed in the air and mixed with
the rain. But in the sky meteorological situations have
Searching through old books, it was surprising to been observed which every day cause the type of rain
find that in the 1700s, scientists had very clear ideas on which falls to vary in an impressive manner. However,
the diffusive potentials of the atmosphere and the the rain that falls to the ground after long periods of
transport capability of the wind. Some interesting drought will be very different from that which falls
quotations are made herewith, starting with a treatise during the rainy period. Consider everyday experi-
written in 1731 by a physician from Leyda, Herman- ence. The water of storms is different from others,
nus Boerhaave, and published at Venice in 1749. The without speaking of the effects of the winds, which
author was accurate, also making reference to the carry atmospheric water from place to place; for this
source of the information, often quoting the name of reason, with persistent winds which always blow
journals or books, volume and page. It is very inter- violently from one zone only, the rain is full of
esting to read his advanced ideas on diffusion: "I know emissions belonging to that remote zone. The winds
for certain that the same earth, which supplies a perturb these bodies [i.e. emissions], they mix them
fundamental constituent for living beings, because of with the rains, they disperse them, carrying them from
its lightness can reach such a [physical] state as to be distant places and sometimes form a mixture which is
removed from soil and fly into the sky. Why? And thus so wonderful that it is a joy when such rains irrigate
the soot deposited by the smoke at the top of very high the plants and the fields. The frequent observations of
chimneys by the combustion of plants, and in chemical the rains falling from the sky during the hot season,
distillation it is transformed into pure earth in a and collected in vases which have been carefully
noticeable quantity. And thus we are certain that the cleaned and then observed for a long time, shows that
smoke which wanders freely in the air carries upwards it putrifies spontaneously being transformed into a
along with it, the earth itself, spreading it everywhere" fetid and putrid lattice" (pp. 229-300).
(p. 243). "The rain which falls in the hot seasons, with strong
"These fossile compounds called sulphurs each time winds, in urban areas, in lowlying [or humble] places
they are burnt, are so completely dispersed in the air consists of very impure water, where putrification
that they disappear: the saline and acid parts are occurs, where animal and vegetable products, and
transformed into suffocating emanations; the oily products of any other nature are dispersed in the air by
 Acid rain and monument deterioration 243

man in great quantities and in various ways. And the pollens, and their different explanations reflect this geo-
rain coming from such places will be even more graphical difference.
impure if the air has been very nebulous, dense and In the following quotation by Fabri, there is the
fetid, such as to carry to horrendous odour to the earliest clear mention of acid rain and its effects on
nostrils, air and emissions that are harmful to the agricultural production. It is of particular importance
lungs. This bad odour often arises for unknown because it was written two centuries before the reports
reasons, and also goes away for no known reason, by Smith: "A certain type of rain causes spot damage
without leaving any trace, and as it has gone, so too, to the fruit, and sometimes the whole fruit is burned,
does it return quite casually" (p. 302). e.g. the rain that falls during the hottest hours in the
"We know from experience that after long intense middle of the day, with rarer but larger drops; as it
periods of drought, periods of continuous hot weather, evaporates rapidly leaves some acid particles on the
that suddenly, after great claps of thunder, heavy rains fruit. Due to their great capacity to acidify, the fruit is
fall which, if collected in carefully cleaned vases, burned, dessiccated, or undergoes spot lesions, or
generate a froth which seems to contain some minute some other damage" (Fabri, 1670, p. 414).
