**4. Conclusion**

298 Cellulose – Medical, Pharmaceutical and Electronic Applications

**Table 5.** Concentrations of heavy metals found in historical process waters.

The results contained from process waters from the Rhine, Main and Moselle region around 1580-1700 are comparable to modern uncontaminated surface water (Pb2+~ 1-10 µg/L), sometimes even higher than today [27]. Remarkable high values were determined in the process waters of the Netherlands around 1680-1735. Here concentrations up to 50 µg/L Zn2+ and 100 µg/L Pb2+ are to be found (Table 6). Specially in the region of Amsterdam and Antwerp, there are no fast flowing rivers as they are found at many other paper producing sites. It is known, that Dutch paper mills used windmills for energy supply instead of water mills. The water in those economical booming regions were only slowly flowing waters - in consequence of the geographical situation of the Netherlands. In consequence the waters of highly populated regions may be heavily loaded with hazardous pollutants. Lead – for example - at this time was commonly used, eg. for the production of tools, bullets, colours, metal type and water technology. Astonishing high values of heavy metals were found in a book, printed in Rouen in the year 1709. Specially the concentration of cadmium calculated from this paper seems to be very high – although this metal at this time was unknown. But Zn2+ in minerals[28] often is accompanied by Cd2+. If it is no modern contamination, the

water came in contact with a (mineral) compound liberating a lot of toxic metals.

the 16.-18. century (Table 5:).

So heavy metal contents of production waters were calculated from the paper of books of

Book Page Date Pb Zn Cu Cd

1 952 1596 9 +/- 3 21 +/-5 3 +/- 0,7 < LOD 2 463 1690 18 +/- 7 67 +/-13 1 +/-1,4 < LOD 3 93 1580 15 +/- 2 4 +/- 5 < LOD +/- 2 < LOD

4 802 1588 23 +/- 6 28 +/- 4 4 +/- 1,5 < LOD

5 553 1735 102 +/-18 61 +/-12 11 +/-1,3 < LOD

6 1697 23,1 +/- 3 25,6 +/- 6,3 23,3 +/- 7,0 4,2 +/- 2,0 7 1697 17,4 +/- 3,3 28,7 +/- 8,2 35,7 +/- 6,0 5,3 +/- 2,2 8 1709 51 +/- 17 182 +/- 28 41 +/- 18 34 +/- 22

862 34 +/- 4 21 +/- 11 3 +/-1,5 < LOD

561 70 +/-7 48 +/-32 15 +/-1,4 < LOD

.of print µg/L µg/L µg/L µg/L

Historical contamination of environmental compartments can be seen as an experiment done by mankind. It allows – in its interpretation – to deduce answers for present environmental questions. So for example in presence the consequences of a change of climate is estimated by the data gained at the shelf ice layer in Arctic and Antarctica regions [29].

In the present work first steps to receive information about the historical environment situation in settlement area were done. We succeeded to determine the historical environmental compartment water by examining historical well dated and localisable commodities of the *homo faber* – old books and its paper.

It could be proved, that the atmosphere surrounding a book for centuries leaves traces in the cellulose of these books. In the center of the books, most anion forming acids are in lower concentrations than cutting edges, being in close contact with the atmosphere. The in historical times often emitted SOx are in much higher concentrations to be found, than the actual dominant NOx, which in former times were very rare, for they are only produced wir modern high temperature burning processes.

Antiquarian Books as Source of Environment Historical Data 301

the production water is – concerning its contamination with heavy metal ions – identical

So a new field of environmental data is accessible, allowing to evaluate historical environmental pollution. In moment one antiquarian book edition, stored in different

Environmental historical data alone allow to evaluate the anthropogenic impact into environment. It is often forgotten, that all scientific predication of future development of environment is extrapolated from historical data. To receive information about the historical environment situation in inhabited regions, we approach to this task examining historical

The work introduced here uses books as a source of environment historical data specially

The paper of historical books is well dated by their printing and allocated by their watermark [30]. Often its owner signs reveal the history of the rooms were it was situated.

