Prognosis of the Surface Water and Groundwater Balance of The

MSc. aus Syrian

Die vorliegende Arbeit wurde von der Fakultät für Geowissenschaften der Ruhr-Universität Bochum als Dissertation zur Erlangung des Grades eines Doktors der Naturwissenschaften (Dr. rer. nat.) anerkannt. 1. Gutachter: Prof. Dr. S. Wohnlich 2. Gutachter: Prof. Dr. A. Schumann 3. Fachfremder Gutachter: Prof. Dr. F. Dickmann Tag der Disputation: 4. 2. 2014

Erklärung gemäß § 8, Abs. 3 der alte Promotionsordnung der Fakultät für Geowissenschaften der Ruhr-Universität Bochum

Ich erkläre hiermit eidesstattlich, dass diese Arbeit selbständig und ohne unerlaubte Hilfen ausgeführt und verfasst wurde. Ich habe alle entnommenen Fakten und Textstellen durch entsprechende Zitate gekennzeichnet. Diese Arbeit wurde in dieser oder ähnlicher Form bei keiner Fakultät noch oder einer anderen Hochschule eingereicht.

Mohammad Alhamed

Bochum, 18. December, 2013

III

Kurzfassung

Das Lottenbachtal ist ein kleines Einzugsgebiet der Ruhr. Dieses Gebiet wurde durch Steinkohlen-Bergbau, durch den Ausbau von Siedlungsflächen und durch landwirtschaftliche Aktivitäten erheblichen anthropogenen Veränderungen unterzogen. Darüber hinaus finden sich in dem Einzugsgebiet Laub- und Nadelwälder. Diese Bedingungen machen das Lottenbachtal zu einem idealen Untersuchungsgebiet für hydrologische und hydrogeologische Eigenschaften unter unterschiedlichen Nutzungen. Ziel der vorliegenden Dissertation ist es, die Wirkung von anthropogenen und geogenen Faktoren auf den quantitativen und qualitativen Wasserhaushalt zu untersuchen. Die zu diesem Zweck eingesetzten Labor- und Geländemessungen umfassen das Sammeln und Analysieren von langfristigen Klimadaten, die Erfassung und Analyse von Wasser-, Boden-und Gesteinsproben, die Erhebung und Analyse von anthropogenen Bodenmaterialien, die Beobachtung und Erprobung des Oberflächenabflusses, die Messung der Bodenfeuchte und die Berechnung der Wasserbilanz. Das Lottenbachtal wird signifikant von Grubenwässern aus stillgelegten Steinkohlebergwerken beeinflusst. Diese Einflüsse machen sich durch erhöhte Eisengehalte in Grundwässern und Oberflächenwässern bemerkbar, wobei Eisen-Konzentration bis zu 18-mal höher als der zulässige Höchstwert für Trinkwasser beobachtet wurden. Hierdurch erhält man einen Indikator für die Oxidation der Schwefel-Mineralien, die an die Kohlelagerstätten gebunden sind. Darüber hinaus wurde festgestellt, dass die Gewässerbelastung mit Eisen räumlich stark schwankt, je nach Entfernung des Probennahmepunktes von dem Grubenwasserzufluss. Zuflüsse von Oberflächenwässern aus Bauschuttablagerungen und aus erweiterten Wohngebieten sind durch die Verwendung von karbonatreichen Materialien verantwortlich für die Erhöhung der Alkalität in den Grubenwässern. Hierdurch erfolgt eine Pufferung der ursprünglich sauren Grubenwässer. Jedoch enthalten auch Ackerböden und Tonsteinlagen Karbonate. Die Verwitterung von Silikaten und Tonmineralen tragen ebenfalls zur Pufferung von Säure bei. Die Anwesenheit von Aluminium im Grund- und Oberflächenwasser ist ein Indikator für die Verwitterung von Silikat und von Tonmineralien. Auf Grund der oben aufgeführten Beobachtungen können geogene und anthropogene Säure-Puffersysteme in diesem Einzugsgebiet unterschieden werden. Das geogene System umfasst die Verwitterung von Silikat und Tonmineralien, die Wiederauflösung von sekundären Mineralien (Hydroxiden), die Auflösung von Karbonaten (enthalten in den karbonen Tonstein- und Kohleschichten), die Oxidation von Eisen sowie den Kationenaustausch in Böden. Dagegen enthält das anthropogene Puffersystem die Auflösung der Karbonate aus Baustoffen, Bauschutt, Zechenabfall und landwirtschaftlich gedüngten Böden. Die qualitativen Auswirkungen dieser Prozesse auf den Wasserhaushalt in dem untersuchten Einzugsgebiet zeigen sich in einer Erhöhung der Konzentrationen von den folgenden chemischen Elementen: Kalzium, Magnesium, Bicarbonat, Sulfat und Eisen. Allerdings sind diese Effekte auch Ergebnisse von anderen anthropogenen Faktoren, wie suburbane und landwirtschaftliche Aktivitäten. Diese sind verantwortlich für

Kurzfassung die zusätzlichen Belastungen durch Kalzium, Magnesium, Natrium, Chlorid, Sulfat und möglicherweise die Hauptquelle von Nitrat. Der Waldboden zeigt saure pH-Werte. Die Sulfatgehalte sind höher als bei Ackerflächen, die fast-neutrale bis neutrale Boden-pH-Werte aufweisen. Darüber hinaus besitzen sie relativ hohe Gehalte an anderen Elementen wie Kalzium, Magnesium, Natrium, Chlorid. Die Variabilität der unterschiedlichen Fließwege erhöht die Komplexität der chemischen Zusammensetzungen der Oberflächen- und Grundwässer. Diese zeigen sich in einer heterogenen Verteilung der hydrochemischen Wassertypen. Auf Grund dieser Ergebnisse war es nicht möglich unterschiedliche Wasserströme hydrochemisch abzugrenzen. Es konnte daher nur eine einfache Methode zur Ganglinienseparation im Oberflächenabfluss verwendet werden. Mit Hilfe einer Wasserbilanz im in dem Untersuchungsgebiet wurden die Abflüsse quantifiziert. Danach beträgt für das Untersuchungsjahr 2011/2012 der Oberflächenabfluss etwa 61% des Gesamtniederschlags, während die Grundwasserneubildung nur etwa 4% des Gesamtniederschlags ausmacht.

Abstract

The Lottenbachtal is a small catchment of the Ruhr. This area was subject to large degrees of anthropogenic changes, due to hard coal mining activities, the expansion of settlement areas and agricultural activities. Deciduous and coniferous forests also exist in this area. These conditions make the Lottenbachtal an experimental catchment, which enables the study of impacts the diversity of land use on hydrological and hydrogeological characteristics of this watershed. The aim of this research is to investigate the effects of anthropogenic and geogenic factors on the quantitative and the qualitative properties of the water balance in this area. Many procedures and experiments were conducted to achieve this purpose. These include collecting and analysing long term climatic data, collecting and analysing water, soil and rock samples, collecting and analysing the anthropogenic materials from anthropogenic sources, observing and sampling the stream flow discharge, measuring the soil moisture and calculating the water balance. The Lottenbachtal is significantly affected by abandoned coal mines. These effects are represented by the pollution of groundwater and surface water by Fe, where the Fe concentration is up to 18 times larger than the permitted value in drinking water. This gives an indicator to oxidation of disulphide minerals which are associated with coal deposits. Moreover, an important spatial variation of the water pollution was noted in this area. These variations may be related to the fact, whether the location of sampling points was close or far from the mine sites. The landfilling processes and the expansion of the residential areas were associated with the use of carbonate rich materials. These materials are the main cause for the increase in alkalinity of the mine water and the subsequent buffering of the acidity. However, the soil of the arable areas and the mudstone deposits also contain carbonates. On the other hand, the weathering of silicate and clay minerals has also contributed to the buffering of the acidity. The aluminium, measured in the water samples, is an indicator for the weathering of silicate and of clay minerals. Thus, the buffering systems of the acidity in this area can be divided into geogenic and anthropogenic. The geogenic system includes the weathering of silicate and clay minerals, the re-dissolution of secondary minerals (hydroxides), the dissolution of carbonate minerals (contained in rock and coal deposits), the oxidation of ferrous iron into ferric and the carbonate and exchangeable elements of the soil cover. Conversely, the anthropogenic buffering system includes the dissolution of carbonate minerals in construction materials, construction waste, mine waste and treated soil for agricultural activities. The impact of these processes on the qualitative properties of the water cycle in this area is represented by the increase of the concentration of chemical elements, which include calcium, magnesium, bicarbonate, sulphate and iron. However, these effects are also results of other anthropogenic factors, such as suburban and agricultural activities. These are responsible for the additional loads of calcium, magnesium, sodium, chloride, sulphate and possibly the main sources of nitrate.

Abstract

The forested soil has acidic pH value. The sulphate contents are higher than in arable areas that have near/neutral to neutral soil pH values and relatively high contents of other elements, such as calcium, magnesium, sodium and chloride. The diversity of the flow-paths increases the complexity of the chemical characteristics of the surface water and the groundwater. These are represented by a wide range of hydrochemical facies of the water sources. According to these conditions, the separation of stream hydrograph to its components by using hydrochemical methods was not possible. Therefore, the simple method was used to separate the stream flow hydrograph. The result of water balance calculation shows that the surface runoff constitutes about 61% of the total precipitation, while the groundwater recharge constitutes only about 4% of the total precipitation.

VII

Table of contents

Kurzfassung ...... IV

Abstract ...... VI

Table of contents ...... VIII

List of figures ...... XII

List of tables ...... XV

List of abbreviations ...... XVI

Acknowledgments ...... XX

1. Introduction ...... 1

1.1. The hydrologic balance at the catchment scale ...... 1

1.2. Impact of mining on hydrological and hydrogeological characteristics of the catchment areas ...... 1

1.2.1. Hydrogeochemistry of mine drainage ...... 2

1.2.2. Hydrogeochemical modelling ...... 6

1.3. Problem statement and the aim of this study ...... 7

1.4. Previous studies ...... 8

2. The Physical Characteristics of the Study Area ...... 10

2.1. Location ...... 10

2.2. Geographic position ...... 11

2.3. General climatic conditions ...... 12

2.4. General geological settings ...... 12

2.5. Landuse ...... 14

2.6. Mining activities ...... 15

2.7. Soil cover ...... 16

2.8. General hydrological and hydrogeological conditions ...... 18

3. Environmental Impact of the Abandoned Coal Mines on the Surface Water and the Groundwater Quality in the South of Bochum, Germany...... 21

3.1. Abstract ...... 21

3.2. Introduction ...... 22

3.3. Regional Setting ...... 23

VIII

Table of contents

3.4. Materials and methods ...... 26

3.5. Results ...... 27

3.5.1. Major ions hydrochemistry...... 27

3.5.2. Heavy and trace elements ...... 30

3.6. Discussions ...... 31

3.7. Conclusions ...... 38

4. Geochemical Processes Controlling the Neutralization Processes of the Acid Mine Drainage in the South of Bochum, Germany...... 39

4.1. Abstract ...... 39

4.2. Introduction ...... 39

4.3. The study area ...... 40

4.4. Materials and methods ...... 43

4.4.1. Hydrogeochemical modeling...... 43

4.4.2. Field Investigations ...... 44

4.4.3. Laboratory works ...... 44

4.4.4. Analysis procedure ...... 45

4.4.5. Data processing and interpretation ...... 45

4.5. Results ...... 46

4.5.1. Hydrogeochemical modeling...... 46

4.5.2. Batch test ...... 47

4.5.2.1. Topsoil ...... 47

4.5.2.2. Artificial Materials ...... 48

4.5.2.3. Carboniferous sandstone and mudstone ...... 49

4.6. Geochemical processes controlling the mitigation of AMD ...... 51

4.7. Conclusion ...... 55

5. Hydrochemical Responses during and after Strom Events and Hydrograph Separation in the Lottental Catchment Area, Bochum, Germany...... 56

5.1. Abstract ...... 56

5.2. Introduction ...... 57

5.3. Site description ...... 59

Table of contents

5.3.1. Stream network and catchment area ...... 59

5.3.2. The general climatic conditions ...... 60

5.3.3. Land use and soil cover ...... 60

5.3.4. Geology and hydrogeology ...... 61

5.4. Materials and methods ...... 62

5.4.1. Field works ...... 62

5.4.2. Laboratory Work ...... 63

5.4.3. Data processing and presentation ...... 64

5.5. Results ...... 64

5.5.1. Wet Depositions ...... 64

5.5.2. Batch Test ...... 64

5.5.3. Chemical hydrograph of the observed flooding events ...... 68

5.5.4. Chemical hydrograph of slow flow conditions...... 74

5.6. Factors controlling the hydrochemical responses of the Lottenbach...... 76

5.7. Hydrograph separation ...... 79

5.8. Conclusions ...... 79

6. The Hydrological, the Hydrogeological and the Hydrochemical Framework of the Lottenbachtal, Bochum, Germany...... 80

6.1. Abstract ...... 80

6.2. Introduction ...... 80

6.3. Study Area ...... 81

6.4. Methodology ...... 83

6.5. Results and discussions ...... 85

6.5.1. Hydro-climatic framework ...... 85

6.5.2. Soil chemistry ...... 87

6.5.3. Hydrochemical characteristics ...... 90

6.5.4. The hydrological and the hydrogeological conceptual model ...... 93

6.5.5. Hydrologic budget ...... 95

6.6. Conclusion ...... 96

7. Summary of the results and recommendations ...... 98 X

Table of contents

References ...... 100

Appendices ...... 116

Appendex I: climate data ...... 117

Appendix II: Stream flow data ...... 127

Appendix III: Hydrogeochemical data ...... 139

Appendix IV: Hydrochemical data ...... 141

Appendix V: Evapotranspiration ...... 143

Appendix VI: Soil moisture ...... 144

Curriculum vitae ...... 146

List of figures

Fig 2.1: Location map of the study area including the Lottenbachtal and the southern banks of the Kemnade lake...... 10 Fig 2.2: The digital elevation model (DEM) of the study area including a topographic cross section (A A1)...... 11 Fig 2.3: Average of the monthly air temperature and the precipitation of Bochum for the period 1888-1985 (modified after GLA-NRW, 1988)...... 12 Fig 2.4: The geologic map and the geologic cross section of the study area (modified after GLA-NRWa, 1988)...... 13 Fig 2.5: The Landuse map of the study area in 2010-2011 (The background map was adopted from Google Earth)...... 15 Fig 2.6: The mining map of the study area including the mine sites and the other facilities such as the drainage adits and the tunnels (modified after GLA-NRW, 1988; Tiedt, 2009)...... 16 Fig 2.7: The soil map of the study area (modified after GLA-NRWc, 1988), the unit numbers are related to the unit numbers in the text...... 18 Fig 2.8: The map of drainage systems in the study area (modified after Viebahn-Sell, 2006)...... 20 Fig 3.1: Location map of the study area including sampling points of surface water and groundwater (April 2011), the stream network and abandoned mine sites and their facilities (location of mines and their facilities modified after Tiedt, 2009)...... 24 Fig 3.2: Geological map and geologic cross section of the study area including the geological units, coal seams and tectonic features (modified after GLA-NRWa, 1988)...... 25 Fig 3.3: The land use of the study area including the sampling points (April 2011) of the surface water and groundwater (the land use map was digitized from Google Earth 2010-2011)...... 26 Fig 3.4: The series plot of the in-situ parameters of the surface water and the groundwater samples, collected from the Lottenbachtal catchment area during April 2011...... 28 Fig 3.5: The series plot of the major elements of the surface water and the groundwater, collected from the Lottenbachtal catchment area during April 2011 (a major cations; b major anions)...... 30 Fig 3.6: The series plot of the minor elements and hydrogen sulphide of the surface water and the groundwater, collected from the Lottenbachtal catchment area during April 2011...... 31 Fig 3.7: Spatial distribution of the major ion hydrochemistry in the south of Bochum, Germany...... 33 Fig 3.8: Traces of the halite (white colour between the blocks) in the facilities of the Ruhr University of Bochum...... 34 Fig 3.9: The Piper diagram showing the hydrochemical characteristics of the water samples listed in Table 3.2...... 38 Fig 4.1: Location map of the study area...... 41

XII

List of figures

Fig 4.2: The geology, the lithology and the tectonics of the Lottenbachtal (modified after GLA-NRWa, 1988)...... 42 Fig 4.3: Location map of the soil and the artificial material samples, collected from the south of Bochum. .. 45 Fig 4.4: The series plots of saturation indices of carbonate and evaporate minerals of the surface water and the groundwater samples collected from the Lottenbachtal during April 2011 and listed in Table 4.2...... 46 Fig 4.5: The spatial distributions of the saturation indices values of the surface water and the groundwater samples collected from the Lottenbachtal during April 2011 and listed in table 4.2EC, pH and carbonate tests...... 47 Fig 4.6: The series plot of the EC and pH values measured for topsoil, slag, mine waste, construction waste concrete and rock samples; A: Soil samples of arable areas, B: Soil samples of forested areas, C: Solid materials, D: Rocks...... 50 Fig 4.7: Series plot of the result of the batch tests performed on the soil and solid samples collected from the south of Bochum; A: Soil samples of arable areas, B: Soil samples of forested areas, C: Solid materials, D: Rocks...... 50 Fig 4.8: The spatial distribution of the hydrochemical parameters of the surface water and the groundwater samples collected from the Lottenbachtal during April 2011 and listed in Table 4.2...... 51 2+ - Fig 4.9: The correlation between Ca and HCO3 of the surface water and the groundwater samples collected from the Lottenbachtal during April 2011 and listed in Table 4.2...... 52 Fig 4.10: The series plot of the Al, Fe of the surface water and the groundwater samples collected from the Lottenbachtal during April 2011 and listed in Table 4.2...... 54 Fig 4.11: Ochre depositions on the watercourse of Lottenbach stream (near sampling point 13)...... 55 Fig 5.1: Location map of the study area, represented by the western part of the Lottenbachtal...... 59 Fig 5.2: The land use and the soil maps of the south of Bochum (the land use was digitized from Google map 2010; the soil map modified after GLA-NRWc, 1988), including the study area that represented by the gauged part of the Lottenbachtal...... 60 Fig 5.3: The Geological map of the study area, represented by the western-gauged part of the Lottenbachtal (modified after GLA-NRWa, 1988)...... 61 Fig 5.4: Location map of the topsoil, artificial materials, rocks and soil profiles samples collected from the south of Bochum (modified after Alhamed and Wohnlich, 2014b)...... 63 Fig 5.5: Results of batch tests of topsoil, artificial materials and rock samples collected from the Lottenbachtal, Bochum, A: The soil samples of arable areas; B: The soil samples of forests; C: the Artificial materials; D: Rocks...... 66 Fig 5.6: Results of batch tests performed on the soil profiles that were sampled from the Lottenbachtal; P1 and P2 arable areas; P4 forested area...... 67 Fig 5.7: Stream and chemical hydrographs of the Lottenbach observed before, during and after storm events in May...... 69

XIII

List of figures

Fig 5.8: Stream and chemical hydrographs of the Lottenbach observed during and after storm events August- September...... 71 Fig 5.9: Stream and chemical hydrographs of the Lottenbach observed during sampled storm event of October...... 72 Fig 5.10: Stream and chemical hydrographs of the Lottenbach observed during slow flow conditions of October-November...... 75 Fig 5.11: Iron hydroxides deposited in the bottom of the Lottenbach stream in the middle part (near sampling point 6, Fig 4.8)...... 77 Fig 6.1: Location map of the study area including the drainage systems, water sampling points (during October 2010) and the site of the soil profiles...... 82 Fig 6.2: Geological map of the study area (modified after GLA-NRWa, 1988)...... 83 Fig 6.3: The relative and the cumulative frequency of the daily precipitation (only rainy days) of the period (1991-2012)...... 85 Fig 6.4: The relative and the cumulative frequency of the daily relative humidity of the period (1991-2012)...... 86

Fig 6.5: The relative and the cumulative frequency of the daily Tmin, Tmax and Taverage of the period (1991- 2012)...... 86 Fig 6.6: The results of the pH, EC and batch tests, performed on soil profiles P2 (arable area)...... 88 Fig 6.7: The Results of pH test, EC test and batch test of the soil profile P4 (forested area)...... 89 Fig 6.8: The correlation between the Na++K+ and Cl- of the water samples collected from the Lottenbachtal during October 2010...... 91 Fig 6.9: The piper diagram of the water sample collected from the Lottenbachtal during October 2010 (Sampling points can be seen in App IV.2 and Fig 6.1)...... 92 Fig 6.10: The hydrological and the hydrogeological conceptual model of the Lottenbachtal (the section A1:A of the geological profile shown in Fig 3.2)...... 94 Fig 6.11: The climatic data used in the calculation of water balance during the period (15.4.2011- 15.4.2012)(obtained from Rudolf Geiger Climate Station)...... 95 Fig 6.12: The direct surface runoff and the base flow discharge of the Lottenbachtal during the period (15.4.2011-15.4.2012)...... 96

XIV

List of Tables

List of tables

Table 3.1: Result of physicochemical, dissolved oxygen and hydrogen sulphide measurements of the surface water and the groundwater samples, collected from the Lottenbachtal catchment area during April 2011. .... 29 Table 3.2: Results of hydrochemical parameters of the water samples collected from surface water and groundwater in the south of Bochum (April 2011)...... 29 Table 3.3: Statistical correlations of the hydrochemical parameters for all water samples, collected from the Lottenbachtal catchment area during April 2011...... 35 Table 3.4: Comparison between the mean chemical composition of the samples affected by abandoned coal mines (group 1) and the samples not affected (group 2)...... 35 Table 3.5: Comparison between the mean chemical compositions of water samples collected south of Bochum (surface water, groundwater and engineered channel), the stream water (Lottenbach) and lake water (Kemnade)...... 36 Table 3.6: Comparison between the mean chemical compositions of the samples affected by abandoned coal mines south of Bochum and the samples of the abandoned coal mining in Upper Bavaria...... 37 Table 4.1: Summary of climatic parameters of the study area (Grudzielanek et al., 2011)...... 42 Table 4.2: The hydrochemical parameters of the surface water and the groundwater of the sampling points shown in Fig 4.8 and located in the south of Bochum (Alhamed and Wohnlich, 2014a)...... 43 Table 4.3: A statistical summary of the result of hydrochemical modelling performed on the surface water and the groundwater samples listed in the Table 4.2...... 46 Table 4.4: Results of the carbonate tests performed on the soil, the rocks and the artificial materials samples collected from the south of Bochum...... 48 Table 4.5: A statistical summary of the pH, EC and (10/1: l/g) batch tests performed with soil and the artificial material samples collected from the south of Bochum...... 49 Table 5.1: A statistical summary of the results of hydrochemical analysis of the rain samples collected from the Lottenbachtal, Bochum...... 64 Table 5.2: A statistical summary of the result of batch tests performed on the soil, artificial materials and rock samples collected from the Lottenbachtal, Bochum...... 65 Tab 6.1: A statistical summary of results of hydrochemical analysis of the water samples collected from the study area during October 2010...... 91 Table 6.2: The component of the water budget of the Lottenbachtal during the period (15.4.2011-15.4.2012)...... 97

List of Abbreviation

List of abbreviations

Al Aluminium

Altotal Aluminium total AMD Acid mine drainage BLFU Bayerisches Landesamt für Umwelt C° Celsius Ca2+ Calcium CdS Greenockite Cl- Cloride cm Centimeter

CO2 Carbon dioxide Corr Correlation

CuFeS2 Chalcopyrite DEM Digital elevation model DIN Deutscher Normenausschuss DO Dissolved oxygen E Evaporation EC Electrical conductivity Eh Redox potential ELAW Environmental Law Alliance Worldwide Erbstollen A drainage tunnel or adit (German term) ETa Actual evapotranspiration

ETp Potential evapotranspiration FAAS Flame atomic absorption spectrometry system FAO Food and Agriculture Organization of the United Nations Fe2+ Ferrous iron Fe3+ Ferric iron FeS Pyrite

Fetotal Iron total Fig Figure G Groundwater flow g/t Gram per Ton Gb Global radiation GIS Geographic Information System XVI

List of Abbreviation

GR Groundwater recharge H Water stage H+ Hydrogen

H2O Water

H2S Hydrogen sulphide HCl Hydrochloric acid

- HCO3 Bicarbonate

HNO3 Nitric acid hrs Hours hrs/a Hours per year IAP Ion activity product ICS Ion chromatography system INAP The International Network for Acid Prevention Jole/cm2 Jole per square centimeter K** Equilibrium constant K+ Potasium km Kilometer km2 Square kilometer l /kg Liter per kilogram LNW Landwirtschaftskammer Nordrhein Westfalen m Meter m/s Meter per second m3/day Cubic meter per day meq/l Milliequivalents per liter mg/l Milligrams per liter Mg2+ Magnesium ml Milliliter mm Milimeter mm/a Millimeter per year mm/day Millimeter per day Mn Manganese

Mntotal Manganese total ms/cm Millisiemens pro centimeter mv Millivolt Na+ Sodium XVII

List of Abbreviation

NIS Millerite NMD Neutral mine drainage

- NO3 Nitrate Nr Number nsoil Porosity P Precipitation PbS Galina pH Decimal logarithm of the reciprocal of the hydrogen ion activity in a solution PHREEQC PH, REDOX, and EQUILIBRIUM - C LANGUAGE

Qsur Direct surface runoff

Qurb Surface runoff formed in urban areas R Surface runoff RF Relative frequency RH Relative humidity SD Saline drainage SI Saturation indices

2- SO4 Sulphate T Air temperature T* Transpiration

T14 Air temperature at 14

Taverage Average air temperature TDS Total dissolved solids

Tmax Maximum air temperature

Tmin Minimum air temperature USDIBR United States Department of The Interior Bureau of Reclamation USGS United States Geological Survey

Vwind Average wind velocity WCI World Coal Institute X The eastward-measured distance Y The northward-measured distance Zn Zinc ZnS Sphalerite

Zntotal Zinc total

ΔSsoil Change in the soil storage Change in storage XVIII

List of Abbreviation

ΔS

% Percentage % v/v Percentage volum/volum (aq) Aqueous (s) Solid µg/l Microgram per liter µm Micrometer µs/cm Microsiemens pro centimeter

XIX

Acknowledgments

At this point; I would like to thank my supervisor, Prof. Dr. Stefan Wohnlich for the supporting, the friendly discussions of this research over the years. Furthermore, I would like to thank all my friends, technician and scientific staff, which include; MSc. M. Celik; BSc. I. Erdem; Dipl.-Geogr. M. Leson; MSc. S. Jakschik; MSc. J. Hovar; MSc. S. Weldesenbet; MSc. M. Hussein; MSc. M. Alqudah; MS. P. Dückershoff ; Dipl. N. Richard, Techn; O. Schuebbe; Techn. D .Barnke; and all other people who have contributed directly or indirectly to the creation of this thesis in the form of technical, scientific or otherwise support. I would like to thank my parents for the love and the encouragement over the duration of the research. I am gratified the Damascus University for admitting the scholarship, which was the most important factor in the completion of this work.

Chapter 1: Introduction

1. Introduction

1.1. The hydrologic balance at the catchment scale

The water balance of a catchment area is the mathematical expression of the water cycle (Knapp, 1979), which usually calculated based on the general law of water balance given by (Subramanya, 2008):

Where P is the precipitation, R is the surface runoff, G is the groundwater flow, E is the evaporation, T* is the transpiration and is the change in storage, represented by the change in surface runoff storage, the change in groundwater storage and the change in soil water storage. Forest canopy, vegetation cover and urban to intercept a part of the precipitation (Knapp, 1979), which could return to the atmosphere via the evaporation (Shaw, 1994). The other part of the precipitation (the excess rainfall) could reach to the earth’s surface and infiltrate into the soil unit filling the whole pore space. Thereafter, runoff forms by the continuation of precipitation. The deep percolation of the soil water forms the groundwater recharge (Shaw, 1994). The estimation and the prediction of the hydrological balance and is a critical issue of water resources management and planning in a catchment area. Mining and post mining activities are significantly influenced the hydrologic cycle of a watershed (Blodgett et al., 2002; Younger, 2003). These effects will be discussed in the following section.

1.2. Impact of mining on hydrological and hydrogeological characteristics of the catchment areas

Mining activities have negative impacts on the hydrological and the hydrogeological system of watershed. These impacts related to mining methods, which are classified into deep and surface methods (Younger, 2003). The surface mining methods are based on excavation techniques, whereby the overburden and large parts of the aquifer sediments or rock may be removed. These processes could increase the contaminate flux via removing the unsaturated zone, which has a significant role in attenuation and hindering the contaminate movements (Younger, 2003). In addition, these methods also cause a disturbance to the landscape due to the massive volumes of waste being produced during the extraction process, which accumulates on the surface. The United States Environmental Protection Agency (EPA, 2000) classifies the mining wastes and the hazardous materials into three classes: overburden, mine water and waste rocks. The overburden includes the surface material (topsoil and rocks), which is usually removed from the surface during operations aimed at exposing the ore located beneath. On the other hand, mine water refers to water entering a surface or underground mines via groundwater seepage, surface water inflow, or direct precipitation. The third class, mine waste, according to EPA classification, is the waste rocks. These materials consist of granulator broken rock and soils removed from, around, or within the ore body during extraction works. Normally, these rocks may contain non-mineralized or low-grade mineralized materials, which can range in size from fine sand to

Chapter 1: Introduction large boulders. The geochemistry and content of these materials depend on the properties and nature of formation. Conversely, in underground mining, tunnels or shafts are used to access the ore deposits. This method generates a connected network of the shafts and tunnels, which increase the access to the ore deposits. Stoping or block caving is another method of the underground mining. This method based on removing of blocks of the rocks in vertical strips. Thus, networks of underground cavities will be generated by using this method (ELAW, 2010). Extraction of ores significantly affects the hydrological and hydrogeological conditions of the catchment areas. These effects change the quantity and the quality of the water balance (Blodgett and Kuipers, 2002). The most common influences on the hydrological cycle are represented by reduction of flood discharges during wet season and increasing of the groundwater discharge (baseflow) during the dry season (Agnew and Corbett, 1969). These conditions resulted by a connection of open cracks with fissures, pits, shafts and tunnels (Blodgett and Kuipers, 2002). In addition, underground mining reduces groundwater levels, which change the flow velocities and rates (Blodgett and Kuipers, 2002), when water flows from the surrounding aquifer to the mining facilities.

Groundwater flows from active mines represented by low acidity and low concentrations of dissolved metals, while the groundwater flows from abandoned coal mines is enriched with undesirable metals and metalloids (EPA, 2000; Johnson, 2003).

1.2.1. Hydrogeochemistry of mine drainage

The International Network for Acid Prevention INAP (2009) classified the mine water into three main types: acid mine drainage AMD by pH< 6, neutral mine drainage NMD and saline drainage SD by pH>6. The distinction between NMD and SD is related to the total dissolved solids TDS (<1000 is NMD and 10000>TDS>1000 is SD). AMD is a worldwide common problem associated abandoned coal mines of abandoned-active coal and metallic sulphide mines (Webba and Sasowsky, 1994). This type of drainage generated when water infiltrates through concentrated zones of iron sulphide minerals (pyrite and marcasite). These minerals are either exposed to atmospheric oxygen during mine-digging processes or in sulfide-rich mine wastes, which are normally dumped on the surface during mine construction and ore exploitation processes (Banks, 2003). Another source of AMD is associated with highway road cuts, and subway and tunnel construction performed through strata enriched with iron disulphide (Caruccio et al., 1988; Skousen et al., 1998). The iron disulphide will oxidize through very complex arrays of chemical reactions. These reactions are catalyzed and thus, enhanced by microbiological activities (Kleinmann, 1998; Wolkersdorfer, 2008) causing release of Fe2+ -2 and SO4 as well as to increase the acidity of the mine water. In addition, they consume dissolved oxygen in the mine water (Evangelou and Zhang, 1995; Banks et al., 1997; Costello, 2003; Lottermoser, 2007; Wolkersdorfer, 2008). The oxidation of pyrite and marcasite is illustrated in the following reaction (Wolkersdorfer, 2008);

Chapter 1: Introduction

2+ 2- + 2FeS2 (s) + 7O2 (aq) + 2H2O 2Fe + 4SO4 + 4H Water and oxygen are major factors controlling iron disulphide oxidation (Hammack and Watzlaf, 1990). So removal of one or both of these factors from the oxidation zone will slow down or cease the process. (Skousen et al., 1998). On the other hand, if sufficient oxygen is present in the oxidation medium, the equilibrium condition of ferrous iron Fe2+) resulting from the above mentioned reaction will change and the iron will oxidize to ferric iron Fe3+ as described in the following reaction (Banks, 2003);

2+ + 3+ 2Fe + ½ O2 + 2H 2Fe + H2O This process is associated with consumption of hydrogen, which reduces the acidity of mine water. As the 3+ reaction continues, the released ferric iron Fe precipitate s as iron hydroxide Fe (OH)3. This process is associated with the release of hydrogen ions and an increase of the acidity of mine water as illustrated as follows (Rose and Cravotta, 1998);

+3 + 2Fe + 6H2O 2Fe(OH)3 (s) + 6H In some cases ferric iron acts as a catalyst and attacks pyrite. This process is independent of oxygen and requires highly acidic conditions (pH ≤ 4). Pyrite oxidation by ferric iron produces more sulphate, ferrous iron and acidity as shown in the following reaction (Wolkersdorfer, 2008);

+3 -2 +2 + 14Fe + FeS2 (s) + 8H2O 2SO4 + 15Fe + 16H Other sulfides and metal minerals, which are often associated with pyrite, are also subject to the same oxidation conditions, when exposed to oxygen and water. These conditions change the equilibrium state of these minerals. Sulphide minerals like galena, sphalerite, greenockite, covellite, chalcopyrite, millerite, and others will also oxidize and cause an additional increase of sulphate and undesirable ions in mine water as described in the following reactions (Younger et al., 2002; Wolkersdorfer, 2008);

2+ 2- PbS(s) + 2O2(aq) = Pb + SO4 2+ 2- NiS(s) + 2O2(aq) = Ni + SO4 2+ 2- CdS(s) + 2O2(aq) = Cd + SO4 2+ 2- CuS(s) + 2O2(aq) = Cu + SO4 2+ 2+ 2- CuFeS2(s) + 2O2(aq) = Cu + Fe + 2SO4 These reactions only increase the sulphate concentration and the associated cations, so no direct acidity will arise from these processes (Banks 2003), but precipitation of releasing metals leads to release of H+ (Wisotzky, 2004). In addition, these minerals have different reaction rates and weathering resistances that affect the concentration of the associated cations over time (Lottermoser, 2007). On the contrary, the alkali and alkaline earth elements reduce or prevent the generation of AMD (Dold, 2005). This phenomenon is related to the consumption of hydrogen ions (Banks, 2003). Carbonate and silicate minerals are the most known natural attenuation minerals of AMD (Younger et al., 2002). In addition, hydroxides, borate, organic ligands, phosphate and ammonia have also buffering capacity to mitigate the AMD (Watzlaf et al., 2004). These reactions consume the acidity of mine water and precipitate the undesirable metals as hydroxides and oxyhydroxides (Banks, 2003; Costello, 2003).

Chapter 1: Introduction

Silicates are the major minerals in the Earth’s crust, and are the main reservoir of buffering capacity in the environment (Lottermoser, 2007). The chemical weathering of silicate minerals consumes hydrogen ions and release dissolved cations (Ca, Na, K, Mg, Mn or Fe) and silicic acid. These processes have buffering capacities that could increase the pH value of groundwater up to 10 (Cherry and Freeze, 1979). Silicate weathering can be divided into congruent and incongruent reactions (Hiscock, 2005). The congruent reactions are represented by full dissolution of the silicate minerals in the solution, while the incongruent reactions are represented by partial dissolution of silicate minerals (Hiscock, 2005). The incongruent types are more common than the congruent reactions and are accompanied with a change in the silicate phase. This change is represented by the formation of clay minerals (Montmorillonite, Kaolinite, Sanidine, Adularia or Microcline) (Lottermoser, 2007);

+ + congruent 2MeAlSiO4(s) + 2H (aq) + H2O → Mex (aq) + Al2Si2O5(OH)4(s) incongruent MeAlSiO + + + 3H O → + + 3+ + H SiO + – 4(s) H (aq) 2 Mex (aq) Al (aq) 4 4(aq) 3OH (aq) Where Me includes Ca, Na, K, Mg, Mn, or Fe. Weathering of Plagioclase consumes the acidity and caused the release of Ca2+, Na+ to the water as described in the following reactions (April et al., 1986; Younger et al., 2002).

+ + 2NaAlSi3O8(s) + 2H + 4H2O(l) → 2Na + Al2Si4O10(OH)2(s) + 2H4SiO4(aq) Albite (aq) (aq) + + 2NaAlSi3O8(s) + 2H (aq) + 9H2O(l) → 2Na (aq) + Al2Si2O5(OH)4(s) + 4H4SiO4(aq) Anorthite CaAl Si O + + + H O → 2+ + Al Si O (OH) + 4H SiO 2 2 8(s) 2H (aq) 2 (l) Ca (aq) 2 2 5 4(s) 4 4(aq) In contrary, K+ can be released by weathering of K-feldspar. This process consumes also the acidity and produces Kaolinite (clay minerals) as described in the following (Deer et al., 2001; Banks, 2003).

2KAlSi O + 2H+ + 9H O → 2K+ + Al Si O (OH) + 4H SiO 3 8(s) (aq) 2 (l) (aq) 2 2 5 4(s) 4 4(aq) The weathering of the resulting Kaolinite will also consume the acidity of the mine water as described in (Banks, 2003):

+ 3+ Al2Si2O5(OH)4(s) + 6H (aq) → 2Al (aq) + 2H4SiO4(aq) + H2O Silicate minerals have different weathering velocities, which are associated with different buffering ranges (Bowell et al., 2000). Anorthite has a fast weathering velocity, while the other plagioclase minerals such as albite, oligoclas, and labradorite have slow weathering velocities. K-feldspar has a very slow weathering velocity (Sverdrup, 1990) in comparison with plagioclase. Sometimes hydrolysis of plagioclase is sufficiently fast to neutralize acidity produced by low rates of iron sulphide oxidation (Suryaningtyas and Gautama, 2008). But in general, weathering of silicate minerals, characterized by a very slow speed (Wollast and Chou, 1988), have low pH buffering values and relatively long lifetime (Wolkersdorfer, 2008). So silicate minerals are considered a long-term source of alkalinity (Lacroix et al., 2012). The neutralization rate of the acidity by each cation is equal to its valence in the mineral structure (Weber et al., 2005). On the other hand, carbonate minerals play an important and maybe prevailing role in the buffering and neutralization of AMD. Their importance is related to their ability to consume the H+ ions that dissolve in the mine water by dissolution processes. Moreover, their rapid solubility increases the alkalinity of the water

Chapter 1: Introduction

(Stumm et al., 1992). In some cases, the rapid dissolution of carbonate minerals contained in mine waste is sufficient to preserve the neutral condition of mine water (Watzlaf et al., 2004). Calcite, dolomite, ankerite and siderite are the most abundant carbonate minerals in mine waste. Their dissolution in the affected water will release calcium, magnesium and iron and additionally increase the alkalinity of the mine water (Al et al., 2000; Younger et al., 2002; Douglas and Degens, 2006). Calcium carbonate is generally used in the mitigation of AMD. This fact relates to its low cost and its low solubility in alkaline conditions (Maree and Du Plessis, 1994). The neutralization mechanisms of AMD through the dissolution of carbonate minerals can be explained by the following chemical reactions (Cravotta III et al., 1990; Cravotta III and Trahanb, 1999; Banwart and Malmström, 2001; Lottermoser, 2007; Turekian et al, 2005; Wolkersdorfer, 2008; White, 2013);

+ 2+ – Calcite CaCO3(s) + H (aq) = Ca (aq) + HCO3 (aq) + 2+ Calcite CaCO3(s) + 2H (aq) = Ca (aq) + H2CO3(aq) + 2+ - Sedirite FeCO3(s) + H (aq) = Fe + HCO3 + 2+ 2+ − Dolomite MgCa(CO3)2(s) + 2H = Mg + Ca + 2HCO3 + 2+ 2+ Dolomite MgCa(CO3)2(s) + 4H = Mg + Ca 2CO2(g) + 2H2O Generally, Calcite and other Carbonate minerals contained in mine tailings and waste have a short attenuation period due to their rapid dissolutions (Banwart and Malmström, 2001). If the sulphide contents of the tailings and the mine waste exceeds the carbonate content, AMD will generate and the water quality will deteriorate due to the decrease of the pH and increase the concentrations of the undesirable metals (Banwart and Malmström, 2001). In addition, the dissolution of carbonate minerals in mine water can be limited by armoring the surface of the minerals (Sasowsky et al., 2000). This process results from precipitation of dissolved metals, such as Al, Fe and Zn, on the surface of the minerals (Banks, 2003). Thus the mobility of the minor elements will reduce by the elevation of the alkalinity (Banks, 2003, Maree et al., 2004). These conditions will reduce the effective reactivity of the carbonate minerals and reduce the neutralization capacity of these minerals (Sasowsky et al., 2000). The most common example of this process can see by the calcium carbonate, which is generally used in the mitigation of AMD according to its low cost and its low solubility in alkaline conditions (Maree and Du Plessis, 1994). This phenomena result of precipitation of siderite, which generates by the reaction of the mine water with the carbonate resulted from the dissolution processes, on the surface of the calcite in the mine water (Al et al., 2000). However, many other chemical compounds such as (phosphate, boron, disulphide, ammonia or organic compounds) are also present in the natural water. These compounds have also the ability to consume the H+ ions as shown in the following reactions (Zhu and Anderson, 2002).

-2 + -2 Phosphate HPO4 + H = H2PO4 + Boron BOH4 + H = BOH + H2O - + Disulphide HS + H = H2S + Ammonia NH3 + H = NH4+

Organic + CH3COO + H = CH3COOH compounds

Chapter 1: Introduction

In addition, hydroxides and exchange compounds of Ca2+, Mg2+ and Na+, present in the soil covers, contribute also in the neutralization process of the acidity as shown in the following reactions (Merkel and Planer-Friedrich, 2008; Tan, 2011; Costello, 2003; Cravotta III et al., 2010 ).

+ 3+ AlOOH + 3H = Al + 2H2O + 3+ Al(OH)3 + 3H = Al + 3H2O + 3+ 2Fe(OH)3(s) + 6H = 2Fe + 6H2O + 3+ Fe(OH)3 + 3H = Fe + 3H2O + 2+ Fe(OH)3 + 2H = Fe + 0.25O2 + 2.5H2O + 2+ Fe(OH)2 + 2H = Fe + 2H2O + 3+ FeOOH(S) + 3H = Fe + 2H2O + +2 Mn(OH)3 + 2H = Mn + 0.25O2 + 2.5H2O + 3+ MnOOH + 3H = Mn + 2H2O + + 2+ Zn(OH) (aq) + H = Zn + H2O + 2+ Zn(OH)2(s) + 2H = Zn + 2H2O + 2+ Mg(OH)2 + 2H = Mg + 2H2O + 2+ Mn(OH)2 + 2H = Mn + 2 H2O + 2+ Ca(OH)2 + 2H = Ca + 2 H2O + + NaOH + H = H2O + Na

1.2.2. Hydrogeochemical modelling

The Hydrogeological models are effective tools, based on the use of mathematical equations of thermodynamics, to estimate the possible reactions and thermodynamic conditions controlling the groundwater quality along the flow path (Plummer et al., 1983) controlling the kinetics of chemical reactions (Zhu, 2009). The processing operations in these models are based on the hydrochemical parameters, which are usually measured in samples that are collected from the aquifers or other water bodies (Plummer et al, 1983). These models have the possibility to simulate a wide range of hydrochemical reactions including the equilibrium reactions between water and minerals, surface complexes, ion exchangers, and other reactions that include solid, gaseous, and solution phases as well as to other processes considering microbial and organic reactions (Charlton and Parkhurst, 2011). The Speciation-Solubility geochemical model describes the equilibrium state of the aqueous solutions (Charlton and Parkhurst, 2002) by calculating the distribution of the aqueous species in the water and determines if a mineral should dissolve or precipitate. Dissolution and precipitation conditions are related directly to the value of the saturation indices (Charlton and Parkhurst, 2002), which represent the degree of equilibrium between water and the minerals (Appelo and Postma, 1993). The calculated value of the saturation index of a mineral gives the possibility to determine the source/sink of this mineral under the natural water conditions (Powell and Larson, 1985). Due to this discussion, calculation of saturation indices serves as a basis to determine the water-rocks interactions (Zhu and Anderson, 2002). In addition, the speciation-solubility geochemical model is considered as a basis for the more complex hydrogeochemical models (Zhu and Anderson, 2002). The saturation index of a mineral can be calculated by the following relationship (Parkhurst and Appelo, 1999, Merkel and Planer-Friedrich, 2008): SI = log (IAP/K**)

Chapter 1: Introduction

Where IAP is the ion activity product and K** is the equilibrium constant. Three states of the equilibrium can be recognized by the calculated saturation index. The subsaturated condition is represented by SI<0, the equilibrium condition by SI=0 or close to 0 and supersaturated condition by SI>0 (Parkhurst and Appelo, 1999, Mande et al, 2011). According to the complexity of the natural water systems, the equilibrium models were divided into homogeneous and heterogeneous groups. This fact is related to the number of substances dissolved in water, whereby the increase of the number of materials dissolved in water is associated with an increase of the concentrations of metals and gases, and the generation of the very complex Three-Phase-System of solid- water-gas (Parkhurst and Appelo, 1999). Whereupon more complex interaction will exist between these phases. Therefore, prediction of real mineral or gas solubility will be very complex and more difficult. In the abandoned coal mines the reactions between some species, resulting from oxidation and neutralization processes in the mine water, will precipitate some compounds due to the accumulation of these salts in mine water, reaching the saturation degree (Bowell, 2002).

1.3. Problem statement and the aim of this study

Germany has the largest coal reserves in the Europa. The coal deposits include lignite, which situated in Rhineland, Lusatia, and central German basins, and hard coal deposits, situated in the Ruhr and the Saar basins (Kelly, 2009; Miller, 2010). The active coal mine will be regulated to close by 2018 and they will be abandoned. These conditions impose the need to assess the effects of these procedures on the hydrological regime of watersheds. The abandoned coal mines in the south of Bochum belongs to the Ruhr hard rock mining, where several coal mines were active between the 17th and 20th centuries (Hermann and Hermann, 2008). Coal deposits were extracted using different techniques including horizontal, inclined and vertical shafts. Deep mining in this area was conducted only in the 20th century after the invention of the steam engines (Huske, 2006). In addition, dewatering and other facility structures such as adits, drainage adits and shafts were also constructed to facilitate the exploitation process as well as to get rid of problems associated with mining works, including the danger caused by flooding and may be drowning the whole mine (Hermann and Hermann, 2008). Due to the exploiting processes, large amounts of coal were extracted and shipped through the Ruhr, while the resulting mining waste were dumped near the shafts and entrances (GLA-NRW 1988). During extraction processes, many mines were connected via shafts and other extraction structures, which in turn increased the rate of coal extraction (Huske, 2006). Coal mining in this area continued until the beginning of the 20th century. In the Lottenbachtal, the last mining activities were suspended in 1961 with the closure of the Klosterbusch mine. The mines were either sealed or backfilled by using various materials, mainly of mining waste and to a lesser extent from ash, garbage, slags, sludge, construction waste, industrial residues and household waste (GLA-NRW, 1988). This area is a catchment of the Ruhr, which represent the water supply source of the industrial and drinking water for its 5 million inhabitants (Bode et al., 2003).

Chapter 1: Introduction

Therefore, studying the impact of abandoned coal mines on the water cycle at the small scale can help in the understanding of the factors and processes governing the water balance at the large basins. Thus, the main objective of this research is studying the hydrological, hydrogeological and hydrogeochemical characteristics of the Lottenbachtal as a small watershed, which influenced by the coal- mining and post mining activities. Many stages must be investigated to achieve the purpose of this thesis, which are;  Study the impact of abandoned coal mines on the surface water and groundwater quality, and determine the severity and the environmental hazard.  Investigate the other factors that contribute to the chemical evolution of the water quality, especially the diversity of the land use.  Studying the hydrochemical behaviors of the Lottenbach during storm events and investigate which factors govern these behaviors.  Select the most appropriate method for hydrograph separation.  Investigate the hydrological, the hydrological and the hydrochemical framework of the Lottenbachtal catchment area, which should be concluded by calculating the water balance, calculate the rations of its component, and establish a conceptual model of the study area. The specific aims of these study include: . Investigate the impact of abandoned coal mines of the Ruhr hard rock mining on the hydrochemical characteristics of the surface water and groundwater. . Investigate the generation of Acid Mine Drainage (AMD) and investigate the passive attenuation. . Identifying the hydrochemical characteristics of the surface water and ground water. . Investigate the hydrochemical behaviours of the stream flow during storm events, the factors governing of these responses, the role of each factor and the potential flow paths. . Identifying the most convenient method of hydrograph separation. . Investigate the physical and the chemical properties of the hydrological, hydrogeological and the hydrochemical framework of the study area. . Identifying the element of the hydrologic cycle of the study area and calculation the water balance. . Construction a conceptual model of the study area, which assess in the understanding of the hydrological and the hydrogeological processes of this catchment. . Prognoses of the surface water and groundwater balance by calculating the relative frequency and the ration of the component of the water balance.

1.4. Previous studies

Due to the small space of the study area, only a very small number of studies have been conducted in this area. However, the Lottental has a special importance because it is the largest stream system in the south of Bochum. The natural conditions of this stream have changed dramatically as a result of urban development

Chapter 1: Introduction and changes in the land use in this watershed and the surrounding areas. Due to the existing of the Refugial- biotope and the possibility of re-development its various lines, this stream has a significant importance for nature development and recreation in the city of Bochum (Viebahn-Sell, 2001). So that several studies were performed by Viebahn-Sell, to evaluate and study the possibility of restoring the stream course with consideration the ecosystem. The main aim of this project was to assess the possibility of reducing the risks caused by floods in order to disclosure of pipe sections, deconstruction of the precast canal sections and realignment of stream sections. So that, the overall considerations and analysis of the connections (the discharge conditions) will be the basis for developing of retention measures. According to the complexity of the hydrological conditions of the study area. The project was divided into two phases; the first phase included the inventory and evaluation of the ecosystem, while the second phase dealt with the development of conceptual measures for the canal retentions, taking into account the ecosystem (Viebahn-Sell, 2006). A total of 20 hydrological connections were ecologically tested to investigate: • The hydraulic characteristics including the computational comparison of acceptances and the actual discharge • The structural features including evaluation of the terrain surveys concerning erosion, deposition and profile geometry. • The hydro-biological parameters with respect of functional analysis of macrozoobenthos groups, analysis of communities and determining the biological quality of the water. The permitted annual connection discharges and the actual runoff discharge, which results from these connections, as well as to factor of the increasing of the potential natural annual runoff were calculated in these studies based on mathematical and result of a large scale hydrological model. The results of the computational methods were complemented by some field investigations of the stream structure and the hydrogeological conditions. In any case, many difficulties emerged during the previous studies as a result of the piping or the removal of the sealed sections of the stream channel, as well as to the changing of the natural gradient as a result of the anthropogenic effects. So that the values of the discharges of the hydraulic connections were overstated. The rehabilitation of some hydraulic connections was also determined based on the results of these studies. According to the result of these studies, the restoration of Lottenbach stream and their connection will only improve the hydroecological conditions of the watercourse. On the other hand, these procedures will also increase the rehabilitation needs. These studies also had recommended that water management principles should be taken into account during the restoration of the hydraulic connections. These procedures aim to provide sufficient support for sensitive sections.

Chapter 2: The Physical Characteristics of the Study Area

2. The Physical Characteristics of the Study Area

2.1. Location

The study area is located in the south of Bochum, a city in the North Rhine-Westphalia state in Germany (Fig 2.1). The study area comprises the Lottental, which is one catchment of the Ruhr and the southern bank of the Kemnade lake. The research area occupies a total area of 9.6 km2, and is situated in the upper terrace level of this river (Viebahn-Sell, 2001).

Fig 2.1: Location map of the study area including the Lottenbachtal and the southern banks of the Kemnade lake.

Chapter 2: The Physical Characteristics of the Study Area

2.2. Geographic position

The study area is located within the transition zone separating the Bergisch-Sauerländischen Uplift to the south and the Westphalian lowlands to the north. The mountainous structure of shallow hills separated by steep sloped v-notched valleys predominate the relief of this area (GLA-NRW, 1988).These hills are characterized by a layered rib landscape, represented by elongated narrow ridges and flat hollows (Viebahn- Sell, 2001). In addition, the natural landscape of the Lottenbach watershed is largely cut up and dissolved (Viebahn-Sell, 2001).

Fig 2.2: The digital elevation model (DEM) of the study area including a topographic cross section (A A1).

Chapter 2: The Physical Characteristics of the Study Area

The highly folded Upper Carboniferous deposits are covered by a low thick cover of the loess (GLA-NRW, 1988). The Lottental valley is a V-shaped valley of small tributaries that also have notched bottoms and low gradients (Viebahn-Sell, 2001). The elevation of the study area ranges between a maximal of about 180 m on the middle and a minimal of about 70 m in the southern part located on the bank of the Kemnade Lake (fig 2.2).

2.3.General climatic conditions

The study area is characterized by marine climate conditions, which is represented by mild winters and cool summers (LANUV, 2010). Sometimes, long periods of high atmospheric pressure of cool periods in the winter and dry-hot weather in the summer are predominate in the study area, these conditions linked to continental effects (LANUV 2010). However, the average of annual air temperature in this area is 10.40 °C. The average minimal annual air temperature is 2.70 °C and average of maximum annual air temperature is 18.50 °C. Average of annual wind velocity is 3.5 m/s, average of annual relative humidity is 75%, average of annual sunshine duration is 1229.50 hrs/a and the average of annual rainfall is 817.6 mm/a (Grudzielanek et al 2011). Fig 2.3 show the mean values of the monthly precipitations data, of the period (1888-1985), and the average of the monthly air temperature, of the period (1912-1985).

Fig 2.3: Average of the monthly air temperature and the precipitation of Bochum for the period 1888- 1985 (modified after GLA-NRW, 1988).

2.4. General geological settings

The Ruhr basin is a portion of the external folding and thrust belt of the Variscan orogeny. The sediments of this basin consist mainly of molasse sequence, which is more than 6000 m thick. These sediments were deposited in Namurian and Westphalian age. Coal deposition had started in the Namurian C, reached its

Chapter 2: The Physical Characteristics of the Study Area maximal capacity in the Westphalian A-B and had ended in the Westphalian D. A total of 250 coal seams were formed in this basin, but only 50 of them have economic value (Drozdzewski, 1993). The Carboniferous deposits in the Ruhr basin are divided into Lower and Upper parts. The Lower Carboniferous (Dinantium) in this area consists mainly of chalky facies (carbonaceous limestone) and clayey-sandy (Kulm) deposits. These deposits were developed in sea and predominate in the Rhenish Massif. The Upper Carboniferous (Selisum) represents the transition from the marine to the non-marine environment (Grabert, 1998). This part was divided into the Namur (A, B, and C), the Westphalian (A, B, C, and D) and Stefan (A, B, and C). The Namur is closely adjoins to the Dinant (Lower Carboniferous), represented by the absence of coal deposits. In general, the Namur doesn’t contain bituminous coal seams.

Fig 2.4: The geologic map and the geologic cross section of the study area (modified after GLA-NRWa, 1988).

Chapter 2: The Physical Characteristics of the Study Area

The Upper Carboniferous in the study area belong to the Westphalian A. These deposits situated under the loss-loam cover, which belong to the Quaternary age and consist mainly of terraces of the Ruhr, melt water- and loess deposits (Littke et al., 1986). The Westphalian A deposits in this area were divided locally into Bochumer Schichten and Wittener Schichten formations as shown in Fig 2.4. The Bochumer Schichten formation is situated in the southern part of the study area and consists mainly of the mudstone, which contains limited deposits of the sandstone. The Bochumer Schichten formation is rich in coal deposits. The total thickness of this formation is about 650 m. The economic coal thickness is ranged between 10 and 20 m (Hahne and Schmidt, 1982), which includes the Präsident, the Sonnenschein and the Plaßhofsbank (GLA-NRWa, 1988). The Bochumer Schichten deposits start with marine horizon, represented by Linguliden, Productiden or Goniatites and situated above the Plaßhofsbank seam. Non-marine effect was also noted in the middle and upper part. This effect represent by plants, non-marine molluscs and ostracod (GLA-NRW, 1988). In the south of the study area, the Westphalian A deposits are called Wittener Schichten. This formation consists of clay, siltstone and sandstone (Littke et al., 1986). The siltstone deposits have sand content ranging from very low to high rates and it ranges in colour from grey to grayish black. The massive sandstone beds of this formation contain several Horizons of Lingula. The sandstone packages lay in the footwall of the seam Finefrau. This unit is mostly interspersed by conglomerates (Hahne and Schmidt, 1982). The coal seams of Finefrau and Geitling, which has economic value, are located in these sediments (GLA- NRW, 1988). The average value of coal deposits in this formation ranged between 14 and 20%. (Hahne and Schmidt, 1982). The study area is characterized by a complex tectonic structure due to Variscan orogeny, which is represented by highly complex tectonic processes. The tectonic structure is characterized by southwest- northeast folds of wide stretched synclines separated by narrow saddles. These folds are associated with overthrust, normal and strike slip faults, which shifted the folds and other structures in horizontal and vertical directions. (Littke et al., 1986).

2.5. Landuse

The study area has been subjected to the anthropogenic effects to a great extent, after it was dominated by pastures and forests (Viebahn-Sell, 2001). The anthropogenic effects result from the mining activities, which extended from the period between the 17th to the 20th centuries. The extraction processes and the construction of the mining facilities including the adits and the shafts changed the topographic relief of the study area. These activities were followed by expansion the settlement areas, especially after the second world war. These processes were associated with landfilling, and road constructions, which increased the area of the impervious area. In addition, the construction of the Ruhr University of Bochum and its infrastructure were associated with sealing and overbuilding a large area in the north-eastern part of the study area (Viebahn- Sell, 2001).

Chapter 2: The Physical Characteristics of the Study Area

However, the study area remains characterized by rural conditions, which could be seen in the rural features of grassland and pasture fields. The deciduous and the small coniferous forests increase the green spaces and the variety of the land use in this area (Viebahn-Sell, 2006) as shown in Fig 2.5, which was digitized from a map that was adopted from Google Earth.

Fig 2.5: The Landuse map of the study area in 2010-2011 (The background map was adopted from Google Earth).

2.6. Mining activities

The study area was subjected in the past to hard coal mining works as a part of mining activities of the Ruhrkarbon deposits (Hermann and Hermann, 2008). Thus, many mines were constructed in this area. The first mine (Zeche Alte Mißgunst) in this area was established on the early of 17th century, while most of the other mines were established in the 18th century (Huske, 2006). In addition many adits, drainage adits and shafts were constructed for mining and dewatering processes. Large amounts of coal were being extracted and mining wastes were dumped on small and large piles near the shafts and mouth of tunnel holes. During extraction processes many mines were consolidated. Coal was extracted through horizontal, inclined, and vertical shafts. Deep mining was conducted in the 20th century as a result of industrial development and the invention of steam engine. Mining activities continued until the early twentieth century, and all mines are

Chapter 2: The Physical Characteristics of the Study Area either sealed or backfilled (Huske, 2006). The location of the hard rock mining and their facilities in the study area are shown in Fig 2.6. Landfill processes of these mines and other mines located in the surroundings have been done in large extent, different materials were used in these processes, these materials conclude mostly stockpiling of tailings .and piling, in addition hollow morphological forms like ash, slags, sludge’s, construction waste, industrial residues and household waste were also used for this purpose (GLA-NRW, 1988).

Fig 2.6: The mining map of the study area including the mine sites and the other facilities such as the drainage adits and the tunnels (modified after GLA-NRW, 1988; Tiedt, 2009).

2.7. Soil cover

Many soil units present in the study area, this represent the top soil zone. The development of these units are significantly related to the geologic and geomorphological conditions (GLA-NRW, 1988). According to fig 2.7; the following soil units are existing in the study area (GLA-NRWc, 1988):  Soil unit 1 (Gleysols): This unit consist of silty-clayey deposits changed from silty loam to strongly loamy silt. Sometimes, the soil of this unit show stony structure situating above sandy-gravelly sediments. These deposits were formed by the sedimentations processes of the Lottenbach stream. Therefore their spread are limited to small scale in the narrow V-shaped valleys of the Lottenbach 16

Chapter 2: The Physical Characteristics of the Study Area

stream and its tributaries. In terms of Hydrogeology, this unit is characterized by moderate to high sorption capacity, which associated with a moderate to high available water capacity and low to medium hydraulic permeability.  Soil unit 2 (Brown earth- Podzol, some places Podzol and Brown earth): The deposits of this unit were formed by weathering of the Upper Carbonferious sandstone. Its sediments extended from slightly loamy-stony sand to silty sand. This unit characterized by low to very low sorption capacity, which accompanied with low to very low available water capacity and high hydraulic permeability. This unit spread as elongated belts that situated on the narrow ridges.  Soil unit 3 (Luvisols, partly Stagnosol-Luvisols or brown earth, in some places eroded): this unit consists of loamy silt changed to silty loam. The silty loam deposits show sometimes a slightly gritty structure. This group is the most widespread one in the study area. Its sediments characterized by high sorption capacity, high available water capacity, moderate hydraulic permeability and waterlogging.  Soil unit 4 (Stagnosol-Luvisol partly Luvisol or Brown earth): This unit composed of weak to strong- loamy silt. Its sediments represented by moderate to high sorption capacity, associated with moderate to high available water capacity and moderate hydraulic permeability.  Soil unit 5 B4 (Brown earth and Luvisols, in some places Stagnosol and Brown earth, often Podzolic): The soil of this group is absent in the Lottental. Its existence is limited to a small plot in the south of the study. Its deposits ranged between sandy-silty loam and silty-loamy sand, which is ofen gravelly. This unit represented by moderate available water capacity and moderate hydraulic permeability.  Soil unit 6 (Brown alluvial partly gleyed): this unit is also absent in the Lottental. Its widespread is limited to the banks of the Kemmade lake, where it is situated as a narrow belt surrounds the lake reservoir. The sediments of this unit consist chiefly of sandy-loamy silt, which could be changed to silty loam. These deposits characterized by high sorption capacity accompanying with usually high available water capacity and moderate to high hydraulic permeability.  Soil unit 7 (Brown earth, some places Rankers, often Podzolic): this group consist of strong stony- loamy silt changed to silty-loamy sand. It depositions spread in the form of a narrow belts extending from north-east to south-west. This soil has low sorption capacity, low available water capacity and moderate to high hydraulic conductivity.  Soil unit 8 (Brown earth, in some places Stagnosol-Brown earth, mostly Podzolic): this deposits vary from stony-silty loam to sandy-silty loam. The presence of this group is limited to a small spot in the western part of the Lottental catchment area and a package of prolonged belts in the south of the study area. this group has moderate sorption capacity, low to moderate available water capacity and moderate hydraulic conductivity  Soil unit 9 (Stagnosol and Luvisol- Stagnosol, in some places gley and Stagnosol): This type of soil spread in areas adjacent to the flood plains of the tributaries of the Lottenbach stream. Its deposits 17

Chapter 2: The Physical Characteristics of the Study Area

vary from loamy to strong-loamy silt and it has moderate sorption capacity, high available water capacity and low to moderate hydraulic conductivity.  Soil unit 10 (Brown alluvial soil): The presence of this group is limited to a small spot in the south of Bochum. Its sediments consist of weak loamy sand, which vary to strong sandy loam. This type of soil has low to moderate sorption capacity, moderate available water capacity and moderate to high hydraulic conductivity.

Fig 2.7: The soil map of the study area (modified after GLA-NRWc, 1988), the unit numbers are related to the unit numbers in the text.

