Effects of Sea Water Scrubbing

Final report

Marc Hufnagl, Research Centre Terramare, Schleusenstrasse 1, 26382 Wilhelmshaven, Germany

Prof. Dr. Gerd Liebezeit, Research Centre Terramare, Schleusenstrasse 1, 26382 Wilhelmshaven,

Germany

Dr. Brigitte Behrends, School of Marine Science and Technology, University of Newcastle,

Newcastle upon Tyne, NE1 7RU, UK

March 2005
I

Index

1 PROJECT DESCRIPTION ......................................................................................................................... 1

2 SUMMARY ................................................................................................................................................... 1

3 INTRODUCTION......................................................................................................................................... 1

4 MATERIAL AND METHODS FOR PRELIMINARY TRIALS............................................................. 5

4.1 PH-BUFFER-CAPACITY OF NATURAL SEAWATER(MIX-TEST)................................................................... 5

4.2 POLYCYCLIC AROMATIC HYDROCARBONS .............................................................................................. 6

5 MATERIAL AND METHODS: DETERMINATION OF ENVIRONMENTAL PARAMETERS AND

POLLUTANTS ................................................................................................................................................... 10

5.1 SAMPLING POINTS, SAMPLING, TRANSPORT AND STORAGE ................................................................... 10

5.1.1 Sampling in February and March ................................................................................................. 10

5.1.2 Sampling in July, September and November................................................................................. 12

5.2 TEMPERATURE, PH, SALINITY, OXYGEN................................................................................................ 14

5.3 METALS AND SULPHATE ........................................................................................................................ 15

5.4 POLYCYCLIC AROMATIC HYDROCARBONS (PAH)................................................................................. 15

5.4.1 Calibration, determination of accuracy, Carry-over .................................................................... 15

5.4.2 Extraction...................................................................................................................................... 20

5.4.3 Determination of the origin of PAHs ............................................................................................ 22

5.5 PLANKTON SAMPLES .............................................................................................................................. 23

6 MATERIAL AND METHODS: TOXICITY TESTS AND ACCUMULATION TEST....................... 24

6.1 LUMISTOX.............................................................................................................................................. 24

6.2 BRINE SHRIMP TEST ............................................................................................................................... 24

6.3 ACCUMULATION TEST ............................................................................................................................ 25

6.3.1 Preparation and Performance....................................................................................................... 25

6.3.2 Analysis and extraction of the mussels.......................................................................................... 27

7 RESULTS OF PRELIMINARY TRIALS ................................................................................................ 29

7.1 PH-MIXTURES........................................................................................................................................ 29

7.1.1 Jade Bay, Wilhelmshaven, Germany ............................................................................................. 29

7.1.2 Ems River, Papenburg, Germany.................................................................................................. 30

7.1.3 Odense, Denmark .......................................................................................................................... 30

7.1.4 Calais, France ............................................................................................................................... 31

7.1.5 Dover, England ............................................................................................................................. 31

7.1.6 Comparison of all results (in equilibrium).................................................................................... 32

7.2 GC-MS VALIDATION............................................................................................................................. 34

7.3 PAH-EXTRACTION, VALIDATION OF METHOD ...................................................................................... 37
II

8 RESULTS AND DISCUSSION OF ENVIRONMENTAL SAMPLINGS ............................................. 41

8.1 1

ST SAMPLING (FEBRUARY) .................................................................................................................... 41

8.1.1 pH, Temperature, Salinity, Conductivity, Oxygen......................................................................... 41

8.1.2 Metals and Sulphate ...................................................................................................................... 42

8.1.3 Nutrients........................................................................................................................................ 43

8.1.4 Polycyclic Aromatic Hydrocarbons .............................................................................................. 44

8.2 2

ND SAMPLING(MARCH)......................................................................................................................... 46

8.2.1 pH, Temperature, Salinity, Conductivity, Oxygen......................................................................... 46

8.2.2 Metals and Sulphate ...................................................................................................................... 48

8.2.3 Nutrients........................................................................................................................................ 51

8.2.4 Polycyclic Aromatic Hydrocarbons .............................................................................................. 52

8.3 3

RD SAMPLING (JULY) ............................................................................................................................. 58

8.3.1 pH, salinity and temperature......................................................................................................... 58

8.3.2 Nutrients........................................................................................................................................ 59

8.3.3 Polycyclic aromatic hydrocarbons................................................................................................ 61

8.4 4

TH SAMPLING (SEPTEMBER)................................................................................................................... 66

8.4.1 pH, salinity and temperature......................................................................................................... 66

8.4.2 Nutrients........................................................................................................................................ 68

8.4.3 Metals and Sulphate ...................................................................................................................... 69

8.4.4 Polycyclic aromatic hydrocarbons................................................................................................ 70

8.5 5

TH SAMPLING (NOVEMBER)................................................................................................................... 75

8.5.1 pH, salinity and temperature......................................................................................................... 75

8.5.2 Metals and Sulphate ...................................................................................................................... 77

8.5.3 Nutrients........................................................................................................................................ 78

8.5.4 Polycyclic Aromatic Hydrocarbons .............................................................................................. 79

8.6 ANNUAL CIRCLE .................................................................................................................................... 84

8.6.1 pH, salinity and temperature......................................................................................................... 84

8.6.2 Nitrate and sulphate ...................................................................................................................... 92

8.6.3 Polycyclic aromatic hydrocarbons................................................................................................ 93

8.6.4 Plankton samples ........................................................................................................................ 100

8.7 RESULTS OF MUSSEL ANALYSIS............................................................................................................ 102

8.8 RESULTS OF SEDIMENT ANALYSIS........................................................................................................ 104

9 RESULTS AND DISCUSSION OF THE TOXICITY AND ACCUMULATION TESTS................. 109

9.1 LUMISTOX TEST ................................................................................................................................... 109

9.2 BRINE SHRIMP TEST ............................................................................................................................. 110

9.3 ACCUMULATION TEST .......................................................................................................................... 111

9.3.1 Mussel analyses: size, weight, condition index, fat content ........................................................ 111

9.3.2 Mussel analyses: PAH content, accumulation, mortality ............................................................ 114

10 CONCLUSIONS ................................................................................................................................... 122

REFERENCES.................................................................................................................................................. 126

REFERENCES WORLD WIDE WEB........................................................................................................... 129
III

LIST OF FIGURES

FIG. 1: GEOGRAPHICAL POSITION OF DOVER AND CALAIS AND ROUTE OF THE “PRIDE OF KENT” INSIDE THE

CHANNEL ....................................................................................................................................................... 10

FIG. 2: DOVER HARBOUR SAMPLING POINTS (LEFT: SAMPLING ON 11.2.2004, RIGHT SAMPLING ON 24.3.2004)..... 11

FIG. 3: PHOTOS OF THE SEAWATER SCRUBBER SAMPLING POINTS INSIDE THE „PRIDE OF KENT“. L.: POINT 1

SEAWATER SCRUBBER INLET. M.L.: POINT 2 SEAWATER SCRUBBER OUTLET. M.R.: POINT 3 AND 5: OUTLET

AND INLET OF US FILTER, TOP OF CYCLONES. R.: POINT 4, 7 AND 8: TUBE GOING TO THE SETTLING TANK AND

TOP AND BOTTOM OF SAMPLING TANK. .......................................................................................................... 12

FIG. 4: VAN VEEN GRAB AND NISKIN LADLE FOR SEDIMENT AND WATER SAMPLES RESPECTIVELY........................ 22

FIG. 5: PICTURE OF ARTEMIA SALINA. THIS ORGANISM WAS USED FOR TOXICITY TESTS .......................................... 24

FIG. 6: PHOTOS OF THE EXPERIMENTAL DESIGN OF THE ACCUMULATION TEST. L.: ALL NINE AQUARIUMS WITH

AERATION PUMP. M.: CLOSE VIEW ON TO AN AQUARIUM WITH AERATION STONE AND MUSSELS PLACED ON

THE PVC NET................................................................................................................................................. 26

FIG. 7: LEFT: DIFFERENT AMOUNTS OF ACIDIFIED (PH 4)JADE BAY SEAWATER MIXED WITH NON-ACIDIFIED JADE

BAY SEAWATER. GIVEN IS THE DEVELOPMENT OF PH OVER TIME IN RELATION TO THE PERCENTAGE OF PH 4

WATER.RIGHT: SAME AS LEFT BUT ONLY 50 : 50 MIXING RATIO WITH DIFFERENT VOLUMES. ........................ 29

FIG. 8: LEFT: 50 : 50 MIXING RATIO OF ACIDIFIED (PH 4) JADE BAY AND NATURAL JADE BAY SEAWATER, WITH

DIFFERENT STIR BAR ROTATION SPEEDS. RIGHT: PH-VALUE IN EQUILIBRIUM IN DEPENDENCY OF MIXING RATIO

(% PH 4 SEAWATER) ...................................................................................................................................... 29

FIG. 9: LEFT: DIFFERENT AMOUNTS OF ACIDIFIED (PH 4) EMS RIVER WATER MIXED WITH NON ACIDIFIED EMS

RIVER WATER. GIVEN IS THE DEVELOPMENT OF PH OVER TIME. RIGHT: PH-VALUE IN EQUILIBRIUM AS

FUNCTION OF MIXING RATIO (% PH 4 SEAWATER) ......................................................................................... 30

FIG. 10: LEFT: DIFFERENT AMOUNTS OF ACIDIFIED (PH 4) ODENSE SEAWATER MIXED WITH NON ACIDIFIED

ODENSE SEAWATER. GIVEN IS THE DEVELOPMENT OF PH OVER TIME. RIGHT: PH-VALUE IN EQUILIBRIUM AS

FUNCTION OF MIXING RATIO (% PH 4 SEAWATER) ......................................................................................... 30

FIG. 11: LEFT: DIFFERENT AMOUNTS OF ACIDIFIED (PH 4) CALAIS SEAWATER MIXED WITH NON ACIDIFIED CALAIS

SEAWATER. GIVEN IS THE DEVELOPMENT OF PH OVER TIME.RIGHT: PH-VALUE IN EQUILIBRIUM AS FUNCTION

OF MIXING RATIO (% PH 4 SEAWATER) .......................................................................................................... 31

FIG. 12: LEFT: DIFFERENT AMOUNTS OF ACIDIFIED (PH 4) DOVER SEAWATER MIXED WITH NON ACIDIFIED DOVER

SEAWATER. GIVEN IS THE DEVELOPMENT OF PH. RIGHT: PH-VALUE IN EQUILIBRIUM AS FUNCTION OF MIXING

RATIO (% PH 4 SEAWATER)............................................................................................................................ 31

FIG. 13: LEFT: PH-VALUE IN EQUILIBRIUM OF MIXING RATIO (% PH 4 SEAWATER) FOR ALL PRELIMINARY PH

TRIALS. RIGHT:MEAN OF ALL TRIALS WITH STANDARD DEVIATION. ............................................................. 32

FIG. 14: LEFT: MEAN PH VALUE (POINTS) AND STANDARD DEVIATION (ERROR BARS) IN EQUILIBRIUM OF MIXING

RATIO (% PH 4 SEAWATER) FOR ALL PRELIMINARY PH TRIALS. THE BLACK LINE SHOWS THE MODEL FITTED

TO THE POINTS AND THE RED LINE SHOWS THE 95 % CONFIDENCE INTERVAL OF THE MODEL. RIGHT: CHANGE

OF PH OVER PERCENTAGE .............................................................................................................................. 32

FIG. 15: RESULTS OF PRELIMINARY TRIALS FOR THE DETERMINATION OF THE RECOVERY RATES OF PAHS FROM

SEAWATER. .................................................................................................................................................... 38
IV

FIG. 16: RESULTS OF PRELIMINARY TRIALS FOR THE DETERMINATION OF RECOVERY RATES OF PAHS FROM

SEAWATER. .................................................................................................................................................... 38

FIG. 17: RESULTS OF PRELIMINARY TRIALS FOR THE DETERMINATION OF RECOVERY RATES OF PAHS FROM

SEAWATER. .................................................................................................................................................... 38

FIG. 18: RECOVERY RATES OF THE SOLUBLE PAHS FROM NATURAL SEAWATER WITH CHROMABOND SPE SORBENT

C18 EC AND ELUTION SOLVENT DCM. LEFT: CALAIS SEAWATER RIGHT: DOVER SEAWATER. ...................... 39

FIG. 19: FRACTIONATION OF PAHS BETWEEN DISSOLVED AND PARTICULATE FRACTION AFTER DIFFERENT

INCUBATION TIMES. ....................................................................................................................................... 40

FIG. 20: MEAN RECOVERY RATE AND STANDARD DEVIATION FOR EIGHT EXTRACTIONS OF DOVER SEAWATER AND

PARTICULATE FRACTION. ............................................................................................................................... 40

FIG. 21: THE AUXILIARY ENGINES AND SWS RUNNING AT THE 24.03.04............................................................... 46

FIG. 22: LEFT: COPPER CONCENTRATION [PPB] RIGHT: MANGANESE CONCENTRATION [PPB] DETERMINED FOR

ECOSILENCER INLET AND OUTLET SAMPLES TAKEN IN CALAIS, DOVER AND THE CHANNEL ON 23/24.03.2004

AND ON 11.02.2004. IAPSO: ATLANTIC WATER SALINITY STANDARD .......................................................... 49

FIG. 23: LEFT: ZINC CONCENTRATION [PPB] RIGHT: BARIUM CONCENTRATION [PPB] DETERMINED FOR

ECOSILENCER INLET AND OUTLET SAMPLES TAKEN IN CALAIS, DOVER AND THE CHANNEL ON 23/24.03.2004

AND ON 11.02.2004. IAPSO: ATLANTIC WATER SALINITY STANDARD .......................................................... 50

FIG. 24: LEFT: LITHIUM CONCENTRATION [PPB] RIGHT: STRONTIUM CONCENTRATION [PPB] DETERMINED FOR

ECOSILENCER INLET AND OUTLET SAMPLES TAKEN IN CALAIS, DOVER AND THE CHANNEL ON 23/24.03.2004

AND ON 11.02.2004. IAPSO: ATLANTIC WATER SALINITY STANDARD .......................................................... 50

FIG. 25: LEFT: CALCIUM CONCENTRATION [PPM] RIGHT: POTASSIUM CONCENTRATION [PPM] DETERMINED FOR

ECOSILENCER INLET AND OUTLET SAMPLES TAKEN IN CALAIS, DOVER AND THE CHANNEL ON 23/24.03.2004

AND ON 11.02.2004. IAPSO: ATLANTIC WATER SALINITY STANDARD .......................................................... 50

FIG. 26: LEFT: MAGNESIUM CONCENTRATION [PPB] RIGHT: SULPHATE CONCENTRATION [PPB] DETERMINED FOR

ECOSILENCER INLET AND OUTLET SAMPLES TAKEN IN CALAIS, DOVER AND THE CHANNEL ON 23/24.03.2004

AND ON 11.02.2004. IAPSO: ATLANTIC WATER SALINITY STANDARD .......................................................... 51

FIG. 27: PLOT OF ISOMERIC PHENANTHRENE/ANTHRACENE RATIOS AGAINST FLUORANTHENE/PYRENE RATIOS FOR

ALL SAMPLES TAKEN IN FEBRUARY AND MARCH .......................................................................................... 54

FIG. 28: PLOT OF ISOMERIC PHENANTHRENE/ANTHRACENE RATIOS AGAINST FLUORANTHENE/PYRENE RATIOS FOR

THE SEAWATER SCRUBBER SAMPLES TAKEN IN FEBRUARY AND MARCH. ...................................................... 55

FIG. 29: RESULTS OF THE PCA OF THE HARBOUR SAMPLES ................................................................................... 57

FIG. 30: REGRESSION BETWEEN 1

ST AND 2ND EXTRACTION LEFT: REGRESSION OF THE AMOUNT OF EXTRACTED

PARTICULATE MATERIAL [G] RIGHT: REGRESSION OF ALLPAHS [NG/L] (SUM PARTICULATE, DISSOLVED).... 62

FIG. 31: PLOT OF ISOMERIC PHENANTHRENE/ANTHRACENE RATIOS AGAINST FLUORANTHENE/PYRENE RATIOS FOR

ALL HARBOUR SAMPLES (LEFT) AND SEAWATER SCRUBBER SAMPLES (RIGHT) .............................................. 62

FIG. 32: RESULTS OF THE PCA OF THE HARBOUR SAMPLES ................................................................................... 65

FIG. 33: REGRESSION BETWEEN 1

ST AND 2ND EXTRACTION LEFT: REGRESSION BETWEEN THE AMOUNT OF

EXTRACTED PARTICULATE MATERIAL [G]. RIGHT: REGRESSION OF ALL DETERMINED PAH CONCENTRATIONS

[NG/L] (SUM, PARTICULATE, DISSOLVED) ....................................................................................................... 71
V

FIG. 34: PLOT OF ISOMERIC PHENANTHRENE/ANTHRACENE RATIOS AGAINST FLUORANTHENE/PYRENE RATIOS FOR

ALL SAMPLES ................................................................................................................................................. 73

FIG. 35: RESULTS OF THE PCA OF THE HARBOUR SAMPLES ................................................................................... 74

FIG. 36: REGRESSION BETWEEN THE FIRST AND THE SECOND EXTRACTION. LEFT: FILTER WEIGHTS, RIGHT: PAH

CONCENTRATIONS.......................................................................................................................................... 80

FIG. 37: PLOT OF ISOMERIC PHENANTHRENE/ANTHRACENE RATIOS AGAINST FLUORANTHENE/PYRENE RATIOS FOR

ALL SAMPLES ................................................................................................................................................. 82

FIG. 38: RESULTS OF THE PCA OF THE HARBOUR SAMPLES ................................................................................... 83

FIG. 39: SALINITY, TEMPERATURE, AND PH MEASURED AT POINT CAL 1 AND CAL 2 ............................................. 84

FIG. 40: SALINITY, TEMPERATURE, AND PH MEASURED AT POINT CAL 3 AND CAL 4 ............................................. 84

FIG. 41: SALINITY, TEMPERATURE, AND PH MEASURED AT POINTC5 AND C50 ..................................................... 85

FIG. 42: SALINITY, TEMPERATURE, AND PH MEASURED AT POINT C350 AND C750 ............................................... 85

FIG. 43: SALINITY, TEMPERATURE, AND PH MEASURED AT POINT DOV 1 AND DOV 2............................................ 86

FIG. 44: SALINITY, TEMPERATURE, AND PH MEASURED AT POINT DOV 3 AND DOV 4............................................ 86

FIG. 45: SALINITY, TEMPERATURE, AND PH MEASURED AT POINT D5 AND D50..................................................... 86

FIG. 46: SALINITY, TEMPERATURE, AND PH MEASURED AT POINT D350 AND D700............................................... 86

FIG. 47: SALINITY, TEMPERATURE, AND PH MEASURED AT POINT SD1 AND SD2 .................................................. 88

FIG. 48: SALINITY, TEMPERATURE, AND PH MEASURED AT POINT SC1 AND SC2................................................... 88

FIG. 49: SALINITY, TEMPERATURE, AND PH MEASURED AT POINT SCH1 AND SCH2 ............................................. 88

FIG. 50: TEMPERATURE DEPENDENCY OF PH. THE RED LINE SHOWS THE COURSE OF THE PH WHEN THE SAMPLE

WAS HEATED AND THE BLUE LINE SHOWS THE COURSE OF THE PH WHEN THE SAMPLE WAS COOLED DOWN

AGAIN. ........................................................................................................................................................... 88

FIG. 51: SALINITY, TEMPERATURE, AND PH MEASURED AT POINT SCH3 AND SCH5 ............................................. 89

FIG. 52: SALINITY, TEMPERATURE, AND PH MEASURED AT POINT SCH6 ............................................................... 89

FIG. 53: PH AND SALINITY IN THE HARBOUR OF DOVER. TRIANGLES REPRESENT THE NATURAL VARIABILITY

DURING ALL SAMPLINGS IN 2004. DIAMONDS REPRESENT THE VALUES OF THE TRANSECT SAMPLES. ............ 90

FIG. 54: PH AND SALINITY IN THE HARBOUR OF CALAIS. TRIANGLES REPRESENT THE NATURAL VARIABILITY

DURING ALL SAMPLINGS IN 2004. DIAMONDS REPRESENT THE TRANSECT VALUES. ....................................... 90

FIG. 55: PH IMPACT OF SWS EFFLUENTS ON THE RECEIVING HARBOUR WATER IN DOVER AND CALAIS AT THREE

SAMPLING (JULY, SEPT. AND NOV.)............................................................................................................... 91

FIG. 56: TEMPERATURE [°C] IMPACT OF SWS EFFLUENTS ON THE RECEIVING HARBOUR WATER IN DOVER AND

CALAIS AT THREE SAMPLING (JULY, SEPT. AND NOV.).................................................................................. 91

FIG. 57: TEMPERATURES [°C] OF HARBOUR AND TRANSECT SAMPLES. .................................................................. 91

FIG. 58: NITRATE CONCENTRATIONS [μMOL L- 1] OBSERVED DURING ALL SAMPLINGS. LEFT: PORT OF CALAIS.