salts similar to nitrates . . . . Thus it is possible to This observation is of great importance because of
understand how such rain can provide greater fertil- the meticulous description which it gives and which
ization for plants. The rain carries these impalpable leaves no doubt about its reliability. It was confirmed
substances in such a way as to administer nutritional 74 years later by Crivelli, who added another inter-
solid and liquid particles to the plants, while it is even pretation of the blood rain, based on the aspect of
an ideal vehicle for the transport of all those things laboratory solutions of acids or alkalis. This claim
that are necessary for their nutrition" (p. 302). may be debatable, but is very expressive: "Especially
In practice, Boerhaave was aware that rainfall during the summertime several mineral substances are
contained gases and particles dispersed in the atmo- lifted [into the air] together with vapours. Such
sphere, but he considered this a positive factor for minerals have several different characteristics and
vegetation (i.e. "necessary for their nutrition") and not properties: for often during the summertime there is
a cause of damage to plants. rainfall with different aspects, and extraordinary
In the previous century, in an extensive treatise of things occur. As a consequence, sometimes rains are
physical and meteorological sciences by Honoratus useful, sometimes dangerous; sometimes they burn the
Fabri (1670), there is a part which deals with "impure" foliage and fruit on to which they fall. For that reason
water. An entire chapter on rain is included, and rain sometimes their colour is yellow or blood red, and that
containing the red Saharan dust which in Medi- struck terror into people's hearts, who believed that it
terranean Europe is often the cause of alkaline pre- was made of blood. We can observe the same colours
cipitation (Camuffo et al., 1984), is also discussed: when we dilute acidic spirits in water, or alkaline salts,
"Sometimes rain of a different colour and smell falls, or sulphur, and so on" (Crivelli, 1744, p. 45)
both because of the mixing of different air masses and Some 50 years later, another Italian physicist wrote:
because of different maturation. Sometimes red rain "Laboratory analyses made by Bergman showed that
can be seen; but that colour was due to the inclusion of snow contains calcareous sea salt and some traces
certain red lime corpuscles which, in the air sometimes of nitrous acid. These substances are found more
seem to condense by accident. Although there is abundantly in rainwater" (Poli, 1798, Vol. 4, pp. 3-4).
nothing strange in this, the common people think that
it sometimes rains blood" (Fabri, 1670, p. 414). The 3. LIMITS T O THE POSSIBILITY O F EXTRACTING
phenomenon is described because of the peculiar INFORMATION
cotour and to explain the common belief about the
raining of blood, although not from the chemical point Many other mentions of sulphur and nitrogen
of view, mostly because this type of rain does not cre- compounds suspended in the atmosphere can be
ate any ecological problem. On the contrary, it pro- found, but these quotations cannot always be accepted
vides natural liming of acid areas (Camuffo, 1990a). literally. In the 17th and 18th centuries, theoretical
However, pollens were also responsible for colouring concepts were absolutely pioneering, being in different
rain: "The same pollen taken from the tips of the flowers ways derived from the Greek philosophy (mainly the
of the male willow and transported from these trees to atomistic theory of Democritus, the four elements of
distant places and therefore, the wind dropping, and Aristotle, i.e. earth, water, air, fire) and three principles
falling from the sky, was wrongly exchanged for sulphur of the Mediaeval alchemy, i.e. salt, sulphur, mercury
dust on the part of the ignorant, and then the credulous (Agazzi et al., 1977).
people believed in sulphur rain (Act. Britann. T.III) and The discovery of refrigerating mixtures in conjunc-
in truth this pollen of a bright red colour led them to tion with the atomistic theory had led to the idea that
believe in rains of blood" (Boerhaave, 1749, p. 243). cold was due to nitre particles suspended in the
Fabri, living on the Mediterranean coast, was familiar atmosphere. It was not possible to carry out any
with the precipitation of Saharan dust and brownish quantitative microanalysis of the quality of the air or
rain; on the other hand, Boerhaave living near the North water to measure the concentration of sulphur or
Sea coast had more experience of rainfall coloured with nitrogen, given the experimental limitations, and the
244 D. CAMUFFO

proving of any hypothesis consisted of reproducing centuries ago: "Also lead, copper, iron when coming
the weather situation in the laboratory, by mixing the into contact with the air are transformed into splin-
refrigerating compounds and checking that these did, ters, material of a lime-like consistency, dust. Then
effectively, reach low temperatures. they finish as rusts, verdigris and white lead. Success-
The suspected cause of cold can be found in an ively, once they have been transformed into impalp-
explanation by the Paduan physicist-meteorologist able dusts, they are seen to be dispersed in the air,
Giovanni Poleni, in one of his letters written in 1740: carried away by the wind. This phenomenon is less
"With reference to the cause of the exceptional cold common with silver, as with gold, or tin: because their
periods, it would be possible to know and say some- saline, volatile, acid, nitrous or marine solvents can
thing certain, if the time ever arrived in which it barely be supported by the air, if not near chemical
appeared most manifest that it could be seen that each industries. On the other hand instead, in America, the
time the spring air is more than usually full of vapour air is so corrosive that it consumes the cooking pots in
so that heavier rain storms than usual occur; because the houses, stone and all metals; as all the British say
each time the air becomes mixed with a much greater unanimously of the air in the Bermudas. There, the
quantity than usual of sulphur particles by which same metals corrode quickly. It seems that, even here,
much more intense storms are set off. Then perhaps it the same thing happens to metal parts exposed to the
will also be much clearer as each time the air is filled air which has always happened to them near gravepits.