2.8. General hydrological and hydrogeological conditions

According to the Landesumweltamt Nordrhein-Westfalen (LUANW, 2002), the Lottenbach stream was classified as a small floodplain in the basement (Viebahn-Sell, 2006). This stream is a v-shaped stream of few kilometers space and it is the largest remaining stream system in the south of Bochum. The Lottenbach and its tributaries were subjected to significant changes as a result of the mining works and the subsequent expansion of the settlement area. These changes are represented by the large number of artificial drainage canals, which connected directly to the main watercourse and its tributaries (Viebahn-Sell, 2001). The 18

Chapter 2: The Physical Characteristics of the Study Area drainage canals included the former drainage adits, which normally establish for the disposal of water percolating into the mines (Hahne and Schmidt, 1982) and storm sewer systems (Viebahn-Sell, 2006). In addition, the natural flow path of this stream was changed as a result reconstruction some of its parts. These parts were built up by concrete plates. The eastern part of this stream was piped completely, where the stream flows through this pipe into the Kemnade Lake (Viebahn-Sell, 2001; Viebahn-Sell, 2006). Three main types of drainage system can be found in the Lottenbachtal. The first type is the combined sewer system, which located in the west and south, characterized mainly by residential areas. In this type, domestic water and rainfall water drain via a common channel that ended at the Ölbachtal wastewater treatment plant, located in the east. However, storm water of this system can also flow into the Lotenbach during heavy precipitation events (Viebahn-Sell, 2006). The second type is the drainage systems of the Lottenbach, which represented by a separated sewer system. This system is represented by separate storm water and waste water channels as shown in fig 2.8. Storm water sewer was limited to two drainage areas, where there is no information about the domestic water sewer in these areas. The former creek of Brenschede (in the west) was subjected to landfill operations. A combined sewer traversed the floodplain of this creek, which dissipates the discharge of the springs in this part. Spring discharge is seen only in the mouth of the creek (Viebahn-Sell, 2001). The general hydrogeology of the study area is characterized by the dominance of hard rock aquifers. These aquifers consist mainly of fissured sandy silt- and mudstone deposits of the Upper Carboniferous (Silesian). The hydraulic characteristics of these aquifers are affected by stratigraphic and tectonic structures. These effects are represented by bedding surfaces, cracks, faults, fractures and joints. So percolated water store in these features and flow through bedding joints and other tectonics structures. (GLA-NRW, 1988). The hydraulic properties of these aquifers range between moderate and very low permeability (GLA-NRWe, 1988). The Kemnade reservoir was established in 1980 and is in the southern part of the study area. This lake was developed for leisure and water sport activity and it has a storage capacity of 3 million cubic meters (Auffermann, 2010).

Chapter 2: The Physical Characteristics of the Study Area

Fig 2.8: The map of drainage systems in the study area (modified after Viebahn-Sell, 2006).

Chapter 3: Environmental Impact of the Abandoned Coal Mines on the Surface Water and the Groundwater Quality in the South of Bochum, Germany.

3. Environmental Impact of the Abandoned Coal Mines on the Surface Water and the Groundwater Quality in the South of Bochum, Germany.

3.1. Abstract

Surface water and groundwater samples were collected from twenty locations, situated in the vicinity of the abandoned coal mine fields south of Bochum. The main objective of this research is to assess the environmental impacts of these mines on the surface water and groundwater quality as well as to determine the factors controlling these impacts. In addition to identifying other potential sources that could contribute to the pollution of surface water and ground water in this area, characterized by the diversity of land use. The water samples collected from streams sources, groundwater, surface water and engineered channels during April 2011. Physico-chemical tests including pH, redox potential (Eh), electrical conductivity (EC), temperature (T) and dissolved oxygen (DO) measured during fieldwork. Water samples were analysed for 2+ 2+ + + 2- - Calcium Ca , Magnesium Mg , Sodium Na , Potassium K , Sulphate SO4 , Chloride Cl , Bicarbonate - - 2+ HCO3 , Nitrate NO3 , Aluminium Altotal, Iron Fetotal, Manganese Mntotal, Ferrous iron Fe , Zinc Zntotal and

Hydrogen sulphide H2S. The hydrochemistry of surface water and the groundwater of this area is 2+ - characterized by near-neutral to alkaline conditions, represented by predominance of Ca , HCO3 and 2- sometimes SO4 . Hence, the surface water and the groundwater quality in this region is significantly affected by abandoned coal mines. These effects resulted by oxidation of iron disulphide minerals that release Fe, 2- + SO4 and H into the impacted water. The presence of carbonate-rich materials, which might be contained within the landfilling materials used in sealing operations, could have led to the mitigation of acidity and 2+ 2+ - releasing of Ca , Mg and HCO3 . This material could be the main source responsible for raising the alkalinity of the affected water. The environmental hazard of the abandoned coal mines in this area is represented by pollution of groundwater and surface water. This is related to the high concentration of Fe, especially in the groundwater, which contains the highest Fe concentration compared to other water sources: the Fe is 18 times larger than the allowed value in drinking water. Significant spatial variations of the water pollution were noted in this study. These variations may be related to the presence of sampling points within or far from the zones of high efficiency. Thus, the presence of surface water and groundwater with higher pollution degrees in the surrounding catchment areas is also possible. For this reason, the environmental hazards of the abandoned coal mines in Germany should be considered at the closure of the coal mines in the near future. These mines will be the sources of an environmental threat unless all necessary measures are taken to reduce their impact. Other environmental impacts on the surface water and groundwater in this area may result from other anthropogenic factors, such as by the suburban and the agricultural activities. These impacts are responsible for the additional loads of 2+ 2+ + - 2- - Ca , Mg , Na , Cl and SO4 and possibly the main sources of NO3 .

Chapter 3: Environmental Impact of the Abandoned Coal Mines on the Surface Water and the Groundwater Quality in the South of Bochum, Germany.

3.2. Introduction

Abandoned coal mines have a negative impact on the environment. These impacts represented by Acid Mine Drainage (AMD), which is a common environmental problem accompanying abandoned and active coal and metallic sulphide mines (Webba and Sasowsky, 1994). In abandoned coal mines, AMD results from the oxidation of iron sulphide minerals associating with coal deposits (WCI, 2005). This process happens by exposure of iron sulphide minerals to atmospheric oxygen and water after the closure of the mines. Water and oxygen are the major factors catalytic the oxidation processes (Hammack and Watzlaf, 1990). Conversely, mine waste, resulting during the excavation process, could also contain sulphide minerals (Lottermoser, 2007). These materials are normally dumped on the surface during mine construction and ore exploitation processes (Younger, 2003). Thus, water infiltrating through these materials can enhance the generation of AMD. AMD has negative impacts on the environment due to threats to human and aquatic organisms (Singh, 1987; Drever, 1997; Jennings et al., 2008). These threats are related to its low pH, which could be destructive to fish and other aquatic life (Lackey, 1938). In addition, the low pH value increases the concentration of total dissolved solids, heavy metals and total suspended solids of the affected groundwater and surface water (Tiwary, 2001; Johnson, 2003). Heavy metals also have a negative impact on human health, plants and animals by disturbing several biochemical processes (Mudgal et al., 2010). However, it should be noted that not all of abandoned mine water is acidic. This is because mine drainage could be neutral or alkaline (Scharer et al., 2000). Therefore, the International Network for Acid Prevention INAP (2009) classified mine water into three main types: acid mine drainage (AMD) by pH< 6, neutral mine drainage (NMD) and saline drainage (SD) by pH>6. The distinction between NMD and SD is related to the total dissolved solids TDS (<1000 is NMD and 10000>TDS>1000 is SD). The generation of AMD from abandoned coal mines has been documented worldwide. Many sites have been shown significant impact such as Witbank Coalfield in South Africa (Bell et al., 2001) and the abandoned coal workings in County Durham, England (Younger, 1995). On the other hand, weak impacts (NMD) have been observed in several other sites such as the Scottish mine waters (Younger, 2001). However, conditions ranging between strongly acidic to near-neutral or alkaline were also found in some abandoned coal fields such as the coalfields of Pennsylvania, United States (Cravotta III et al., 1999) and Makum Coalfield, India (Equeenuddin et al., 2010). Germany is world’s seventh-largest coal producer and has the largest coal reserves in the Europa. The three main coalfields of lignite deposits, which belong to the Tertiary age, are present in the Rhineland, Lusatia, and Central German basins. Significant hard coal coalfields are present in the Ruhr, the area in which the study took place, and Saar basins (Kelly, 2009; Miller, 2010). For this reason, the Ruhr area is the most densely populated zone in Europe. The coal deposits of this area belong to the Carboniferous age (Miller, 2010). The water supply depends largely on the surface waters of the Ruhr and its tributaries. This includes the industrial and drinking water for its 5 million inhabitants (Bode et al., 2003).

Chapter 3: Environmental Impact of the Abandoned Coal Mines on the Surface Water and the Groundwater Quality in the South of Bochum, Germany.

Following legislative action taken by the German government, all remaining black coal mines in Germany will be shut down by 2018. Thus, these mines will pose a real environmental threat, unless appropriate procedures taken, during and after the closures. Scientific research related to the environmental impact of abandoned coal mines on water quality are almost non-existent in Germany. Therefore, the main aim of this research studying examples of the groundwater and surface water affected by abandoned coal mines, discuss factors controlling the evolution of the hydrochemical composition, and evaluate the pollution and the environmental hazards caused by these mines and comparing them with other sites. Finally, this study aims to determine other factors that could affect the quality of groundwater and surface water, assess the gross risk resulting from all possible factors, and attempt to generalize the results to include larger watersheds.

3.3.Regional Setting

The study area (9.6 km2) is located in the south of Bochum (Fig 3.1). This area is a part of the climate zone of northwest Germany, characterizing by marine climate of cool summers and mild winters. Even though continental effects sometimes dominate, represented by long periods of high atmospheric pressure, associated with dry and hot weather in the summer and cool periods in the winter (LANUV, 2010). The average annual rainfall in the study area is 817.6 mm/a. The average air temperature ranges between 2.7 C° in the winter and 18.5 C° in the summer with an annual average of 10.4 C°. The study area is dominated by south and southwest winds, with mean velocities of 3.5 m・s-1. In addition, it has relatively high humidity with an average value of 75%. Cloudy conditions are typical, with a sunshine duration of 1229.5 hrs (Grudzielanek et al., 2011). Geographically, the study area and its surroundings are located in the transition zone separating the Bergisch-Sauerlandischen Uplands in the south and the Westphalian lowlands in the north. The topography is characterized by a layer ribs landscape that consist of small hills separated by steeply sloping v-notched valleys (GLA-NRW, 1988). The geology of the study area is characterized by the presence of Upper Carboniferous deposits (Fig 3.2), consisting mainly of the Upper Westfal A. These deposits are subdivided locally into the Bochumer Schichten and Wittener Schichten formations. Limited exposures of the Upper Namur C deposits are located in the southern part of the area (Littke et al., 1986). These deposits consist of coal seams, clay, and sandstone. In addition, the Wittener Schichten contains non-marine beds of sandy silt, sandstones, and Kaolin-Coal-Clay stone (Hesemann, 1975).

The Upper Carboniferous deposits were subjected to complex tectonic processes during the Variscan Orogeny, represented by folding and associated with over thrusts as well as normal and strike slip faults (Littke et al., 1986) as shown in Fig 3.2. The hydraulic properties of these aquifers range from moderate to very low permeability (GLA-NRWa, 1988). With regard to surface hydrology, the Lottenbach is the largest remaining stream system in the south of Bochum. This stream and its tributaries were subjected to significant changes, represented by reconstruction along sections of the flow path and by a large number of artificial drainage canals that connected directly to 23

Chapter 3: Environmental Impact of the Abandoned Coal Mines on the Surface Water and the Groundwater Quality in the South of Bochum, Germany. the main watercourse and its tributaries (Viebahn-Sell unpublished report Concept for the natural development of Lottenbach stream. Unpublished report commissioned by the civil engineering department of the city of Bochum, city of Bochum, department of civil engineering. Bochum, 2001)

Fig 3.1: Location map of the study area including sampling points of surface water and groundwater (April 2011), the stream network and abandoned mine sites and their facilities (location of mines and their facilities modified after Tiedt, 2009).

Chapter 3: Environmental Impact of the Abandoned Coal Mines on the Surface Water and the Groundwater Quality in the South of Bochum, Germany.

, as a result of the mining activities and subsequent expansion of the settlement area. The eastern part of this stream was piped completely and the stream flows through this pipe into the Kemnade Lake. The Kemnade Lake reservoir was established in 1980 on the Ruhr and forms the southern boundary of the study area. This lake was developed for leisure and water sport activities and has a total storage capacity up to a maximum of 3 million cubic meters (Auffermann, 2010)

Fig 3.2: Geological map and geologic cross section of the study area including the geological units, coal seams and tectonic features (modified after GLA-NRWa, 1988). The land use (Fig 3.3) is a combination of rural activities (fields and intensive grassland) and forests. Suburban areas are situated in the western, middle and southern part of the study area consisting of

Chapter 3: Environmental Impact of the Abandoned Coal Mines on the Surface Water and the Groundwater Quality in the South of Bochum, Germany. residential areas in the west and the middle and the campus of the Ruhr University of Bochum in the south (Viebahn-Sell, 2006).

Fig 3.3: The land use of the study area including the sampling points (April 2011) of the surface water and groundwater (the land use map was digitized from Google Earth 2010-2011).

3.4. Materials and methods

In-situ measurements, including (pH), electrical conductivity (EC), water temperature (T), dissolved oxygen (DO) and oxidation-redox potential (Eh), were performed during the field investigations. WTW and Consort portable meters were used. EC was measured by using a WTW Condi340i meter. Redox potential (Eh) was measured by CONSORT C931. (DO), (T) and (pH) were measured by CONSORT C932. Each of these instruments was calibrated using standard solutions prior to field measuring. Water samples from groundwater, surface water and engineered channels (open channels and pipes) were collected during April 2011 from 20 sites, as shown in Fig 3.1. These samples were collected intensively to include all water sources in the study area. Samples were analysed for major ions (calcium Ca2+, magnesium Mg2+, sodium Na+, potassium K+, sulphate 2- - - - SO4 , chloride Cl , bicarbonate HCO3 and nitrate NO3 ), minor elements (aluminium Altotal, iron Fetotal, 2+ manganese Mntotal, ferrous iron Fe and Zinc Zntotal) and hydrogen sulphide (H2S). According to the diversity

Chapter 3: Environmental Impact of the Abandoned Coal Mines on the Surface Water and the Groundwater Quality in the South of Bochum, Germany. of the preparation procedure required by some elements, each sample set was divided into the following sub- - 2- - samples; major anions sub-samples (Cl , SO4 and NO3 ) were collected by 50 ml polyethylene bottles after they passed through a 0.45 µm membrane filter. 2+ 2+ + + Major and minor cation sub-samples (Ca , Mg , Na and K , Fetotal, Mntotal , Zntotal and Altotal) were collected by 50 ml bottles, filtered by a 0.45 µm membrane filter and preserved by concentrated nitric acid, HNO3 1 % v/v, to prevent microbial degradation and maintain the constituents of the water samples (Nielsen and Nielsen, 2006). Ferrous iron Fe2+ sub-samples included 25 ml of water collected using 50 ml polyethylene bottles and preserved with acetic acid. - Bicarbonate sub-samples HCO3 were collected using 250 ml glass bottles. All samples were kept in a cool box and were transported to the laboratory, where they were stored below 4 C° to limit bacterial activities - 2- and the degradation of nutrient species, including (NO3 and SO4 ) (Hiscock, 2005). Hydrochemical analyses were performed by using the instruments as follows: Major dissolved ions + 2+ 2+ - 2- - (including K , Ca , Mg , Cl , SO4 and NO3 ) were analysed by the DIONEX Ion Chromatography System - model ICS-1000. HCO3 was determined using titration assay. Fetotal and Mntotal were analysed using

VARIAN Flame Atomic Absorption Spectrometry System (FAAS) model AA240F. Zntotal and Altotal were determined by UNICAM Graphite Tube Atomic Absorption Spectrometry model (q2939). All of the aforementioned analyses were performed at the hydrochemistry laboratory of the Department of Applied Geology in the Faculty of Geosciences at the Ruhr University of Bochum. The results of field measurements and hydrochemical analyses were organized in a Microsoft Excel spreadsheet. Other software was used to perform data processing as follows: calculation of total dissolved solids TDS was processed using AquaChem software v 4.0.284 Waterloo 2003. Series plot charts of field measurements and laboratory tests were plotted using OriginLab software version 8.6. All maps used in this study were digitized using Geographic Information System, ArcMap version 9.3 of ESRI 2008, and reproduced using CorelDraw X6, Corel Corporation 2012.

3.5. Results

3.5.1. Major ions hydrochemistry

The results of field measurements and hydrochemical analyses of water samples are listed in Table 3.1 and Table 3.2. Table 3.3 shows the correlation between the hydrochemical parameters for all water samples. Fig 3.4 shows a series plot of in-situ measurements, while the series plot of the major and minor ions are shown in Fig 3.5 and 3.6, respectively. Hydrogen sulphide is also included in Fig 3.6, a. The spatial distributions of the major ions chemistry are shown in Fig 3.7 and the Piper diagram shown in Fig 3.7. The surface water and groundwater of the study area varied from weak acidic to alkaline, where pH values range between 5.95 and 8.37. The maximum value was measured at sampling point 6, while the minimum value was measured at sampling point 19. EC value ranges between 306 µs/cm, measured at sampling point 7, and 762 µs/cm, measured at sampling point 17. Table 3.1 and Fig 3.4a show high EC values measured in the surrounding area of the Ruhr University of Bochum (samples 1, 2 and 11). 27

Chapter 3: Environmental Impact of the Abandoned Coal Mines on the Surface Water and the Groundwater Quality in the South of Bochum, Germany.

Fig 3.4: The series plot of the in-situ parameters of the surface water and the groundwater samples, collected from the Lottenbachtal catchment area during April 2011. The values of dissolved oxygen measured during the field campaign show that the water in this area is generally characterized by high to medium oxygenated conditions, as shown in table 3.1 and Fig 3.4b. However, sampling points 13 and 17 show a high consumption of oxygen, especially in the deep groundwater well where the dissolved oxygen concentration had a value of 0.27 mg/l (sample 17 in Fig 3.4b). These conditions are associated with oxidation-redox potential values range between 149 and 281.2 mv and have an average of 212.57 mv. The maximum value was measured at sample 16, which represents the shallow groundwater while the minimum value was measured at sample 19, which represents the surface water of Lottenbach Stream. The results of hydrochemical analyses of water samples collected from the study area showed that Ca2+ is the dominant cation (Fig 3.5), with a concentration ranging between 1.27 and 4.9 meq/l and an average of 2.91 meq/l. The maximum value was measured in sample 5, while the minimum value was measured in sample 7. Mg2+ concentrations ranged between 0.58 meq/l in lake water and 2.84 meq/l in deep groundwater, with an average value of 1.25 meq/l. Generally, samples 1, 2, 8, 11, 14 and 17 show relatively high concentrations of Mg2+ in comparison with the other samples. Na++K+ ranged between 0.38 and 2.09 meq/l. The maximum value was measured at the drainage channel of the Ruhr University of Bochum (sampling point 11), and the minimum value was measured at sampling point 5. In general, relatively high concentrations were measured on the surface Water (samples 18, 19 and 20), deep groundwater (sample Nr 17), springs (1, 2, 6 and 11) and channel (samples 12, 14 and 15). These samples have Na++K+ value ranging between 1-2 meq/l, while other samples contained Na++ K+ concentrations less than 1 meq/l.

Chapter 3: Environmental Impact of the Abandoned Coal Mines on the Surface Water and the Groundwater Quality in the South of Bochum, Germany.

Table 3.2: Results of hydrochemical parameters of the water samples collected from surface water and groundwater in the south of Bochum (April 2011).

Chapter 3: Environmental Impact of the Abandoned Coal Mines on the Surface Water and the Groundwater Quality in the South of Bochum, Germany.

- Fig 3.5b shows that HCO3 dominates the anionic composition of samples 3, 4, 5, 10, 13, 16 and 17. The maximum value of 5.4 meq/l was measured in the groundwater (sample 17), while the minimum value of - 2- 0.65 was measured at sampling point 6. The average value of HCO3 is 2.69 meq/l. SO4 dominates in the surroundings of the settlement areas including samples 1, 2, 9 and 11, as well as sample 8. This sample is located downstream area of the adjacent mine sites as shown in Fig 3.1. The maximum value is 4.58 meq/l measured at sampling point 1, whereas the minimum value is 0.26 meq/l measured at sampling point 13. The 2- - average value of SO4 in this area is 1.72 meq/l. Cl ranges between 0.52 and 0.96 meq/l, with a maximum concentration in sample 11 and a minimum concentration in sample 8. In general, Cl- concentrations of more - than 1 meq/l were measured in channel water, surface water (samples 2 and 6). NO3 was also detected in this area and its concentration range between 0.02 - 0.71 meq/l and has an average of 0.26 meq/l.

Fig 3.5: The series plot of the major elements of the surface water and the groundwater, collected from the Lottenbachtal catchment area during April 2011 (a major cations; b major anions).

The calculated TDS of the water samples show that the study area is characterized by fresh water, with TDS values less than 1000 mg/l (Cherry and Freeze 1979). The TDS values range between 658.9 and 178 mg/l. The maximum value was calculated for sample 17, collected from deep groundwater wells, while the minimum value was calculated for sample 7. The average TDS value in this area is 392 mg/l. All samples had an ion balance error less than 10%. An exception was found for sample 11, which has error close to 11%. The ion balance error could be the result systematic laboratory error including salt standards and dilutions, and could be either positively or negatively charged (Fritz, 1994).

3.5.2. Heavy and trace elements

The Zntotal concentration ranged between 6 and 67 µg/l, the minimum value measured in the samples 1, 3, 5,

10, 11 and 19 and the maximum value measured in the lake water (sample 20). Fig 3.6.a shows that Altotal has a high concentration of 215 µg/l in the lake water (sample 20). This value is the maximum value measured in the study, while the minimum value is 8 µg/l measured in sample 7, and the average concentration is 46.58 µg/l.

Chapter 3: Environmental Impact of the Abandoned Coal Mines on the Surface Water and the Groundwater Quality in the South of Bochum, Germany.

Fig 3.6: The series plot of the minor elements and hydrogen sulphide of the surface water and the groundwater, collected from the Lottenbachtal catchment area during April 2011.

Fetotal concentration ranged from undetectable (< 0.1 mg/l), measured in samples 2, 3, 5, 9, 11, 15 and 19, and 4.9 mg/l, measured in sample 17 (deep groundwater), with an average of 0.81 mg/l. Fe2+ showed a measurement error resulting from the chosen reagent and is not included in these results. Mntotal was undetectable (< 0.1 mg/l) for all samples in this study and was also not included herein. H2S showed a relatively high value of 39 µg/l in sample 13. This value is associated with a high-depleted concentration of 2- SO4 , while all other samples showed low H2S concentrations that ranged between 0 and 9 µg/l.

3.6. Discussions

The results of the hydrochemical analyses show that the surface water and groundwater samples can be divided into two groups: the first group includes samples 4, 6, 8, 12, 13, 14, 17, 18 and 20, while the second group includes samples 1, 2, 3, 5, 7, 9, 10, 11, 15, and 19. This classification is based on the concentration of the minor elements especially Fetotal. Consequently, the water samples that had Fetotal concentration greater than 0.2 mg/l were included in the first group, while the other water samples, which had Fetotal concentration equal to or smaller than 0.2 mg/l, were included in the second group. Samples of the first group were also characterized by high relatively concentrations of Zntotal and Altotal compared to the sample of the second group. Sample 16 contained no data about heavy and trace elements. Therefore, this sample can only be used to compare the major ion composition with the other samples.

The relatively high concentrations of minor elements of the first group were accompanied by the presence of 2- SO4 . In addition, the sampling sites of these samples located in the vicinity or the downhill of the abandoned coal mines and their facilities as shown in Fig 3.1 and Fig 3.7. These conditions give a strong indication of the impact of the abandoned mines on these samples. This impact may be represented by the oxidation of sulphide minerals (pyrite, marcasite and sphalerite), associated with coal deposits (Skousen et 2+ 2+ 2- + al., 2000), which lead to the release of Fe , Zn , SO4 and H (Evangelou and Zhang, 1995; Banks et al. 1997; Costello 2003; Lottermoser, 2007). Oxidation of iron disulphide (pyrite and marcasite) can be described in the following reactions (Wolkersdorfer, 2008): 2+ 2- + 2FeS2(s) +7O2 (aq) +2H2O 2Fe +4SO4 +4H reaction 1 31

Chapter 3: Environmental Impact of the Abandoned Coal Mines on the Surface Water and the Groundwater Quality in the South of Bochum, Germany.

This reaction causes an increase in the acidity of the mine water and consumption DO. Microbiological activities catalyse and enhance this reaction (Kleinmann, 1998). Water and oxygen are major factors controlling the oxidation reaction (Hammack and Watzlaf, 1990). Thus, removal of one or both of these factors from the oxidation zone will slow down or cease the process (Skousen et al., 1998). In contrast, if sufficient oxygen is present in the oxidation medium, the equilibrium condition of ferrous iron Fe2+ resulting from reaction 1 will change, and the iron will oxidize to ferric iron Fe3+ as described in the following reaction (Banks, 2003):

2+ + 3+ 2Fe + 1/2O2 + 2H 2Fe + H2O reaction 2

This process is associated with consumption of hydrogen, which reduces the acidity of mine water. As the 3+ reaction continues, the released ferric iron Fe precipitates as iron hydroxide Fe(OH)3. This process is associated with the release of hydrogen ions, which again increases the acidity of mine water as illustrated in the following reaction (Rose and Cravotta III, 1998):

3+ + 2Fe +6H2O 2Fe(OH)3(s)+6H reaction 3

Sphalerite is often associated with pyrite in coal deposits, this mineral also oxidizes by exposure to oxygen and water as described by the following reaction (Younger et al., 2002):

2+ 2- ZnS(s) + 2O2(aq) Zn +SO4 reaction 4

2+ 2+ This reaction only increases the Zn and SO4 concentration. Therefore, no direct acidity will arise from these processes (Banks, 2003). In contrast, samples of the second group are characterized by low contents of minor elements compared to the first group, despite the fact that most of them (such as 1, 2, 3, 5, 7, 9, 10, 11 and 19) have been taken from the surrounding areas of the mines or mine facilities. These conditions may be related to the presence of these points within zones of low sulphide-content, whereas other points, such as 7 and 10, may represent the surface water drained from the settled areas as shown in Fig 3.3. Samples 1, 2, 7, 9 and 11 are also located in the vicinity of the settlements. Some of these sampling sites present near a drainage adit, such as 1, 2, 7 and 11, and show relatively high concentrations of several major ions, such as Ca2+, Na+, Cl- as shown in Fig 3.7. Hence, the chemical composition of this water could be affected largely by the urbanization. In particular, the relatively high concentrations of Na+ and Cl- in samples 1, 2 and 11, located in the surroundings of the Ruhr University of Bochum can be considered. Samples 15 and 19, representing surface water, show similar conditions. The most likely source of these two elements is the road salt, used heavily during snowy and icy conditions. The highly correlated relationship between Na+ and Cl-, shown in Table 3.3, reinforces this hypothesis. Traces of the halite in the facilities of the Ruhr University of Bochum, shown in Fig 3.8, is further evidence of the anthropogenic source the Na+ and Cl-.

Chapter 3: Environmental Impact of the Abandoned Coal Mines on the Surface Water and the Groundwater Quality in the South of Bochum, Germany.

Fig 3.7: Spatial distribution of the major ion hydrochemistry in the south of Bochum, Germany. Additional anthropogenic influences on the quality of surface water and groundwater in this area could arise from diversity in land use, which is characterized by pastures and fields (Fig 3. 3). These influences are - 2- + + represented by the additional load of several nutrients, such as NO3 , SO4 and other elements (Na , K , Ca2+and Mg2+) contained in the fertilizer widely used in Germany (BLFU, 2004; LNW, 2012). A significant match was found between the average of the major ion chemistry of the first group and the second group as 2+ - shown in Table 3.4, especially Ca and HCO3 dominating the ions compositions of the most samples of these groups. The high correlation between calcium-carbonate and magnesium-carbonate, shown in Table 3.3, gives an indication of the dissolution of carbonates.

Chapter 3: Environmental Impact of the Abandoned Coal Mines on the Surface Water and the Groundwater Quality in the South of Bochum, Germany.

Fig 3.8: Traces of the halite (white colour between the blocks) in the facilities of the Ruhr University of Bochum. These reactions consume H+ ions, releasing by oxidation of iron sulphide minerals or by precipitation of metal hydroxides. The dissolution of carbonates can be described by (Younger et al 2002; Wolkersdorfer, 2008);

+ 2+ - CaCO3(s) + H Ca + HCO3 reaction 5 + 2+ 2+ - CaMg(CO3)2(s)+2H Ca +Mg +2HCO3 reaction 6 However, carbonate minerals are not common in the study area. Therefore, anthropogenic sources may be the main source of carbonates control the neutralization of the abandoned mine water in this area. The anthropogenic sources can be related to the materials used in sealing of the coal mines. These materials consist mainly of mining waste and to lesser extent of ash, garbage, slags, sludge, construction waste, industrial residue and household waste (GLA-NRW, 1988).

Mine waste was also used in road construction (Schulz, 2002a). These materials often have low amounts of Calcite (Strömberg and Banwart, 1999). Dissolution of these carbonates in some cases could be adequate to change the mine water from acidic to neutral conditions (Watzlaf et al., 2004). In addition, these materials could also include sulphide minerals (Schulz, 2002b).

Chapter 3: Environmental Impact of the Abandoned Coal Mines on the Surface Water and the Groundwater Quality in the South of Bochum, Germany.

Table 3.3: Statistical correlations of the hydrochemical parameters for all water samples, collected from the Lottenbachtal catchment area during April 2011.

Element Parameter T PH EC Eh DO H2S Ca Mg Na K HCO3 SO4 Cl NO3 Fe Al Zn T Pearson Corr. 1.00 PH Pearson Corr. 0.28 1.00 EC Pearson Corr. -0.15 0.18 1.00 Eh Pearson Corr. -0.09 -0.89 -0.25 1.00 DO Pearson Corr. -0.20 0.49 -0.11 -0.44 1.00

H2S Pearson Corr. 0.01 -0.12 -0.39 0.12 -0.60 1.00 Ca Pearson Corr. 0.14 0.13 0.85 -0.18 -0.33 -0.19 1.00 Mg Pearson Corr. 0.02 -0.02 0.88 -0.05 -0.44 -0.29 0.80 1.00 Na Pearson Corr. -0.61 0.20 0.57 -0.33 0.32 -0.17 0.15 0.32 1.00 K Pearson Corr. -0.31 0.01 0.50 -0.09 0.04 -0.14 0.21 0.47 0.52 1.00

HCO3 Pearson Corr. 0.44 0.27 0.53 -0.28 -0.39 0.04 0.78 0.57 -0.08 -0.10 1.00

SO4 Pearson Corr. -0.23 -0.18 0.83 0.13 -0.19 -0.39 0.65 0.80 0.45 0.64 0.26 1.00 Cl Pearson Corr. -0.49 0.18 0.39 -0.23 0.37 -0.20 -0.06 0.12 0.89 0.38 -0.30 0.26 1.00

NO3 Pearson Corr. -0.10 -0.17 -0.14 0.06 0.25 -0.21 -0.23 -0.29 0.07 0.12 -0.49 -0.21 0.25 1.00 Fe Pearson Corr. 0.36 -0.18 0.43 0.02 -0.66 0.14 0.58 0.66 -0.15 0.12 0.66 0.29 -0.38 -0.24 1.00 Al Pearson Corr. -0.17 -0.02 0.09 -0.26 0.01 0.06 0.08 0.15 0.17 0.05 0.32 -0.04 -0.11 -0.15 0.53 1.00 Zn Pearson Corr. -0.25 0.00 0.09 -0.27 0.04 0.27 0.13 0.12 0.18 0.02 0.33 -0.05 -0.15 -0.18 0.49 0.92 1.00 pearson Corr. pearson Correlation Thus, the dissolution of carbonates may be responsible for reducing the oxidation of sulphides in these materials and in the abandoned coal mines of this area. Construction waste and slags could also contain significant amounts of calcium and magnesium carbonate (Hime, 2001; Melzer, 2011). Dissolution of the 2+ 2+ - carbonate contents of these materials can participate in the increasing of the Mg , Ca , HCO3 as well as the pH value of the water flow through the mines. Conversely, coal beds and the hosted rocks of this area also contain carbonates (Kukuk et al., 1962). These carbonates could also be dissolved in water flowing into - mines and contribute in elevation of the HCO3 and the other associating cations. Table 3.4: Comparison between the mean chemical composition of the samples affected by abandoned coal mines (group 1) and the samples not affected (group 2).

Statistical parameter Element Units Group Min Max Average Std Group 1 1.87 4.95 3.03 1.01 Ca2+ meq/l Group 2 1.27 4.85 2.81 1.18 Group 1 0.58 2.84 1.33 0.74 Mg2+ meq/l Group 2 0.68 2.01 1.18 0.48 Group 1 0.54 1.30 0.94 0.29 Na+ meq/l Group 2 0.38 1.91 0.80 0.40 Group 1 0.03 0.16 0.09 0.04 K+ meq/l Group 2 0.00 0.26 0.10 0.07 Group 1 0.65 5.40 3.22 1.40 HCO - meq/l 3 Group 2 0.75 4.93 2.25 1.10 Group 1 0.26 3.04 1.49 0.82 SO 2- meq/l 4 Group 2 0.94 4.58 1.91 1.16 Group 1 0.52 2.23 1.14 0.52 Cl- meq/l Group 2 0.56 2.96 1.15 0.66 Group 1 0.00 0.71 0.21 0.25 NO - meq/l 3 Group 2 0.03 0.60 0.24 0.16 Group 1 0.20 4.90 1.03 1.39 Fe mg/l total Group 2 0.10 0.20 0.13 0.05 Group 1 17.00 215.00 81.11 66.64 Al µg/l total Group 2 8.00 38.00 15.50 9.00 Group 1 8.00 67.00 28.67 17.83 Zn µg/l total Group 2 6.00 8.00 6.70 0.90 Group 1 269.10 668.92 408.85 132.62 TDS mg/l Group 2 205.90 578.91 378.65 135.49

Chapter 3: Environmental Impact of the Abandoned Coal Mines on the Surface Water and the Groundwater Quality in the South of Bochum, Germany.

In addition, Table 3.5 shows a convergence between averages of the major ion chemistry of all samples collected south of Bochum and the sample taken from Kemnade Lake that receives its water from a relatively larger catchment area. These conditions could be an indication of the similarity of the conditions controlling the hydrochemical evolution of the surface water and ground water in the south of Bochum and the surface water and groundwater feeding the Kemnade Lake, which represents the surface water of the Ruhr. On the other hand, the lake water shows a low concentration of Fetotal and very high concentration of Altotal and

Zntotal. Nevertheless, deep groundwater has a very high concentration of Fetotal compared to the surface water and the shallow groundwater, while the content of Altotal and Zntotal is fairly similar to lake water. Stream water has relatively low concentrations of these elements compared to the ground water and lake water. Most 2+ 2+ + - 2- of the major elements of the lake water, such as Ca , Mg , K , HCO3 and SO4 , have concentrations much lower than the concentration of groundwater and slightly lower compared with stream water. These situations may be the result of a higher impact of the abandoned coal mines and post-mining activities on the groundwater and the surface water (stream water) in comparison with other sources feeding into the lake or it may be caused by dilution of lake water by precipitation. Table 3.5: Comparison between the mean chemical compositions of water samples collected south of Bochum (surface water, groundwater and engineered channel), the stream water (Lottenbach) and lake water (Kemnade).

2+ 2+ + + - 2- - - Sample T pH EC Eh DO H2S Ca Mg Na K HCO3 SO4 Cl NO3 Fetotal Altotal Zntotal TDS No C° - µs/cm mv mg/l µg/l meq/l meq/l meq/l meq/l meq/l meq/l meq/l meq/l mg/L µg/l µg/l mg/l A 10.89 7.01 541.05 215.03 5.66 3.89 2.95 1.28 0.84 0.10 2.72 1.75 1.14 0.23 0.86 37.22 14.33 395.95 18 9.60 7.37 542.00 197.30 7.15 9.00 3.04 1.11 0.94 0.09 2.84 1.42 1.27 0.00 0.70 32.00 31.00 404.27 20 5.70 7.10 482.00 165.80 10.52 - 2.12 0.58 1.30 0.09 2.00 1.11 1.30 0.27 0.20 215.00 67.00 321.76 A: average value of all samples collected from the south of Bochum Significant differences were found by comparing the chemical composition of the water samples affected by the mines in the south of Bochum and samples taken from the abandoned Upper Bavarian coal mining (tertiary age) (Wolkersdorfer, 2009) as shown in Table 3.6. The Upper Bavarian abandoned coal mines are represented by wider ranges and higher maximum values of all the elements compared with south of Bochum. These conditions could be an indication of the largest 2- vulnerability by abandoned mines, especially the very high concentrations of SO4 and Fe. Conversely, the very high concentrations of the other elements can be most likely caused by geogenic factors related to the lithology and the geographical position. Nevertheless, the possibility of generating mine drainage with higher concentrations of sulphate and iron south of Bochum remains possible, due to the fact that the rain drainage system were connected directly to the shafts and adits so that the storm water or surface runoff generated on the urban areas enters the mine facilities cause dilution of the mine drainage. This situation can be responsible for the non-predominant anion of the most of sampling points shown in the Piper diagram (Fig 3.9). In addition, the presence most of the samples affected by mines within the dilution-mixing zone on the Piper diagram could be another indication of the dilution processes. The classification of water samples collected south of Bochum into three groups on the Piper diagram was created based on the well-known

Chapter 3: Environmental Impact of the Abandoned Coal Mines on the Surface Water and the Groundwater Quality in the South of Bochum, Germany. samples, so that the strong abandoned coal mines- affected zone was chosen based on samples 8 and 13. These samples represent water flowing directly from the mines as shown in Fig 3.1. Table 3.6: Comparison between the mean chemical compositions of the samples affected by abandoned coal mines south of Bochum and the samples of the abandoned coal mining in Upper Bavaria.

ElementUnit Location Min Max Average STD South Bochum 1.87 4.95 3.03 1.01 Ca2+ meq/l South Bavaria 3.24 20.26 2.32 1.94 South Bochum 0.58 2.84 1.33 0.74 Mg2+ meq/l South Bavaria 1.14 9.66 3.82 3.19 South Bochum 0.54 1.30 0.94 0.29 Na+ meq/l South Bavaria 0.04 26.97 4.56 7.41 South Bochum 0.03 0.16 0.09 0.04 K+ meq/l South Bavaria 0.02 4.99 0.51 1.22 South Bochum 0.65 5.40 3.22 1.40 HCO - meq/l 3 South Bavaria 2.54 13.93 7.34 3.16 South Bochum 0.26 3.04 1.49 0.82 SO 2- meq/l 4 South Bavaria 0.25 50.67 11.43 16.97 South Bochum 0.52 2.23 1.14 0.52 Cl- meq/l South Bavaria 1.20 97.80 14.40 22.60 South Bochum 0.00 0.71 0.21 0.25 NO - meq/l 3 South Bavaria 0.00 0.47 0.10 0.13 South Bochum 0.20 4.90 1.03 1.39 Fe mg/l total South Bavaria 0.04 12.6 1.7 3.72

The location of the strong urbanization-affected zone was based on samples 1, 2 and 9, which were collected directly from the surrounding of the settled areas as shown in Fig 3.3. The dilution-mixing zone was determined by depending on the surface water samples of the Lottenbach stream and Kemnade Lake, which normally consists of different water sources of the Lottental and the other watersheds, respectively. Other sulphides, such as galena, greenockite, covellite, chalcopyrite, millerite and others, are often associated with pyrite. These minerals are also subject to the same oxidation conditions of iron disulphide minerals when exposed to oxygen and water (Wolkersdorfer 2008). Thus, oxidation of these minerals causes an additional increase of sulphate and undesirable ions, such as Pb, Ni, Cd and Cu, in mine water (Younger et al., 2002). Most of these metals exist in very low concentrations in abandoned mine-affected water (Wolkersdorfer, 2009). Thus, no direct environmental hazard could exist from these elements. Investigation of these elements has were intended to be a focus in this study, but unfortunately, these tests were not possible due to financial and technical issues.

Chapter 3: Environmental Impact of the Abandoned Coal Mines on the Surface Water and the Groundwater Quality in the South of Bochum, Germany.

Fig 3.9: The Piper diagram showing the hydrochemical characteristics of the water samples listed in Table 3.2.

3.7.Conclusions

The abandoned coal mines of the Upper Carboniferous, located south of Bochum, have a negative impact on surface water and ground water. This impact is represented by the pollution of groundwater and surface water by Fe, as a result of the oxidation of pyrite and marcasite, as well as the generation of AMD. Materials used in the sealing and settlement expansion include relatively high contents of carbonates. The dissolution + 2+ 2+ - of these minerals increase pH, consume H and release Ca , Mg and HCO3 to the affected water. This process mitigates the generated AMD. Thus, the discharge from abandoned mines in this area is mainly characterized by near-neutral to alkaline conditions. However, the likelihood of generating acid drainage, with high concentrations of heavy metals, is still possible especially during low flow conditions from mines or adits. The deep groundwater is characterized by weak acidic conditions and very high concentration of Fe. Therefore, the use of surface water and groundwater, affected by abandoned coal mines, locally for water supply requires detailed studies to determine the temporal and spatial variations that could occur to the concentrations. Additionally, it allows for the determination of the concentrations of other harmful elements that could be associated with iron. All harmful elements must be removed from the water before delivering it for residents.

Chapter 4: Geochemical Processes Controlling the Neutralization Processes of the Acid Mine Drainage in the South of Bochum, Germany.

4. Geochemical Processes Controlling the Neutralization Processes of the Acid Mine Drainage in the South of Bochum, Germany.

4.1. Abstract

Geochemical processes controlling the neutralization processes of the acid mine drainage AMD was investigated south of Bochum, Germany. Several methods were used to achieve this objective. These methods include hydrogeochemical modelling and hydrochemical analysis of water samples collected from the study area as well as pH, carbonate, batch tests performed on soil, rock and artificial material samples collected from the study area. The results of integration of the above mentioned methods show that the neutralization processes of the AMD in this area are controlled by dissolution processes of carbonate minerals, weathering processes of silicate and clay minerals, re-dissolution of secondary minerals (hydroxides) and agricultural activities. Carbonate minerals, which participate in the neutralization processes of the AMD in this area, have anthropogenic and geogenic sources. The anthropogenic source includes the dissolution of carbonate minerals contained in building materials, construction waste, landfill materials, engineering activities and land treatment for agricultural activities. The carbonate minerals of these materials were generated by the reaction of CO2 of the air with calcium hydroxide and magnesium hydroxide. The geogenic sources of carbonates, which contribute to the neutralization processes of the AMD, include dissolution of low content of carbonate minerals in the mudstone and in the remaining coal deposits. The relatively high concentrations of the Al in the surface water and groundwater of the study area are an indicator of the weathering processes of the silicate minerals.

4.2. Introduction

Acid Mine Drainage is a common problem associated with abandoned coal mines (Fripp et al., 2000; Younger et al.; 2002, Wolkersdorfer, 2008). This problem arises when iron disulphide minerals, which associate with coal deposits, are exposure to atmospheric oxygen and water during mining and post-mining activities (Skousen et al., 1998; Jennings et al., 2008). So that the iron disulphide minerals oxidize and release of sulphate SO42-, ferrous iron Fe2+and hydrogen H+, which increases the acidity of the mine water (Rose and Cravotta III, 1998; Blowes et al., 2003). The solubility of undesirable elements are also increased and consequently deteriorates the quality of the mine water (Singh, 1987). In contrast, the presence of alkali and alkaline earth elements, such as carbonate, silicate, hydroxides and other exchangeable cations, in pyrite oxidation zones decrease or prevent the generation of AMD (Dold, 2005). This phenomenon is related to the consumption of hydrogen ions, which causes the low pH value of the mine water (Banks, 2004). Dissolutions of carbonate and silicate minerals are the most known natural attenuation of AMD (Younger et al., 2002). Hydroxides, borate, organic ligands, phosphate and ammonia 39

Chapter 4: Geochemical Processes Controlling the Neutralization Processes of the Acid Mine Drainage in the South of Bochum, Germany. can also neutralize the AMD (Watzlaf et al., 2004). These reactions consume the acidity of mine water and lead to precipitation of undesirable metals such as hydroxides and oxyhydroxides (Banks, 2004; Costello, 2003). The neutralization reactions can occur simultaneously with the formation of AMD in the disulphide oxidation zones (Lottermoser, 2007). The neutralized AMD has near-neutral-to-neutral pH values and is usually called Neutral Mine Drainage NMD (Banks et al., 2002). Calcium-magnesium oxides have also the ability to raise the pH to relatively high degrees (Skousen et al., 1998). Germany is seventh-largest coal producer in the world and has the biggest coal reserves in Europe. The main coalfield of lignite deposits belong to the Tertiary age. These fields are located in the Rhineland, Lusatia, and Central German basins. Despite this, important hard coal deposits exist in the Ruhr and Saar basins (Kelly, 2009; Miller, 2010). Therefore, the Ruhr area is the highest dense populated zone in Europe. The coal formations in this area belong to the Upper Carboniferous age (Miller, 2010). Water supply in this area consist mainly of the surface waters of the Ruhr. This source feeds the drinking and industrial water for its 5 million inhabitants (Bode et al., 2003). A decision has been taken by the German government to shut down remaining black coalmines in Germany by 2018. Therefore, an environmental threat will arise if no appropriate procedures taken during and after the mines closing. The hydrochemical study performed by (Alhamed and Wohnlich, 2014a) in the south of Bochum, which is a part of the Ruhr hard coal mining activities, proved the generation of AMD in the abandoned coal mines of the Ruhrkarbon mining fields. However, the elevated values of pH, measured at the sampling points of surface water and groundwater, have led to the conclusion that the generated AMD was subject to neutralization processes. These conditions were associated with relatively low concentrations of many undesirable elements such as Mn, Zn, Al and a relatively high concentration of Fe. However, the impact of AMD still weak in this area, which is very good for drinking water. Scientific research related to the geochemical processes controlling the neutralization processes of the AMD are almost non-existent in Germany. Therefore, the main aim of this research studying the possible buffering systems contributing to the mitigation of AMD using hydrogeochemical models and hydrochemical analyses of the surface water and ground water, as well as to batch tests combined with pH and carbonate measurements performed on soil, rocks and landfilling materials.

4.3. The study area

The study area is located south of Bochum (Fig 4.1). It is located in the transition zone between the Bergisch-Sauerländischen Uplift in the south and the Westphalian lowlands in the north. This location is characterized by a mountainous structure, represented by shallow hills separated by steep sloped v-notched valleys (GLA-NRW, 1988). The study area belongs to the climate zone the northwestern Germany, which is characterized by marine climate of mild winters and cool summers. Continental effects are occasionally noted in this area.

Chapter 4: Geochemical Processes Controlling the Neutralization Processes of the Acid Mine Drainage in the South of Bochum, Germany.

Fig 4.1: Location map of the study area.

These effects are represented by long periods of high atmospheric pressure, associated with cool periods in the winter and dry, hot weather in the summer (LANUV, 2010). The climatic parameters of the study area are summarized in Table 4.1 (Grudzielanek et al., 2011).

Chapter 4: Geochemical Processes Controlling the Neutralization Processes of the Acid Mine Drainage in the South of Bochum, Germany.

Table 4.1: Summary of climatic parameters of the study area (Grudzielanek et al., 2011).

Parameter Value Unit

Average of annual air temperature 10,40 C° Average of annual precipitation 817.6 mm Average of Minimal annual air temperature 2.70 C° Average of maximal annual air temperature 18.50 C° Average of annual wind velocity 3.50 m/s Average of annual relative humidity 75.00 % Average annual sunshine duration 1229.50 hrs/a

Sandstone, mudstone and coal deposits of the Upper Carboniferous predominate the geology of the study area. These deposits were divided locally into the following three formations; ―Bochumer Schichten‖, ―Wittener Schichten‖ and ―Sprockhöveler Schichten‖ (GLA-NRWa, 1988). The ―Sprockhöveler Schichten‖ is limited to a small exposure of the Upper Namur C localized in the southern part of the studied area as shown in Fig 4.2 (Littke et al., 1986).

Fig 4.2: The geology, the lithology and the tectonics of the Lottenbachtal (modified after GLA-NRWa, 1988).

Chapter 4: Geochemical Processes Controlling the Neutralization Processes of the Acid Mine Drainage in the South of Bochum, Germany.

These deposits were subject to intensive folding processes during the Variscan orogeny period. So that a very complex tectonic structure is represented by folds and faults (Littke et al., 1986). In terms of hydrology, the study area is characterized by complex hydrologic conditions. These conditions are related to the variety of the land use that is represented by crops, grassland and forested areas. In addition, the existence of the suburban areas in the west, the middle and the south contribute to the hydrologic complexity by increasing the sealed areas (Viebahn-Sell, 2006). The Lottenbach stream, which is the main watercourse in this area, was subject to significant anthropogenic changes during and after the mining period (1632 - 1961) (Huske, 1998). These changes are represented by the sealing of several parts of its canals as well as to the presence of artificial drainage canals that return to the former mining activities and the drainage systems of the storm water (Viebahn-Sell, 2001).

4.4. Materials and methods

Many methods and procedures were used in this study to investigate factors governing the neutralization processes of the AMD in this area. These methods and procedures include:

4.4.1. Hydrogeochemical modeling

Mass balance inverse modelling was performed with the result of hydrochemical analysis of water samples collected from the study area and published in (Alhamed and Wohnlich, 2014a) and listed in Table 4.2. Table 4.2: The hydrochemical parameters of the surface water and the groundwater of the sampling points shown in Fig 4.8 and located in the south of Bochum (Alhamed and Wohnlich, 2014a).

+ + 2+ 2+ 2- - - - Sample T PH EC Eh DO Na K Ca Mg SO4 HCO3 Cl NO3 Fetotal Al Nr C° - µs/cm mv mg/l meq/l meq/l meq/l meq/l meq/l meq/l meq/l meq/l mg/l µg/l 1 10 6.29 739 253 5.2 0.9 0.3 4.3 2.0 4.6 2.7 0.8 0.2 0.1 10 2 8.6 6.46 758 239 4.3 1.0 0.1 4.6 2.0 3.5 3.3 1.5 0.1 <0,1 12 3 9.3 6.11 384 266 3.1 0.5 0.0 1.9 0.7 1.3 1.6 0.7 0.2 <0,1 15 4 15.1 7.3 384 200 5.5 0.5 0.0 2.1 0.7 0.7 4.6 0.7 0.1 0.9 98 5 14.2 7.57 606 187 6.4 0.4 0.0 4.9 1.1 0.9 4.9 0.6 0.4 <0,1 11 6 8.2 5.95 543 259 5.9 1.2 0.1 1.9 1.2 1.4 0.7 2.2 0.7 0.3 43 7 11.9 6.3 306 246 7.3 0.6 0.1 1.3 0.7 1.0 0.8 1.0 0.4 0.1 8 8 11 7.52 580 184 5.0 0.6 0.1 3.6 1.9 1.4 3.8 0.5 0.0 0.9 87 9 10 6.37 387 233 5.0 0.6 0.0 1.9 0.8 1.4 1.2 0.7 0.2 <0,1 12 10 10.2 7.95 445 173 7.7 0.7 0.2 1.9 0.8 1.0 1.9 1.0 0.2 0.2 11 11 8.4 7.69 744 181 7.6 1.9 0.2 3.0 1.7 3.0 2.5 3.0 0.1 <0,1 38 12 9.4 7.44 573 197 7.3 1.2 0.1 3.4 0.9 1.4 2.6 1.4 0.6 0.4 34 13 10.7 6.5 310 246 1.1 0.6 0.1 2.1 0.7 0.3 2.5 0.7 0.1 0.5 29 14 10.7 7.56 756 186 5.5 1.3 0.1 4.1 2.2 2.7 4.5 1.4 0.0 0.5 17 15 11.6 7.38 500 191 7.6 0.9 0.1 2.3 1.0 1.3 1.3 1.5 0.6 <0,1 11 16 12 6.7 407 281 8.0 0.5 0.0 2.1 0.9 1.4 2.2 0.6 0.0 - - 17 12.3 6.4 762 221 0.3 0.8 0.2 5.0 2.8 3.0 5.4 0.6 0.1 4.9 175 18 9.6 7.37 542 197 7.2 0.9 0.1 3.0 1.1 1.4 2.8 1.3 0.0 0.7 32 19 13.7 8.37 554 149 7.8 0.8 0.1 2.8 1.3 1.5 2.1 1.3 0.3 <0,1 27 20 5.7 7.1 482 166 10.5 1.3 0.1 2.1 0.6 1.1 2.0 1.3 0.3 0.2 215

Chapter 4: Geochemical Processes Controlling the Neutralization Processes of the Acid Mine Drainage in the South of Bochum, Germany.

4.4.2. Field Investigations

Soil, mine waste, construction waste and construction material samples were collected from the study area during 2011. The sampling points are shown in Fig 4.3. Soil samples were collected from topsoil horizons. Sampling points were selected so as to represent the different types of the land use present in the study area. Soil samples were taken from the earth surface up to 40 cm depth. These samples include Nr. 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 and 12 in Fig 4.3. Each sample was filled in plastic bags, labelled and tightly closed. The samples were then transported to the nearby hydrochemical laboratory of the Department of Hydrogeology in the Faculty of Geoscience at Ruhr University of Bochum. Immediately after arriving to the laboratory, the samples were deep frozen to await further analysis. Artificial materials, including slag, mine waste, construction waste, and rock samples were collected from different sites in the study area. The construction materials included concrete, which was taken from the main Lottenbach stream channel (sample 19 Fig 4.3). In contrast, the backfilling materials included slag (samples 18 and 21), construction waste (sample 20), mine waste (samples 14 and 16) and rubble. Rock samples were also tested in this study. These samples were taken from the drilling cores of wells located in Lottental (sample 22) and on the bank of the Kemnade Lake (sample 23). Sample 22 represents mudstone deposits, while sample 23 represents sandstone deposits of the Upper Carboniferous formations in this area. Samples 13 and 15 represent stockpile materials. These materials consist of a mixing of different materials of mine waste, construction waste and mudstone.

4.4.3. Laboratory works

PH and EC tests were performed on the soil, rocks and artificial material samples that were collected during this study. PH was measured according to (DIN ISO 19682-13, 2009). A portable CONSORT C932 meter was used to achieve these measurements. Conversely, EC was measured according to (DIN ISO 11265, 1997). WTW Condi 340i portable meter was used to achieve these measurements. Each instrument was calibrated against standard solutions. A rapid carbonate test was performed on the collected samples to get an idea about the carbonate content of these samples. This test was done according to (DIN ISO 19682-13, 2009). HCl 10% was used to achieve this test. Batch tests (10/1: l /kg) were conducted on all collected samples to determine the potential contents of the major ions (especially that contribute in the neutralization processes of the AMD). This test was performed according to (DIN EN 12457-2, 2003). The extraction solutions were divided into the following subsamples. - 2- -  Major anions sub-samples (Cl , SO4 and NO3 ): These sub-samples were filled in 50 ml polyethylene bottles after they passed through a 0.45 µm pressure filter.  Major cation sub-samples (Ca2+, Mg2+, Na+ and K+): These sub-samples were collected in 50 ml bottles and they were also filtered by a 0.45 µm membrane filter and preserved by concentrated

nitric acid HNO3 (1 % v/v).

Chapter 4: Geochemical Processes Controlling the Neutralization Processes of the Acid Mine Drainage in the South of Bochum, Germany.

Fig 4.3: Location map of the soil and the artificial material samples, collected from the south of Bochum.

4.4.4. Analysis procedure

+ +2 +2 - -2 - Major dissolved ions, including K , Ca , Mg , Cl , SO4 and NO3 , were tested by DIONEX Ion Chromatography System model ICS-1000 at the Department of Hydrogeology in the Faculty of Science at the Ruhr University of Bochum.

4.4.5. Data processing and interpretation

Results of hydrogeochemical modeling, pH, EC, rapid carbonate test and batch tests were organized in Microsoft Excel spreadsheets. Other scientific computer codes were used to perform data processing and presentation as follows:  Series plot charts of field measurements and laboratory tests were plotted using Origin Lab software version 8.6.  Soil profiles were plotted by using Stratos 98 (RockWare, 1997), and reproduced by the CorelDraw X6 (Corel Corporation, 2012).  All maps produced in this study were generated or digitized using Geographic Information System, ArcMap version 9.3 (ESRI, 2008) and redrawn using CorelDraw X6 (Corel Corporation, 2012).

Chapter 4: Geochemical Processes Controlling the Neutralization Processes of the Acid Mine Drainage in the South of Bochum, Germany.

4.5. Results

4.5.1. Hydrogeochemical modeling

A statistical summary of the results of hydrogeochemical modeling is shown in Table 4.3. Fig 4.4 illustrates the series plots of the processed saturation indices and Fig 4.5 shows the spatial distributions of their values in the study area. Table 4.3: A statistical summary of the result of hydrochemical modelling performed on the surface water and the groundwater samples listed in the Table 4.2.

Minerals Min Max Average

SI (Gypsum) -2.59 -1.23 -1.83 SI (Anhydrite) -2.84 -1.48 -2.08 SI (Calcite) -2.59 0.58 -0.83 SI (Aragonite) -2.75 0.42 -0.99 SI (Dolomite) -5.51 0.79 -2.13 SI (Siderite) -2.47 0.09 -1.06

The detailed description of the results can be summarized as follows; the saturation index values of calcite range between -2.59 and 0.58 and have an average of -0.83. These values specify conditions from undersaturated to supersaturated. Similar to the calcite, the saturation indices of the Aragonite also show the all three saturation conditions. Their values range between -2.75 and 0.42 and they have an average of -0.99.

Fig 4.4: The series plots of saturation indices of carbonate and evaporate minerals of the surface water and the groundwater samples collected from the Lottenbachtal during April 2011 and listed in Table 4.2.

Chapter 4: Geochemical Processes Controlling the Neutralization Processes of the Acid Mine Drainage in the South of Bochum, Germany.

The calculated saturation indices of the dolomite also showed the same conditions that have been observed for both Calcite and Aragonite. Its value ranges between -5.51 and 0.79 and has an average of -2.13. SI of siderite located within the domain -2.47_ 0.09 and have an average of -1.06. The SI of Anhydrite extended between - 2.84 and - 1.48 and had an average of -2.08. Finally, the gypsum showed a similar condition of the Anhydrite. In this way, the undersaturated state characterizes all the water samples collected from this area. The saturation indices of this mineral ranged between -2.59 and -1.23 and had an average of -1.83.

Fig 4.5: The spatial distributions of the saturation indices values of the surface water and the groundwater samples collected from the Lottenbachtal during April 2011 and listed in table 4.2EC, pH and carbonate tests.

4.5.2. Batch test

4.5.2.1. Topsoil The pH value of the topsoil samples extended from 4.01 in forested areas and 7.04 in agricultural fields, as shown in Fig 4.6. This range specifies conditions from acidic to neutral. Generally, soil samples collected from the forested areas are characterized by acidic conditions and a pH value less than 4.5. An increase in the pH value was noted in the topsoil samples collected from the agricultural fields, where the pH values extended between 5.6 and 7.04. The average value of the pH in this group was 5.97. These conditions are associated with poor to low carbonate contents as shown in Table 4.4.

Chapter 4: Geochemical Processes Controlling the Neutralization Processes of the Acid Mine Drainage in the South of Bochum, Germany.

Table 4.4: Results of the carbonate tests performed on the soil, the rocks and the artificial materials samples collected from the south of Bochum.

EC values ranged between 21 and 92.8 µs/cm. The minimum value was measured in sample 10, while the maximum value was measured in sample 3. The average value of EC in this group was 59.37 µs/cm. Table 4.5 shows the statistical summaries of the (10/1:l/kg) batch tests. The Ca2+ values ranged between an undetectable value referred as 0 (sample 12) and 273.88 g/t (sample 3) and had an average value of 60.27 g/t. Mg2+ ranged between undetectable values (samples 1, 10, 11 and 12) and 42.13 g/t (sample 3). The average value of the Mg2+ in this group was 6.31 g/t. Na+ ranges between 6.5 (sample 11) and 63.2 g/t (sample 3). K+ ranges between 3.87 (sample 12) and 97.45 g/t (sample 6). In general, samples taken from the forested area had lower K+ content than the samples taken from agricultural fields. 2- 2- For anions, SO4 ranged between 15.94 (sample 8) and 94.19 g/t (sample 12). The average value of SO4 in - the collected samples was 48.07 g/t. NO3 concentrations ranged between 3.87 g/t and 372.94 g/t. The - - average value of NO3 in this group was 83.69 g/t. Cl ranged between 2.17 and 62.93 g/t. The minimum value was measured at sampling point 11and the maximum value was measured in the sampling point 9. Samples taken from the forested areas had relatively smaller chloride contents in comparison with samples taken from the other sampling points.

4.5.2.2. Artificial Materials This group includes slag, mine waste, construction waste and concrete samples. The samples belonging to this group showed relatively high to extremely high buffering capacity compared with the samples of the other groups as shown in Fig 4.6. The pH values ranged between 6.43 (sample 15) and 11.71 (sample 19).

Chapter 4: Geochemical Processes Controlling the Neutralization Processes of the Acid Mine Drainage in the South of Bochum, Germany.

Table 4.5: A statistical summary of the pH, EC and (10/1: l/g) batch tests performed with soil and the artificial material samples collected from the south of Bochum.

This group had a pH average value of 9.06. The buffering conditions of this group are associated with carbonate content, which extends from very low to very high, as shown in Table 4.4. EC values range between 21.6 (sample 15) and 1550 µs/cm (sample 21). The average value of EC in this group is 250.75 µs/cm. The Ca2+ content of this group shows a greater range in comparison with the first group, when the Ca2+ value ranged between 24.13 (sample 15) and 1088.25 g/t (sample 19) and had an average of 332.26 g/t. Mg2+ also showed a larger extended range than the topsoil sample group. Its values extended between undetectable values (samples 19 and 21) and 423.91 (sample 20). The average value of Mg2+ in this group was 81.14 g/t. Na+ concentrations extended from undetectable to 14.68 g/t. The minimum was measured in samples 17 and 18 and the maximum was measured in sample 14. The average value of Na+ is 6.49 g/t. The K+ concentrations had a range, which was approximately similar to the first group. Its value extended from - - undetectable in sample 18 to 119.18 g/t in sample 16. Cl and NO3 in this group also had a scope similar to the first group. The Cl- values varied from 1.43 in sample 13 and 74.16 in sample 19 and they have an average value of - 12.06 g/t. NO3 extends from undetectable values to 386.19 g/t. The minimum was measured in sample 18 - whereas the maximum was measured in sample 19. The average value of NO3 in this group was 60.33 g/t. 2- SO4 showed a larger extent in comparison with its value in the first group. Its concentrations ranged between 5.56 in sample 17 and 257.14 in sample 19 and it had an average value of 53.50 g/t.

4.5.2.3. Carboniferous sandstone and mudstone Rock samples showed near-neutral to neutral buffering conditions as shown in Fig 4.6. Their pH values ranged between 6.64 in the sandstone and 7.17 in the mudstone. The EC had values of 11.51 µs/cm in the

Chapter 4: Geochemical Processes Controlling the Neutralization Processes of the Acid Mine Drainage in the South of Bochum, Germany. sandstone sample and 71.9 µs/cm in the mudstone. The element concentrations in the sandstone were lower in comparison with the mudstone.