RIGHT: PORT OF DOVER................................................................................................................................. 92

FIG. 59: REGRESSION BETWEEN 1

ST AND 2ND EXTRACTION LEFT: REGRESSION BETWEEN THE AMOUNT OF

EXTRACTED PARTICULATE MATERIAL [G]. RIGHT: REGRESSION OF ALL DETERMINED PAH CONCENTRATIONS

[NG/L] (SUM, PARTICULATE, DISSOLVED) ....................................................................................................... 97

FIG. 60: RESULTS OF THE PCA OF ALL HARBOUR SAMPLES TAKEN IN FEBRUARY (F), MARCH (M), JULY (J),

NOVEMBER (N) AND SEPTEMBER (S)............................................................................................................. 98
VI

FIG. 61: PLOT OF ISOMERIC PHENANTHRENE/ANTHRACENE AND FLUORANTHENE/PYRENE RATIOS OF THE SEDIMENT

SAMPLES TAKEN IN DOVER AND CALAIS IN JULY, SEPTEMBER AND NOVEMBER. ........................................ 106

FIG. 62: PRINCIPAL COMPONENT ANALYSIS OF THE RELATIVE PAH CONCENTRATIONS (PERCENTAGES) OF THE

WATER, SEDIMENT AND MUSSEL SAMPLES TAKEN IN DOVER AND CALAIS IN JULY, SEPTEMBER AND

NOVEMBER. FIRST LETTER: W=WATER SAMPLE, S=SEDIMENT SAMPLE, M=MUSSEL SAMPLE (SMAL=SMALL

20-30MM, MEDI=MEDIUM 30-40MM, LARG=LARGE 40-50 MM). SECOND LETTER: J=JULY, S=SEPTEMBER,

N=NOVEMBER.LAST FOUR LETTERS: SAMPLING POINT............................................................................... 107

FIG. 63: RESULTS OF LUMISTOX TEST. SHOWN ARE THE DIFFERENCES BETWEEN SEAWATER SCRUBBER INLET AND

OUTLET WATER TAKEN DURING THE SAMPLING IN SEPTEMBER. THE PH SHOWN WAS THE PH OF THE OUTLET

SAMPLE ........................................................................................................................................................ 109

FIG. 64: MEAN PERCENTAGES OF SHELL, DRY AND WET TISSUE WEIGHT FOR ALL MUSSELS USED IN THE

ACCUMULATION TEST. LEFT: PERCENTAGES FOR EACH TEST. RIGHT: MEAN FOR ALL TESTS ........................ 112

FIG. 65: CORRELATION PLOTS. LEFT: WHOLE WET WEIGHT AGAINST LENGTH. RIGHT: SHELL WEIGHT AGAINST

LENGTH. IN BOTH CASES THE RED LINE SHOWS THE NONLINEAR MODEL AND THE BLACK LINES THE 95 %

CONFIDENCE INTERVAL................................................................................................................................ 113

FIG. 66: CORRELATION PLOTS: LEFT: WET TISSUE WEIGHT AGAINST LENGTH. MIDDLE: DRY TISSUE WEIGHT

AGAINST LENGTH. RIGHT: DRY TISSUE WEIGHT AGAINST WET TISSUE WEIGHT. IN BOTH CASES THE RED LINE

SHOWS THE NONLINEAR MODEL AND THE BLACK LINES THE 95 % CONFIDENCE INTERVAL.......................... 113

FIG. 67: LEFT: COMPARISON OF PAH CONCENTRATIONS DETERMINED IN THE STANDARD MUSSEL TISSUE AND THE

ORIGINAL CONCENTRATIONS. RIGHT: CORRELATION COEFFICIENTS, STEEPNESS AND SECTION OF THE

EXTERNAL REFERENCE LINES....................................................................................................................... 115

FIG. 68: MEAN CONCENTRATIONS OF THE ADDED PAHS, DETERMINED FOR THE DIFFERENT ACCUMULATION TESTS.

.................................................................................................................................................................... 116

FIG. 69: MEAN CONCENTRATIONS OF THE PAHS WHICH WERE NOT ADDED DURING THE TEST, DETERMINED FOR

THE DIFFERENT ACCUMULATION TESTS........................................................................................................ 116

FIG. 70: CONCENTRATIONS OF PHENANTHRENE, ANTHRACENE, FLUORANTHENE, PYRENE AND CHRYSENE IN NG L-1

MEASURED IN THE AQUARIUMS OF THE CONTROLS, THE PARTICULATE AND THE DISSOLVED TEST ONE HOUR

AFTER A WATER EXCHANGE AND RIGHT BEFORE THE FOLLOWING WATER EXCHANGE (3 DAYS).

CONCENTRATIONS ARE SEPARATED INTO THE DISSOLVED AND THE PARTICULATE FRACTIONS.................... 118
VII

List of tables

TABLE 1: COMPOSITIONS OF MIXTURES FOR PH-BUFFER-CAPACITY MIX TEST. (MIXTURES WRITTEN IN ITALICS

WERE NOT PERFORMED FOR EVERY TRIAL) ...................................................................................................... 5

TABLE2: PROPERTIES OF THE DIFFERENT RIVER- AND SEAWATER SAMPLES USED FOR THE PRELIMINARY TRIALS .. 5

TABLE3: SAMPLING POINTS IN DOVER 11.02.2004 AND 24.03.2004-05-28 .......................................................... 11

TABLE4: SAMPLING POINTS IN CALAIS ................................................................................................................. 11

TABLE5: SAMPLING POINTS ON BOARD „PRIDE OF KENT“ ..................................................................................... 11

TABLE6: SAMPLING POINTS IN CALAIS FOR THE SAMPLINGS IN JULY, SEPTEMBER AND NOVEMBER .................... 13

TABLE7: SAMPLING POINTS IN DOVER FOR THE SAMPLINGS IN JULY, SEPTEMBER AND NOVEMBER..................... 13

TABLE8: EBB AND FLOW DATES FOR ALL SAMPLINGS (HTTP://WWW.MOBILEGEOGRAPHICS.COM) ........................ 13

TABLE9: COORDINATES OF SAMPLING POINTS AND TIME AND DATE FOR SAMPLINGS ........................................... 14

TABLE10: GROUPS OF PAHS DEFINED FOR GC-MS SIM-METHOD ....................................................................... 15

TABLE11: STRUCTURES AND MAJOR PHYSICAL PROPERTIES OF THE 16 EPA-PAHS ............................................. 18

TABLE12: CATEGORIZATION OF THE ACCUMULATION TESTS. ............................................................................... 25

TABLE 13: MEAN PAH COMPOSITION IN THE SEAWATER SCRUBBER OUTLET SAMPLES (MARCH AND JULY), PAH

CONCENTRATIONS IN THE ACETONE SOLUTION AND RESULTING PAH CONCENTRATION IN THE AQUARIUM .. 26

TABLE14: DATES FOR WATER EXCHANGE DURING THE ACCUMULATION TEST ...................................................... 27

TABLE15: VALUES OBTAINED BY FITTING EQU. 12 TO THE PH-VALUES ................................................................ 33

TABLE16: STANDARD DEVIATION OF THREE DIFFERENT STANDARD DILUTION SERIES. ......................................... 34

TABLE17: ACCURACY OF THE GC MS (INCLUDING INJSTD, INTEGRATION AND MEASUREMENT)........................ 35

TABLE 18: F-TEST FOR LINEARITY OF THE GC MS. SHOWN RESULTS WERE CALCULATED WITH ALL DILUTION

STEPS RANGING FROM 2,5 TO 1000 μG L-1....................................................................................................... 35

TABLE 19: F-TEST FOR LINEARITY OF THE GC MS. SHOWN RESULTS WERE CALCULATED WITH ALL DILUTION

STEPS RANGING FROM 2,5 TO 100 μG L-1........................................................................................................ 36

TABLE20: LIMIT OF DETECTION (LOD) FOR DETERMINED PAHS.......................................................................... 36

TABLE 21: MEAN RECOVERY RATES AND STANDARD DEVIATION DETERMINED FOR PRELIMINARY TRIALS WITH

ARTIFICIAL SEAWATER................................................................................................................................... 39

TABLE 22: AIR AND WATER TEMPERATURE [°C], SALINITY [PSU], PH VALUE AND OXYGEN [MG L-1] DURING

SAMPLING IN CALAIS HARBOUR ON 11.2.2004............................................................................................... 41

TABLE 23: WATER TEMPERATURE [°C], SALINITY [PSU] AND PH-VALUE DURING SAMPLING IN DOVER HARBOUR

ON 11.2.2004 ................................................................................................................................................. 41

TABLE 24: CONCENTRATIONS OF THE INTERNATIONAL ASSOCIATION FOR PHYSICAL SCIENCE OF THE OCEAN

STANDARD FOR NATURAL ATLANTIC SEAWATER. .......................................................................................... 42

TABLE 25: SULPHATE, EARTH AND TRANSITION METALS DETERMINED FOR THE SAMPLES TAKEN ON 11.02.2004.

FIELDS SIGNED WITH”-“ SHOW CONCENTRATIONS BELOW DETECTION LIMIT................................................. 43

TABLE26: NUTRIENT CONCENTRATIONS DETERMINED FOR THE SAMPLES TAKEN ON 11.02.2004......................... 43

TABLE 27: REGRESSION OF SAMPLE POINTS (SAMPLING 11.2.04). COLOURS ARE ADDED FOR A BETTER

VISUALISATION. YELLOW HIGHLY CORRELATED, RED MODERATE OR LOW CORRELATION, DARK RED NO

SIGNIFICANT. CORRELATION. ......................................................................................................................... 45
VIII

TABLE 28: REGRESSION OF COMPOUND CONCENTRATIONS DETERMINED FOR THE SAMPLES TAKEN ON 11.2.04.

COLOURS ARE ADDED FOR A BETTER VISUALISATION. YELLOW HIGHLY CORRELATED, RED MODERATE OR

LOW CORRELATION, DARK RED NO SIGNIFICANT CORRELATION. .................................................................... 45

TABLE 29: AIR AND WATER TEMPERATURE [°C], SALINITY [PSU], PH VALUE AND OXYGEN [MG L-1] DURING

SAMPLING IN CALAIS HARBOUR ON 23.3.2004............................................................................................... 46

TABLE 30: AIR AND WATER TEMPERATURE [°C], SALINITY [PSU], PH VALUE AND OXYGEN [MG L-1] DURING

SAMPLING IN DOVER HARBOUR ON 24.3.2004 ............................................................................................... 47

TABLE 31: AIR AND WATER TEMPERATURE [°C], SALINITY [PSU], PH VALUE AND OXYGEN [MG L-1] DURING

SAMPLING IN DOVER HARBOUR ON 24.3.2004 ............................................................................................... 47

TABLE 32: SULPHATE, EARTH AND TRANSITION METAL CONCENTRATIONS DETERMINED FOR THE SAMPLES TAKEN

IN JULY .......................................................................................................................................................... 49

TABLE33: NUTRIENT CONCENTRATIONS DETERMINED FOR THE SAMPLES TAKEN ON 24.03.2004......................... 52

TABLE34: INDICES FOR THE DETERMINATION OF THE ORIGIN OF THE PAHS (SAMPLES 11.02.04) ........................ 53

TABLE35: INDICES FOR THE DETERMINATION OF THE ORIGIN OF THE PAHS (HARBOUR SAMPLES 24.03.04) ....... 53

TABLE 36: INDICES FOR THE DETERMINATION OF THE ORIGIN OF THE PAHS (HARBOUR ECOSILENCER SAMPLES

24.03.04) ....................................................................................................................................................... 54

TABLE 37: INDICES FOR THE DETERMINATION OF THE ORIGIN OF THE PAHS (CANNEL OF DOVER ECOSILENCER

SAMPLES 24.03.04)........................................................................................................................................ 54

TABLE 38: REGRESSION CHART FOR THE ANALYSIS OF THE SAMPLING POINTS (SAMPLING MARCH). COLOURS ARE

ADDED FOR A BETTER VISUALISATION. YELLOW HIGHLY CORRELATED, ORANGE AND RED MODERATE OR LOW

CORRELATION, DARK RED NO SIGNIFICANT. CORRELATION............................................................................ 55

TABLE 39: REGRESSION OF COMPOUND CONCENTRATIONS DETERMINED FOR THE SAMPLES TAKEN ON 24.03.04.

COLOURS ARE ADDED FOR A BETTER VISUALISATION. YELLOW HIGHLY CORRELATED, RED MODERATE OR

LOW CORRELATION, DARK RED NO SIGNIFICANT. CORRELATION.................................................................... 56

TABLE40: FEATURE VECTOR FOR THE PCA OF THE HARBOUR SAMPLES................................................................ 57

TABLE 41: TEMPERATURE, SALINITY AND PH DATA MEASURED AT THE DIFFERENT SAMPLING POINTS IN CALAIS

HARBOUR ....................................................................................................................................................... 58

TABLE 42: TEMPERATURE, SALINITY AND PH DATA MEASURED AT THE DIFFERENT SAMPLING POINTS IN DOVER

HARBOUR ....................................................................................................................................................... 58

TABLE43: SEAWATER SCRUBBER TEMPERATURES, SALINITIES AND PH DATA....................................................... 59

TABLE 44: CHLOROPHYLL, SESTON AND NUTRIENT CONCENTRATIONS DETERMINED FOR THE SAMPLES TAKEN IN

JULY 2004...................................................................................................................................................... 60

TABLE45: QUOTIENT OF BENZ[A]ANTHRACENE AND CHRYSENE. .......................................................................... 63

TABLE46: REGRESSION OF PAH COMPONENTS, YELLOW SHOWS HIGH CORRELATION.......................................... 63

TABLE 47: REGRESSION OF SAMPLING POINTS. COLOURS ARE ADDED FOR A BETTER VISUALISATION. YELLOW

HIGHLY CORRELATED, DARK RED NO SIGNIFICANT CORRELATION. ................................................................ 64

TABLE48: FEATURE VECTOR FOR THE PCA OF THE HARBOUR SAMPLES................................................................ 65

TABLE 49: TEMPERATURE, SALINITY AND PH DATA MEASURED AT THE DIFFERENT SAMPLING POINTS IN CALAIS

HARBOUR IN SEPTEMBER ............................................................................................................................... 66
IX

TABLE 50: TEMPERATURE, SALINITY AND PH DATA MEASURED AT THE DIFFERENT SAMPLING POINTS IN DOVER

HARBOUR IN SEPTEMBER ............................................................................................................................... 66

TABLE 51: TEMPERATURE, SALINITY AND PH DATA MEASURED AT THE DIFFERENT SAMPLING POINTS IN THE

SEAWATER SCRUBBER IN SEPTEMBER............................................................................................................ 67

TABLE 52: CHLOROPHYLL, SESTON AND NUTRIENT CONCENTRATIONS DETERMINED FOR THE SAMPLES TAKEN IN

SEPTEMBER 2004........................................................................................................................................... 68

TABLE53: SULPHATE, EARTH AND TRANSITION METALS DETERMINED FOR THE SAMPLES TAKEN IN SEPTEMBER . 69

TABLE 54: REGRESSION OF COMPOUNDS. COLOURS ARE ADDED FOR A BETTER VISUALISATION. YELLOW HIGHLY

CORRELATED, DARK RED NO SIGNIFICANT CORRELATION. ............................................................................. 72

TABLE 55: REGRESSION OF SAMPLING POINTS. COLOURS ARE ADDED FOR A BETTER VISUALISATION. YELLOW

HIGHLY CORRELATED, DARK RED NO SIGNIFICANT CORRELATION. ................................................................ 72

TABLE 56: THE QUOTIENT OF BENZ[A]ANTHRACENE TO CHRYSENE CAN BE USED AS MARKER FOR THE ORIGIN OF A

SAMPLE .......................................................................................................................................................... 73

TABLE57: FEATURE VECTOR FOR THE PCA OF THE HARBOUR SAMPLES................................................................ 74

TABLE 58: TEMPERATURE, SALINITY AND PH DATA MEASURED AT THE DIFFERENT SAMPLING POINTS IN CALAIS

HARBOUR IN NOVEMBER................................................................................................................................ 75

TABLE 59: TEMPERATURE, SALINITY AND PH DATA MEASURED AT THE DIFFERENT SAMPLING POINTS IN DOVER

HARBOUR IN NOVEMBER................................................................................................................................ 76

TABLE 60: TEMPERATURE, SALINITY AND PH DATA MEASURED AT THE DIFFERENT SAMPLING POINTS IN THE

SEAWATER SCRUBBER HARBOUR IN NOVEMBER............................................................................................ 76

TABLE61: SULPHATE, EARTH AND TRANSITION METALS DETERMINED FOR THE SAMPLES TAKEN IN NOVEMBER.. 77

TABLE 62: SESTON AND NUTRIENT CONCENTRATIONS DETERMINED FOR THE SAMPLES TAKEN IN NOVEMBER 2004

...................................................................................................................................................................... 78

TABLE 63: REGRESSION OF PAH COMPOUNDS. COLOURS ARE ADDED FOR A BETTER VISUALISATION. YELLOW

HIGHLY CORRELATED, DARK RED NO SIGNIFICANT CORRELATION. ................................................................ 81

TABLE 64: REGRESSION OF SAMPLING POINTS. COLOURS ARE ADDED FOR A BETTER VISUALISATION. YELLOW

HIGHLY CORRELATED, DARK RED NO SIGNIFICANT CORRELATION. ................................................................ 81

TABLE65: ISOMERIC RATIOS OF BENZ[A]ANTHRACENE AND CHRYSENE ................................................................ 81

TABLE66: FEATURE VECTOR FOR THE PCA OF THE HARBOUR SAMPLES................................................................ 83

TABLE 67: DIFFERENCES BETWEEN THE INLET AND OUTLET SAMPLES TAKEN FROM THE SEAWATER SCRUBBER

SYSTEM IN CALAIS, DOVER AND THE CHANNEL.LEFT: PH DIFFERENCE.RIGHT: TEMPERATURE DIFFERENCE87

TABLE68: COMPARISON OF SULPHATE INLET AND OUTLET CONCENTRATIONS [PPM]............................................ 92

TABLE 69: SUM OF ALL 16 EPA-PAHS (PARTICULATE AND DISSOLVED, EXCLUDING NAPHTHALENE)

CONCENTRATIONS IN NG L

-1

FOR ALL SAMPLINGS (N.D. = NOT DETERMINED)................................................. 93

TABLE70: PAH CONCENTRATIONS IN NG L-1. LISTED ARE THE CONCENTRATIONS OF THE SINGLE PAH COMPOUNDS

IN ALL SAMPLES. CONCENTRATIONS ARE GIVEN AS DISSOLVED/PARTICULATE PAH. DASHES INDICATE

CONCENTRATIONS BELOW THE LIMIT OF DETECTION. (N.D. = NOT DETERMINED)........................................... 93

TABLE 71: SUM OF BBF, BGHIP, BKF, BAP, FLUA, INDE. CALCULATED AS CARBON WEIGHT (N.D. NOT

DETERMINED) ................................................................................................................................................ 95
X

TABLE 72: PAH CONCENTRATIONS IN NG L-1 DETERMINED FOR THE SEAWATER SCRUBBER SAMPLES. LISTED ARE

THE CONCENTRATIONS OF THE SINGLE PAH COMPOUNDS IN ALL SAMPLES. CONCENTRATIONS ARE GIVEN AS

DISSOLVED/PARTICULATE PAH. DASHES INDICATE CONCENTRATIONS BELOW THE LIMIT OF DETECTION. (N.D.