with such a large quantity of nitrous particles which They recount, in fact, that fossile materials extracted
are the cause of such severe cold. In fact, that the cold from the ground and exposed to the air, behave in the
[-weather] is born, or anyway its intensity is increased same singular way" (Boerhaave, 1749, pp. 246-247).
above all because the nitre is ignited, is demonstrated Outside industrialized England, that the dissolution
in the first place by the ice made artificially which of building stones and monuments was due to rainfall
freezes more and more (as demonstrated by various was evident a century before the report by Smith,
and convincing experiments) or because of the in- although it was not clear whether the dissolution was
creased percentage of nitre mixed with the ice, or by the consequence of the acidity of the rain or the
the use of more concentrated nitre" (Poleni, 1740, pp. mechanical impact of falling droplets. In fact, at
451-452). Padova the astronomer-meteorologist Giuseppe
Thunder claps and bolts of lightnings were claimed Toaldo (1786) wrote: "With reference to the corrosion,
to be the result of explosions between these hypothe- dissolution, or decomposition that the Greek wind
tical sulphurous and nitrogenous mixtures set off by [i.e. the northeastern Bora] causes on stones and
casual sparks (Crivelli, 1744, p. 156), based on an buildings, I believe that it can be explained by the
anology with the composition of the gunpowder. mechanical action of rainfall. We must start by saying
Boerhaave reports a couple of other examples derived that in Autumn and Winter the near totality of
from the previous century (i.e. 1600s): "It is not rainfall, and especially the most intense, occurs with
possible to doubt from the above (Hooke's theory the Greek wind, although this is generated by the
about hail) that Nitre and Sulphur are necessary to Sirocco [southeastern wind]. Now, the inclined path of
form thunder and lightning. When hard hailstones windborne raindrops causes splashings on mortars
casually collide violently, they provoke a lot of fire, and stones. Bricks and stones always have small or
and this is sufficient to cause loud thunder claps" large fissures, cracks or pores into which water can
(Boerhaave, 1749, p. 238). The above idea was derived penetrate, forced by the wind. The repeated striking of
from Latin writers who claimed that bolts of light- the drops detaches the parts. Often water freezes in
nings were produced by the collision of clouds (see e.g. their interiors and its expansion cracks and detaches
Seneca, Quaest. Nat. II, 32, 2; Lucretius, De Rerum parts, until they fall as powder, and walls are deterior-
Nat., VI, 96-107; Camuffo, 1990b). ated. This can be demonstrated when a wall exposed
Lightning was also claimed to be due to burning to the northeast is completely or partially shielded by
and exploding of the hypothetical "sulphur" dissolved a further wall or building, the shielded part being
in the atmosphere, and it was supposed that during undamaged . . . . This is the reason why it is always
thunderstorms the concentration of atmospheric sul- suggested that the facades of houses should be built
phur was so high that rainfall was unable to extinguish facing the Sirocco and the sides facing the Greek wind,
the burning and the explosions. "It is said, that the fall by building here more resistent walls with very good
of sulphureous rain with a bolt of lightning that, cements and plasters with pozzolana, putting in that
burning, could not be extinguished, neither by water side the rooms where people live in less, or those that
nor by motion (Nova Literaria A 1684, p. 63)" (Boer- are mitigated by fires, such as kitchens or other
haave, 1749, pp. 245-246). Of course, in this context we workshops" (Toaldo, 1786, pp. 132 133).