Fig 4.6: The series plot of the EC and pH values measured for topsoil, slag, mine waste, construction waste concrete and rock samples; A: Soil samples of arable areas, B: Soil samples of forested areas, C: Solid materials, D: Rocks. The concentrations in the sandstone sample had values of 7.35 g/t for Na+, 11.75 g/t for K+, undetectable 2+ 2+ - 2- - values for Ca and Mg , 1.68 g/t for Cl and 7.58 g/t for SO4 . NO3 showed a very high value, which may be due to the contamination of HNO3. In contrast, the element concentration in the mudstone sample are 40.48 g/t for Na+, 84.65 g/t for K+, 14.54 g/t for Mg2+, 63.46 g/t for Ca2+, 5.29 g/t for Cl-, 140.13 g/t for 2- - SO4 and 17.19 g/t for NO3 .

Fig 4.7: Series plot of the result of the batch tests performed on the soil and solid samples collected from the south of Bochum; A: Soil samples of arable areas, B: Soil samples of forested areas, C: Solid materials, D: Rocks.

Chapter 4: Geochemical Processes Controlling the Neutralization Processes of the Acid Mine Drainage in the South of Bochum, Germany.

4.6.Geochemical processes controlling the mitigation of AMD

Results of hydrogeochemical modelling and hydrochemical analysis (of the surface water and groundwater samples), as well as results of a pH tests, carbonate tests and batch tests (of the soil and solid materials) show that the neutralization processes of AMD south of Bochum are controlled by the dissolution of carbonate minerals and weathering processes of the silicate and clay minerals. This conclusion is linked to the weak acidic, near-neutral and neutral conditions of the water samples collected from the study area (Alhamed and Wohnlich, 2014 a), listed in tab 2 and shown in fig 4.8. 2+ 2+ - These conditions were associated with relatively high concentrations of Ca , Mg and HCO3 , which indicate carbonate dissolution. This hypothesis was supported by the supersaturated and equilibrium situations of the carbonate minerals, resulting from the hydrogeochemical modelling as shown in Fig 4.4 and 2+ - Fig 4.5. Additionally, the highly correlated relationship between Ca and HCO3 , shown in Fig 4.9, enhances the hypothesis of the dissolution of carbonates.

Fig 4.8: The spatial distribution of the hydrochemical parameters of the surface water and the groundwater samples collected from the Lottenbachtal during April 2011 and listed in Table 4.2. However, the most of the sampling points, shown in Fig 4.5 and including sampling points 1, 2, 3, 4, 6, 7, 9, 11, 12, 13, 15, 16, 17, 18 and 20, have undersaturated conditions of most of carbonate minerals. Although, 2+ - these points have relatively high concentrations of Ca and HCO3 , as shown in Fig 4.8, and they also contribute to the highly correlated relationship of Ca-HCO3 in fig 4.9. The most likely factors controlling 51

Chapter 4: Geochemical Processes Controlling the Neutralization Processes of the Acid Mine Drainage in the South of Bochum, Germany. these conditions could be related to the high partial pressure of the CO2, which is linked to the CO2 emissions.

Due to the geological position of the study area, CO2 emissions could result from bacterial-mediated fermentation of the lignite materials in the aquifer (Chapelle and Knobel, 1985; Grossman et al., 1989), oxidation processes of organic matter of the soil and sediments (Venturelli et al., 2003; Liu et al., 2007; Atkinson, 1977; Grossman et al., 1989), decomposition of carbonates in acidic environments as described in reaction, and anaerobic microbial oxidation of methane in deep groundwater (Kotelnikova, 2002).

+ 2+ 2+ MgCa(CO3)2(s) + 4H = Mg + Ca 2CO2(g) + 2H2O

The CO2 emissions increase the dissolution capacity of the carbonates and reduce the value of the saturation index (Liu et al., 2007, Larson and Buswell, 1942). Dilution effects by precipitations could also contribute to the undersaturated state of the carbonate minerals (Liu et al., 2007).

2+ - Fig 4.9: The correlation between Ca and HCO3 of the surface water and the groundwater samples collected from the Lottenbachtal during April 2011 and listed in Table 4.2.

The results of the pH, carbonate and batch test show that backfill materials, stockpile, mine waste, slag, concrete and construction waste show relatively high concentrations of Ca2+ and Mg2+ Fig 4.7, associated with different rates of carbonates as shown in Table 4.4. In contrast, the soil of the arable areas also contain carbonates (Table 4.4), accompanying with relatively high concentration of Ca2+ and Mg2+ in comparison with forested areas as shown in Fig 4.7.

Construction materials also contain carbonate, as shown in Table 4.4. The carbonate content of these materials and the most of the construction waste results chiefly by corrosion of calcium and magnesium hydroxides, which are the major content of these materials (Hime, 2001). Slag carbonates arise from the

Chapter 4: Geochemical Processes Controlling the Neutralization Processes of the Acid Mine Drainage in the South of Bochum, Germany. same reason (BLU, 2002). These materials were used largely in the mine-sealing and the landfilling processes of the study area (GLA-NRW, 1988). The carbonate content of the arable soil could be caused by the soil treatment for agricultural activities; this procedure may be used for improving the soil quality in order to become suitable for agricultural use. Soil also contains natural carbonates, which contribute to the total carbonate content of the soil section (Merkel and Planer-Friedrich, 2008). Mine waste was also used in the mine-sealing road construction and the landfilling processes (Schulz, 2002a); these materials have also small amounts of Calcite (Strömberg and Banwart, 1999). However, the coal beds and the hosted rocks of this area have also small amounts of carbonates (Kukuk, Et al., 1962), these represent another geogenic source of the carbonates in this area. The dissolution of carbonate minerals take place through the following reactions (Cravotta III and Trahanb, 1999; Lottermoser, 2007; Turekian et al, 2005; Wolkersdorfer, 2008; White, 2013):

+ 2+ – Calcite CaCO3(s) + H (aq) = Ca (aq) + HCO3 (aq) + 2+ - Siderite FeCO3(s) + H (aq) = Fe + HCO3 MgCa(CO ) + + = 2+ + 2+ + − Dolomite 3 2(s) 2H Mg Ca 2HCO3

These reactions contribute to consume the acidity and to increase the alkalinity and other associated cations of the mine water. On the other hand, the relatively high concentration of Al (Fig 4.10), measured in some of the water samples collected from the study area is an indicator of the silicate and clay minerals, which occurs through the following reactions (April et al., 1986; Deer et al., 2001; Younger et al., 2002; Banks, 2003):

+ + 2NaAlSi3O8(s) + 2H + 4H2O(l) → 2Na + Al2Si4O10(OH)2(s) + 2H4SiO4(aq) Albite (aq) (aq) + + 2NaAlSi3O8(s) + 2H (aq) + 9H2O(l) → 2Na (aq) + Al2Si2O5(OH)4(s) + 4H4SiO4(aq) + 2+ Anorthite CaAl2Si2O8(s) + 2H (aq) + H2O(l) → Ca (aq) + Al2Si2O5(OH)4(s) + 4H4SiO4(aq) - + + K feldspar 2KAlSi3O8(s) + 2H (aq) + 9H2O(l) → 2K (aq) + Al2Si2O5(OH)4(s) + 4H4SiO4(aq) Al Si O (OH) + + → 3+ + 2H SiO + H O Kaolinite 2 2 5 4(s) 6H (aq) 2Al (aq) 4 4(aq) 2

These reactions contribute to the consumption of the acidity and rise the alkalinity of the water sources in this area.

Ochre was observed along the Lottenbach stream bed (Fig 4.11), while aluminum hydroxide was noted in water sample 19. These hydroxides could be dissolved once more through the following reactions (Costello, 2003; Merkel and Planer-Friedrich, 2008; Cravotta III et al, 2010): + 3+ AlOOH + 3H = Al + 2H2O

+ 3+ Al(OH)3 + 3H = Al + 3H2O

+ 3+ 2Fe(OH)3(s) + 6H = 2Fe + 6H2O

+ 3+ Fe(OH)3 + 3H = Fe + 3H2O

+ 2+ Fe(OH)3 + 2H = Fe + 0.25O2 + 2.5H2O + 2+ Fe(OH)2 + 2H = Fe + 2H2O

+ 3+ FeOOH(S) + 3H = Fe + 2H2O

Chapter 4: Geochemical Processes Controlling the Neutralization Processes of the Acid Mine Drainage in the South of Bochum, Germany.

Thus, dissolution of these compounds also contributes to the neutralization of AMD in this area. Subsequent oxidation processes of ferrous iron to ferric iron can arise with continued the interaction. The oxidation of the ferrous iron also plays a role in the mitigation processes of the AMD in this area as described in the following reaction (Banks, 2003) 2+ + 3+ 2Fe + ½ O 2 + 2H 2Fe + H 2O

Fig 4.10: The series plot of the Al, Fe of the surface water and the groundwater samples collected from the Lottenbachtal during April 2011 and listed in Table 4.2. Soil contains various hydroxides, and the exchangeable compounds (such as Ca2+, Mg2+ and Na+) of the soil cover contribute to the neutralization process of the acidity (Merkel and Planer-Friedrich, 2008). Thus, the neutralization buffering systems of the AMD in abandoned coal mines south of Bochum can be divided anthropogenic and geogenic systems; the geogenic system includes the weathering of silicate and clay minerals, the re-dissolution of secondary minerals (hydroxides), the dissolution of carbonate minerals contained in the rock and coal deposits, the oxidation of ferrous iron into ferric and the carbonate and exchangeable elements of the soil cover, while the anthropogenic buffering system includes the dissolution of carbonate minerals, included in the construction materials, construction waste, mine waste and treated soil for agricultural activities. These systems contribute to the neutralization processes of the generated AMD in this area together. Hence, it is not possible to quantify and structure the singular participation of each component of these systems in the mitigation of the AMD in this area. This fact relates to the high complexity and the heterogeneity of the study area.

Chapter 4: Geochemical Processes Controlling the Neutralization Processes of the Acid Mine Drainage in the South of Bochum, Germany.

Fig 4.11: Ochre depositions on the watercourse of Lottenbach stream (near sampling point 13).

4.7. Conclusion

Hydrogeochemical modelling, hydrochemical analysis of the surface water and groundwater, as well as pH, carbonate and batch testing on soil and solid samples were performed to determine the factors controlling the neutralization processes of the AMD in the south of Bochum. Results of these tests showed that the neutralization of AMD in this area is controlled by geogenic and anthropogenic buffering systems, including the dissolution of carbonate minerals, the weathering processes of the silicate and clay minerals, the re- dissolution of secondary minerals of hydroxides, the oxidation of ferrous iron and the natural buffering capacity of the soil cover. Carbonate minerals that contribute to the neutralization processes of the AMD contain geogenic and anthropogenic sources. The geogenic source correlates with the low content of carbonates in the coal beds and mudstone formations, while the anthropogenic source includes the dissolution of the carbonate content of the concrete, construction waste, mine waste, landfill materials and land treatment for agricultural activities. These processes increased the alkalinity of the mine water and are responsible for reducing the concentration of Fe and Al by precipitating them as hydroxides. Therefore, construction of artificial pounds containing limestone along the watercourse is recommended in this area to increase the alkalinity of the surface and ground water.

Chapter 5: Hydrochemical Responses during and after Strom Events and Hydrograph Separation in the Lottental Catchment Area, Bochum, Germany.

5. Hydrochemical Responses during and after Strom Events and Hydrograph Separation in the Lottental Catchment Area, Bochum, Germany.

5.1. Abstract

A gauged station was installed at the Lottenbach, located in the south of Bochum, to record water heads and electrical conductivities at high-resolution time intervals. In addition, water samples were collected from rainwater and stream water during storm events and slow flow conditions to determine concentrations of 2+ 2+ + + 2- - - 2+ major ions including (Ca , Mg , Na , K , SO4 , NO3 and Cl ) and minor elements of (Fe, Fe , Al, Zn, + - NH4 , F and NO2). DOC was measured only during the storm event and slow flow conditions of October- November. Batch tests were performed on artificial materials, rocks, and soil samples collected from the - - - topsoil and soil profiles to measure concentrations of Na+, K+, Cl , NO3 , F and the organic contents. These procedures aims to determine the hydrochemical responses of the Lottenbach during storm events, factors controlling these responses and investigate the possibility to determine the potential flow-paths and separate the stream hydrograph based on the results of the above-mentioned tests. Results of hydrochemical analysis and EC measurements show an adverse response between some elements 2+ 2+ + + 2- and the water heads. These elements including the EC and the major ions of (Ca , Mg , Na , K , SO4 , - - NO3 and Cl ) during relatively intensive precipitation events. For this reason, the most common behaviors noted for these elements are represented by drop from a primary level into minimum values at the flow peaks, taking into account the multi flow peaks that are similarly associated with relatively low concentrations. These conditions were followed by returning most of the elements to their initial conditions after the precipitation effects. This situation was also noted at the small rain event. An exception was noted for K+ and EC, which showed adverse responses. Minor elements including of (Fe, Fe2+, Al and Zn) showed more complex responses. These conditions are represented by maximum concentrations at the beginning of storm events. Relatively high concentrations of these elements were also measured during the flow peaks. F- shows an increase in its concentrations during the falling limbs of the hydrographs and during slow flow conditions. Sometimes, the same situation was noted at some flow peaks. DOC showed adverse responses of the major ions. Maximum values of the DOC were measured during the falling limbs and during the slow flow conditions. NH4+ showed positive responses during runoff generation. This response is represented by increasing its values from 0 to maximums measured during the flow peaks. Slight fluctuations of the all elements were noted during the slow flow conditions. The hydrochemical behaviours of the Lottenbach during storm events is controlled by many factors, including the dilution processes, wet and dry depositions, urbanization, agricultural activities, forests and abandoned coal mines. The dilution factor is responsible for the decreasing of the major ions concentrations during the flood events, while the effect of wet and dry depositions is represented by the sudden rise of these elements at the beginning of the events and during the low precipitation conditions. Effects of urbanization is responsible for the behaviors of Na+ and Cl-, which show relatively high concentrations at the flow peaks in low-precipitation events. The other effects of the urbanization are related to the gas missions that were 56

Chapter 5: Hydrochemical Responses during and after Strom Events and Hydrograph Separation in the Lottental Catchment Area, Bochum, Germany.

+ - included in the dry and wet depositions (NH4 and NO2 ). Agricultural activities are responsible to leaching + + - nutrients such as K , NH4 and F that showed different behaviours of the major ions. Additionally, the - + + - sudden rise of the other elements of (NO3 , K , Na and Cl ), during the depletion of surface runoff, is also related to the agricultural activities. The highest concentrations of the DOC measured in October are the result of the forest impact. The effect of the abandoned coalmines can be seen by the relatively high concentrations of the minor elements (Fe, Fe2+, Zn and Al) measured at the beginning of the stream flow generations and at the flow peaks. These effects resulted by flushing of the hydroxides and by oxidation of sulphide minerals. During the slow flow conditions, most of the all tested elements showed semi-stable conditions, which is represented by fluctuations in their concentrations. These conditions are related to difference of feeding rates of the water sources contributing to feeding the stream flow, which has different hydrochemical characteristics. This study showed the complexity of hydrochemical responses of the Lottenbach and the complexity of the factors controlling these responses. In additions, this research also showed the importance of coupling the results of hydrochemical analyses of water samples with the results of chemical analysis of the batch tests in + + - - determine the flow-paths. Finally, behaviours of some elements of Na , K , Cl and NO3 during the depletion of the runoff can help later in the separation processes of the stream hydrograph by determining the time of concentrations of Lottenbachtal. Performing the hydrochemical model to separate the stream hydrograph in this study was not possible due to technical issues.

5.2. Introduction

The hydrochemical characteristics of direct surface runoff and base flow of a catchment area are controlled by geogenic and anthropogenic factors (Thyne et al., 2004; Hugenschmidt et al., 2010). The reactions of the rainfall or precipitation with the geological, soil covers and organic materials, of which exposure to the surface or situate in the geologic section are the major factors controlling the chemical fluxes of the surface runoff and base flow respectively (Semkin et al., 1994; Hensel and Elsenbeer, 1997). Other factors such as precipitation quantities and qualities, evaporation processes, weathering of minerals, topographic relief, biological activities (Semkin et al., 1994), land use (Mulholland, 1993), soil properties (including water retention curve, saturated hydraulic conductivity, preferential pathways), variability of precipitation according to canopy interception (Weiler and Jost, 2005) also contribute to the development of the chemical composition of the stream flow. Studying hydrochemical responses of the stream flow during storm events preoccupied many researchers. So that, several studies were performed worldwide to investigate these responses. At times, these studies were only limited to investigating the impact of acidification processes on the ecosystems (Jenkins, 1989; Soulsby, 1995; Negishi et al., 2007; Edwards, 2002), while most other studies performed in this subject were used in the separation processes of stream hydrographs (Hugenschmidt et al., 2010). The use of a hydrochemical parameter in hydrograph separations is related to the fact that the major ions showed conservative behaviours

Chapter 5: Hydrochemical Responses during and after Strom Events and Hydrograph Separation in the Lottental Catchment Area, Bochum, Germany. in some cases (Hooper and Shoemaker, 1986) and quasi-conservative behaviours in the other cases (Richey et al., 1998). Further, the delay resulting from flowing of storm water in different storage media contributes in generation of the hydrochemical signature of each storage medium (flow path) (Mulholland et al., 1990). The generation of the hydrochemical signature, of each storage medium, is related to the chemical properties of the medium and reaction rate that related to the residence time of the water in each medium (Maher, 2011). The residence times of the storage media in the catchment areas are controlled by catchment terrain indices representing by the flow path gradient and the distance to the stream network; therefore, an inverse relationship between the residence time and the catchment terrain indices was found (McGuire et al., 2005). The unsaturated zone has also an important role in controlling the residence time of the delaying water as well (Dunn et al., 2007). Several methods based on the hydrochemical signature and mass balance approaches (Weiler et al., 1999) were developed to separate the main component of the stream hydrograph. These methods arose after the classical methods, including the normal depletion method or master depletion curve (Horton, 1933 in Chow et al., 1988) and the graphical separation methods (including constant-discharge method, constant-slope method and concave method (McCuen, 1997) were the only methods used in hydrograph separation. Hydrochemical separation methods of the stream hydrograph were divided into two methods. The simplest one was focused on separation of hydrograph into two components. So stream flow was separated into new and old components (Robson and Neal, 1990; Weiler et al., 1999; Amidou et al., 2012). Limitation in the application of this method in more complicated cases resulted in the developed of three component tracer method (Rice and Bricker, 1996). This method gave the possibility to separate the stream flow into groundwater, soil water and overland flow (Dewalle et al., 1988; Hangen et al., 2001). However, using this model alone showed a high degree of uncertainty (Rice and Hornberger, 1998). These uncertainties are related to the temporal and spatial variability of solute concentrations of stream flow (Ogunkoya and Jenkins, 1993; Piatek et al., 2009), the change in the soil water content (Ball and Trudgill, 1997) and the sessional variations of climatic and wet depositions (Ball and Trudgill, 1997). The real quantification of the hydrograph components remain impossible (Hoeg et al., 2000). Due to this, coupling of hydrochemical tracers and hydrometric data were introduced as a satisfying method in hydrograph separation (Buttle, 1994; Bonel; Fritsch, 1997). In addition, measurements of electrical conductivity showed satisfactory results in hydrograph separations under certain hydrological and lithological conditions (Laudon and Slaymaker, 1997). The catchment area of the Lottenbach stream under consideration was subjected to intensive anthropogenic activities. These activities are represented by the mining and post-mining of the Ruhrkarbon deposit, expansion of residential areas and the agricultural activities. The mining activities changed the hydrochemical conditions of the study area. These changes represented by generation of acid mine drainage (Alhamed and Wohnlich, 2014a). In addition, high diversity of the hydrochemical characteristic were observed in the sample collected from the surface water and groundwater of this area (Alhamed and Wohnlich, 2014a). However, the post mining activities and the expansion of the residence areas are

Chapter 5: Hydrochemical Responses during and after Strom Events and Hydrograph Separation in the Lottental Catchment Area, Bochum, Germany. associating with intensive landfilling and sealing processes. The materials used in these processes have wide range of chemical compositions (Alhamed and Wohnlich, 2014b). What is more, the chemical compositions of the soil covers are also different as a result of the diversity of land uses (Alhamed and Wohnlich, 2014 b). This research aims to study the hydochemical responses of the Lottenbach before, during and after storm events, determine factors controlling these responses, and investigate the possibility to determine the potential flow-paths and separate the stream hydrograph based on the results of the performed tests.

5.3. Site description

5.3.1. Stream network and catchment area

The studied stream of Lottenbach is a tributary of the Ruhr. This stream is the largest natural-stream system in the south of Bochum (Viebahn-Sell, 2006). The Lottenbach stream has a west-east flow direction. Its network was subjected to large anthropogenic effects represented by sealing many parts of its canals as well as to the large number of drainage pipes that connected directly to its network (Viebahn-Sell, 2001). In the eastern part, the stream drains into the Kemnade Lake via a drain pipe.

The catchment area of Lottenbach stream is characterized by complex topographical conditions. It is located within the transition zone that separate between the Bergisch-Sauerländischen uplands in the south and the Westphalian lowlands in the north (GLA-NRW 1988). Several small hills that separated by steeply sloping v-notched valleys characterized the topographic structure of this area (GLA-NRW 1988).

Fig 5.1: Location map of the study area, represented by the western part of the Lottenbachtal.

Chapter 5: Hydrochemical Responses during and after Strom Events and Hydrograph Separation in the Lottental Catchment Area, Bochum, Germany.

5.3.2. The general climatic conditions

As a result of its position in the North-Western Germany climate zone, the study area is characterized by marine climate of mild winters and cool summers (LANUV, 2010). At times, continental effects are predominated the climate conditions of these areas. These Effects are represented by long periods of high atmospheric pressure of cool periods in the winter and dry-hot weather in the summer (LANUV, 2010). According to the long-term climatic study published by Grudzielanek et al. (2011), the average of annual air temperature in this area is 10.40 C°. The average minimal annual air temperature is 2.70 C° and average of maximal annual air temperature is 18.5 C°. Average of annual wind velocity is 3.5 m/s, average of annual relative humidity is 75%, average of annual sunshine duration is 1229.50 hrs./a and average of annual rainfall is 817.6 mm/a.

5.3.3. Land use and soil cover

The land use of the study area is affected by the expansion of the resident areas represented by the campus of the Ruhr University of Bochum in the south and the settlement areas in the middle and the west. These effects are represented by increase the impervious areas (Viebahn-Sell, 2006). However, the study area remains characterized by rural conditions. These conditions are seen in the rural features of grassland and pasture fields. The small coniferous forests spread in the catchment area increasing the green spaces and the variety of the land use in this area as shown in Fig 5.2. The soil covering this area consists mainly of Luvisols, Gleysols, Brown earth, Stagnosol- Luvisols and Brown earth- Podzol and secondarily of Brown earth- alluvial, brawn alluvial, Brown earth- Luvisols and Stagnosol and Brown Earth-Stagnosol soils as shown in Fig 5.2.

Fig 5.2: The land use and the soil maps of the south of Bochum (the land use was digitized from Google map 2010; the soil map modified after GLA-NRWc, 1988), including the study area that represented by the gauged part of the Lottenbachtal.

Chapter 5: Hydrochemical Responses during and after Strom Events and Hydrograph Separation in the Lottental Catchment Area, Bochum, Germany.

5.3.4. Geology and hydrogeology

The catchment area of Lottenbach stream is predominated by the thick deposits of the Upper Carboniferous. These deposits were divided locally into ―Bochumer Schichten‖ formations in the North, ―Wittener Schichten‖ formations in the South and ―Sprockhöveler Schichten‖ formations that limited to a small exposure within the ―Wittener Schichten‖ as shown in Fig 5.3 (GLA-NRWa, 1988). In terms of lithology, the Upper Carboniferous deposits in this area consist mainly of sandstone, mudstone and coal (GLA-NRW, 1988). These deposits were subjected to high tectonic development during the Variscan orogeny period. These processes represented by folding and plate movements processes, which indicates by folds and faults spread in the study area (Littke et al., 1986). From the standpoint of hydrogeology, the Upper Carboniferous deposits form the main aquifers of the study area (GLA-NRW, 1988). The hydraulic properties of these deposits are controlled by the tectonic structure, when faults, cracks, bedding planes, joints, and fractures are the main flow-paths (GLA-NRWb, 1988). In addition, extraction of coal deposits and the subsequent landfill processes of mined levels were changed the natural hydrogeological conditions on the studied area. Generally speaking, the natural permeability of these aquifers is extended from moderate to very low values (GLA-NRW, 1988).

Fig 5.3: The Geological map of the study area, represented by the western-gauged part of the Lottenbachtal (modified after GLA-NRWa, 1988).

Chapter 5: Hydrochemical Responses during and after Strom Events and Hydrograph Separation in the Lottental Catchment Area, Bochum, Germany.

5.4.Materials and methods

5.4.1. Field works

Water stages were measured continuously by a gauging station consisting of compound weir and Baro-Diver (Van Essen) system. This station was installed at the western part of the Lottenbach stream, an area mainly characterized by open canal flow conditions. The compound weir consists of a V-Notch weir at the lower part and rectangular weir at the upper part. This weir was designed in a way that allows measuring the water discharge during the dry and wet seasons. The Baro-Diver system was installed in a stilling well behind the weir plate. The installation process was performed according to United States Department of the Interior Bureau of Reclamation (USDIBR, 2001). The water levels were measured at intervals of 10 and 15 minutes. A CTD-Diver (Van Essen) was also installed in this station. This diver measured the electrical conductivity (EC) of the stream water at the same intervals of the Baro-Diver system. Due to technical issues, the EC value was measured manually at the observed storm event in august. Precipitations data were obtained from the Rudolf Geiger Climate Station of the Department of Geography within the Faculty of Geoscience at the Ruhr University of Bochum. These data include the rainfall intensity of 10 min intervals. A rain collector was installed at the facility of the Ruhr University of Bochum to collect rain samples. Rain samples were collected during March, April and October to gather information about the wet deposition processes. Water samples were also collected from the Lottenbach stream during three flooding events and one dry period. Flooding events included the periods (16.5-18.5.2011, 25.8-3.9.2011 and 10.10-21.10.2011), while the dry period extends from 15.10 to 25.11.2011. Two sub-groups of water samples were collected during this study. The first one included samples for measuring major elements including (Ca+2, Mg+2, Na+, + - -2 - + - - K , Cl , SO4 and NO3 ) , while the second one for measuring minor elements including (NH4 , F , NO2 , Al, Zn, Fe2+ and Fe ). All samples were collected by 50 ml bottles and were passed through a 0.45 µm membrane filter. The major and minor cations sub-sample includes (Ca+2, Mg+2, Na+, K+, Al, Zn and Fe) was preserved 2+ by concentrated HNO3 (1 % v/v). The Fe sub-samples were collected also in 50 ml and preserved by acetic acid. All samples were transported by a cool box to the laboratory and kept under 4 C° temperature to prevent the bacterial activities and biodegradation of nutrient species (Hiscock, 2005). Al and Zn measurements were missed during the flooding and the dry conditions of the stream flow in October- November due to technical issues. However, dissolved organic carbon DOC sub-samples were collected during this period. These sub-samples were collected by 250 ml glass bottles. Topsoil, artificial materials, rock samples shown in Fig 5.4 as well as to soil samples taken from soil profiles P1, P2 and P4 were collected from the study area. This procedure aimed to determine the concentration of + + - - - some elements including (Na , K , F , NO3 and Cl ), which help in determination the potential flow-paths. In addition to these elements, determining of organic matter was performed on selected zones of the soil profiles.

Chapter 5: Hydrochemical Responses during and after Strom Events and Hydrograph Separation in the Lottental Catchment Area, Bochum, Germany.

Fig 5.4: Location map of the topsoil, artificial materials, rocks and soil profiles samples collected from the south of Bochum (modified after Alhamed and Wohnlich, 2014b).

5.4.2. Laboratory Work

+2 +2 + + - -2 - Major ions, including Ca , Mg , Na , K , Cl , SO4 and NO3 as well as some minor elements, including + - NH4 , F and SO2 were analysed by DIONEX Ion Chromatography System model ICS-1000. Minor elements including Fe and Mn were tested by VARIAN Flame Atomic Absorption Spectrometry System (FAAS) model AA240F, while Zn an Al were tested by UNICAM Graphite Tube Atomic Absorption Spectrometry model (q2939). Fe2+ was measured by PERKIN-ELMER Spectrophotometer model 5515. Batch tests (10/1: l/kg) according to (DIN EN 12457-2, 2002) were performed on the soil, artificial materials + + - - - and the rocks to determine the potential contents the (Na , K , F , NO3 and Cl ). The batch test solutions were filled in 50 ml polyethylene bottles after they passed through a 0.45 µm pressure filter. The cations bottles were preserved by concentrated nitric acid HNO3 (1 % v/v). The ion concentrations of the requested elements were determined by DIONEX Ion Chromatography System model ICS-1000. Organic carbon contents of the soil samples were determined at the hydrochemistry laboratory of the department of hydrogeology in the Faculty of Geoscience at the Ruhr University of Bochum. 63

Chapter 5: Hydrochemical Responses during and after Strom Events and Hydrograph Separation in the Lottental Catchment Area, Bochum, Germany.

5.4.3. Data processing and presentation

Origin Lab V9 was used to establish the stream-solute hydrographs and series plots of batch tests results. Soil profiles were constructed by using Stratos 98 (RockWare 1997). All of these charts were reproduced using CorelDraw X6 (Corel Corporation 2012). Geographic Information System Arc Map version 9.3 (ESRI 2008) was used to digitizing all maps produced in this study. These maps were also rearranged by CorelDraw X6.

5.5. Results

5.5.1. Wet Depositions

Table 5.1 shows a statistical summary of the results of hydrochemical analysis of the rain samples.

Table 5.1: A statistical summary of the results of hydrochemical analysis of the rain samples collected from the Lottenbachtal, Bochum.

Na+ NH + K+ Mg2+ Ca2+ F- Cl- NO - NO - SO 2- Parameter 4 2 3 4 mg/l mg/l mg/l mg/l mg/l mg/l mg/l mg/l mg/l mg/l Min 0.00 0.00 0.20 0.00 0.30 0.10 0.60 0.00 1.40 2.60 Max 0.80 2.90 0.50 0.10 1.50 0.10 2.00 0.20 8.30 11.50 Average 0.45 1.98 0.30 0.05 0.80 0.10 1.25 0.10 4.33 7.63 Ca2+ extends between 0.3 and 1.5 mg/l. The minimum was measured during March and the maximum was measured during April. The average value of the Ca2+ in these samples is 0.8 mg/l. Mg2+ ranged between undetectable and very low concentrations not exceeding 0.1 mg/l. Na+ extends between undetectable value measured during October and 0.8 mg/l measured during April. The average value of the Na2+ is 0.45 mg/l. K+ ranges between 0.2 and 0.3 mg/l. The minimum was measured during March and October, while the maximum was measured during April. + + The average value of the K is 0.3 mg/l. NH4 extends between undetectable value and 2.9 mg/l. The minimum was measured during October and the maximum was measured during April. The average value of + the NH4 in these samples is 2 mg/l.

2- SO4 ranges between 2.6 and 11.5 mg/l. The minimum was measured during October and the maximum was 2- - measured during March. SO4 in these samples has an average value of 7.6 mg/l. The NO3 concentrations extend between 1.4 and 8.3 mg/l. The minimum was measured during October and the maximum during - - March. The average value of the NO3 is 4.3 mg/l. Cl ranges between 0.6 mg/l during October and 2 mg/l - during April and has an average value of 1.3 mg/l. NO2 shows undetectable values. An exception was found - - during March, which showed that NO2 had a value of 0.2 mg/l. F also shows undetectable values. An exception was found during April, which showed F- has a value of 0.1 mg/l.

5.5.2. Batch Test

Table 5.2: shows a statistical summary of the batch tests results performed on the soil, artificial materials, and rock samples. Fig 5.5 shows results of batch tests of topsoil, artificial materials, and rock samples while Fig 5.6 shows results of these tests in soil profiles. 64

Chapter 5: Hydrochemical Responses during and after Strom Events and Hydrograph Separation in the Lottental Catchment Area, Bochum, Germany.

Na+ ranges between undetectable value (referred as 0) and 63.2 g/t. The minimum value was measured in samples 17 and 18 while the maximum value was measured in sample 3. Samples 17 and 18 belong to the artificial materials of construction waste and slag, while sample 3 was taken from an agricultural field. Soil samples collected from the agricultural field have relatively high to middle contents of Na+. Mudstone has also contained a relatively high content of Na+, while artificial materials samples have relatively low contents of Na+. Sandstone and soil samples collected from the forests have relatively low content of Na+. K+ ranges between undetectable value (referred as 0) and 119.2 g/t. The maximum value was measured at sample 18 and the minimum was measured at sample 16. Both samples were taken from the artificial materials, Sample 18 represent slag and sample 16 represents mine waste. Similar to Na+, soil samples collected from the agricultural fields have relatively high to middle K+ contents. Mudstone has also relatively high content of K+, artificial materials have relatively low content of K+. Sandstone and soil samples of the forested area also have low contents of K+.

Table 5.2: A statistical summary of the result of batch tests performed on the soil, artificial materials and rock samples collected from the Lottenbachtal, Bochum.

Na K Cl NO3 F parameter mg/l mg/l mg/l mg/l mg/l Min 0,00 0,00 1,34 0,00 1,09 Max 63,20 119,18 74,16 386,19 23,17 Average 17,55 36,35 16,11 67,31 8,37 - NO3 ranges between an undetectable value referred to as 0 and 386.2 g/t. The maximum was measured in the sample 19 while the minimum was measured in the sample 5. Sample 19 belongs to the artificial materials whereas sample 5 was taken from an agricultural field. Soil samples of the agricultural fields have - NO3 ranged from relatively high to low contents, while soil samples of the forested areas exhibited relatively - - low NO3 contents. Most samples of the artificial materials also contain relatively low amount of NO3 , which was also noted in the mudstone sample. Cl- ranges between 1.3 in sample 13, which belongs to artificial materials (stockpiles materials), and 74.2 g/t in sample 19, which also belongs to artificial materials (concrete). Generally, Cl- contents of the agricultural field extended from relatively high to low contents, while soil samples of the forested areas have relatively low Cl- contents. This was also found in rock samples and the most of the artificial materials. F- extends between 1.1 g/t and 23.2 g/t. The minimum was measured in a forested area (Sample 11) and the artificial materials (Sample 17), while the maximum was measured in an agricultural field (Sample 3). In general, samples collected from the agricultural fields have relatively middle to high F- contents, while soil of the forested areas has relatively low F- contents. The same situation was found in rock samples. The artificial materials have relatively mid to low F- contents.

Chapter 5: Hydrochemical Responses during and after Strom Events and Hydrograph Separation in the Lottental Catchment Area, Bochum, Germany.

Fig 5.5: Results of batch tests of topsoil, artificial materials and rock samples collected from the Lottenbachtal, Bochum, A: The soil samples of arable areas; B: The soil samples of forests; C: the Artificial materials; D: Rocks. For soil profile P1, Na+ ranges between undetectable value referred as 0 and 49.8 g/t. the minimum value was measured at the levels extend from 50 to 100 cm while the maximum value was measured at the top level (0-10). The average value of Na+ in this profile is 16.7 g/t. K+ extends between 14.2 and 38.4 g/t. The minimum value was measured at the level (10-20) and the maximum value was measured at the top level (0- 10). The average value of K+ at P1 is 27.6 g/t. For anions, Cl- ranges between 1.8 and 62.9 g/t. the minimum value was measured at the sampling level (70-80) while the maximum value was measured at the sampling - - level (0-10). P1 has an average value of 16.4 g/t for Cl . NO3 extends between values less than 1.77 and 83.5 g/t. the maximum was measured at the level (20-30) while the minimum was measured at the all other levels except the top level, which has a value of 62.9 g/t. F- falls in the range 4.0 -7.8 g/t. the maximum was measured at sampling level (10-20), while the minimum value was measured at the sampling level (80-90). The average value of F- is 5.8 g/t. The organic content of P1 extends between 0.01 and 0.08 %. The minimum was measured at the levels (50-60) and (60-70), whereas the maximum was measured at the levels (0-10) and (20-30). The average value of organic matter in this profile is 0.04%. For soil profile P2, Na+ extends between undetectable and 21.21 g/t. The minimum of Na+ was measured at the horizons (40-50) and (90-100) and the maximum was measured at the top horizon (0-10). The average value of Na+ in this profile is 9.04 g/t. K+ ranges between 5.38 and 22.50 g/t. The minimum value was

Chapter 5: Hydrochemical Responses during and after Strom Events and Hydrograph Separation in the Lottental Catchment Area, Bochum, Germany. measured at the level (20-30) and the maximum value was measured at the level (90-100). The average value of K+ in P2 is 13.71 g/t. For anions, Cl- ranges between 15.42 and value less than 1.77 g/t. The maximum value was measured at the top level (0-10) and the minimum value was measured at the levels (40-50) and (60-70). Cl- concentrations - in this profile have an average value of 4.62 g/t. NO3 ranges between 15.42 g/t and value less than 1.7 g/t. The maximum value was measured at a depth (0-10) while the minimum value was measured among all other sampling levels except the depth (80-90) with a value close to 5 g/t. F- extends between 2.7 and 12.2 g/t. The

Fig 5.6: Results of batch tests performed on the soil profiles that were sampled from the Lottenbachtal; P1 and P2 arable areas; P4 forested area.

Minimum value was measured at the level (80-90) and the maximum at the level (20-30). The average value of the F- in this profile is 6.66 g/t. 67

Chapter 5: Hydrochemical Responses during and after Strom Events and Hydrograph Separation in the Lottental Catchment Area, Bochum, Germany.

The organic carbon contents range between 0.02 and 0.05 %. The minimum content was found at the depth (50-60) whereas the maximum content was found at the top level (0-10). The average value of organic carbon is 0.03%. For Profile P4, Na+ falls in the range 8.8-20.2 g/t. The minimum was measured at the level (50-60) and The maximum was measured at the level (70-80). The average value of Na+ in this profile is 18.2 g/t. K+ ranges between 3.8 and 10.2 g/t. The maximum value was measured at the sampling levels (90-100) whereas the minimum was measured at the sampling level (50-60). The average value of K+ is 8.9 g/t. For anions, Cl- concentrations fall within the domain (2.5-4.1) g/t. the minimum was measured at the level (70-80) and the maximum was measured at the level (20-30). The average value of Cl- is 3.3 g/t. F- has a value of 1.1 g/t along this profile, an exception was found at the level (90-100), which has a value of 4.3 g/t. The average - - value of F in P4 is 2.7g/t. NO3 ranges between values less than 1.8 and 38.8 g/t. The maximum was measured at the level (30-40), while the minimum was measured at the levels (50-60), (70-80) and (90-100). - NO3 in this profile has an average value of 9.6 g/t. Organic matter of this profile is ranged between 0.01 %, measured at the levels (70-80) and (90-100) and 7.6% measured at the humus level (0-20). This level has the highest organic matter content of the all tested levels in the study area. The average value of organic matter for this profile is 1%.

5.5.3. Chemical hydrograph of the observed flooding events

Fig 5.7, Fig 5.8 and Fig 5.9 show the rain intensity R, water head H, water temperature T, electrical conductivity EC, major ions chemistry and minor ions chemistry records of the Lottenbach during the selected rain event in May, August-September and October respectively. Fig 5.9 also includes the DOC record that measured only during the October event. Water heads show a hydrological response of the small rain event that was observed during May. This response is represented by a slight increase of the water head, which is associated with an increase in the value of the EC at the flow peaks, represented by sawtooth shape. Then, the EC responses drop slightly until they reached a minimum level of 0.73 at the falling limb. Thereafter, EC values rise gradually again until they back to their initial level. Major cations including Ca2+, Mg2+ and Na+ show drops in their concentrations as a result of rising water levels. The pre-storm concentrations of these elements are 68.2, 13.5 and 15 mg/l respectively. The minimum concentrations of Mg2+ and Na+ (7.7 and 9.8 mg/l consecutively) were observed at the flow peak, while the minimum value of Ca2+, with a value of 42.5 mg/l, was measured at the falling limb of the hydrograph. Subsequently, the concentrations of these elements are gradually increasing until they reached their primary levels as shown in + + Fig 5.7. In contrast, K and NH4 show completely different conditions in comparison with the previous elements. Their concentrations increase to reach the maximum at the flow peak (4.4 and 46.3 mg/l sequencing). Thereafter, their concentrations gradually drop until reaching the initial conditions. The 2- - - minimum values of these elements are 3.1 and 0 mg/l. Major anions including SO4 , Cl and NO3 show a 2- - drop in their concentration during the storm event. The minimum values of SO4 and Cl , which are 44.3 - and 18.7 mg/l respectively, were observed at the flow peak. At the same time, the minimal value of NO3

Chapter 5: Hydrochemical Responses during and after Strom Events and Hydrograph Separation in the Lottental Catchment Area, Bochum, Germany.

Fig 5.7: Stream and chemical hydrographs of the Lottenbach observed before, during and after storm events in May.

2- - was observed at the falling limb. Concentrations of SO4 and Cl increase after the peak of discharge until - they reached their primary levels, whereas NO3 showed different conditions as shown in Fig 5.7. Responses of minor elements including of Fe, Fe2+, Al and Zn are represented by an increase their concentrations as a result of the increase of the stream discharge. The maximum concentrations of these elements, which have a value of 2.2 mg/l for Fe, 1.2 mg/l for Fe2+, 126 µg/l for Al and 61 µg/l for Zn were measured at the peak of discharge. Thereafter, the concentrations of Fe and Fe2+ decrease until they reached the initial levels then start to increase again exceeding the primary level, whereas Al and Zn show slightly different behaviours. These behaviours are represented by drop their concentrations after the peak discharge period then their

Chapter 5: Hydrochemical Responses during and after Strom Events and Hydrograph Separation in the Lottental Catchment Area, Bochum, Germany. values oscillate before reaching a constant level. After that, their concentrations start to increase without returning to the primal levels. The minimum values of these elements are 0.4 mg/l for Fe, 0.3 mg/l for Fe2+, 5 - µg/l for Al and 5 µg/l for Zn. Finally, NO2 has undetectable values before the storm event. Its values increase with rising of water head until they reached a constant level of 0.5 mg/l at the falling limb, then they drop to their initial conditions. F- isn’t affected by this storm event. This situation is represented by their constant concentrations of 0.2 mg/l during the runoff generation period. In August, EC shows adverse responses of the water heads when its values drop from a value of about 0.51 ms/cm to relatively minimum values measured at the flow peaks. The minimum value, which has a value of 0.18 ms/cm, was measured at the flow peak 4. Thereafter, EC values increase gradually until reaching the primary level. Values of the other flow peaks and other falling limbs are not available in this period according to missing the continuous measurements. These conditions are associated with solute behaviour that can be described as follows: Ca2+ shows similar conditions of EC, represented by relatively low concentrations at the peaks of discharges. The primary level has a value of about 60 mg/l (prior the storm event). While the minimal has a value of 23.1 mg/l. This value was measured at the flow peak 2. After the peaks, Ca2+ concentrations increase until they reached their initial conditions. Mg2+ showed similar conditions of Ca2+. Its concentration drops from about 13 mg/l (before the rain event) to relatively low values at the flow peaks. The minimum of 3.9 mg/l was measured at the flow peak 2. Similar to Ca2+, Mg2+ returns to its initial condition and stabilize at this level during slow flow conditions. Na+ shows fairly similar conditions of the Ca2+ and Mg2+. These conditions are represented by a drop in concentrations from initial concentrations of 13 mg/l to 4.1 mg/l at the flow peak 1 and 3.9 mg/l at the flow peak 2, then the Na+ concentration increases to 4.9 mg/l at the peak discharge 4 and 8 mg/l at the peak 6. At the end of quick flow condition, the Na+ concentrations rise until they reached their primary conditions and then rise again exceeding the initial condition. After that, Na+ drops again and reaching a value less than the initial level. K+ shows a slightly difference behaviours compared with the previous elements. This difference is represented by the sudden rise of its concentration at the flow peak 2, while the other elements show minimum concentrations at this point. The maximum has a value of 25.1 mg/l. This value was measured during the slow flow conditions. On the other hand, k+ shows similar situation of Na+ after the quick flow conditions. This situation represented by increasing its concentrations exceeding the initial level before they falling again to a value lower than the primary level. The initial level of K+ in this event has a value closed to 5 mg/l. The minimum of 3.6 mg/l was measured during the flow peak 4. In contrast, the maximum value of 5.9 2- mg/l was measured at the slow flow conditions as show in Fig 5.8. For major anions, SO4 drops from a primary concentration level closed to 65 mg/l into a minimum value of 14.4 mg/l measured during the flow peak 2. This concentration increased slowly until it reached the primary level and thereafter it showed stable - 2- conditions during slow flow. NO3 shows similar conditions of SO4 . Its concentrations also dropped from an initial level of about 12 mg/l into a minimum of 3.7 mg/l, measured during the flow peak 2. Afterwards, the concentrations increased to a level fluctuating gently around the primary level. Cl- also shows similar 2- conditions of SO4 . Its concentrations dropped from a primary value of 44 mg/l into a minimum value

Chapter 5: Hydrochemical Responses during and after Strom Events and Hydrograph Separation in the Lottental Catchment Area, Bochum, Germany. measured during the peak 2. However, its concentrations increased after the quick flow conditions until it reached the primary level and then dropped a little bit down this level. Minor elements show contrasting behaviours of the major ions. These behaviours can be summarized in the following way: Fe concentrations increase from an initial value of 0.9 mg/l to a maximum value of 1.5 mg/l at the beginning of the storm event. After that, the concentrations decreased and increased independently of the water level. Minimum values of 0.4 mg/l were measured at the peak discharge 6 and during the slow flow conditions. Fe2+ showed similar conditions of Fe despite the differences in the magnitude. An increase of the Fe2+ concentration was also noted at the beginning of the storm event. However, the maximum concentration of Fe2+, with a value of 0.2 mg/l, was measured during the peak 4. A minor concentration was measured during the falling limb of the peak 1. Fe2+ also shows fluctuations that are independent of the water level.

Fig 5.8: Stream and chemical hydrographs of the Lottenbach observed during and after storm events August-September.

Chapter 5: Hydrochemical Responses during and after Strom Events and Hydrograph Separation in the Lottental Catchment Area, Bochum, Germany.

F- showed complex responses during this event. These responses are representing by rise the concentration of F- during peak 1 before it decrease during the flow peak 2 to a level situating under the primary level. During the flow peak 4, the concentration increased again exceeding the primary level before it dropped to the primary level during the flow peak 6 and slow flow conditions. Other increases of the concentration were also noted during the slow flow conditions, followed by decreasing of the concentrations to the primary level. The primary level of the fluoride during this storm was 0.2 mg/l. The minimum value is 0.1 mg/l measured at the falling limb of the peak 2 and the maximum value is 0.3 mg/l measured during the falling limb of the peak 1, at the peak 4 and during the slow flow conditions.

Fig 5.9: Stream and chemical hydrographs of the Lottenbach observed during sampled storm event of October.

Chapter 5: Hydrochemical Responses during and after Strom Events and Hydrograph Separation in the Lottental Catchment Area, Bochum, Germany.

Similar to Fe, Al and Zn reached their maximum values of 99 and 76 µg/l at the beginning of the storm event. Following this, their values alternate up and down without returning to the initial values for Zn as shown in Fig 5.8. The initial values of the Al and Zn are 74 and 35 µg/l respectively and the minimum values are 31 and 35 µg/l measured during the slow flow conditions of Al and at the peak 4 for Zn. In October, the sampling processes and EC measurements were started after the beginning of the storm event due to technical problems. Anyway, the behaviours of the solutes during this storm show similar conditions of August-September event. These conditions can be described as following: EC values show adverse matching of the water heads as shown in Fig 5.9. The minimum value of the EC, which has a value of 0.21 ms/cm, was measured at the flow peak 3. Thereafter, the EC value gradually increased until it reached a constant level of about 0.6 ms/cm. In contrast, the flow peaks 4 and 5 showed different responses, when no response of EC rose during the peak 4 and there was noted a small diverse response during the peak 5 in comparison with the other flow peaks. The behaviours of major ions during this storm can be described as follows: during the rising limb of the peak 1, Ca2+ has a value of 35.9 mg/l. This value drops to the minimum with a value of 14 mg/l at the peak discharge of this peak. Thereafter, Ca2+ concentration gradually increases during the falling limb. However, it decreases again during the generation of the peak 3. Then, the Ca2+ concentration increases until it reaches a constant level of about 49 ms/cm. Mg2+ shows an identical curve of the Ca2+ with a difference in the magnitude. During the rising limb of the peak flow 1, Mg2+ has a value of 7 mg/l. This value drops into 2 mg/l at the peak flow1. Then Mg2+ increases at the falling limb of this peak before it drop again during the generation of peak 3, after that, its concentration increases until reaching a constant level of about 11 mg/l. The sudden drop of Mg2+ before the flow peak 4 resulted by the precipitation. Na+ and K+ also have identical curves. Their concentrations decrease from values of 12.7 and 4.7 mg/l (respectively) at the rising limb of the peak 1 into 6.7 and 3.4 mg/l (respectively) at the peak 1. After that, their concentrations increase and decrease corresponding to the hydrograph’s development and they reached their maximum (24.4 for Na+ and 7.3 for K+) at the falling limb of the peak 3. Thereafter, the + + + concentrations decrease again reaching semi-stable levels of about 22 mg/l for Na and 6 mg/l for K . NH4 behaviours are quite different from the other elements. This difference represented by increasing its concentration during the generation of the peak discharges, which is contrary to the behaviours of other + elements. The maximum of NH4 (8.5 mg/l) was measured during the generation of the flow peak 3 (Fig 5.8), whereas its concentration decreased during the rising and the falling limb and it reached zero level at 2- - the slow flow conditions. For major anions; SO4 and Cl show similar curves (taking into account the difference in the concentrations ranges). Concentrations of 30.3 and 20 mg/l (respectively) were measured during the generation of the flow peak 1 (at the rising limb). These values dropped to minimum values of 10.5 and 7.6 mg/l respectively at the flow peak 1. Thereafter, the concentrations of these elements increased and decreased due to the decrease and increase the water head, respectively. Then the concentrations 2- - increased again until reaching a semi-stable condition of values about 58 mg/l for SO4 and 41 mg/l for Cl - 2- - during the slow flow conditions. NO3 showed very different conditions than SO4 and Cl . These differences are represented by its fluctuations up and down irregularly and independently of the water level. In addition,

Chapter 5: Hydrochemical Responses during and after Strom Events and Hydrograph Separation in the Lottental Catchment Area, Bochum, Germany. this element doesn’t reach the semi-stable conditions during the slow flow conditions. The minimum value of 5.1 mg/l was measured at the falling limb of the flow peak 3. Minor elements including Fe and Fe2+have the maximum values of 1.4 and 0.8 mg/l, respectively, at the peak 1. The flow Peak 2 also shows relatively high concentrations as shown in Fig 5.9. From this point, the concentrations of Fe and Fe2+ dropped until they reached the minimum value of 0.1 mg/l for Fe on the rising limb of the flow peak 3 and a value of 0.15 mg/l for Fe2+ during the early stage of the slow flow conditions. Measuring errors should be taken into account in this situation especially at low concentrations of Fe2+. Generally, fluctuation of the concentrations was also noted during the generation and the regression of the flow peaks. Thereafter, the concentration of Fe started to increase randomly until it reached a value of 0.6 mg/l and then started to drop again (during slow flow conditions). However, Fe2+ showed relatively more stable conditions during the slow flow conditions that are subsequent to the flow peaks. These conditions followed by rising the Fe2+ values again as shown in Fig 5.9. The behaviour of DOC during this storm is represented by a stable level of value about 6 mg/l during the generation of the flow peak 1 as shown in Fig 5.9. Then, the DOC increase progressively and reaching a maximum of 8 mg/l during the peak discharge 2. Thereafter, the concentration dropped during the generation of the peak flow 3 and it reached a relatively low concentration. After that, the concentration rose again and reached the maximum concentration once again during the falling limb of the peak 3. From this point, the concentration dropped again to a semi-stable level (during the slow flow conditions), which is peppered by slightly rises and descends as shown in Fig 5.9. The minimum value of 4.3 mg/l was measured during these conditions.

5.5.4. Chemical hydrograph of slow flow conditions

As shown in Fig 5.10, relatively stable or semi-stable conditions were observed for Na+, K+, Mg2+ and Ca2+ during this period. Na+ dropped slightly from 22.3 mg/l (at the beginning of the slow flow conditions) into a minimum value of 17.9 mg/l. Thereafter, Na+ concentration rose into value of 20 mg/l. similar conditions was found for K+. Its concentrations dropped from a value of 6.5 mg/l reaching a minimum value of 3.7 mg/l. then the concentration rise into a value of 4.9 mg/l. Mg2+ shows adverse condition. Their value increased from a value of 11.5 mg/l until reaching a maximal value of 13.5 mg/l before dropping to a value of 12.3 mg/l. Ca2+ also increased from a level of 49 mg/l reaching a maximal value of 65.1 mg/l before it 2- drops to a value of 53.6 mg/l. SO4 shows high degree of stability. Its concentrations showed minimal fluctuations along the observation line. This line had values close to 60 mg/l. Cl- showed different conditions. Its curve shows a slight concave of maximum value 42 mg/l at the beginning. This concave is - followed by narrow and more extended convex of a minimum value of about 36 mg/l. NO3 show also a concave of a maximum of 20 mg/l. This concave is followed by a convex of a minimum of 15 mg/l. For minor elements, Fe decreased from a value of 0.6 mg/l at the beginning and reaching a minimum value of 0.2 mg/l, and then the concentration increased until it reached the maximal concentration of 0.7 mg/l, measured at the end of the observation. F- shows a constant rate of 0.4 mg/l in most of the points. A value of 1 mg/l was observed in two points along the F- curve. DOC shows a small concave, showing an increase from a

Chapter 5: Hydrochemical Responses during and after Strom Events and Hydrograph Separation in the Lottental Catchment Area, Bochum, Germany. value of 3.34 mg/l into a maximal value of 5.03mg/l, at the beginning. Then, its value dropped again until reaching a semi-stable level of values close to 3.5 mg/l.

Fig 5.10: Stream and chemical hydrographs of the Lottenbach observed during slow flow conditions of October-November. 75

Chapter 5: Hydrochemical Responses during and after Strom Events and Hydrograph Separation in the Lottental Catchment Area, Bochum, Germany.

5.6. Factors controlling the hydrochemical responses of the Lottenbach

The hydrochemical responses of the Lottenbach during the observed events show different behaviours. The Lottenbach shows a hydrochemical response even during the small rainfall-runoff event observed in May (Fig 5.7), when the total rainfall amount of this event didn’t exceed 2.2 mm and the rising of the water head doesn’t exceed 5 cm. The slight rise of EC values, observed after the beginning of the storm event, are associated with rising of Na+ and K+ values at the convolution point of the rising limb of the stream 2- - - hydrograph. In addition, SO4 , Cl and NO3 also showed increases in their concentrations at this point. Many factors are responsible for the behaviours of the above-mentioned elements. A dilution process is responsible for the decrease concentrations of most major elements at the flow peaks. On the other hand, generation of direct surface runoff on roads and other impervious areas (including the residential areas, parking spots and the facilities of the Ruhr University of Bochum) is also one of the main factors controlling the hydrochemical responses of the Lottenbach. Road salt, used largely in the study area during the winter season, may be the responsible for the sudden rise of the Na+ and Cl- at the convolution point of the stream hydrograph at the beginning of the storm event, where the remaining salt particles from the roads and other sealed areas could be flushed by direct surface runoff. Wet depositions are another factor controlled the hydrochemical + responses of the Lottenbach. The effects are represented by the relatively high concentrations of the NH4 , noted during the flow peaks developments especially at the convolution point. This suggestion was provided + + by the relatively high concentration of the NH4 in the rain sample of April. The source of NH4 is the emission in the rainwater, which related directly to the traffic activities (Löflund et al., 2002). Rising of the - NO3 concentration at the convolution point of the hydrograph is another evidence of the wet depositions, in - which NO3 of the rainwater resulted by the oxidation processes of the automobile ammonium (Langguth and 2- Voigt, 2004). The rise of the SO4 concentration at the convolution point is also related to the wet deposition, 2- when a part of SO4 resulted by burning of fossil fuel. Its effects represented by the wet deposition of SO2 2- 2- and SO4 (EPA, 1999). The hydrolyzed and the oxidized of SO2 produced SO4 , which can be deposited from the air to water (Yi et al., 1997; Tasdemir and Gunez, 2006). Cl- and compounds of the sulphur and the nitrogen can also be deposited directly from the air to the surfaces (Davidson and Wu, 1990). These elements dissolve in the direct surface runoff and find their way to the stream channel. The effects of dry deposition could be involved in the sudden rise of the elements concentrations at the convolution point of the hydrograph due to the flushing of the impervious areas by the generated runoff. A third factor controlling the hydrochemical responses of the Lottenbach during this period is agricultural activities. These effects is + represented by the behaviours of the NH4 during the falling limb of the hydrograph and by behaviours of K+, represented by a concave curve in which the maximum value is matched the peak discharge. These situations refer to generate the direct surface runoff and the interflow on the agricultural fields. This suggestion was supported by the result of the batch tests performed on the soil samples collected from the topsoil zones and soil profiles (Fig 5.5 and Fig 5.6), in which the topsoil zone of the agricultural fields has relatively high concentrations of these elements in comparison with the forested areas. The soil content of these elements and other elements such as Cl- and Na+ is related to the fertilization processes (BLFU, 2004; 76

Chapter 5: Hydrochemical Responses during and after Strom Events and Hydrograph Separation in the Lottental Catchment Area, Bochum, Germany.

LNW, 2012) noted before the sampling processes. These elements dissolved in the direct surface runoff and interflow to contribute to the total solute concentrations of the stream flow. A fourth factor controlling the hydrochemical responses of the Lottenbachtal is the abandoned coalmines of this area. The effects of these sites are represented by the behaviours of Fe, Fe2+, Al and Zn, caused by the generation of acid mine drainage (Alhamed and Wohnlich, 2014a). The correspondence between the maximal concentrations of these elements and the peak discharge of the hydrographs could be related to drift and re-dissolutions hydroxides of these elements that deposited on the bottom of the stream course (Alhamed and Wohnlich, 2014a) and adits (Fig 5.11).

Fig 5.11: Iron hydroxides deposited in the bottom of the Lottenbach stream in the middle part (near sampling point 6, Fig 4.8).

The effects of the dilution process were stronger during August-September and October events. This situation is related directly to the differences in the precipitation amounts, which have a total value of 26.8 mm during the event observed in august and 43.1 mm in October. The decrease of most of major ions was more oblivious during these events, especially at the flow peaks that associated with the minimum or relatively low concentrations. The responses of EC, which show similar conditions of the most major elements, support this suggestion. The effects of the foregoing factors (which described for May event) were also noted during these events, in which the sudden rise of K+ during the flow peak 2 of August (Fig 5.8)

Chapter 5: Hydrochemical Responses during and after Strom Events and Hydrograph Separation in the Lottental Catchment Area, Bochum, Germany. refer to increase the overland flow and the interflow of the agricultural fields. In addition, the responses of the F- (Fig 5.8) and the relatively high concentrations of the F- in the soil zones of the agricultural fields (Fig 5.5 and Fig 5.6) refer to contribute the interflow and the direct surface runoff of the agricultural fields to the - + total stream discharge. NO3 and NH4 showed very different responses than May, which may be related to consume the compound containing these elements. On the other hand, effects of the abandoned coalmines were also represented by maximum concentrations of minor elements, except Fe2+, at the beginning of the storm during the observed event in August-September. This relates to flushing of hydroxides from the stream channel. Otherwise, the relatively high concentrations observed during the peak flow in Fig 5.8 and at the peak flow 1 Fig 5.9 refer to flooding the abandoned mines, where the ions release by the oxidation of sulphide minerals, re-dissolution of metals hydroxides and dissolve of hydroxysulphates salts of the Fe could be dissolved in mine water (Younger, 1997). The reaction of sulphides with rainwater, which enter the mine facilities, also causes the releasing of minor elements even during the high intense precipitation (Davies et al., 2011). After the flushing phenomena, the minor elements show typical fluctuations noted largely at several flooded mine sites (Wolkersdorfer, 2008). The F- behaviours during slow flow conditions of August- September and October, seen by increasing its concentrations from the initial level, are a further evidence of the mines discharge. This suggestion was concluded from the results of the batch tests performed on artificial material including the mine waste and the sealing materials (Fig 5.5). The correlation between the behaviours of F- and other minor elements are supported this suggestion. So the F- contents of the above-mentioned materials leached by flood discharge. However, the interflow generated at the agricultural field also leached F-. The effects of the wet and dry depositions during these events were smaller than May. This situation may be returned to the high dilution process, which is related to the amount of precipitation. Conversely, the effect of forested area on the hydrochemical responses of the Lottebach was only noted at October event. This effect was noted due to DOC behaviour measured during this event. The very high content of organic matter that observed in the humus zone of the forested area (Fig 5.6) is responsible for the high concentration of DOC during the flow peak 2 and 3 in Fig 5.9. DOC contributes also in determination the other flow-paths. The relatively intermediate concentration of the DOC measured during the flow peak 1 and at the falling limb of the peak 3 could be referring to the direct surface runoff of the agricultural fields. This statement was deduced from the relatively high organic matter of the topsoil zone of the agricultural fields in comparison with the other zones of the soil profiles shown in Fig 5.6. The relatively low concentration of the DOC during the slow flow conditions refers to the generation of the interflow of the other soil zones or perhaps to the increasing the contribution of groundwater to the stream flow. The lowest concentrations measured during the slow flow conditions could refer to mine discharge, which has normally low concentrations of the DOC (Wallis et al., 1983; Watzlaf et al., 2004). The other possibility of the low concentration of DOC is the release of rainwater from the water control system of the Ruhr University of Bochum and the residential area located in the west. A mixture of different water including the retention runoff, the interflow, the groundwater flow and the mine discharge control the hydrochemical characteristics of the Lottenbach during the slow flow conditions. The

Chapter 5: Hydrochemical Responses during and after Strom Events and Hydrograph Separation in the Lottental Catchment Area, Bochum, Germany. above-mentioned water sources have different hydrochemical characteristics (Alhamed and Wohnlich, 2014 a). So that, the depletion of one or more feeding source will changes the hydrochemical composition of the stream water. This could be responsible of the fluctuations of the elements shown in Fig 5.10.

5.7. Hydrograph separation

+ + - - The sudden increasing of some elements, including of Na , K , Cl and NO3 , observed at the last falling limbs of the stream hydrographs, is associated with return some of other elements to their primitive level. 2+ 2+ 2+ These elements include Ca , Mg and SO4 . Behaviours of these elements refer directly to depletion of surface runoff. Behaviors the elements of the first group could be resulted by flushing effects that normally associated the depletion of the surface runoff (Elsenbeer et al., 1994). These situations were accompanied by change in the regression of the stream hydrograph as shown in Fig 5.8 and Fig 5.9. According to the complexity of the hydrological and hydrogeological conditions of the study area, represented by the diversity of the flow paths and the processes controlling the hydrochemical characteristics, the simple classical hydrograph separation methods, such as constant-discharge method, constant-slope method and concave method, is recommended for hydrograph separation in this area.

5.8. Conclusions

Three storm events and one slow flow condition were recorded and sampled during May, August-September and October 2011. The main aims of this study are investigate the hydrochemical response of the Lottenbach to the storm events, the factors controlling these responses and the possibility of identifying potential flow- paths and separate the stream hydrograph based on the results of the collected information were investigated. Wet depositions and batch tests, performed on soil, rocks and artificial materials, were also done to achieve these targets. Results of this study showed complex responses resulted by coupling of several factors including the dilution effect, wet and dry depositions, urbanisation, agricultural activities and abandoned coalmines. Additionally, this study also showed the importance of integration between the behaviours of chemical elements during periods of flooding and slow runoff and results of batch tests in determining the + + - - potential flow-paths of surface water and groundwater. Some elements including Na , K , NO3 and Cl showed special behaviours at the depletions of the quick flow. These behaviours can help later in separation of stream hydrograph by determine the time of concentration of the catchment area. However, the application of hydrochemical separation of the hydrograph during this study was not possible due to some technical problems.