= NOT DETERMINED) ...................................................................................................................................... 95

TABLE 73: DIFFERENCES [NG L-1] BETWEEN INLET AND OUTLET SAMPLES TAKEN IN MARCH, JULY, SEPTEMBER

AND NOVEMBER IN DOVER, CALAIS AND THE CHANNEL. SHOWN ARE THE MEAN, THE STANDARD DEVIATION

AND THE MINIMUM AND MAXIMUM VALUES. ................................................................................................. 96

TABLE 74: FEATURE VECTOR FOR THE PCA OF ALL HARBOUR SAMPLES TAKEN IN FEBRUARY, MARCH, JULY,

NOVEMBER AND SEPTEMBER......................................................................................................................... 98

TABLE75: RESULTS OF PLANKTON CELL COUNTING. CONCENTRATIONS ARE GIVEN IN CELLS PER ML................ 100

TABLE 76: DIN DIFFERENCES BETWEEN INLET AND OUTLET SAMPLES TAKEN IN DOVER, CALAIS AND THE

CHANNEL..................................................................................................................................................... 102

TABLE 77: PAH CONCENTRATIONS [NG G-1] MEASURED IN MUSSELS TAKEN FROM THE QUAY WALLS AT SAMPLING

POINT C0 AND BIO CONCENTRATIONFACTORS (BCF). ............................................................................... 102

TABLE 78: PAH CONCENTRATIONS DETERMINED FOR SEDIMENT SAMPLES TAKEN IN JULY, SEPTEMBER AND

NOVEMBER.................................................................................................................................................. 104

TABLE 79: PAH COMPOSITION OF THE SEDIMENT SAMPLES TAKEN IN CALAIS AND DOVER IN JULY, SEPTEMBER

AND NOVEMBER IN PERCENT. ...................................................................................................................... 105

TABLE 80: FEATURE VECTOR FOR THE PCA OF THE WATER, SEDIMENT AND MUSSEL SAMPLES TAKEN IN DOVER

AND CALAIS INJULY, SEPTEMBER AND NOVEMBER .................................................................................... 107

TABLE81: RESULTS OF THE BRINE SHRIMP TEST PERFORMED WITH 24 H OLD JUVENILE ARTEMIA SALINA ............ 110

TABLE82: RESULTS OF THE BRINE SHRIMP TEST PERFORMED WITH 4 WEEKS OLD JUVENILE ARTEMIA SALINA ..... 110

TABLE 83: LENGTH [MM] OF ALL MUSSELS EMPLOYED FOR THE ACCUMULATION TEST. THE COLOURS SEPARATE

THE TABLE IN THE MAIN CLASSES USED FOR THE PAH DETERMINATION. THE FIRST CLASS SMALLER THAN 50

MM AND THE SECOND CLASS BETWEEN 50 MM AND 60 MM.......................................................................... 112

TABLE84: RESULTS OF LINEAR AND NONLINEAR REGRESSION ............................................................................ 113

TABLE 85: PAH CONCENTRATIONS [NG G-1] DETERMINED FOR THE MUSSELS FROM THE ACCUMULATION TEST.

WRITTEN IN ITALICS ARE THOSE COMPOUNDS ADDED DAILY. EXT ARE THE MUSSELS TAKEN FROM THE

EXTERNAL BASIN, 02, 05 AND 08 ARE THE CONTROLS, 03, 06 AND 09 ARE THE MUSSELS FROM THE DISSOLVED

TEST AND 01, 04 AND 07 ARE THE MUSSELS FROM THE PARTICULATE TEST. ................................................ 115

TABLE 86: EXPECTED PAH CONCENTRATIONS IN THE MUSSELS IF ALL ADDED PAHS WOULD HAVE BEEN

ACCUMULATED ............................................................................................................................................ 116

TABLE87: PERCENTAGE OF ACCUMULATED PAHS, CALCULATED AS QUOTIENT OF EXPECTED AND OBSERVED PAH

CONCENTRATION IN THE MUSSELS. .............................................................................................................. 117

TABLE88: PH, SALINITY AND TEMPERATURE DETERMINED IN THE AQUARIUMS DURING THE TEST ..................... 119

TABLE 89: TOTAL PAH AMOUNTS [MG] THAT WILL BE THEORETICALLY INTRODUCED DURING ONE DAY INTO THE

PORTS OF DOVER AND CALAIS AND THEORETICAL CONCENTRATION INCREASE [PG L-1] .............................. 120

TABLE 90: MEAN ACCUMULATION RATE, TOTAL ACCUMULATION PER DAY AND YEAR AND RESULTING

CONTAMINATION AFTER ONE YEAR FOR A 20 MM MUSSEL. .......................................................................... 120
XI

TABLE 91: MEAN SHELL INDEX AND FAT CONTENT DETERMINED FOR THE MUSSELS OF THE ACCUMULATION TEST

AND FOR THE MUSSELS TAKEN IN CALAIS .................................................................................................... 121
XII

Abbreviations

Anth Anthracene

BaA Benz[a]anthracene

Chry Chrysene

DCM Dichloromethane

DIN Dissolved inorganic nitrogen

DIN Deutsche Industrie Norm

DOM Dissolved organic material

DOP Dissolved organic phosphorus

EPA Environmental Protection Agency

Flu Fluoranthene

FMN Flavin mononucleotid

GC-FID Gas-Chromatography Flame Ionisation Detector

GC-MS Gas-Chromatography Mass Spectroscopy

IAPSO International Association for Physical Science of the Ocean

ICP-OES Inductively Coupled Plasma Optical Emission Spectroscopy

IDL Instrument Detection Limit

InjSTD Injection Standard

ISTD Internal Standard

LOD Limit of Detection

PAH Polycyclic Aromatic Hydrocarbon

Phe Phenanthrene

PIP Particulate inorganic phosphorus

PoK “Pride of Kent” the ferry on which the seawater scrubber is installed

POP particulate organic phosphorus

Pyr Pyrene

RDP Reactive dissolved phosphorus

SI Shell Index

SIM Single Ion Monitoring

SPE Solid Phase Extraction

SQU Squalane (used as Injection Standard)

SWS Seawater scrubber

TBrB 1,2,4,5-Tetrabromobenzene (used as Injection Standard)

TDP Total dissolved phosphorus

TCHL Total chlorophyll

TPP total particulate phosphorus
1 Project description

2 Summary

1

1 Project description

In May 2003 BP-Marine in co-operation with P&O Ferries built a flue gas desulphurisation system

prototype manufactured by DME Canada into a channel ferry (“Pride of Kent”), operating between

Dover (UK) and Calais (France). To fulfil the legal requirements of Marpol Annex VI this seawater

scrubber should remove mainly SO2from the exhaust gases. In addition other harmful emissions and

noise should also be reduced. The analysis of the liquid effluents as well as their influence on the

marine environment, especially that of the ports, was carried out by Terramare Research Centre in

Wilhelmshaven, Germany.

2 Summary

Within this project the effects of a seawater scrubber onto the environment were analysed. During five

sampling campaigns in 2004 the main focus was laid on pH, nutrients, temperature, trace metals,

polycyclic aromatic hydrocarbons (PAH) and plankton. Additionally one accumulation and two toxicity

tests were performed. For the observation of a whole annual cycle, samples were taken in February,

March, July, September and November inside the harbours of Dover and Calais and on board the

“Pride of Kent” (PoK). Inside the ferry’s seawater scrubber system very low pH values and high PAH

concentrations, even in the outlet, were measured. Sulphate and nitrate concentrations were also

higher on board than in samples from the harbour environment. Metal contents, especially of iron and

vanadium, which were leached from the steel, could also be detected in high amounts inside the

system. A decrease of the pH inside the ports or close to the ferry was never observed. Only in one

case the temperature was slightly higher in front of the effluent outlet. Although PAH concentrations

were high in the effluent, no increased concentrations were observed inside the harbours or in front of

the ship. Significant contents of heavy metals or eutrophication effects were also not detected. In

summary, no negative influence of the scrubbing system on the port environments was observed.
3 Introduction

1

3 Introduction

Marine diesel engines are among the most fuel-efficient combustion sources for moving goods

[Corbett and Koehler, 2003]. Nevertheless they also contribute significantly to air pollution (e.g.

Capaldo et al., 1999; Streets et al., 2000). In the past regulations have been passed which dealt

especially with the SO2 emissions from land based combustion sources. Examples for these are the

European Union Directives 1999/30/EC, 2001/81/EC and 1999/32/EC. But since there were no

sulphur limits for marine heavy fuel oils, these now contain a high amount of sulphur relative to other

fuels.

Burning of fuel gives rise to SO2 and SOxformation, which damages sensitive ecosystems and

buildings. In the marine boundary layer especially ships contribute to a high input [Capaldo et al.,

1999]. Another by-product of fossil fuel burning is the emission of NOx. In marine regions with high

traffic, ships may increase NOxlevels significantly. Both, SOx and NOx and additionally soot particles

not only cause environmental damage but also health damage. NOxfor example increases, as well as

volatile organic compounds, the formation of ground level ozone. If the O3 concentration is elevated

above national standard levels (US EPA: 0.12 ppm) it may cause lung and respiratory disorders.

Additionally some materials like rubber, nylon, plastic, dyes and paints might be damaged by ozone. A

study revealed that children from rural Ontario communities show a decrease in lung function and

higher susceptibility for bronchitis [Mac Phail et al.]. Also plants, e.g. agricultural crops and trees, are

negatively affected by increased ozone concentrations [WHO 1997].

SOx and also NOx are also responsible for the formation of acid rain. Acid rain describes a

phenomenon which has been known since the early 1970s and which has caused a number of

problems [Driscoll et al. 2001]. For example in soils cations like Mg2+ and Ca2+ are leached whereas

sulphur and nitrogen concentrations increase. Additionally the harmful dissolved inorganic Al3+

increases which influences the water uptake capacity of trees. Moreover tree mortality has risen

because calcium is leached from the needles of gymnosperms thereby increasing their susceptibility

to freezing injury. In lakes the acid neutralising capacity is still decreasing resulting in an increasing

acidification and aluminium contents resulting in a decreasing species diversity. Model calculations

show that only with a marked reduction in sulphur emissions a measurable chemical improvement of

the affected ecosystems is possible. In many areas, mainly close to the major shipping routes and

harbours, sulphur emissions from ships may equal natural sources. The European Environment

Agency estimates that shipborne contributions from international shipping in the North Sea and northeast Atlantic Ocean to total European acidifying emissions may about double by 2010 as a result of

increasing marine traffic (Fig. 1, EEA, 2000).
3 Introduction

2

Fig. 1 Estimates of shipborne contributions to total European NOx and SO2 emissions 1990 – 2010 (EEA,

2000)

To regulate especially this anthropogenic impact of SOx, an international instrument on air pollution

from ships was developed by the Maritime Organisation in 1997: Marpol Annex VI. Marpol Annex VI

was ratified in May 2004 by 15 flag states representing at least 50 % of the gross tonnage of the world

merchant shipping. It will come into force in May 2005. Furthermore, it has to be taken into account

that the cost of limiting the sulphur content of marine bunker oils in the North and Baltic Seas to 1.5 %

(the maximum value accepted by MARPOL) has been estimated at about 87 million €per year.

Equivalent reductions in total emissions from landbased sources (such as power stations) would cost

about 1,150 million €per year.

Among other regulations, Marpol Annex VI will introduce a 4.5 % sulphur limit for marine fuels and a

1.5 % sulphur limit for marine fuels burned in the so-called SOx emission control areas. Burning of fuel

with higher sulphur content is only allowed when technologies are used which reduce the atmospheric

emissions from ships to less than 6 g kWh-1(as SO2 mass). Fluegas desulphurisation processes like

for examples seawater scrubbing are one possible technology [Tokerud, 1989]. These systems are no

new technology but have been used world wide since 1930 in coal power plants located close to the

sea (cf. Behrends and Liebezeit, 2003). Their main task is to reduce the sulphur dioxide (SO2) and

other sulphur oxides (SOx) contents in the exhaust gases which are produced from burning high

sulphur content coal. Additionally nitrogen oxides (NOx) and particulates are removed partially from the

exhaust gas. The reduction and the theoretical effects of a seawater scrubber system are described in

detail in Behrends and Liebezeit [2003]. Thereafter SOx and NOx dissolve within the scrubber effluent

and form nitric, nitrous and sulphuric acids. These might, on one hand, reduce the pH of the receiving

waters and, on the other hand, might due to the input of nitrate lead to eutrophication.

Besides gaseous components soot is also formed, especially during incomplete combustion. This is

mainly made up of elemental carbon with the particular features of a large surface area and a

hydrophobic character. Nonpolar substances immediately adsorb onto these particles and are then

transported with the soot from the combustion source. Polycyclic aromatic hydrocarbons (PAHs

constitute a major group of these substances. While the low molecular weight PAHs such as
3 Introduction

3

naphthalene (two rings) or phenanthrene and anthracene (three rings) are mainly found unbound in

the gaseous phase already a major fraction of the four-ring members like pyrene, chrysene and

benz[a]anthracene are bound to these carbon particles.

The formation of PAHs and a major part of all reactions that take place during combustion have been

presented by Duran et al. 2004. In addition to this pyrolytic formation there are several other PAH

sources such as petrogenic oil formation processes. In this case these compounds are created during

the slow maturation of organic material. With regard to the sources of PAHs there is a broad spectrum

of possibilities for them to enter the environment: industrial wastewater, street dust runoff discharges,

deposition of fossil fuel combustion particles, carbonized coal product spills, forest and grass fires,

volcanic particles, oil spills or natural oil seeps [Witt and Trost, 1999; Lake et al. 1979, Lee et al.

1981]. Usually PAHs are occurring in a complex mixture of isomers and alkylated isomers [Wise et al.,

1993]. Low molecular weight PAHs with two or three rings are present normally in dissolved form in

water or gaseous in atmosphere. The higher the molecular weight the more hydrophobic they behave

and the more they are bound to particles [Ahrens, Depree, 2004, Pleil et al., 2004, Doong and Lin,

2004]. Therefore highest PAH concentrations are to be found in sediments [Neff 1979; Pearlman et

al., 1984].

Taking all sources in consideration it is not surprising that PAHs have not only been detected in

sediments but also in the atmosphere, water and soils all over the world [Fung et al. 2004; Soclo et al.

2000; Potrykus et al. 2003, Prevedouros et al. 2003]. Because some of them are toxic [Bispo et al.

1999; El-Alawi et al., 2001], some inhibit plant growth [Sudhakar Babu et al. 2001, Marwood et al.

2001] and some are carcinogenic and mutagenic [ATSDR 1997] their distribution and behaviour in the

environment has been subject to several studies.

When PAHs are introduced into the environment several reactions may occur. Besides to the

described adsorption to particles and also dissolved organic material (DOM) [Sun et al., 2003],

photooxidation is one of the major reactions. In most cases these photooxidized forms are even more

toxic than the parent compounds [Sudhakar Babu et al., 2001; El Alawi et al., 2001; McConkey et al.,

1997; Ankley et al. 1994]. For example the photooxidized form of anthracene inhibits the

photosynthetic electron transport system [Huang et al., 1997]

Biological degradation, mainly due to microbial action [Weissenfels et al., 1992; Heitkamp and

Cerniglia 1989], is another important factor in alteration and reduction. In this case it has to be taken

into consideration, that degradation of combustion derived PAHs is expected to be slower for PAHs

from petrogenic origin [Yunker et al., 1996; Mc Groddy and Farrington, 1995; Gustafsson et al., 1997]:

In addition, the PAH concentrations [Yuan et al. 2001], the amount of total organic carbon [Hinga

2003; Webster et al., 2001] and the particle size [Schnelle-Kreis et al. 1999] seem to play a role in

removing and degradation of PAHs from or in the water.

Additionally it has to be taken into account that because of the different sources of these PAHs, they

show a distinct seasonal variability [Prevedouros et al., 2004] and also degradation might show

seasonality [Pohlman et al. 2002]. These changes concern mainly combustion-derived PAHs. During
3 Introduction

4

wintertime when there is lot of wood and oil burning, environmental concentrations rise. In some

regions forest fires in summer might also influence the seasonality.

The determination of the origin of PAHs is normally performed by the aid of different indices [Soclo et

al., 2000; Potrykus et al., 2003, Lake et al., 1979; see below]. All in all about 600 PAH-structures

[NIST 1997] have been classified and 16 of them have been defined by the United States

Environmental Protection agency (US-EPA) to be environmentally relevant [US-EPA 610]. These are

also the most common and best examined PAHs in the literature.

During the present study the impact of a Seawater Srubber (SWS) to reduce atmospheric emissions

was examined. The ship which was equipped with this technology was the "Pride of Kent", a ferry

operating between the harbours of Dover and Calais. The main focus of the survey was the harbours

and the seawater within the system of the SWS. Five samplings were performed, one sampling while

the SWS was not in use (11.02.2004) and four when the SWS was partially in use (March, July,

September and November), which means that only the seawater scrubbers for the auxiliary engines

were working.

Because both ports are influenced by tidal currents, the pH and the salinity showed a high natural

variability. In front of the outlet of the seawater scrubber no decrease in pH could be detected, but

effluent water was about 0.4 to 1.8 pH units lower than the inflow and the water within the harbour. An

effect on temperature could only be determined during the sampling in July and September.

Determined metal concentrations inside the harbour were mostly within the range of the used Atlantic

water salinity standard. The comparison between the SWS-inlet and the SWS-outlet water did only

indicate a rise of the zinc concentration which might haven been an effect of the sampling. Inside the

system iron and vanadium were increased but most of it was amassed inside the settling tank.