cannot assume that sulphur compounds were dis- A similar, but less accurate observation, was made
solved in the atmosphere. by the French physician Pierre Thouvenel, who after
the French Revolution came to live in Italy and noted
4. D A M A G E TO M O N U M E N T S
that the deterioration of monuments was greater in
The impact of atmospheric pollutants on both the correspondence with certain stormy wind directions:
environment and buildings was also described some "This negative influence of the Sirocco and especially
 Acid rain and monument deterioration 245

the Libeccio [southwestern wind] is shown on plants, pieces of litmus paper. We do not know whether he
because of the diseases that they cause, as well as on was so ingenuous as to suppose that each corner was
monuments, wall plasters, paintings and also stones, representative for the air flow arriving from the frontal
because of the corrosion that they produce" (Thouv- direction or was so clever as to build shields which
enel, 1797, p. 177). An important point is that people of were able to allow a better exchange of air with one
that time assisted in some deterioration of monuments particular wind direction. The ribbons faded following
and crops, and the damage was related to rainfall and the diurnal path of solar radiation, while the pieces of
acidic particles transported by rain. litmus paper to the east turned slightly red. Toaldo
No special compliants on stone weathering were thought that there was an excess of acid in that region,
found in archive documents written during the Italian even though he admitted that the experiment was too
Renaissance (i.e. 1400s and 1500s), when people were rough and ready to draw any real conclusion (Toaldo,
particularly interested in discovering and describing 1786, p. 132). In any case, his conclusion was substan-
classic monuments. The architect Andrea Palladio, tially correct: at that time the tower was on the
acute and expert observer, in his four famous books on southwestern side of the town, and at Padova the
Architecture (Palladio, 1570, book 2, Ch. 12) wrote prevalent wind direction is from northeast, trans-
that the state of conservation of old buildings, as well porting all the domestic and handicraft-industry pol-
as the upper part of local stones, are an index of the air lutants. An important source of SO2 was the habit of
healthiness (Camuffo and Enzi, 1988). He mentioned burning sulphur when drying cloths in order to make
in particular the damage caused by climatic factors, them whiter. This practice was described by the physi-
and at first sight one could suppose that he was cian Bernardino Ramazzini, who lived in Modena and
probably holding the classic line of Hippocrates. How- Padova and published a book in 1700 on the diseases
ever, the deterioration limited to the upper part of of workers (Ramazzini, 1700, Chs 9 and 14).
local stones (i.e. the part where meteoric water stays Other local, small causes for acidification were
longer and that receives nutrients as well as the present. Although fire was sometime lighted with
maximum amount of solar radiation) is very typical of sulphur rolls (Ramazzini, 1700, Ch. 9), domestic
the biological deterioration (e.g. by lichens) and not of heating, mainly due to wood combustion, was very
rain dissolution that, on the contrary, follows the modest in Italy. Waste products were eliminated
downward path of run off and the direction of wind- incorrectly: workers drained basins of sulphuric or
borne droplets. If we consider that lichens can only nitric acid near their workshops. This bad habit had
live in unpolluted areas, Palladio's description leads to very negative local consequences, but was probably
exclude the conclusion that in the 1500s stone weath- negligible on the larger scale. The worst period, in
ering was mainly due to acid rain. terms of acidity, was said to be the summer (when even
Many very ancient works of art remained, until domestic heating could not be blamed), even though it
recent times, in reasonably good condition, although is not possible to make a valid comparison with the
made of poorly resistant material, such as sandstone. winter, as there was no fruit to ripen.
As the action of rainfall continued for millennia on Several archive sources, as well as recent papers
these monuments, we are induced to suppose that (Lamb, 1970; Bullard, 1978; Simkin et al., 1981;
initially the dissolution of stones was a negligible Romano and Sturiale, 1982; Chester et al., 1985) show
phenomenon, that became more and more evident the activity of the Mediterranean volcanoes. Although
starting in the 1700s, when compliants appeared wide- some early events may not have been recorded or
spread in several regions with different culture. some data may have been lost during the Middle Ages,
the documentation after 1200 can be considered sub-
stantially reliable. These data show that the overall
5. CAUSES O F ACIDIFICATION volcanic activity, after having remained very low for
several centuries, noticeably increased starting from
The problem arises when trying to establish the the second half of the 16th century, and reached its
cause of acidification at that time when industry was maximum in the first half of this one; then dropped
practically non-existent and the population, decim- again. In particular, Etna (38°N, 14°E) increased its
ated by wars and pestilence, was rather reduced in activity beginning from the 16th century; Vesuvius
number: the population of Italy in 1650 totalled (41°N, 14°E) in the second half of the 17th century;
11,543,000, while the total in Europe was 100,000,000; Vulcano (38.5°N, 15°E) at the beginning of the 18th
whereas in 1700 it was, respectively, 13,375,000 and century; Stromboli (38.8°N, 15.2°E) in the second half
115,000,000 (Rossini and Vanzetti, 1986). of the 18th century (Fig. 1). Recently, the Italian
In 1786 Toaldo carried out some experiments on the volcanoes have been recognized to represent a major
acidity of the atmosphere. For approximately 2 natural source of atmospheric sulphuric acidity, espe-
months during the summer, on the four corners of the cially the SO 2 emissions of Etna, which constitute
observatory tower, and protected against the rain, he 1000-2000 ton d-1, on average (Lo~e-Pilot et al.,
exposed various coloured silk ribbons following the 1986).