Chapter 6:The Hydrological, the Hydrogeological and the Hydrochemical Framework of the Lottenbachtal, Bochum, Germany.

6. The Hydrological, the Hydrogeological and the Hydrochemical Framework of the Lottenbachtal, Bochum, Germany.

6.1. Abstract

This study was performed to investigate the hydrological, the hydrogeological and the hydrogeochemical framework of the Lottenbachtal in Bochum. Long term climatic data were statistically analysed, water and soil samples were collected and analysed, stream flow discharge was measured and separated, the hydrological balance of the catchment area was calculated and a hydrological and hydrogeological conceptual model was constructed. The Lottenbachtal is largely affected the diversity of the land use, which include forests, arable areas, abandoned coal mines and settlement areas. The soil of the forested area represented by relatively high acidic conditions and relatively high sulphate concentrations, while the soil of the arable areas represented by near-neutral conditions associated with relatively high concentrations of the nutrients. The impact of the settlement areas represented by dry and wet depositions as well as to the chemical elements including in constructions and landfilling materials. The impact of the mentioned factors use is represented by the complex water types of Ca-Na-Mg-

Cl-SO4-HCO3, Ca-Mg-HCO3-SO4, Ca-Na-Mg-Cl-SO4, Ca-Na-Mg-Cl-SO4 and Ca-HCO3, which represent the diversity of the flow-paths of the water as well as to mixing processes. The above mentioned factors were also affected the physical hydrological and hydrogeological characteristics of the study area, which represented by the extremely high direct surface runoff rates, especially in settlement areas, as well as to reduce the groundwater recharge.

6.2. Introduction

Understanding the hydrological cycle and its hydrochemical evolution is a critical issue for water resources management and planning in a catchment area. Generally, studying of the hydrological cycle in small watersheds provides very high quality measurements. These measurements facilitate the investigation of the complexity that results from combination of physical, chemical and biological processes. In addition, these measurements contribute to understanding the significance of the environmental variations (such as the change of the land use) (Schumann et al, 2010). Most studies performed on small watersheds are aimed at estimating the leaching of sediment, nitrogen, and phosphorus in arable areas, while the acidification processes are the main seeking phenomena in the forested areas (Nilssen, 1980). Other studies, which have been held in the field, aimed to regionalization the hydrological and hydrogeological parameters obtained from small watersheds to larger watersheds (Lee et al., 2005; Jin et al., 2009). Underground mining usually affect the hydrological cycle of the small catchments areas. These effects, as a result of extractions and stockpile impoundments near the mines, are represented by changing geologic, geomorphologic and land use of the exploiting fields (Blodgett et al., 2002). Thus, mining processes changed the flow system of the aquifers in the mining areas. Water quality was also affected by underground mining 80

Chapter 6:The Hydrological, the Hydrogeological and the Hydrochemical Framework of the Lottenbachtal, Bochum, Germany. operations. These effects were represented by high concentrations of undesirable elements (Banks et al., 1997). Surface mining also affected the hydrological and hydrogeological system of the catchments areas located within the exploiting zones. These effects resulted from the excavation processes that removed part of the aquifers. Generally, post-mining pit-lakes form after the mine closure and receive their water from groundwater. Thus, the surface mining consumes the groundwater storage of the aquifers. Moreover, the pit- lakes lose a large portion of their water by evaporation. In addition, materials removed by mining, which are normally barrier to contaminants, increase the possibility of groundwater contamination (Younger, 2003). The leaching from tailings and waste rock, via soil water and surface runoff, causes contamination of groundwater and surface water by toxic constituents, contained in these materials (ELAW, 2010). The conceptual model of small watersheds is an effective tool, which facilitates the management and the restoration of streams and watersheds (Cleaves, 2003). This model can also help in predicting the impact of some hydrological parameters, (Wegehenkel, 2002), climate change (Ruelland et al., 2012), or of variations in fracture connectivity (Krzeminska, 2012), on the hydrological system. In the south of Bochum many coal mines were constructed between the 17th and 20th centuries as a part of Ruhrkarbon mining activities (Hermann and Hermann, 2008). Coal deposits were extracted by using different methods, including horizontal, inclined and vertical shafts. Deep mining in this area was not conducted until the 20th century, after the invention of the steam engine (Huske, 2006). In addition, dewatering and other facility structures such as adits, drainage adits and shafts were also constructed to facilitate the exploitation process as well as to eliminate dangers associated with mining. Such dangers included the unexpected collapse of the water, drowning whole mines (Hermann and Hermann 2008). Large amounts of coal were extracted and shipped through the Ruhr, while the resulting mining wastes were dumped near the shafts and entrances (GLA-NRW, 1988). During extraction processes, many mines were connected via shafts and other extraction structures, which in turn increased the rate of coal extraction (Huske, 2006). Coal mining in this area continued until the beginning of the 20th century. The mines were either sealed or backfilled by using various materials, consisted mainly of mining waste and to a lesser from ash, garbage, slags, sludge, construction waste, industrial residues and household waste (GLA-NRW, 1988). The main aim of this study is to investigate the hydrological and the hydrogeological framework of the Lottenbachtal catchment area, characterized by a hard rock aquifer that was subjected to mining and urbanization activities. Furthermore, other purpose is to calculate the components of the hydrological balance in this area. This research also intended to provide a conceptual model of the study area for sharing with the water sector to restore the channel of the main watercourse of the Lottenbach stream, taking into consideration the ecosystem.

6.3. Study Area

The Lottenbachtal catchment area is situated south of Bochum. The gauged part covers an area of about 5 km2. This area located within the marine climatic zone of the north-west Germany, characterized by average

Chapter 6:The Hydrological, the Hydrogeological and the Hydrochemical Framework of the Lottenbachtal, Bochum, Germany. annual rainfall of 817.6 mm/a, average air temperature of 2.7 C° in the winter and 18.5 C° in the summer, south and south-west winds of mean velocities of 3.5 m・s-1, an average value of relative humidity of 75% and cloudy conditions associated with sunshine duration of 1229.5 hrs/a (Grudzielanek et al., 2011). Thus, the climate in the study area is characterized by mild winters and cool summers (LAVUV, 2010).

Fig 6.1: Location map of the study area including the drainage systems, water sampling points (during October 2010) and the site of the soil profiles.

Chapter 6:The Hydrological, the Hydrogeological and the Hydrochemical Framework of the Lottenbachtal, Bochum, Germany.

The geology of the study area is represented by the hard-rock formations of the Upper Carboniferous (Fig 6.2), which consist chiefly of coal seams, mudstone and sandstone deposits (Littke et al., 1986). These deposits were subjected to complex tectonic developments in the Variscan Orogeny, associated with over thrusts, strike slip and normal faults (Littke et al., 1986) as shown in Fig 6. 2. These formations form the main aquifer in this area, which is characterised by very low to moderate hydraulic conductivity (GLA- NRWd, 1988).

Fig 6.2: Geological map of the study area (modified after GLA-NRWa, 1988).

6.4.Methodology

Climatic data for 21 years were obtained from the Rudolf-Geiger climate station of the Department of Geography in the Faculty of Geoscience at the Ruhr University of Bochum. This data includes the daily values of precipitation P, average relative humidity RH, minimal air temperature Tmin, maximal air temperature Tmax, average air temperature Taverage and the average wind velocity Vwind for the extended period between 1991 and 2012. The frequency analysis of the climatic data was performed by OriginPro V9 (OriginLap Corporation, 2012). pH according to (DIN ISO 19682-13, 2009), electrical conductivity EC according to (DIN ISO 11265, 1997), carbonate test according to (DIN ISO 19682-13, 2009) and batch test 10/1 l/kg according to (DIN EN

Chapter 6:The Hydrological, the Hydrogeological and the Hydrochemical Framework of the Lottenbachtal, Bochum, Germany.

12457-2, 2003) were performed on soil samples, collected from the selected soil profiles shown in Fig 6.1. The soil profile P2 was chosen in an arable area, while the soil profile P4 was chosen in a forested area. 2+ 2+ + + - 2- - Major ions including of Ca , Mg , Na , K , Cl , SO4 and NO3 were tested in the extracted samples. A gauge station was installed in the eastern part of the Lottenbach stream to measure the water head of the stream. Van Essen Baro-Diver system was used to achieve this purpose. The recorded water heads were converted to discharge values by instantaneous tracer dilution (Morgenschweis, 2010) and volumetric method (FAO, 1993). A total of 6 well-known water source points were sampled during October 2010. Water-sample 1 was taken from the drainage system of the Ruhr University of Bochum, water-sample 2 was taken from a mine shaft, water-sample 3 from the shallow groundwater, water-sample 4 was taken from the drainage system of the settlement area in the west, water-sample 5 was taken from the Lottenbach stream at the gauging station and water-sample 6 was taken from an open pit lake located in the east of the study area. The locations of these samples are shown in Fig 6.1. Physico-chemical parameters including pH, EC, dissolve oxygen DO and 2+ 2+ + + - 2- redox potential Eh were measured in the field. Concentrations of major ions (Ca , Mg , Na , K , Cl , SO4 , - - NO3 ) were determined in the hydrochemistry laboratory at the Ruhr University of Bochum. HCO3 was calculated by the ion balance equation. The results of the hydrochemical analysis were plotted on piper diagram to determine the hydrochemical facies of the water sources. The potential evapotranspiration was calculated by the Haude method (Haude, 1955). According to the diversity in land use of the study, the actual evapotranspiration was measured by integrations of Renger & Wessolek (Renger and Wessolek, 1990) and Bagrov & Glugla (Bagrov, 1953; Glugla et al, 1976) methods. The Renger & Wessolek method enables to calculate the actual evapotranspiration of arable, grassland and coniferous-forested areas, while Bagrov & Glugla method enables to calculate the actual evapotranspiration of urban area and deciduous forests. The stream hydrograph was separated into direct surface runoff and base flow using BFI digital filter version 3 (Hydro-Office; Software for Water Science). Local minimum method, with coefficients of n*=5 and f*= 0.9, was used to perform the separation processes. Ground water recharge was calculated by a method suggested by (Lillich, 1970) for German conditions, where the base flow can consider the groundwater recharge. Soil samples were collected from profiles 2 and 4 to calculate the change in the soil moisture between the initial and the final conditions of the study period. Soil moisture was determined according to (DIN 18121-1, 1998). Soil parameter including average of 3 the porosity (nsoil), which has a value of 0.46 %, and average of bulk density, which has a value of 1.4 g/cm ,was obtained from (Tursun, 2012). On the other hand, the mean thickness of the soil cover has a mean value of 1 m (GLA-NRWc, 1988). Water losses from settlement area via (sewer system) were calculated by the water balance equation (modified after Davie, 2008).

Qurb= − a−퐺 -Qsur ±ΔSsoil

Chapter 6:The Hydrological, the Hydrogeological and the Hydrochemical Framework of the Lottenbachtal, Bochum, Germany.

Where Qurb is surface runoff formed in urban areas, which flow directly into a separate sewer systems (mm), P is the precipitation (mm), ETa is the actual evapotranspiration (mm), GR is ground water recharge (mm) and ΔSsoil is the change in the soil storage. The average value of the all parameters at the catchment scale was calculated by the Geographic Information System ArcMap GIS V 9.3 (Esri, 2008). A conceptual model of the study area was established based on the geological, the hydrological and the hydrogeological characteristics of the study area. ArcMap GIS V 9.3 (Esri, 2008) and CorelDraw X6 (Corel Corporation, 2102) were used to achieve this purpose.

6.5. Results and discussions

6.5.1. Hydro-climatic framework

Fig 6.3 shows the relative and the cumulative frequency of the daily precipitation (only rainy days). The study area is characterized chiefly by relatively low daily precipitation, when 66 % of the rainy days fall within the range (0.1-5) mm/day and 19 % of them within (5-10) mm/day. Smaller relative frequencies of 7.69 % and 3.43 % present for the precipitation domains (10-15) and (15-20) mm/day respectively, while a relatively small relative frequency of 1.71 % exists for the domain (20-25) mm/day. Other precipitation ranges, up to 45 mm/day, have a relative frequency less than 0.1%.

Fig 6.3: The relative and the cumulative frequency of the daily precipitation (only rainy days) of the period (1991-2012). Relative humidity shows more homogeneous conditions as shown in Fig 6.4. The relative frequencies of the RH domains lie in two main extents of (5 %< RF <10%) and (10 %< RF<15%). RH domains of [(45-50), (50-55), (80-85), (85-90) belong to the first extent, while domains of [(55-60), (60-56), (65-70), (70-75), (75- 80)] belong to the second one. However, the domains of [(35-40), (40-45), (90-95)] % fall within the range (1 %< RF < 5%). Saturation conditions and high deficit conditions of the vapour are very rare and have very low relative frequency.

Chapter 6:The Hydrological, the Hydrogeological and the Hydrochemical Framework of the Lottenbachtal, Bochum, Germany.

Fig 6.4: The relative and the cumulative frequency of the daily relative humidity of the period (1991- 2012).

The study area characterized by mild winter that represented by the predominance of the Tmin ranges of [(0- 5), (5-10), (0-15)] C°, located within the RF extent of (20 %

10), (-10 - -5), (35-40)] C°. RF values of (1< RF< 15%) were fund for the relatively low Tmax of the winter and the relatively high Tmax in the summer, represented by Tmax domains [(-5-0), (0-5), (25-30), (30-35)] C°.

The moderate Tmax, represented by domains [(5-10), (10-15), (15-20), (20-25), fall within the range (15<

RF< 20%). The relative and the cumulative frequencies of the Tmin, Tmax and Taverage are shown in Fig 6.5.

Fig 6.5: The relative and the cumulative frequency of the daily Tmin, Tmax and Taverage of the period (1991-2012)

Chapter 6:The Hydrological, the Hydrogeological and the Hydrochemical Framework of the Lottenbachtal, Bochum, Germany.

6.5.2. Soil chemistry

The results of the pH, EC and batch tests, performed on soil profiles P2 and P4, are shown Fig 6.6 and Fig 6.7 respectively. The soil profile P2, sampled from arable area, characterized by near-neutral to neutral conditions. This because that the pH values range between 5.53 at the level (10-20) and 6.59 at the level (80- 90) as shown in Fig 6.6. A relatively low pH value was noted in the topsoil horizon up to 40 cm depth. After that, the pH values increase until reaching the maximum value at the level (80-90). An oscillation of the pH value can be seen explicitly along this profile. The average value of the pH in this profile is 6.17. EC shows more stability in comparison with pH. Its value ranges between 16.67 and 28.10 µs/cm. The minimum value was measured at the level (30-40) whereas the maximum value was measured at the level (20-30). These conditions are associated with the poor carbonate content of (0.5 < CO3 < 2 %) along this profile. In addition, samples collected from this profile are characterized by low concentration of major ions. The Ca2+ concentrations range between 12.01 g/t, measured at the level (80-90), and 34.07 g/t, measured at the top level (0-10). The Ca2+ has an average value of 21.58 g/t. The Mg2+ concentrations show undetectable values along this profile. An exception was found at the level (30-40) with a very low content of 1.84 g/t. In these circumstances the measuring errors should be considered for this element. The Na+ and the K+ concentrations have close ranges. The Na+ values fall within the range (undetectable-21.21) g/t, while K+ falls within the range (5.38-21.40) g/t. The minimum of Na+ measured at the levels (40-50) while the maximum measured at the top level (0-10). Conversely, the minimum of K+ measured at the level (20-30) and the maximum measured at the level (80-90) g/t. The average values of Na+ and K+ in this profile are 10.04 and 12.74 g/t respectively. 2- For anions, SO4 range between 9.48g/t, measured at the level (40-50), and 30.85 g/t, measured at the level 2- - (0-10). The average value of the SO4 in this profile is 18.94 g/t. Cl shows relatively low concentration in comparison with other elements. The maximum value of 15.42 g/t was measured at the top level (0-10), while concentrations less than 1.77 g/t were measured at the levels (40-50) and (60-70). The average value of - - Cl in this profile is 4.93 g/t. NO3 shows values less than 1.77 along the soil profile, except for levels (0-10) and (80-90) where values of 15.42 g/t and 5.15 g/t were measured respectively. On the other hand, the soil profile P4 was sampled from a forested area. This profile shows more acidic condition than the P2 as shown in Fig 6.7. The pH values of P4 range between 4, measured at the top of the humus level and 4.28, measured at the level (30-40). The average value of pH in this profile is 4.16. The pH values along this soil profile are more stable than P2. The EC shows a very high value of 232 µs/cm in the humus; while the unconsolidated materials located at the level (90-100) have the minimum value of 26.2 µs/cm. The average of the EC in this profile is 63.34 µs/cm. All sampled points in this profile show undetectable values for Ca2+ (Fig 6.7). An exception was found in the unconsolidated materials situated at the level (90-100), where the Ca2+ has a value of 16.26 g/t. The Mg2+ has undetectable values for all sampled levels, whereas, Na2+ has an extension that asymptotically matched of its extent in profile P2. Its value ranges between 8.75 g/t at the level (50-60), and 20.16 g/t, at the level (70-80). The average value of the Na+ is 13.08 g/t. The K+ concentrations have a less extended range in comparison with P2. Its value ranges 87

Chapter 6:The Hydrological, the Hydrogeological and the Hydrochemical Framework of the Lottenbachtal, Bochum, Germany. between 3.75 g/t, measured at the level (50-60), and 10.17 g/t, measured at the level (90-100). The average value of K+ in this profile is 5.63 g/t.

Fig 6.6: The results of the pH, EC and batch tests, performed on soil profiles P2 (arable area).

Chapter 6:The Hydrological, the Hydrogeological and the Hydrochemical Framework of the Lottenbachtal, Bochum, Germany.

Fig 6.7: The Results of pH test, EC test and batch test of the soil profile P4 (forested area).

Chapter 6:The Hydrological, the Hydrogeological and the Hydrochemical Framework of the Lottenbachtal, Bochum, Germany.

2- For anions, SO4 concentrations extend between 94.19 and 191.17 g/t specified a more extensive range than the profile P2. The maximum was measured at the level (90-100) while the minimum was measured at the 2- - level (20-30). The average value of the SO4 in this profile is 115.68 g/t. The Cl concentrations in this profile show similar conditions compared with P2 and are also characterized by low concentrations. The maximum value of 5.16 g/t was measured at the top level (0-10) while the minimum value of 2.52g/t was - measured at the levels (70-80). The average value in this profile is 3.59 g/t. NO3 shows a relatively high concentration of 38.76 g/t at the level (30-40). While values less than 1.77 g/t were measured at most levels along this profile as shown in Fig 6.7. The differences in the element concentrations represent the impact of 2- the variety of the land use on the soil chemistry. Higher concentrations of the SO4 , associated with low values of H+, in the forested area could be an indicator of high organic sulfur content (Mayer et al, 1995) or by the higher oxidation rate of the disulphide minerals, which may be contained in this soil, compared to the arable areas. On the other hand, higher concentrations of other elements in soil samples collected from the arable field may be related to the soil treatment and agricultural activities.

6.5.3. Hydrochemical characteristics

A statistical summary of the results of the hydrochemical parameters measured in the water samples collected from the Lottenbachtal catchment area are presented in Tab 1. The water samples are characterized by neutral conditions, when pH varies from 6.45 in the shallow groundwater and 7.81 in the drainage system of the Ruhr University of Bochum. EC values ranged between 381 µs/cm, in the shallow groundwater, and 1364 µs/cm in the drainage system of the Ruhr University of Bochum. The concentration of Na+ and K+ vary from 14.9 to 105 and 2.8 to 18.8 mg/l respectively. The Ca2+ and Mg2+ 2- - - concentrations extend from 33.5 to 124 and 9.4 to 38 mg/l respectively. For anions, SO4 , Cl and NO3 concentrations range between 47 to 242, 31 to 193 and 2.1 to 37.9 mg/l respectively. 2+ 2+ - The relatively high concentrations of Ca , Mg and HCO3 in the surface water and groundwater in this area are derived from calcium rich materials, which include landfilling, construction materials, mine waste and the geological formations (Alhamed and Wohnlich, 2014b). The soil of the arable fields also contains Ca2+ - and HCO3 , as shown in Fig (6.6). Thus, flow of soil water through the soil section increase the calcium and carbonate content of the percolated water. Thus, the agricultural activities also contribute to the evolution of the chemical composition of the surface water and groundwater. These conditions relate to the leaching of nutrients, especially from the topsoil (Fig 6.6), into stream water and groundwater.

The Na+, K+ and Cl- concentrations in the water samples are mostly related to dissolution of road salt that used largely in winter. This related to the existing the sampling points next to road or settlement areas. The situation of relation between Na++K+ and Cl- close to the 1:1 line in Fig 6.8 enhance this hypothesis.

Chapter 6:The Hydrological, the Hydrogeological and the Hydrochemical Framework of the Lottenbachtal, Bochum, Germany.

Tab 6.1: A statistical summary of results of hydrochemical analysis of the water samples collected from the study area during October 2010.

Parameter Unit Min Max Average

EC µs/cm 381 1364 687 DO mg/l 6.72 9.87 8.08 pH - 6.45 7.81 7.33167 Eh mv 168 455 354.45 Ca mg/l 33.50 124.00 83.22 Mg mg/l 9.40 38.00 19.05 Na mg/l 14.90 105.00 37.02 K mg/l 2.80 18.80 8.10

SO4 mg/l 47.00 242.00 103.02 Cl mg/l 31.30 193.00 66.60 2.10 37.90 12.60 NO3 mg/l

However, Na+ and K+ can also result from the weathering of silicate minerals. This represented by the slight deviation of the relation Na++K+ :Cl- from the 1:1 line toward the Na++K+ in Fig 6.8.

Fig 6.8: The correlation between the Na++K+ and Cl- of the water samples collected from the Lottenbachtal during October 2010.

The top soil horizon of the arable fields also contains Na+, K+ and Cl- Fig 6.6. The most likely source of these elements in this area is the fertilization. Thus, the leaching of these elements by the infiltrated water raises

Chapter 6:The Hydrological, the Hydrogeological and the Hydrochemical Framework of the Lottenbachtal, Bochum, Germany.

- the concentrations of these elements in this water. The NO3 contents resulted from agricultural activities, especially in groundwater and overland flow that generate on the arable areas. This suggestion supported by - the relatively high concentrations of NO3 detected in the topsoil horizon of the arable area, shown in Fig 6.6. - Wet and dry deposition could also contribute to the NO3 and other elements in the groundwater and surface water of this area (Alhamed and Wohnlich, 2014c). Abandoned coal mines of this area also affecting the hydrochemical characteristics of the surface water and the groundwater. These effects were discussed by (Alhamed and Wohnlich, 2014 a). The results of the hydrochemical analysis were plotted on the Piper diagram Fig 6.9 to determine the hydrochemical facies of the water resources in the Lottenbachtal catchment area.

Five main water types can be noted in the study area, which are Ca-Na-Mg-Cl-SO4-HCO3 in the drainage system of the Ruhr University of Bochum, Ca-Mg-HCO3-SO4 in the mine-shaft and the stream water, Ca-Na-

Mg-Cl-SO4 in the urban water, Ca-Na-Mg-Cl-SO4 in the shallow groundwater and Ca-HCO3 in the open pit lake. These facies are an indicator of the complexity controlling the evolution of the surface water and groundwater hydrochemistry, where the mixing process and the multi-flow paths are the main factors responsible for the formation of the above mentioned water types.

Fig 6.9: The piper diagram of the water sample collected from the Lottenbachtal during October 2010 (Sampling points can be seen in App IV.2 and Fig 6.1).

Chapter 6:The Hydrological, the Hydrogeological and the Hydrochemical Framework of the Lottenbachtal, Bochum, Germany.

This conclusion was introduced by the result of the batch test performed on soil and artificial materials (Alhamed and Wohnlich, 2014b), where wide range of concentrations was found in these materials. Significant variability of the soil chemistry could also see in Fig 6.6 and Fig 6.7, where important differences can be clearly be seen between the soil samples of the arable and the forested area. In addition, the difference in concentrations can be seen along each profile separately. The linear trend of the hydrochemical properties, shown in Fig 6.9, from the lake water toward the groundwater is another indicator of the water mixing and the variety of the flow paths. These conditions also refer to contribute different type of water sources to groundwater and the surface water.

6.5.4. The hydrological and the hydrogeological conceptual model

The catchment area of Lottenbachtal is characterized by mountainous structure, represented by shallow hills separated by steep sloped V-notched valleys (GLA-NRW, 1988). The Lottenbachtal is a V-shaped valley represented by small tributaries, which also characterized by notched bottom as well as to low gradient (Viebahn-Sell, 2001). The Lottenbach is the main watercourse in the study area. This stream was classified as a small floodplain in the basement (Viebahn-Sell, 2006). The land use of the gaged part of the Lottenbachtal catchment, shown in Fig (5.2), area consists mainly of urban districts with 54% of the total area. This includes the residential area, transport and other facilities. Agricultural fields constitute 13 % of the total area, and consist mainly of wheat. Grassland occupies 11% of the area, which is used as open pastures. Deciduous forests comprise 10%, and consist mainly of beech. Mixing land of weeds and shrubbery also constitutes 10 %. Coniferous forests, consisting mainly of spruce, occupy 1%. According to the classification of the United States department of agriculture (USAD, 2007), the soil cover of the Lottenbachtal catchment area consists mainly of D hydrological soil group (HSG), which has a mean hydraulic conductivity of 4.62*10-6 m/s (GLA-NRWb, 1988). This soil group is normally characterized by low to very low hydraulic conductivity, associated with high potential runoff. However, the generation of runoff is also related to the land use. The hydrologic soil group C occupies a small portion of the study area, as shown in Fig 6.10. This group extends as narrow belt with a southwest-northeast direction and characterized by low the hydraulic conductivity of about 8.1*10-5 m/s. (GLA-NRWb, 1988). Thus, the hydrological characteristics of the soil cover in the study area increase the potential runoff and reduce the groundwater recharge. The western part of the study area and the most of the settlement area are drained by a separate sewer system (Fig 6.1). Thus, no direct surface runoff arises to the stream from this area. A conceptual model of the study area is shown in Fig 6.10. The Upper Carboniferous mudstone and sandstone deposits are the main aquifer in this area. These formations are overlaid by loss-loam, which is characterized by low hydraulic conductivity and constitute an aquitard layer. Fig 6.10 shows that the groundwater ﬂow takes place chiefly through faults and mine-shafts. These features form high flow conduits of the groundwater. Fracture networks, joints and bedding planes are other flow-

Chapter 6:The Hydrological, the Hydrogeological and the Hydrochemical Framework of the Lottenbachtal, Bochum, Germany. paths. Fractures are scattered within the impermeable rock matrix. So that, groundwater could also flow through the primary pore space and fracture networks. In addition, the intersection between the faults, joints and bedding planes systems could be form local traps of the groundwater. Joints and bedding planes enhance the vertical and semi-vertical groundwater flow. However, the complex interconnection between fractures, fault, shafts and bedding planes increase the heterogeneity and the complexity of the groundwater flow system in this area. The intersection points between these features could contribute in the formation of water springs on the slopes or at the bottom of the valleys Fig 6.10 also show that the groundwater, including the mine water, occurs chiefly by infiltration of the precipitation through the mine facilities, the faults, the joints, the bedding planes and the fracture networks. This hypothecs enhanced by the hydrochemical characteristics of the shallow groundwater, represented by

Ca-Na-Mg-Cl-SO4 water type, where the absence of the predominant ions refers to the contribution of the different water sources to the groundwater recharge in this area. The groundwater recharge through the soil cover could be negligible in this area, due to the hydraulic properties of the soil. However, the infiltration rate through soil profiles related to land use (USAD, 2000). Thus, the infiltration rate in the arable fields must be much higher than in forests in this area. The impervious area and other urban-facilities should significantly reduce the groundwater recharge. Therefore, different mechanism and important spatial variations predominant the groundwater recharge in the Lottenbachtal catchment area.

Fig 6.10: The hydrological and the hydrogeological conceptual model of the Lottenbachtal (the section A1:A of the geological profile shown in Fig 3.2).

Chapter 6:The Hydrological, the Hydrogeological and the Hydrochemical Framework of the Lottenbachtal, Bochum, Germany.

6.5.5. Hydrologic budget

Fig 6.11 shows the climatic parameter, including the daily precipitations, the daily average of the air temperatures, the minimal and the maximal daily air temperatures, the daily average of the relative humidity and the daily sum of the global radiations Gb. Fig 6.12 shows the stream flow discharge, separated into its main components.

According to the climatic data (Fig 6.11), the measured stream flow, the soil moisture and the other hydrological parameters, the hydrological budget of the gauged part of the Lottentalbach catchment area can be described as following; the annual precipitation during the study period is 944.5 mm, average of relative humidity is 61.74%, average of air temperature at 14:00 hrs. is 14.09 C °, the average of Tmax is 16.36 C°, the average of the Tmin is 7.2 C° and the average of mean temperature is 11.55 C°. The minimal air temperature value of -14.5 C° was measured in the winter, and the maximal value of 34 C°, was measured in the summer. The actual evapotranspiration value during the study period, resulted by integration of Renger & Wessolek and Bagrov & Glugla methods, is 301.25 mm.

Fig 6.11: The climatic data used in the calculation of water balance during the period (15.4.2011- 15.4.2012)(obtained from Rudolf Geiger Climate Station). The total stream flow during the study period is 497863 m3 (99.57 mm), while the total value of the base flow is 192049 m3 (38.41 mm). On the other hand, the total value of the direct surface runoff during the study period is 305815 m3 (61.16 mm). The mean change in the soil moisture is 24 mm, which represent 122218 m3. Thus, the total stream flow constitutes only 10.5 % of the total precipitation, where the base flow constitutes 4% and the direct surface runoff, which flow into the stream, constitutes 6.5 %. The change in the soil moisture constitutes only 3%, whereas the actual evaporation constitutes 32%. The direct surface runoff (water losses), generated over the urban area, should be 54.56% of the total precipitation. Thus the total direct surface runoff in this area constitutes 61% of the total precipitation.

Chapter 6:The Hydrological, the Hydrogeological and the Hydrochemical Framework of the Lottenbachtal, Bochum, Germany.

Fig 6.12: The direct surface runoff and the base flow discharge of the Lottenbachtal during the period (15.4.2011-15.4.2012).

6.6.Conclusion

The Lottenbachtal characterized by very complex hydrological and hydrogeological characteristics due to the variety of land use and the complex geological structure. The mining activities of the Ruhr Carboniferous disturbed the natural hydrogeological conditions by conduits, represented by drainage shafts. These features have relatively high flow velocities. The mining shafts intersect with other tectonic and lithological feature and forming a complex groundwater flow system. The soil cover of the study area has extremely low hydraulic conductivity, which increase the direct surface runoff and reduce the groundwater recharge. The same influences resulted by the settlement areas. The groundwater recharge occurs chiefly via the mining and the tectonic features. The non-predominance water types of the most water sources in this area is another result of the impact of the land use diversity, where the surface water and the groundwater flow through different flow paths. This situation increases the complexity of the hydrochemical characteristics. The groundwater recharge of the Lottenbachtal constitutes only 4% of the total precipitation. The direct surface runoff of the stream flow constitutes 6.5 %, while the direct surface runoff of the urban area constitutes 54.56% of the total precipitation. Thus the total direct surface runoff of the study area constitutes 61 % of the total precipitation. On the other hand, the actual evapotranspiration constitutes 32 % of the total precipitation as shown in table 6.2.

Chapter 6:The Hydrological, the Hydrogeological and the Hydrochemical Framework of the Lottenbachtal, Bochum, Germany.

Table 6.2: The component of the water budget of the Lottenbachtal during the period (15.4.2011- 15.4.2012).

The absolute value The absolute value Ratio The component m3 mm % Precipitation 944500.00 944.50 100.00 The total stream flow 99570.00 99.57 10.54 The direct surface runoff of the stream flow 61160.00 61.16 6.48 The base flow 38410.00 38.41 4.07 The direct surface runoff of the suburban areas 515320.00 515.32 54.56 The total dircet surface runoff values 576480.00 576.48 61.04 Actual evapotranspiration 301250.00 301.25 31.90 The change in the soil moisture 122218.00 24.00 3.00

Chapter 7: Summary of the results and recommendations

7. Summary of the results and recommendations

The Lottenbach is one of the small catchment of the Ruhr, which is represented by the presence of the abandoned coal mines, the expansion of the settled areas, the presence of coniferous and deciduous forest as well as to the agricultural activities. The main aim of this research was to prognosis of the surface water and the groundwater balance of this catchment area as well as to investigate the impact of the diversity of the land use on the surface water and the groundwater quality. Intensive field, laboratories and data analysis works were conducted to achieve this purpose. The result of these works showed that the Lottenbachtal is characterized by high relatively direct surface runoff discharge, of about 50% of the total precipitation, and very low groundwater recharge, only 4% of the total precipitation. This situation is resulted mainly by the expansion of the resident areas, the low hydraulic conductivity of the soil and the land use. The statistical analysis of the climate data showed that the most of the daily rainfall value is less than 10 mm/day, where the heavily storm events are too rare in this area.

The abandoned coal mines of the Upper Carboniferous in this area have a negative impact on surface water and ground water, represented by the pollution of groundwater and surface water by Fe. The oxidation of the pyrite and marcasite is one of the factors causing this pollution. However, the mixing process between the abandoned coal mine drainage and the other water sources, especially the urban runoff, have significantly contributed to the dilution of iron concentration in the stream and the lake water. Moreover, the materials used in the sealing and the expansion of the resident areas include relatively high contents of carbonates. The dissolution of these minerals increase pH, consume H+ and release calcium, magnesium and bicarbonate to the affected water. This process mitigates the generated AMD. Therefore, the discharge from abandoned mines in this area is mainly characterized by near-neutral to alkaline conditions. However, the likelihood of generating acid drainage, with high concentrations of heavy metals, is still possible especially during low flow conditions from mines or adits. The diversity of the land use is also affected the surface water and the groundwater quality. This is because the soil of the arable areas represented by near-neutral to neutral conditions associating with relatively high concentrations of the nutrients and the other elements especially at the topsoil, while the forest soil is represented by acidic conditions associating with a relatively high concentration of sulphate and organic matter as well as the relatively low concentrations of the other elements. The impact of these conditions is represented by the leaching of nutrient and the other elements, resulted by the fertilization or by the treatment of the soil in the arable areas. The leaching increase the alkalinity and the concentration of the other ions, such as calcium, sodium, potassium, chloride, sulphate, of the soil water one hand, but on the other hand, it leads to the increasing the concentrations of some undesirable elements, such as nitrate, in this water. Geogenic factors such as dissolution of carbonate minerals and the chemical weathering of the geological depositions also contribute to the development of the chemical composition of water.

Chapter 7: Summary of the results and recommendations

The effect of the forests is represented by increase the acidity, the concentrations of sulphate and the concentration of the dissolved organic carbon of the soil water. The road salt increases the concentrations of sodium and chloride of the surface water and the shallow groundwater. In addition, wet and dry depositions form additional load of the chemical elements to the hydrologic cycle of the Lottenbachtal. These conditions are responsible of the complex hydrochemical responses of the Lottenbach during and after the storm events. The variety of the flow paths limited the possibility of using chemical methods to separate the stream hydrograph. The water types of the main water sources in this area, represented by the non- predominant water types, are another result of the diversity of the land use. However, this property was help in understanding the circulation of the water in this catchment, where rapid circulations characterized the hydrologic cycle in this area. The linear trend, observed between the water sources of this area, deduces this suggestion. It is recommended to use rich carbonate materials in the sealing and closing of the coal mines. This procedure will prevent or mitigate the hazard of the abandoned coal mines. In addition to that, the increase of the impervious area in the coal field will increase the surface runoff, which causes the dilution of the mine water. In this situation the concentration of the undesirable metals, which resulted from the mining sites, will significantly decrease and thus the hazard of the abandoned coal mines will also decrease. The construction of suburbs in the underground mining fields will help to achieve this purpose by reduction the infiltration into the mining facilities and preventing the oxidation of the sulfide minerals in these mines.

References

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115

Appendices

116

Appendices

Appendex I: climate data

Table App. I.1: Daily climatic data of the period 1.4.2011-30.4.2012 (obtained from Rudolf Geiger Climate Station)

Air pressure Air temperature Air humidity Wind velocity Precipitation 2m above the surface Daily average Date Daily average Daily average Maximum Minimum Relative Absolute predominant direction Mean velocity Rainfall amount Value Measuring Value Measuring hPa C° C° time C° time % g/m3 Morning Afternoon m/s mm 01/04/2011 1019.1 13.7 16.3 17:00 11.5 22:30 82 9.7 0.0 0.0 2.0 . 02/04/2011 1011.6 17.8 24.2 14:50 9.8 04:40 57 8.3 S SSW 1.9 0.2 03/04/2011 1010.9 13.0 18.8 00:20 9.8 24:00 84 9.4 W SW 1.0 7.6 04/04/2011 1018.4 10.5 14.8 16:30 7.2 00:00 74 7.1 SW WSW 1.7 0.8 05/04/2011 1022.6 10.0 14.4 13:50 6.0 02:40 61 5.6 SW SW 2.8 . 06/04/2011 1023.7 15.5 22.4 16:20 10.2 00:10 70 9.1 SW WSW 2.3 . 07/04/2011 1022.0 15.4 20.5 13:20 9.5 00:00 67 8.7 WSW N 2.0 . 08/04/2011 1022.4 11.9 19.0 15:30 5.0 06:10 66 6.6 WNW N 1.3 . 09/04/2011 1022.6 11.4 18.3 16:30 6.7 05:20 59 5.7 NNE NNE 1.4 . 10/04/2011 1021.9 11.9 19.9 16:30 4.0 05:50 59 5.9 NE NE 1.4 . 11/04/2011 1016.3 14.9 23.8 15:30 5.7 05:30 57 6.7 SW W 1.4 4.4 12/04/2011 1021.1 8.9 14.1 00:40 5.2 00:00 62 3.1 W NW 1.8 3.1 13/04/2011 1019.0 8.5 14.5 13:50 2.6 03:40 63 5.1 WSW WNW 1.5 . 14/04/2011 1017.4 8.3 13.0 14:30 1.3 06:00 63 5.1 E NE 0.8 0.1 15/04/2011 1019.0 9.7 16.3 13:50 1.8 05:40 56 4.7 ENE ENE 1.3 . 16/04/2011 1020.5 11.0 17.0 13:50 3.5 06:10 50 4.8 ESE S 1.1 . 17/04/2011 1022.3 12.5 18.6 13:00 5.5 05:50 51 5.2 ENE ENE 1.3 . 18/04/2011 1017.3 12.7 21.1 15:10 4.0 04:10 53 5.5 E SE 1.2 . 19/04/2011 1013.9 15.4 24.1 15:20 6.4 05:40 50 6.2 ESE ENE 1.2 . 20/04/2011 1013.5 16.0 25.2 15:50 6.0 05:50 55 6.8 ENE ENE 0.9 . 21/04/2011 1012.3 17.3 26.2 16:20 7.6 03:20 54 7.2 ENE ENE 0.9 . 22/04/2011 1008.7 18.4 26.9 14:50 9.7 04:40 53 7.9 ENE ENE 1.5 . 23/04/2011 1009.7 19.0 27.1 13:50 11.4 04:00 52 8.1 NE ENE 1.6 . 24/04/2011 1014.7 17.3 25.0 14:20 8.8 05:30 55 7.7 ENE NE 1.7 . 25/04/2011 1017.9 15.8 23.3 14:20 7.0 05:40 54 6.8 ENE ENE 1.5 . 26/04/2011 1017.3 14.9 21.8 14:10 6.6 05:50 57 6.8 ENE NNE 1.8 . 27/04/2011 1016.2 10.9 15.0 17:20 8.9 04:20 88 8.8 NE ENE 1.0 3.8 28/04/2011 1011.8 12.9 19.2 13:40 9.3 00:30 85 9.5 ENE ENE 1.4 0.7 29/04/2011 1009.0 15.8 22.6 14:40 10.3 00:40 70 9.0 ENE ENE 2.4 2.1 30/04/2011 1008.0 14.9 21.0 15:00 9.1 05:30 52 6.6 ENE ENE 3.0 . Monthly 1016.7 13.5 20.1 7.0 62 6.9 1.6 22.8 mean

Air pressure Air temperature Air humidity Wind velocity Precipitation 2m above the surface Daily average Date Daily average Daily average Maximum Minimum Relative Absolute predominant direction Mean velocity Rainfall amount Value Measuring Value Measuring hPa C° C° time C° time % g/m3 Morning Afternoon m/s mm 01/05/2011 1009.7 12.4 18.5 14:00 6.4 05:40 45 4.8 ENE ENE 2.8 . 02/05/2011 1009.5 9.1 14.5 14:00 3.6 05:20 56 4.9 ENE ENE 2.8 . 03/05/2011 1014.5 7.9 14.0 16:00 2.2 17:10 55 4.4 NE NE 2.0 . 04/05/2011 1019.1 8.0 15.0 15:40 -0.1 04:50 64 5.0 ENE ENE 1.0 . 05/05/2011 1020.6 10.9 19.1 17:10 1.0 04:50 59 5.3 ENE SE 0.9 . 06/05/2011 1017.7 15.6 22.8 16:20 7.2 02:00 46 5.8 SE ENE 1.2 . 07/05/2011 1015.5 20.6 28.1 13:40 10.8 00:40 42 7.3 SE SSE 1.3 . 08/05/2011 1016.2 21.1 27.9 16:30 12.6 04:50 38 6.8 NE E 1.5 . 09/05/2011 1020.3 21.0 27.5 17:10 13.2 24:00 41 7.1 S ENE 1.3 . 10/05/2011 1021.4 18.9 26.3 15:20 11.0 03:20 58 8.9 ENE WSW 0.9 . 11/05/2011 1018.8 18.6 24.0 15:20 14.2 23:50 55 8.4 WSW SW 1.3 . 12/05/2011 1016.2 14.8 20.8 14:40 8.6 24:00 61 7.6 ENE WNW 1.1 0.2 13/05/2011 1017.8 14.2 20.6 15:30 7.9 00:40 60 7.0 SW ENE 1.4 . 14/05/2011 1014.1 13.4 18.1 16:00 8.4 01:50 60 6.8 WSW WNW 1.4 0.6 15/05/2011 1019.2 12.0 18.2 15:30 8.1 03:10 66 6.8 WSW WNW 1.5 1.1 16/05/2011 1019.2 12.2 14.4 10:10 10.1 00:50 84 9.1 SW WSW 2.4 2.5 17/05/2011 1017.6 13.7 18.4 15:10 9.1 23:20 78 9.1 SW WSW 1.7 0.1 18/05/2011 1013.9 15.2 21.9 17:00 8.5 04:10 69 8.6 SSW ENE 1.3 . 19/05/2011 1014.9 16.0 21.4 14:30 10.8 03:20 75 10.0 ENE ENE 1.0 . 20/05/2011 1016.1 17.5 23.6 13:00 11.3 03:00 66 9.5 NNE NE 1.1 . 21/05/2011 1017.2 18.0 24.9 16:40 12.6 05:30 61 9.1 NE E 1.0 . 22/05/2011 1015.8 17.2 24.3 12:10 11.2 23:40 62 9.0 S WSW 1.7 10.1 23/05/2011 1019.6 16.2 23.1 17:20 9.5 04:40 53 7.0 SW SW 2.0 . 24/05/2011 1023.2 15.3 19.5 16:30 7.5 00:00 49 6.4 WSW W 1.9 . 25/05/2011 1021.3 15.0 23.3 16:10 6.1 03:20 50 6.0 SSW ENE 1.2 . 26/05/2011 1008.0 17.1 25.5 11:00 8.9 03:30 47 6.8 S WSW 2.9 . 27/05/2011 1013.6 13.4 17.2 15:10 9.3 00:00 65 7.5 WSW W 2.4 0.7 28/05/2011 1012.7 14.2 19.7 13:50 6.8 01:20 61 7.1 SSW WSW 2.1 . 29/05/2011 1012.3 17.0 23.9 16:10 12.3 05:40 62 8.8 SW WSW 2.4 . 30/05/2011 1008.6 22.1 30.2 16:50 11.1 04:40 51 8.9 ENE S 1.4 0.2 31/05/2011 1014.6 14.2 20.2 00:10 10.8 23:10 86 10.5 WSW NNE 1.1 19.5 Monthly 1016.1 15.2 21.5 8.7 59 7.4 1.6 35.0 mean

117

Appendices

Air pressure Air temperature Air humidity Wind velocity Precipitation 2m above the surface Daily average Date Daily average Daily average Maximum Minimum Relative Absolute predominant direction Mean velocity Rainfall amount Value Measuring Value Measuring hPa C° C° time C° time % g/m3 Morning Afternoon m/s mm 01/06/2011 1025.9 14.3 19.6 15:00 8.8 05:00 61 6.0 NNE NNE 1.8 . 02/06/2011 1029.2 15.8 23.6 15:20 6.3 04:50 51 6.4 ENE NE 2.0 . 03/06/2011 1024.8 19.2 25.6 15:50 10.5 15:40 61 9.5 ENE ENE 2.5 . 04/06/2011 1014.5 22.6 29.2 14:20 15.7 04:20 56 10.8 ENE NE 2.3 1.2 05/06/2011 1005.3 19.7 27.5 12:50 16.2 03:50 80 13.5 NE E 1.1 5.4 06/06/2011 1001.7 20.1 27.0 14:20 15.6 04:10 75 12.6 SW WSW 1.4 4.6 07/06/2011 1003.1 17.8 22.9 16:50 13.9 07:20 73 10.8 WSW ENE 1.5 13.4 08/06/2011 1005.4 14.4 18.8 00:10 9.6 23:40 76 9.2 W WSW 1.6 1.2 09/06/2011 1012.7 14.9 20.8 14:20 9.6 00:30 58 7.1 WSW SW 1.7 . 10/06/2011 1012.8 13.9 19.0 18:20 8.3 02:50 78 9.2 ENE ENE 1.0 3.0 11/06/2011 1015.1 13.2 19.3 13:30 9.9 05:40 73 8.2 WSW S 1.4 3.4 12/06/2011 1015.9 14.5 21.1 15:30 7.8 04:20 65 7.7 SSW SW 1.1 . 13/06/2011 1012.9 17.7 21.3 17:40 13.3 00:40 63 9.6 SSW SW 1.9 9.8 14/06/2011 1015.5 18.2 22.3 13:40 13.3 23:30 76 11.6 SSW W 1.1 . 15/06/2011 1013.8 19.0 24.3 14:30 11.6 02:00 73 11.8 SSE SW 1.0 0.1 16/06/2011 1009.6 17.2 22.8 11:00 11.4 23:50 82 12.0 SSW SW 1.6 22.3 17/06/2011 1008.5 15.4 21.7 14:00 10.2 04:10 64 8.1 SW E 1.9 1.3 18/06/2011 1001.9 14.7 18.1 15:20 11.9 16:20 73 9.2 SW WSW 3.0 5.1 19/06/2011 1007.9 13.5 17.8 14:00 11.0 23:40 80 9.4 SW WSW 3.0 2.5 20/06/2011 1011.7 14.0 17.6 16:40 9.4 05:10 79 9.5 SW SSW 1.5 2.4 21/06/2011 1010.6 18.2 23.6 16:20 14.2 00:20 77 11.8 SW SW 1.9 1.3 22/06/2011 1009.4 17.4 21.7 10:30 14.3 22:30 78 11.6 SSW SW 2.0 7.4 23/06/2011 1012.8 15.8 20.8 15:10 12.8 23:40 67 8.8 WSW SW 2.6 . 24/06/2011 1018.5 14.0 19.1 12:10 10.9 23:40 72 8.7 SW SW 2.1 . 25/06/2011 1020.7 13.0 16.2 23:30 10.5 01:20 91 10.5 SSW SW 1.7 3.6 26/06/2011 1020.7 18.9 24.9 17:40 15.8 00:10 82 13.0 WSW ENE 1.2 . 27/06/2011 1015.6 23.7 31.2 16:50 13.4 04:30 60 12.0 ENE ENE 1.3 . 28/06/2011 1012.0 27.6 34.0 16:40 20.6 02:50 48 12.6 SSW ESE 1.5 0.9 29/06/2011 1017.1 19.5 25.8 10:10 14.5 24:00 80 13.5 E N 1.4 1.2 30/06/2011 1022.3 15.6 20.6 14:50 11.1 05:00 68 8.8 N SW 1.2 0.3 Monthly 1013.6 17.1 22.6 12.1 71 10.1 1.7 90.4 mean

Air pressure Air temperature Air humidity Wind velocity Precipitation 2m above the surface Daily average Date Daily average Daily average Maximum Minimum Relative Absolute predominant direction Mean velocity Rainfall amount Value Measuring Value Measuring hPa C° C° time C° time % g/m3 Morning Afternoon m/s mm 01/07/2011 1018.4 14.3 19.2 13:00 10.3 24:00 72 8.7 NNW NW 1.0 4.5 02/07/2011 1012.9 13.8 19.3 14:30 8.7 02:30 70 8.1 WNW N 1.1 0.2 03/07/2011 1012.2 14.5 17.3 16:00 12.3 16:50 70 8.7 NW NE 1.1 . 04/07/2011 1014.7 14.8 19.9 16:10 11.3 24:00 76 9.6 NE ENE 1.2 . 05/07/2011 1010.7 18.3 27.2 16:10 8.7 04:40 61 8.8 ENE ENE 1.1 . 06/07/2011 1007.0 19.5 25.5 14:20 13.4 23:30 59 9.8 WSW WSW 2.0 . 07/07/2011 1006.7 19.3 25.3 16:50 13.1 00:40 58 9.2 S SW 1.2 1.2 08/07/2011 1009.0 18.2 23.8 17:00 13.3 23:10 60 9.1 SW SW 1.9 2.1 09/07/2011 1012.7 19.1 26.1 12:40 13.3 01:20 65 10.4 SSW WSW 1.8 0.1 10/07/2011 1016.0 19.7 24.4 13:30 15.1 05:00 58 9.5 SW NE 0.9 . 11/07/2011 1017.0 19.4 25.6 16:10 11.6 03:50 59 9.4 ENE ENE 1.0 . 12/07/2011 1009.5 21.3 29.9 15:00 14.0 05:20 61 10.9 NE ENE 1.3 2.3 13/07/2011 1007.3 15.2 18.1 00:20 12.4 23:30 93 12.1 SW WSW 1.7 3.2 14/07/2011 1009.7 13.5 16.7 14:00 11.9 23:10 84 9.8 SW SW 4.3 5.9 15/07/2011 1014.6 15.9 22.9 17:10 11.7 00:40 73 9.5 WSW WSW 2.3 0.2 16/07/2011 1003.5 19.0 25.6 13:20 11.9 02:20 58 9.0 SSW SSW 2.2 11.4 17/07/2011 997.0 17.3 20.9 13:40 13.5 06:30 67 9.7 SW SW 2.8 . 18/07/2011 1000.0 16.9 21.2 14:00 14.3 23:20 61 8.7 SSW SSW 2.9 . 19/07/2011 1002.7 17.1 23.5 13:40 12.6 04:50 70 9.9 S ENE 1.4 8.2 20/07/2011 1006.2 15.9 19.5 11:30 13.7 05:10 90 12.2 SSW ENE 0.9 0.3 21/07/2011 1007.6 16.9 21.0 18:00 13.8 02:20 86 9.4 ENE NNE 0.9 12.1 22/07/2011 1009.2 15.3 20.6 15:10 11.1 05:10 67 8.5 NNE WNW 1.3 . 23/07/2011 1007.0 13.7 17.6 15:50 10.3 05:00 70 8.1 WSW WSW 2.1 17.5 24/07/2011 1005.6 11.6 13.6 13:30 9.9 02:50 91 9.5 SW WSW 2.8 24.6 25/07/2011 1007.0 15.2 21.8 15:50 9.7 05:00 76 9.5 SW SSE 1.2 2.6 26/07/2011 1011.2 16.1 20.7 14:30 13.4 04:50 82 11.2 SE ENE 0.9 . 27/07/2011 1015.2 17.1 24.6 13:50 14.2 05:00 83 11.9 ENE E 1.0 7.0 28/07/2011 1016.2 17.5 26.2 14:40 13.9 05:20 86 12.6 ENE ENE 0.9 43.2 29/07/2011 1017.1 16.3 19.5 16:30 14.3 05:20 78 10.7 NNE N 1.1 0.6 30/07/2011 1015.7 14.6 16.6 12:30 12.8 05:50 80 10.0 N NNE 0.9 0.9 31/07/2011 1014.9 14.8 18.8 17:00 11.8 23:00 68 8.5 NE ENE 0.7 . Monthly 1010.1 16.5 21.7 12.3 72 9.8 1.5 148.1 mean

118

Appendices

Air pressure Air temperature Air humidity Wind velocity Precipitation 2m above the surface Daily average Date Daily average Daily average Maximum Minimum Relative Absolute predominant direction Mean velocity Rainfall amount Value Measuring Value Measuring hPa C° C° time C° time % g/m3 Morning Afternoon m/s mm 01/08/2011 1014.2 17.3 26.0 17:20 7.9 05:10 67 9.5 ENE ENE 1.1 . 02/08/2011 1013.8 21.3 28.9 16:00 13.3 05:10 65 11.4 ENE E 1.0 0.6 03/08/2011 1011.9 20.4 25.9 09:50 16.0 16:30 79 13.8 E SW 1.3 0.1 04/08/2011 1011.3 21.4 28.1 16:30 16.0 05:10 71 12.8 SW SW 1.7 4.6 05/08/2011 1010.6 19.2 24.0 15:10 16.0 23:00 78 12.7 W W 1.2 . 06/08/2011 1001.9 20.0 25.4 15:00 16.5 00:20 84 14.3 E SSW 1.3 13.6 07/08/2011 1003.9 17.0 21.5 15:30 13.8 06:10 70 9.9 SW SSE 2.0 1.6 08/08/2011 1004.5 15.0 18.1 10:40 12.8 07:40 77 9.9 S SW 2.5 11.9 09/08/2011 1016.0 14.7 19.5 15:00 11.5 24:00 77 9.6 WSW W 2.0 1.7 10/08/2011 1018.3 16.0 20.9 16:10 9.7 05:20 62 8.1 SW SW 2.4 . 11/08/2011 1009.7 20.0 24.8 15:20 16.2 07:00 47 8.1 SW SW 3.0 1.3 12/08/2011 1008.1 18.0 22.6 14:50 15.6 00:30 85 13.0 SW WSW 1.9 8.8 13/08/2011 1007.4 18.2 23.2 13:50 15.9 01:40 86 13.3 SSW SW 1.1 5.6 14/08/2011 1005.0 17.8 20.5 17:00 14.4 23:50 89 13.6 SW WSW 1.6 5.0 15/08/2011 1013.7 17.2 23.0 15:20 12.3 04:20 73 10.5 SSW NNE 1.1 . 16/08/2011 1015.9 17.0 22.7 16:00 12.3 02:30 72 10.1 SW SW 1.0 . 17/08/2011 1013.9 20.5 26.0 14:20 15.8 00:10 63 11.1 SW NE 1.2 . 18/08/2011 1010.8 20.7 28.5 15:20 15.5 05:40 76 13.3 NE ENE 1.8 38.0 19/08/2011 1015.6 17.8 21.8 15:30 11.3 23:40 78 11.7 WSW W 1.4 0.2 20/08/2011 1018.0 17.9 26.4 16:40 9.6 04:40 69 9.9 ENE ENE 1.0 . 21/08/2011 1012.7 20.8 30.3 14:00 13.6 02:30 79 14.2 E SSW 1.2 6.3 22/08/2011 1015.9 19.0 22.5 11:40 15.8 05:30 85 13.7 SW E 0.8 12.4 23/08/2011 1011.1 21.3 27.8 16:40 16.7 04:00 82 15.2 NE SW 1.2 . 24/08/2011 1012.8 21.0 27.1 12:20 16.0 23:10 76 13.7 SSW WSW 1.2 . 25/08/2011 1011.0 20.2 26.7 13:40 13.2 05:40 77 13.1 S SE 1.0 . 26/08/2011 1004.1 20.7 30.1 11:10 15.3 23:40 80 14.0 E SW 1.7 22.3 27/08/2011 1010.5 14.9 19.0 15:40 12.7 22:40 88 11.1 SSW SW 1.7 4.5 28/08/2011 1014.3 14.6 18.0 12:40 12.0 03:20 74 9.1 SW SW 2.5 . 29/08/2011 1013.1 13.8 17.0 13:30 11.7 20:10 75 8.8 SW WSW 2.2 . 30/08/2011 1013.7 13.4 17.5 14:30 10.3 05:10 78 8.9 SW SW 1.4 . 31/08/2011 1013.0 13.8 20.2 13:00 7.9 05:50 77 8.9 SSW ENE 1.0 . Monthly 1011.5 18.1 23.7 13.5 75 11.5 1.5 138.5 mean

Air pressure Air temperature Air humidity Wind velocity Precipitation 2m above the surface Daily average Date Daily average Daily average Maximum Minimum Relative Absolute predominant direction Mean velocity Rainfall amount Value Measuring Value Measuring hPa C° C° time C° time % g/m3 Morning Afternoon m/s mm 01/09/2011 1013.3 14.2 21.1 14:40 8.7 02:10 72 8.5 ENE ENE 1.0 . 02/09/2011 1010.7 18.5 27.6 14:20 9.0 04:40 73 11.3 E SE 1.0 . 03/09/2011 1009.0 22.7 29.8 16:30 15.7 17:30 69 13.4 S S 1.1 0.5 04/09/2011 1007.2 21.2 26.4 11:50 17.6 23:40 84 15.5 S WSW 1.3 5.9 05/09/2011 1013.4 16.5 20.4 15:10 13.2 06:10 68 9.5 SW WSW 2.3 0.1 06/09/2011 1011.5 15.8 19.4 12:00 13.0 05:10 70 9.4 SSW SSW 3.2 16.5 07/09/2011 1008.6 15.0 18.5 12:10 13.1 06:30 75 9.5 WSW WSW 3.3 4.5 08/09/2011 1007.5 13.6 14.9 16:50 11.8 05:00 91 10.7 WSW WSW 2.7 5.1 09/09/2011 1009.7 15.3 19.8 12:00 14.0 00:10 93 12.1 SW SW 2.2 . 10/09/2011 1007.1 22.9 26.5 14:00 17.9 01:00 72 14.5 SSE SE 3.3 . 11/09/2011 1007.9 17.5 24.0 00:10 14.1 24:00 88 12.7 SW S 1.8 14.1 12/09/2011 1007.5 18.1 23.8 14:20 13.5 06:10 73 11.1 SSW SW 3.6 . 13/09/2011 1010.3 16.9 20.6 13:00 14.5 24:00 66 9.4 WSW WSW 2.9 . 14/09/2011 1015.5 14.3 18.3 13:10 10.9 20:20 69 8.4 WSW SW 2.6 . 15/09/2011 1018.8 14.0 19.0 13:10 9.3 23:50 78 9.2 SW E 1.3 . 16/09/2011 1013.0 14.8 21.2 14:10 7.5 06:10 73 8.9 ENE ESE 1.2 . 17/09/2011 1007.6 16.7 19.9 12:20 13.5 23:50 70 10.0 SW SW 2.0 3.1 18/09/2011 1003.0 13.1 16.4 14:10 11.2 20:10 79 9.0 SSW SW 1.6 1.1 19/09/2011 1012.6 13.3 18.3 16:20 9.7 23:50 79 8.9 S SW 1.3 . 20/09/2011 1020.0 14.1 17.3 12:50 9.5 01:50 81 9.8 SSW SSW 1.4 . 21/09/2011 1016.6 16.2 18.6 16:10 14.0 04:50 68 9.3 SW SW 1.5 . 22/09/2011 1017.0 15.2 18.8 14:40 11.8 24:00 73 9.5 WSW SW 1.9 . 23/09/2011 1016.8 13.4 19.7 12:40 9.3 22:10 81 9.3 S E 1.0 . 24/09/2011 1013.9 14.9 23.3 14:00 7.5 06:10 74 9.0 SE SSE 1.0 . 25/09/2011 1016.9 16.1 23.6 14:20 9.4 03:30 77 10.2 SE ENE 0.9 . 26/09/2011 1021.3 18.7 25.1 16:20 12.2 01:40 73 11.4 S SW 1.1 . 27/09/2011 1027.2 17.4 22.2 13:10 13.8 22:50 85 12.4 ENE ENE 0.8 . 28/09/2011 1026.9 17.7 26.8 14:10 11.5 04:20 79 11.6 E E 0.9 . 29/09/2011 1025.2 18.6 26.9 15:50 12.7 06:40 72 10.8 E E 0.9 . 30/09/2011 1023.7 18.8 27.6 13:50 11.3 06:50 65 9.8 NE SE 1.0 . Monthly 1014.0 16.5 21.9 12.0 76 10.5 1.7 50.9 mean

119

Appendices

Air pressure Air temperature Air humidity Wind velocity Precipitation 2m above the surface Daily average Date Daily average Daily average Maximum Minimum Relative Absolute predominant direction Mean velocity Rainfall amount Value Measuring Value Measuring hPa C° C° time C° time % g/m3 Morning Afternoon m/s mm 01/10/2011 1024.0 18.2 28.5 16:10 10.9 06:50 71 10.3 E E 0.6 . 02/10/2011 1022.5 17.6 26.4 14:10 10.6 06:10 76 11.0 ENE ENE 0.6 . 03/10/2011 1018.8 18.0 25.2 15:50 9.8 18:00 69 10.1 SW SW 1.4 . 04/10/2011 1017.7 17.5 19.8 00:30 15.6 19:40 74 11.0 SW SW 2.2 . 05/10/2011 1016.7 17.1 18.9 14:50 15.6 02:20 77 11.1 WSW SW 2.4 0.3 06/10/2011 1006.4 14.0 17.2 01:50 9.4 22:40 75 9.2 SW SW 3.0 13.2 07/10/2011 1009.5 9.9 14.1 13:50 7.1 05:30 85 7.9 WSW W 2.3 7.4 08/10/2011 1013.5 8.7 12.5 15:00 6.1 24:00 88 7.6 WSW WNW 1.3 4.6 09/10/2011 1016.3 8.8 13.5 14:40 3.2 05:40 86 7.5 SSW SSW 2.0 4.3 10/10/2011 1012.8 16.5 18.7 15:00 12.9 00:10 85 12.0 WSW WSW 3.2 1.7 11/10/2011 1013.8 14.6 15.5 01:30 11.8 23:40 93 11.6 WSW WSW 3.3 23.0 12/10/2011 1018.2 10.5 12.8 05:30 8.1 23:20 94 9.2 NE ENE 1.1 18.5 13/10/2011 1027.7 9.0 14.3 13:30 5.2 24:00 85 7.4 E ENE 0.9 . 14/10/2011 1030.9 7.3 14.0 14:10 2.1 06:10 78 5.9 E ENE 1.2 . 15/10/2011 1026.5 6.9 15.6 14:30 0.7 07:00 77 5.6 ENE ENE 1.0 . 16/10/2011 1022.3 8.1 16.2 15:30 0.9 07:10 73 5.8 ENE SSW 1.1 . 17/10/2011 1017.7 10.9 15.7 14:40 7.0 01:40 77 7.5 S S 1.6 . 18/10/2011 1008.3 9.8 14.5 08:50 7.5 13:10 85 7.9 SSW SW 2.6 4.0 19/10/2011 1013.7 8.5 12.4 12:10 5.3 17:50 81 6.8 SW SW 2.0 5.9 20/10/2011 1022.9 7.2 11.6 12:50 4.9 04:30 81 6.3 SW SW 1.6 0.2 21/10/2011 1025.3 6.4 11.5 14:20 2.0 07:20 74 5.3 SSW S 1.3 . 22/10/2011 1019.1 7.4 13.7 15:20 1.6 05:10 60 4.6 SSE SSE 1.6 . 23/10/2011 1014.3 9.5 15.5 13:20 5.7 07:20 57 5.2 S SE 1.8 . 24/10/2011 1006.1 10.3 15.2 13:50 4.7 02:30 59 5.5 E ESE 2.2 . 25/10/2011 1002.9 11.2 12.7 00:10 9.5 19:30 63 6.4 E E 1.6 0.5 26/10/2011 1011.3 10.7 15.0 14:50 5.2 23:50 72 7.0 SSW E 1.7 . 27/10/2011 1013.3 9.9 16.3 11:50 3.3 06:20 80 7.3 E S 1.6 . 28/10/2011 1021.1 13.3 19.6 15:10 10.0 06:00 77 8.7 S SE 1.3 . 29/10/2011 1020.7 14.5 19.6 12:10 10.3 05:00 74 9.0 SE SSW 1.2 . 30/10/2011 1019.6 14.4 19.0 13:30 11.8 19:30 85 10.4 SSE SSW 1.1 . 31/10/2011 1016.3 12.3 17.6 15:10 8.0 08:00 89 9.4 SSW SSE 0.8 . Monthly 1017.1 11.6 16.6 7.3 77 8.1 1.7 83.6 mean