Within the harbours a seasonal variability of PAHs was determined with generally higher

concentrations in the winter, early spring and late autumn. Comparing the seawater inlet and outlet

samples, PAH-concentrations in the outlet were about two orders of magnitude higher than in the inlet.

Sulphate and nitrate were only increased inside the seawater scrubber but not inside the ports. The

toxicity tests did not clearly reveal an increased toxicity.
4. Material and Methods

5

4 Material and Methods

4.1 pH - buffer capacity of natural seawater

The aim of this test was to estimate the buffer capacity of seawater and the time necessary to reach

pH-equilibrium after acid addition. The results could aid to predict the influence of the Ecosilencer

impact.

Five different natural sea- and brackish water samples (Jade Bay, Wilhelmshaven, Germany; Ems

River, Papenburg, Germany; Odense harbour, Denmark; Dover harbour, England; Calais harbour,

France). The different seawater properties are listed in Table 1.

Table 1: Properties of the different river- and seawater samples used for the assays

origin salinity

[ppt]

pH sampling

temperature

[°C]

test

temperature

[°C]

Nassau harbour, Jade Bay,

Wilhelmshaven, Germany

30 8,0 3 22,5

Meyer Werft, Ems River,

Papenburg, Germany

0,3 7,71 3,1 22,6

Lindoe, Odense, Denmark 21,4 7,97 3,4 20,1

Calais harbour, France 18,3 7,81 7,3 22,4

Dover harbour, England 34,3 7,86 7,4 22,4

500 mL seawater each were acidified with a mixture of HNO3 and H2SO4 (1 : 1.48, v:v) to a final pH of

4.0. The mixing ratio of 1 to 1.48 was chosen because of the expected composition of the SWS

Ecosilencer effluent (sulphur content in fuel = 3.5 % and four main engines and two generators

running at 85 % MCR). The pH-value of pH 4 was chosen because of the worst case estimated pH of

the SWS Ecosilencer and cooling water mixture effluent discharges. The acidified water was then

mixed with the untreated seawater in different combinations (Table 2).

Table 2: Compositions of mixtures for pH buffer capacity test. (Mixtures in italics were not performed for every

assay)

acidified seawater

(pH 4) [mL]

natural seawater

(about pH 8) [mL]

stirring speed

[rpm]

50 450 250

100 400 250

150 350 250

200 300 250

250 250 250

250 250 250

300 200 250

350 150 250

400 100 250

450 50 250

250 250 0

1000 1000 250

500 500 250

250 250 1000
4. Material and Methods

6

After mixing the natural and the acidified samples, the pH was measured in regular intervals until no

significant change in pH could be observed any more. Normally the test was stopped after three days.

The pH for the different fractions was plotted against time and the pH in equilibrium was plotted

against the percentage of pH 4 seawater in mixture and analysed.

4.2 Polycyclic Aromatic Hydrocarbons

Several tests were performed to establish the best method for the extraction of PAHs on the basis of

the highest recovery rate. In the past liquid-liquid extraction was the commonly used technique to

extract PAHs from aqueous solutions, but as this method is cumbersome, labour intensive, expensive

and not environment-friendly due to its large solvent consumption, a less expensive and easier

method was developed. Solid phase extraction (SPE) was considered to be the best method,

especially as this method is favourably reported in literature [Crozier et al., 2001; Titato and Lanças,

2000; Garcia-Falcon et al. 2004] and different applications are available [Agilent Technologies;

Macherey Nagel]. Therefore different Solid Phase Extraction sorbents, different sample preparations

and different solvents were tested. For a comparison of the results the traditional liquid-liquid

extraction (LLE) was also applied. In a series of assays the following topics were investigated:

 influence of SPE-sorbent

 influence of elution solvent

 influence of acetone addition before extraction

 recoveries for Dover and Calais waters

 incubation time of internal standard mix (fractionation of particulate and soluble PAH fractions)

 recovery rate in artificial seawater for liquid-liquid-extraction (LLE) with n-hexane

For statistical reliability at least 3 parallel experiments were performed for every test. In every

experiment 500 mL of the matrix were spiked with 1 mL of a 100 μg L

-1

PAH mixture in acetone

(Sigma-Aldrich Chemie GmbH, Taufkirchen Germany) containing acenaphthylene, anthracene,

benzo(a)anthracene, benzo(b)fluoranthene, benzo(k)fluoranthene, benzo(g)perylene, benzo(a)pyrene,

chrysene, dibenzo(ah)anthracene, fluorene, indeno(1,2,3-cd)pyrene, phenanthrene and pyrene. The

final concentration was 200 ng PAH L

-1

. Additionally 1 mL of a 100 μl L

-1

Internal PAH Standard Mix

solution in acetone was added (Dr. Ehrenstorfer GmbH, Augsburg, Germany) containing

acenaphthene-D10, chrysene-D12, perylene-D12 and phenanthrene-D10. The first three tests which

are mentioned above were performed in artificial seawater [RiPSUa et al. 1979] produced with

deionised water, the remaining tests with natural seawater.

The SPE-cartridges were conditioned with 5 mL Methanol and flushed with about 100 mL deionised

water. Thereafter 500 mL sample were aspirated slowly over the SPE sorbent. For extraction 2 + 3 mL
4. Material and Methods

7

dichloromethane (DCM) were used. An aliquot of 1000 μL from the resulting 5 mL extract was

transferred into a 2 mL amber glass-vial and 100 μl of a 10 μg mL-1TBrB were added as injection

standard (InjSTD). The aliquot was analysed by gas chromatography/mass spectrometry (GC-MS;

GC: HP 6890, MS: HP MSD 5973, Software: Chemstation G1701 CA) in Single Ion Monitoring (SIM;

see Table 10).

Recoveries were determined by calculating the ratio of the measured PAH concentration and the

concentration added to the matrix. The means and the standard deviations were calculated. In the

following part the different assays are described in detail.

1. Influence of SPE-sorbent

Three different SPE-sorbents were used, all manufactured by Macherey-Nagel GmbH & Co KG,

Düren, Germany.

 Chromabond EASY: a bifunctional modified polystyrene divinylbenzene copolymer phase (specific

surface 650 - 700 m2 g-1, particle size 80 μm, pore size 50 Ångstrom, pH-range 1-14).

 Chromabond C18 ec: an octadecyl silica endcapped sorbent (base material silica, pore size 60 Å,

particle size 45 μm for C18 ec, 100 μm for C18 ec f (fast flow), specific surface 500 m2g

-1

, pH

stability 2 - 8, endcapped, carbon content 14 %).

 Chromabond C18 PAH: an octadecyl silica phase for PAH analysis (60 Å, particle size 45 μm,

specific surface 500 m2 g-1, pH stability 2 - 8).

Experiments were performed using artificial seawater.

2. Influence of Elution Solvent

SPE-cartridges filled with Chromabond C18 ec were used for extraction, two different elution solvents

were tested:

 dichloromethane

 n-hexane

Experiments were performed using artificial seawater.

3. Influence of Acetone Addition before Extraction

The extraction was performed using Chromabond C18 ec and DCM as elution solvent. During these

assays three different amounts of acetone were added to the sample before extraction.

 2 mL acetone (0.2 %)

 5 mL acetone (1 %)

 10 mL acetone (2 %)
4. Material and Methods

8

The matrix was artificial seawater.

4. Recovery rates in Dover and Calais harbour waters

As natural seawater taken from Dover and Calais harbours was already contaminated with PAHs,

another recovery experiment than that described above had to be executed. In this case three

samples of 500 mL Dover (11.02.04, station 7) and Calais (11.02.04, station 2) seawater were filled

into round flasks and spiked with 1 mL of a 100 ng mL-1standard and internal standard solution.

These samples were then extracted using SPE-C18 ec and DCM as elution solvent. Three additional

500 mL samples from each harbour were spiked only with the internal standard. The recoveries are

then calculated by difference (see eq. 1).

100

1 1



  



spike

InjST Cal

BS

InjST Cal

s

C

PA St

PA

PA Sl

PA

RR (1)

PAs = peak area of spiked sample

PAInjSTD = peak area of Injection Standard

SlCal = slope of calibration line

PABS = peak area of unspiked blank sample

Cspike = concentration of PAH spike

6. Incubation of Internal Standard Mix (Fractionation of Particulate and Soluble Fractions)

For this experiment ten subsamples of 0.5 L each, taken from a 20 L sample (24.3.2004, station 6:

Dover, “Prince of Whales Pier”) were filled into 1 L amber glass bottles, acidified with 2.5 mL 50 % HCl

and mixed with 0.5 mL 3 % sodium thiosulphate. Additionally the samples were spiked with 1 mL of a

100 μg L

-1

PAH-mix and an equally concentrated ISTD Mix, closed and fixed on an orbital shaker. Two

subsamples made up one group and were extracted after 1 h, 2 h, 4 h, 8 h and 16 h. Then the

recoveries and the percentages of the soluble and the particulate fraction were determined. This

protocol was also used for the determination of the method repeatability and for the calculation of the

accuracy of the method.

7. Liquid-Liquid-Extraction

As liquid-liquid-extraction (LLE) was for long time the standard method to extract PAH from water, this

test was performed as reference. For extraction 500 mL artificial seawater were spiked with 1 mL

100 μg L-1PAH-Mix and 1 mL 100 μg L

-1

ISTD, acidified with 2.5 mL HCl (50%) and filled into a 1 L

separation funnel. The PAHs were then extracted with n-hexane (20 mL, 10 mL, 10 mL). All extracts
4. Material and Methods

9

were combined, reduced in a rotary evaporator to dryness, taken up in 1 mL DCM and, after addition

of InjSTD, analysed by GC MS.
5. Material and Methods: Determination of environmental parameters and pollutants

10

5 Material and Methods: Determination of environmental

parameters and pollutants

5.1 Sampling points, Sampling, Transport and Storage

5.1.1 Sampling in February and March

Samples were taken at nine different station inside the harbours of Dover (Fig. 3 and Table 3) and

Calais and at two (11.2.04) and twelve (24.3.04) places, respectively, inside the engine room of the

“Pride of Kent” during her operation inside the harbours and on the shipping route between Dover and

Calais (Fig. 2).

Fig. 2: Geographical position of Dover and Calais and route of the “Pride of Kent” in the Channel

As the Ecosilencer was not operative during the first sampling on 11.2.2004, only two samples were

taken from the seawater scrubber system: one from the inlet and one from the outlet. The samples

shown in Fig. 3 (left) were also taken from the seawater inlet. While the ship was entering the

harbours of Dover and Calais, samples were taken from the inlet and outlet. In the Channel additional

samples were taken at the points listed in Table 5 after some time of operation at normal load.

For the first sampling cleaned 2 L polyethylene flasks were used and rinsed with sample water before

filling. For the second sampling, the PAH-samples were stored in 1 L amber glass bottles (baked out

at 250 °C for 24 h and rinsed with 5 % HCl). Each one was filled with 1 L of sample and after that 5 mL

50 % HCl and 1 mL 3 % sodium thiosulphate were added to deactivate free chlorine and to prevent

samples from microbial degradation. For nutrient and metal samples 1 L polyethylene flasks treated as

the other polyethylene flasks mentioned before were used.
5. Material and Methods: Determination of environmental parameters and pollutants

11

Table 3: Sampling points in Dover 11.02.2004 and 24.03.2004-05-28

11.2.2004 23/24.03.2004

sampling point description sampling point description

7 harbour entrance 5 Churchill Hotel Beach

8 middle port 6 Prince of Wales Pier

9 Quay 4 7 back of “Pride of Kent”

8 middle of “Pride of Kent”

9 front of “Pride of Kent”

7

9

8

6

7

5

8

9

Fig. 3: Dover harbour sampling points (left: 11.2.2004, right: 24.3.2004)

Table 4: Sampling points in Calais

Sampling point Description

Cal 1 Quai en eau profonde

Cal 2 Quai de service

Cal 3 Quai de la Loire

Cal 4 Jetee Ouest

Cal 1

Cal 2

Cal 3

Cal 4

2,5 km

Table 5: Sampling points on board „Pride of kent“

Sampling point Description

1 seawater inlet

2 diluted overboard discharge

3 outlet from US filter

4 dirty water to settling tank

5 inlet to US filter

6 water return from Ecosilencer

7 top of settling tank

8 bottom of settling tank

inlet

outlet

Ecosilencer

Cyclone US-Filter

Settling

tank inlet

outlet

Ecosilencer

Cyclone US-Filter

Settling

tank

1

2

3 4

5

6

7

8
5. Material and Methods: Determination of environmental parameters and pollutants

12

Fig. 4: Photographs of the seawater scrubber sampling points inside the “Pride of Kent”. L.: Point 1 seawater

scrubber inlet. M.l.: Point 2 seawater scrubber outlet. M.r.: Point 3 and 5: outlet and inlet of US filter,

top of cyclones. R.: Point 4, 7 and 8: tube going to the settling tank and top and bottom of sampling

tank.

Inside the harbours 50 mL water samples for plankton determination were taken as well. These were

mixed with 10 drops “Lugol’s solution” (20 g KJ, 20 g J2, 200 mL deionised water, 20 mL acetic acid).

All bottles were transported in cooling boxes directly to the laboratory (max. 30 h), where they were

stored, with exception of the plankton samples, deep frozen at -18°C until further treatment or

extraction. The plankton samples were allowed to settle and the sample was analysed under an

inverted microscope.

5.1.2 Sampling in July, September and November

As for the samplings in July, September and November two small boats were available. The sampling

points changed and samples were also taken inside the harbours and within a transect from the outlet

of the seawater scrubber towards the entrance of the harbours. The sampling points, the description

and coordinates are given in Table 6, Table 7 and Table 9. In Table 9 the sampling times are also

given. The sampling points SD1, SD2, SC1, SC2 and SCH1 to SCH8 refer to the sampling points of

the seawater scrubber inside the “Pride of Kent”, where SD are the seawater scrubber samples taken

in Dover, SC are the samples taken in Calais and SCH are the samples taken during the Channel

crossing. Hih and low water times and flow for all samplings are shown in Table 8. As the “Pride of

Kent” did not berth at the predicted quay during the sampling in September the point C 0 was not

taken at the same place as C 5 but at a parallel quay.
5. Material and Methods: Determination of environmental parameters and pollutants

13

Table 6: Sampling points in Calais for the samplings in July, September and November

Sampling point Description

Cal 1 Quai en eau profonde

Cal 2 Quai de service

Cal 3 Quai de la Loire

Cal 4 Jetee Ouest

C 0 before arrival of “PoK”

C 5 5 m from the outlet

C 50 50 m from the outlet

C 350 350 m from the outlet

C 700 700 m from the outlet

Cal 1

Cal 2

Cal 3

Cal 4

C 0

C 5

C 50

C 350

C 700

2,5 km

Table 7: Sampling points in Dover for the samplings in July, September and November

Sampling point Description

Dov 1 eastern entrance

Dov 2 western entrance

Dov 3 middle port

Dov 4 close to Prince of Wales pier

D 0 before arrival of “PoK”

D 5 5 m from the outlet

D 50 50 m from the outlet

D 350 350 m from the outlet

D 700 700 m from the outlet

Table 8: High and low water times (http://www.mobilegeographics.com)

sampling port flow low water high water

February Calais 11.2.04 3:44 11.2.04 10:45 11.2.04 16:07

Dover 11.2.04 15:37 11.2.04 22:37 12.2.04 2:56

March Calais 23.3.04 14:21 23.3.04 21:14 24.3.04 2:36

Dover 24.3.04 0:04 24.3.04 7:04 24.3.04 12:23

July Calais 13.7.04 10:50 13.7.04 17:35

Dover 13.7.04 9:09 13.7.04 16:11

September Calais 8.9.04 8:06 8.9.04 14:32

Dover 7.9.04 4:29 7.9.04 11:07 7.9.04 17:01

November Calais 17.11.04 3:27 17.11.04 10:37 17.11.04 15:52

Dover 16.11.04 12:33 16.11.04 19:48
5. Material and Methods: Determination of environmental parameters and pollutants

14

Table 9: Coordinates of sampling points and time and date for samplings

Point coord. N coord. E July September November

Cal 1 50° 58.161' 1° 51.491' 13.7.04 08:40 8.9.04 8:50 17.11.04 10:30

Cal 2 50° 58.180' 1° 52.042' 13.7.04 09:00 8.9.04 9:05 17.11.04 10:00

Cal 3 50° 57.385' 1° 51.562' 13.7.04 09:40 8.9.04 8:30 17.11.04 09:40

Cal 4 50° 58.010 1° 50.582 13.7.04 10:00 8.9.04 8:15 17.11.04 09:30

C 0 50° 58.052' 1° 51,382' - 8.9.04 11:15 17.11.04 11:00

C 5 50° 58.044' 1° 50.927' 13.7.04 11:50 8.9.04 11:45 17.11.04 11:40

C 50 50° 58.079' 1° 50.846' 13.7.04 12:00 8.9.04 12:00 17.11.04 11:50

C 350 50° 58.153' 1° 50 634' 13.7.04 12:10 8.9.04 12:05 17.11.04 11:55

C 700 50° 58.311' 1° 50.457' 13.7.04 12:30 8.9.04 12:10 17.11.04 12:00

Dov 1 51° 07.109' 1° 20.459' 14.7.04 13:45 7.9.04 14:45 16.11.04 12:35

Dov 2 51° 06.914' 1° 19.749' 14.7.04 13:50 7.9.04 15:05 16.11.04 13:00

Dov 3 51° 07.100' 1° 19.854' 14.7.04 14:00 7.9.04 15:10 16.11.04 13:05

Dov 4 51° 07.149' 1° 19.327' 14.7.04 14:05 7.9.04 15:17 16.11.04 13:10

D 0 51° 07.584' 1° 20.406' 14.7.04 12:50 16.11.04 13:15

D 5 51° 07.570' 1° 20.361' 14.7.04 13:05 7.9.04 14:10 16.11.04 13:20

D 50 51° 07.526' 1° 20.387' 14.7.04 13:15 7.9.04 14:25 16.11.04 13:30

D 350 51° 07.411' 1° 20.500' 14.7.04 13:20 7.9.04 14:35 16.11.04 13:25

D 700 51° 07.292' 1° 20.589' 14.7.04 13:30 7.9.04 14:40 16.11.04 13:35

SD1 - - 14.7.04 18:00 7.9.04 19:30 16.11.04 18:15

SD2 - - 14.7.04 18:00 7.9.04 19:30 16.11.04 18:15

SCH1 - - 14.7.04 18:30 7.9.04 20:00 16.11.04 18:50

SCH2 - - 14.7.04 18:30 7.9.04 20:00 16.11.04 18:50

SCH3 - - 14.7.04 18:55 7.9.04 20:10 16.11.04 18:50

SCH4 - - - 7.9.04 20:10 16.11.04 18:55

SCH5 - - 14.7.04 19:10 7.9.04 20:15 16.11.04 18:00

SCH6 - - 14.7.04 19:15 7.9.04 20:15 16.11.04 18:55

SCH7 - 7.9.04 20:20 -

SCH8 - - - 16.11.04 19:00

SC1 - - 14.7.04 19:25 7.9.04 20:55 16.11.04 19:40

SC2 - - 14.7.04 19:25 7.9.04 20:55 16.11.04 19:40

5.2 Temperature, pH, Salinity, Oxygen

pH-values were measured directly after sampling using a pH-Meter (WTW pH 320/WTW-SenTix 81)

calibrated with two different buffer solutions (pH 7.00 and pH 4.01, Mettler-Toledo GmbH, Analytical,

Schwerzenbach, Switzerland). Salinity, conductivity and temperature were determined electronically

(WTW Cond 315i, Weilheim, Germany) as well.