In the Instrumental Analysis cellulose is often used as a trap of traces of analyts. So in gaseous phase it enriches middle polar up to polar compounds as NOx, SOx, HCl, organic acids or esters. In aqueous phases they additionally have to a certain extend the properties of ion exchanging polymers. Both processes can be used to make a new approach to aquire environmental historical data. Historical papers mostly are produced from cellulose – e.g. of a pulp produced by old tatters. For this process is well documented, it is possible to use them as passive samplers for airborne and aqueous contaminants – so opening an new

Airborne contaminants enter a book only by its cutting edge and not by the air-impermeable cover. In consequence a gradient between the centre of the pages and its border, representing an transportation process of the contaminants like in a analytical passive

The cellulose of historical paper is a trap for traces of heavy metals and other compounds contaminating their production water in historical times. Great amounts of water were brought into contact with the paper pulp in historical paper mill process. The cellulose of the pulp acts as ion exchange material for heavy metals, forming a dynamic equilibrium.

Ancient papers from well dated and located books are eluted without destruction of their paper and the resulting solution is analysed towards its contaminants, caused either by the storing of the books in library (airborne contaminants) or by adsorption from its production

water (water-borne contaminants) with modern methods of instrumental analysis.

method to get environmental historical data of the compartments air and water.

with the water of the corresponding river.

**5. Summary** 

sampling equipment.

libraries is in investigation to assure the principle.

well dated and locatable products of the homo faber.

for the environmental compartment of water and air.

So the acid catalysed decay of cellulose of antiquarian books becomes not only a consequence of modern production techniques, but as well of historical environmental conditions. If we succeed to understand the kinetics of the "passive sampler" book, we will even be able to describe these historical environments.

At present, the distribution of organic acids with the same technique and organic components with the principle of thermal extraction as well as its adsorption kinetics are under investigation in antiquarian books. In another long-term framework of this project is to explain the basis of the data thus obtained material is a correlation between damage type, degree of damage and concentration of individual pollutants present in the respective storage areas.

The information thus obtained will then provide the basis to develop in later projects concepts that allow to keep the content to be at particularly harmful gas components in library spaces as small as possible. Thought is the use of specific sorbent into the air intake side of the usually existing climate systems. From the experience gained here is a concept for the safe storage of records can be developed.

In addition, new contributions made to the environmental history, it might even succeed in using the information obtained to infer historical air pollution.

Ancient papers from well dated books are eluted without destruction of their paper and the resulting solution is analysed by ETAAS and Invers Stripping Voltammetry to determine the historical impact of metals. Afterwards in a flow-system the eluted paper spot is equilibrated with different concentration of heavy metals (Cu2+, Pb2+, Zn2+, Cd2+) to plot the adsorption isotherm of that very spot.

It could be shown that the gained values concerning the content of some heavy metal ions in the pulp production water are plausible and seem to be realistic.

Yet there seems to be no contradiction to define the process water to be identical with the river water.

Such a correlation would be very essential for environmental history, Therefore it is necessary to discuss how realistic this approach could be. Nearly all contemporary pictures of the 16. -18. century show a beck or river directly "behind the windows of the building". So the water for the pulp production in most cases will be directly taken from the river / beck into the production container. In this filling process an additional contamination is not very probable. Contamination is more supposable by desorption from the container material. All bequeathed pulp mills use wooden casks or granite vats for the hand paper production. Both material should not have any significant influence on the heavy metal content of the production water. So to our opinion it is allowed to draw the conclusion that the production water is – concerning its contamination with heavy metal ions – identical with the water of the corresponding river.

So a new field of environmental data is accessible, allowing to evaluate historical environmental pollution. In moment one antiquarian book edition, stored in different libraries is in investigation to assure the principle.

## **5. Summary**

300 Cellulose – Medical, Pharmaceutical and Electronic Applications

modern high temperature burning processes.

the safe storage of records can be developed.

adsorption isotherm of that very spot.

using the information obtained to infer historical air pollution.

the pulp production water are plausible and seem to be realistic.

storage areas.

river water.

even be able to describe these historical environments.

actual dominant NOx, which in former times were very rare, for they are only produced wir

So the acid catalysed decay of cellulose of antiquarian books becomes not only a consequence of modern production techniques, but as well of historical environmental conditions. If we succeed to understand the kinetics of the "passive sampler" book, we will

At present, the distribution of organic acids with the same technique and organic components with the principle of thermal extraction as well as its adsorption kinetics are under investigation in antiquarian books. In another long-term framework of this project is to explain the basis of the data thus obtained material is a correlation between damage type, degree of damage and concentration of individual pollutants present in the respective