Air pressure Air temperature Air humidity Wind velocity Precipitation 2m above the surface Daily average Date Daily average Daily average Maximum Minimum Relative Absolute predominant direction Mean velocity Rainfall amount Value Measuring Value Measuring hPa C° C° time C° time % g/m3 Morning Afternoon m/s mm 01/11/2011 1012.0 13.1 18.2 13:10 9.9 03:30 77 8.7 S S 1.7 . 02/11/2011 1009.4 13.3 16.4 13:10 11.5 07:30 79 9.1 SSE SE 1.4 . 03/11/2011 1001.9 16.1 18.6 12:10 13.5 04:50 59 8.1 SSW SSW 2.0 0.2 04/11/2011 1002.0 16.5 21.5 13:50 12.5 04:40 54 7.5 SSW SSE 1.5 . 05/11/2011 1004.9 13.5 20.3 14:40 8.3 23:40 74 8.5 NE ENE 0.8 . 06/11/2011 1013.6 10.1 16.3 13:20 7.1 07:20 86 8.1 ENE NNE 1.3 . 07/11/2011 1016.3 7.8 9.0 17:50 6.8 02:40 92 7.6 NE ENE 2.4 . 08/11/2011 1015.8 7.5 12.4 13:30 4.0 07:50 89 7.1 ENE ENE 1.3 . 09/11/2011 1018.3 8.5 17.7 14:10 3.4 05:40 84 7.0 NE ENE 0.8 . 10/11/2011 1019.9 4.7 8.3 15:20 1.9 07:50 94 6.3 ENE ENE 1.2 . 11/11/2011 1020.8 7.9 12.8 13:50 4.6 22:30 70 5.7 ENE SE 1.7 . 12/11/2011 1027.2 7.8 14.6 15:20 3.9 23:00 70 5.7 SSE SSE 1.4 . 13/11/2011 1029.4 2.3 7.3 14:20 -1.6 00:00 95 5.4 ENE ENE 0.9 . 14/11/2011 1023.7 3.7 13.7 14:30 -2.2 07:50 78 4.7 ENE ENE 0.9 . 15/11/2011 1019.9 2.4 8.3 14:50 -2.2 07:30 83 4.7 ENE NE 1.2 . 16/11/2011 1019.1 2.0 7.5 14:10 -2.5 07:40 80 4.4 ENE ENE 1.3 . 17/11/2011 1019.5 5.7 11.9 13:40 0.4 03:30 77 5.5 S S 1.4 . 18/11/2011 1020.4 9.2 11.1 13:30 6.2 23:50 83 7.4 S SSE 1.0 . 19/11/2011 1017.9 10.0 14.6 14:00 6.2 00:40 68 6.2 SE SSE 1.2 . 20/11/2011 1017.8 6.0 11.3 14:50 2.2 08:00 85 6.1 ENE ENE 0.7 . 21/11/2011 1015.2 6.1 13.5 14:10 2.4 04:00 84 6.1 E ENE 0.8 . 22/11/2011 1017.1 5.9 11.7 12:30 0.5 08:10 87 6.3 ENE NE 0.7 . 23/11/2011 1024.1 7.6 12.2 14:40 1.5 05:30 93 7.6 SSW SW 0.9 0.1 24/11/2011 1028.0 9.2 11.7 14:00 7.8 20:20 84 7.5 SW S 1.3 . 25/11/2011 1022.8 7.4 10.4 12:20 4.0 07:30 71 5.7 SSW WSW 2.5 0.3 26/11/2011 1024.1 8.2 11.1 14:30 5.3 06:50 80 6.7 SW SW 3.2 . 27/11/2011 1018.9 8.8 11.1 15:50 6.3 00:00 77 6.7 SW WSW 3.8 1.8 28/11/2011 1023.5 6.0 10.5 13:40 2.5 06:10 78 5.6 SW S 1.5 . 29/11/2011 1014.2 6.2 10.7 23:10 3.6 05:20 79 5.8 S SSW 2.4 0.4 30/11/2011 1022.8 8.0 11.2 14:20 3.7 22:40 76 6.3 SW S 1.8 . Monthly 1018.0 8.0 12.9 4.4 80 6.6 1.5 2.8 mean

120

Appendices

Air pressure Air temperature Air humidity Wind velocity Precipitation 2m above the surface Daily average Date Daily average Daily average Maximum Minimum Relative Absolute predominant direction Mean velocity Rainfall amount Value Measuring Value Measuring hPa C° C° time C° time % g/m3 Morning Afternoon m/s mm 01/12/2011 1009.7 9.6 12.6 17:50 5.3 00:10 82 7.5 SSW SSW 2.9 7.3 02/12/2011 1009.5 8.0 13.1 04:10 4.8 19:30 87 7.2 SSW SW 2.2 3.9 03/12/2011 1001.9 7.2 9.6 17:30 5.4 05:50 85 6.7 SSW WSW 3.6 10.7 04/12/2011 996.1 8.3 9.3 04:10 7.4 23:30 77 6.5 WSW SW 2.7 2.3 05/12/2011 1001.9 4.2 7.9 00:10 1.1 17:20 85 5.5 WSW WSW 3.1 4.0 06/12/2011 1003.8 3.9 5.8 13:00 1.7 14:50 86 5.4 WSW WSW 3.2 7.3 07/12/2011 1000.9 6.2 8.3 13:00 2.3 03:20 76 5.6 SW WSW 3.8 2.5 08/12/2011 1006.9 6.9 10.9 23:40 3.5 08:40 72 5.6 WSW SSW 4.0 7.1 09/12/2011 1004.2 6.4 11.6 01:30 2.8 23:10 68 5.2 WSW WSW 3.4 2.2 10/12/2011 1010.0 3.8 5.9 14:50 2.1 23:50 81 5.0 SW SW 2.4 . 11/12/2011 1006.9 3.0 6.0 23:50 0.5 05:50 75 4.4 SW SSW 1.7 0.3 12/12/2011 1004.4 7.0 9.1 14:10 5.1 22:50 81 6.3 SSW SW 2.6 13.0 13/12/2011 995.3 6.9 10.0 14:40 4.3 05:00 80 6.2 SSW SW 4.0 7.4 14/12/2011 996.6 6.0 8.8 10:20 3.5 15:10 82 6.0 SSW SW 3.4 12.2 15/12/2011 1000.1 5.9 6.9 12:10 4.9 03:40 73 5.3 SSW SW 3.8 8.5 16/12/2011 980.3 4.7 9.6 11:50 1.8 15:10 91 6.1 SSW W 2.8 13.0 17/12/2011 1000.9 3.6 5.9 14:00 1.7 19:40 91 5.6 W WSW 2.8 3.2 18/12/2011 1008.0 1.5 3.5 15:20 0.5 07:10 97 5.2 WSW WSW 2.5 0.5 19/12/2011 1013.6 1.7 3.0 13:50 0.7 03:40 91 4.9 WSW SSW 2.3 0.7 20/12/2011 1007.2 3.4 6.3 16:30 0.3 02:20 92 5.7 SSW WSW 2.4 5.1 21/12/2011 1015.1 4.5 5.5 21:00 3.3 07:40 94 6.2 SW WSW 1.5 2.5 22/12/2011 1018.7 7.7 10.0 16:00 4.7 02:10 96 7.8 SW W 1.6 4.8 23/12/2011 1015.3 8.9 9.9 14:50 7.1 23:10 92 8.1 WSW SW 2.4 8.4 24/12/2011 1022.0 5.6 8.0 02:20 4.1 19:10 84 6.0 W WSW 2.5 0.1 25/12/2011 1026.8 7.3 9.5 22:00 4.6 00:20 89 7.0 SW SW 3.0 0.4 26/12/2011 1031.3 9.2 10.0 13:40 8.3 01:20 95 8.5 SW SW 2.5 0.7 27/12/2011 1032.4 8.5 9.8 00:10 6.9 23:40 84 7.2 WSW SW 1.4 . 28/12/2011 1019.5 6.9 9.5 12:20 5.6 22:20 84 6.5 SSW SW 2.4 0.7 29/12/2011 1011.6 5.5 7.4 21:00 3.6 15:20 82 5.8 WSW WSW 3.9 13.6 30/12/2011 1010.7 4.2 6.4 15:10 2.2 03:30 88 5.6 W WSW 2.3 1.8 31/12/2011 1008.2 5.7 10.5 23:10 2.4 05:20 93 6.8 SSE SW 1.7 5.6 Monthly 1008.7 5.9 8.4 3.6 85 6.2 2.7 149.8 mean

Air pressure Air temperature Air humidity Wind velocity Precipitation 2m above the surface Daily average Date Daily average Daily average Maximum Minimum Relative Absolute predominant direction Mean velocity Rainfall amount Value Measuring Value Measuring hPa C° C° time C° time % g/m3 Morning Afternoon m/s mm 01/01/2012 1006.6 11.3 13.3 23:10 9.8 00:10 98 9.9 WSW SW 2.6 14.3 02/01/2012 1007.9 7.5 12.2 00:10 4.3 23:50 95 7.7 WSW WSW 2.5 3.6 03/01/2012 1004.9 6.8 11.1 18:30 4.1 12:20 84 6.5 SW WSW 3.8 5.2 04/01/2012 1008.3 5.7 7.6 00:10 4.3 08:20 82 5.8 WSW WSW 4.1 12.3 05/01/2012 992.7 5.8 8.1 07:50 1.8 23:50 89 6.4 WSW W 6.0 20.1 06/01/2012 1014.9 5.1 7.1 14:20 2.2 00:10 88 6.0 W WNW 3.9 5.2 07/01/2012 1013.1 5.5 7.8 10:30 3.7 01:30 94 6.6 SW W 3.7 12.4 08/01/2012 1018.5 5.5 6.8 13:00 4.2 05:00 94 6.6 W W 3.2 2.2 09/01/2012 1023.7 6.5 7.8 14:40 5.0 05:40 99 7.5 WSW WSW 2.2 1.4 10/01/2012 1029.4 7.2 8.1 13:30 6.0 09:10 90 7.1 W SW 1.8 . 11/01/2012 1028.9 8.0 9.3 13:50 7.4 04:00 92 7.6 WSW WSW 2.1 0.3 12/01/2012 1015.1 7.2 8.3 16:20 4.6 00:00 93 7.3 WSW W 3.8 4.0 13/01/2012 1023.6 4.1 5.2 13:40 3.0 03:20 84 5.4 W WNW 3.7 . 14/01/2012 1024.9 3.8 5.7 14:00 2.3 09:00 84 5.3 W NW 2.1 . 15/01/2012 1024.4 0.9 4.3 13:50 -2.3 22:10 95 4.9 SW NE 0.9 . 16/01/2012 1026.0 -1.6 3.5 14:40 -3.9 07:40 94 4.0 ENE NE 0.7 . 17/01/2012 1027.3 -1.5 4.5 14:00 -5.0 07:50 89 3.8 SW SW 0.7 . 18/01/2012 1023.8 1.5 4.7 13:40 -2.7 02:30 85 4.6 SSW WSW 2.0 9.3 19/01/2012 1012.8 5.9 8.5 11:30 4.1 00:10 98 7.1 WSW WSW 2.8 22.1 20/01/2012 1012.1 2.7 5.7 00:10 0.9 23:40 95 5.6 W WSW 3.0 12.1 21/01/2012 1003.8 5.3 9.4 14:20 0.9 00:20 95 6.6 SW W 3.7 9.1 22/01/2012 1006.0 5.8 8.3 17:30 3.9 12:40 84 6.0 W W 5.1 3.6 23/01/2012 1011.6 4.1 6.2 13:20 1.9 22:20 93 5.9 WSW WSW 2.6 3.6 24/01/2012 1017.4 2.3 4.9 13:30 -0.6 22:00 98 4.3 WSW WSW 1.3 . 25/01/2012 1018.5 1.6 5.9 13:40 -1.0 02:20 89 4.8 SSW E 0.9 . 26/01/2012 1014.4 2.9 5.1 14:10 1.7 00:10 82 4.8 SSE S 1.7 1.0 27/01/2012 1019.1 2.9 7.0 14:50 0.3 23:50 91 5.4 SSW SW 1.1 . 28/01/2012 1024.7 0.5 4.0 13:30 -1.4 07:30 94 4.7 S NE 1.4 . 29/01/2012 1026.4 -1.9 -0.4 00:10 -2.5 08:50 91 3.9 NE NE 2.0 . 30/01/2012 1023.4 -1.4 -0.2 12:40 -2.3 00:10 87 3.8 ENE ENE 1.4 . 31/01/2012 1023.8 -4.1 -1.5 15:10 -7.3 23:50 74 2.7 NE ENE 3.3 . Monthly 1017.0 3.7 6.4 1.5 90 5.8 2.6 141.8 mean

121

Appendices

Air pressure Air temperature Air humidity Wind velocity Precipitation 2m above the surface Daily average Date Daily average Daily average Maximum Minimum Relative Absolute predominant direction Mean velocity Rainfall amount Value Measuring Value Measuring hPa C° C° time C° time % g/m3 Morning Afternoon m/s mm 01/02/2012 1028.8 -6.8 -2.9 15:10 -8.9 06:50 62 1.8 S ENE 4.2 . 02/02/2012 1031.3 -8.7 -5.4 15:30 -10.8 08:30 59 1.5 ENE ENE 3.5 . 03/02/2012 1033.7 -9.2 -4.5 15:00 -13.4 19:40 76 1.9 ENE NE 0.8 . 04/02/2012 1035.5 -9.3 -5.5 15:10 -11.7 07:50 88 2.2 NNE ENE 1.0 . 05/02/2012 1030.4 -7.9 -3.2 15:10 -11.4 00:10 62 1.7 S ESE 1.0 . 06/02/2012 1032.3 -8.0 -3.4 14:50 -12.2 08:00 59 1.6 S ENE 1.1 . 07/02/2012 1035.0 -10.5 -6.5 23:20 -14.5 07:10 75 1.7 NE ENE 2.3 . 08/02/2012 1036.0 -5.3 -2.5 15:40 -7.6 00:00 71 2.4 ENE ENE 3.5 . 09/02/2012 1034.2 -5.3 -1.1 15:50 -9.7 05:00 84 2.8 NE NE 1.5 . 10/02/2012 1036.2 -5.6 -2.7 15:30 -9.0 24:00 74 2.4 NE ENE 2.5 . 11/02/2012 1033.2 -8.0 -3.6 15:00 -12.2 08:10 76 2.1 ENE ENE 2.1 . 12/02/2012 1029.3 -6.0 -2.9 15:10 -11.2 06:00 83 2.6 SW WSW 1.1 0.1 13/02/2012 1018.2 -0.8 1.5 16:50 -3.2 01:00 99 4.6 SW WSW 1.7 1.3 14/02/2012 1012.9 2.1 4.2 14:30 0.3 07:20 96 5.4 SW W 2.0 4.9 15/02/2012 1010.5 3.8 4.8 13:20 1.8 22:20 89 5.6 WNW WNW 4.2 0.2 16/02/2012 1020.5 3.1 5.3 15:50 0.3 07:40 99 6.0 W WSW 1.9 2.5 17/02/2012 1019.1 4.6 5.4 23:40 4.0 05:40 100 6.6 WSW WSW 2.0 1.3 18/02/2012 1010.2 6.4 8.0 14:00 5.1 03:10 97 7.2 SW SW 2.5 4.3 19/02/2012 1017.0 2.7 6.6 00:10 -0.6 24:00 90 5.3 W W 3.2 0.1 20/02/2012 1030.9 0.6 3.9 14:10 -1.6 02:50 90 4.5 SW SW 1.5 . 21/02/2012 1027.0 3.9 8.1 15:20 1.0 01:40 76 4.8 SW SW 2.3 . 22/02/2012 1025.8 5.8 9.3 14:10 2.5 01:50 74 5.2 SW WSW 2.4 1.8 23/02/2012 1019.6 6.8 9.0 24:00 4.2 00:30 99 7.6 WSW WSW 2.6 0.7 24/02/2012 1021.9 8.7 9.1 21:20 6.7 24:00 100 8.6 WSW W 3.0 2.2 25/02/2012 1016.0 5.6 7.7 13:00 2.7 03:10 90 6.4 SW W 2.2 0.8 26/02/2012 1023.1 4.8 7.1 15:40 2.3 23:40 96 6.4 W W 2.0 . 27/02/2012 1021.9 5.5 9.0 15:20 1.4 02:40 91 6.4 SW WSW 1.8 0.4 28/02/2012 1020.8 7.7 8.8 20:00 6.5 00:10 100 8.1 WSW WSW 2.0 1.9 29/02/2012 1022.5 9.5 10.5 14:20 8.4 06:10 100 9.1 WSW SW 1.0 0.1 Monthly 1025.3 -0.3 2.6 -3.1 85 4.6 2.2 22.6 mean

Air pressure Air temperature Air humidity Wind velocity Precipitation 2m above the surface Daily average Date Daily average Daily average Maximum Minimum Relative Absolute predominant direction Mean velocity Rainfall amount Value Measuring Value Measuring hPa C° C° time C° time % g/m3 Morning Afternoon m/s mm 01/03/2012 1014.1 16.0 19.4 14:20 11.3 06:50 75 10.3 ENE W 2.0 . 02/03/2012 1011.3 15.7 22.5 15:40 12.3 05:10 88 11.7 WNW WSW 1.4 1.0 03/03/2012 1008.9 13.6 16.3 12:10 10.8 17:30 82 9.6 SW SW 1.3 0.1 04/03/2012 1002.2 14.8 20.1 14:40 10.2 24:00 69 8.5 SW W 2.2 7.3 05/03/2012 1004.8 7.9 10.2 00:10 6.6 23:50 96 7.9 N NE 1.9 7.4 06/03/2012 1009.5 6.8 8.7 15:00 5.7 05:50 94 7.2 ENE N 1.9 2.7 07/03/2012 1015.8 8.8 14.8 17:00 5.3 05:40 83 7.1 N E 1.0 . 08/03/2012 1009.2 15.1 21.1 14:10 5.9 00:10 66 8.0 SSW SW 1.5 . 09/03/2012 1011.3 16.4 20.7 15:40 13.2 04:10 82 11.5 SW WSW 1.5 0.5 10/03/2012 1013.1 20.0 25.4 15:50 13.3 00:10 77 13.1 SW SW 1.5 0.2 11/03/2012 1018.7 17.3 22.2 00:10 10.2 24:00 78 11.7 W W 2.6 2.8 12/03/2012 1030.6 9.2 12.6 16:20 5.0 24:00 72 6.4 WNW NW 2.5 0.1 13/03/2012 1027.1 7.7 14.2 16:50 0.8 05:00 71 5.5 SW SSW 1.0 . 14/03/2012 1013.6 12.0 19.0 17:20 4.0 02:10 61 6.2 SW W 1.8 1.2 15/03/2012 1008.7 8.4 12.4 00:10 6.4 22:20 85 7.2 W W 2.0 7.9 16/03/2012 1019.9 7.8 11.6 17:20 4.4 24:00 77 6.2 W WNW 3.4 2.4 17/03/2012 1016.4 9.6 16.9 17:00 0.7 04:50 65 5.6 SSW E 1.4 . 18/03/2012 1007.0 14.4 19.4 13:20 10.9 00:10 60 7.5 E SW 1.7 . 19/03/2012 1008.6 16.7 22.5 15:40 12.3 04:30 73 10.1 SW ENE 1.1 . 20/03/2012 1004.1 18.2 24.6 17:00 11.4 05:00 75 11.4 E ENE 1.3 . 21/03/2012 998.8 18.7 23.9 16:10 11.8 04:50 78 12.2 ENE NE 1.3 0.1 22/03/2012 1005.9 21.6 28.7 17:40 14.0 05:00 71 12.8 ENE E 1.0 . 23/03/2012 1018.0 19.3 28.4 13:30 15.4 24:00 88 14.4 WSW SW 1.0 5.8 24/03/2012 1022.2 20.6 27.1 15:00 13.8 03:50 71 12.3 ENE ENE 2.4 . 25/03/2012 1022.5 18.3 23.6 15:40 12.5 05:00 49 7.4 ENE ENE 3.1 . 26/03/2012 1019.3 18.0 24.2 16:50 8.6 04:40 56 8.3 ENE ENE 2.1 . 27/03/2012 1016.6 17.8 25.1 18:30 10.5 05:20 66 9.5 NE ENE 1.0 . 28/03/2012 1012.2 19.5 25.4 17:20 11.9 04:10 66 10.6 SW WNW 1.9 . 29/03/2012 1012.7 16.9 22.5 15:30 11.5 02:20 76 10.9 W WNW 1.9 . 30/03/2012 1015.4 16.3 21.6 16:10 9.3 05:10 67 9.1 NE NW 1.4 . 31/03/2012 1012.9 15.8 21.3 09:10 11.9 02:50 85 11.3 WSW W 2.1 4.5 Monthly 1013.3 14.8 20.2 9.4 74 9.4 1.7 44.0 mean

122

Appendices

Air pressure Air temperature Air humidity Wind velocity Precipitation 2m above the surface Daily average Date Daily average Daily average Maximum Minimum Relative Absolute predominant direction Mean velocity Rainfall amount Value Measuring Value Measuring hPa C° C° time C° time % g/m3 Morning Afternoon m/s mm 01/04/2012 1014.9 4.0 8.9 16:50 -2.9 06:30 73 4.5 N W 2.2 . 02/04/2012 1008.0 6.4 10.3 13:50 2.9 01:20 80 5.9 WSW SSW 1.3 . 03/04/2012 1001.0 9.3 15.5 14:20 2.5 13:30 74 6.4 E NE 1.2 1.5 04/04/2012 1006.9 8.1 10.2 15:30 5.7 24:00 93 7.7 ENE ENE 1.6 2.0 05/04/2012 1014.5 5.7 7.0 15:30 4.5 04:10 88 6.2 ENE ENE 2.6 . 06/04/2012 1008.9 6.4 10.2 16:10 4.0 05:50 71 5.2 N W 1.9 5.1 07/04/2012 1006.4 4.4 7.2 13:30 1.9 09:40 72 4.7 NNW N 2.2 1.2 08/04/2012 1011.5 4.6 9.1 16:20 -0.9 06:20 55 3.6 NNE WSW 1.2 3.4 09/04/2012 999.8 7.4 10.1 13:40 4.7 03:50 91 7.3 SW SW 2.0 5.8 10/04/2012 992.9 10.3 13.7 18:00 7.4 23:10 84 8.0 SW SW 1.9 4.1 11/04/2012 997.5 9.0 14.0 16:10 6.3 06:20 77 6.6 WSW WSW 1.8 0.6 12/04/2012 1000.5 7.7 11.1 16:20 4.5 22:00 84 6.7 S SW 1.5 2.2 13/04/2012 1003.1 7.5 12.1 16:00 3.8 05:40 81 6.3 SW W 1.4 . 14/04/2012 1003.2 6.7 12.0 14:10 1.7 03:50 87 6.5 E N 1.3 4.5 15/04/2012 1010.5 6.3 8.2 14:40 4.1 23:50 82 6.1 N N 3.0 . 16/04/2012 1018.1 4.9 8.9 15:30 0.5 24:00 69 4.5 N NNW 2.2 . 17/04/2012 1005.2 5.6 12.0 15:10 -2.3 03:40 65 4.3 SW WSW 1.9 0.2 18/04/2012 992.2 8.4 13.2 13:40 3.7 04:30 75 6.3 SW NNW 1.7 2.9 19/04/2012 989.4 9.9 13.7 16:40 6.1 23:20 69 6.4 WSW SW 1.4 0.5 20/04/2012 994.6 9.0 14.5 16:30 4.2 05:20 76 6.5 SW WSW 1.5 6.9 21/04/2012 997.5 7.5 11.3 13:40 5.3 14:10 85 6.8 SW WSW 1.5 6.4 22/04/2012 1003.0 7.4 11.8 17:00 4.6 23:20 86 6.7 SW WSW 1.9 3.8 23/04/2012 998.7 9.0 14.2 14:10 4.0 05:20 72 6.1 SW E 1.8 . 24/04/2012 994.7 8.8 12.2 12:50 6.0 22:20 83 7.2 WSW WSW 1.3 4.3 25/04/2012 998.4 10.1 13.8 12:30 6.5 05:10 81 7.5 WSW WSW 1.8 6.7 26/04/2012 1004.2 11.6 14.4 13:40 9.6 06:10 74 7.6 SW SW 2.3 0.6 27/04/2012 1013.3 12.4 15.6 10:20 9.3 01:10 72 7.7 SW W 1.7 6.2 28/04/2012 1008.9 18.1 26.2 16:50 10.2 01:00 71 10.1 ENE ENE 1.7 . 29/04/2012 1005.6 15.7 21.7 16:20 12.0 05:40 79 10.4 ENE W 2.0 . 30/04/2012 1013.2 16.8 22.5 17:10 9.8 05:00 66 9.0 SW ENE 2.2 2.0 Monthly 1003.9 8.6 12.9 4.7 77 6.6 1.8 70.9 mean

123

Appendices

Fig App. I.1: Daily minimal, maximal and average temperature of the period 1991-2012(obtained from Rudolf Geiger Climate Station).

124

Appendices

Fig App. I.2: Daily precipitation and average relative humidity of the period 1991-2012 (obtained from Rudolf Geiger Climate Station).

125

Appendices

Table App. I.2: Daily global radiations of the period 15.4.2011-15.4.2012(obtained from Rudolf Geiger Climate Station).

Date Gb Date Gb Date Gb Date Gb Date Gb Date Gb Jole/cm2 Jole/cm2 Jole/cm2 Jole/cm2 Jole/cm2 Jole/cm2 16/04/11 1564.89 01/05/11 2577.07 01/06/11 2705.36 01/07/11 1940.18 01/09/11 1661.10 01/08/11 2396.24 17/04/11 1895.11 02/05/11 2538.77 02/06/11 3050.18 02/07/11 1459.00 02/09/11 1788.87 02/08/11 1121.75 18/04/11 2204.55 03/05/11 2536.52 03/06/11 2805.50 03/07/11 734.50 03/09/11 1882.98 03/08/11 2296.09 19/04/11 2205.69 04/05/11 1723.54 04/06/11 2617.00 04/07/11 1368.75 04/09/11 1024.78 04/08/11 1558.08 20/04/11 2015.90 05/05/11 2439.57 05/06/11 1335.28 05/07/11 2848.33 05/09/11 1455.33 05/08/11 1020.08 21/04/11 1929.54 06/05/11 2141.51 06/06/11 2262.12 06/07/11 2069.54 06/09/11 1008.86 06/08/11 1423.00 22/04/11 2047.12 07/05/11 2333.27 07/06/11 1748.57 07/07/11 1986.73 07/09/11 922.60 07/08/11 1268.78 23/04/11 2173.76 08/05/11 2362.90 08/06/11 1297.36 08/07/11 1915.12 08/09/11 292.84 08/08/11 1268.78 24/04/11 2173.30 09/05/11 2362.90 09/06/11 2427.73 09/07/11 1917.22 09/09/11 621.94 09/08/11 0.00 25/04/11 2352.06 10/05/11 2079.80 10/06/11 1113.47 10/07/11 1800.84 10/09/11 1570.07 10/08/11 1779.30 26/04/11 2068.06 11/05/11 2445.94 11/06/11 2233.28 11/07/11 2066.88 11/09/11 473.26 11/08/11 1948.55 27/04/11 405.43 12/05/11 1448.40 12/06/11 2595.55 12/07/11 1727.91 12/09/11 1212.77 12/08/11 1167.38 28/04/11 983.76 13/05/11 2267.42 13/06/11 1674.25 13/07/11 365.04 13/09/11 1267.22 13/08/11 976.10 29/04/11 1859.86 14/05/11 1716.78 14/06/11 2051.65 14/07/11 730.35 14/09/11 1348.24 14/08/11 701.45 30/04/11 2355.21 15/05/11 1631.47 15/06/11 1449.99 15/07/11 1672.59 15/09/11 1108.53 15/08/11 1771.42 01/04/12 1287.05 16/05/11 750.07 16/06/11 1177.34 16/07/11 1790.86 16/09/11 1256.77 16/08/11 1307.66 02/04/12 855.75 17/05/11 921.25 17/06/11 2092.67 17/07/11 1719.04 17/09/11 1226.34 17/08/11 1980.04 03/04/12 1290.50 18/05/11 1920.29 18/06/11 1706.35 18/07/11 1767.74 18/09/11 982.02 18/08/11 1847.00 04/04/12 321.83 19/05/11 1371.11 19/06/11 940.45 19/07/11 1761.99 19/09/11 1182.47 19/08/11 1203.49 05/04/12 287.86 20/05/11 1972.96 20/06/11 1619.81 20/07/11 605.09 20/09/11 520.63 20/08/11 2255.99 06/04/12 1242.95 21/05/11 2461.49 21/06/11 1732.00 21/07/11 876.21 21/09/11 644.44 21/08/11 1421.95 07/04/12 916.30 22/05/11 1648.24 22/06/11 1156.60 22/07/11 1469.72 22/09/11 960.17 22/08/11 861.13 08/04/12 1608.86 23/05/11 2775.20 23/06/11 2005.65 23/07/11 1333.00 23/09/11 898.16 23/08/11 1564.47 09/04/12 605.39 24/05/11 2068.10 24/06/11 1749.28 24/07/11 480.99 24/09/11 1409.50 24/08/11 1484.72 10/04/12 474.96 25/05/11 2898.29 25/06/11 634.12 25/07/11 2286.19 25/09/11 1411.43 25/08/11 1660.99 11/04/12 1662.61 26/05/11 2377.18 26/06/11 1525.09 26/07/11 1381.00 26/09/11 1114.95 26/08/11 1347.76 12/04/12 1201.00 27/05/11 1126.71 27/06/11 2935.41 27/07/11 1559.31 27/09/11 843.04 27/08/11 1041.51 13/04/12 1833.98 28/05/11 2115.28 28/06/11 2734.60 28/07/11 1511.24 28/09/11 1402.99 28/08/11 1027.66 14/04/12 1087.31 29/05/11 2187.62 29/06/11 960.21 29/07/11 970.99 29/09/11 1385.18 29/08/11 827.11 15/04/12 433.84 30/05/11 2742.39 30/06/11 1560.86 30/07/11 638.27 30/09/11 1430.96 30/08/11 966.34 31/05/11 326.41 31/07/11 2624.42 31/08/11 1490.03

Date Gb Date Gb Date Gb Date Gb Date Gb Date Gb Jole/cm2 Jole/cm2 Jole/cm2 Jole/cm2 Jole/cm2 Jole/cm2 01/10/11 1362.34 01/11/11 743.15 01/12/11 51.59 01/01/12 71.06 01/02/12 684.72 01/03/12 271.34 02/10/11 1275.27 02/11/11 455.48 02/12/11 156.31 02/01/12 161.34 02/02/12 704.55 02/03/12 612.23 03/10/11 1247.09 03/11/11 313.94 03/12/11 42.23 03/01/12 82.21 03/02/12 518.98 03/03/12 314.65 04/10/11 400.60 04/11/11 674.68 04/12/11 101.54 04/01/12 155.19 04/02/12 678.80 04/03/12 697.93 05/10/11 436.10 05/11/11 459.98 05/12/11 172.55 05/01/12 147.95 05/02/12 674.84 05/03/12 597.64 06/10/11 276.80 06/11/11 635.21 06/12/11 135.70 06/01/12 175.71 06/02/12 751.79 06/03/12 986.98 07/10/11 657.54 07/11/11 87.07 07/12/11 186.62 07/01/12 85.44 07/02/12 514.88 07/03/12 453.49 08/10/11 644.48 08/11/11 592.66 08/12/11 169.75 08/01/12 158.08 08/02/12 594.92 08/03/12 626.90 09/10/11 949.52 09/11/11 636.89 09/12/11 294.66 09/01/12 69.55 09/02/12 192.35 09/03/12 1089.78 10/10/11 293.56 10/11/11 486.82 10/12/11 200.32 10/01/12 245.61 10/02/12 811.78 10/03/12 191.77 11/10/11 158.17 11/11/11 543.91 11/12/11 223.67 11/01/12 175.06 11/02/12 815.32 11/03/12 448.07 12/10/11 202.94 12/11/11 634.34 12/12/11 147.09 12/01/12 123.47 12/02/12 324.21 12/03/12 211.18 13/10/11 885.93 13/11/11 590.26 13/12/11 78.53 13/01/12 273.71 13/02/12 206.10 13/03/12 211.85 14/10/11 1136.60 14/11/11 635.95 14/12/11 90.26 14/01/12 279.90 14/02/12 226.92 14/03/12 630.34 15/10/11 1149.45 15/11/11 625.03 15/12/11 89.85 15/01/12 450.65 15/02/12 243.79 15/03/12 1492.55 16/10/11 1132.87 16/11/11 572.48 16/12/11 52.91 16/01/12 494.38 16/02/12 180.41 16/03/12 1455.72 17/10/11 836.45 17/11/11 515.40 17/12/11 199.30 17/01/12 440.63 17/02/12 143.17 17/03/12 650.96 18/10/11 209.56 18/11/11 163.36 18/12/11 220.50 18/01/12 355.57 18/02/12 156.34 18/03/12 407.75 19/10/11 651.01 19/11/11 470.32 19/12/11 106.55 19/01/12 46.49 19/02/12 647.25 19/03/12 1442.99 20/10/11 795.21 20/11/11 340.97 20/12/11 96.07 20/01/12 132.10 20/02/12 748.85 20/03/12 1489.25 21/10/11 978.32 21/11/11 476.55 21/12/11 53.20 21/01/12 88.98 21/02/12 1050.49 21/03/12 1520.42 22/10/11 1021.65 22/11/11 369.97 22/12/11 35.60 22/01/12 66.23 22/02/12 1039.46 22/03/12 1611.61 23/10/11 986.84 23/11/11 218.62 23/12/11 54.88 23/01/12 177.95 23/02/12 652.44 23/03/12 1638.10 24/10/11 966.39 24/11/11 366.58 24/12/11 154.11 24/01/12 357.90 24/02/12 202.49 24/03/12 1571.21 25/10/11 226.38 25/11/11 265.03 25/12/11 55.56 25/01/12 525.56 25/02/12 335.43 25/03/12 1791.89 26/10/11 632.08 26/11/11 257.51 26/12/11 81.40 26/01/12 267.09 26/02/12 125.34 26/03/12 1786.98 27/10/11 681.32 27/11/11 77.46 27/12/11 57.35 27/01/12 407.30 27/02/12 171.52 27/03/12 1587.26 28/10/11 748.64 28/11/11 475.12 28/12/11 298.33 28/01/12 524.05 28/02/12 355.27 28/03/12 1642.91 29/10/11 457.11 29/11/11 340.44 29/12/11 138.46 29/01/12 102.46 29/03/12 524.91 30/10/11 606.35 30/11/11 401.41 30/12/11 67.67 30/01/12 137.96 30/03/12 388.76 31/10/11 599.92 31/12/11 57.35 31/01/12 627.75 31/03/12 571.34 126

Appendices

Appendix II: Stream flow data

Table App. II.1: Daily water head record of the Lottenbach of the period 15.4.2011-15.4.2012 (obtained from Rudolf Geiger Climate Station).

127

Appendices

Table App. II.2: High resolution record of water head and electrical conductivity (at 15 min intervals) of the Lottenbach of the period 16.5.2011-19.5.2011.

128

Appendices

Table App. II 3: High resolution record of water head and temperature (at 10 min intervals) of the Lottenbach of the period 20.8.2011-6.9.2011.

Date T H Date T H Date T H Date T H Date T H C° cm C° cm C° cm C° cm C° cm 20/08/2011 00:00 14.95 13.70 20/08/2011 16:30 14.64 14.70 21/08/2011 09:00 14.51 14.50 22/08/2011 01:30 15.03 14.00 22/08/2011 18:00 15.03 13.70 20/08/2011 00:10 14.92 14.07 20/08/2011 16:40 14.63 14.70 21/08/2011 09:10 14.51 14.17 22/08/2011 01:40 15.03 14.20 22/08/2011 18:10 15.02 13.67 20/08/2011 00:20 14.92 14.23 20/08/2011 16:50 14.67 14.80 21/08/2011 09:20 14.52 14.63 22/08/2011 01:50 15.05 13.70 22/08/2011 18:20 15.03 13.43 20/08/2011 00:30 14.92 14.00 20/08/2011 17:00 14.67 14.50 21/08/2011 09:30 14.53 14.50 22/08/2011 02:00 15.05 13.70 22/08/2011 18:30 15.03 13.60 20/08/2011 00:40 14.91 14.40 20/08/2011 17:10 14.69 14.37 21/08/2011 09:40 14.53 14.43 22/08/2011 02:10 15.06 14.03 22/08/2011 18:40 14.99 13.33 20/08/2011 00:50 14.91 14.20 20/08/2011 17:20 14.69 14.33 21/08/2011 09:50 14.53 14.47 22/08/2011 02:20 15.09 14.07 22/08/2011 18:50 15.03 13.77 20/08/2011 01:00 14.90 14.30 20/08/2011 17:30 14.70 14.00 21/08/2011 10:00 14.52 14.50 22/08/2011 02:30 15.07 13.90 22/08/2011 19:00 15.03 13.90 20/08/2011 01:10 14.89 14.00 20/08/2011 17:40 14.72 14.30 21/08/2011 10:10 14.53 14.50 22/08/2011 02:40 15.09 14.00 22/08/2011 19:10 15.03 13.83 20/08/2011 01:20 14.88 14.40 20/08/2011 17:50 14.71 14.40 21/08/2011 10:20 14.52 14.30 22/08/2011 02:50 15.09 13.90 22/08/2011 19:20 15.02 13.77 20/08/2011 01:30 14.91 14.60 20/08/2011 18:00 14.73 14.50 21/08/2011 10:30 14.51 14.50 22/08/2011 03:00 15.09 13.70 22/08/2011 19:30 15.05 13.30 20/08/2011 01:40 14.88 14.30 20/08/2011 18:10 14.73 14.27 21/08/2011 10:40 14.51 14.90 22/08/2011 03:10 15.09 13.77 22/08/2011 19:40 15.02 13.67 20/08/2011 01:50 14.87 14.40 20/08/2011 18:20 14.74 14.03 21/08/2011 10:50 14.52 14.70 22/08/2011 03:20 15.11 13.83 22/08/2011 19:50 15.05 13.43 20/08/2011 02:00 14.87 14.00 20/08/2011 18:30 14.73 14.00 21/08/2011 11:00 14.51 14.40 22/08/2011 03:30 15.10 13.80 22/08/2011 20:00 15.03 13.40 20/08/2011 02:10 14.85 14.50 20/08/2011 18:40 14.75 13.97 21/08/2011 11:10 14.52 14.10 22/08/2011 03:40 15.12 13.83 22/08/2011 20:10 15.05 13.30 20/08/2011 02:20 14.85 14.80 20/08/2011 18:50 14.75 14.23 21/08/2011 11:20 14.50 14.10 22/08/2011 03:50 15.12 13.87 22/08/2011 20:20 15.03 13.10 20/08/2011 02:30 14.85 14.50 20/08/2011 19:00 14.74 13.90 21/08/2011 11:30 14.50 14.20 22/08/2011 04:00 15.12 14.00 22/08/2011 20:30 15.05 13.30 20/08/2011 02:40 14.83 14.80 20/08/2011 19:10 14.77 13.93 21/08/2011 11:40 14.50 14.23 22/08/2011 04:10 15.11 14.17 22/08/2011 20:40 15.02 13.43 20/08/2011 02:50 14.82 14.00 20/08/2011 19:20 14.77 13.87 21/08/2011 11:50 14.51 14.07 22/08/2011 04:20 15.09 13.93 22/08/2011 20:50 15.05 13.07 20/08/2011 03:00 14.81 14.60 20/08/2011 19:30 14.78 13.90 21/08/2011 12:00 14.52 14.50 22/08/2011 04:30 15.12 13.90 22/08/2011 21:00 15.03 13.00 20/08/2011 03:10 14.77 14.70 20/08/2011 19:40 14.77 14.10 21/08/2011 12:10 14.52 14.50 22/08/2011 04:40 15.09 13.80 22/08/2011 21:10 15.03 13.77 20/08/2011 03:20 14.77 14.60 20/08/2011 19:50 14.79 14.00 21/08/2011 12:20 14.52 14.10 22/08/2011 04:50 15.12 13.60 22/08/2011 21:20 15.01 13.83 20/08/2011 03:30 14.77 14.50 20/08/2011 20:00 14.78 14.60 21/08/2011 12:30 14.51 14.10 22/08/2011 05:00 15.12 13.80 22/08/2011 21:30 15.03 14.00 20/08/2011 03:40 14.74 14.57 20/08/2011 20:10 14.75 14.57 21/08/2011 12:40 14.53 14.17 22/08/2011 05:10 15.13 13.73 22/08/2011 21:40 15.05 13.60 20/08/2011 03:50 14.75 14.53 20/08/2011 20:20 14.80 14.43 21/08/2011 12:50 14.51 13.93 22/08/2011 05:20 15.13 13.47 22/08/2011 21:50 14.85 13.80 20/08/2011 04:00 14.73 14.60 20/08/2011 20:30 14.79 14.50 21/08/2011 13:00 14.52 13.60 22/08/2011 05:30 15.11 13.40 22/08/2011 22:00 15.03 13.80 20/08/2011 04:10 14.71 14.80 20/08/2011 20:40 14.81 14.27 21/08/2011 13:10 14.51 13.60 22/08/2011 05:40 15.12 13.30 22/08/2011 22:10 15.03 13.67 20/08/2011 04:20 14.72 14.50 20/08/2011 20:50 14.81 14.33 21/08/2011 13:20 14.51 13.80 22/08/2011 05:50 15.12 13.40 22/08/2011 22:20 15.03 13.53 20/08/2011 04:30 14.70 14.60 20/08/2011 21:00 14.81 14.30 21/08/2011 13:30 14.51 13.70 22/08/2011 06:00 15.11 13.40 22/08/2011 22:30 15.02 13.60 20/08/2011 04:40 14.69 14.73 20/08/2011 21:10 14.81 14.23 21/08/2011 13:40 14.53 13.73 22/08/2011 06:10 15.12 13.40 22/08/2011 22:40 15.02 13.53 20/08/2011 04:50 14.69 14.77 20/08/2011 21:20 14.82 14.47 21/08/2011 13:50 14.53 13.77 22/08/2011 06:20 15.13 13.40 22/08/2011 22:50 15.03 13.57 20/08/2011 05:00 14.67 14.30 20/08/2011 21:30 14.84 14.50 21/08/2011 14:00 14.54 13.20 22/08/2011 06:30 15.11 13.60 22/08/2011 23:00 15.03 13.60 20/08/2011 05:10 14.65 14.43 20/08/2011 21:40 14.84 14.40 21/08/2011 14:10 14.54 13.33 22/08/2011 06:40 15.11 13.57 22/08/2011 23:10 15.01 14.17 20/08/2011 05:20 14.65 14.47 20/08/2011 21:50 14.83 14.20 21/08/2011 14:20 14.54 12.97 22/08/2011 06:50 15.11 13.33 22/08/2011 23:20 14.99 13.73 20/08/2011 05:30 14.63 14.50 20/08/2011 22:00 14.83 14.50 21/08/2011 14:30 14.55 13.00 22/08/2011 07:00 15.12 13.70 22/08/2011 23:30 14.99 13.90 20/08/2011 05:40 14.64 14.63 20/08/2011 22:10 14.85 14.10 21/08/2011 14:40 14.56 13.10 22/08/2011 07:10 15.11 13.57 22/08/2011 23:40 15.01 13.80 20/08/2011 05:50 14.60 14.57 20/08/2011 22:20 14.83 14.70 21/08/2011 14:50 14.57 13.20 22/08/2011 07:20 15.10 13.63 22/08/2011 23:50 14.99 13.60 20/08/2011 06:00 14.59 14.50 20/08/2011 22:30 14.82 14.50 21/08/2011 15:00 14.59 13.40 22/08/2011 07:30 15.11 13.50 23/08/2011 00:00 14.99 13.20 20/08/2011 06:10 14.57 14.70 20/08/2011 22:40 14.83 14.27 21/08/2011 15:10 14.62 13.00 22/08/2011 07:40 15.11 13.63 23/08/2011 00:10 15.01 13.50 20/08/2011 06:20 14.57 14.90 20/08/2011 22:50 14.85 14.03 21/08/2011 15:20 14.59 13.00 22/08/2011 07:50 15.11 13.47 23/08/2011 00:20 15.01 13.60 20/08/2011 06:30 14.53 14.80 20/08/2011 23:00 14.85 14.40 21/08/2011 15:30 14.63 13.20 22/08/2011 08:00 15.12 13.30 23/08/2011 00:30 15.01 13.90 20/08/2011 06:40 14.54 14.50 20/08/2011 23:10 14.84 14.57 21/08/2011 15:40 14.61 13.03 22/08/2011 08:10 15.10 13.87 23/08/2011 00:40 15.01 14.03 20/08/2011 06:50 14.53 14.80 20/08/2011 23:20 14.84 14.73 21/08/2011 15:50 14.63 13.07 22/08/2011 08:20 15.10 13.43 23/08/2011 00:50 15.01 13.97 20/08/2011 07:00 14.51 14.60 20/08/2011 23:30 14.85 14.70 21/08/2011 16:00 14.65 12.80 22/08/2011 08:30 15.09 13.70 23/08/2011 01:00 14.99 14.10 20/08/2011 07:10 14.52 14.53 20/08/2011 23:40 14.82 14.60 21/08/2011 16:10 14.67 12.63 22/08/2011 08:40 15.09 13.90 23/08/2011 01:10 14.99 13.80 20/08/2011 07:20 14.52 14.47 20/08/2011 23:50 14.85 14.30 21/08/2011 16:20 14.69 12.47 22/08/2011 08:50 15.09 14.00 23/08/2011 01:20 14.99 14.00 20/08/2011 07:30 14.51 14.50 21/08/2011 00:00 14.83 14.50 21/08/2011 16:30 14.69 12.60 22/08/2011 09:00 15.09 13.80 23/08/2011 01:30 14.99 14.00 20/08/2011 07:40 14.49 14.63 21/08/2011 00:10 14.82 14.07 21/08/2011 16:40 14.71 12.67 22/08/2011 09:10 15.09 13.97 23/08/2011 01:40 14.97 13.40 20/08/2011 07:50 14.46 14.57 21/08/2011 00:20 14.81 14.13 21/08/2011 16:50 14.72 12.33 22/08/2011 09:20 15.09 13.63 23/08/2011 01:50 14.95 13.60 20/08/2011 08:00 14.45 14.50 21/08/2011 00:30 14.81 14.20 21/08/2011 17:00 14.73 12.70 22/08/2011 09:30 15.07 13.90 23/08/2011 02:00 14.98 13.50 20/08/2011 08:10 14.46 14.57 21/08/2011 00:40 14.80 14.30 21/08/2011 17:10 14.74 12.77 22/08/2011 09:40 15.09 13.87 23/08/2011 02:10 14.95 13.57 20/08/2011 08:20 14.45 14.93 21/08/2011 00:50 14.81 14.10 21/08/2011 17:20 14.73 13.53 22/08/2011 09:50 15.08 14.03 23/08/2011 02:20 14.98 13.03 20/08/2011 08:30 14.45 14.70 21/08/2011 01:00 14.79 14.30 21/08/2011 17:30 14.75 14.10 22/08/2011 10:00 15.09 13.90 23/08/2011 02:30 14.95 13.90 20/08/2011 08:40 14.44 14.93 21/08/2011 01:10 14.80 14.67 21/08/2011 17:40 14.75 16.53 22/08/2011 10:10 15.08 13.90 23/08/2011 02:40 14.97 12.30 20/08/2011 08:50 14.43 14.87 21/08/2011 01:20 14.80 14.23 21/08/2011 17:50 14.77 21.87 22/08/2011 10:20 15.07 13.70 23/08/2011 02:50 14.97 11.70 20/08/2011 09:00 14.44 14.90 21/08/2011 01:30 14.80 14.00 21/08/2011 18:00 14.81 18.40 22/08/2011 10:30 15.07 13.90 23/08/2011 03:00 14.97 13.00 20/08/2011 09:10 14.42 14.93 21/08/2011 01:40 14.78 14.03 21/08/2011 18:10 14.77 16.87 22/08/2011 10:40 15.08 13.77 23/08/2011 03:10 14.97 14.20 20/08/2011 09:20 14.42 14.77 21/08/2011 01:50 14.77 13.97 21/08/2011 18:20 14.77 15.73 22/08/2011 10:50 15.07 14.03 23/08/2011 03:20 14.97 26.80 20/08/2011 09:30 14.41 14.80 21/08/2011 02:00 14.75 14.30 21/08/2011 18:30 14.77 15.90 22/08/2011 11:00 15.07 13.70 23/08/2011 03:30 14.99 24.60 20/08/2011 09:40 14.44 14.43 21/08/2011 02:10 14.75 14.47 21/08/2011 18:40 14.79 16.13 22/08/2011 11:10 15.06 13.73 23/08/2011 03:40 15.06 33.67 20/08/2011 09:50 14.42 14.37 21/08/2011 02:20 14.75 14.43 21/08/2011 18:50 14.80 15.87 22/08/2011 11:20 15.06 13.77 23/08/2011 03:50 15.03 28.83 20/08/2011 10:00 14.44 14.30 21/08/2011 02:30 14.77 14.60 21/08/2011 19:00 14.79 15.00 22/08/2011 11:30 15.05 13.70 23/08/2011 04:00 15.05 26.30 20/08/2011 10:10 14.45 14.23 21/08/2011 02:40 14.75 14.50 21/08/2011 19:10 14.81 14.27 22/08/2011 11:40 15.05 14.30 23/08/2011 04:10 15.02 24.87 20/08/2011 10:20 14.45 14.17 21/08/2011 02:50 14.75 14.40 21/08/2011 19:20 14.79 13.93 22/08/2011 11:50 15.03 14.20 23/08/2011 04:20 14.98 23.73 20/08/2011 10:30 14.46 14.20 21/08/2011 03:00 14.74 14.40 21/08/2011 19:30 14.77 13.70 22/08/2011 12:00 15.06 14.30 23/08/2011 04:30 14.97 21.10 20/08/2011 10:40 14.47 14.43 21/08/2011 03:10 14.73 14.53 21/08/2011 19:40 14.80 13.93 22/08/2011 12:10 15.05 13.97 23/08/2011 04:40 14.95 19.23 20/08/2011 10:50 14.47 14.67 21/08/2011 03:20 14.73 14.27 21/08/2011 19:50 14.79 13.87 22/08/2011 12:20 15.06 13.63 23/08/2011 04:50 14.93 18.37 20/08/2011 11:00 14.47 14.60 21/08/2011 03:30 14.72 14.50 21/08/2011 20:00 14.81 13.50 22/08/2011 12:30 15.02 13.80 23/08/2011 05:00 14.91 17.80 20/08/2011 11:10 14.49 14.80 21/08/2011 03:40 14.72 14.27 21/08/2011 20:10 14.82 13.33 22/08/2011 12:40 15.05 13.77 23/08/2011 05:10 14.91 17.17 20/08/2011 11:20 14.49 14.80 21/08/2011 03:50 14.71 14.73 21/08/2011 20:20 14.80 13.27 22/08/2011 12:50 15.03 14.23 23/08/2011 05:20 14.91 17.23 20/08/2011 11:30 14.50 14.60 21/08/2011 04:00 14.70 14.90 21/08/2011 20:30 14.78 13.00 22/08/2011 13:00 15.03 14.10 23/08/2011 05:30 14.91 16.30 20/08/2011 11:40 14.48 14.90 21/08/2011 04:10 14.70 14.73 21/08/2011 20:40 14.81 13.10 22/08/2011 13:10 15.03 13.97 23/08/2011 05:40 14.91 15.93 20/08/2011 11:50 14.49 14.90 21/08/2011 04:20 14.70 14.67 21/08/2011 20:50 14.72 13.20 22/08/2011 13:20 15.03 13.83 23/08/2011 05:50 14.88 15.67 20/08/2011 12:00 14.51 15.00 21/08/2011 04:30 14.67 14.40 21/08/2011 21:00 14.81 13.30 22/08/2011 13:30 15.05 13.70 23/08/2011 06:00 14.91 15.70 20/08/2011 12:10 14.49 14.60 21/08/2011 04:40 14.70 14.47 21/08/2011 21:10 14.85 13.27 22/08/2011 13:40 15.02 13.87 23/08/2011 06:10 14.89 15.40 20/08/2011 12:20 14.50 15.10 21/08/2011 04:50 14.69 14.53 21/08/2011 21:20 14.85 12.63 22/08/2011 13:50 15.03 13.43 23/08/2011 06:20 14.91 15.40 20/08/2011 12:30 14.53 15.10 21/08/2011 05:00 14.69 14.80 21/08/2011 21:30 14.85 13.10 22/08/2011 14:00 15.03 13.30 23/08/2011 06:30 14.89 15.10 20/08/2011 12:40 14.51 14.80 21/08/2011 05:10 14.67 15.17 21/08/2011 21:40 14.88 14.50 22/08/2011 14:10 15.03 13.70 23/08/2011 06:40 14.89 15.47 20/08/2011 12:50 14.51 14.50 21/08/2011 05:20 14.66 15.23 21/08/2011 21:50 14.91 18.20 22/08/2011 14:20 15.01 14.10 23/08/2011 06:50 14.91 15.03 20/08/2011 13:00 14.52 14.70 21/08/2011 05:30 14.66 14.60 21/08/2011 22:00 14.94 18.10 22/08/2011 14:30 15.03 14.00 23/08/2011 07:00 14.90 15.10 20/08/2011 13:10 14.52 14.37 21/08/2011 05:40 14.64 14.27 21/08/2011 22:10 14.94 19.30 22/08/2011 14:40 15.06 14.43 23/08/2011 07:10 14.91 14.63 20/08/2011 13:20 14.52 14.53 21/08/2011 05:50 14.63 14.13 21/08/2011 22:20 14.95 19.10 22/08/2011 14:50 15.05 14.77 23/08/2011 07:20 14.89 14.77 20/08/2011 13:30 14.51 14.60 21/08/2011 06:00 14.63 14.60 21/08/2011 22:30 14.97 22.40 22/08/2011 15:00 15.05 14.20 23/08/2011 07:30 14.91 14.80 20/08/2011 13:40 14.53 14.47 21/08/2011 06:10 14.61 14.63 21/08/2011 22:40 15.05 22.20 22/08/2011 15:10 15.03 13.87 23/08/2011 07:40 14.89 14.83 20/08/2011 13:50 14.53 14.13 21/08/2011 06:20 14.60 14.57 21/08/2011 22:50 15.08 20.00 22/08/2011 15:20 15.06 14.33 23/08/2011 07:50 14.90 15.07 20/08/2011 14:00 14.53 14.10 21/08/2011 06:30 14.59 14.50 21/08/2011 23:00 15.03 18.00 22/08/2011 15:30 15.05 14.30 23/08/2011 08:00 14.90 14.90 20/08/2011 14:10 14.53 13.97 21/08/2011 06:40 14.62 14.73 21/08/2011 23:10 15.05 17.10 22/08/2011 15:40 15.05 13.43 23/08/2011 08:10 14.89 14.90 20/08/2011 14:20 14.54 14.03 21/08/2011 06:50 14.59 14.97 21/08/2011 23:20 15.01 16.20 22/08/2011 15:50 15.05 13.97 23/08/2011 08:20 14.88 15.10 20/08/2011 14:30 14.55 14.00 21/08/2011 07:00 14.57 15.00 21/08/2011 23:30 15.02 15.60 22/08/2011 16:00 15.03 14.10 23/08/2011 08:30 14.87 14.80 20/08/2011 14:40 14.55 13.73 21/08/2011 07:10 14.56 14.77 21/08/2011 23:40 15.01 15.27 22/08/2011 16:10 15.03 13.23 23/08/2011 08:40 14.89 14.47 20/08/2011 14:50 14.56 13.97 21/08/2011 07:20 14.53 14.93 21/08/2011 23:50 15.01 15.03 22/08/2011 16:20 15.02 13.47 23/08/2011 08:50 14.88 14.33 20/08/2011 15:00 14.57 14.30 21/08/2011 07:30 14.54 15.10 22/08/2011 00:00 15.01 14.70 22/08/2011 16:30 15.03 13.60 23/08/2011 09:00 14.89 14.30 20/08/2011 15:10 14.57 14.67 21/08/2011 07:40 14.54 14.70 22/08/2011 00:10 15.01 14.57 22/08/2011 16:40 15.05 13.83 23/08/2011 09:10 14.91 14.47 20/08/2011 15:20 14.57 14.43 21/08/2011 07:50 14.54 14.70 22/08/2011 00:20 15.01 14.43 22/08/2011 16:50 15.03 13.97 23/08/2011 09:20 14.88 14.13 20/08/2011 15:30 14.59 14.50 21/08/2011 08:00 14.53 14.30 22/08/2011 00:30 15.01 14.30 22/08/2011 17:00 15.02 14.00 23/08/2011 09:30 14.90 14.40 20/08/2011 15:40 14.60 14.50 21/08/2011 08:10 14.53 14.47 22/08/2011 00:40 15.02 14.23 22/08/2011 17:10 15.03 13.50 23/08/2011 09:40 14.88 14.57 20/08/2011 15:50 14.62 14.60 21/08/2011 08:20 14.52 14.83 22/08/2011 00:50 15.03 14.07 22/08/2011 17:20 15.03 13.90 23/08/2011 09:50 14.85 14.33 20/08/2011 16:00 14.59 14.50 21/08/2011 08:30 14.53 14.80 22/08/2011 01:00 15.03 14.00 22/08/2011 17:30 15.02 13.70 23/08/2011 10:00 14.88 13.70 20/08/2011 16:10 14.63 14.50 21/08/2011 08:40 14.53 14.57 22/08/2011 01:10 15.05 13.97 22/08/2011 17:40 15.03 13.70 23/08/2011 10:10 14.88 13.80 20/08/2011 16:20 14.63 14.30 21/08/2011 08:50 14.53 14.63 22/08/2011 01:20 15.05 14.33 22/08/2011 17:50 15.03 13.90 23/08/2011 10:20 14.87 13.80 129