Oxygen during the first sampling was determined by using a Winkler titration Kit (Merck, Germany).

During the second sampling (24.3.04) an oxygen electrode was used (Hach LDO HQ 10, range 0-

20 mg L

-1

, Düsseldorf, Germany).
5. Material and Methods: Determination of environmental parameters and pollutants

15

5.3 Metals and sulphate

Metals were determined using Inductively Coupled Plasma Optical Emission Spectroscopy (ICPOES). Pre-treatment included acidification (5 % HNO3

) and filtration (Syrfil Mixed Cellulose Ester

Filter,  25mm, 0.22 μm MF, Whatman, Maidstone, England; Norm Jet syringe, Tuttlingen, Germany).

For determination mainly elements which are included in the ships processes were chosen. These

include the transition metals vanadium, chromium, manganese, iron, cobalt, nickel, copper zinc and

molybdenum. Additionally the earth metals barium, lithium, strontium, calcium, potassium, magnesium

and the sulphate contents were measured. All samples were analysed by the working group “Inorganic

Geochemistry” at the Institute for Chemistry and Biology of the Sea (ICBM) at Oldenburg University,

Germany.

5.4 Polycyclic Aromatic Hydrocarbons (PAH)

5.4.1 Calibration, determination of accuracy, Carry-over

As the 16 EPA PAHs are the most widespread and commonly determined PAHs, these compounds

were also chosen for determination during this work. A composition of the names, synonyms and

major physical properties is shown in Table 11.

Table 10: Groups of PAHs defined for GC-MS SIM-method

group Ret. time Compound MS mass

1 - naphthalene 128

12.52 acenaphthylene 152

13.06 acenaphthene 154

2

2

2 12.96 acenaphtene-D10 164

3 14.80 fluorene 166

3 17.14 1,2,4,5-tetrabromobenzene 393.7

18,11 phenanthrene-D10 190

18.16 phenanthrene 178

4

4

4 18.32 anthracene 178

22.49 fluoranthene 202

23.19 pyrene 202

27.41 benzo[a]anthracene 228

27.52 chrysene-D12 240

5

5

5

5

5 27.96 chrysene 228

benzo[b]fluoranthene 252 31.16 benzo[k]fluoranthene 252

32.10 benzo[a]pyrene 252

6

6

6

6 32.33 perylene 264

35.23 dibenz[a,h]anthracene 278

35.37 indeno (1,2,3,c,d) pyrene 276

7

7

7 36.07 benzo[ghi]perylene 276

Calibration was performed by diluting a 500 mg L-1PAH Mix (Sigma-Aldrich Chemie GmbH,

Taufkirchen Germany) to concentrations in a range from 1 to 1000 ng mL-1three times. From every

dilution of the standard 1 mL was filled into an amber glass GC-vial and 50 μL of a 10 μg mL-1of
5. Material and Methods: Determination of environmental parameters and pollutants

16

1,2,4,5-tetrabromobenzene (TBrB) and 50 μL of a 10 μg mL-1squalane solution were added as

injection standards (InjSTD). For the samples that have been taken during the fourth, fifth and sixth

sampling squalane was not used as injection standard. The calibration standards were prepared for

each chromatographic run and measured randomLy distributed over each analysis sequence. For

linear regression between concentrations and peak areas in relation to InjSTD the statistic program

Systat 8.0 was used (command file see appendix).

For determination of the linear range of the GC, a calibration series using nine concentrations in the

range from 2.5 ng mL-1to 1000 ng mL-1 was analysed. The linearity was then determined by linear and

nonlinear regression of the calibration series with the nine different dilution steps. For linear regression

the function

y a x b (2)

and for nonlinear regression the function

y a b x cx2 (3)

were fitted to the data. With these the value yˆcould be calculated, which in the best case should be

the same value as the concentration y of the standard. In the next step the residual-standard-deviation

was calculated according to

 









N

i

y linear i i

y y

N

s

1

2

_ ˆ

2

1

(4)

 



 

N

i

y nonlinear i i

y y

N

s

1

2

_ ˆ

3

1

(5)

where N is the number of dilution steps, y the employed concentration and yˆthe concentration

calculated with the linear and nonlinear functions, respectively. From these values the difference DS2

can be calculated according to

    2

_

2

2 2 y _ linear 3 y nonlinear DS N  s N  s (6)

With this value the examination variable EV as

2

_

2

y nonlinear s

DS

EV  (7)

was determined and compared to F (P=099%, f1 = 1, f2 = N-3) from a F-table. If EV was smaller or

equal F the nonlinear function was not significantly better than the linear function. If this was not the

case, the highest concentration was taken out of the calculation, a new function was calculated and

EV was calculated again.
5. Material and Methods: Determination of environmental parameters and pollutants

17

Accuracy of the GC was determined by measuring the 25 ng mL-1and 500 ng mL-1concentrations

eight times. To check for carry over, solvent blanks (DCM) were analysed distributed randomLy over

the chromatographic run.

The limit of detection (LOD) was determined as three times the standard deviation (IUPAC criterion) of

the 25 ng mL-1concentration.

These tests were performed for the analyses with the split splitless injector and also for the samples

analysed with the cold injections system.
5. Material and Methods: Determination of environmental parameters and pollutants

18

Table 11: Structures and major physical properties of the 16 EPA-PAHs

PAHs

EPA

Name and Synonyms Form. CAS Log KOW

(Exp./Calc.)

[1]

Tboil

[°C]

[2]

Tfus

[°C]

[2]

Density

[g cm-3]

at 20°C [3]

Vapour

pressure

[Pa] [4]

Solub.

H2O

[mg/l] [4]

Molec.

weight

Risk phrases Safety

phrases

hazard

symbol

naphthalene C10H8 91-20-3 3,33 / 3,17 217,0 80,2 - 1.0x102 31 128,17 20,21, 22,36,

37,38, 43,45

16,26, 36,37,

39,45

T

acenaphthylene

1,2-dihydroacenaphthylene

1,8-dihydroacenapthalin

1,8-ethylenenapthalene

1,2-dihydroacenapththylene

C12H8 208-96-8 3,94 / 3,94 280,2 89,6 -

93,4 - 9.0x10-1 16 152,19 22, 36, 37, 38 26, 36, 37, 39

Xn

acenaphthene,

cyclopenta[d,e]naphthalene

paranaphthalene

C12H10 83-32-9 3,92 / 4,15 279,2 94 1.225 3.0x10-1 3.8 154,21 36, 37, 38 26, 36

Xi

fluorene

ortho-biphenylene methane

diphenylenemethane

2,2-methylene biphenyl

2.3-benzidene

C13H10 86-73-7 4,18 / 4,02 294,2 -

298,2 115 - 9.0x10-2 1.9 166,22 - -

Xn

anthracene

anthracin

green oil

C14H10 120-12-7 4,46 / 4,35 340 217 - 1.0x10-3 0.045 178,23

20, 21, 22,

36, 37, 38,

42,43

26, 36

Xn

phenanthrene

phenantrin C14H10 85-01-8 4,45 / 4,35 328,15 -340,15 99 0.980at 4 °C 2.0x10-2 1.1 178,23 20, 21, 22,36, 37, 38, 40

26, 27, 36, 37,

39, 45

Xn

fluoranthene

1.2-[1,8-Naphthylene]-benzene

1.2-benzacenaphthene

1.2-[1.8- naphthalenediyl]benzene

benzo[j,k]fluorene

C16H10 206-44-0 5,16 / 4,93 -

108 -

113 - 1.2x10-3 0.26 202,25 22, 36, 37,38, 40 -

Xn

pyrene

benzo[d,e,f]phenanthrene

8-pyrene

C16H10 129-00-0 4,88 / 4,93 - 151 1.271

at 23 °C 6.0x10-4 0.13 202,25 26, 36, 37, 38 -

Xn

benzo[a]anthracene

BA;benz[a]anthracene

1,2-benzanthracene

benzo[b]phenanthrene

2,3-phenanthrene

2,3-benzophenanthrene

tetraphene,

benzo[e]fluoranthene

C18H12 56-55-3 5,76 / 5,52 437,8 159 1.274

at 20 °C

2.8x10-5 0.011 228,29 45, 50, 53 45, 53, 60, 61 T

N
5. Material and Methods: Determination of environmental parameters and pollutants

19

chrysene

1.2-benzophenanthrene

benzo[a]-phenanthrene

1,2benzphenanthrene

benz[a]phenanthrene

1,2,5,6-dibenzonaphthalene

C18H12 218-01-9 5,81 / 5,52 448,2 254,35 -

258,4 - 5.7x10-7 0.006 228,29 20, 21, 22,45, 46

3, 7, 9, 36, 37,

39, 45

T

benzo[b]fluoranthene

3,4-Benz[e]acephenanthrylene

2,3-benzfluoranthene

3,4-benzfluoranthene

2,3benzofluoranthene

3,4-benzofluoranthene

benzo[e]fluoranthene

C20H12 205-99-2 5,78 / 6,11 - - - - 0.0015 252,31 45, 50, 53 45, 53, 60, 61 T

N

benzo[k]fluoranthene

8.9-benzfluoranthene

8.9-benzofluoranthene

11.12benzofluoranthene

2,3,1.8-binaphthylene

dibenzo[b,j,k]fluorine

C20H12 207-08-9 6,11 / 6,11 480 217 - 5.2x10-8 0.0008 252,31 45 45, 53

Xn

benzo[a]pyrene

benzo[d,e,f]chrysene

3-4 benzopyrene

3,4-benzpyrene

benz[a]pyrene;BP

C20H12 50-32-8 6,13 / 6,11 495,2 177 1.351 7.0x10-7 0.0038 252,31 45, 46, 50,

53, 60, 61 45, 53, 60, 61

T

dibenz[a,h]anthracene

DB[a,h]A

DBA

1,2:5,6 dibenz[a]anthracene

C22H14 53-70-3 -- / 6,70 524,2 260,15 -

271,2 1.282 3.7x10-10 0.0006 278,35

indeno (1,2,3,c,d) pyrene

indenopyrene

IP;orthophenylenepyrene

1,10-ortho-phenylene]pyrene

1,10-[1,2-phenylene]pyrene

2,3-ortho-phenylenepyrene

C22H12 193-39-5 6,63 / 6,70 -

162 -

163 - - 0.00019 276,33 - -

Xn

benzo[ghi]perylene

1,12-benzoperylene C22H12 191-24-2 6,80* / 6,70 - 280 - 1.4x10-8 0.00026 276,33 - 22, 24, 25 -

* Average from 3 reverences

[1] Heiden A.C., Hoffmann A., Kolahgar, B., (2001), Comparison of the Sensitivity of Solid Phase MicroExtraction (SPME) and Stir Bar Sorptive Extraction (SBSE) for the Dertermination of Polycyclic

Aromatic Hydrocarbons (PAHs) in Water and Soil Samples, Gerstel AppNote 8/2001, http://www.gerstelus.com/appnotes/new/Gerstel%202001/an-2001-08.pdf

[2] NIST Chemistry WebBook, http://webbook.nist.gov/chemistry

[3] Tox Probe; Ten Carcinogens in Toronto; benzo[a]pyrene and other polycyclic aromatic hydrocarbons, http://www.city.toronto.on.ca/health/pdf/cr_appendix_b_pah.pdf

[4] Staffan Lundstedt; 2003, Analysis of PAHs and their transformation products in contaminated soil and remedial processes http://publications.uu.se/umu/fulltext/nbn_se_umu_diva-57.pdf
5. Material and Methods: Determination of environmental parameters and pollutants

20

5.4.2 Extraction

Water samples:

All vessels used for extraction were rinsed with deionised water, methanol and DCM before use. After

thawing, 1 mL of 100 ng mL-1internal standard solution was added to 0.5 L sample. After thorough

mixing, the sample was filtered with a preextracted (10 mL DCM) glassfibre filter (GF/C, Whatman,

Maidstone, England).

The filter was cut in small pieces and the particulate matter was extracted ultrasonically three times for

10 min with a mixture of dichloromethane/acetone (5:1 v:v). For the first step 15 mL and for the

second and third step 10 mL of this mix were used. To remove particles the extract was cleaned with

the SPE C18 cartridge used for the extraction of the dissolved PAHs. The extract was concentrated to

about 0.5 mL by rotary evaporation (Büchi, Switzerland, 35°C, 700-500 hPa) and transferred to an

amber glass GC-vial. The flask was then rinsed with DCM and the rinse was added to the extract. The

whole volume was then concentrated to 1 mL (N2) and the InjSTD was added.

The seawater filtrate was extracted by SPE using C18ec cartridges, which turned out to give the best

recovery rate (see 4.2). Before extraction the cartridges were conditioned with 5 mL methanol, which

was left for some time to soak into the SPE material. Then about 100 mL doubly de-ionised water

followed by the sample were aspirated slowly over the cartridge using a vacuum pump (Saskia

Hochvakuum). The sample flask was washed twice with 100 mL doubly de-ionised water which was

aspirated over the cartridge as well, followed by 3 mL of a water/isopropanol (80:20) mixture.

For desorption of the PAHs 2 mL plus 3 mL DCM were used. From the resulting 5 mL extract 1 mL

was transferred into an amber glass GC-vial and mixed with InjSTD TBrB .

All samples were measured randomLy within one gas chromatic run for each extraction.

Concentrations and the proportions of the analyte between dissolved and particulate fractions were

determined by using the ISTD closest to the retention time of the substance according to equations (8)

to (11).

Dil

CL

CL

PA

PA

Conc

ascent

tion

TBrB

analyte

vial 











 



sec

(8)

Concvial = concentration of the analyte in the vial [ng mL-1]

PAanalyte = peak area determined by GC MS of the analyte

PATBrB = peak area determined by GC MS of TBrB

CLsection = section of the calibration line

CLascent = ascent of the calibration line

Dil = dilution factor

100

_

_ lub _ 





deut add

deut so deut part

PAH

PAH PAH

R (9)
5. Material and Methods: Determination of environmental parameters and pollutants

21

100

_

_ lub

lub  

deut add

deut so

so PAH

PAH

F 100

_

_  

deut add

deut part

part PAH

PAH

F (10)

R = recovery rate [%]

PAHdeut_solub = concentration of deuterated PAH determined for the soluble fraction [ng mL-1]

PAHdeut_part = concentration of deuterated PAH determined for the particulate fraction [ng mL-1]

PAHdeut_added = concentration of deuterated PAH added to the sample [ng mL-1]

Fsolub = soluble fraction of the deuterated PAH [%]

Fpart = particulate fraction of the deuterated PAH [%]

 

g

ng V

V

F

R

Conc Conc

Conc Vial

sample

vial so vial part

analyte



1000 _ lub _ 1    



 (11)

Concanalyte = concentration of the analyte in the water-sample [ng l-1]

Concvial_solub = concentration of the soluble fraction of the analyte in the vial [ng mL-1]

Concvial_part = concentration of the particulate fraction of the analyte in the vial [ng mL-1]

F = soluble particulate fraction, respectively

Vsample = volume of the sample extracted

VVial = volume of the extract in the vial

Sediment and Mussel samples

Mussel samples were only taken once in Calais during the sampling in November. Those mussels

were taken from a harbour stilt during ebb tide a point C0. About 60 mussels were collected randomly

and put into a freeze bag. The extraction and analysis of these mussels was performed in the same

way as described in section 6.3.2. To determine the accuracy of the extraction method a standard

reference mussel tissue was extracted. This was obtained from LGC Promochem (NIST-2977 Mussel

tissue - Organics and trace elements) and extracted twice at the same time as the mussels of the

accumulation test.

Sediments were taken in July at points C1, C5, C700 and D5, in September at points C5, C700 and

D700 and in November at points C5, C700 and D5. All samples were taken with a van Veen grab (Fig.

5), which takes abovut 150 cm2 of the surface sediment, and were then transported to the lab in a

freeze bag. There they were deep frozen at -18 °C until extraction. Before the extraction the sediment

was freeze dried, coarse particles were removed and the remainder was ground in an agate ball mill

for 30 min at 180 rpm. From this fine, dried sediment 5 g were weight into a glass bottle and the

internal standard was added. The extraction was performed ultrasonically with 20 mL and two times

15 mL n-hexane for 15 min. As elemental sulphur negatively affects gas chromatographic analysis it

was removed with elemental copper. Oxides on the copper surface were removed by washing three

times with hydrochloric acid. The acid was removed by washing three times with deionised water and

the water was removed by washing three times with methanol. The methanol and eventually

remaining organic compounds bound to the copper surface were removed by washing three times with

DCM. About ten of these cleaned and activated copper filings were than added to the extracts and left

there for at least two hours. In those cases where the copper spans turned totally black (copper

sulphide) again about ten pieces were added and left in the extract for additional two hours. The

desulphurised extract was then filtered over NaSO4to remove the copper spans and remaining water
5. Material and Methods: Determination of environmental parameters and pollutants

22

from the extract and was then reduced to about 2 mL in a rotary evaporator. The clean-up was

performed on a silica column (5 g silica deactivated with 5 % H2O) and PAHs were eluted with 15 mL

n-hexane and with 20 mL of a n-hexane and DCM (5:1) mix. Both extracts were combined, reduced to

approximately 1 mL, transferred quantitatively into an amber glass 2 mL GC-vial and reduced to 1 mL

under N2. The injection standard was added and PAH concentrations were determined by GC-MS

Fig. 5: Van Veen grab and Niskin sampler for sediment and water samples respectively.

5.4.3 Determination of the origin of PAHs

PAHs in the environment might have different origins. Although there are some natural sources such

as oil seeps or some specific organisms, the main sources are anthropogenic. These include oil

released during normal ship operation or from accidents and products of incomplete combustion of

recent or fossil organic matter. To distinguish between these origins of a PAH mixture, some indices

have been developed in the past. The major aspect used is the thermodynamic stability. For example

phenanthrene (Phe) is thermodynamically more stable than its structural isomer anthracene (Anth).

The same is valid for fluoranthene (Flu) and pyrene (Pyr) pair. Concerning to these facts the Phe/Anth

ratio is higher in petrogenic (>10) than in pyrolytic pollution (<10). For Flu/Pyr a quotient of one was

determined. Thus a Flu/Pyr ration>1 points to a pyrolytic, while a Flu/Pyr rations <1 indicates a

petrogenic origin.

The chrysene (Chry) and benzo[a]anthracene (BaA) ratio is the basic for another index used. Chry

and BaA are derived from combustion processes at high temperatures with a Chry/BaA ratio <1. Also

an indicator for combustion derived PAHs is a higher abundance of four-, five- and six-ring PAHs in

comparison to the two- and three-ring PAHs, prominent in petrogenic sources.
5. Material and Methods: Determination of environmental parameters and pollutants

23

An additional method which was used to determine the origin of the PAHs was principal component

analysis and the regression of samples and compounds resulting in different regression charts.