method described by Robert Boyle a century earlier Other eruptions in the Mediterranean were due to:
(see Brimblecombe, 1987, p. 76), but also added blue Santorin (36.5°N, 25.5°E) with major eruptions in
246 D. CAMUFFO

6O This phenomenon will be extensively discussed in

another paper.
50 _ - - Vulcono
Scientists of the time had some ideas about this
-- Stromboli
situation. Crivelli (1744, p. 77) mentions the great
40
volcanic activity of both Vesuvius and Etna. Boer-
3O haave mentions the long-range transport of ash, quot-
ing also some existing literature: "We should
20 remember that the winds carry in the air, like waves,
the sand from Egypt and Libya and transport the
10
ashes of Etna over great distances; The dusts of
I I Vesuvius were dispersed in the air for over one hun-
0
1000 1200 1400 1600 1800 2000 dred miles. (Act. Britann. Comp T 11 p. 142)"... "The
ashes erupting from the volcano (Vesuvius) were found
300 to have been transported over one hundred miles
away (Act Britann. No. 21, p. 377)" (Boerhaave, 1749,
250 - Vesuvius
p. 243). Probably the author refers to the major
Etno
eruption of Etna which occurred in 1669, the year
200 preceding the publication of the treatise by Fabri.
~sol A similar situation to that described by Fabri was
documented after the Tambora eruption of 1815,
100 which released lots of HF which caused fluorisis to
cattle and vegetation. The lieutenant governor of Java,
50 Thomas Stamford Raffles, made an inquiry and wrote
of many things including: "An injury of a more serious
0
1000 1200 t400 1600 1800 2000 nature threatened the crops of rice.., dust falling
upon the newly transplanted grain in many cases
Fig. 1. Cumulative number o f years characterized by erup-
tions of the Italian volcanoes Vulcano, Stromboli, Vesuvius
destroyed the young p l a n t s . . , its effects were more
and Etna, during the last millennium. powerful towards the period of termination of the
rains. Falling upon the young plants sparingly sup-
plied with water it would, from its clayey nature,
absorb their juices and destroy them" (Brimblecombe,
1650, 1707, and a minor one in 1866; another sub- pers. comm.). In the same year some "corrosive rains"
marine eruption in front of Sicily occurred in 1731. occurred in Italy, that were called "salty" by people
Only few eruptions were particularly violent with (Filiasi, 1816). A more recent example was found at the
ejecta reaching the stratosphere. Minor activity was beginning of this century around Naples, when Vesuv-
very frequent and continued for several years, so that ian emissions damaged local crops (Bottini, 1939).
the emissions mainly remained in the troposphere
causing acidification. In addition to the Mediterran-
ean volcanoes, others played an important role in the 6. C O N C L U S I O N S
acidification of the troposphere over Europe, e.g. 1557:
Hekla, Iceland (64°N, 19.5°W); 1721: Katla, Iceland At one time, anthropogenic air pollution was lim-
(63.5°N, 19°W); 1733?: Lanzarote, Canary Islands ited to relatively few compounds, mainly released
(29°N, 13.5°W); 1783; Laki, Iceland (64°N, 18°W); inside or near the towns, where the majority of historic
1875?: Askja, Iceland (65°N, 17°W); 1866: Santorin. buildings and monuments was concentrated. It was,
Several "dry fogs" (i.e. with low relative humidity) however, unable to account for the total acidification
covered the whole of Italy and sometimes also Europe. that can be deduced from the old writings. A major
These unusual fogs appeared in association with source for large-scale pollution, dry fogs and acidic
purple sunrises and sunsets and were generated by precipitation in Italy, and sometimes over the whole
aerosols emitted by volcanic eruptions. Sometimes, Europe, was due to volcanic eruptions, especially of
their acidity caused serious diseases to people and Mediterranean and Icelandic volcanoes which in-
animals and damage to crops and cannot be confused creased their activity beginning in the 1500s, 1600s
with the Harmattan wind, which transports desert and 1700s.