Appendices

Date T H Date T H Date T H Date T H Date T H C° cm C° cm C° cm C° cm C° cm 23/08/2011 11:20 14.91 14.23 24/08/2011 4:00 15.12 13.00 24/08/2011 20:40 15.08 13.03 25/08/2011 13:20 14.91 12.63 26/08/2011 6:00 15.03 13.20 23/08/2011 11:30 14.89 13.90 24/08/2011 4:10 15.12 13.27 24/08/2011 20:50 15.08 12.77 25/08/2011 13:30 14.91 12.50 26/08/2011 6:10 15.03 12.80 23/08/2011 11:40 14.89 13.90 24/08/2011 4:20 15.11 13.03 24/08/2011 21:00 15.08 12.70 25/08/2011 13:40 14.91 12.63 26/08/2011 6:20 15.03 13.40 23/08/2011 11:50 14.91 14.10 24/08/2011 4:30 15.12 12.90 24/08/2011 21:10 15.08 12.33 25/08/2011 13:50 14.89 12.47 26/08/2011 6:30 15.05 13.20 23/08/2011 12:00 14.90 14.30 24/08/2011 4:40 15.10 13.43 24/08/2011 21:20 15.09 12.57 25/08/2011 14:00 14.90 12.60 26/08/2011 6:40 15.03 13.30 23/08/2011 12:10 14.91 14.00 24/08/2011 4:50 15.10 13.27 24/08/2011 21:30 15.08 12.50 25/08/2011 14:10 14.91 12.00 26/08/2011 6:50 15.01 13.70 23/08/2011 12:20 14.89 14.40 24/08/2011 5:00 15.12 13.40 24/08/2011 21:40 15.09 12.33 25/08/2011 14:20 14.90 12.30 26/08/2011 7:00 15.02 12.90 23/08/2011 12:30 14.91 14.00 24/08/2011 5:10 15.12 13.30 24/08/2011 21:50 15.09 12.57 25/08/2011 14:30 14.89 12.40 26/08/2011 7:10 15.03 13.27 23/08/2011 12:40 14.89 13.80 24/08/2011 5:20 15.11 13.50 24/08/2011 22:00 15.09 12.40 25/08/2011 14:40 14.89 12.37 26/08/2011 7:20 15.02 13.43 23/08/2011 12:50 14.91 12.80 24/08/2011 5:30 15.11 13.20 24/08/2011 22:10 15.09 12.53 25/08/2011 14:50 14.90 12.03 26/08/2011 7:30 15.03 13.10 23/08/2011 13:00 14.89 13.90 24/08/2011 5:40 15.11 13.40 24/08/2011 22:20 15.08 12.47 25/08/2011 15:00 14.91 12.00 26/08/2011 7:40 15.01 13.43 23/08/2011 13:10 14.91 13.67 24/08/2011 5:50 15.11 13.40 24/08/2011 22:30 15.10 12.60 25/08/2011 15:10 14.91 11.97 26/08/2011 7:50 15.01 13.17 23/08/2011 13:20 14.91 13.43 24/08/2011 6:00 15.11 13.40 24/08/2011 22:40 15.09 12.63 25/08/2011 15:20 14.91 12.13 26/08/2011 8:00 15.01 13.30 23/08/2011 13:30 14.91 13.40 24/08/2011 6:10 15.11 13.23 24/08/2011 22:50 15.10 12.77 25/08/2011 15:30 14.91 12.10 26/08/2011 8:10 15.01 13.17 23/08/2011 13:40 14.91 13.53 24/08/2011 6:20 15.09 13.47 24/08/2011 23:00 15.11 13.00 25/08/2011 15:40 14.91 12.20 26/08/2011 8:20 15.02 13.73 23/08/2011 13:50 14.93 13.57 24/08/2011 6:30 15.11 13.30 24/08/2011 23:10 15.09 13.03 25/08/2011 15:50 14.93 12.00 26/08/2011 8:30 15.01 13.20 23/08/2011 14:00 14.92 13.40 24/08/2011 6:40 15.09 13.43 24/08/2011 23:20 15.09 13.17 25/08/2011 16:00 14.91 12.40 26/08/2011 8:40 15.01 13.30 23/08/2011 14:10 14.93 13.17 24/08/2011 6:50 15.09 13.57 24/08/2011 23:30 15.10 12.90 25/08/2011 16:10 14.93 12.40 26/08/2011 8:50 14.99 13.20 23/08/2011 14:20 14.91 13.13 24/08/2011 7:00 15.08 13.40 24/08/2011 23:40 15.11 12.70 25/08/2011 16:20 14.91 12.10 26/08/2011 9:00 15.01 13.40 23/08/2011 14:30 14.95 13.40 24/08/2011 7:10 15.10 13.50 24/08/2011 23:50 15.11 12.80 25/08/2011 16:30 14.93 12.00 26/08/2011 9:10 14.99 12.93 23/08/2011 14:40 14.91 14.13 24/08/2011 7:20 15.09 13.40 25/08/2011 0:00 15.10 12.80 25/08/2011 16:40 14.94 12.17 26/08/2011 9:20 14.99 12.87 23/08/2011 14:50 14.94 13.77 24/08/2011 7:30 15.09 13.30 25/08/2011 0:10 15.12 12.57 25/08/2011 16:50 14.92 12.23 26/08/2011 9:30 15.01 13.10 23/08/2011 15:00 14.94 13.80 24/08/2011 7:40 15.07 13.30 25/08/2011 0:20 15.12 12.93 25/08/2011 17:00 14.90 12.20 26/08/2011 9:40 15.00 13.00 23/08/2011 15:10 14.94 13.57 24/08/2011 7:50 15.09 13.50 25/08/2011 0:30 15.10 12.80 25/08/2011 17:10 14.92 12.67 26/08/2011 9:50 14.98 12.70 23/08/2011 15:20 14.95 13.53 24/08/2011 8:00 15.08 13.20 25/08/2011 0:40 15.11 12.80 25/08/2011 17:20 14.94 12.33 26/08/2011 10:00 14.99 13.10 23/08/2011 15:30 14.94 13.40 24/08/2011 8:10 15.08 13.33 25/08/2011 0:50 15.13 12.80 25/08/2011 17:30 14.95 12.60 26/08/2011 10:10 15.01 12.80 23/08/2011 15:40 14.97 13.60 24/08/2011 8:20 15.08 13.27 25/08/2011 1:00 15.10 12.90 25/08/2011 17:40 14.93 12.20 26/08/2011 10:20 14.98 13.10 23/08/2011 15:50 14.97 13.30 24/08/2011 8:30 15.06 13.20 25/08/2011 1:10 15.12 12.93 25/08/2011 17:50 14.95 12.60 26/08/2011 10:30 14.99 12.70 23/08/2011 16:00 14.97 13.20 24/08/2011 8:40 15.06 13.60 25/08/2011 1:20 15.10 12.77 25/08/2011 18:00 14.94 12.10 26/08/2011 10:40 14.99 12.77 23/08/2011 16:10 14.97 13.47 24/08/2011 8:50 15.07 13.60 25/08/2011 1:30 15.10 12.80 25/08/2011 18:10 14.95 12.47 26/08/2011 10:50 14.99 12.73 23/08/2011 16:20 14.97 13.33 24/08/2011 9:00 15.07 13.60 25/08/2011 1:40 15.09 12.77 25/08/2011 18:20 14.94 12.13 26/08/2011 11:00 14.99 12.50 23/08/2011 16:30 15.01 13.50 24/08/2011 9:10 15.06 13.80 25/08/2011 1:50 15.10 12.63 25/08/2011 18:30 14.97 11.90 26/08/2011 11:10 14.98 12.23 23/08/2011 16:40 14.99 13.13 24/08/2011 9:20 15.07 13.70 25/08/2011 2:00 15.10 12.50 25/08/2011 18:40 14.97 12.07 26/08/2011 11:20 14.97 12.67 23/08/2011 16:50 14.99 13.27 24/08/2011 9:30 15.09 13.40 25/08/2011 2:10 15.09 12.80 25/08/2011 18:50 14.97 12.13 26/08/2011 11:30 14.99 12.70 23/08/2011 17:00 15.01 13.30 24/08/2011 9:40 15.06 13.20 25/08/2011 2:20 15.09 12.40 25/08/2011 19:00 14.98 12.20 26/08/2011 11:40 14.99 12.23 23/08/2011 17:10 15.02 13.13 24/08/2011 9:50 15.06 13.70 25/08/2011 2:30 15.10 12.70 25/08/2011 19:10 14.97 12.37 26/08/2011 11:50 15.00 12.37 23/08/2011 17:20 15.02 13.47 24/08/2011 10:00 15.06 13.60 25/08/2011 2:40 15.10 12.77 25/08/2011 19:20 14.98 12.23 26/08/2011 12:00 15.01 12.20 23/08/2011 17:30 15.03 13.40 24/08/2011 10:10 15.06 13.60 25/08/2011 2:50 15.09 12.83 25/08/2011 19:30 14.99 12.40 26/08/2011 12:10 15.01 11.93 23/08/2011 17:40 15.03 13.47 24/08/2011 10:20 15.03 13.60 25/08/2011 3:00 15.09 12.50 25/08/2011 19:40 14.99 12.30 26/08/2011 12:20 15.01 11.77 23/08/2011 17:50 15.05 13.33 24/08/2011 10:30 15.05 13.50 25/08/2011 3:10 15.08 13.10 25/08/2011 19:50 15.00 12.30 26/08/2011 12:30 15.01 11.90 23/08/2011 18:00 15.06 13.90 24/08/2011 10:40 15.06 13.47 25/08/2011 3:20 15.08 12.50 25/08/2011 20:00 14.99 12.80 26/08/2011 12:40 14.98 12.40 23/08/2011 18:10 15.06 13.93 24/08/2011 10:50 15.06 13.63 25/08/2011 3:30 15.09 12.40 25/08/2011 20:10 15.01 12.30 26/08/2011 12:50 15.01 12.80 23/08/2011 18:20 15.08 13.67 24/08/2011 11:00 15.05 13.60 25/08/2011 3:40 15.10 12.57 25/08/2011 20:20 15.01 12.50 26/08/2011 13:00 15.01 12.60 23/08/2011 18:30 15.08 13.70 24/08/2011 11:10 15.05 13.40 25/08/2011 3:50 15.09 17.23 25/08/2011 20:30 15.01 12.30 26/08/2011 13:10 15.01 11.70 23/08/2011 18:40 15.09 13.97 24/08/2011 11:20 15.03 12.90 25/08/2011 4:00 15.07 12.90 25/08/2011 20:40 15.01 12.73 26/08/2011 13:20 14.99 11.50 23/08/2011 18:50 15.09 13.53 24/08/2011 11:30 15.06 12.90 25/08/2011 4:10 15.09 12.53 25/08/2011 20:50 15.01 12.37 26/08/2011 13:30 15.01 11.80 23/08/2011 19:00 15.09 12.80 24/08/2011 11:40 15.05 13.23 25/08/2011 4:20 15.09 12.57 25/08/2011 21:00 15.02 12.90 26/08/2011 13:40 15.01 11.50 23/08/2011 19:10 15.05 12.90 24/08/2011 11:50 15.05 12.67 25/08/2011 4:30 15.08 12.40 25/08/2011 21:10 15.01 12.60 26/08/2011 13:50 15.01 12.20 23/08/2011 19:20 15.10 13.10 24/08/2011 12:00 15.06 13.10 25/08/2011 4:40 15.08 12.83 25/08/2011 21:20 15.03 12.40 26/08/2011 14:00 15.03 11.90 23/08/2011 19:30 15.11 13.50 24/08/2011 12:10 15.05 12.73 25/08/2011 4:50 15.09 12.67 25/08/2011 21:30 15.02 12.40 26/08/2011 14:10 14.94 12.03 23/08/2011 19:40 15.10 13.07 24/08/2011 12:20 15.07 13.07 25/08/2011 5:00 15.06 12.80 25/08/2011 21:40 15.03 12.50 26/08/2011 14:20 15.03 11.77 23/08/2011 19:50 15.10 13.23 24/08/2011 12:30 15.05 12.80 25/08/2011 5:10 15.07 12.80 25/08/2011 21:50 15.03 12.60 26/08/2011 14:30 15.02 11.90 23/08/2011 20:00 15.09 12.90 24/08/2011 12:40 15.07 13.03 25/08/2011 5:20 15.08 12.70 25/08/2011 22:00 15.03 12.90 26/08/2011 14:40 15.03 11.83 23/08/2011 20:10 15.09 12.67 24/08/2011 12:50 15.07 12.97 25/08/2011 5:30 15.07 13.10 25/08/2011 22:10 15.05 12.83 26/08/2011 14:50 15.05 11.77 23/08/2011 20:20 15.09 13.13 24/08/2011 13:00 15.06 12.60 25/08/2011 5:40 15.06 13.13 25/08/2011 22:20 15.03 12.47 26/08/2011 15:00 15.05 11.80 23/08/2011 20:30 15.09 12.80 24/08/2011 13:10 15.06 12.90 25/08/2011 5:50 15.05 12.67 25/08/2011 22:30 15.05 12.40 26/08/2011 15:10 15.06 11.67 23/08/2011 20:40 15.09 12.97 24/08/2011 13:20 15.06 12.60 25/08/2011 6:00 15.05 12.90 25/08/2011 22:40 15.05 12.57 26/08/2011 15:20 15.05 11.63 23/08/2011 20:50 15.10 12.93 24/08/2011 13:30 15.09 12.60 25/08/2011 6:10 15.03 12.90 25/08/2011 22:50 15.05 12.83 26/08/2011 15:30 15.06 11.50 23/08/2011 21:00 15.11 13.00 24/08/2011 13:40 15.09 12.83 25/08/2011 6:20 15.05 13.10 25/08/2011 23:00 15.05 13.00 26/08/2011 15:40 15.05 11.63 23/08/2011 21:10 15.10 13.43 24/08/2011 13:50 15.09 12.87 25/08/2011 6:30 15.03 13.40 25/08/2011 23:10 15.03 12.93 26/08/2011 15:50 15.05 11.27 23/08/2011 21:20 15.13 12.97 24/08/2011 14:00 15.09 13.00 25/08/2011 6:40 15.05 13.30 25/08/2011 23:20 15.05 12.57 26/08/2011 16:00 15.09 12.00 23/08/2011 21:30 15.10 13.20 24/08/2011 14:10 15.10 12.67 25/08/2011 6:50 15.02 13.00 25/08/2011 23:30 15.03 12.70 26/08/2011 16:10 15.08 12.30 23/08/2011 21:40 15.09 13.53 24/08/2011 14:20 15.09 12.63 25/08/2011 7:00 15.03 13.10 25/08/2011 23:40 15.05 13.17 26/08/2011 16:20 15.09 15.30 23/08/2011 21:50 15.11 13.17 24/08/2011 14:30 15.08 12.20 25/08/2011 7:10 15.02 13.30 25/08/2011 23:50 15.05 12.53 26/08/2011 16:30 15.09 14.50 23/08/2011 22:00 15.11 13.30 24/08/2011 14:40 15.10 12.23 25/08/2011 7:20 15.01 12.90 26/08/2011 0:00 15.05 12.30 26/08/2011 16:40 15.11 13.23 23/08/2011 22:10 15.12 13.33 24/08/2011 14:50 15.55 12.77 25/08/2011 7:30 15.01 12.70 26/08/2011 0:10 15.05 12.57 26/08/2011 16:50 15.12 15.87 23/08/2011 22:20 15.10 13.67 24/08/2011 15:00 15.13 12.70 25/08/2011 7:40 14.99 13.00 26/08/2011 0:20 15.05 12.73 26/08/2011 17:00 15.13 16.20 23/08/2011 22:30 15.12 13.60 24/08/2011 15:10 15.07 12.43 25/08/2011 7:50 15.01 12.90 26/08/2011 0:30 15.07 12.50 26/08/2011 17:10 15.15 16.80 23/08/2011 22:40 15.13 13.67 24/08/2011 15:20 15.05 12.77 25/08/2011 8:00 14.99 13.00 26/08/2011 0:40 15.06 12.60 26/08/2011 17:20 15.16 20.60 23/08/2011 22:50 15.13 13.43 24/08/2011 15:30 15.02 12.50 25/08/2011 8:10 14.99 13.60 26/08/2011 0:50 15.06 12.80 26/08/2011 17:30 15.13 19.60 23/08/2011 23:00 15.13 13.50 24/08/2011 15:40 15.01 12.47 25/08/2011 8:20 15.00 13.20 26/08/2011 1:00 15.05 12.80 26/08/2011 17:40 15.20 19.77 23/08/2011 23:10 15.12 13.37 24/08/2011 15:50 15.01 12.53 25/08/2011 8:30 14.98 13.30 26/08/2011 1:10 15.05 12.47 26/08/2011 17:50 15.19 19.23 23/08/2011 23:20 15.15 13.53 24/08/2011 16:00 15.02 12.50 25/08/2011 8:40 14.98 13.60 26/08/2011 1:20 15.08 12.73 26/08/2011 18:00 15.19 18.50 23/08/2011 23:30 15.13 13.70 24/08/2011 16:10 15.01 12.83 25/08/2011 8:50 14.97 13.30 26/08/2011 1:30 15.06 12.50 26/08/2011 18:10 15.20 17.67 23/08/2011 23:40 15.13 13.23 24/08/2011 16:20 15.01 12.97 25/08/2011 9:00 14.98 13.20 26/08/2011 1:40 15.08 12.70 26/08/2011 18:20 15.19 17.43 23/08/2011 23:50 15.13 13.37 24/08/2011 16:30 15.01 12.40 25/08/2011 9:10 14.95 13.37 26/08/2011 1:50 15.05 12.50 26/08/2011 18:30 15.19 16.60 24/08/2011 0:00 15.13 13.60 24/08/2011 16:40 15.02 12.57 25/08/2011 9:20 14.95 13.23 26/08/2011 2:00 15.08 12.50 26/08/2011 18:40 15.19 16.10 24/08/2011 0:10 15.13 13.73 24/08/2011 16:50 15.02 12.83 25/08/2011 9:30 14.95 13.20 26/08/2011 2:10 15.07 12.53 26/08/2011 18:50 15.18 15.60 24/08/2011 0:20 15.13 13.57 24/08/2011 17:00 15.03 12.50 25/08/2011 9:40 14.95 12.53 26/08/2011 2:20 15.07 12.67 26/08/2011 19:00 15.20 16.10 24/08/2011 0:30 15.13 13.60 24/08/2011 17:10 15.03 13.03 25/08/2011 9:50 14.94 12.97 26/08/2011 2:30 15.05 12.90 26/08/2011 19:10 15.19 15.20 24/08/2011 0:40 15.13 13.80 24/08/2011 17:20 15.02 12.37 25/08/2011 10:00 14.92 13.30 26/08/2011 2:40 15.06 12.47 26/08/2011 19:20 15.19 15.50 24/08/2011 0:50 15.13 13.60 24/08/2011 17:30 15.02 12.50 25/08/2011 10:10 14.94 13.07 26/08/2011 2:50 15.05 12.63 26/08/2011 19:30 15.20 15.30 24/08/2011 1:00 15.13 13.40 24/08/2011 17:40 15.02 13.00 25/08/2011 10:20 14.94 13.33 26/08/2011 3:00 15.05 12.50 26/08/2011 19:40 15.19 14.80 24/08/2011 1:10 15.13 13.37 24/08/2011 17:50 15.03 13.10 25/08/2011 10:30 14.91 13.20 26/08/2011 3:10 15.05 12.80 26/08/2011 19:50 15.19 15.00 24/08/2011 1:20 15.12 13.63 24/08/2011 18:00 15.03 12.80 25/08/2011 10:40 14.92 12.83 26/08/2011 3:20 15.05 12.70 26/08/2011 20:00 15.19 14.70 24/08/2011 1:30 15.13 13.70 24/08/2011 18:10 15.03 12.93 25/08/2011 10:50 14.92 12.67 26/08/2011 3:30 15.05 12.90 26/08/2011 20:10 15.20 15.00 24/08/2011 1:40 15.13 13.47 24/08/2011 18:20 15.05 12.67 25/08/2011 11:00 14.91 12.70 26/08/2011 3:40 15.06 13.03 26/08/2011 20:20 15.21 14.60 24/08/2011 1:50 15.13 13.23 24/08/2011 18:30 15.05 12.90 25/08/2011 11:10 14.91 13.03 26/08/2011 3:50 15.05 13.27 26/08/2011 20:30 15.20 14.80 24/08/2011 2:00 15.13 13.40 24/08/2011 18:40 15.05 13.03 25/08/2011 11:20 14.91 12.97 26/08/2011 4:00 15.06 13.10 26/08/2011 20:40 15.20 14.20 24/08/2011 2:10 15.13 13.37 24/08/2011 18:50 15.05 13.17 25/08/2011 11:30 14.90 13.30 26/08/2011 4:10 15.05 13.50 26/08/2011 20:50 15.20 13.80 24/08/2011 2:20 15.12 13.43 24/08/2011 19:00 15.05 13.10 25/08/2011 11:40 14.91 13.23 26/08/2011 4:20 15.07 12.70 26/08/2011 21:00 15.20 14.40 24/08/2011 2:30 15.12 13.70 24/08/2011 19:10 15.06 13.03 25/08/2011 11:50 14.92 13.17 26/08/2011 4:30 15.06 12.90 26/08/2011 21:10 15.20 14.40 24/08/2011 2:40 15.13 13.47 24/08/2011 19:20 15.05 12.47 25/08/2011 12:00 14.91 12.60 26/08/2011 4:40 15.05 12.60 26/08/2011 21:20 15.22 14.40 24/08/2011 2:50 15.13 13.33 24/08/2011 19:30 15.05 12.40 25/08/2011 12:10 14.91 12.57 26/08/2011 4:50 15.05 12.70 26/08/2011 21:30 15.22 15.20 24/08/2011 3:00 15.12 13.00 24/08/2011 19:40 15.06 12.40 25/08/2011 12:20 14.89 12.63 26/08/2011 5:00 15.03 12.60 26/08/2011 21:40 15.21 15.03 24/08/2011 3:10 15.13 13.37 24/08/2011 19:50 15.06 12.90 25/08/2011 12:30 14.91 12.40 26/08/2011 5:10 15.05 12.80 26/08/2011 21:50 14.84 15.47 24/08/2011 3:20 15.13 13.73 24/08/2011 20:00 15.06 12.90 25/08/2011 12:40 14.90 12.63 26/08/2011 5:20 15.05 13.10 26/08/2011 22:00 15.21 16.70 24/08/2011 3:30 15.13 13.50 24/08/2011 20:10 15.08 12.87 25/08/2011 12:50 14.91 12.27 26/08/2011 5:30 15.03 13.00 26/08/2011 22:10 15.23 16.17 24/08/2011 3:40 15.11 13.37 24/08/2011 20:20 15.07 12.73 25/08/2011 13:00 14.91 12.40 26/08/2011 5:40 15.05 13.00 26/08/2011 22:20 15.23 16.83 24/08/2011 3:50 15.13 13.03 24/08/2011 20:30 15.08 12.70 25/08/2011 13:10 14.89 12.27 26/08/2011 5:50 15.05 13.00 26/08/2011 22:30 15.25 17.30

130

Appendices

Date T H Date T H Date T H Date T H Date T H C° cm C° cm C° cm C° cm C° cm 26/08/2011 22:50 15.25 17.13 27/08/2011 15:30 15.07 16.50 28/08/2011 08:10 14.82 14.77 29/08/2011 00:50 14.66 15.13 29/08/2011 17:30 14.41 14.70 26/08/2011 23:00 15.25 17.60 27/08/2011 15:40 15.09 16.30 28/08/2011 08:20 14.81 15.23 29/08/2011 01:00 14.65 15.30 29/08/2011 17:40 14.39 14.70 26/08/2011 23:10 15.25 16.93 27/08/2011 15:50 15.08 16.30 28/08/2011 08:30 14.80 15.10 29/08/2011 01:10 14.66 15.23 29/08/2011 17:50 14.39 14.70 26/08/2011 23:20 15.23 17.47 27/08/2011 16:00 15.06 16.00 28/08/2011 08:40 14.81 14.87 29/08/2011 01:20 14.65 14.57 29/08/2011 18:00 14.41 15.10 26/08/2011 23:30 15.25 17.50 27/08/2011 16:10 15.06 16.07 28/08/2011 08:50 14.79 14.73 29/08/2011 01:30 14.63 15.00 29/08/2011 18:10 14.39 14.83 26/08/2011 23:40 15.25 17.27 27/08/2011 16:20 15.08 16.03 28/08/2011 09:00 14.78 14.60 29/08/2011 01:40 14.65 15.03 29/08/2011 18:20 14.39 14.67 26/08/2011 23:50 15.23 17.43 27/08/2011 16:30 15.07 16.30 28/08/2011 09:10 14.79 14.63 29/08/2011 01:50 14.63 15.07 29/08/2011 18:30 14.41 14.50 27/08/2011 00:00 15.23 16.70 27/08/2011 16:40 15.07 15.73 28/08/2011 09:20 14.79 15.07 29/08/2011 02:00 14.62 15.00 29/08/2011 18:40 14.39 14.50 27/08/2011 00:10 15.26 16.17 27/08/2011 16:50 15.05 15.97 28/08/2011 09:30 14.77 14.70 29/08/2011 02:10 14.62 14.83 29/08/2011 18:50 14.38 14.50 27/08/2011 00:20 15.25 15.83 27/08/2011 17:00 15.07 16.00 28/08/2011 09:40 14.79 14.87 29/08/2011 02:20 14.60 15.37 29/08/2011 19:00 14.39 14.90 27/08/2011 00:30 15.25 15.70 27/08/2011 17:10 15.06 15.63 28/08/2011 09:50 14.81 14.93 29/08/2011 02:30 14.62 15.00 29/08/2011 19:10 14.39 14.33 27/08/2011 00:40 15.26 15.70 27/08/2011 17:20 15.07 15.07 28/08/2011 10:00 14.79 15.10 29/08/2011 02:40 14.59 15.23 29/08/2011 19:20 14.38 14.97 27/08/2011 00:50 15.24 15.90 27/08/2011 17:30 15.06 15.00 28/08/2011 10:10 14.79 15.20 29/08/2011 02:50 14.57 15.37 29/08/2011 19:30 14.39 14.40 27/08/2011 01:00 15.23 16.80 27/08/2011 17:40 15.06 15.27 28/08/2011 10:20 14.78 14.80 29/08/2011 03:00 14.57 15.30 29/08/2011 19:40 14.37 14.73 27/08/2011 01:10 15.23 17.37 27/08/2011 17:50 15.05 20.03 28/08/2011 10:30 14.78 15.00 29/08/2011 03:10 14.59 14.80 29/08/2011 19:50 14.38 14.47 27/08/2011 01:20 15.24 20.63 27/08/2011 18:00 15.05 18.60 28/08/2011 10:40 14.81 15.10 29/08/2011 03:20 14.59 14.80 29/08/2011 20:00 14.37 14.40 27/08/2011 01:30 15.28 19.60 27/08/2011 18:10 15.05 20.83 28/08/2011 10:50 14.80 14.90 29/08/2011 03:30 14.56 14.70 29/08/2011 20:10 14.38 14.70 27/08/2011 01:40 15.25 20.47 27/08/2011 18:20 15.05 22.07 28/08/2011 11:00 14.78 15.30 29/08/2011 03:40 14.57 14.83 29/08/2011 20:20 14.38 14.20 27/08/2011 01:50 15.27 21.53 27/08/2011 18:30 15.06 20.20 28/08/2011 11:10 14.78 14.97 29/08/2011 03:50 14.57 15.27 29/08/2011 20:30 14.38 13.90 27/08/2011 02:00 15.27 22.50 27/08/2011 18:40 15.03 19.13 28/08/2011 11:20 14.77 14.73 29/08/2011 04:00 14.55 15.10 29/08/2011 20:40 14.38 14.23 27/08/2011 02:10 15.26 21.80 27/08/2011 18:50 15.03 18.27 28/08/2011 11:30 14.77 14.90 29/08/2011 04:10 14.54 15.17 29/08/2011 20:50 14.37 14.17 27/08/2011 02:20 15.26 22.80 27/08/2011 19:00 15.05 18.20 28/08/2011 11:40 14.78 14.53 29/08/2011 04:20 14.53 15.03 29/08/2011 21:00 14.36 14.10 27/08/2011 02:30 15.26 22.20 27/08/2011 19:10 15.03 18.13 28/08/2011 11:50 14.75 14.97 29/08/2011 04:30 14.53 14.90 29/08/2011 21:10 14.36 14.30 27/08/2011 02:40 15.23 21.30 27/08/2011 19:20 15.03 17.47 28/08/2011 12:00 14.78 14.70 29/08/2011 04:40 14.54 14.93 29/08/2011 21:20 14.36 14.10 27/08/2011 02:50 15.25 20.30 27/08/2011 19:30 15.03 16.80 28/08/2011 12:10 14.77 14.90 29/08/2011 04:50 14.52 14.97 29/08/2011 21:30 14.36 14.20 27/08/2011 03:00 15.23 18.90 27/08/2011 19:40 15.02 16.80 28/08/2011 12:20 14.78 15.00 29/08/2011 05:00 14.53 14.80 29/08/2011 21:40 14.34 14.47 27/08/2011 03:10 15.22 18.67 27/08/2011 19:50 15.01 16.60 28/08/2011 12:30 14.77 15.00 29/08/2011 05:10 14.50 14.93 29/08/2011 21:50 14.35 14.13 27/08/2011 03:20 15.20 18.83 27/08/2011 20:00 15.03 16.20 28/08/2011 12:40 14.77 14.77 29/08/2011 05:20 14.53 14.97 29/08/2011 22:00 14.35 14.10 27/08/2011 03:30 15.19 18.40 27/08/2011 20:10 15.02 16.20 28/08/2011 12:50 14.75 15.03 29/08/2011 05:30 14.52 15.00 29/08/2011 22:10 14.35 14.17 27/08/2011 03:40 15.21 18.20 27/08/2011 20:20 15.03 16.20 28/08/2011 13:00 14.75 15.50 29/08/2011 05:40 14.51 14.70 29/08/2011 22:20 14.35 14.33 27/08/2011 03:50 15.20 18.20 27/08/2011 20:30 15.03 15.70 28/08/2011 13:10 14.75 14.77 29/08/2011 05:50 14.49 14.70 29/08/2011 22:30 14.32 14.60 27/08/2011 04:00 15.20 18.40 27/08/2011 20:40 15.02 15.87 28/08/2011 13:20 14.75 15.03 29/08/2011 06:00 14.48 15.20 29/08/2011 22:40 14.33 14.13 27/08/2011 04:10 15.19 17.83 27/08/2011 20:50 15.02 15.43 28/08/2011 13:30 14.77 15.10 29/08/2011 06:10 14.51 14.77 29/08/2011 22:50 14.31 14.17 27/08/2011 04:20 15.20 19.47 27/08/2011 21:00 15.01 15.60 28/08/2011 13:40 14.75 15.00 29/08/2011 06:20 14.48 14.83 29/08/2011 23:00 14.31 14.00 27/08/2011 04:30 15.22 18.80 27/08/2011 21:10 15.03 15.17 28/08/2011 13:50 14.77 14.60 29/08/2011 06:30 14.47 14.80 29/08/2011 23:10 14.29 14.50 27/08/2011 04:40 15.19 18.40 27/08/2011 21:20 15.02 15.13 28/08/2011 14:00 14.73 14.90 29/08/2011 06:40 14.48 15.27 29/08/2011 23:20 14.31 14.10 27/08/2011 04:50 15.19 19.20 27/08/2011 21:30 14.99 15.40 28/08/2011 14:10 14.75 14.97 29/08/2011 06:50 14.46 15.03 29/08/2011 23:30 14.29 14.10 27/08/2011 05:00 15.17 18.80 27/08/2011 21:40 14.99 15.20 28/08/2011 14:20 14.75 14.63 29/08/2011 07:00 14.46 15.10 29/08/2011 23:40 14.27 14.53 27/08/2011 05:10 15.19 18.50 27/08/2011 21:50 14.99 15.00 28/08/2011 14:30 14.75 14.60 29/08/2011 07:10 14.46 15.10 29/08/2011 23:50 14.26 13.87 27/08/2011 05:20 15.16 19.80 27/08/2011 22:00 14.99 15.30 28/08/2011 14:40 14.73 14.93 29/08/2011 07:20 14.44 15.10 30/08/2011 00:00 14.25 14.20 27/08/2011 05:30 15.19 20.10 27/08/2011 22:10 15.01 15.23 28/08/2011 14:50 14.74 14.57 29/08/2011 07:30 14.46 15.40 30/08/2011 00:10 14.28 14.27 27/08/2011 05:40 15.18 22.33 27/08/2011 22:20 15.02 15.27 28/08/2011 15:00 14.74 14.60 29/08/2011 07:40 14.45 15.13 30/08/2011 00:20 14.25 14.33 27/08/2011 05:50 15.15 22.17 27/08/2011 22:30 15.01 15.60 28/08/2011 15:10 14.75 14.63 29/08/2011 07:50 14.41 15.37 30/08/2011 00:30 14.25 14.40 27/08/2011 06:00 15.16 22.80 27/08/2011 22:40 15.01 15.17 28/08/2011 15:20 14.73 14.87 29/08/2011 08:00 14.42 15.20 30/08/2011 00:40 14.24 14.43 27/08/2011 06:10 15.17 22.33 27/08/2011 22:50 15.01 15.53 28/08/2011 15:30 14.74 14.70 29/08/2011 08:10 14.45 14.90 30/08/2011 00:50 14.23 14.37 27/08/2011 06:20 15.15 22.07 27/08/2011 23:00 15.00 14.80 28/08/2011 15:40 14.73 14.47 29/08/2011 08:20 14.45 14.80 30/08/2011 01:00 14.25 14.40 27/08/2011 06:30 15.16 21.40 27/08/2011 23:10 15.01 15.00 28/08/2011 15:50 14.73 15.03 29/08/2011 08:30 14.42 14.90 30/08/2011 01:10 14.26 14.43 27/08/2011 06:40 15.15 20.73 27/08/2011 23:20 15.01 15.00 28/08/2011 16:00 14.73 14.60 29/08/2011 08:40 14.44 15.37 30/08/2011 01:20 14.24 14.37 27/08/2011 06:50 15.13 22.47 27/08/2011 23:30 14.99 15.20 28/08/2011 16:10 14.73 14.63 29/08/2011 08:50 14.43 15.03 30/08/2011 01:30 14.21 14.60 27/08/2011 07:00 15.13 22.00 27/08/2011 23:40 14.99 15.20 28/08/2011 16:20 14.73 15.07 29/08/2011 09:00 14.41 15.10 30/08/2011 01:40 14.24 14.20 27/08/2011 07:10 15.12 19.83 27/08/2011 23:50 14.99 15.20 28/08/2011 16:30 14.73 15.00 29/08/2011 09:10 14.42 15.10 30/08/2011 01:50 14.24 14.20 27/08/2011 07:20 15.15 19.17 28/08/2011 00:00 14.99 15.00 28/08/2011 16:40 14.72 14.93 29/08/2011 09:20 14.41 15.40 30/08/2011 02:00 14.21 14.10 27/08/2011 07:30 15.13 18.90 28/08/2011 00:10 14.98 14.83 28/08/2011 16:50 14.73 14.67 29/08/2011 09:30 14.42 15.00 30/08/2011 02:10 14.23 14.03 27/08/2011 07:40 15.13 18.13 28/08/2011 00:20 15.01 14.87 28/08/2011 17:00 14.72 15.10 29/08/2011 09:40 14.41 15.43 30/08/2011 02:20 14.23 13.97 27/08/2011 07:50 15.09 18.57 28/08/2011 00:30 14.99 14.80 28/08/2011 17:10 14.73 14.83 29/08/2011 09:50 14.41 15.27 30/08/2011 02:30 14.21 14.00 27/08/2011 08:00 15.11 17.90 28/08/2011 00:40 14.97 14.77 28/08/2011 17:20 14.72 14.87 29/08/2011 10:00 14.39 15.30 30/08/2011 02:40 14.21 14.30 27/08/2011 08:10 15.10 17.37 28/08/2011 00:50 14.99 14.93 28/08/2011 17:30 14.71 14.50 29/08/2011 10:10 14.39 15.27 30/08/2011 02:50 14.21 14.00 27/08/2011 08:20 15.10 17.13 28/08/2011 01:00 14.98 14.70 28/08/2011 17:40 14.73 14.80 29/08/2011 10:20 14.41 15.33 30/08/2011 03:00 14.21 14.20 27/08/2011 08:30 15.10 17.00 28/08/2011 01:10 14.98 15.07 28/08/2011 17:50 14.70 14.70 29/08/2011 10:30 14.39 15.10 30/08/2011 03:10 14.21 13.97 27/08/2011 08:40 15.10 16.93 28/08/2011 01:20 14.95 15.13 28/08/2011 18:00 14.72 14.40 29/08/2011 10:40 14.39 15.27 30/08/2011 03:20 14.20 14.13 27/08/2011 08:50 15.10 16.67 28/08/2011 01:30 14.99 15.20 28/08/2011 18:10 14.72 14.20 29/08/2011 10:50 14.43 15.43 30/08/2011 03:30 14.18 13.60 27/08/2011 09:00 15.10 16.60 28/08/2011 01:40 14.97 15.10 28/08/2011 18:20 14.73 14.10 29/08/2011 11:00 14.41 15.50 30/08/2011 03:40 14.19 13.87 27/08/2011 09:10 15.09 16.57 28/08/2011 01:50 14.97 15.00 28/08/2011 18:30 14.72 14.00 29/08/2011 11:10 14.39 15.17 30/08/2011 03:50 14.18 13.83 27/08/2011 09:20 15.11 16.73 28/08/2011 02:00 14.97 15.00 28/08/2011 18:40 14.72 14.50 29/08/2011 11:20 14.41 15.13 30/08/2011 04:00 14.18 13.90 27/08/2011 09:30 15.09 16.50 28/08/2011 02:10 14.95 15.00 28/08/2011 18:50 14.72 14.60 29/08/2011 11:30 14.41 15.00 30/08/2011 04:10 14.18 13.63 27/08/2011 09:40 15.11 16.60 28/08/2011 02:20 14.95 15.20 28/08/2011 19:00 14.73 14.40 29/08/2011 11:40 14.43 15.40 30/08/2011 04:20 14.18 14.27 27/08/2011 09:50 15.11 16.30 28/08/2011 02:30 14.95 15.20 28/08/2011 19:10 14.72 14.30 29/08/2011 11:50 14.42 15.20 30/08/2011 04:30 14.17 14.10 27/08/2011 10:00 15.11 16.00 28/08/2011 02:40 14.94 15.30 28/08/2011 19:20 14.72 14.30 29/08/2011 12:00 14.42 15.40 30/08/2011 04:40 14.16 13.97 27/08/2011 10:10 15.11 16.23 28/08/2011 02:50 14.94 14.90 28/08/2011 19:30 14.72 14.70 29/08/2011 12:10 14.41 15.10 30/08/2011 04:50 14.16 13.93 27/08/2011 10:20 15.10 15.77 28/08/2011 03:00 14.97 14.90 28/08/2011 19:40 14.70 14.37 29/08/2011 12:20 14.41 15.40 30/08/2011 05:00 14.17 14.00 27/08/2011 10:30 15.10 16.00 28/08/2011 03:10 14.92 15.20 28/08/2011 19:50 14.73 14.43 29/08/2011 12:30 14.42 15.40 30/08/2011 05:10 14.17 13.97 27/08/2011 10:40 15.10 16.47 28/08/2011 03:20 14.92 15.30 28/08/2011 20:00 14.70 14.70 29/08/2011 12:40 14.41 15.40 30/08/2011 05:20 14.17 14.13 27/08/2011 10:50 15.09 17.23 28/08/2011 03:30 14.93 14.70 28/08/2011 20:10 14.70 14.60 29/08/2011 12:50 14.41 15.00 30/08/2011 05:30 14.16 13.80 27/08/2011 11:00 15.09 16.30 28/08/2011 03:40 14.95 14.87 28/08/2011 20:20 14.70 14.40 29/08/2011 13:00 14.41 15.20 30/08/2011 05:40 14.13 13.73 27/08/2011 11:10 15.10 16.33 28/08/2011 03:50 14.92 14.93 28/08/2011 20:30 14.70 14.40 29/08/2011 13:10 14.43 15.03 30/08/2011 05:50 14.15 13.77 27/08/2011 11:20 15.09 16.47 28/08/2011 04:00 14.92 15.40 28/08/2011 20:40 14.71 14.63 29/08/2011 13:20 14.41 14.87 30/08/2011 06:00 14.14 14.00 27/08/2011 11:30 15.09 16.40 28/08/2011 04:10 14.93 14.90 28/08/2011 20:50 14.72 14.47 29/08/2011 13:30 14.42 14.90 30/08/2011 06:10 14.16 13.67 27/08/2011 11:40 15.09 16.20 28/08/2011 04:20 14.91 14.90 28/08/2011 21:00 14.69 14.50 29/08/2011 13:40 14.41 14.83 30/08/2011 06:20 14.14 13.73 27/08/2011 11:50 15.09 16.50 28/08/2011 04:30 14.91 14.60 28/08/2011 21:10 14.71 14.87 29/08/2011 13:50 14.39 14.97 30/08/2011 06:30 14.13 14.10 27/08/2011 12:00 15.09 16.10 28/08/2011 04:40 14.91 15.13 28/08/2011 21:20 14.71 15.13 29/08/2011 14:00 14.41 15.30 30/08/2011 06:40 14.13 13.97 27/08/2011 12:10 15.09 16.00 28/08/2011 04:50 14.91 14.97 28/08/2011 21:30 14.69 14.70 29/08/2011 14:10 14.41 15.00 30/08/2011 06:50 14.11 14.13 27/08/2011 12:20 15.09 16.10 28/08/2011 05:00 14.91 15.10 28/08/2011 21:40 14.69 14.90 29/08/2011 14:20 14.41 14.90 30/08/2011 07:00 14.09 14.10 27/08/2011 12:30 15.09 15.80 28/08/2011 05:10 14.91 14.80 28/08/2011 21:50 14.69 15.00 29/08/2011 14:30 14.41 14.80 30/08/2011 07:10 14.07 14.30 27/08/2011 12:40 15.09 15.53 28/08/2011 05:20 14.89 15.00 28/08/2011 22:00 14.67 14.90 29/08/2011 14:40 14.39 14.67 30/08/2011 07:20 14.07 14.30 27/08/2011 12:50 15.10 15.47 28/08/2011 05:30 14.90 15.00 28/08/2011 22:10 14.67 14.93 29/08/2011 14:50 14.41 14.83 30/08/2011 07:30 14.04 14.10 27/08/2011 13:00 15.08 15.60 28/08/2011 05:40 14.90 15.03 28/08/2011 22:20 14.70 15.27 29/08/2011 15:00 14.39 15.20 30/08/2011 07:40 14.06 13.93 27/08/2011 13:10 15.09 15.73 28/08/2011 05:50 14.90 15.07 28/08/2011 22:30 14.67 15.00 29/08/2011 15:10 14.41 15.13 30/08/2011 07:50 14.07 13.97 27/08/2011 13:20 15.08 16.07 28/08/2011 06:00 14.88 15.30 28/08/2011 22:40 14.67 15.00 29/08/2011 15:20 14.41 15.27 30/08/2011 08:00 14.03 13.90 27/08/2011 13:30 15.08 16.20 28/08/2011 06:10 14.88 15.50 28/08/2011 22:50 14.69 15.20 29/08/2011 15:30 14.41 15.00 30/08/2011 08:10 14.04 14.17 27/08/2011 13:40 15.08 16.13 28/08/2011 06:20 14.89 15.50 28/08/2011 23:00 14.70 15.30 29/08/2011 15:40 14.41 14.80 30/08/2011 08:20 14.02 14.03 27/08/2011 13:50 15.09 15.67 28/08/2011 06:30 14.87 15.10 28/08/2011 23:10 14.69 14.73 29/08/2011 15:50 14.41 15.10 30/08/2011 08:30 14.03 14.40 27/08/2011 14:00 15.08 15.50 28/08/2011 06:40 14.85 15.20 28/08/2011 23:20 14.69 14.77 29/08/2011 16:00 14.39 15.40 30/08/2011 08:40 14.02 13.93 27/08/2011 14:10 15.08 15.30 28/08/2011 06:50 14.85 14.90 28/08/2011 23:30 14.67 14.40 29/08/2011 16:10 14.41 14.97 30/08/2011 08:50 14.03 14.37 27/08/2011 14:20 15.09 16.00 28/08/2011 07:00 14.85 14.80 28/08/2011 23:40 14.67 14.80 29/08/2011 16:20 14.39 14.63 30/08/2011 09:00 14.01 14.30 27/08/2011 14:30 15.09 15.70 28/08/2011 07:10 14.85 14.77 28/08/2011 23:50 14.66 14.90 29/08/2011 16:30 14.39 14.60 30/08/2011 09:10 14.03 14.00 27/08/2011 14:40 15.09 16.10 28/08/2011 07:20 14.84 14.73 29/08/2011 00:00 14.66 15.10 29/08/2011 16:40 14.39 14.90 30/08/2011 09:20 14.00 14.20 27/08/2011 14:50 15.08 16.20 28/08/2011 07:30 14.83 14.50 29/08/2011 00:10 14.66 15.03 29/08/2011 16:50 14.39 15.00 30/08/2011 09:30 14.01 14.50 27/08/2011 15:00 15.07 16.50 28/08/2011 07:40 14.83 14.80 29/08/2011 00:20 14.67 15.17 29/08/2011 17:00 14.39 14.90 30/08/2011 09:40 14.01 14.43 27/08/2011 15:10 15.09 16.50 28/08/2011 07:50 14.84 14.90 29/08/2011 00:30 14.66 14.50 29/08/2011 17:10 14.39 14.53 30/08/2011 09:50 14.02 14.07 27/08/2011 15:20 15.07 16.70 28/08/2011 08:00 14.84 14.70 29/08/2011 00:40 14.65 15.07 29/08/2011 17:20 14.39 14.57 30/08/2011 10:00 14.01 14.00 131

Appendices

Date T H Date T H Date T H Date T H Date T H C° cm C° cm C° cm C° cm C° cm 30/08/2011 10:10 14.03 14.27 31/08/2011 03:00 13.92 13.10 31/08/2011 19:50 13.85 13.70 01/09/2011 12:40 13.57 14.00 02/09/2011 05:20 13.32 13.97 30/08/2011 10:20 14.03 14.33 31/08/2011 03:10 13.93 13.07 31/08/2011 20:00 13.83 14.00 01/09/2011 12:50 13.62 14.20 02/09/2011 05:30 13.35 14.30 30/08/2011 10:30 14.01 14.40 31/08/2011 03:20 13.90 13.53 31/08/2011 20:10 13.85 13.90 01/09/2011 13:00 13.61 14.20 02/09/2011 05:40 13.30 14.20 30/08/2011 10:40 14.03 14.63 31/08/2011 03:30 13.89 13.60 31/08/2011 20:20 13.85 14.00 01/09/2011 13:10 13.63 13.83 02/09/2011 05:50 13.25 14.50 30/08/2011 10:50 14.01 14.87 31/08/2011 03:40 13.89 13.63 31/08/2011 20:30 13.86 13.90 01/09/2011 13:20 13.61 13.97 02/09/2011 06:00 13.31 14.60 30/08/2011 11:00 14.03 14.50 31/08/2011 03:50 13.88 13.67 31/08/2011 20:40 13.85 13.83 01/09/2011 13:30 13.64 14.00 02/09/2011 06:10 13.27 14.43 30/08/2011 11:10 14.01 14.03 31/08/2011 04:00 13.87 13.40 31/08/2011 20:50 13.83 13.87 01/09/2011 13:40 13.62 13.70 02/09/2011 06:20 13.31 14.37 30/08/2011 11:20 14.02 14.07 31/08/2011 04:10 13.85 13.97 31/08/2011 21:00 13.87 13.90 01/09/2011 13:50 13.65 13.70 02/09/2011 06:30 13.29 14.30 30/08/2011 11:30 14.01 14.00 31/08/2011 04:20 13.82 13.83 31/08/2011 21:10 13.85 13.87 01/09/2011 14:00 13.65 13.70 02/09/2011 06:40 13.29 14.43 30/08/2011 11:40 14.03 13.87 31/08/2011 04:30 13.83 14.00 31/08/2011 21:20 13.86 14.23 01/09/2011 14:10 13.65 13.60 02/09/2011 06:50 13.23 14.47 30/08/2011 11:50 14.05 14.33 31/08/2011 04:40 13.83 13.57 31/08/2011 21:30 13.87 14.00 01/09/2011 14:20 13.65 13.70 02/09/2011 07:00 13.27 14.40 30/08/2011 12:00 14.05 14.40 31/08/2011 04:50 13.82 13.53 31/08/2011 21:40 13.87 13.67 01/09/2011 14:30 13.67 13.50 02/09/2011 07:10 13.26 14.50 30/08/2011 12:10 14.05 14.40 31/08/2011 05:00 13.75 13.60 31/08/2011 21:50 13.87 13.53 01/09/2011 14:40 13.65 13.73 02/09/2011 07:20 13.29 14.40 30/08/2011 12:20 14.05 14.50 31/08/2011 05:10 13.72 13.67 31/08/2011 22:00 13.85 13.60 01/09/2011 14:50 13.65 13.97 02/09/2011 07:30 13.26 14.40 30/08/2011 12:30 14.05 14.20 31/08/2011 05:20 13.65 13.73 31/08/2011 22:10 13.85 13.83 01/09/2011 15:00 13.67 14.00 02/09/2011 07:40 13.24 14.47 30/08/2011 12:40 14.08 14.10 31/08/2011 05:30 13.57 13.80 31/08/2011 22:20 13.88 13.77 01/09/2011 15:10 13.68 14.10 02/09/2011 07:50 13.25 14.83 30/08/2011 12:50 14.07 14.20 31/08/2011 05:40 13.48 13.63 31/08/2011 22:30 13.85 14.10 01/09/2011 15:20 13.69 14.30 02/09/2011 08:00 13.27 14.70 30/08/2011 13:00 14.07 14.40 31/08/2011 05:50 13.42 13.47 31/08/2011 22:40 13.87 13.83 01/09/2011 15:30 13.68 14.20 02/09/2011 08:10 13.21 14.90 30/08/2011 13:10 14.07 14.13 31/08/2011 06:00 13.36 13.80 31/08/2011 22:50 13.87 14.07 01/09/2011 15:40 13.67 13.93 02/09/2011 08:20 13.21 14.80 30/08/2011 13:20 14.06 14.67 31/08/2011 06:10 13.32 13.67 31/08/2011 23:00 13.87 14.00 01/09/2011 15:50 13.68 14.07 02/09/2011 08:30 13.25 14.30 30/08/2011 13:30 14.05 14.40 31/08/2011 06:20 13.40 13.83 31/08/2011 23:10 13.87 13.60 01/09/2011 16:00 13.67 14.10 02/09/2011 08:40 13.21 14.57 30/08/2011 13:40 14.07 14.60 31/08/2011 06:30 13.47 14.10 31/08/2011 23:20 13.85 13.60 01/09/2011 16:10 13.71 14.00 02/09/2011 08:50 13.04 14.53 30/08/2011 13:50 14.08 14.20 31/08/2011 06:40 13.43 13.87 31/08/2011 23:30 13.85 13.70 01/09/2011 16:20 13.68 13.80 02/09/2011 09:00 13.11 14.90 30/08/2011 14:00 14.08 14.10 31/08/2011 06:50 13.43 14.13 31/08/2011 23:40 13.83 13.87 01/09/2011 16:30 13.69 14.00 02/09/2011 09:10 13.25 14.57 30/08/2011 14:10 14.05 14.23 31/08/2011 07:00 13.49 13.80 31/08/2011 23:50 13.83 14.03 01/09/2011 16:40 13.70 13.77 02/09/2011 09:20 13.26 14.63 30/08/2011 14:20 14.07 14.17 31/08/2011 07:10 13.43 14.20 01/09/2011 00:00 13.80 13.60 01/09/2011 16:50 13.71 13.83 02/09/2011 09:30 13.31 14.50 30/08/2011 14:30 14.07 14.20 31/08/2011 07:20 13.40 14.20 01/09/2011 00:10 13.76 13.83 01/09/2011 17:00 13.70 13.70 02/09/2011 09:40 13.29 14.50 30/08/2011 14:40 14.07 14.40 31/08/2011 07:30 13.42 14.00 01/09/2011 00:20 13.67 14.07 01/09/2011 17:10 13.71 13.93 02/09/2011 09:50 13.29 14.40 30/08/2011 14:50 14.07 14.40 31/08/2011 07:40 13.41 13.90 01/09/2011 00:30 13.63 14.00 01/09/2011 17:20 13.71 13.77 02/09/2011 10:00 13.27 14.50 30/08/2011 15:00 14.06 14.50 31/08/2011 07:50 13.44 13.80 01/09/2011 00:40 13.61 14.20 01/09/2011 17:30 13.71 14.10 02/09/2011 10:10 13.32 14.30 30/08/2011 15:10 14.07 14.50 31/08/2011 08:00 13.37 13.30 01/09/2011 00:50 13.61 13.90 01/09/2011 17:40 13.71 13.93 02/09/2011 10:20 13.32 14.50 30/08/2011 15:20 14.07 14.10 31/08/2011 08:10 13.37 13.93 01/09/2011 01:00 13.58 14.00 01/09/2011 17:50 13.71 13.77 02/09/2011 10:30 13.33 14.30 30/08/2011 15:30 14.07 14.40 31/08/2011 08:20 13.37 13.77 01/09/2011 01:10 13.58 13.80 01/09/2011 18:00 13.71 13.60 02/09/2011 10:40 13.36 14.43 30/08/2011 15:40 14.07 13.83 31/08/2011 08:30 13.41 13.70 01/09/2011 01:20 13.48 14.00 01/09/2011 18:10 13.72 13.40 02/09/2011 10:50 13.37 14.17 30/08/2011 15:50 14.07 14.07 31/08/2011 08:40 13.39 14.23 01/09/2011 01:30 13.57 13.80 01/09/2011 18:20 13.73 13.80 02/09/2011 11:00 13.39 14.10 30/08/2011 16:00 14.06 14.20 31/08/2011 08:50 13.46 13.97 01/09/2011 01:40 13.57 14.03 01/09/2011 18:30 13.72 14.00 02/09/2011 11:10 13.42 14.10 30/08/2011 16:10 14.07 14.20 31/08/2011 09:00 13.46 14.10 01/09/2011 01:50 13.58 13.77 01/09/2011 18:40 13.73 13.67 02/09/2011 11:20 13.43 14.00 30/08/2011 16:20 14.06 14.20 31/08/2011 09:10 13.46 13.73 01/09/2011 02:00 13.51 13.80 01/09/2011 18:50 13.72 13.73 02/09/2011 11:30 13.44 13.80 30/08/2011 16:30 14.08 13.90 31/08/2011 09:20 13.46 13.77 01/09/2011 02:10 13.55 13.90 01/09/2011 19:00 13.75 14.90 02/09/2011 11:40 13.46 13.93 30/08/2011 16:40 14.08 13.93 31/08/2011 09:30 13.35 13.70 01/09/2011 02:20 13.55 14.10 01/09/2011 19:10 13.74 13.63 02/09/2011 11:50 13.47 13.67 30/08/2011 16:50 14.07 14.17 31/08/2011 09:40 13.43 13.77 01/09/2011 02:30 13.52 13.50 01/09/2011 19:20 13.73 13.87 02/09/2011 12:00 13.49 13.80 30/08/2011 17:00 14.07 13.90 31/08/2011 09:50 13.46 13.73 01/09/2011 02:40 13.47 13.73 01/09/2011 19:30 13.76 13.80 02/09/2011 12:10 13.51 13.63 30/08/2011 17:10 14.07 13.90 31/08/2011 10:00 13.50 14.00 01/09/2011 02:50 13.49 13.77 01/09/2011 19:40 13.75 13.80 02/09/2011 12:20 13.49 13.67 30/08/2011 17:20 14.07 13.80 31/08/2011 10:10 13.51 14.00 01/09/2011 03:00 13.50 13.90 01/09/2011 19:50 13.76 14.00 02/09/2011 12:30 13.49 13.60 30/08/2011 17:30 14.07 14.00 31/08/2011 10:20 13.50 13.90 01/09/2011 03:10 13.50 13.97 01/09/2011 20:00 13.75 13.80 02/09/2011 12:40 13.50 13.67 30/08/2011 17:40 14.07 13.97 31/08/2011 10:30 13.51 13.60 01/09/2011 03:20 13.47 13.53 01/09/2011 20:10 13.76 14.17 02/09/2011 12:50 13.51 13.23 30/08/2011 17:50 14.07 14.13 31/08/2011 10:40 13.48 14.00 01/09/2011 03:30 13.44 13.80 01/09/2011 20:20 13.77 13.73 02/09/2011 13:00 13.53 13.10 30/08/2011 18:00 14.07 13.40 31/08/2011 10:50 13.54 13.50 01/09/2011 03:40 13.43 13.80 01/09/2011 20:30 13.76 13.90 02/09/2011 13:10 13.52 13.53 30/08/2011 18:10 14.08 13.90 31/08/2011 11:00 13.55 13.70 01/09/2011 03:50 13.34 14.00 01/09/2011 20:40 13.77 13.87 02/09/2011 13:20 13.53 13.17 30/08/2011 18:20 14.07 13.80 31/08/2011 11:10 13.55 13.90 01/09/2011 04:00 13.45 13.80 01/09/2011 20:50 13.77 13.83 02/09/2011 13:30 13.52 13.30 30/08/2011 18:40 14.08 13.73 31/08/2011 11:20 13.55 13.90 01/09/2011 04:10 13.42 13.80 01/09/2011 21:00 13.75 13.60 02/09/2011 13:40 13.55 13.27 30/08/2011 18:50 14.07 13.97 31/08/2011 11:30 13.57 14.00 01/09/2011 04:20 13.43 14.10 01/09/2011 21:10 13.77 14.03 02/09/2011 13:50 13.54 13.03 30/08/2011 19:00 14.07 13.90 31/08/2011 11:40 13.59 14.00 01/09/2011 04:30 13.40 14.50 01/09/2011 21:20 13.79 14.07 02/09/2011 14:00 13.53 13.50 30/08/2011 19:10 14.08 14.00 31/08/2011 11:50 13.55 14.00 01/09/2011 04:40 13.43 14.07 01/09/2011 21:30 13.78 14.20 02/09/2011 14:10 13.55 13.77 30/08/2011 19:20 14.07 13.50 31/08/2011 12:00 13.65 13.90 01/09/2011 04:50 13.43 14.13 01/09/2011 21:40 13.79 14.03 02/09/2011 14:20 13.55 13.33 30/08/2011 19:30 14.07 13.90 31/08/2011 12:10 13.64 13.97 01/09/2011 05:00 13.42 14.30 01/09/2011 21:50 13.80 14.27 02/09/2011 14:30 13.55 12.80 30/08/2011 19:40 14.07 13.97 31/08/2011 12:20 13.64 14.03 01/09/2011 05:10 13.45 14.40 01/09/2011 22:00 13.75 14.30 02/09/2011 14:40 13.57 13.33 30/08/2011 19:50 14.07 13.83 31/08/2011 12:30 13.65 13.70 01/09/2011 05:20 13.44 14.10 01/09/2011 22:10 13.79 14.27 02/09/2011 14:50 13.57 13.27 30/08/2011 20:00 14.07 13.80 31/08/2011 12:40 13.67 13.60 01/09/2011 05:30 13.42 14.10 01/09/2011 22:20 13.79 14.33 02/09/2011 15:00 13.58 13.40 30/08/2011 20:10 14.07 14.30 31/08/2011 12:50 13.69 13.70 01/09/2011 05:40 13.43 13.97 01/09/2011 22:30 13.78 13.90 02/09/2011 15:10 13.58 13.07 30/08/2011 20:20 14.07 15.30 31/08/2011 13:00 13.69 13.60 01/09/2011 05:50 13.39 14.03 01/09/2011 22:40 13.78 14.23 02/09/2011 15:20 13.58 13.23 30/08/2011 20:30 14.07 14.70 31/08/2011 13:10 13.71 13.70 01/09/2011 06:00 13.43 14.20 01/09/2011 22:50 13.77 14.07 02/09/2011 15:30 13.60 13.50 30/08/2011 20:40 14.07 14.43 31/08/2011 13:20 13.71 13.80 01/09/2011 06:10 13.43 13.93 01/09/2011 23:00 13.77 14.10 02/09/2011 15:40 13.61 13.30 30/08/2011 20:50 14.07 14.17 31/08/2011 13:30 13.72 13.80 01/09/2011 06:20 13.39 14.67 01/09/2011 23:10 13.75 14.20 02/09/2011 15:50 13.60 13.20 30/08/2011 21:00 14.07 14.30 31/08/2011 13:40 13.71 13.27 01/09/2011 06:30 13.37 14.10 01/09/2011 23:20 13.75 13.90 02/09/2011 16:00 13.63 12.90 30/08/2011 21:10 14.07 14.40 31/08/2011 13:50 13.71 13.43 01/09/2011 06:40 13.34 13.93 01/09/2011 23:30 13.75 14.20 02/09/2011 16:10 13.64 12.90 30/08/2011 21:20 14.07 14.10 31/08/2011 14:00 13.72 13.70 01/09/2011 06:50 13.40 14.17 01/09/2011 23:40 13.75 14.27 02/09/2011 16:20 13.64 12.80 30/08/2011 21:30 14.07 14.70 31/08/2011 14:10 13.72 13.73 01/09/2011 07:00 13.43 13.70 01/09/2011 23:50 13.72 13.83 02/09/2011 16:30 13.61 12.80 30/08/2011 21:40 14.08 14.63 31/08/2011 14:20 13.76 13.27 01/09/2011 07:10 13.43 13.90 02/09/2011 00:00 13.72 13.70 02/09/2011 16:40 13.65 13.17 30/08/2011 21:50 14.07 13.87 31/08/2011 14:30 13.75 13.30 01/09/2011 07:20 13.43 14.30 02/09/2011 00:10 13.71 13.73 02/09/2011 16:50 13.67 13.23 30/08/2011 22:00 14.08 13.80 31/08/2011 14:40 13.75 13.50 01/09/2011 07:30 13.37 14.50 02/09/2011 00:20 13.71 13.57 02/09/2011 17:00 13.67 13.40 30/08/2011 22:10 14.07 13.73 31/08/2011 14:50 13.74 13.90 01/09/2011 07:40 13.29 14.17 02/09/2011 00:30 13.61 13.90 02/09/2011 17:10 13.67 13.17 30/08/2011 22:20 14.07 13.47 31/08/2011 15:00 13.75 13.60 01/09/2011 07:50 13.39 14.23 02/09/2011 00:40 13.57 13.67 02/09/2011 17:20 13.70 13.23 30/08/2011 22:30 14.07 13.40 31/08/2011 15:10 13.75 13.70 01/09/2011 08:00 13.29 14.50 02/09/2011 00:50 13.51 14.13 02/09/2011 17:30 13.69 12.70 30/08/2011 22:40 14.06 13.50 31/08/2011 15:20 13.76 13.40 01/09/2011 08:10 13.41 14.27 02/09/2011 01:00 13.51 13.80 02/09/2011 17:40 13.68 13.07 30/08/2011 22:50 14.07 14.20 31/08/2011 15:30 13.78 13.40 01/09/2011 08:20 13.39 14.13 02/09/2011 01:10 13.49 14.07 02/09/2011 17:50 13.70 13.33 30/08/2011 23:00 14.07 14.00 31/08/2011 15:40 13.75 13.30 01/09/2011 08:30 13.39 14.10 02/09/2011 01:20 13.47 14.03 02/09/2011 18:00 13.71 13.10 30/08/2011 23:10 14.07 13.87 31/08/2011 15:50 13.78 13.50 01/09/2011 08:40 13.43 14.37 02/09/2011 01:30 13.47 13.80 02/09/2011 18:10 13.73 13.07 30/08/2011 23:20 14.07 13.73 31/08/2011 16:00 13.77 13.50 01/09/2011 08:50 13.35 14.43 02/09/2011 01:40 13.43 14.23 02/09/2011 18:20 13.74 12.63 30/08/2011 23:30 14.05 13.70 31/08/2011 16:10 13.79 13.37 01/09/2011 09:00 13.39 14.10 02/09/2011 01:50 13.48 13.97 02/09/2011 18:30 13.75 12.50 30/08/2011 23:40 14.07 13.60 31/08/2011 16:20 13.80 13.73 01/09/2011 09:10 13.37 14.33 02/09/2011 02:00 13.48 14.20 02/09/2011 18:40 13.73 12.83 30/08/2011 23:50 14.06 14.30 31/08/2011 16:30 13.78 13.40 01/09/2011 09:20 13.36 14.47 02/09/2011 02:10 13.44 14.10 02/09/2011 18:50 13.75 13.37 31/08/2011 00:00 14.05 14.00 31/08/2011 16:40 13.80 13.40 01/09/2011 09:30 13.45 14.40 02/09/2011 02:20 13.47 14.10 02/09/2011 19:00 13.76 13.50 31/08/2011 00:10 14.07 13.73 31/08/2011 16:50 13.79 13.50 01/09/2011 09:40 13.34 14.37 02/09/2011 02:30 13.47 14.10 02/09/2011 19:10 13.75 13.40 31/08/2011 00:20 14.05 13.97 31/08/2011 17:00 13.79 13.50 01/09/2011 09:50 13.43 14.33 02/09/2011 02:40 13.44 13.97 02/09/2011 19:20 13.75 13.50 31/08/2011 00:30 14.03 13.50 31/08/2011 17:10 13.79 13.47 01/09/2011 10:00 13.29 14.30 02/09/2011 02:50 13.45 13.73 02/09/2011 19:30 13.76 13.30 31/08/2011 00:40 14.03 13.60 31/08/2011 17:20 13.80 13.33 01/09/2011 10:10 13.29 14.00 02/09/2011 03:00 13.39 13.70 02/09/2011 19:40 13.78 12.90 31/08/2011 00:50 14.03 13.60 31/08/2011 17:30 13.79 13.60 01/09/2011 10:20 13.45 14.30 02/09/2011 03:10 13.40 14.07 02/09/2011 19:50 13.77 13.30 31/08/2011 01:00 14.03 13.60 31/08/2011 17:40 13.80 13.27 01/09/2011 10:30 13.44 14.50 02/09/2011 03:20 13.43 14.33 02/09/2011 20:00 13.76 13.10 31/08/2011 01:10 14.03 13.47 31/08/2011 17:50 13.82 13.73 01/09/2011 10:40 13.46 14.10 02/09/2011 03:30 13.40 14.10 02/09/2011 20:10 13.76 13.37 31/08/2011 01:20 14.00 13.43 31/08/2011 18:00 13.79 13.30 01/09/2011 10:50 13.47 14.30 02/09/2011 03:40 13.44 14.17 02/09/2011 20:20 13.79 13.33 31/08/2011 01:30 14.01 13.10 31/08/2011 18:10 13.79 13.33 01/09/2011 11:00 13.49 14.50 02/09/2011 03:50 13.40 14.53 02/09/2011 20:30 13.80 13.40 31/08/2011 01:40 14.01 13.03 31/08/2011 18:20 13.81 13.17 01/09/2011 11:10 13.51 14.27 02/09/2011 04:00 13.39 14.40 02/09/2011 20:40 13.79 12.90 31/08/2011 01:50 13.99 13.47 31/08/2011 18:30 13.83 13.00 01/09/2011 11:20 13.52 14.43 02/09/2011 04:10 13.35 14.37 02/09/2011 20:50 13.81 13.00 31/08/2011 02:00 13.97 13.10 31/08/2011 18:40 13.85 13.67 01/09/2011 11:30 13.51 14.00 02/09/2011 04:20 13.37 14.13 02/09/2011 21:00 13.79 13.30 31/08/2011 02:10 13.96 13.07 31/08/2011 18:50 13.81 13.53 01/09/2011 11:40 13.53 14.53 02/09/2011 04:30 13.35 14.10 02/09/2011 21:10 13.80 13.17 31/08/2011 02:20 13.95 13.33 31/08/2011 19:00 13.81 13.90 01/09/2011 11:50 13.54 14.27 02/09/2011 04:40 13.34 14.50 02/09/2011 21:20 13.80 13.43 31/08/2011 02:30 13.93 13.40 31/08/2011 19:10 13.81 13.70 01/09/2011 12:00 13.55 14.30 02/09/2011 04:50 13.30 13.90 02/09/2011 21:30 13.83 13.20 31/08/2011 02:40 13.95 13.03 31/08/2011 19:20 13.82 13.70 01/09/2011 12:10 13.55 14.40 02/09/2011 05:00 13.33 13.90 02/09/2011 21:40 13.83 13.13 31/08/2011 02:50 13.93 13.17 31/08/2011 19:30 13.85 13.60 01/09/2011 12:20 13.55 14.40 02/09/2011 05:10 13.30 13.93 02/09/2011 21:50 13.83 13.27 01/09/2011 02:50 13.93 13.17 31/08/2011 19:40 13.85 13.70 01/09/2011 12:30 13.58 14.00 03/09/2011 05:10 13.30 13.93 02/09/2011 22:00 13.85 13.30 132