Principal component analyses (PCA) is a useful technique that has found application in fields such as

face recognition and image compression, and is a common technique for finding patterns in data of

high dimension. Therefore PCA has also been used to determine the origin of PAHs [Boehm et al.,

1997; Stella et al., 2002; Burns et al., 1997; Branislav et al., 2001]. The background of this method is

based in matrix algebra. In this case the analyses were performed by using a Matlab script, written by

M. Hufnagl (see Appendix). In the first step the data are standardised by substracting the mean. The

next step calculates the covariance matrix and then the eigenvector and the eigenvalues of this matrix.

In this case the feature vector, which is later used for the transformation of the data, was only made up

from the first two eigenvectors.

The regression of the compounds and the regression of the sampling points were performed using the

statistic program Systat. The source code is similar to that one shown in the Appendix. In the literature

this method was also used to determine PAH pollution sources [Adami et al. 2000].

5.5 Plankton samples

During the sampling in February and March plankton samples were taken in 50 mL bottles and

analysed qualitatively. During the samplings in July, September and November plankton samples

were taken from one, two and three meters water depth. From each depth one litre was taken with a

Niskin sampler (Fig. 5) and all three water samples were collected in a three litre PVC bottle. In the

laboratory the water was filtered over a 10 μm plankton net and 5 mL of the concentrated sample were

transferred to an Uttermöhl counting chamber where the cells were allowed to settle overnight. The

counting was performed with an inverted microscope. At 30 to 50 randomLy chosen points all plankton

cells within the given grid of the microscope were counted. The concentration of the counted cells

were then determined using the following equation

conc

S

ex V

V

fields V

A

cells ml 

 

 

0.105626

506.71 /

where A is the amount of cells counted in the examined volume Vex. VS is the volume of the sample

and Vconc is the volume of the concentrated sample.
6 Material and Methods: Toxicity and accumulation test

24

6 Material and Methods: Toxicity and accumulation tests

For these tests water was taken from the seawater scrubber inlet and outlet at point SCH1 and SCH2

during the fourth sampling which was performed in September. The samples were filled into Winklerbottles (250 mL) which disabled the gas exchange between the samples and the atmosphere. This

allows the examination of the samples in the laboratory at nearly unchanged conditions. The water

samples, five from the inlet and five form the outlet, where transported to the lab in cooling boxes and

then stored at 4 °C for two days before the toxicity tests were performed.

6.1 Lumistox

The bacterium used for this test was Vibrio fischeri. The enzymatically induced luminescence of this

bacterium is quantitatively easy to determine. The reaction that takes place is that the enzyme

luciferase oxidises chemical compounds like long chain aldehydes by aid of reduced FMN (flavin

mononucleotide) and O2to the corresponding fatty acid. Within this reaction electrons are directly

transferred from the FMNH2to the oxygen and energy is set free by emittance of light.

The test, produced by Dr. Bruno Lange GmbH, Berlin, is a standardized DIN (Deutsche Industrie

Norm) method used to analyze the contamination of water. The test was performed according to the

instructions given in the norm. From three different samples two parallels were screened resulting in

six values for the inlet and six values for the outlet. As blank a 2 % NaCl solution was analyzed.

6.2 Brine shrimp test

Another possibility to determine the toxicity of a substance is the mortality of organisms exposed to

that substance. Therefore during this test the mortality of juvenile and adult brine shrimp Artemia

salina (Fig. 6) was observed after placing it into subsamples of the inlet and outlet water.

Fig. 6: Picture of Artemia salina. This organism was used for toxicity tests

Due to the natural habitat of Artemia salina this organism is able to build long lasting eggs. Two days

before starting the test, about 200 mg of these eggs were placed into 1000 mL artificial seawater
6 Material and Methods: Toxicity and accumulation test

25

[RiPSUa et al., 1979]. For aeration an aquarium pump was used. From the seawater that included the

hatched juveniles 1 mL with about 30 to 70 organisms were taken and pipetted into Petri dishes

containing the inlet and outlet water (4 mL). The amount of individuals added was counted and after

6 h and 24 h the mortality was determined. The same was performed with 4 week old adult Artemia

salina specimen. These were kept in an aquarium filled with seawater taken from the Jade Bay

(Wilhelmshaven Germany) and fed with an Isochrysis galbana culture until the performance of the

test. To prevent the organisms from starvation additionally 1 mL of this Isochrysis galbana culture was

added.

6.3 Accumulation test

6.3.1 Preparation and Performance

This accumulation test was performed to assess the uptake of the released PAHs by mussels.

Additionally it was used as toxicity test by observing the mussel mortality when exposed to the PAH

concentrations observed in the outlet of the seawater scrubber. As a high volume of water was

necessary for this test (2 m3) the water could not be taken directly from the inlet and outlet of the

“Pride of Kent” and be transported to the laboratory in Germany. Therefore the PAH concentrations

observed in the outlet samples of the seawater scrubber were determined and seawater taken from

the Jade Bay in Wilhelmshaven Germany was spiked with the the major five observed PAHs.

Table 12: Categorisation of the accumulation tests.

number assay volume [l] amount of

mussels

1 particulate 17 30

2 control 17 30

3 dissolved 17 30

4 particulate 17 30

5 control 17 30

6 dissolved 17 30

7 particulate 17 30

8 control 17 30

9 dissolved 17 30

10 control external basin 12000 appr. 100

The test was separated into three subtests with three separate approaches (Table 12), three controls,

three accumulation tests for PAHs bound to particulate material and three assays for the

determination of accumulation of dissolved PAHs. For all experiments seawater taken from the Jade

Bay was pumped into 1 m3 storage tanks and was centrifuged with a continuous centrifuge (Carl

Padberg, Zentrifugenbau GmbH, Lahr Germany). The particulates were collected and freeze dried.

The water was kept in another firmly closed 1 m3 storage tank from which 20 L canisters, one for every

assay, were filled with 17 L of the seawater. These canisters were then placed into the laboratory

where the assays were performed for temperature equilibration.

About 400 mussels (Mytilus edulis) were collected on a mussel bank (Swinnplate) from the backbarrier

area of the East Frisian island Spiekeroog and placed into an external basin filled with approximately
6 Material and Methods: Toxicity and accumulation test

26

12 m3 seawater taken from the Jade Bay. From these mussels 270 species were chosen randomly

and cleaned from barnacles, shell fragments and byssal threats. The cleaned mussels were laid into

the aquariums each filled with 17 L of the water taken from the canisters. To prevent the mussels from

lying directly on the ground of the aquarium and filtering their own faeces, plastic mats were placed on

the bottom (Fig. 7). Aeration for all aquariums was by an aquarium pump (ACO-003, magnetic piston,

35 W, 3600 l/h), PVC tubes and aeration stones (Fig. 7).

Fig. 7: Photographs of the experimental design of the accumulation test. L.: all nine aquariums with aeration

pump. M.: close view on to an aquarium with aeration stone and mussels placed on the PVC net. R.:

mussels on PVC net.

Before starting the experiments the mussels were kept for 5 days in the aquarium to allow

accommodation. Due to the low water volume in relation to the high amount of mussels, the water was

exchanged twice during that time and later twice a week. Every day 2 mL of a highly concentrated

Phaeodactylum tricornutum cultur were added to each aquarium. These algae were cultured in a 40 L

bioreactor. Every second day 20 L were filtered over a plankton net (mesh size 10 μm). The

concentrated Phaeodactylum tricornutum suspension was then stored at -18 °C.

Table 13: Mean PAH composition of the seawater scrubber outlet samples (March and July), PAH concentrations

in the acetone solution and resulting PAH concentration in the aquaria

compound mean % in

samples

mg in 100 mL

acetone

ng L-1in

aquarium

phenanthrene 100 5.125 1507

pyrene 42 2.142 630

chrysene 39 1.997 587

fluoranthene 17 0.872 256

anthracene 3 0.150 44

As explained above each subtest was performed with three separate approaches. For the assay with

the particulate matter to each aquarium 2 mL algal suspension, 5 mL of a seston solution and 0.5 mL

of a PAH solution in acetone was added. The seston solution contained the dried seston gained from

the seawater used and additionally dried silt and clay to give an overall concentration of 240 mg L-1.

The addition of 5 mL of this solution to the water in the aquarium lead to a particle concentration of

70 μg L

-1

. The composition of the PAH solution and the resulting PAH concentrations in the aquarium

are given in Table 13. The phenanthrene concentration (1500 ng L-1) was chosen because this was

the maximum phenanthrene concentration detected in the outlet samples in March and July.

To the aquariua that contained the mussels for the dissolved test, also 0.5 mL of the acetone/PAH

solution was added but instead of the seston, an aqueous quartz (Sigma Aldrich Laborchemikalien

GmbH, Seelze, Germany) solution was added resulting in 70 μg L

-1

quartz inside the aquarium. Quartz
6 Material and Methods: Toxicity and accumulation test

27

was chosen because it has only a small active surface and therefore only a low percentage of the

PAHs adsorb to it. Therefore the PAHs, as intended, remain dissolved. Particulate material has to be

added because otherwise the mussels would not be active and remain closed all the time. Before

adding the quartz to the solution, it was ground in a wolfram crucible so that particle size decreased

and the quartz particles lasted for a long time suspended in the water. To the controls both quartz and

seston were added so that the water in the aquarium contained 70 μg L

-1

of each.

The PAHs and the seston or quartz were added every day. Additionally 2 mL of the Phaeodactylum

suspension were added. Water exchange was performed every third or fourth day (Table 14).

Table 14: Dates for water exchange during the accumulation test

date days

start 15.11.2004 0

1. water exchange 18.11.2004 3

2. water exchange 22.11.2004 7

3. water exchange 25.11.2004 10

4. water exchange 29.11.2004 14

5. water exchange 02.12.2004 17

6. water exchange 06.12.2004 21

7. water exchange 09.12.2004 24

8. water exchange 13.12.2004 28

9. water exchange 15.12.2004 30

6.3.2 Analysis and extraction of the mussels

After 30 days the tests the mussels of each aquarium were trasnferred to freezer bags and deep

frozen at -18 °C. For each specimen shell length, total weight, shell weight as well as wet and dry

weights (freeze drying) were determined. The mussels were than divided into size groups. As only few

small mussels were available, mussels smaller than 50 mm were regarded as one class and mussels

between 50 and 60 mm as another class. From both classes 7 specimen each were taken and ground

in a wolfram crucible in a ball mill (Fritsch Pulverisette 5) over 30 min with a rotation speed of 120 rpm.

From the pulverized mussel tissue about 0.5 g were weighed into a glass flask and 5 mL of a 5M KOH

solution and 1 mL of the internal standard (acenaphthene-D10, phenathrene-D10, chrysene-D12,

perylene-D12) were added. The mixture was well mixed and left overnight to hydrolyse the cell walls.

The following day the lysate was neutralized with 5 mL 5M hydrochloric acid. Then 5 mL deionised

water and 40 mL n-hexane (Pestanal, Sigma Aldrich, Seelze, Germany) were added. This viscous

solution was placed into an ultrasonic bath for 15 min to separate the organic and aqueous phases.

The organic phase was transferred into a roundbottom flask and the procedure was repeated twice

with 30 mL n-hexane. The combined extracts were filtered over NaSO4 to remove remaining water and

then evaporated to a final volume of about 2 mL. After quantitative transfer to a silica column (10 g, 5

% deactivated with H2O) PAHs were eluted with 35 mL n-hexane and 40 mL of a n-hexane/DCM

solution (5:1 v:v). Both fractions were combined and the solvents evaporated to about 1 mL which was

transferred quantitatively into a 2 mL amber glass GC vial. After n-hexane evaporation to 1 mL under

N2the injection standard was added.
6 Material and Methods: Toxicity and accumulation test

28

To check the constitution of the mussels, the fat content was determined according to Smedes and

also the condition index (CI) was determined as the quotient of dry weight and shell weight multiplied

with 100. This index can be interpreted as an index of growth [Smaal and Staben 1990] and as an

indirect reflection of the food availability [Pérez Camacho et al 1995]. The fat content was determined

for one mussel of each assay and the CI was determined for all mussels and the mean was calculated

for each run.
8 Results and Discussion of environmental samplings

29

7 Results

7.1 pH-Mixtures

7.1.1 Jade Bay, Wilhelmshaven, Germany

In Fig. 8 and Fig. 9 the time-dependent results for the mixtures of natural acidified Jade Bay seawater

are shown. Fig. 9 also shows the pH in equilibrium in dependency of the percentage of pH 4 seawater

in the mixture. The mixtures stirred with 250 rpm with a total volume of 500 mL reach equilibrium after

about 24 hours. The higher the stirring speed the faster the equilibrium is reached. For the 50 %

mixture stirred with 1000 rpm equilibrium is reached after about 2 hours, while the unstirred sample

needed over 72 h. A similar behaviour can be observed for the 50 % mixtures with different volumes

(100 mL, 250 mL, 500 mL, 1000 mL) but the same stirring speed (250 rpm). The greater the volume

the longer the time until the equilibrium is reached. The 100 mL:100 mL mixture needed about 8 h

whereas the 1000 mL:1000 mL mixture again needed over 72 h.

The results for all 500 mL mixtures (250 rpm) in equilibrium show that there is no significant change up

until 50 % acidified water were added and a change is mainly evident between 80 %, 90 % and 100 %

(Fig. 2 left).

5,2

5,4

5,6

5,8

6,0

6,2

6,4

6,6

6,8

7,0

7,2

7,4

7,6

7,8

8,0

8,2

0 12 24 36 48 60 72

time [h]

pH-value

10%

20%

30%

40%

50%

60%

70%

80%

90%

6,0

6,2

6,4

6,6

6,8

7,0

7,2

7,4

7,6

7,8

8,0

0 24 48 72 96 120 144 168 192

time [h]

pH-value

100 : 100

250 : 250

500 : 500

1000 : 1000

Fig. 8: Left: Different amounts of acidified (pH 4) Jade Bay seawater mixed with non-acidified Jade Bay

seawater. Given is the development of pH over time in relation to the percentage of pH 4 water. Right:

same as left but only 50:50 mixing ratio with different volumes.

6,0

6,2

6,4

6,6

6,8

7,0

7,2

7,4

7,6

7,8

8,0

0 24 48 72 96 120 144 168

time [h]

pH-value

0 rpm

250 rpm

1000 rpm

8,04 8,13 8,10 8,07 8,05 7,94 7,86 7,72 7,49

6,99

4,00

3,0

4,0

5,0

6,0

7,0

8,0

9,0

0 10 20 30 40 50 60 70 80 90 100

percentage of pH 4 seawater

pH-value

Fig. 9: Left: 50:50 mixing ratio of acidified (pH 4) Jade Bay and natural Jade Bay seawater, with different stir

bar rotation speeds. Right: pH-value in equilibrium as function of mixing ratio (% pH 4 seawater)
8 Results and Discussion of environmental samplings

30

7.1.2 Ems River, Papenburg, Germany

Fig. 10. shows the results for the pH mix test determined with Ems River water taken at the Meyer

Werft in Papenburg, Germany. Although the water had only a very low salinity it shows a similar

behaviour to the experiment performed with seawater. This is due to its high sediment load and

therefore high carbonate content. The equilibrium in this case is reached as fast as in the test with

Jade Bay seawater, after about 12 h. However, a continuous decrease in pH can be observed in 1:1

mixtures (100 mL) until the percentage of pH 4-water has reached about 80 %.

5,6

5,8

6,0

6,2

6,4

6,6

6,8

7,0

7,2

7,4

7,6

7,8

8,0

8,2

8,4

8,6

0 12 24 36 48 60

time [h]

pH-value

10

20

30

40

50_1

50_2

60

70

80

90

8,51 8,47 8,43 8,30 8,21 8,05 8,18 8,16 8,00 7,82

7,30

4,00

3,0

4,0

5,0

6,0

7,0

8,0

9,0

0 10 20 30 40 50 60 70 80 90 100

percentage of pH 4 seawater [%]

pH-value

Fig. 10: Left: Different amounts of acidified (pH 4) Ems River water mixed with non-acidified Ems River water.

Given is the development of pH over time. Right: pH-value in equilibrium as function of mixing ratio

(% pH 4 seawater)

7.1.3 Odense, Denmark

Fig. 11 shows the results for the tests performed with Odense seawater. Also in this case equilibrium

is reached within about 12 h after mixing the two water bodies. The first significant change is

observable for mixtures containing more than 50 %.pH 4-water.

5,6

5,8

6,0

6,2

6,4

6,6

6,8

7,0

7,2

7,4

7,6

7,8

8,0

8,2

8,4

8,6

0 12 24 36 48 60

time [h]

pH-value

10

20

30

40

50_1

50_2

60

70

80

90

8,22 8,22 8,20 8,12 8,07 7,84 7,69 7,45

7,04

7,99

7,93

4,00

3,5

4,5

5,5

6,5

7,5

8,5

0 10 20 30 40 50 60 70 80 90 100

percentage of pH 4 seawater [%]

pH-value

Fig. 11: Left: Different amounts of acidified (pH 4) Odense seawater mixed with non acidified Odense seawater.

Given is the development of pH over time. Right: pH-value in equilibrium as function of mixing ratio

(% pH 4 seawater)
8 Results and Discussion of environmental samplings

31

7.1.4 Calais, France

Fig. 12 shows the results obtained with Calais seawater. Noticeable in this case is that there is, for all

mixtures up to 60 % pH 4-seawater, no temporal behaviour of the pH until the equilibrium is reached.

For the rest of the mixtures equilibrium is reached after maximally 6 h. A change of the pH in

equilibrium out of the error range is first observable at a percentage of 60 % pH 4-seawater.

6,2

6,4

6,6

6,8

7,0

7,2

7,4

7,6

7,8

8,0

8,2

8,4

8,6

8,8

0 6 12 18 24 30 36

time [h]

pH-value

10

20

30

40

50_1

50_2

60

70

80

90

8,60 8,62 8,56 8,52 8,45 8,26 8,19 8,02

7,63

8,40

8,45

4,00

3,5

4,5

5,5

6,5

7,5

8,5

9,5

0 10 20 30 40 50 60 70 80 90 100

percentage of acidified (pH 4) seawater [%]

pH-value

Fig. 12: Left: Different amounts of acidified (pH 4) Calais seawater mixed with non acidified Calais seawater.

Given is the development of pH over time. Right: pH-value in equilibrium as function of mixing ratio

(% pH 4 seawater)

7.1.5 Dover, England

A similar behaviour as observed for Calais seawater was found for Dover seawater. Fig. 13 shows the

results for this test. For a mixing ration of 50:50 no significant temporal development of the pH can be

observed. The first pH change in equilibrium greater than the error range is observable for

percentages greater than 50 % pH 4-seawater

6,0

6,2

6,4

6,6

6,8

7,0

7,2

7,4

7,6

7,8

8,0

8,2

8,4

0 12 24 36 48 60 72 84

time [h]

pH-value

10

20

30

40

50_1

50_2

60

70

80

90

8,27 8,21 8,14 8,10 8,05 7,90 7,77 7,57

7,09

7,99

7,95

4,00

3,5

4,5

5,5

6,5

7,5

8,5

9,5

0 10 20 30 40 50 60 70 80 90 100

percentage of pH4 seawater[%]

pH-value

Fig. 13: Left: Different amounts of acidified (pH 4) Dover seawater mixed with non acidified Dover seawater.