dust. The most famous fog occurred in 1783 and was The problem has both a qualitative and a quantitat-
attributed by Lamb (1970) to the Icelandic volcano ive aspect. Nowadays air pollution is distributed
Laki, but the Italian volcanos Stromboli, Vesuvius and worldwide and has become a global problem. The
Vulcano were also active in the same period, and increased acidity of both wet and dry deposition is
caused extended fogs in the whole of Italy. Good more active in dissolving monuments. Nowadays
documentation was found for the occurrence of dry there are many species of pollutants and catalysts,
fogs even during the summertime, especially in the several of them are new or recent and with their
period from 1740 to 1832 and then in 1866 and 1869. synergisms may increase deterioration. For example,
 Acid rain and monument deterioration 247

oil-fired carbonaceous particles play an important Camuffo D. (1990b) Clima e Uomo. Garzanti; Milano.
role in the formation of black gypsum crusts on Camuffo D. and Enzi S. (1988) II clima a misura d'uomo e di
marble monuments, due to their catalytic activity and monumento. Arab. Risorse Salute 76, 46-48.
Camuffo D., Del Monte M., Sabbioni C. and Vittori O. (1982)
the absorption of atmospheric pollutants also in the
Wetting, deterioration and visual features of stone surfaces
dry phase (Camuffo et al., 1982). The building-up of in an urban area. Atmospheric Environment 16, 2253-2259.
black crusts is now impressive. Camuffo D., Del Monte M. and Ongaro A. (1984) The pH of
In the past, when pollution levels were low, biolo- atmospheric precipitation in Venice, related to both the
gical deterioration dominated; now pollution has dynamics of precipitation events and weathering of monu-
ments. Sci. Total Envir. 40, 125-140.
killed lichens and algae, at least in the urban environ- Chester D. K., Duncan A. M., Guest J. E. and Kolburn
ment, but the deterioration rate of monuments has C. R. J. (1985) Mount Etna. Chapman and Hall, London.
increased due to the physical and chemical weathering Crivelli G. (1744) Elementi di Fisica. Occhi, Venice.
that occur on the weakened surfaces (Del Monte, Del Monte M. (1989) Report on research projects supported
by the Commission of the European Communities. Eur.
1989). The problem facing conservation cannot be
Cult. Heritage Newslett. Res. 3, 2, 12-16.
attributed to one or a few chemical compounds, to one Fabri H. (1670) Physica, id est Scientia Return Corporearum,
or a few different processes, but must be considered Vol. 3, Anisson, Lyon.
globally, with all their synergisms. Atmospheric pollu- Filiasi J. (1816) Relazione dal 1 Gennaio 1815 a tutto Agosto
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higher levels than nowadays; however, the present-day Lo~'e-Pilot M. D., Martin J. M. and Morelli J. (1986)
situation is the most critical one, due especially to the Influence of Saharan dust on the rain acidity and atmo-
spheric input to the Mediterranean. Nature 321, 427-428.
large amount of chemical species dispersed in the
Palladio A. (1570) I quattro Libri delrArchitettura. De
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Perkins H. C. (1974) Air Pollution. McGraw-Hill, Tokyo.
Acknowledgements--Special thanks are due to Dr Peter Poleni I. (1740) Ioannis Poleni ad Nobilissimum Virum
Brimblecombe (University of East Anglia), Prof. Virgilio Comitem Alexandrum De Pompeis Patricium Veronen-
Giormani (University of Padova) and Dr Silvia Enzi (CNR- sem Epistola qua Nonnulae Observationes Astronomicae
ICTR) for many useful discussions and suggestions about the et Meteorologicae Continetur. Commentari Accademiae
environmental history and its interpretation. This research Scientilicae Petropolitanae T. 8, 1739, lap. 439-452.
was funded by the Commission of the European Com- Poli S. (1798) Elementidi Fisica Sperimentale, Vol. 4, 3rd edn.,
munities, under the STEP Programme, contract nos EV4V- Pasquzli, Venice.
0051-1 and CT90-0107 SSMA. Ramazzini B. (1700) De Morbis Artificum Diatriba. Capponi,
Modena.
Romano R. and Sturiale C. (1982) The historical eruptions of
Mt Etna. Mere. Soc. Geol. It. 23, 75-79.
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