Appendices

Date T H Date T H Date T H Date T H Date T H C° cm C° cm C° cm C° cm C° cm 02/09/2011 22:10 13.83 13.73 03/09/2011 15:00 13.99 12.70 04/09/2011 07:50 14.37 13.60 05/09/2011 00:30 15.10 16.10 05/09/2011 17:20 14.87 13.77 02/09/2011 22:20 13.85 13.47 03/09/2011 15:10 14.00 12.77 04/09/2011 08:00 14.38 13.50 05/09/2011 00:40 15.09 16.07 05/09/2011 17:30 14.87 13.50 02/09/2011 22:30 13.85 13.30 03/09/2011 15:20 14.01 12.83 04/09/2011 08:10 14.35 13.50 05/09/2011 00:50 15.13 16.13 05/09/2011 17:40 14.87 13.70 02/09/2011 22:40 13.88 13.23 03/09/2011 15:30 14.03 12.70 04/09/2011 08:20 14.38 13.70 05/09/2011 01:00 15.10 16.20 05/09/2011 17:50 14.87 13.70 02/09/2011 22:50 13.87 13.67 03/09/2011 15:40 14.05 12.70 04/09/2011 08:30 14.37 13.90 05/09/2011 01:10 15.10 16.17 05/09/2011 18:00 14.87 13.70 02/09/2011 23:00 13.86 13.50 03/09/2011 15:50 14.05 12.90 04/09/2011 08:40 14.37 13.80 05/09/2011 01:20 15.10 15.83 05/09/2011 18:10 14.87 13.00 02/09/2011 23:10 13.88 13.67 03/09/2011 16:00 14.07 12.60 04/09/2011 08:50 14.37 13.70 05/09/2011 01:30 15.11 15.70 05/09/2011 18:20 14.85 12.90 02/09/2011 23:20 13.88 13.73 03/09/2011 16:10 14.07 12.60 04/09/2011 09:00 14.37 13.80 05/09/2011 01:40 15.12 16.10 05/09/2011 18:30 14.85 13.30 02/09/2011 23:30 13.88 13.70 03/09/2011 16:20 14.07 12.80 04/09/2011 09:10 14.36 13.63 05/09/2011 01:50 15.11 16.20 05/09/2011 18:40 14.85 13.03 02/09/2011 23:40 13.89 13.70 03/09/2011 16:30 14.08 12.40 04/09/2011 09:20 14.38 13.47 05/09/2011 02:00 15.11 16.10 05/09/2011 18:50 14.85 12.67 02/09/2011 23:50 13.89 13.70 03/09/2011 16:40 14.09 12.40 04/09/2011 09:30 14.36 13.90 05/09/2011 02:10 15.13 15.70 05/09/2011 19:00 14.87 13.10 03/09/2011 00:00 13.88 13.70 03/09/2011 16:50 14.11 12.30 04/09/2011 09:40 14.37 14.07 05/09/2011 02:20 15.10 15.70 05/09/2011 19:10 14.85 12.93 03/09/2011 00:10 13.89 13.30 03/09/2011 17:00 14.11 12.40 04/09/2011 09:50 14.37 13.93 05/09/2011 02:30 15.11 16.00 05/09/2011 19:20 14.85 13.37 03/09/2011 00:20 13.90 13.20 03/09/2011 17:10 14.14 12.43 04/09/2011 10:00 14.37 13.70 05/09/2011 02:40 15.13 15.90 05/09/2011 19:30 14.85 13.20 03/09/2011 00:30 13.88 13.10 03/09/2011 17:20 14.13 12.27 04/09/2011 10:10 14.37 13.83 05/09/2011 02:50 15.12 15.50 05/09/2011 19:40 14.85 13.30 03/09/2011 00:40 13.89 13.47 03/09/2011 17:30 14.14 12.40 04/09/2011 10:20 14.35 13.37 05/09/2011 03:00 15.11 15.70 05/09/2011 19:50 14.85 13.40 03/09/2011 00:50 13.91 13.93 03/09/2011 17:40 14.15 12.50 04/09/2011 10:30 14.37 13.60 05/09/2011 03:10 15.10 15.30 05/09/2011 20:00 14.85 13.10 03/09/2011 01:00 13.91 13.60 03/09/2011 17:50 14.16 12.10 04/09/2011 10:40 14.38 13.60 05/09/2011 03:20 15.10 15.60 05/09/2011 20:10 14.84 13.17 03/09/2011 01:10 13.91 13.70 03/09/2011 18:00 14.17 12.30 04/09/2011 10:50 14.37 13.70 05/09/2011 03:30 15.09 15.40 05/09/2011 20:20 14.84 12.83 03/09/2011 01:20 13.91 13.60 03/09/2011 18:10 14.17 12.47 04/09/2011 11:00 14.37 13.60 05/09/2011 03:40 15.10 15.20 05/09/2011 20:30 14.84 12.90 03/09/2011 01:30 13.90 14.10 03/09/2011 18:20 14.17 12.23 04/09/2011 11:10 14.36 13.63 05/09/2011 03:50 15.09 15.50 05/09/2011 20:40 14.81 12.83 03/09/2011 01:40 13.92 13.97 03/09/2011 18:30 14.19 12.80 04/09/2011 11:20 14.38 13.87 05/09/2011 04:00 15.09 15.70 05/09/2011 20:50 14.84 13.07 03/09/2011 01:50 13.91 13.83 03/09/2011 18:40 14.20 12.80 04/09/2011 11:30 14.35 13.90 05/09/2011 04:10 15.07 15.53 05/09/2011 21:00 14.82 13.00 03/09/2011 02:00 13.89 14.20 03/09/2011 18:50 14.20 12.50 04/09/2011 11:40 14.35 13.67 05/09/2011 04:20 15.10 15.37 05/09/2011 21:10 14.85 12.57 03/09/2011 02:10 13.90 14.20 03/09/2011 19:00 14.20 12.30 04/09/2011 11:50 14.37 14.03 05/09/2011 04:30 15.08 15.00 05/09/2011 21:20 14.82 12.93 03/09/2011 02:20 13.91 14.10 03/09/2011 19:10 14.23 12.10 04/09/2011 12:00 14.38 14.10 05/09/2011 04:40 15.08 15.10 05/09/2011 21:30 14.82 12.80 03/09/2011 02:30 13.92 13.80 03/09/2011 19:20 14.21 12.70 04/09/2011 12:10 14.36 14.07 05/09/2011 04:50 15.08 15.10 05/09/2011 21:40 14.81 13.17 03/09/2011 02:40 13.93 13.83 03/09/2011 19:30 14.23 12.70 04/09/2011 12:20 14.38 13.33 05/09/2011 05:00 15.07 15.00 05/09/2011 21:50 14.81 13.33 03/09/2011 02:50 13.93 14.17 03/09/2011 19:40 14.24 12.60 04/09/2011 12:30 14.39 13.60 05/09/2011 05:10 15.07 15.17 05/09/2011 22:00 14.79 12.90 03/09/2011 03:00 13.92 13.90 03/09/2011 19:50 14.21 12.60 04/09/2011 12:40 14.38 13.33 05/09/2011 05:20 15.07 15.13 05/09/2011 22:10 14.76 13.00 03/09/2011 03:10 13.93 13.83 03/09/2011 20:00 14.24 13.00 04/09/2011 12:50 14.39 13.67 05/09/2011 05:30 15.07 15.00 05/09/2011 22:20 14.79 13.00 03/09/2011 03:20 13.93 13.57 03/09/2011 20:10 14.26 12.73 04/09/2011 13:00 14.38 13.30 05/09/2011 05:40 15.08 14.57 05/09/2011 22:30 14.75 12.80 03/09/2011 03:30 13.93 14.00 03/09/2011 20:20 14.25 12.97 04/09/2011 13:10 14.37 13.47 05/09/2011 05:50 15.07 15.13 05/09/2011 22:40 14.74 12.93 03/09/2011 03:40 13.93 13.87 03/09/2011 20:30 14.25 12.90 04/09/2011 13:20 14.38 13.03 05/09/2011 06:00 15.07 14.70 05/09/2011 22:50 14.73 13.17 03/09/2011 03:50 13.93 13.93 03/09/2011 20:40 14.27 12.87 04/09/2011 13:30 14.42 12.20 05/09/2011 06:10 15.09 15.10 05/09/2011 23:00 14.72 13.00 03/09/2011 04:00 13.93 14.00 03/09/2011 20:50 14.29 12.63 04/09/2011 13:40 14.42 13.47 05/09/2011 06:20 15.06 15.00 05/09/2011 23:10 14.70 13.23 03/09/2011 04:10 13.93 13.97 03/09/2011 21:00 14.27 12.90 04/09/2011 13:50 14.42 13.43 05/09/2011 06:30 15.07 15.30 05/09/2011 23:20 14.71 13.57 03/09/2011 04:20 13.93 14.13 03/09/2011 21:10 14.29 12.97 04/09/2011 14:00 14.45 19.60 05/09/2011 06:40 15.05 14.97 05/09/2011 23:30 14.70 13.60 03/09/2011 04:30 13.93 13.90 03/09/2011 21:20 14.31 13.03 04/09/2011 14:10 14.45 29.73 05/09/2011 06:50 15.03 15.03 05/09/2011 23:40 14.69 13.83 03/09/2011 04:40 13.93 13.87 03/09/2011 21:30 14.31 12.80 04/09/2011 14:20 14.49 44.07 05/09/2011 07:00 15.06 14.70 05/09/2011 23:50 14.69 13.77 03/09/2011 04:50 13.93 13.93 03/09/2011 21:40 14.31 13.23 04/09/2011 14:30 14.61 48.10 05/09/2011 07:10 15.05 14.80 06/09/2011 00:00 14.69 13.80 03/09/2011 05:00 13.95 14.30 03/09/2011 21:50 14.31 13.07 04/09/2011 14:40 14.94 43.37 05/09/2011 07:20 15.03 14.50 06/09/2011 00:10 14.67 13.67 03/09/2011 05:10 13.92 13.60 03/09/2011 22:00 14.29 13.10 04/09/2011 14:50 15.33 31.63 05/09/2011 07:30 15.05 14.70 06/09/2011 00:20 14.65 13.43 03/09/2011 05:20 13.93 13.90 03/09/2011 22:10 14.31 13.43 04/09/2011 15:00 15.29 26.10 05/09/2011 07:40 15.03 14.77 06/09/2011 00:30 14.65 13.30 03/09/2011 05:30 13.93 13.90 03/09/2011 22:20 14.31 13.27 04/09/2011 15:10 15.17 22.60 05/09/2011 07:50 15.03 15.13 06/09/2011 00:40 14.59 13.57 03/09/2011 05:40 13.93 13.63 03/09/2011 22:30 14.32 13.20 04/09/2011 15:20 15.06 20.90 05/09/2011 08:00 15.01 14.90 06/09/2011 00:50 14.53 13.33 03/09/2011 05:50 13.93 13.97 03/09/2011 22:40 14.32 13.57 04/09/2011 15:30 14.99 19.70 05/09/2011 08:10 15.03 14.90 06/09/2011 01:00 14.51 13.50 03/09/2011 06:00 13.93 13.80 03/09/2011 22:50 14.35 12.83 04/09/2011 15:40 14.93 18.57 05/09/2011 08:20 15.01 15.00 06/09/2011 01:10 14.49 13.13 03/09/2011 06:10 13.93 13.80 03/09/2011 23:00 14.35 13.10 04/09/2011 15:50 14.92 17.63 05/09/2011 08:30 14.99 15.10 06/09/2011 01:20 14.47 12.97 03/09/2011 06:20 13.91 13.80 03/09/2011 23:10 14.34 13.33 04/09/2011 16:00 14.89 17.30 05/09/2011 08:40 14.99 15.00 06/09/2011 01:30 14.46 13.00 03/09/2011 06:30 13.92 13.70 03/09/2011 23:20 14.36 13.17 04/09/2011 16:10 14.90 17.13 05/09/2011 08:50 14.99 15.10 06/09/2011 01:40 14.48 13.00 03/09/2011 06:40 13.93 14.17 03/09/2011 23:30 14.35 13.20 04/09/2011 16:20 14.90 16.77 05/09/2011 09:00 14.99 14.90 06/09/2011 01:50 14.45 13.30 03/09/2011 06:50 13.91 13.83 03/09/2011 23:40 14.34 13.00 04/09/2011 16:30 14.90 16.60 05/09/2011 09:10 14.98 15.03 06/09/2011 02:00 14.45 13.30 03/09/2011 07:00 13.91 13.90 03/09/2011 23:50 14.37 13.30 04/09/2011 16:40 14.91 16.43 05/09/2011 09:20 14.97 15.07 06/09/2011 02:10 14.41 13.37 03/09/2011 07:10 13.93 13.90 04/09/2011 00:00 14.35 13.10 04/09/2011 16:50 14.90 16.27 05/09/2011 09:30 14.95 15.00 06/09/2011 02:20 14.41 13.13 03/09/2011 07:20 13.92 14.00 04/09/2011 00:10 14.36 12.97 04/09/2011 17:00 14.91 15.80 05/09/2011 09:40 14.95 14.93 06/09/2011 02:30 14.35 13.40 03/09/2011 07:30 13.92 13.90 04/09/2011 00:20 14.35 13.43 04/09/2011 17:10 14.93 15.93 05/09/2011 09:50 14.92 14.67 06/09/2011 02:40 14.35 13.73 03/09/2011 07:40 13.91 14.00 04/09/2011 00:30 14.35 13.20 04/09/2011 17:20 14.93 15.87 05/09/2011 10:00 14.92 14.60 06/09/2011 02:50 14.39 13.27 03/09/2011 07:50 13.90 14.00 04/09/2011 00:40 14.35 13.50 04/09/2011 17:30 14.93 15.90 05/09/2011 10:10 14.93 14.90 06/09/2011 03:00 14.34 13.20 03/09/2011 08:00 13.91 13.90 04/09/2011 00:50 14.36 13.80 04/09/2011 17:40 14.94 15.83 05/09/2011 10:20 14.92 14.90 06/09/2011 03:10 14.35 13.70 03/09/2011 08:10 13.89 13.87 04/09/2011 01:00 14.36 13.90 04/09/2011 17:50 14.94 15.77 05/09/2011 10:30 14.91 14.80 06/09/2011 03:20 14.32 13.40 03/09/2011 08:20 13.91 13.93 04/09/2011 01:10 14.35 13.57 04/09/2011 18:00 14.98 16.00 05/09/2011 10:40 14.92 14.97 06/09/2011 03:30 14.33 13.00 03/09/2011 08:30 13.93 13.80 04/09/2011 01:20 14.34 13.63 04/09/2011 18:10 14.97 15.87 05/09/2011 10:50 14.88 15.23 06/09/2011 03:40 14.34 13.67 03/09/2011 08:40 13.92 13.53 04/09/2011 01:30 14.37 13.50 04/09/2011 18:20 14.97 16.13 05/09/2011 11:00 14.91 15.10 06/09/2011 03:50 14.33 13.43 03/09/2011 08:50 13.90 14.37 04/09/2011 01:40 14.36 13.30 04/09/2011 18:30 15.01 15.60 05/09/2011 11:10 14.91 14.60 06/09/2011 04:00 14.33 14.00 03/09/2011 09:00 13.90 14.50 04/09/2011 01:50 14.37 13.60 04/09/2011 18:40 15.01 15.63 05/09/2011 11:20 14.91 14.90 06/09/2011 04:10 14.31 13.90 03/09/2011 09:10 13.92 14.37 04/09/2011 02:00 14.35 13.40 04/09/2011 18:50 15.01 15.47 05/09/2011 11:30 14.91 14.90 06/09/2011 04:20 14.33 13.60 03/09/2011 09:20 13.89 13.93 04/09/2011 02:10 14.37 13.73 04/09/2011 19:00 15.00 15.60 05/09/2011 11:40 14.90 14.77 06/09/2011 04:30 14.32 13.60 03/09/2011 09:30 13.89 13.90 04/09/2011 02:20 14.38 13.77 04/09/2011 19:10 15.07 21.90 05/09/2011 11:50 14.88 15.23 06/09/2011 04:40 14.29 13.43 03/09/2011 09:40 13.91 14.20 04/09/2011 02:30 14.37 13.60 04/09/2011 19:20 15.09 32.90 05/09/2011 12:00 14.91 15.10 06/09/2011 04:50 14.29 13.47 03/09/2011 09:50 13.92 13.80 04/09/2011 02:40 14.38 13.53 04/09/2011 19:30 15.20 31.10 05/09/2011 12:10 14.91 14.77 06/09/2011 05:00 14.27 13.30 03/09/2011 10:00 13.91 13.80 04/09/2011 02:50 14.37 13.27 04/09/2011 19:40 15.27 35.07 05/09/2011 12:20 14.89 15.03 06/09/2011 05:10 14.28 13.43 03/09/2011 10:10 13.91 14.13 04/09/2011 03:00 14.38 13.60 04/09/2011 19:50 15.28 28.63 05/09/2011 12:30 14.90 15.20 06/09/2011 05:20 14.31 13.87 03/09/2011 10:20 13.91 14.17 04/09/2011 03:10 14.35 13.53 04/09/2011 20:00 15.24 24.80 05/09/2011 12:40 14.89 15.20 06/09/2011 05:30 14.29 13.90 03/09/2011 10:30 13.90 13.70 04/09/2011 03:20 14.37 13.37 04/09/2011 20:10 15.18 22.27 05/09/2011 12:50 14.89 15.00 06/09/2011 05:40 14.28 13.97 03/09/2011 10:40 13.90 13.40 04/09/2011 03:30 14.36 13.40 04/09/2011 20:20 15.13 20.43 05/09/2011 13:00 14.88 14.80 06/09/2011 05:50 14.29 13.73 03/09/2011 10:50 13.91 13.40 04/09/2011 03:40 14.35 13.77 04/09/2011 20:30 15.07 19.30 05/09/2011 13:10 14.88 14.63 06/09/2011 06:00 14.27 13.80 03/09/2011 11:00 13.91 13.60 04/09/2011 03:50 14.38 13.73 04/09/2011 20:40 15.09 18.30 05/09/2011 13:20 14.87 14.57 06/09/2011 06:10 14.27 13.90 03/09/2011 11:10 13.92 13.33 04/09/2011 04:00 14.37 13.60 04/09/2011 20:50 15.05 17.60 05/09/2011 13:30 14.88 14.40 06/09/2011 06:20 14.27 13.60 03/09/2011 11:20 13.91 13.47 04/09/2011 04:10 14.38 13.53 04/09/2011 21:00 15.05 17.10 05/09/2011 13:40 14.90 14.57 06/09/2011 06:30 14.25 13.80 03/09/2011 11:30 13.90 13.80 04/09/2011 04:20 14.37 13.47 04/09/2011 21:10 15.05 17.07 05/09/2011 13:50 14.90 14.53 06/09/2011 06:40 14.25 13.77 03/09/2011 11:40 13.91 13.17 04/09/2011 04:30 14.38 13.70 04/09/2011 21:20 15.05 17.53 05/09/2011 14:00 14.90 14.90 06/09/2011 06:50 14.25 13.83 03/09/2011 11:50 13.92 13.53 04/09/2011 04:40 14.36 13.43 04/09/2011 21:30 15.07 17.10 05/09/2011 14:10 14.87 14.77 06/09/2011 07:00 14.23 13.90 03/09/2011 12:00 13.93 13.10 04/09/2011 04:50 14.35 13.47 04/09/2011 21:40 15.07 16.87 05/09/2011 14:20 14.87 14.33 06/09/2011 07:10 14.23 13.77 03/09/2011 12:10 13.93 13.47 04/09/2011 05:00 14.38 13.40 04/09/2011 21:50 15.06 16.83 05/09/2011 14:30 14.87 14.50 06/09/2011 07:20 14.23 13.53 03/09/2011 12:20 13.95 13.03 04/09/2011 05:10 14.38 13.47 04/09/2011 22:00 15.05 16.40 05/09/2011 14:40 14.88 14.17 06/09/2011 07:30 14.19 13.50 03/09/2011 12:30 13.93 12.60 04/09/2011 05:20 14.37 13.63 04/09/2011 22:10 15.08 16.43 05/09/2011 14:50 14.87 14.13 06/09/2011 07:40 14.19 13.70 03/09/2011 12:40 13.93 12.87 04/09/2011 05:30 14.36 13.60 04/09/2011 22:20 15.06 16.57 05/09/2011 15:00 14.87 14.20 06/09/2011 07:50 14.19 14.10 03/09/2011 12:50 13.95 12.73 04/09/2011 05:40 14.37 13.47 04/09/2011 22:30 15.05 16.20 05/09/2011 15:10 14.84 14.10 06/09/2011 08:00 14.18 13.80 03/09/2011 13:00 13.93 13.10 04/09/2011 05:50 14.38 13.73 04/09/2011 22:40 15.08 16.37 05/09/2011 15:20 14.87 14.00 06/09/2011 08:10 14.17 13.50 03/09/2011 13:10 13.95 13.07 04/09/2011 06:00 14.37 13.80 04/09/2011 22:50 15.07 16.23 05/09/2011 15:30 14.87 14.10 06/09/2011 08:20 14.19 13.90 03/09/2011 13:20 13.95 13.23 04/09/2011 06:10 14.37 13.57 04/09/2011 23:00 15.09 15.80 05/09/2011 15:40 14.87 14.07 06/09/2011 08:30 14.18 13.80 03/09/2011 13:30 13.95 13.00 04/09/2011 06:20 14.37 13.33 04/09/2011 23:10 15.09 16.20 05/09/2011 15:50 14.87 14.33 06/09/2011 08:40 14.18 13.70 03/09/2011 13:40 13.95 12.93 04/09/2011 06:30 14.37 13.40 04/09/2011 23:20 15.09 16.50 05/09/2011 16:00 14.85 14.00 06/09/2011 08:50 14.18 13.80 03/09/2011 13:50 13.95 12.77 04/09/2011 06:40 14.37 13.40 04/09/2011 23:30 15.09 16.30 05/09/2011 16:10 14.84 13.93 06/09/2011 09:00 14.17 14.30 03/09/2011 14:00 13.95 12.60 04/09/2011 06:50 14.36 13.50 04/09/2011 23:40 15.09 16.17 05/09/2011 16:20 14.83 13.57 06/09/2011 09:10 14.17 13.93 03/09/2011 14:10 13.96 12.50 04/09/2011 07:00 14.39 13.40 04/09/2011 23:50 15.11 15.93 05/09/2011 16:30 14.87 13.50 06/09/2011 09:20 14.15 13.97 03/09/2011 14:20 13.98 12.60 04/09/2011 07:10 14.37 13.83 05/09/2011 00:00 15.08 15.90 05/09/2011 16:40 14.85 13.43 06/09/2011 09:30 14.16 14.20 03/09/2011 14:30 13.99 12.70 04/09/2011 07:20 14.36 13.77 05/09/2011 00:10 15.09 15.90 05/09/2011 16:50 14.87 13.97 06/09/2011 09:40 14.17 13.97 03/09/2011 14:40 13.99 12.77 04/09/2011 07:30 14.36 13.80 05/09/2011 00:20 15.13 15.80 05/09/2011 17:00 14.87 13.70 06/09/2011 09:50 14.17 14.33 03/09/2011 14:50 13.99 12.63 04/09/2011 07:40 14.37 13.80 06/09/2011 00:20 15.13 15.80 05/09/2011 17:10 14.85 13.43 06/09/2011 10:00 14.18 14.10 133

Appendices

Table App. II. 4: High resolution record of water head, electrical conductivity and temperature (at 10 min intervals) of the Lottenbach of the period 10.10.2011-20.10.2011.

Date T EC H Date T EC H Date T EC H Date T EC H Date T EC H

C° ms/cm cm C° ms/cm cm C° ms/cm cm C° ms/cm cm C° ms/cm cm 111010 00:00:00 17.70 12.27 111010 16:40:00 15.40 12.45 111011 09:20:00 16.33 12.69 111012 02:00:00 21.50 12.88 111012 18:40:00 32.80 0.29 12.88 111010 00:10:00 17.33 12.27 111010 16:50:00 15.40 12.45 111011 09:30:00 16.50 12.69 111012 02:10:00 21.70 12.91 111012 18:50:00 33.20 0.27 12.89 111010 00:20:00 17.47 12.27 111010 17:00:00 15.60 12.45 111011 09:40:00 16.90 12.70 111012 02:20:00 22.50 12.89 111012 19:00:00 33.20 0.26 12.89 111010 00:30:00 17.00 12.25 111010 17:10:00 14.97 12.47 111011 09:50:00 16.90 12.69 111012 02:30:00 22.90 12.89 111012 19:10:00 33.07 0.26 12.89 111010 00:40:00 17.50 12.27 111010 17:20:00 15.03 12.45 111011 10:00:00 17.40 12.70 111012 02:40:00 23.33 12.90 111012 19:20:00 32.73 0.26 12.89 111010 00:50:00 17.20 12.25 111010 17:30:00 15.20 12.44 111011 10:10:00 17.00 12.70 111012 02:50:00 23.47 12.89 111012 19:30:00 33.00 0.23 12.89 111010 01:00:00 17.40 12.25 111010 17:40:00 15.43 12.48 111011 10:20:00 16.60 12.69 111012 03:00:00 23.10 12.91 111012 19:40:00 35.73 0.21 12.89 111010 01:10:00 17.30 12.25 111010 17:50:00 15.07 12.47 111011 10:30:00 16.60 12.69 111012 03:10:00 23.03 12.91 111012 19:50:00 36.47 0.21 12.89 111010 01:20:00 17.50 12.25 111010 18:00:00 15.20 12.47 111011 10:40:00 17.07 12.69 111012 03:20:00 23.07 12.91 111012 20:00:00 35.50 0.22 12.90 111010 01:30:00 17.70 12.25 111010 18:10:00 15.33 12.47 111011 10:50:00 17.43 12.69 111012 03:30:00 23.10 12.91 111012 20:10:00 34.43 0.23 12.90 111010 01:40:00 17.67 12.27 111010 18:20:00 15.37 12.45 111011 11:00:00 17.60 12.69 111012 03:40:00 23.30 12.90 111012 20:20:00 33.07 0.23 12.90 111010 01:50:00 17.63 12.28 111010 18:30:00 15.50 12.48 111011 11:10:00 17.10 12.69 111012 03:50:00 23.60 12.91 111012 20:30:00 32.40 0.22 12.88 111010 02:00:00 17.40 12.27 111010 18:40:00 15.20 12.50 111011 11:20:00 17.50 12.70 111012 04:00:00 23.80 12.91 111012 20:40:00 33.83 0.21 12.90 111010 02:10:00 17.40 12.27 111010 18:50:00 15.70 12.47 111011 11:30:00 17.20 12.72 111012 04:10:00 23.63 12.91 111012 20:50:00 35.97 0.21 12.88 111010 02:20:00 17.60 12.24 111010 19:00:00 15.40 12.48 111011 11:40:00 16.87 12.70 111012 04:20:00 23.37 12.91 111012 21:00:00 37.10 0.21 12.90 111010 02:30:00 17.40 12.25 111010 19:10:00 15.00 12.49 111011 11:50:00 16.73 12.71 111012 04:30:00 23.30 12.91 111012 21:10:00 35.90 0.23 12.91 111010 02:40:00 17.57 12.28 111010 19:20:00 14.90 12.49 111011 12:00:00 16.80 12.72 111012 04:40:00 22.90 12.91 111012 21:20:00 34.20 0.23 12.91 111010 02:50:00 17.03 12.28 111010 19:30:00 15.30 12.49 111011 12:10:00 16.67 12.73 111012 04:50:00 22.90 12.90 111012 21:30:00 32.40 0.26 12.91 111010 03:00:00 17.00 12.27 111010 19:40:00 15.37 12.51 111011 12:20:00 16.53 12.72 111012 05:00:00 22.60 12.90 111012 21:40:00 30.80 0.26 12.88 111010 03:10:00 16.87 12.27 111010 19:50:00 15.23 12.51 111011 12:30:00 16.60 12.72 111012 05:10:00 22.43 12.89 111012 21:50:00 29.90 0.29 12.90 111010 03:20:00 16.93 12.28 111010 20:00:00 15.10 12.51 111011 12:40:00 16.60 12.70 111012 05:20:00 22.77 12.91 111012 22:00:00 28.50 0.31 12.89 111010 03:30:00 17.10 12.27 111010 20:10:00 14.73 12.51 111011 12:50:00 17.00 12.72 111012 05:30:00 23.70 12.91 111012 22:10:00 27.67 0.35 12.89 111010 03:40:00 17.17 12.27 111010 20:20:00 14.97 12.51 111011 13:00:00 16.80 12.73 111012 05:40:00 23.93 12.93 111012 22:20:00 26.83 0.38 12.88 111010 03:50:00 16.83 12.27 111010 20:30:00 14.70 12.52 111011 13:10:00 16.87 12.73 111012 05:50:00 23.77 12.87 111012 22:30:00 26.40 0.42 12.88 111010 04:00:00 17.70 12.28 111010 20:40:00 15.23 12.51 111011 13:20:00 16.73 12.72 111012 06:00:00 24.20 12.90 111012 22:40:00 25.67 0.42 12.89 111010 04:10:00 17.33 12.28 111010 20:50:00 14.87 12.53 111011 13:30:00 17.10 12.71 111012 06:10:00 24.60 12.91 111012 22:50:00 25.13 0.45 12.89 111010 04:20:00 17.37 12.29 111010 21:00:00 15.20 12.53 111011 13:40:00 16.77 12.74 111012 06:20:00 25.00 12.89 111012 23:00:00 25.10 0.44 12.89 111010 04:30:00 17.10 12.31 111010 21:10:00 14.83 12.52 111011 13:50:00 16.93 12.74 111012 06:30:00 25.40 12.90 111012 23:10:00 24.43 0.45 12.89 111010 04:40:00 17.37 12.31 111010 21:20:00 15.17 12.51 111011 14:00:00 16.90 12.73 111012 06:40:00 25.27 12.89 111012 23:20:00 24.37 0.46 12.87 111010 04:50:00 17.13 12.33 111010 21:30:00 15.20 12.55 111011 14:10:00 16.27 12.73 111012 06:50:00 26.73 12.90 111012 23:30:00 24.50 0.46 12.87 111010 05:00:00 17.30 12.31 111010 21:40:00 15.00 12.55 111011 14:20:00 17.43 12.73 111012 07:00:00 27.00 12.91 111012 23:40:00 24.43 0.46 12.88 111010 05:10:00 17.57 12.31 111010 21:50:00 15.00 12.51 111011 14:30:00 17.50 12.73 111012 07:10:00 27.27 12.93 111012 23:50:00 24.07 0.47 12.87 111010 05:20:00 17.23 12.31 111010 22:00:00 14.90 12.55 111011 14:40:00 17.53 12.75 111012 07:20:00 26.53 12.90 111013 00:00:00 24.00 0.48 12.87 111010 05:30:00 17.50 12.31 111010 22:10:00 14.93 12.55 111011 14:50:00 17.67 12.73 111012 07:30:00 27.30 12.91 111013 00:10:00 23.53 0.48 12.87 111010 05:40:00 17.97 12.33 111010 22:20:00 14.67 12.58 111011 15:00:00 17.60 12.75 111012 07:40:00 28.33 12.89 111013 00:20:00 23.77 0.49 12.87 111010 05:50:00 17.93 12.31 111010 22:30:00 14.40 12.57 111011 15:10:00 18.17 12.75 111012 07:50:00 28.67 12.91 111013 00:30:00 23.30 0.48 12.85 111010 06:00:00 17.80 12.32 111010 22:40:00 14.77 12.53 111011 15:20:00 17.53 12.75 111012 08:00:00 30.00 12.89 111013 00:40:00 23.63 0.50 12.86 111010 06:10:00 17.60 12.34 111010 22:50:00 14.73 12.55 111011 15:30:00 17.90 12.73 111012 08:10:00 31.97 12.91 111013 00:50:00 23.17 0.49 12.85 111010 06:20:00 17.70 12.35 111010 23:00:00 14.50 12.58 111011 15:40:00 17.73 12.73 111012 08:20:00 33.63 12.90 111013 01:00:00 23.10 0.49 12.86 111010 06:30:00 17.60 12.35 111010 23:10:00 14.73 12.57 111011 15:50:00 17.97 12.73 111012 08:30:00 35.10 12.90 111013 01:10:00 22.60 0.50 12.84 111010 06:40:00 17.80 12.33 111010 23:20:00 14.37 12.59 111011 16:00:00 18.70 12.73 111012 08:40:00 36.10 12.90 111013 01:20:00 22.80 0.49 12.86 111010 06:50:00 17.40 12.35 111010 23:30:00 14.40 12.57 111011 16:10:00 17.90 12.73 111012 08:50:00 38.50 12.89 111013 01:30:00 22.50 0.50 12.83 111010 07:00:00 17.60 12.34 111010 23:40:00 14.53 12.57 111011 16:20:00 17.70 12.76 111012 09:00:00 40.70 12.89 111013 01:40:00 22.20 0.49 12.85 111010 07:10:00 17.60 12.34 111010 23:50:00 14.47 12.59 111011 16:30:00 17.80 12.77 111012 09:10:00 41.70 12.91 111013 01:50:00 22.10 0.50 12.83 111010 07:20:00 17.40 12.35 111011 00:00:00 14.40 12.57 111011 16:40:00 17.83 12.73 111012 09:20:00 41.60 12.93 111013 02:00:00 22.30 0.50 12.83 111010 07:30:00 17.30 12.34 111011 00:10:00 14.43 12.59 111011 16:50:00 18.17 12.74 111012 09:30:00 40.20 12.93 111013 02:10:00 22.10 0.52 12.83 111010 07:40:00 17.23 12.34 111011 00:20:00 14.67 12.59 111011 17:00:00 18.30 12.75 111012 09:40:00 39.80 12.93 111013 02:20:00 22.10 0.50 12.83 111010 07:50:00 17.27 12.35 111011 00:30:00 14.50 12.59 111011 17:10:00 18.13 12.76 111012 09:50:00 40.30 12.91 111013 02:30:00 22.20 0.50 12.81 111010 08:00:00 17.10 12.33 111011 00:40:00 14.57 12.59 111011 17:20:00 18.17 12.77 111012 10:00:00 40.30 12.91 111013 02:40:00 21.80 0.50 12.81 111010 08:10:00 17.37 12.37 111011 00:50:00 14.43 12.59 111011 17:30:00 17.70 12.77 111012 10:10:00 40.90 12.91 111013 02:50:00 22.00 0.52 12.81 111010 08:20:00 17.43 12.35 111011 01:00:00 14.60 12.60 111011 17:40:00 18.10 12.77 111012 10:20:00 42.60 12.91 111013 03:00:00 21.70 0.52 12.80 111010 08:30:00 17.30 12.37 111011 01:10:00 14.87 12.59 111011 17:50:00 18.10 12.77 111012 10:30:00 43.00 12.91 111013 03:10:00 22.03 0.52 12.79 111010 08:40:00 17.43 12.35 111011 01:20:00 15.03 12.61 111011 18:00:00 18.30 12.77 111012 10:40:00 42.93 12.91 111013 03:20:00 21.57 0.52 12.79 111010 08:50:00 17.17 12.37 111011 01:30:00 14.20 12.62 111011 18:10:00 18.43 12.78 111012 10:50:00 42.77 12.90 111013 03:30:00 21.50 0.52 12.78 111010 09:00:00 17.00 12.37 111011 01:40:00 14.37 12.59 111011 18:20:00 18.97 12.77 111012 11:00:00 42.70 12.91 111013 03:40:00 21.70 0.54 12.77 111010 09:10:00 16.67 12.35 111011 01:50:00 14.33 12.60 111011 18:30:00 19.20 12.77 111012 11:10:00 41.00 12.91 111013 03:50:00 21.50 0.54 12.80 111010 09:20:00 16.93 12.37 111011 02:00:00 14.50 12.62 111011 18:40:00 19.40 12.78 111012 11:20:00 38.00 12.91 111013 04:00:00 21.90 0.53 12.77 111010 09:30:00 17.20 12.37 111011 02:10:00 14.63 12.62 111011 18:50:00 19.40 12.77 111012 11:30:00 34.70 12.91 111013 04:10:00 21.63 0.54 12.76 111010 09:40:00 17.30 12.38 111011 02:20:00 14.57 12.61 111011 19:00:00 20.10 12.80 111012 11:40:00 31.90 12.90 111013 04:20:00 21.27 0.54 12.77 111010 09:50:00 17.00 12.39 111011 02:30:00 14.80 12.63 111011 19:10:00 20.10 12.80 111012 11:50:00 30.40 12.89 111013 04:30:00 21.10 0.54 12.77 111010 10:00:00 17.00 12.38 111011 02:40:00 14.73 12.63 111011 19:20:00 19.90 12.81 111012 12:00:00 28.80 0.36 12.89 111013 04:40:00 21.50 0.55 12.76 111010 10:10:00 16.67 12.37 111011 02:50:00 14.97 12.65 111011 19:30:00 19.90 12.78 111012 12:10:00 27.33 0.36 12.89 111013 04:50:00 21.60 0.55 12.75 111010 10:20:00 16.83 12.39 111011 03:00:00 15.00 12.62 111011 19:40:00 20.17 12.80 111012 12:20:00 26.87 0.41 12.89 111013 05:00:00 21.50 0.55 12.77 111010 10:30:00 16.90 12.37 111011 03:10:00 15.00 12.62 111011 19:50:00 20.43 12.80 111012 12:30:00 26.50 0.39 12.89 111013 05:10:00 21.60 0.55 12.73 111010 10:40:00 16.77 12.40 111011 03:20:00 15.10 12.62 111011 20:00:00 20.40 12.83 111012 12:40:00 26.13 0.40 12.88 111013 05:20:00 21.40 0.54 12.73 111010 10:50:00 16.93 12.38 111011 03:30:00 14.70 12.65 111011 20:10:00 19.93 12.80 111012 12:50:00 25.37 0.39 12.88 111013 05:30:00 21.30 0.54 12.74 111010 11:00:00 16.70 12.38 111011 03:40:00 15.03 12.62 111011 20:20:00 19.67 12.80 111012 13:00:00 25.50 0.40 12.88 111013 05:40:00 21.20 0.54 12.73 111010 11:10:00 16.83 12.37 111011 03:50:00 15.17 12.65 111011 20:30:00 19.60 12.81 111012 13:10:00 26.67 0.40 12.87 111013 05:50:00 21.20 0.54 12.72 111010 11:20:00 16.57 12.40 111011 04:00:00 15.60 12.63 111011 20:40:00 19.10 12.83 111012 13:20:00 26.43 0.41 12.87 111013 06:00:00 20.80 0.57 12.73 111010 11:30:00 16.30 12.39 111011 04:10:00 15.27 12.63 111011 20:50:00 19.00 12.83 111012 13:30:00 26.90 0.40 12.89 111013 06:10:00 20.97 0.54 12.70 111010 11:40:00 16.37 12.38 111011 04:20:00 15.23 12.62 111011 21:00:00 19.10 12.81 111012 13:40:00 26.50 0.39 12.87 111013 06:20:00 21.33 0.56 12.71 111010 11:50:00 16.43 12.39 111011 04:30:00 15.30 12.62 111011 21:10:00 19.07 12.83 111012 13:50:00 26.90 0.39 12.89 111013 06:30:00 21.00 0.56 12.69 111010 12:00:00 16.40 12.40 111011 04:40:00 15.37 12.66 111011 21:20:00 19.13 12.83 111012 14:00:00 26.70 0.40 12.89 111013 06:40:00 20.77 0.57 12.69 111010 12:10:00 16.60 12.38 111011 04:50:00 15.43 12.65 111011 21:30:00 19.00 12.81 111012 14:10:00 25.83 0.43 12.88 111013 06:50:00 20.83 0.55 12.69 111010 12:20:00 16.30 12.41 111011 05:00:00 15.60 12.63 111011 21:40:00 18.53 12.83 111012 14:20:00 25.47 0.44 12.87 111013 07:00:00 20.90 0.55 12.70 111010 12:30:00 16.30 12.41 111011 05:10:00 15.77 12.65 111011 21:50:00 18.37 12.84 111012 14:30:00 24.70 0.44 12.87 111013 07:10:00 20.70 0.58 12.69 111010 12:40:00 16.27 12.40 111011 05:20:00 15.63 12.65 111011 22:00:00 18.50 12.83 111012 14:40:00 24.23 0.45 12.88 111013 07:20:00 20.50 0.56 12.69 111010 12:50:00 16.23 12.41 111011 05:30:00 15.20 12.66 111011 22:10:00 18.13 12.85 111012 14:50:00 23.47 0.45 12.87 111013 07:30:00 20.60 0.56 12.68 111010 13:00:00 16.20 12.41 111011 05:40:00 15.90 12.65 111011 22:20:00 18.17 12.84 111012 15:00:00 23.50 0.46 12.89 111013 07:40:00 20.40 0.56 12.66 111010 13:10:00 16.13 12.41 111011 05:50:00 15.90 12.66 111011 22:30:00 17.90 12.83 111012 15:10:00 23.10 0.47 12.89 111013 07:50:00 20.90 0.60 12.53 111010 13:20:00 16.27 12.41 111011 06:00:00 15.70 12.66 111011 22:40:00 17.73 12.83 111012 15:20:00 22.80 0.47 12.88 111013 08:00:00 -- 0.56 12.51 111010 13:30:00 15.80 12.40 111011 06:10:00 15.97 12.66 111011 22:50:00 17.97 12.85 111012 15:30:00 23.00 0.47 12.87 111013 08:10:00 -- 0.58 12.50 111010 13:40:00 15.50 12.41 111011 06:20:00 16.43 12.69 111011 23:00:00 17.90 12.85 111012 15:40:00 23.23 0.47 12.89 111013 08:20:00 -- 0.61 12.47 111010 13:50:00 16.00 12.41 111011 06:30:00 16.40 12.65 111011 23:10:00 18.30 12.85 111012 15:50:00 23.17 0.48 12.88 111013 08:30:00 -- 0.61 12.47 111010 14:00:00 15.80 12.41 111011 06:40:00 16.47 12.67 111011 23:20:00 19.30 12.85 111012 16:00:00 23.20 0.48 12.89 111013 08:40:00 -- 0.57 12.44 111010 14:10:00 15.57 12.42 111011 06:50:00 16.83 12.65 111011 23:30:00 20.50 12.83 111012 16:10:00 23.20 0.48 12.90 111013 08:50:00 -- 0.58 12.45 111010 14:20:00 15.93 12.42 111011 07:00:00 16.90 12.67 111011 23:40:00 22.27 12.85 111012 16:20:00 23.10 0.49 12.89 111013 09:00:00 18.70 0.61 12.43 111010 14:30:00 15.40 12.42 111011 07:10:00 16.97 12.68 111011 23:50:00 23.03 12.84 111012 16:30:00 23.10 0.49 12.89 111013 09:10:00 18.73 0.61 12.43 111010 14:40:00 16.00 12.41 111011 07:20:00 17.33 12.69 111012 00:00:00 22.70 12.85 111012 16:40:00 23.73 0.50 12.89 111013 09:20:00 18.57 0.58 12.41 111010 14:50:00 15.60 12.43 111011 07:30:00 16.90 12.69 111012 00:10:00 22.60 12.88 111012 16:50:00 24.07 0.50 12.89 111013 09:30:00 19.10 0.58 12.39 111010 15:00:00 15.80 12.43 111011 07:40:00 17.27 12.68 111012 00:20:00 22.50 12.88 111012 17:00:00 24.10 0.48 12.89 111013 09:40:00 19.00 0.61 12.38 111010 15:10:00 16.03 12.43 111011 07:50:00 17.13 12.67 111012 00:30:00 21.70 12.88 111012 17:10:00 24.50 0.48 12.89 111013 09:50:00 19.10 0.61 12.39 111010 15:20:00 15.67 12.44 111011 08:00:00 17.10 12.69 111012 00:40:00 21.83 12.87 111012 17:20:00 25.10 0.45 12.87 111013 10:00:00 18.80 0.61 12.39 111010 15:30:00 15.90 12.42 111011 08:10:00 16.93 12.68 111012 00:50:00 21.77 12.89 111012 17:30:00 27.50 0.42 12.87 111013 10:10:00 19.23 0.57 12.37 111010 15:40:00 15.80 12.41 111011 08:20:00 16.67 12.69 111012 01:00:00 21.60 12.89 111012 17:40:00 28.63 0.36 12.89 111013 10:20:00 18.97 0.58 12.33 111010 15:50:00 15.80 12.45 111011 08:30:00 16.50 12.68 111012 01:10:00 21.27 12.89 111012 17:50:00 29.87 0.33 12.89 111013 10:30:00 18.90 0.61 12.32 111010 16:00:00 15.40 12.45 111011 08:40:00 16.73 12.68 111012 01:20:00 21.53 12.87 111012 18:00:00 31.50 0.31 12.89 111013 10:40:00 19.47 0.61 12.32 111010 16:10:00 15.27 12.43 111011 08:50:00 16.77 12.69 111012 01:30:00 21.30 12.89 111012 18:10:00 31.87 0.31 12.88 111013 10:50:00 19.23 0.60 12.31 111010 16:20:00 15.43 12.44 111011 09:00:00 16.40 12.69 111012 01:40:00 21.37 12.89 111012 18:20:00 31.63 0.29 12.89 111013 11:00:00 19.00 0.60 12.26 111010 16:30:00 15.70 12.45 111011 09:10:00 16.27 12.69 111012 01:50:00 21.13 12.90 111012 18:30:00 31.80 0.29 12.89 111013 11:10:00 18.90 0.60 12.26

134

Appendices

Date T EC H Date T EC H Date T EC H Date T EC H Date T EC H

C° ms/cm cm C° ms/cm cm C° ms/cm cm C° ms/cm cm C° ms/cm cm 111013 11:20:00 19.00 0.60 12.23 111014 04:00:00 18.70 0.63 11.29 111014 20:40:00 18.53 0.62 12.02 111016 22:40:00 17.90 0.64 10.85 111017 15:30:00 17.40 0.63 9.29 111013 11:30:00 19.30 0.60 12.23 111014 04:10:00 18.83 0.63 11.29 111014 20:50:00 18.37 0.62 12.03 111016 22:50:00 18.00 0.64 10.83 111017 15:40:00 17.40 0.63 9.26 111013 11:40:00 19.33 0.60 12.21 111014 04:20:00 19.17 0.63 11.29 111014 21:00:00 18.40 0.62 12.03 111016 23:00:00 17.50 0.64 10.83 111017 15:50:00 17.50 0.62 9.28 111013 11:50:00 19.37 0.60 12.19 111014 04:30:00 19.20 0.63 11.24 111014 21:10:00 18.83 0.62 12.02 111016 23:10:00 17.83 0.64 10.83 111017 16:00:00 17.40 0.62 9.18 111013 12:00:00 19.70 0.60 12.18 111014 04:40:00 18.77 0.63 11.25 111014 21:20:00 18.47 0.62 12.03 111016 23:20:00 17.87 0.64 10.82 111017 16:10:00 17.23 0.61 9.22 111013 12:10:00 19.67 0.60 12.18 111014 04:50:00 19.13 0.63 11.25 111014 21:30:00 18.60 0.62 12.03 111016 23:30:00 17.90 0.64 10.83 111017 16:20:00 16.87 0.62 9.23 111013 12:20:00 19.43 0.60 12.15 111014 05:00:00 19.00 0.63 11.24 111014 21:40:00 18.60 0.63 12.02 111016 23:40:00 17.73 0.64 10.81 111017 16:30:00 17.00 0.62 9.14 111013 12:30:00 18.90 0.60 12.15 111014 05:10:00 18.77 0.63 11.23 111014 21:50:00 18.50 0.63 12.03 111016 23:50:00 18.07 0.64 10.80 111017 16:40:00 0.62 9.23 111013 12:40:00 18.90 0.60 12.12 111014 05:20:00 18.73 0.63 11.22 111014 22:00:00 18.50 0.63 12.03 111017 00:00:00 17.80 0.64 10.77 111017 16:50:00 0.62 9.13 111013 12:50:00 19.00 0.60 12.12 111014 05:30:00 18.60 0.63 11.19 111014 22:10:00 18.83 0.63 12.01 111017 00:10:00 17.43 0.64 10.74 111017 17:00:00 0.62 9.22 111013 13:00:00 19.20 0.60 12.08 111014 05:40:00 18.63 0.63 11.20 111014 22:20:00 18.57 0.63 11.98 111017 00:20:00 17.77 0.64 10.74 111017 17:10:00 0.62 9.31 111013 13:10:00 19.53 0.60 12.06 111014 05:50:00 18.97 0.63 11.17 111014 22:30:00 18.50 0.63 11.98 111017 00:30:00 17.40 0.64 10.70 111017 17:20:00 0.61 9.21 111013 13:20:00 19.27 0.60 12.06 111014 06:00:00 18.80 0.63 11.12 111014 22:40:00 18.83 0.63 11.97 111017 00:40:00 17.70 0.64 10.69 111017 17:30:00 0.62 9.18 111013 13:30:00 19.40 0.60 12.03 111014 06:10:00 19.13 0.63 11.12 111014 22:50:00 18.87 0.63 11.97 111017 00:50:00 17.70 0.64 10.67 111017 17:40:00 0.62 9.13 111013 13:40:00 19.07 0.60 12.01 111014 06:20:00 19.07 0.63 11.14 111014 23:00:00 18.60 0.63 11.95 111017 01:00:00 17.70 0.64 10.65 111017 17:50:00 0.62 9.17 111013 13:50:00 19.03 0.60 12.04 111014 06:30:00 19.00 0.63 11.14 111014 23:10:00 18.90 0.63 11.97 111017 01:10:00 17.50 0.64 10.65 111017 18:00:00 0.62 9.07 111013 14:00:00 19.00 0.59 11.99 111014 06:40:00 18.97 0.64 11.19 111014 23:20:00 18.60 0.63 11.95 111017 01:20:00 17.70 0.64 10.61 111017 18:10:00 0.62 9.02 111013 14:10:00 19.30 0.59 11.97 111014 06:50:00 18.53 0.64 11.13 111014 23:30:00 18.80 0.63 11.96 111017 01:30:00 17.70 0.64 10.63 111017 18:20:00 0.63 9.02 111013 14:20:00 18.90 0.59 11.95 111014 07:00:00 18.70 0.64 11.19 111014 23:40:00 18.93 0.63 11.95 111017 01:40:00 18.10 0.64 10.59 111017 18:30:00 0.63 9.06 111013 14:30:00 18.90 0.59 11.95 111014 07:10:00 19.23 0.64 11.21 111014 23:50:00 18.57 0.63 11.95 111017 01:50:00 17.70 0.65 10.56 111017 18:40:00 0.61 9.05 111013 14:40:00 19.37 0.59 11.96 111014 07:20:00 19.27 0.63 11.19 111015 00:00:00 18.30 0.63 11.94 111017 02:00:00 17.80 0.65 10.56 111017 18:50:00 0.61 8.96 111013 14:50:00 19.23 0.59 11.95 111014 07:30:00 19.30 0.64 11.12 111015 00:10:00 18.60 0.63 11.95 111017 02:10:00 17.77 0.65 10.55 111017 19:00:00 0.62 8.91 111013 15:00:00 19.00 0.59 11.95 111014 07:40:00 19.17 0.64 11.16 111015 00:20:00 18.30 0.63 11.95 111017 02:20:00 17.83 0.65 10.51 111017 19:10:00 16.60 0.62 8.95 111013 15:10:00 19.07 0.59 11.93 111014 07:50:00 18.93 0.64 11.17 111015 00:30:00 18.60 0.64 11.93 111017 02:30:00 17.80 0.65 10.54 111017 19:20:00 16.00 0.63 8.98 111013 15:20:00 18.63 0.59 11.94 111014 08:00:00 18.60 0.62 11.18 111015 00:40:00 18.80 0.63 11.91 111017 02:40:00 17.87 0.65 10.52 111017 19:30:00 16.40 0.63 8.89 111013 15:30:00 19.00 0.59 11.95 111014 08:10:00 18.83 0.64 11.19 111015 00:50:00 18.80 0.63 11.90 111017 02:50:00 18.13 0.65 10.49 111017 19:40:00 16.50 0.63 8.90 111013 15:40:00 19.20 0.59 11.92 111014 08:20:00 19.07 0.61 11.19 111015 01:00:00 18.60 0.63 11.87 111017 03:00:00 18.00 0.65 10.47 111017 19:50:00 16.60 0.62 8.91 111013 15:50:00 18.80 0.59 11.91 111014 08:30:00 19.20 0.64 11.23 111015 01:10:00 18.63 0.64 11.87 111017 03:10:00 17.73 0.65 10.43 111017 20:00:00 16.70 0.63 8.89 111013 16:00:00 18.80 0.59 11.91 111014 08:40:00 18.87 0.64 11.23 111015 01:20:00 18.67 0.64 11.84 111017 03:20:00 17.77 0.65 10.46 111017 20:10:00 16.80 0.62 8.94 111013 16:10:00 19.03 0.59 11.91 111014 08:50:00 18.83 0.62 11.29 111015 01:30:00 18.70 0.64 11.85 111017 03:30:00 17.80 0.65 10.42 111017 20:20:00 16.90 0.63 8.89 111013 16:20:00 18.87 0.59 11.90 111014 09:00:00 18.70 0.62 11.24 111015 01:40:00 18.40 0.64 11.81 111017 03:40:00 17.77 0.65 10.37 111017 20:30:00 16.70 0.63 8.80 111013 16:30:00 18.60 0.59 11.89 111014 09:10:00 18.63 0.64 11.24 111015 01:50:00 18.40 0.64 11.76 111017 03:50:00 17.93 0.65 10.41 111017 20:40:00 16.50 0.63 8.80 111013 16:40:00 18.83 0.59 11.88 111014 09:20:00 18.77 0.64 11.25 111015 02:00:00 18.60 0.64 11.76 111017 04:00:00 17.90 0.65 10.41 111017 20:50:00 16.90 0.63 8.78 111013 16:50:00 18.57 0.59 11.90 111014 09:30:00 18.80 0.64 11.30 111015 02:10:00 18.27 0.64 11.71 111017 04:10:00 18.07 0.64 10.33 111017 21:00:00 16.60 0.62 8.82 111013 17:00:00 18.70 0.59 11.87 111014 09:40:00 19.50 0.64 11.32 111015 02:20:00 18.43 0.64 11.71 111017 04:20:00 17.83 0.64 10.34 111017 21:10:00 17.10 0.62 8.88 111013 17:10:00 18.73 0.59 11.87 111014 09:50:00 18.90 0.64 11.28 111015 02:30:00 18.60 0.64 11.69 111017 04:30:00 17.70 0.64 10.33 111017 21:20:00 16.60 0.63 8.87 111013 17:20:00 18.37 0.59 11.87 111014 10:00:00 18.90 0.64 11.29 111015 02:40:00 18.87 0.64 11.66 111017 04:40:00 17.80 0.65 10.31 111017 21:30:00 16.70 0.63 8.79 111013 17:30:00 18.50 0.59 11.87 111014 10:10:00 18.67 0.64 11.31 111015 02:50:00 18.73 0.64 11.65 111017 04:50:00 18.10 0.64 10.30 111017 21:40:00 16.90 0.62 8.79 111013 17:40:00 18.50 0.59 11.87 111014 10:20:00 18.83 0.61 11.30 111015 03:00:00 18.30 0.64 11.60 111017 05:00:00 17.90 0.64 10.28 111017 21:50:00 17.40 0.62 8.87 111013 17:50:00 18.60 0.59 11.85 111014 10:30:00 19.00 0.63 11.33 111015 03:10:00 18.47 0.64 11.55 111017 05:10:00 18.23 0.64 10.25 111017 22:00:00 17.50 0.62 8.88 111013 18:00:00 18.50 0.59 11.88 111014 10:40:00 18.93 0.63 11.30 111015 03:20:00 18.93 0.64 11.49 111017 05:20:00 17.97 0.64 10.23 111017 22:10:00 17.20 0.62 8.96 111013 18:10:00 18.53 0.59 11.85 111014 10:50:00 18.97 0.63 11.33 111015 03:30:00 18.80 0.64 11.46 111017 05:30:00 18.00 0.65 10.20 111017 22:20:00 17.40 0.62 8.90 111013 18:20:00 18.57 0.60 11.88 111014 11:00:00 19.00 0.63 11.37 111015 03:40:00 19.20 0.64 11.43 111017 05:40:00 18.00 0.62 10.24 111017 22:30:00 17.10 0.63 8.89 111013 18:30:00 18.90 0.60 11.87 111014 11:10:00 18.80 0.63 11.37 111015 03:50:00 19.10 0.64 11.43 111017 05:50:00 18.00 0.65 10.19 111017 22:40:00 17.10 0.63 8.77 111013 18:40:00 18.93 0.60 11.87 111014 11:20:00 18.60 0.63 11.36 111015 04:00:00 19.10 0.64 11.40 111017 06:00:00 18.10 0.65 10.20 111017 22:50:00 17.10 0.62 8.68 111013 18:50:00 19.17 0.60 11.87 111014 11:30:00 18.60 0.63 11.36 111015 04:10:00 19.00 0.64 11.36 111017 06:10:00 18.33 0.65 10.19 111017 23:00:00 17.20 0.62 8.74 111013 19:00:00 18.80 0.60 11.88 111014 11:40:00 18.33 0.63 11.38 111015 04:20:00 18.70 0.65 11.34 111017 06:20:00 17.77 0.64 10.17 111017 23:10:00 17.50 0.63 8.69 111013 19:10:00 19.00 0.60 11.84 111014 11:50:00 18.67 0.63 11.42 111015 04:30:00 18.80 0.65 11.32 111017 06:30:00 18.00 0.64 10.14 111017 23:20:00 17.30 0.62 8.78 111013 19:20:00 18.50 0.60 11.86 111014 12:00:00 18.40 0.62 11.46 111015 04:40:00 18.80 0.65 11.28 111017 06:40:00 17.73 0.64 10.12 111017 23:30:00 17.10 0.62 8.72 111013 19:30:00 18.60 0.60 11.85 111014 12:10:00 18.40 0.62 11.47 111015 04:50:00 18.80 0.65 11.28 111017 06:50:00 18.07 0.64 10.10 111017 23:40:00 16.60 0.63 8.67 111013 19:40:00 18.43 0.60 11.87 111014 12:20:00 18.60 0.62 11.50 111015 05:00:00 18.50 0.64 11.27 111017 07:00:00 17.80 0.64 10.10 111017 23:50:00 16.80 0.63 8.68 111013 19:50:00 18.97 0.60 11.85 111014 12:30:00 18.40 0.62 11.51 111015 05:10:00 18.17 0.64 11.23 111017 07:10:00 17.93 0.64 10.06 111018 00:00:00 17.20 0.62 8.57 111013 20:00:00 18.50 0.60 11.85 111014 12:40:00 18.17 0.62 11.52 111015 05:20:00 18.43 0.65 11.22 111017 07:20:00 18.17 0.65 10.02 111018 00:10:00 17.00 0.63 8.53 111013 20:10:00 18.23 0.60 11.81 111014 12:50:00 18.53 0.62 11.54 111015 05:30:00 18.40 0.65 11.20 111017 07:30:00 17.60 0.65 10.02 111018 00:20:00 17.20 0.62 8.51 111013 20:20:00 18.57 0.61 11.83 111014 13:00:00 18.30 0.62 11.56 111015 05:40:00 18.90 0.65 11.15 111017 07:40:00 17.87 0.65 10.02 111018 00:30:00 17.70 0.62 8.51 111013 20:30:00 18.60 0.61 11.84 111014 13:10:00 18.33 0.62 11.56 111015 05:50:00 18.40 0.65 11.12 111017 07:50:00 17.73 0.65 10.01 111018 00:40:00 17.00 0.63 8.67 111013 20:40:00 18.23 0.61 11.84 111014 13:20:00 18.17 0.62 11.57 111015 06:00:00 18.70 0.63 11.11 111017 08:00:00 17.90 0.64 10.02 111018 00:50:00 17.70 0.62 8.57 111013 20:50:00 18.37 0.61 11.81 111014 13:30:00 18.20 0.62 11.58 111015 06:10:00 18.47 0.65 11.10 111017 08:10:00 17.77 0.64 9.99 111018 01:00:00 17.60 0.63 8.55 111013 21:00:00 18.50 0.61 11.77 111014 13:40:00 18.07 0.62 11.62 111015 06:20:00 18.43 0.65 11.06 111017 08:20:00 17.83 0.65 9.97 111018 01:10:00 17.60 0.62 8.53 111013 21:10:00 18.73 0.61 11.81 111014 13:50:00 18.33 0.62 11.68 111015 06:30:00 18.60 0.65 11.04 111017 08:30:00 17.80 0.64 9.94 111018 01:20:00 17.60 0.62 8.45 111013 21:20:00 18.57 0.61 11.78 111014 14:00:00 18.50 0.61 11.67 111015 06:40:00 19.17 0.65 11.00 111017 08:40:00 18.00 0.64 9.95 111018 01:30:00 18.10 0.63 8.37 111013 21:30:00 18.80 0.61 11.77 111014 14:10:00 18.10 0.61 11.70 111015 06:50:00 19.03 0.65 10.98 111017 08:50:00 18.00 0.65 9.94 111018 01:40:00 17.70 0.63 8.43 111013 21:40:00 18.50 0.61 11.83 111014 14:20:00 18.30 0.61 11.76 111015 07:00:00 19.20 0.63 10.97 111017 09:00:00 17.70 0.64 9.93 111018 01:50:00 17.50 0.62 8.40 111013 21:50:00 18.80 0.61 11.82 111014 14:30:00 18.40 0.61 11.76 111015 07:10:00 18.83 0.65 10.93 111017 09:10:00 18.17 0.64 9.92 111018 02:00:00 17.20 0.62 8.40 111013 22:00:00 19.00 0.61 11.82 111014 14:40:00 18.40 0.61 11.78 111015 07:20:00 18.87 0.63 10.93 111017 09:20:00 18.03 0.64 9.90 111018 02:10:00 17.70 0.62 8.49 111013 22:10:00 18.73 0.61 11.77 111014 14:50:00 17.60 0.61 11.78 111015 07:30:00 18.80 0.65 10.94 111017 09:30:00 18.00 0.64 9.84 111018 02:20:00 17.70 0.62 8.44 111013 22:20:00 18.57 0.61 11.76 111014 15:00:00 18.10 0.61 11.82 111015 07:40:00 18.50 0.63 10.92 111017 09:40:00 17.70 0.64 9.89 111018 02:30:00 17.00 0.62 8.50 111013 22:30:00 18.70 0.61 11.75 111014 15:10:00 18.10 0.61 11.86 111015 07:50:00 18.60 0.62 10.92 111017 09:50:00 18.10 0.64 9.82 111018 02:40:00 17.50 0.62 8.51 111013 22:40:00 18.77 0.61 11.73 111014 15:20:00 18.10 0.61 11.86 111015 08:00:00 18.50 0.65 10.88 111017 10:00:00 18.20 0.64 9.82 111018 02:50:00 17.20 0.63 8.54 111013 22:50:00 18.83 0.61 11.69 111014 15:30:00 18.00 0.61 11.88 111015 08:10:00 18.33 0.65 10.88 111017 10:10:00 18.03 0.64 9.80 111018 03:00:00 17.30 0.63 8.48 111013 23:00:00 18.60 0.61 11.71 111014 15:40:00 17.97 0.61 11.89 111015 08:20:00 18.67 0.63 10.85 111017 10:20:00 18.07 0.64 9.79 111018 03:10:00 17.40 0.62 8.46 111013 23:10:00 18.80 0.61 11.65 111014 15:50:00 17.53 0.61 11.92 111015 08:30:00 18.80 0.63 10.84 111017 10:30:00 17.90 0.64 9.76 111018 03:20:00 17.20 0.63 8.42 111013 23:20:00 18.90 0.61 11.65 111014 16:00:00 18.20 0.61 11.93 111015 08:40:00 18.77 0.65 10.85 111017 10:40:00 17.57 0.64 9.75 111018 03:30:00 16.90 0.62 8.41 111013 23:30:00 18.90 0.61 11.64 111014 16:10:00 18.13 0.61 11.93 111015 08:50:00 18.63 0.66 10.88 111017 10:50:00 17.83 0.64 9.69 111018 03:40:00 17.00 0.62 8.38 111013 23:40:00 18.87 0.61 11.60 111014 16:20:00 17.87 0.61 11.96 111015 09:00:00 18.70 0.65 10.81 111017 11:00:00 18.10 0.63 9.67 111018 03:50:00 16.80 0.63 8.27 111013 23:50:00 18.63 0.62 11.61 111014 16:30:00 17.60 0.61 11.95 111015 09:10:00 18.83 0.63 10.82 111017 11:10:00 18.37 0.63 9.68 111018 04:00:00 17.30 0.62 8.39 111014 00:00:00 18.70 0.61 11.58 111014 16:40:00 18.03 0.61 11.95 111015 09:20:00 18.57 0.66 10.82 111017 11:20:00 18.03 0.63 9.67 111018 04:10:00 17.30 0.63 8.36 111014 00:10:00 18.97 0.61 11.61 111014 16:50:00 18.17 0.61 11.97 111015 09:30:00 18.80 0.65 10.79 111017 11:30:00 17.60 0.63 9.71 111018 04:20:00 17.20 0.62 8.39 111014 00:20:00 18.93 0.61 11.60 111014 17:00:00 18.40 0.61 11.96 111015 09:40:00 18.53 0.65 10.80 111017 11:40:00 17.53 0.63 9.67 111018 04:30:00 17.20 0.63 8.30 111014 00:30:00 18.90 0.62 11.58 111014 17:10:00 18.23 0.61 11.98 111015 09:50:00 18.87 0.65 10.83 111017 11:50:00 17.77 0.63 9.74 111018 04:40:00 17.30 0.63 8.29 111014 00:40:00 18.83 0.62 11.58 111014 17:20:00 18.37 0.61 11.98 111015 10:00:00 19.00 0.65 10.79 111017 12:00:00 17.60 0.63 9.67 111018 04:50:00 17.60 0.62 8.19 111014 00:50:00 18.97 0.62 11.56 111014 17:30:00 18.50 0.61 11.99 111015 10:10:00 18.57 0.63 10.78 111017 12:10:00 17.40 0.63 9.59 111018 05:00:00 17.70 0.63 8.27 111014 01:00:00 18.70 0.62 11.52 111014 17:40:00 18.07 0.61 11.97 111015 10:20:00 18.73 0.63 10.75 111017 12:20:00 17.80 0.63 9.59 111018 05:10:00 17.20 0.63 8.41 111014 01:10:00 19.03 0.62 11.51 111014 17:50:00 18.33 0.61 11.99 111015 10:30:00 18.50 0.65 10.75 111017 12:30:00 18.00 0.63 9.57 111018 05:20:00 17.50 0.63 8.36 111014 01:20:00 18.87 0.62 11.52 111014 18:00:00 17.90 0.61 11.98 111015 10:40:00 18.97 0.65 10.73 111017 12:40:00 17.87 0.62 9.52 111018 05:30:00 17.50 0.63 8.28 111014 01:30:00 19.10 0.62 11.50 111014 18:10:00 17.97 0.61 11.95 111015 10:50:00 18.83 0.65 10.71 111017 12:50:00 17.43 0.64 9.46 111018 05:40:00 17.50 0.62 8.29 111014 01:40:00 18.57 0.62 11.47 111014 18:20:00 18.13 0.61 12.01 111015 11:00:00 18.60 0.65 10.70 111017 13:00:00 17.50 0.62 9.44 111018 05:50:00 17.40 0.63 8.29 111014 01:50:00 19.33 0.62 11.49 111014 18:30:00 18.10 0.62 12.02 111015 11:10:00 18.63 0.65 10.70 111017 13:10:00 17.53 0.62 9.45 111018 06:00:00 17.30 0.64 8.36 111014 02:00:00 18.90 0.62 11.46 111014 18:40:00 18.20 0.62 12.01 111015 11:20:00 18.47 0.65 10.67 111017 13:20:00 17.67 0.62 9.49 111018 06:10:00 17.80 0.64 8.36 111014 02:10:00 18.50 0.62 11.47 111014 18:50:00 18.00 0.62 12.03 111015 11:30:00 18.10 0.65 10.65 111017 13:30:00 17.80 0.62 9.54 111018 06:20:00 17.50 0.63 8.27 111014 02:20:00 18.60 0.62 11.45 111014 19:00:00 18.10 0.62 12.02 111015 11:40:00 18.53 0.64 10.64 111017 13:40:00 17.27 0.62 9.59 111018 06:30:00 18.00 0.63 8.19 111014 02:30:00 18.70 0.62 11.41 111014 19:10:00 18.20 0.62 12.02 111015 11:50:00 18.47 0.64 10.66 111017 13:50:00 17.63 0.62 9.66 111018 06:40:00 17.00 0.63 8.29 111014 02:40:00 18.57 0.62 11.41 111014 19:20:00 18.40 0.62 12.02 111015 12:00:00 18.10 0.64 10.69 111017 14:00:00 17.30 0.62 9.59 111018 06:50:00 17.70 0.63 8.34 111014 02:50:00 18.73 0.62 11.42 111014 19:30:00 18.50 0.62 12.03 111015 12:10:00 18.10 0.64 10.66 111017 14:10:00 17.33 0.62 9.56 111018 07:00:00 17.60 0.63 8.39 111014 03:00:00 18.50 0.62 11.40 111014 19:40:00 18.47 0.62 12.06 111015 12:20:00 18.60 0.64 10.66 111017 14:20:00 17.47 0.63 9.42 111018 07:10:00 17.80 0.63 8.29 111014 03:10:00 18.90 0.62 11.38 111014 19:50:00 18.63 0.62 12.03 111015 12:30:00 18.00 0.64 10.68 111017 14:30:00 17.40 0.62 9.42 111018 07:20:00 17.40 0.62 8.30 111014 03:20:00 18.70 0.62 11.38 111014 20:00:00 18.20 0.62 12.03 111015 12:40:00 18.37 0.64 10.66 111017 14:40:00 17.03 0.62 9.32 111018 07:30:00 17.60 0.63 8.26 111014 03:30:00 18.90 0.62 11.35 111014 20:10:00 18.63 0.62 12.01 111015 12:50:00 18.03 0.64 10.56 111017 14:50:00 17.27 0.62 9.24 111018 07:40:00 17.50 0.62 8.32 111014 03:40:00 18.77 0.62 11.35 111014 20:20:00 18.37 0.62 12.02 111015 13:00:00 18.00 0.63 10.56 111017 15:00:00 17.50 0.63 9.25 111018 07:50:00 17.90 0.63 8.40 111014 03:50:00 19.13 0.63 11.34 111014 20:30:00 18.40 0.62 12.01 111015 13:10:00 17.90 0.63 10.56 111017 15:10:00 17.53 0.63 9.25 111017 15:20:00 17.27 0.61 9.25 135