Given is the development of pH. Right: pH-value in equilibrium as function of mixing ratio (% pH 4

seawater)
8 Results and Discussion of environmental samplings

32

7.1.6 Comparison of all results (in equilibrium)

Looking at the figures Fig. 8 to Fig. 13 it can be seen that during the experiments with Ems river water,

Nassau harbour and Odense seawater the mixtures are in equilibrium after about the same time. For

Dover and Calais seawater, equilibrium is reached much faster.

In equilibrium all values, even the river water values, are about the same. Highest values were

observed for Calais seawater. Dover Jade and Odense values in equilibrium are, when error range of

the pH meter is taken in consideration, the same for all mixtures.

3,8

4,2

4,6

5,0

5,4

5,8

6,2

6,6

7,0

7,4

7,8

8,2

8,6

9,0

0 10 20 30 40 50 60 70 80 90 100

percentage of pH 4 seawater[%]

pH-value

Jade

Odense

Ems

Calais

Dover

8,33 8,33 8,29 8,22 8,17 8,10 8,00 7,87 7,67

7,21

4,00 3,8

4,2

4,6

5,0

5,4

5,8

6,2

6,6

7,0

7,4

7,8

8,2

8,6

9,0

0 10 20 30 40 50 60 70 80 90 100

percentage of pH 4 seawater[%]

pH-value

Fig. 14: Left: pH-value in equilibrium of mixing ratio (% pH 4 seawater) for all pH tests. Right: Mean of all tests

with standard deviation.

3,8

4,2

4,6

5,0

5,4

5,8

6,2

6,6

7,0

7,4

7,8

8,2

8,6

9,0

0 10 20 30 40 50 60 70 80 90 100

percentage of pH 4 seawater[%]

pH-value

d pH/ d percentage

0,00

0,05

0,10

0,15

0,20

0,25

0,30

0,35

0 10 20 30 40 50 60 70 80 90 100

percentage of pH 4 seawater in mixture

Fig. 15: Left: mean pH value (points) and standard deviation (error bars) in equilibrium of mixing ratio (% pH 4

seawater) for all pH tests. The black line shows the model fitted to the points and the red line shows

the 95 % confidence interval of the model. Right: change of pH over percentage

From all pH values determined for the different mixtures in equilibrium the mean and the standard

deviation was calculated and plotted against the percentage of the pH 4 water in the mixture. For

these values an easy function was searched which fits the values best. Therefore the free available

software LAB fit (LAB fit Curve fitting software V 7.2.6.) was used. The determined function

d percentage

b c percentage

a percentage pH value  

 

   (12)
8 Results and Discussion of environmental samplings

33

was then fitted to the data by using the software Systat 8.0 (command file see appendix). The result is

shown in Fig. 15. The raw R-square (1-Residual/Total), the mean corrected R-square (1-

Residual/Corrected) and the R (observed vs. predicted) square values, which were calculated with

Systat, equalled 1.000.

The values obtained are listed in Table 15. For 0 % the pH is defined as

b

a

pH  .

Table 15: Values obtained by fitting equation 12 to the pH-values

parameter low 95 % optimum up 95 %

A -101.784 -101.646 -101.508

B -12.209 -12.1645 -12.120

C 0.117 0.117793 0.118

D -0.004 -0.00273782 -0.002

According to this function it is possible to mix natural seawater with acidified seawater in a relation of

60:40 to give a pH change of 0.2 pH units. According to the EPA regulations 0.2 units is maximum

allowed pH change in the initial mixing zone.
8 Results and Discussion of environmental samplings

34

7.2 GC-MS Validation

For GC MS validation, one time three different dilution series with concentrations of 1, 10, 50 and

100 ng l-1and one series made of 9 dilutions (2.5, 25, 25, 50, 50, 100, 250, 500, 1000 μg l-1) in which

some dilutions were prepared double but were diluted down from different concentrations. From this

series one of the 25 μg l-1and the 500 μg l-1concentrations were measured 8 times.

The three different dilution series were prepared to estimate the error due to the handling and the

diluting (Table 16). The calibration series with the nine different steps was prepared to determine the

linearity of the GC MS and the 8-fold measurements were performed to determine the accuracy of the

GC MS including the integration of the peak areas.

From Table 10 it can be seen that the relative standard error for the three different dilution series is

low. As the stock solution is a mix of all PAHs, it is admissible to calculate the mean of all compounds.

Therefore the error concerning to handling, loss to the walls of the vessels and additionally the GC MS

is 5.4 %. The accuracy of the GC MS alone is listed in Table 17.

The accuracy for the low molecular weight PAHs is higher than for the high molecular PAHs. The

difference between the relative standard deviations of low and high concentrations is to due to to

mathematical reasons. If the peak area error is always the same, the relative error is higher for low

peak areas than for higher peak areas. As all samples were concentrated within the range of 25 to

500 ng mL-1it is admissible to calculate the mean of all standard deviations, which results in 2.5 %.

This is about the half of the relative standard deviation calculated for the three different dilution series.

Table 16: Standard deviation of three different standard dilution series.

compound rel. stand dev.

acenaphthylene 4.7

acenaphthene 4.7

acenaphthene-D10 9.7

fluorene 4.9

phenanthrene-D10 4.5

anthracene 6.0

phenanthrene 5.1

fluoranthene 4.1

pyrene 5.8

benz[a]anthracene 6.4

chrysene-D12 6.8

chrysene 9.7

benzo[b]+benzo[k]fluoranthene 5.4

benzo[a]pyrene 4.1

perylene-D12 3.6

dibenz[a,h]anthracene 2.4

benzo[ghi]perylene 3.7

indeno(1,2,3,c,d)pyrene 5.1

mean 5.4
8 Results and Discussion of environmental samplings

35

Table 17: Accuracy of the GC/MS analysis (including InjSTD, integration and measurement)

compound mean

25 μg L-1

std. dev.

25 μg L-1

rel. std. dev.

25 μg L-1

mean

500 μg L-1

std. dev.

500μg l-1

rel. std. dev.

500 μg L-1

acenaphthylene 0.133 0.002 1.4 2.865 0.015 0.5

acenaphthene 0.086 0.001 1.4 1.848 0.009 0.5

acenaphthene-D10 0.066 0.001 0.8 1.407 0.006 0.4

fluorene 0.092 0.002 1.6 2.029 0.011 0.5

phenanthrene-D10 0.110 0.001 0.8 2.382 0.007 0.3

phenanthrene 0.142 0.002 1.2 3.117 0.019 0.6

anthracene 0.133 0.002 1.1 2.982 0.019 0.7

fluoranthene 0.134 0.002 1.2 2.978 0.016 0.5

pyrene 0.135 0.002 1.8 2.975 0.017 0.6

benz[a]anthracene 0.090 0.005 5.5 2.449 0.069 2.8

chrysene-D12 0.083 0.003 3.1 2.281 0.018 0.8

chrysene 0.103 0.004 3.8 2.707 0.032 1.2

benzo[b]fluoranthene

+benzo[k]fluoranthene

0.168 0.009 5.4 4.608 0.072 1.6

benzo[a]pyrene 0.056 0.004 7.2 1.609 0.045 2.8

perylene-D12 0.045 0.003 6.5 1.263 0.031 2.4

dibenz[a,h]anthracene 0.028 0.003 9.4 0.868 0.033 3.8

benzo[ghi]perylene 0.040 0.002 5.9 1.065 0.024 2.3

indeno(1.2.3.c.d)pyrene 0.030 0.002 7.5 1.015 0.031 3.0

Table 18: F-Test for linearity of the GC/MS analysis. Shown results were calculated for all dilution steps ranging

from 2.5 to 1000 μg L-1

compound 2

y _linear s

2

y _ nonlinear s DS2 EV F (1.6)

acenaphthylene 33.39 13.75 151.27 11.00 13.745 linear

acenaphthene 33.39 13.75 151.27 11.00 13.745 linear

acenaphthene-D10 20.01 6.03 103.93 17.24 13.745 linear

fluorene 30.66 33.53 13.40 0.40 13.745 linear

phenanthrene-D10 21.90 15.16 62.34 4.11 13.745 linear

phenanthrene 33.10 35.98 15.79 0.44 13.745 linear

anthracene 114.90 101.42 195.76 1.93 13.745 linear

fluoranthene 111.32 85.86 264.07 3.08 13.745 linear

pyrene 110.49 70.20 352.21 5.02 13.745 linear

benz[a]anthracene 1999.05 316.49 12094.41 38.21 13.745 nonlinear

chrysene-D12 686.38 265.45 3211.96 12.10 13.745 linear

chrysene 342.60 241.16 951.23 3.94 13.745 linear

benzo[b]fluoranthene

benzo[k]fluoranthene

2050.00 419.41 11833.50 28.21 13.745 nonlinear

benzo[a]pyrene 2410.91 222.39 15542.04 69.89 13.745 nonlinear

perylene-D12 2583.90 277.91 16419.87 59.08 13.745 nonlinear

dibenz[a.h]anthracene 1834.48 125.87 12086.15 96.02 13.745 nonlinear

benzo[ghi]perylene 1558.59 190.58 9766.67 51.25 13.745 nonlinear

indeno(1.2.3.c.d)pyrene 2554.00 343.29 15818.21 46.08 13.745 nonlinear
8 Results and Discussion of environmental samplings

36

The results for the check on linearity are shown in Table 18 and Table 19. For the low molecular

weight PAHs linearity is given for a range from 2.5 to 1000 ng mL-1. This group includes

acenaphthylene, acenaphthene, acenaphthene-D10, fluorene, phenanthrene-D10, phenanthrene,

anthracene fluoranthene, pyrene, chrysene and chrysene-D12. For the high molecular weight PAHs a

lower linear range was determined. This group includes benz[a]anthracene, benzo[b]fluoranthene +

benzo[k]fluoranthene, benzo[a]pyrene, perylene-D12, dibenz[a,h]anthracene, benzo[ghi]perylene and

indeno(1,2,3,c,d)pyrene. The linearity for these PAHs ranged from 1 to 100 ng mL-1.

Based on these results all samples with a concentration above the determined linearity range were

diluted to a concentration within this range.

Table 19: F-Test for linearity of the GC/MS analysis. Results were calculated with all dilution steps ranging from

2.5 to 100 μg L-1

compound 2

y _ linear s

2

y _ nonlinear s

DS2 EV F (1,6)

benz[a]anthracene 4.21 1.245424 13.1 10.52 21.198 linear

benzo[b]fluoranthene

benzo[k]fluoranthene

9.766 3.208492 29.44 9.175 21.198 linear

benzo[a]pyrene 4.932 2.068914 13.52 6.534 21.198 linear

perylene-D12 5.842 455.1465 -1342 2.949 21.198 linear

dibenz[a,h]anthracene 11.4 5.994801 27.6 4.605 21.198 linear

benzo[ghi]perylene 7.665 6.968051 9.756 1.4 21.198 linear

indeno(1,2,3,c,d)pyrene 7.988 8.354367 6.889 0.825 21.198 linear

The limit of detection was determined as three times the 25 ng mL-1concentration standard deviation.

The results are shown in Table 20.

Table 20: Limit of detection (LOD) for determined PAHs

compound LOD [ng mL-1]

acenaphthylene 1

acenaphthene 1

acenaphthene-D10 1

fluorene 2

phenanthrene-D10 1

phenanthrene 1

anthracene 1

fluoranthene 1

pyrene 1

benz[a]anthracene 4

chrysene-D12 3

chrysene 3

benzo[b]fluoranthene

benzo[k]fluoranthene

4

benzo[a]pyrene 5

perylene-D12 5

dibenz[a,h]anthracene 8

benzo[ghi]perylene 4

indeno(1,2,3,c,d)pyrene 5
8 Results and Discussion of environmental samplings

37

7.3 PAH-Extraction, Validation of Method

As in the most cases PAHs are extracted from fresh water or sediments most applications are fitted for

these matrices. Therefore tests (Chapter 4.2) were performed to determine the extraction efficiency,

the accuracy and the reproducibility of the method.

As there is no reference material for PAH in seawater available, for the recovery tests a certified PAH

mix in acetone was diluted, added to seawater and extracted as described before. The results of the

tests with the different SPE sorbents and the different elution solvents (Table 21) show that the best

recovery rate with the lowest standard deviation was obtained with the SPE C18ec cartridges and

DCM as elution solvent. The EASY material showed only low recovery rates (Fig. 16) for the high

molecular PAHs. The same was observed when using SPE C18ec and n-hexane (Fig. 17) as elution

solvent. Almost as good results as for C18ec and DCM were observed for C18 PAH SPE sorbent (Fig.

18). But as these cartridges were only available with a load of 500 mg, the flow was much slower and

the drying took longer than for C18ec. Therefore in all assays C18ec cartridges and DCM were used

to extract the soluble fraction of the PAHs. LLE also showed good recovery rates, but PAHs with high

vapour pressure were lost during evaporation in the rotary evaporator.

The recovery rate in natural seawater in Fig. 19 was low for high molecular PAHs when only the liquid

fraction was considered. Therefore additionally the filter was extracted. The results are shown in Fig.

21. Highest recovery rates close to 100 % were observed for fluorene, phenanthrene, pyrene and

dibenz[a,h]anthracene. The lowest recovery rate was determined for chysene-D12 with 66.4 %. The

mean recovery rate for all compounds was determined to be 86.1 % 10.6.

Fig. 20 shows that >90 % of acenaphthylene, acenaphthene, fluorene, phenanthrene-D10 and

anthracene are present in the dissolved form. Benzo[b]fluoranthene, benzo[k]fluoranthene,

benzo[a]pyrene, perylene-D12, dibenz[a,h]anthracene, benzo[ghi]perylene and indeno(1,2,3,c,d)

pyrene are mainly (>90 %) adsorbed to particles. Benz[a]anthracene, chrysene and chrysene-D12 are

distributed about 50:50 between particulate and aqueous phase. The results of this test showed that a

the highest recoveries were found after 2 h and 4 h. Extraction time had a significant influence on

phenanthrene, benz[a]anthracene, chrysene-D12 and chrysene only. For these compounds the

soluble fraction was rising with time.
8 Results and Discussion of environmental samplings

38

0

20

40

60

80

100

120

acenaphthylene

acenaphthene-D10

fluor en

phen anthrene-D10

phenanthrene

anthracene

pyrene

benz[a]anthracene

chrysene-D12

chrysene

benzo[b+k]fluoranth

benzo[ a]pyrene

perylen-D12

dibenz[a,h]anthracene

benzo[ghi]perylene

in deno(1,2,3,c,d)pyrene

0

20

40

60

80

100

120

acenaphthylene

acenaphthene-D10

fluoren

phenanthrene-D10

phenanthrene

anthr acene

pyrene

benz[a]an thracene

chrysene-D12

chrysene

benzo[b+k]fluoranth

benzo[a]pyrene

perylen-D 12

dibenz[a,h]anthr acene

benzo[ghi]perylene

in deno(1,2,3,c,d)pyrene

Fig. 16: Results of tests for the determination of the recovery rates of PAHs from seawater. Left: Results of

Liquid-Liquid-Extraction. Shown are the recovery rates for the different PAHs and the overall mean and

standard deviation. Right: Same for extraction with SPE sorbent Chromabond EASY.

0

20

40

60

80

100

120

acenaphthylene

acenaphthene-D 10

fluoren

phen anthr en e-D10

phenanthrene

anthracene

pyrene

benz[a]anthracene

chrysene-D12

chrysene

benzo[b+k]fluoranth

benzo[a]pyrene

perylen-D12

dibenz[a,h]anthracene

benzo[ghi]perylene

indeno(1,2,3,c,d)pyrene

0

20

40

60

80

100

120

acenaphthylene

acenaphthene-D10

fluoren

phenanthrene-D10

anthr acene

phenanthrene

pyrene

benz[a]anthracene

chrysene-D12

chrysene

benzo[b+k]fluor anth

benzo[a]pyrene

perylen-D12

dibenz[a,h]anthracene

benzo[ghi]perylene

indeno(1,2,3,c,d)pyrene

Fig. 17: Results of tests for the determination of recovery rates of PAHs from seawater. Left: Extraction by SPE

with sorbent Chromabond C18 ec with elution solvent DCM. Shown are the recovery rates for the

different PAHs and the overall mean and standard deviation. Right: Same for SPE sorbent

Chromabond C18 ec but with elution solvent n-hexane.

0

20

40

60

80

100

120

acenaphthylene

acenaphthene-D10

fluor en

phen anthrene-D10

anthracene

phenanthr ene

pyrene

benz[a]anth racene

chrysene-D 12

chrysene

benzo[b+k]fluoranth

benzo[a]pyrene

perylen-D12

dibenz[a,h]anth racene

benzo[ghi]perylene

indeno(1,2,3,c,d)pyrene

0

20

40

60

80

100

120

acenaphthylene

acenaphthene-D10

fluoren

phenanthrene-D10

phenanthrene

anthracene

pyrene

benz[a]an th racene

chrysene-D12

chrysene

benzo[b+k]fluoranth

benzo[a]pyrene

perylen-D12

dibenz[a,h]anth

racene

benzo[ghi]perylene

indeno(1,2,3,c,d)pyrene

Fig. 18: Results of tests for the determination of recovery rates of PAHs from seawater. Left: Extraction by SPE

with sorbent Chromabond C18 PAH with elution solvent DCM. Shown are the recovery rates for the

different PAHs and the overall mean and standard deviation. Right: Influence of addition of different

amounts of acetone to the sample.
8 Results and Discussion of environmental samplings

39

0

20

40

60

80

100

120

140

acenaphthylene

acenaphth ene-D10

fluoren

p henanthrene-D10

phenanthrene

anthr acene

pyrene

b enz[a]anthracene

ch rysene-D12

chrysene

benzo[b+k]fluoranth

benzo[a]pyrene

perylen-D12

diben z[a,h]anthracene

benzo[gh i]perylene

indeno(1,2,3,c,d)pyrene

0

20

40

60

80

100

120

140

acenaphthylene

acenaphthene-D10

fluoren

phenanthrene-D10

phenanthrene

anthr acene

pyrene

benz[a]anthracen e

chrysene-D12

chrysene

benzo[b+k]fluoranth

benzo [a]pyrene

perylen-D12

dibenz[a,h]anthracene

benzo[gh i]perylene

indeno(1,2,3,c,d)pyrene

Fig. 19: Recovery rates of the soluble PAHs from natural seawater with Chromabond SPE sorbent C18 ec and

elution solvent DCM. Left: Calais seawater Right: Dover seawater.

Table 21: Mean recovery rates and standard deviations determined for tests with artificial seawater.