The information thus obtained will then provide the basis to develop in later projects concepts that allow to keep the content to be at particularly harmful gas components in library spaces as small as possible. Thought is the use of specific sorbent into the air intake side of the usually existing climate systems. From the experience gained here is a concept for

In addition, new contributions made to the environmental history, it might even succeed in

Ancient papers from well dated books are eluted without destruction of their paper and the resulting solution is analysed by ETAAS and Invers Stripping Voltammetry to determine the historical impact of metals. Afterwards in a flow-system the eluted paper spot is equilibrated with different concentration of heavy metals (Cu2+, Pb2+, Zn2+, Cd2+) to plot the

It could be shown that the gained values concerning the content of some heavy metal ions in

Yet there seems to be no contradiction to define the process water to be identical with the

Such a correlation would be very essential for environmental history, Therefore it is necessary to discuss how realistic this approach could be. Nearly all contemporary pictures of the 16. -18. century show a beck or river directly "behind the windows of the building". So the water for the pulp production in most cases will be directly taken from the river / beck into the production container. In this filling process an additional contamination is not very probable. Contamination is more supposable by desorption from the container material. All bequeathed pulp mills use wooden casks or granite vats for the hand paper production. Both material should not have any significant influence on the heavy metal content of the production water. So to our opinion it is allowed to draw the conclusion that Environmental historical data alone allow to evaluate the anthropogenic impact into environment. It is often forgotten, that all scientific predication of future development of environment is extrapolated from historical data. To receive information about the historical environment situation in inhabited regions, we approach to this task examining historical well dated and locatable products of the homo faber.

The work introduced here uses books as a source of environment historical data specially for the environmental compartment of water and air.

The paper of historical books is well dated by their printing and allocated by their watermark [30]. Often its owner signs reveal the history of the rooms were it was situated.

In the Instrumental Analysis cellulose is often used as a trap of traces of analyts. So in gaseous phase it enriches middle polar up to polar compounds as NOx, SOx, HCl, organic acids or esters. In aqueous phases they additionally have to a certain extend the properties of ion exchanging polymers. Both processes can be used to make a new approach to aquire environmental historical data. Historical papers mostly are produced from cellulose – e.g. of a pulp produced by old tatters. For this process is well documented, it is possible to use them as passive samplers for airborne and aqueous contaminants – so opening an new method to get environmental historical data of the compartments air and water.

Airborne contaminants enter a book only by its cutting edge and not by the air-impermeable cover. In consequence a gradient between the centre of the pages and its border, representing an transportation process of the contaminants like in a analytical passive sampling equipment.

The cellulose of historical paper is a trap for traces of heavy metals and other compounds contaminating their production water in historical times. Great amounts of water were brought into contact with the paper pulp in historical paper mill process. The cellulose of the pulp acts as ion exchange material for heavy metals, forming a dynamic equilibrium.

Ancient papers from well dated and located books are eluted without destruction of their paper and the resulting solution is analysed towards its contaminants, caused either by the storing of the books in library (airborne contaminants) or by adsorption from its production water (water-borne contaminants) with modern methods of instrumental analysis.

In case of airborne contaminants like NOx, SOx, HCl, organic acids it is possible to prove that acids in the paper are not only introduced by production, but to a great extend as well trapped from environment. We further on show, that some organic acid are set free by the books into the environment.

Antiquarian Books as Source of Environment Historical Data 303

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A well defined pulp production process, starting with used clothes, so allows to estimate the historical heavy metal concentration (Cu2+ , Pb2+, Zn2+, Cd2+) in the production water.

In a flow-system the paper is first eluted and then the eluted paper spot is equilibrated with different concentration of heavy metals to plot the adsorption isotherm of that very spot.

Both data together allow a calculation of the heavy metal content of the historical river. For different waters of Germany and the Netherlands of the 16.-18. century the heavy metal load could be estimated. The resulting concentrations mostly were similar to the level of modern surface waters, but in the case of the dutch waters of the 17. century, they were e.g. for Pb2+ significantly higher than modern values.

In summary this new field of research opens a new source of environmental historical data, which may at least help to understand local environmental processes and the long time stability of paper.