Appendices

Date T EC H Date T EC H Date T EC H Date T EC H

C° ms/cm cm C° ms/cm cm C° ms/cm cm C° ms/cm cm 111018 08:00:00 17.50 0.62 8.36 111019 00:40:00 18.00 0.63 10.21 111019 17:20:00 17.40 0.62 8.67 111020 10:00:00 18.10 0.62 8.26 111018 08:10:00 17.70 0.63 8.40 111019 00:50:00 17.80 0.63 10.20 111019 17:30:00 17.20 0.63 8.55 111020 10:10:00 17.80 0.64 8.28 111018 08:20:00 17.60 0.62 8.31 111019 01:00:00 18.00 0.63 10.20 111019 17:40:00 17.30 0.63 8.49 111020 10:20:00 17.70 0.64 8.39 111018 08:30:00 17.90 0.63 8.36 111019 01:10:00 18.20 0.63 10.17 111019 17:50:00 17.20 0.63 8.46 111020 10:30:00 18.40 0.64 8.43 111018 08:40:00 17.40 0.62 8.40 111019 01:20:00 18.60 0.63 10.10 111019 18:00:00 19.20 0.64 8.36 111020 10:40:00 18.30 0.64 8.54 111018 08:50:00 17.70 0.63 8.50 111019 01:30:00 18.50 0.63 10.13 111019 18:10:00 23.90 0.64 8.41 111020 10:50:00 17.90 0.64 8.55 111018 09:00:00 17.40 0.63 8.44 111019 01:40:00 18.00 0.63 10.07 111019 18:20:00 24.80 0.63 8.41 111020 11:00:00 18.10 0.64 8.49 111018 09:10:00 17.50 0.63 8.48 111019 01:50:00 17.70 0.63 10.05 111019 18:30:00 22.80 0.63 8.43 111020 11:10:00 18.10 0.64 8.48 111018 09:20:00 16.80 0.63 8.59 111019 02:00:00 18.30 0.63 10.00 111019 18:40:00 21.90 0.64 8.52 111020 11:20:00 18.30 0.64 8.50 111018 09:30:00 17.30 0.62 8.72 111019 02:10:00 18.20 0.63 10.00 111019 18:50:00 20.60 0.64 8.48 111020 11:30:00 18.10 0.64 8.55 111018 09:40:00 16.70 0.63 8.78 111019 02:20:00 18.30 0.63 9.97 111019 19:00:00 20.60 0.65 8.36 111020 11:40:00 18.00 0.64 8.64 111018 09:50:00 17.30 0.63 8.76 111019 02:30:00 18.60 0.63 9.90 111019 19:10:00 20.40 0.65 8.27 111020 11:50:00 17.70 0.64 8.68 111018 10:00:00 17.10 0.63 8.79 111019 02:40:00 18.40 0.63 9.91 111019 19:20:00 20.70 0.65 8.28 111020 12:00:00 17.40 0.64 8.74 111018 10:10:00 16.90 0.63 8.78 111019 02:50:00 18.50 0.63 9.93 111019 19:30:00 19.80 0.64 8.26 111020 12:10:00 17.70 0.64 8.75 111018 10:20:00 16.90 0.63 8.79 111019 03:00:00 18.70 0.63 9.90 111019 19:40:00 20.10 0.64 8.25 111020 12:20:00 17.50 0.63 8.77 111018 10:30:00 16.80 0.63 8.83 111019 03:10:00 18.30 0.63 9.89 111019 19:50:00 19.30 0.64 8.22 111020 12:30:00 17.90 0.63 8.85 111018 10:40:00 16.50 0.63 8.75 111019 03:20:00 18.40 0.63 9.87 111019 20:00:00 19.00 0.64 8.34 111020 12:40:00 17.80 0.63 8.88 111018 10:50:00 16.40 0.63 8.84 111019 03:30:00 18.30 0.63 9.89 111019 20:10:00 19.00 0.64 8.36 111020 12:50:00 17.30 0.63 8.94 111018 11:00:00 17.00 0.62 8.85 111019 03:40:00 18.50 0.63 9.82 111019 20:20:00 18.80 0.64 8.25 111020 13:00:00 17.20 0.63 9.01 111018 11:10:00 16.50 0.63 8.83 111019 03:50:00 18.80 0.63 9.79 111019 20:30:00 18.70 0.64 8.20 111020 13:10:00 17.40 0.63 9.03 111018 11:20:00 17.40 0.63 8.91 111019 04:00:00 18.30 0.63 9.79 111019 20:40:00 18.90 0.64 8.19 111020 13:20:00 16.90 0.63 9.07 111018 11:30:00 16.80 0.63 8.95 111019 04:10:00 18.20 0.63 9.78 111019 20:50:00 18.40 0.64 8.33 111020 13:30:00 17.40 0.63 9.12 111018 11:40:00 16.30 0.63 9.03 111019 04:20:00 17.80 0.63 9.72 111019 21:00:00 18.40 0.64 8.28 111020 13:40:00 17.60 0.63 9.17 111018 11:50:00 17.00 0.63 9.07 111019 04:30:00 18.20 0.63 9.71 111019 21:10:00 18.20 0.64 8.20 111020 13:50:00 17.50 0.63 9.21 111018 12:00:00 17.00 0.63 9.06 111019 04:40:00 18.10 0.63 9.68 111019 21:20:00 18.40 0.64 8.25 111020 14:00:00 18.00 0.63 9.18 111018 12:10:00 16.80 0.62 9.12 111019 04:50:00 18.40 0.63 9.68 111019 21:30:00 18.20 0.64 8.23 111020 14:10:00 17.00 0.63 9.23 111018 12:20:00 17.10 0.62 9.14 111019 05:00:00 18.40 0.63 9.67 111019 21:40:00 18.40 0.64 8.21 111020 14:20:00 17.10 0.63 9.25 111018 12:30:00 17.10 0.63 9.13 111019 05:10:00 18.10 0.63 9.66 111019 21:50:00 18.10 0.64 8.17 111020 14:30:00 17.40 0.63 9.26 111018 12:40:00 17.30 0.63 9.22 111019 05:20:00 17.90 0.63 9.63 111019 22:00:00 18.60 0.64 8.19 111020 14:40:00 17.20 0.63 9.32 111018 12:50:00 17.40 0.63 9.26 111019 05:30:00 18.20 0.63 9.65 111019 22:10:00 18.50 0.64 8.23 111020 14:50:00 17.20 0.63 9.33 111018 13:00:00 17.50 0.63 9.32 111019 05:40:00 18.00 0.63 9.59 111019 22:20:00 18.10 0.64 8.26 111020 15:00:00 17.20 0.63 9.34 111018 13:10:00 17.60 0.63 9.32 111019 05:50:00 17.80 0.63 9.58 111019 22:30:00 18.40 0.64 8.25 111020 15:10:00 17.80 0.63 9.37 111018 13:20:00 17.70 0.63 9.37 111019 06:00:00 18.10 0.63 9.57 111019 22:40:00 18.40 0.64 8.14 111020 15:20:00 17.10 0.63 9.41 111018 13:30:00 17.70 0.63 9.41 111019 06:10:00 18.30 0.63 9.54 111019 22:50:00 18.30 0.64 8.08 111020 15:30:00 17.20 0.63 9.43 111018 13:40:00 18.20 0.63 9.43 111019 06:20:00 18.20 0.63 9.49 111019 23:00:00 18.60 0.64 8.13 111020 15:40:00 17.30 0.63 9.49 111018 13:50:00 18.40 0.63 9.45 111019 06:30:00 18.00 0.63 9.45 111019 23:10:00 18.00 0.64 8.10 111020 15:50:00 17.40 0.63 9.52 111018 14:00:00 18.40 0.63 9.46 111019 06:40:00 18.30 0.63 9.36 111019 23:20:00 18.00 0.64 8.08 111020 16:00:00 17.20 0.63 9.59 111018 14:10:00 18.80 0.63 9.48 111019 06:50:00 17.70 0.63 9.31 111019 23:30:00 17.80 0.64 8.04 111020 16:10:00 17.60 0.63 9.66 111018 14:20:00 18.60 0.63 9.52 111019 07:00:00 18.10 0.63 9.30 111019 23:40:00 18.00 0.64 8.08 111020 16:20:00 17.30 0.63 9.67 111018 14:30:00 18.50 0.63 9.53 111019 07:10:00 18.30 0.63 9.29 111019 23:50:00 17.90 0.64 8.23 111020 16:30:00 17.20 0.63 9.69 111018 14:40:00 18.70 0.63 9.59 111019 07:20:00 18.50 0.63 9.24 111020 00:00:00 18.10 0.64 8.36 111020 16:40:00 16.90 0.63 9.70 111018 14:50:00 19.00 0.63 9.59 111019 07:30:00 17.90 0.63 9.23 111020 00:10:00 17.90 0.64 8.31 111020 16:50:00 17.30 0.63 9.75 111018 15:00:00 19.60 0.62 9.66 111019 07:40:00 18.50 0.63 9.23 111020 00:20:00 17.70 0.64 8.31 111020 17:00:00 17.10 0.63 9.77 111018 15:10:00 19.20 0.62 9.66 111019 07:50:00 17.80 0.63 9.23 111020 00:30:00 18.20 0.64 8.28 111020 17:10:00 17.40 0.63 9.79 111018 15:20:00 19.30 0.62 9.67 111019 08:00:00 18.20 0.63 9.18 111020 00:40:00 18.10 0.64 8.10 111020 17:20:00 17.20 0.63 9.81 111018 15:30:00 19.40 0.63 9.72 111019 08:10:00 17.80 0.63 9.23 111020 00:50:00 18.00 0.64 8.02 111020 17:30:00 17.20 0.63 9.83 111018 15:40:00 19.00 0.63 9.77 111019 08:20:00 17.70 0.63 9.21 111020 01:00:00 18.10 0.64 8.03 111020 17:40:00 17.20 0.63 9.87 111018 15:50:00 18.70 0.63 9.79 111019 08:30:00 18.10 0.63 9.14 111020 01:10:00 18.40 0.64 7.97 111020 17:50:00 17.40 0.63 9.89 111018 16:00:00 19.30 0.61 9.86 111019 08:40:00 18.30 0.63 9.15 111020 01:20:00 18.60 0.64 8.04 111020 18:00:00 17.60 0.63 9.89 111018 16:10:00 18.80 0.63 9.84 111019 08:50:00 17.90 0.63 9.12 111020 01:30:00 17.90 0.64 8.02 111020 18:10:00 17.60 0.63 9.90 111018 16:20:00 19.00 0.63 9.89 111019 09:00:00 18.20 0.63 9.12 111020 01:40:00 18.30 0.64 8.03 111020 18:20:00 17.00 0.63 9.89 111018 16:30:00 18.70 0.63 9.92 111019 09:10:00 18.20 0.63 9.07 111020 01:50:00 18.30 0.64 8.07 111020 18:30:00 17.50 0.63 9.90 111018 16:40:00 18.10 0.63 9.97 111019 09:20:00 18.20 0.63 9.13 111020 02:00:00 17.90 0.64 8.22 111020 18:40:00 17.60 0.63 9.93 111018 16:50:00 18.30 0.63 9.97 111019 09:30:00 17.80 0.63 9.03 111020 02:10:00 18.10 0.64 8.22 111020 18:50:00 17.30 0.63 9.95 111018 17:00:00 18.70 0.63 10.02 111019 09:40:00 18.10 0.63 8.99 111020 02:20:00 18.20 0.65 8.14 111020 19:00:00 17.00 0.63 9.95 111018 17:10:00 18.50 0.63 10.02 111019 09:50:00 17.90 0.63 9.01 111020 02:30:00 18.10 0.64 8.17 111020 19:10:00 17.40 0.63 9.99 111018 17:20:00 18.20 0.63 10.04 111019 10:00:00 18.00 0.63 8.96 111020 02:40:00 18.10 0.64 8.08 111020 19:20:00 17.70 0.63 10.01 111018 17:30:00 18.60 0.63 10.05 111019 10:10:00 18.00 0.63 8.97 111020 02:50:00 18.60 0.64 8.02 111020 19:30:00 17.60 0.63 10.00 111018 17:40:00 18.10 0.63 10.09 111019 10:20:00 18.40 0.63 9.00 111020 03:00:00 18.30 0.64 7.96 111020 19:40:00 17.50 0.63 10.01 111018 17:50:00 18.00 0.63 10.10 111019 10:30:00 18.20 0.63 8.91 111020 03:10:00 18.00 0.65 7.93 111020 19:50:00 17.80 0.63 10.02 111018 18:00:00 18.50 0.63 10.10 111019 10:40:00 18.00 0.63 8.91 111020 03:20:00 17.60 0.65 7.91 111020 20:00:00 17.80 0.63 10.03 111018 18:10:00 17.90 0.63 10.10 111019 10:50:00 18.00 0.63 8.89 111020 03:30:00 18.00 0.65 7.84 111020 20:10:00 17.40 0.63 10.04 111018 18:20:00 18.10 0.62 10.11 111019 11:00:00 17.60 0.63 8.96 111020 03:40:00 17.90 0.65 8.05 111020 20:20:00 17.60 0.63 10.02 111018 18:30:00 18.20 0.63 10.10 111019 11:10:00 17.90 0.63 8.92 111020 03:50:00 17.90 0.65 8.11 111020 20:30:00 17.70 0.63 10.04 111018 18:40:00 18.10 0.63 10.12 111019 11:20:00 18.20 0.63 8.88 111020 04:00:00 18.20 0.64 8.09 111020 20:40:00 17.60 0.63 10.07 111018 18:50:00 18.10 0.63 10.13 111019 11:30:00 18.10 0.63 8.84 111020 04:10:00 17.90 0.64 8.20 111020 20:50:00 17.60 0.63 10.09 111018 19:00:00 18.50 0.62 10.15 111019 11:40:00 18.50 0.63 8.84 111020 04:20:00 17.90 0.64 8.06 111020 21:00:00 17.50 0.63 10.07 111018 19:10:00 17.90 0.63 10.16 111019 11:50:00 17.80 0.63 8.87 111020 04:30:00 18.10 0.64 7.95 111020 21:10:00 17.50 0.63 10.07 111018 19:20:00 17.80 0.63 10.19 111019 12:00:00 18.10 0.62 8.84 111020 04:40:00 18.10 0.64 7.90 111020 21:20:00 17.60 0.63 10.07 111018 19:30:00 18.20 0.62 10.19 111019 12:10:00 18.40 0.62 8.86 111020 04:50:00 18.10 0.64 7.84 111020 21:30:00 17.70 0.63 10.07 111018 19:40:00 18.00 0.63 10.21 111019 12:20:00 18.10 0.62 8.83 111020 05:00:00 17.80 0.64 8.03 111020 21:40:00 17.50 0.63 10.10 111018 19:50:00 17.90 0.63 10.20 111019 12:30:00 17.80 0.62 8.82 111020 05:10:00 18.10 0.64 8.06 111020 21:50:00 17.60 0.64 10.10 111018 20:00:00 17.90 0.63 10.20 111019 12:40:00 17.50 0.62 8.80 111020 05:20:00 17.80 0.64 7.87 111020 22:00:00 17.30 0.63 10.09 111018 20:10:00 17.80 0.63 10.22 111019 12:50:00 17.60 0.62 8.79 111020 05:30:00 17.90 0.64 7.79 111020 22:10:00 17.70 0.63 10.11 111018 20:20:00 18.10 0.62 10.22 111019 13:00:00 17.70 0.62 8.79 111020 05:40:00 18.10 0.64 7.81 111020 22:20:00 18.20 0.63 10.10 111018 20:30:00 17.80 0.62 10.24 111019 13:10:00 17.60 0.62 8.75 111020 05:50:00 17.80 0.64 7.79 111020 22:30:00 17.80 0.63 10.10 111018 20:40:00 17.70 0.62 10.24 111019 13:20:00 17.40 0.62 8.73 111020 06:00:00 18.20 0.64 7.91 111020 22:40:00 17.40 0.64 10.11 111018 20:50:00 17.60 0.64 10.25 111019 13:30:00 17.00 0.62 8.73 111020 06:10:00 18.20 0.64 8.06 111020 22:50:00 17.80 0.64 10.10 111018 21:00:00 18.30 0.62 10.28 111019 13:40:00 17.30 0.63 8.65 111020 06:20:00 18.50 0.64 8.02 111020 23:00:00 17.80 0.64 10.14 111018 21:10:00 18.00 0.62 10.26 111019 13:50:00 17.20 0.62 8.62 111020 06:30:00 18.10 0.64 8.03 111020 23:10:00 18.30 0.64 10.13 111018 21:20:00 17.60 0.64 10.25 111019 14:00:00 17.40 0.62 8.60 111020 06:40:00 18.40 0.64 7.92 111020 23:20:00 17.80 0.64 10.13 111018 21:30:00 17.90 0.63 10.26 111019 14:10:00 17.90 0.63 8.71 111020 06:50:00 18.10 0.64 7.85 111020 23:30:00 17.90 0.64 10.13 111018 21:40:00 18.00 0.63 10.27 111019 14:20:00 17.10 0.63 8.63 111020 07:00:00 18.00 0.64 7.86 111020 23:40:00 17.90 0.64 10.11 111018 21:50:00 17.80 0.63 10.29 111019 14:30:00 17.40 0.61 8.60 111020 07:10:00 18.40 0.64 7.97 111020 23:50:00 17.70 0.64 10.10 111018 22:00:00 17.70 0.64 10.28 111019 14:40:00 17.50 0.61 8.60 111020 07:20:00 18.50 0.64 7.92 111018 22:10:00 17.60 0.63 10.28 111019 14:50:00 17.50 0.61 8.61 111020 07:30:00 18.10 0.64 7.92 111018 22:20:00 17.90 0.64 10.27 111019 15:00:00 17.30 0.61 8.60 111020 07:40:00 18.10 0.64 7.91 111018 22:30:00 17.80 0.63 10.27 111019 15:10:00 17.20 0.61 8.60 111020 07:50:00 18.00 0.64 7.87 111018 22:40:00 18.00 0.63 10.29 111019 15:20:00 17.00 0.62 8.64 111020 08:00:00 17.90 0.64 7.86 111018 22:50:00 18.10 0.63 10.28 111019 15:30:00 17.10 0.62 8.64 111020 08:10:00 18.20 0.64 7.94 111018 23:00:00 18.30 0.63 10.28 111019 15:40:00 17.30 0.62 8.56 111020 08:20:00 17.70 0.64 7.97 111018 23:10:00 18.10 0.63 10.27 111019 15:50:00 17.40 0.62 8.52 111020 08:30:00 17.90 0.64 8.07 111018 23:20:00 17.90 0.63 10.28 111019 16:00:00 17.20 0.62 8.53 111020 08:40:00 17.90 0.64 8.04 111018 23:30:00 18.30 0.63 10.28 111019 16:10:00 17.20 0.62 8.50 111020 08:50:00 18.00 0.64 8.04 111018 23:40:00 18.20 0.63 10.27 111019 16:20:00 17.30 0.62 8.54 111020 09:00:00 18.30 0.64 7.99 111018 23:50:00 18.10 0.63 10.28 111019 16:30:00 17.60 0.62 8.63 111020 09:10:00 18.10 0.64 7.98 111019 00:00:00 18.10 0.63 10.27 111019 16:40:00 17.80 0.62 8.67 111020 09:20:00 18.10 0.62 8.14 111019 00:10:00 18.20 0.63 10.25 111019 16:50:00 18.00 0.62 8.79 111020 09:30:00 17.90 0.64 8.15 111019 00:20:00 17.90 0.63 10.26 111019 17:00:00 17.50 0.62 8.72 111020 09:40:00 17.90 0.64 8.25 111019 00:30:00 18.00 0.63 10.21 111019 17:10:00 17.90 0.63 8.72 111020 09:50:00 18.00 0.64 8.23 136

Appendices

Fig App. II.1: The rating curve of the Lottenbach (water head: stream discharge).

Fig App. II.2: Daily record of the stream flow discharge of the Lottenbach during the period 15.4.2011- 15.4.2014. 137

Appendices

Fig App. II.3: Daily record of the surface runoff of the Lottenbach during the period 15.4.2011-15.4.2014.

Fig App. II.4: Daily record of the base flow discharge of the Lottenbach during the period 15.4.2011- 15.4.2014.

138

Appendices

Appendix III: Hydrogeochemical data

Table. App. III.1: The results of the hydrogeochemical modelling performed on water samples collected during April 2011 from the surface water and groundwater in the Lottenbachtal .

Sample Nr SI (Gypsum) SI (Anhydrite) SI (Calcite) SI (Aragonite) SI (Dolomite) SI (Siderite)

1 -1.23 -1.48 -1.32 -1.47 -3.06 -2.06 2 -1.30 -1.56 -1.04 -1.20 -2.56 -1.83 3 -1.95 -2.21 -1.97 -2.13 -4.48 -2.36 4 -2.18 -2.43 -0.59 -0.74 -1.69 -0.10 5 -1.82 -2.07 0.38 0.23 0.09 - 6 -1.97 -2.23 -2.59 -2.75 -5.51 -2.47 7 -2.22 -2.47 -2.25 -2.41 -4.84 -2.43 8 -1.75 -2.01 -0.18 -0.34 -0.73 0.05 9 -1.93 -2.18 -1.84 -2.00 -4.16 - 10 -2.07 -2.33 -0.07 -0.23 -0.61 -0.72 11 -1.52 -1.77 -0.54 -0.69 -1.38 -1.30 12 -1.75 -2.01 -0.26 -0.41 -1.21 -0.34 13 -2.59 -2.84 -1.34 -1.49 -3.25 -1.09 14 -1.49 -1.73 0.32 0.17 0.42 0.09 15 -1.94 -2.20 -0.71 -0.86 -1.84 -1.18 16 -1.88 -2.14 -1.20 -1.36 -2.86 - 17 -1.37 -1.62 -0.82 -0.97 -1.94 0.02 18 -1.79 -2.04 -0.31 -0.47 -1.16 -0.11 19 -1.79 -2.04 0.58 0.42 0.79 - 20 -1.98 -2.24 -0.93 -1.09 -2.60 -1.08 Table. App. III.2: The results of the batch test performed topsoil, artificial materials and rock samples, collected from the Lottenbachtal.

F Na K Mg Ca Cl NO3 SO4 Sample Nr g/t g/t g/t g/t g/t g/t g/t g/t 1 42.91 85.82 0.00 27.46 15.45 41.20 15.45 58.36 2 18.32 83.46 10.18 101.78 44.78 99.74 14.25 44.78 3 63.20 10.53 42.14 273.88 37.92 229.64 23.17 61.10 4 9.67 37.07 0.00 19.34 6.45 19.34 11.28 22.57 5 20.07 47.44 1.82 10.95 7.30 not measured 1.82 47.44 6 28.11 97.45 1.87 59.97 24.36 372.94 18.74 28.11 7 21.38 62.18 5.83 56.35 23.32 27.20 17.49 31.09 8 11.04 36.79 6.13 42.92 9.81 42.92 7.36 15.94 9 49.82 31.47 7.87 83.91 62.93 62.93 10.49 89.15 10 21.21 21.21 0.00 34.70 15.42 15.42 9.64 30.85 11 6.52 8.69 0.00 11.95 2.17 5.43 1.09 53.21 12 11.61 3.87 0.00 0.00 5.16 3.87 2.58 94.19 13 5.38 13.44 21.50 114.23 1.34 6.72 12.77 27.55 14 14.68 20.72 21.58 221.87 8.63 12.09 8.63 47.48 15 5.22 15.65 3.91 24.13 3.26 9.78 2.61 11.74 16 6.36 119.18 71.51 371.85 1.59 90.58 9.53 30.19 17 n.d 2.23 13.35 58.97 10.01 1.11 1.11 5.56 18 0.00 n.d 12.21 260.09 1.88 0.00 1.88 10.33 19 10.59 31.78 n.d 1088.25 74.16 386.19 3.85 257.14 20 5.07 5.07 423.91 52.74 3.04 26.37 2.03 22.31 21 4.61 5.54 n.d 798.21 4.61 10.15 11.07 69.21 22 40.48 84.65 14.54 63.46 5.29 17.19 3.97 140.13 23 7.35 11.75 0.00 0.00 1.68 800.29 1.68 7.58 139

Appendices

Table. App. III.3: The results of the batch test, pH, and carbonate and EC tests performed on soil samples collected from the selected soil profiles (P1 and P2 collected from arable area; P4 collected from a forest).

P1 Sample pH EC Carbonate Ca Mg Na K SO4 Cl NO3 Corg F level (cm) - µs/cm % g/t g/t g/t g/t g/t g/t g/t % g/t 0 - 10 5.66 21.00 0 - 0.5 83.91 7.87 49.82 31.47 89.15 62.93 62.93 0.08 5.61 10 - 20 5.68 26.70 0 - 0.5 55.08 0.00 31.98 14.21 39.09 12.44 1.77 0.07 7.84 20 - 30 5.69 28.10 0 - 0.5 39.94 0.00 16.34 21.78 32.67 18.15 83.50 0.08 6.76 30 - 40 5.82 16.67 0 - 0.5 1.77 1.77 33.55 28.26 130.69 26.49 1.77 0.05 6.84 40 - 50 6.50 19.90 0 - 0.5 0.00 0.00 18.29 38.41 14.63 12.80 1.77 0.02 4.17 50 - 60 6.53 20.20 0 - 0.5 26.76 0.00 0.00 30.33 26.76 3.57 1.77 0.01 6.77 60 - 70 6.57 22.60 0 - 0.5 24.48 0.00 0.00 30.13 35.78 7.53 1.77 0.01 4.48 70 - 80 6.48 16.89 0 - 0.5 22.44 0.00 0.00 28.06 31.80 1.77 1.77 0.02 5.64 80 - 90 6.59 18.98 0 - 0.5 25.61 0.00 0.00 25.61 36.58 1.83 1.77 0.02 3.97

P2 Sample pH EC Carbonate Ca Mg Na K SO4 Cl NO3 Corg F level (cm) - µs/cm % g/t g/t g/t g/t g/t g/t g/t % g/t 0 - 10 5.60 74.80 0 - 0.5 34.70 0.00 21.21 21.21 30.85 15.42 15.42 0.05 8.19 10 - 20 5.53 24.00 0 - 0.5 26.77 0.00 8.37 6.69 15.06 3.35 1.77 0.04 12.11 20 - 30 5.84 18.56 0 - 0.5 23.31 0.00 8.97 5.38 17.93 3.59 1.77 0.03 12.24 30 - 40 6.40 15.24 0 - 0.5 31.24 1.84 7.35 7.35 14.70 3.68 1.77 0.03 8.05 40 - 50 6.28 20.50 0 - 0.5 17.06 0.00 0.00 9.48 9.48 1.77 1.77 0.03 9.56 50 - 60 6.40 15.28 0 - 0.5 14.36 0.00 8.97 8.97 16.15 3.59 1.77 0.02 5.39 60 - 70 6.49 15.61 0 - 0.5 15.29 0.00 15.29 15.29 15.29 1.77 1.77 0.03 2.77 70 - 80 6.17 11.24 0 - 0.5 19.45 0.00 11.67 21.40 25.29 7.78 1.77 0.03 2.76 80 - 90 6.50 15.80 0 - 0.5 12.01 0.00 8.58 18.88 25.74 3.43 5.15 0.03 2.73 90 - 100 6.57 14.24 0 - 0.5 26.25 0.00 0.00 22.50 33.75 1.83 1.77 0.03 2.76

P4 Sample pH EC Carbonate Ca Mg Na K SO4 Cl NO3 Corg F level (cm) - µs/cm % g/t g/t g/t g/t g/t g/t g/t % g/t 0 - 10 4.00 232.00 0 - 0.5 ------10 - 20 4. 23 232.00 0 - 0.5 ------20 - 30 4.01 41.10 0 - 0.5 0.00 0.00 11.61 3.87 94.19 5.16 3.87 7.60 - 30 - 40 4.28 45.00 0 - 0.5 0.00 0.00 12.92 4.70 99.84 3.52 38.76 0.08 1.14 40 - 50 4.25 35.60 0 - 0.5 ------0.05 1.09 50 - 60 4.25 34.80 0 - 0.5 0.00 0.00 8.75 3.75 101.26 3.75 1.77 0.05 -- 60 - 70 4.26 41.60 0 - 0.5 ------0.05 1.12 70 - 80 4.13 50.40 0 - 0.5 0.00 0.00 20.16 7.56 113.41 2.52 1.77 0.04 -- 80 - 90 4.19 26.20 0 - 0.5 16.27 0.00 16.27 10.17 191.17 4.07 1.77 0.01 1.13 90 - 100 ------0.01 4.30 _Not measured - 140

Appendices

Appendix IV: Hydrochemical data

Table.App. IV.1: the results of wet deposition analysis (rain chemistry).

Datum Na NH4+ K Mg Ca F Cl NO2- NO3 SO4 mg/L mg/L mg/L mg/L mg/L mg/L mg/L mg/L mg/L mg/L 19.03.2011 0.5 2.8 0.2 0.1 0.3 < 0,1 1.2 0.2 8.3 11.5 04.04.2011 0.5 2.9 0.3 0.1 1.5 < 0,1 1.2 0 4.8 8.7 12.04.2011 0.8 2.2 0.5 0 0.9 0.1 2.0 < 0,1 2.8 7.7 11.10.2011 0 0 0.2 0 0.5 < 0,1 0.6 < 0,1 1.4 2.6

Table App. IV.2: the results of hydrochemical analysis of water samples collected from the main water sources of Lottenbach during October 2010.

Sample Nr Parameter unit 1 2 3 4 5 6 EC µs/cm 1364 923 459 381 511 482 DO mg/l 8.25 6.72 7.15 9.87 9.74 6.76 pH - 7.81 7.22 6.45 7.78 7.30 7.43 EH mv 395 168 455 401 392 317 Ca mg/l 113.00 124.00 33.50 37.90 66.90 124.00 Mg mg/l 38.00 26.00 12.80 9.40 14.10 14.00 Na mg/l 105.00 37.50 29.30 14.90 16.70 18.70 K mg/l 18.80 9.70 4.60 9.30 2.80 3.40 SO4 mg/l 242.00 135.00 67.30 47.00 63.80 63.00 Cl mg/l 193.00 52.20 57.00 32.40 33.70 31.30 NO3 mg/l 5.50 2.10 37.90 12.80 11.70 5.60

141

Appendices

Table App. IV.3: the results of hydrochemical parameters of water samples collected from the gauged stations of the Lottenbach before, during and after storm events.

Sample EC Ca Mg Na K NH4+ F SO4 Cl NO3 Fe Fe2+ DOC Al Zn

Fig5.7-fig ms/cm mg/l mg/l mg/l mg/l mg/l mg/l mg/l mg/l mg/l mg/l mg/l mg/l µg/l µg/l 5.10

A1 - 68.20 13.50 15.00 2.00 0.00 0.20 68.60 26.70 13.30 - - - B1 - 69.00 13.40 21.70 3.90 39.80 0.20 70.30 28.20 16.70 0.40 0.60 - 5 5

C1 - 45.70 7.70 9.80 4.40 46.30 0.20 44.30 18.70 13.30 2.20 1.20 - 126 61

D1 - 42.50 8.30 14.00 4.10 3.90 0.20 44.30 24.60 12.20 0.70 0.40 - 86 42 E1 - 51.70 10.00 13.60 3.10 5.80 0.20 51.30 22.10 12.00 0.60 0.30 - 78 23

F1 - 66.30 12.90 14.70 2.50 4.80 0.20 65.40 26.10 13.20 0.70 0.30 - 81 29

G1 - 67.70 13.10 14.10 1.90 5.40 0.20 67.80 27.50 13.60 0.60 0.30 - 54 25 H1 - 65.30 12.60 15.60 2.10 0.10 0.20 70.40 28.50 13.90 0.40 0.30 - 53 24

I1 - 69.20 13.60 14.60 2.10 3.90 0.20 70.00 27.80 15.10 0.90 0.90 - 68 45 A2 0.506 59.4 12.7 23.2 4.9 n. m. 0.2 63.8 43.4 11.6 0.9 0.13 - 74 35

B2 0.505 59.9 13.1 23.5 4.8 g 0.2 64.9 44 11.8 1.5 0.16 - 99 76

C2 0.209 44.4 4.1 10.9 3.9 g 0.3 25.2 17.7 9.2 0.6 0.07 - 64 41 D2 0.239 23.1 3.9 7.9 4.2 g 0.1 14.4 12.2 3.7 0.5 0.13 - 69 38

E2 0.183 25.7 4.9 11.2 3.6 n. m. 0.3 26.1 19.8 6.4 0.8 0.22 - 83 37

F2 0.39 41.5 8.1 17.2 4.6 g 0.2 36.4 24.1 10.2 0.4 0.18 - 43 44

G2 0.487 57 12 24.4 5.5 n. m. 0.2 56.9 39.9 10.7 0.5 0.13 - 47 41

H2 0.503 58.2 12.7 24.8 5.6 n. m. 0.3 61.1 42.9 12.9 0.9 0.17 - 61 52

I2 0.509 57.4 12.4 25.1 5.9 n. m. 0.3 61.9 43.6 11.6 0.8 0.18 - 39 43

J2 0.514 58.2 12.8 24.8 5.6 n. m. 0.2 63.8 45.1 13.3 0.4 0.21 - 22 47

K2 0.51 58.2 12.8 24.5 5.6 n. m. 0.2 63.5 44.5 12 0.6 0.16 - 34 39 L2 0.49 59.7 12.6 20.3 4.7 n. m. 0.2 61.7 39.6 11.3 0.7 0.14 - 31 41

A3 - 35.90 7.00 12.70 4.70 4.50 0.40 30.30 20.00 6.00 0.60 0.26 6.16 - -

B3 - 14.00 2.10 6.70 3.40 5.90 0.30 10.50 7.60 5.40 1.40 0.78 6.12 - -

C3 - 23.90 3.80 9.00 4.70 4.90 0.40 17.50 11.40 8.40 1.10 0.56 7.92 - -

D3 - 32.30 5.60 14.00 5.10 4.20 0.50 27.90 17.40 6.50 0.30 0.16 7.39 - -

E3 - 21.10 3.30 11.90 4.30 8.50 0.40 19.30 14.40 9.60 0.10 0.18 6.81 - -

F3 - 27.30 4.50 11.90 4.60 7.50 0.40 22.40 15.30 5.10 0.20 0.15 7.32 - -

G3 - 38.10 7.00 16.30 6.10 0.30 0.50 33.40 20.90 8.30 0.40 0.18 7.93 - -

H3 - 47.80 9.60 23.70 6.70 0.00 0.50 52.70 34.50 12.00 0.20 0.29 6.00 - -

I3 - 49.10 10.70 24.40 7.30 0.10 0.50 56.60 46.50 16.80 0.40 0.17 4.76 - -

J3 - 49.00 10.80 23.40 7.00 0.00 0.50 56.00 36.60 14.50 0.30 0.16 4.66 - -

K3 - 49.10 11.00 23.20 6.90 0.00 0.40 56.40 37.20 14.10 0.30 0.15 5.09 - -

L3 - 48.60 11.10 22.30 6.60 0.00 0.40 57.60 38.40 15.10 0.40 0.15 4.71 - - M3 - 49.30 11.30 22.70 6.60 0.20 0.40 55.80 39.40 15.70 0.40 0.35 4.85 - -

N3/A4 - 49.40 11.50 22.20 6.10 0.00 0.40 58.00 40.70 17.40 0.60 - 3.34 - - O3/B4 - 49.30 11.60 22.00 6.50 0.00 0.40 58.40 41.60 17.40 0.40 0.18 4.56 - -

P3/C4 - 48.90 5.80 21.60 5.80 -- 0.40 58.20 41.40 19.50 0.20 0.25 5.03 - -

Q3/D4 - 48.70 11.70 21.60 5.40 9.60 0.40 59.70 42.00 19.50 0.20 0.16 3.66 - - E4 - 50.90 12.20 20.60 5.20 0.00 0.40 58.60 40.40 19.80 0.30 - 3.46 - -

F4 - 53.60 12.30 20.00 4.90 0.10 1.00 59.60 39.70 17.50 0.40 - 3.33 - - G4 - 57.20 12.70 19.10 4.50 9.00 0.40 61.00 38.60 14.70 0.50 0.35 3.95 - -

H4 - 65.10 13.50 17.90 3.70 0.10 0.40 60.50 35.90 11.50 0.60 - 3.61 - -

I4 - 53.60 12.30 20.00 4.90 0.10 1.00 59.60 39.70 17.50 0.70 - - -

- Not measured

142

Appendices

Appendix V: Evapotranspiration

Table App. V.1: The potential evapotranspiration according to Haude method.

Climatic parameters Grass Wheat Beech Spruce Month RH T14 es ea f ET0 ET0 f ET0 ET0 f ET0 ET0 f ET0 ET0

% C° g/m3 g/m4 - mm/day mm/month - mm/day mm/month - mm/day mm/month - mm/day mm/month April 45.30 18.28 20.95 9.49 0.24 2.75 82.52 0.29 3.32 99.72 0.1 1.15 34.39 0.35 4.01 120.35

may 47.55 19.15 22.13 10.52 0.29 3.37 104.34 0.29 3.37 104.34 0.23 2.67 82.75 0.39 4.53 140.31

June 57.27 20.22 23.63 13.53 0.29 2.93 87.86 0.28 2.83 84.83 0.28 2.83 84.83 0.34 3.43 103.01

July 53.23 19.08 22.02 11.72 0.28 2.88 89.40 0.26 2.68 83.02 0.32 3.30 102.17 0.31 3.19 98.98

August 56.94 21.66 25.82 14.70 0.26 2.89 89.62 0.25 2.78 86.18 0.26 2.89 89.62 0.25 2.78 86.18

September 56.68 20.29 23.73 13.45 0.23 2.36 70.94 0.23 2.36 70.94 0.17 1.75 52.44 0.2 2.06 61.69

October 60.97 15.03 17.04 10.39 0.2 1.33 41.24 0.22 1.46 45.36 0.1 0.67 20.62 0.13 0.86 26.80

November 65.10 11.91 13.92 9.06 0.2 0.97 29.14 0.2 0.97 29.14 0.01 0.05 1.46 0.07 0.34 10.20

December 81.96 6.99 10.00 8.19 0.2 0.36 11.18 0.2 0.36 11.18 0.01 0.02 0.56 0.05 0.09 2.80

January 82.88 5.66 9.13 7.56 0.2 0.31 9.69 0.2 0.31 9.69 0.01 0.02 0.48 0.08 0.13 3.88

February 73.63 1.46 6.79 5.00 0.2 0.36 10.38 0.2 0.36 10.38 0 0.00 0.00 0.04 0.07 2.08

March 62.77 11.87 13.88 8.71 0.23 1.19 36.84 0.25 1.29 40.04 0.04 0.21 6.41 0.14 0.72 22.42

April 58.40 11.53 13.57 7.92 0.24 1.35 40.64 0.29 1.64 49.11 0.1 0.56 16.93 0.35 1.98 59.27 Sum mm/a 703.80 Sum mm/a 723.92 Sum mm/a 492.66 Sum mm/a 737.96 Table App. V.2: The actual evapotranspiration of urban and deciduous forests according to Bagrov & Glugla method.

ET0 turc-Windel f ETmax Pkorr Pkorr/Etmax ETa/Etmax ETa Landuse mm/a - mm/a mm/a - - mm/a urban 712.45 0.80 569.96 944.50 1.66 0.38 216.5859 Deciduous forest 712.45 1.28 911.94 944.50 1.04 0.20 182.3881

Table App. V.3: The actual evapotranspiration of arable, grassland and coniferous forest according to Renger & Wessolek method.

a P b PWi c log WPfl d Etp e nfk ETa Land use So mm mm mm mm Fields 0.39 499.9 0.08 444.6 153 2.17 0.12 723.92 -109 149.37 541.06 Grass 0.48 499.9 0.1 444.6 286 2.16 0.1 703.80 -330 145.34 643.23 Coniferous forest 0.33 499.9 0.29 444.6 166 2.20 0.19 737.96 -127 157.78 671.99 Table App. V.4: The actual evapotranspiration of the gauged area of the Lottenbachtal.

Area ETa Landuse % mm Fields 13.00 70.34 Grass 11.00 70.76 Coniferous forest 1.00 6.72 Deciduous forest 20.00 36.48 Urban 54.00 116.96 Sum 100.00 301.25

143

Appendices

Appendix VI: Soil moisture

Table App. VI.1: Soil moisture data measured in the soil profiles P1, P2 and P3

3/06/2011 P4 P2 P1 10/06/2011 P4 P2 P1 1/08/2011 P4 P2 P1 0-10cm 0.15 0.18 0.18 0-10cm 0.17 0.18 0.23 0-10cm 0.20 0.43 - 10-20cm 0.15 0.11 0.10 10-20cm 0.14 0.27 0.17 10-20cm 0.16 0.29 - 20-30cm 0.12 0.18 0.11 20-30cm 0.11 0.23 0.14 20-30cm 0.10 0.25 - 30-40cm 0.13 0.16 0.16 30-40cm 0.12 0.16 0.15 30-40cm 0.11 0.25 - 40-50cm 0.11 0.10 0.11 40-50cm 0.12 0.15 0.16 40-50cm 0.10 0.27 - 50-60cm 0.13 0.18 0.17 50-60cm 0.13 0.18 0.18 50-60cm 0.12 0.25 - 60-70cm 0.12 0.20 0.17 60-70cm 0.12 0.18 0.21 60-70cm 0.13 0.25 - 70-80cm 0.10 0.18 0.18 70-80cm 0.10 0.18 0.18 70-80cm - 0.23 - 80-90cm 0.11 0.18 0.13 80-90cm 0.11 0.22 0.18 80-90cm - 0.22 - 90-100cm 0.20 0.15 90-100cm 0.19 0.19 90-100cm - 0.21 -

5/08/2011 P4 P2 P1 16/06/2011 P4 P2 P1 24/06/2011 P4 P2 P1 0-10cm 0.20 0.43 0.38 0-10cm 0.16 0.17 0.18 0-10cm 0.15 0.19 0.21 10-20cm 0.16 0.29 0.24 10-20cm 0.15 0.13 0.11 10-20cm 0.19 0.22 0.14 20-30cm 0.10 0.25 0.22 20-30cm 0.18 0.12 0.13 20-30cm 0.10 0.16 0.18 30-40cm 0.11 0.25 0.22 30-40cm 0.14 0.14 0.14 30-40cm 0.09 0.16 0.14 40-50cm 0.10 0.27 0.21 40-50cm 0.14 0.16 0.17 40-50cm 0.24 0.25 0.18 50-60cm 0.12 0.25 0.21 50-60cm 0.14 0.17 0.18 50-60cm 0.12 0.18 0.18 60-70cm 0.13 0.25 0.21 60-70cm 0.10 0.18 0.21 60-70cm 0.11 0.19 0.21 70-80cm - 0.23 0.20 70-80cm 0.11 0.13 0.18 70-80cm 0.11 0.20 0.14 80-90cm - 0.22 0.22 80-90cm 0.12 0.17 0.18 80-90cm 0.11 0.19 0.18 90-100cm - 0.21 0.22 90-100cm 0.18 0.17 90-100cm 0.19 0.18

23/08/2011 P4 P2 P1 30/06/2011 P4 P2 P1 7/07/2011 P4 P2 P1 0-10cm 0.21 0.34 0.40 0-10cm 0.16 0.19 0.21 0-10cm 0.15 0.18 0.20 10-20cm 0.25 0.25 0.27 10-20cm 0.15 0.20 0.22 10-20cm 0.18 0.21 0.20 20-30cm 0.13 0.26 0.25 20-30cm 0.13 0.17 0.20 20-30cm 0.16 0.19 0.21 30-40cm 0.11 0.27 0.25 30-40cm 0.13 0.18 0.17 30-40cm 0.15 0.17 0.19 40-50cm 0.11 0.28 0.26 40-50cm 0.11 0.16 0.18 40-50cm 0.14 0.16 0.17 50-60cm 0.11 0.30 0.27 50-60cm 0.12 0.14 0.18 50-60cm 0.14 0.16 0.18 60-70cm 0.11 0.29 0.28 60-70cm 0.11 0.18 0.21 60-70cm 0.12 0.18 0.19 70-80cm - 0.26 0.28 70-80cm 0.10 0.18 0.15 70-80cm 0.11 0.19 0.17 80-90cm - 0.28 0.26 80-90cm 0.17 0.18 80-90cm 0.18 0.16 90-100cm - 0.32 0.25 90-100cm 0.17 0.19 90-100cm 0.19 0.15

29/08/2011 P4 P2 P1 6/09/2011 P4 P2 P1 15/07/2011 P4 P2 P1 0-10cm 0.21 0.38 0.37 0-10cm 0.19 0.36 0.38 0-10cm 0.12 0.23 0.14 10-20cm 0.18 0.25 0.25 10-20cm 0.15 0.24 0.27 10-20cm 0.09 0.21 0.11 20-30cm 0.13 0.24 0.24 20-30cm 0.12 0.24 0.25 20-30cm 0.06 0.19 0.12 30-40cm 0.12 0.26 0.24 30-40cm 0.12 0.24 0.24 30-40cm 0.07 0.20 0.14 40-50cm 0.11 0.28 0.24 40-50cm 0.12 0.26 0.25 40-50cm 0.08 0.21 0.16 50-60cm 0.11 0.19 0.25 50-60cm 0.13 0.24 0.24 50-60cm 0.11 0.23 0.19 60-70cm 0.11 0.44 0.26 60-70cm 0.13 0.27 0.25 60-70cm 0.09 0.23 0.22 70-80cm - 0.25 0.26 70-80cm - 0.27 0.26 70-80cm 0.11 0.24 0.21 80-90cm - 0.24 0.24 80-90cm - 0.31 0.25 80-90cm - 0.24 0.22 90-100cm - 0.25 0.24 90-100cm - 0.27 0.23 90-100cm - 0.22 0.23

22/07/2011 P4 P2 P1 12/09/2011 P4 P2 P1 27.9.2011 P4 P2 P1 0-10cm 0.16 0.32 0.30 0-10cm 0.18 0.41 0.42 0-10cm 0.14 0.31 0.38 10-20cm 0.11 0.29 0.21 10-20cm 0.15 0.26 0.30 10-20cm 0.11 0.24 0.27 20-30cm 0.09 0.17 0.12 20-30cm 0.12 0.25 0.26 20-30cm 0.09 0.24 0.22 30-40cm 0.09 0.18 0.15 30-40cm 0.11 0.26 0.24 30-40cm 0.10 0.24 0.23 40-50cm 0.08 0.22 0.19 40-50cm 0.12 0.27 0.25 40-50cm 0.09 0.26 0.24 50-60cm 0.10 0.23 0.20 50-60cm 0.13 0.27 0.28 50-60cm 0.12 0.25 0.25 60-70cm 0.09 0.23 0.20 60-70cm 0.13 0.29 0.27 60-70cm - 0.19 0.25 70-80cm - 0.23 0.20 70-80cm - 0.31 0.27 70-80cm - 0.35 0.26 80-90cm - 0.23 0.21 80-90cm - 0.31 0.25 80-90cm - 0.24 0.26 90-100cm - 0.20 0.22 90-100cm - 0.45 0.25 90-100cm - 0.24 0.26

144

Appendices

4/10/2011 P4 P2 P1 13/10/2011 P4 P2 P1 18.1.2012 P4 P2 P1 0-10cm 0.13 0.34 0.36 0-10cm 0.18 0.28 0.39 0-10cm 0.24 0.40 - 10-20cm 0.11 0.24 0.22 10-20cm 0.12 0.24 0.25 10-20cm 0.22 0.20 - 20-30cm 0.08 0.25 0.22 20-30cm 0.08 0.25 0.25 20-30cm 0.20 0.21 - 30-40cm 0.08 0.25 0.23 30-40cm 0.08 0.27 0.25 30-40cm 0.21 0.20 - 40-50cm 0.10 0.27 0.23 40-50cm 0.11 0.26 0.26 40-50cm 0.23 0.21 - 50-60cm 0.10 0.28 0.23 50-60cm 0.10 0.32 0.25 50-60cm 0.21 0.15 - 60-70cm 0.12 0.29 0.23 60-70cm 0.12 0.28 0.27 60-70cm 0.21 0.22 - 70-80cm - 0.29 0.26 70-80cm - 0.31 0.27 70-80cm - 0.24 - 80-90cm - 0.31 0.26 80-90cm - 0.28 0.27 80-90cm - 0.39 - 90-100cm - 0.30 0.28 90-100cm - 0.25 0.27 90-100cm - 0.22 -

31/01/2012 P4 P2 P1 27/10/2011 P4 P2 P1 4/11/2011 P4 P2 P1 0-10cm 0.27 0.36 0.36 0-10cm 0.15 0.41 0.44 0-10cm 0.13 0.38 0.33 10-20cm 0.26 0.23 0.24 10-20cm 0.12 0.27 0.45 10-20cm 0.11 0.38 0.23 20-30cm 0.20 0.20 0.25 20-30cm 0.09 0.28 0.24 20-30cm 0.08 0.28 0.23 30-40cm 0.20 0.25 0.24 30-40cm 0.09 0.28 0.23 30-40cm 0.08 0.27 0.23 40-50cm 0.21 0.26 0.25 40-50cm 0.11 0.25 0.23 40-50cm 0.08 0.26 0.24 50-60cm 0.19 0.18 0.27 50-60cm 0.12 0.26 0.25 50-60cm 0.11 0.27 0.25 60-70cm 0.21 0.24 0.26 60-70cm 0.11 0.24 0.25 60-70cm 0.11 0.27 0.24 70-80cm - 0.21 0.28 70-80cm - 0.27 0.27 70-80cm - 0.28 0.25 80-90cm - 0.25 0.26 80-90cm - 0.27 0.26 80-90cm - 0.22 0.25 90-100cm - 0.33 0.23 90-100cm - 0.28 0.25 90-100cm - 0.28 0.23

21.2.2012 P4 P2 P1 27.2.2012 P4 P2 P1 14/11/2011 P4 P2 P1 0-10cm 0.28 0.46 0.48 0-10cm 0.36 0.34 0.61 0-10cm 0.13 0.39 0.43 10-20cm 0.25 0.28 0.27 10-20cm 0.29 0.30 0.30 10-20cm 0.11 0.26 0.25 20-30cm 0.21 0.27 0.24 20-30cm 0.22 0.30 0.24 20-30cm 0.10 0.27 0.23 30-40cm 0.41 0.28 0.24 30-40cm 0.21 0.27 0.25 30-40cm 0.09 0.28 0.23 40-50cm 0.21 0.27 0.24 40-50cm 0.23 0.28 0.25 40-50cm 0.10 0.28 0.23 50-60cm 0.21 0.29 - 50-60cm 0.24 0.29 0.26 50-60cm 0.12 0.19 0.25 60-70cm 0.21 0.28 0.60 60-70cm 0.22 0.26 0.26 60-70cm 0.11 0.28 0.25 70-80cm - 0.29 0.36 70-80cm - 0.28 0.27 70-80cm - 0.31 0.26 80-90cm - 0.29 0.07 80-90cm - 0.27 0.28 80-90cm - 0.30 0.25 90-100cm - 0.28 - 90-100cm - 0.28 0.29 90-100cm - 0.28 0.25

24/11/2011 P4 P2 P1 20.3.2012 P4 P2 P1 28.3.2012 P4 P2 P1 0-10cm 0.13 0.33 0.34 0-10cm 0.24 0.46 0.48 0-10cm 0.29 0.36 0.35 10-20cm 0.10 0.24 0.23 10-20cm 0.20 0.28 0.27 10-20cm 0.24 0.25 0.33 20-30cm 0.08 0.26 0.22 20-30cm 0.27 0.27 0.24 20-30cm 0.26 0.25 0.29 30-40cm 0.11 0.27 0.23 30-40cm 0.23 0.28 0.24 30-40cm 0.20 0.25 0.23 40-50cm 0.13 0.27 0.23 40-50cm 0.21 0.27 0.24 40-50cm 0.22 0.25 0.24 50-60cm 0.14 0.26 0.24 50-60cm 0.38 0.29 - 50-60cm 0.22 0.25 0.24 60-70cm 0.11 0.26 0.25 60-70cm 0.28 0.28 0.60 60-70cm 0.20 0.16 0.25 70-80cm - 0.30 0.26 70-80cm - 0.29 0.36 70-80cm - 0.39 0.25 80-90cm - 0.29 0.26 80-90cm - 0.29 0.07 80-90cm - 0.27 0.27 90-100cm - 0.31 0.28 90-100cm - 0.28 - 90-100cm - 0.29 0.27

21/12/2011 P4 P2 P1 30.12.2011 P4 P2 P1 11.4.2012 P4 P2 P1 0-10cm 0.24 0.42 0.37 0-10cm 0.35 0.36 0.39 0-10cm 0.28 0.47 0.46 10-20cm 0.21 0.26 0.24 10-20cm 0.46 0.26 0.27 10-20cm 0.25 0.32 0.26 20-30cm 0.13 0.27 0.24 20-30cm 0.20 0.28 0.26 20-30cm 0.18 0.30 0.24 30-40cm 0.15 0.27 0.27 30-40cm 0.31 0.28 0.24 30-40cm 0.19 0.30 0.23 40-50cm 0.15 0.30 0.26 40-50cm 0.14 0.25 0.25 40-50cm 0.20 0.29 0.24 50-60cm 0.13 0.28 0.28 50-60cm 0.19 0.29 0.29 50-60cm 0.21 0.29 0.26 60-70cm 0.13 0.30 - 60-70cm 0.19 0.31 0.29 60-70cm 0.20 0.28 0.24 70-80cm - 0.28 0.49 70-80cm - 0.31 0.29 70-80cm - 0.27 0.26 80-90cm - 0.23 0.35 80-90cm - - 0.23 80-90cm - 0.28 0.29 90-100cm - 0.27 - 90-100cm - - - 90-100cm - 0.29 0.27

145

Curriculum vitae

CURRICULUM VITAE

PERSONAL DETAILS

Name Mohammad Alhamed Date of Birth 3. January 1983 Place of Birth Hama/Syria E-mail [email protected] [email protected]

EDUCATION

2000 – 2004 BSc-Geology Applied Geology. Department of Geology in Damascus university, Syria 2004 – 2005 Diploma in Petrology and Geochemistry. Department of Geology in Damascus university, Syria 2005 – 2006 Diploma in Hydrogeology. Department of Geology in Damascus university, Syria 2006 – 2007 Assistance position . Department of Geology in Damascus university, Syria Since 2008 to date Scientific scholarship from Damascus university, Syria

Publications Alhamed M and Wohnlich S (2010): Estimation of Direct Runoff and Groundwater Recharge of Fractured Sandstone by Using Hydrologic Modeling and Hydrometric Measurement of Element of Hydrologic Budget in Lotten Valley, Germany. Grundwasser für Die Zukunft Tagung 12-16 mai 2010. Tübingen. Germany. Poster. Alhamed M and Wohnlich S (2010): Estimation of Direct and Groundwater Recharge of Fractured Sandstone by Coupling Water Budget, Evapotranspiration and Hydrologic models in Lottental, South of Bochum, Germany. 4. Bochumer Grundwassertag. Bochum. Germany. Poster. Alhamed M (2010): Estimation of Direct Surface Runoff and Groundwater Recharge by using of water budget, hydrological and evapo-transpiration models of fractured sandstone Formation in the Lottental Catchment Area, South of Bochum. Germany. Master thesis. Department of Hydrogeology. Faculty of Geoscience. Ruhr University of Bochum. 120 p. Alhamed M and Wohnlich S (2012): Investigation Impact of Abandoned Coal Mines on Surface Water and Groundwater Quality in the South of Bochum. 5. Bochumer Grundwassertag. Bochum. Germany. Poster. Alhamed M and Wohnlich S (submitted): Environmental Impact of the Abandoned Coal Mines on the Surface Water and the Groundwater in the South of Bochum, Germany. Submitted to a peer-reviewed journal. Alhamed M and Wohnlich S (submitted): Geochemical Processes Controlling the Neutralization Processes of the Acid Mine Drainage in the South of Bochum, Germany. Submitted to a peer-reviewed journal. 146

Curriculum vitae

Alhamed M and Wohnlich S (submitted): Hydrochemical Responses during and after Strom Events and Hydrograph Separation in the Lottental Catchment Area, Bochum, Germany. Submitted to a peer-reviewed journal. Alhamed M and Wohnlich S (to be submitted): The hydrological, The Hydrogeological and The Hydrochemical Framework of the Lottenbachtal, Bochum, Germany.

Languages Arabic Native speaker English Good

German Good

Current address

Mohammad Alhamed NA 4/132 Lehrstuhl für Angewandte Geologie Fakülitäte für Geowissenschafter Universitätstr 150 44809 Bochum

147