PAH EASY C18PAH C18ec/ DCM C18ec/Hexane LLE

mean sd mean sd mean sd mean sd mean sd

acenaphthylene 79.6 10.0 87.9 4.7 89.5 11.3 97.4 6.5 9.0 16.9

acenaphthene-D10 76.3 9.8 76.3 6.4 80.8 8.5 90.1 8.0 8.3 18.3

fluorene 87.8 12.0 89.6 9.6 94.4 16.2 105.5 11.0 13.2 24.4

phenanthrene-D10 76.6 7.9 80.8 6.1 88.4 5.7 89.8 5.5 28.4 28.5

phenanthrene 91.9 6.9 97.0 5.6 104.0 10.6 106.4 5.4 31.2 30.8

anthracene 72.8 7.3 76.3 6.5 82.5 8.5 88.1 3.8 28.0 25.7

pyrene 81.9 9.1 91.9 9.7 107.3 8.7 95.3 2.3 76.6 32.0

benz[a]anthracene 59.0 2.8 67.9 5.1 92.2 8.1 57.9 4.1 75.5 6.3

chrysene-D12 54.8 5.3 62.4 3.4 83.9 12.7 53.3 1.5 68.3 5.6

chrysene 59.1 10.7 65.1 4.0 92.5 13.6 57.6 0.3 76.2 4.7

benzo[b]fluoranthene

+benzo[k]fluoranthene

45.6 3.3 66.7 4.4 78.1 5.7 49.9 2.7 74.1 3.5

benzo[a]pyrene 33.7 9.4 41.4 3.3 57.8 15.5 30.8 3.2 62.1 11.9

perylene-D12 34.3 4.0 46.6 8.4 59.4 6.9 37.2 6.5 68.4 4.0

dibenz[a,h]anthracene 33.5 7.4 61.1 3.2 69.3 9.5 41.3 0.1 72.6 16.5

benzo[ghi]perylene 38.1 3.9 88.1 8.4 85.8 18.2 63.7 2.0 86.0 9.8

indeno(1,2,3,c,d)pyrene 36.9 6.0 70.5 2.7 76.9 5.4 48.7 1.6 71.4 7.4

mean + standard deviation 60.1 21.1 73.1 16.0 84.0 13.8 69.6 25.8 53.1 27.9
8 Results and Discussion of environmental samplings

40

0

10

20

30

40

50

60

70

80

90

100

acenaphthylene

acenaphthene-D10

fluoren

phenanthrene-D10

anthracene

phenanthrene

pyrene

benz[a]anthracene

chrysene-D12

chrysene

benzo[b+k]fluoranth

benzo[a]pyrene

perylen-D12

dibenz[a,h]anthracene

benzo[ghi]perylene

i ndeno(1,2,3,c,d)pyrene

1 h

2 h

4 h

10 h

Fig. 20: Fractionation of PAHs between dissolved and particulate fraction after different incubation times.

79,8

88,2

99,9

90,4

101,6

86,1

96,6

70,6

66,4

71,5

76,3

86,8

89,2

96,7

90,1

87,4

0

20

40

60

80

100

120

acen aphthylene

acenaphthen e-D10

fluoren

phenanthrene-D10

anthracene

phenanthrene

pyren e

benz[a]anthracene

chrysene-D12

chrysene

benzo[b+k]fluoranth

benzo[a]pyrene

perylen-D12

dibenz[a,h]anthracene

benzo[ghi]perylen e

inden o(1,2,3,c,d)pyrene

Fig. 21: Mean recovery rate and standard deviation for eight extractions of Dover seawater and particulate

fraction.
8 Results and Discussion of environmental samplings

41

8 Results and Discussion of environmental samplings

In this chapter the results of the different samplings are shown. The pH, salinity, temperature, metal,

sulphate, nutrients, plankton and PAH data will first be shown and described for each sampling and

then the variations over the annual circle will be presented.

8.1 1

st sampling (February)

8.1.1 pH, Temperature, Salinity, Conductivity, Oxygen

Table 22 shows the pH, water temperature, air temperature, salinity and oxygen contents measured

during the sampling on 11.02.2004. The most eastern point (Point Cal 2: Quai de service) showed the

lowest pH and the lowest salinity. The highest salinity (31 PSU) was observed for the point the closest

to the open sea. The temperature was nearly the same for all points. Only at Cal 1 (Quai en eau

profonde) water temperature was a little lower (8.2 °C). Oxygen was saturated at all points.

Table 22: Air and water temperature [°C], salinity [PSU], pH value and oxygen [mg l-1] during sampling in Calais

harbour on 11.2.2004

temp. air

[°C]

temp. water

[°C]

salinity

[PSU]

pH oxygen

[mg L-1]

Cal 1 Quai en eau profonde 8.2 7.4 27.0 7.97 9.7

Cal 2 Quai de service 8.8 7.3 18.3 7.81 9.3

Cal 3 Quai de la Loire 8.8 7.3 29.6 8.04 10.3

Cal 4 Jetee ouest 8.8 7.4 31.0 8.02 8.4

All samples in Calais were taken between 8:45 am and 10:30 am (CET). According to Table 8 low tide

was at 10:45 am, so all samples were taken during ebb tide. All samples in Dover were taken between

18:30 and 19:00 (CET). According to Table 8 low tide on 11.2.2004 was at 21:39. Therefore all

samples in Dover were also taken at ebb tide.

Table 23 shows the water temperature, the salinity and the pH for the samples taken in Dover during

the sampling on 11.02.2004. For all stations the results are similar. pH was with 8.10 higher than in

Calais. The temperature 8.4 °C was about 0.4 °C colder and salinity was about 3 units higher than in

Calais.

Table 23: Water temperature [°C], salinity [PSU] and pH-value during sampling in Dover harbour on 11.2.2004

and on board of the “Pride of Kent”

temp. water

[°C]

salinity

[PSU]

pH

Point 7 Harbour entrance 8.5 34.1 8.10

Point 8 Middle port 8.4 34.0 8.10

Point 9 Quay 4 8.1 34.1 8.11

Point SCH1 Channel SWS inlet 9.2 34.3 8.06

Point SCH2 Channel SWS outlet 22.3 34.9 7.99
8 Results and Discussion of environmental samplings

42

Despite dilution by the cooling water the temperature was higher in the outflow than in the inlet water

(inlet 9.2 °C outlet 22.3°C). Although this increase will have no or only little direct influence on the

ecosystem it will influence the physical behaviour of the effluent. Higher temperatures at constant

salinity increase the buoyancy of the effluent in comparison to the surrounding water. This may

partially hinder the water bodies from effective mixing. A change in salinity, which would support or

reduce this effect, was not observed. Another effect of higher water temperatures is the lower solubility

of gaseous compounds in warmer water. This could lead to oxygen depletion. As oxygen was

saturated in all samples no adverse effect was observed. Besides, a negative effect of cooling water

discharges from ships on the surrounding environment was, concerning to the knowledge of the

author, never reported.

8.1.2 Metals and Sulphate

Metal and sulphate concentrations determined by ICP-OES are shown in Table 25. The determined

metals are listed in chapter 5.3 on page 15. Concentrations below the detection limit are marked by a

dash. The concentration of the sea salt standard (International Association for Physical Science of the

Ocean, IAPSO) are given in Table 24.

Table 24: Contents of the International Association for Physical Science of the Ocean standard for natural

Atlantic seawater.

element Ba Ca Cd Co Cr Cu Fe K Li Mg

unit ppb ppm ppb ppb ppb ppb ppb ppm ppb ppm

concentration 14 412 0.01 0.05 0.04 0.1 2 387 180 1294

element Mn Mo Ni Pb SO4 Sr V Zn

unit ppb ppb ppb ppb ppm ppb ppb ppb

concentration 0.2 10 0.2 0.003 2712 8000 2.5 0.1

During the sampling on 11.2.2003 none of the examined transition metals were found inside the

harbours with the exception of Calais point Cal 2: Quai de service. Here a manganese concentration

of 69 ppb was detected. At this point earth metals were with the exception of barium lower in

comparison to the other points, whereas at the harbour entrance in Dover Ba, Li, Sr, Ca, K and Mg

concentrations were slightly higher than at the other points. The sulphate concentration was highest at

this point too. Both, the high sulphate and the high earth metal concentrations are mainly due to the

higher salinity at this point. The comparison between seawater scrubber inlet and outlet water showed

a slight increase of the zinc concentration in the outlet water. This is most probably due to a

contamination from for example the tubing, the fittings or the pumps.
8 Results and Discussion of environmental samplings

43

Table 25: Sulphate, earth and transition metals determined for the samples taken on 11.02.2004. Fields with”-“

show concentrations below the detection limit.

Cal 1 Cal 2 Cal 3 Cal 4 7 8 9 21 22

Ba ppb 17 21 18 16 20 14 14 13 12

Ca ppm 339 263 359 369 509 391 390 395 401

Cd ppb - - - - - - - - -

Co ppb - - - - - - - - -

Cr ppb - - - - - - - -

Cu ppb - - - - - - - - -

Fe ppb - - - - - - - - -

K ppm 280 180 310 352 475 352 373 357 376

Li ppb 148 112 161 169 232 185 186 181 185

Mg ppm 994 664 1071 1113 1567 1183 1191 1219 1254

Mn ppb - 68 - - - - - - -

Mo ppb - - - - - - - - -

Ni ppb - - - - - - - - -

Pb ppb - - - - - - - - -

SO4 ppm 2161 1479 2399 2461 3831 2857 2853 2842 2874

Sr ppb 6392 4448 6853 7223 10188 7889 7863 7907 8093

V ppb - - - - - - - - -

Zn ppb - - - - - - - - 143

8.1.3 Nutrients

Table 26 shows the nutrients concentrations determined for the samples taken on 11.02.2004. The

following abbreviations are used. Total chlorophyll (THCL), particulate inorganic phosphorus (PIP),

particulate organic phosphorus (POP), total particulate phosphorus (TPP), reactive dissolved

phosphorus (RDP), dissolved organic phosphorus (DOP), total dissolved phosphorus (TDP), dissolved

inorganic nitrogen (DIN).

The chlorophyll concentration was highest at point Cal 4 and lowest in the seawater scrubber outlet. At

point Cal 4 also the phosphorus and nitrogen compounds were high, but highest at point Cal 2. This

might indicate a higher amount of diatoms or a starting bloom.

Table 26: Nutrient concentrations determined for the samples taken on 11.02.2004

TCHL Seston PIP POP TPP RDP DOP TDP

[μg L-1] [mg L-1] [μmol L -1] [μmol L-1] [μmol Ll-1] [μmol L-1] [μmol L-1] [μmol L-1]

Cal 1 2.2 62.8 0.80 0.70 1.50 0.51 8.14 8.65

Cal 2 2.6 39.1 0.88 0.82 1.69 5.23 5.28 10.51

Cal 3 2.7 42.5 0.25 0.38 0.63 0.70 5.42 6.12

Cal 4 6.6 138.6 0.08 0.82 0.90 0.51 6.12 6.63

7 (Dover) 2.5 122.7 0.25 0.58 0.83 0.26 5.43 5.69

8 (Dover) 2.4 120.8 0.22 0.60 0.82 0.35 3.52 3.88

9 (Dover) 3.0 108.8 0.29 0.42 0.71 0.35 2.83 3.18

SCH1 1.4 75.1 0.10 0.36 0.45 0.35 4.20 4.55

SCH2 0.9 55.3 0.05 0.32 0.36 0.26 4.97 5.23
8 Results and Discussion of environmental samplings

44

NO2

- NO3- NH4+ DIN Si(OH)4

[μmol L-1] [μmol L-1] [μmol L-1] [μmol L-1] [μmol L-1]

Cal 1 0.90 42.09 24.31 67.30 54.27

Cal 2 2.03 74.66 107.64 184.32 92.78

Cal 3 1.15 61.89 15.29 78.33 34.95

Cal 4 0.74 41.86 10.41 53.02 24.50

7 (Dover) 0.22 15.97 1.49 17.69 6.31

8 (Dover) 0.23 15.21 18.96 34.40 6.57

9 (Dover) 0.44 20.10 19.25 39.79 9.38

SCH1 0.33 16.41 1.53 18.26 5.63

SCH2 0.22 11.41 1.53 13.16 7.37

8.1.4 Polycyclic Aromatic Hydrocarbons

Table 69 gives the total amounts of the 16 EPA-PAHs (without naphthalene), n Table 70 the

concentrations of the dissolved and the particulate are shown. The highest concentration was

determined for point Cal 4: Jetee Ouest, the lowest concentration for point Cal 3 Quai de la Loire. For

points Cal 2 and Cal 3 total concentrations of 267 ng L-1and 354 ng L-1 were determined. In all cases

phenanthrene was dominating and only at point 4 a higher amount of low molecular weight PAHs was

found.

In Dover at all sampling points the PAH amounts were about equally high, and in the same order of

magnitude as in Calais. The dominating compound was in Dover phenanthrene too. High molecular

weight PAHs had extremely low contents.

The PAH contents determined for the Ecosilencer inlet and outlet are shown in Table 72. In these

samples phenanthrene was dominating too. The total amount of PAHs determined at the outlet was

16-fold higher than the amount determined in the inlet water. In the outlet water the particulate fraction

was about five times higher than the dissolved fraction.

To determine whether the PAHs are similarly distributed and show similar patterns a regression of the

compounds was performed. The results are shown in Table 28. It can be seen that the range of the

correlation coefficients is widely distributed from not significant to 0.999. Highest R2 values were

observed between the more soluble two- and three-ring compounds whereas the relation between the

soluble and insoluble PAHs is lower. As this method might be influenced by great differences in

concentrations of the single compounds a regression of the concentrations at the different sampling

points was performed (Table 27). The difference between these two approaches is that the regression

of the compounds shows high correlation coefficients if for example anthracene is high at all points

where phenanthrene is low. The correlation coefficient for the regression of the sampling points

reflects the relation of all compounds to each other. The regression of the sampling points delivered

high correlations coefficients for all regressions. This indicates that the PAHs are similarly distributed

at all points. The results of the compound regression are shown in Table 28. It can be seen that the

low molecular weight PAHs are highly correlated with the remaining low molecular weight PAHs and

the high molecular weight PAHs with the remaining high molecular weight PAHs. But the high

molecular compounds are not correlated with the low molecular compounds. This shows that the PAH
8 Results and Discussion of environmental samplings

45

load of the water has a similar composition at all points, whereas the PAHs bound to particles show a

different composition.

Table 27: Regression of sample points (Sampling 11.2.04). Colours are added for a better visualisation. Yellow -

highly correlated, red - moderate or low correlation, dark red - no significant. correlation.

C

al1

C

al2

C

al3

C

al4

789S

C

H1

S

C

H

2

Cal1 1 0.997 0.987 0.874 0.995 0.95 0.997 0.999 0.982

Cal2 1 0.986 0.855 0.995 0.951 0.992 0.995 0.986

Cal3 1 0.859 0.99 0.937 0.979 0.989 0.978

Cal4 1 0.833 0.822 0.884 0.865 0.786

7 1 0.946 0.987 0.997 0.993

8 1 0.947 0.947 0.932

9 1 0.995 0.97

SCH1 1 0.985

SCH2 1

Table 28: Regression of compound contents determined for the samples taken on 11.2.04. Colours are added for

a better visualisation. Yellow - highly correlated, red - moderate or low correlation, dark red - no

significant correlation.

A

T

H

Y

A

T

H

E

FLR

E

P

H

E

N

A

N

T

H

FLU

A

P

Y

R

B

a

A

C

H

RY

BbkFB

a

P

D

ahA

BghiPIN

D

E

ATHY 1 0.994 0.988 0.988 0.954 0.989 0.746 NS 0.405 NS NS NS NS NS

ATHE 1 0.995 0.995 0.967 0.995 0.753 NS 0.412 NS NS NS NS NS

FLRE 1 0.999 0.965 0.997 0.738 NS 0.404 NS NS NS NS NS

PHEN 1 0.969 0.999 0.756 NS 0.418 NS NS NS NS NS

ANTH 1 0.971 0.778 NS 0.419 NS NS NS NS NS

FLUA 1 0.779 NS 0.441 NS NS NS NS NS

PYR 1 0.497 0.821 0.418 0.403 NS 0.309 0.304

BaA 1 0.665 0.672 0.571 NS 0.435 0.417

CHRY 1 0.71 0.742 NS 0.602 0.567

BbkF 1 0.959 NS 0.913 0.835

BaP 1 NS 0.915 0.814

DahA 1 NS NS

BghiP 1 0.957

INDE 1
8 Results and Discussion of environmental samplings

46

8.2 2

nd sampling (March)

During this sampling the Ecosilencer was not fully operating. Problems were encountered, because

the velocity of the exhaust gas was too high (17 m s-1). For an optimal operation velocity should be

<7 m s

-1

to allow condensation in the funnel. Therefore, acidic droplets left the exhaust funnels. Only

the exhaust gases of the four auxiliary engines were scrubbed, whereas SWS 3 was shut off, due to

corrosion problems. Also auxialary engine 2 was off, but with the SWS running (Fig. 22).

SWS1 SWS2 SWS3 SWS3

Auxiliary

engine 1

(650-700 kW)

Auxiliary

engine 2

(650-700 kW)

Auxiliary

engine 3

(900 kW)

Auxiliary

engine 4

(650-700 kW)

= off

Fig. 22: The auxiliary engines and SWS running at the 24.03.04

Engine no. 2 did not produce exhaust gas, therefore the SWS 2 did not adsorb any SO2 and others

constituents of the gas. The exhaust gas of engine 3, the one with the maximum power escapes

directly into the atmosphere. Thus, only half of the planned SO2 was scavenged by the system.

8.2.1 pH, Temperature, Salinity, Conductivity, Oxygen

Table 29 shows the pH, water and air temperatures, salinity and oxygen content determined for the

samples taken in Calais on 23.3.2004. Values measured at points Cal 1, Cal 2 and Cal 4 are nearly

the same with the highest pH value measured at point Cal 4 and the highest salinity measured at point

Cal 2. Point Cal 3 is in all cases an exception. At this point an unusually high pH value and oxygen

content were measured. Also a lower temperature and salinity were observed.

Table 29: Air and water temperature [°C], salinity [PSU], pH value and oxygen [mg L-1] during sampling in Calais

harbour on 23.3.2004

temp. air

[°C]

temp. water

[°C]

salinity

[PSU]

pH oxygen

[mg L-1]

Cal 1 Quai en eau profonde 8.6 8.5 31.2 8.42 9.85

Cal 2 Quai de service 8.1 8.5 31.7 8.50 9.79

Cal 3 Quai de la Loire 9.4 7.7 27.5 9.35 >20

Cal 4 Jetee ouest 8.1 8.5 31.5 8.63 9.87
8 Results and Discussion of environmental samplings

47

All samples in Calais were taken between 16:00 and 18:30 (CET). According to Table 8 high tide was

at 14:21 and therefore samples were taken at ebb tide.

Table 30 shows the pH, water and air temperatures, salinities and oxygen contents determined for the

samples taken in Dover on 24.03.2004. The samples from points 5 and 6 were taken between 8:40

and 10:00 (Table 9) and therefore shortly after low tide (Table 8). Samples at point 7, 8 and 9 were

taken between 13:15 and 13:35 and therefore quite exactly at high tide. The lowest temperature was

measured at point 6 the other values determined for this point are about the same as those measured

close to the „Pride of kent“. The sample take at the beach at point 5 had the lowest salinity and the

lowest pH.

Table 30: Air and water temperatures [°C], salinity [PSU], pH value and oxygen [mg L-1] during sampling in Dover

harbour on 24.3.2004

Dover temp. air

[°C]

temp. water

[°C]

salinity

[PSU]

pH oxygen

[mg L-1]

Point 5 Churchill Hotel Beach 9.0 11.0 27.0 7.68 9.52

Point 6 Prince of Wales pier 7.4 8.9 34.3 7.86 10.1

Point 7 Back of „Pride of kent“ 12.3 8.8 34.2 7.95

Point 8 Middle of „Pride of kent“ 12.3 8.8 34.4 7.95

Point 9 Front of „Pride of kent“ 12.3 8.8 34.4 8.00

Table 31 shows the pH, the salinities and the temperatures measured inside the seawater scrubber

system. Looking at the inlet samples, the temperature was highest inside the Channel (15.2°C). The

lowest salinity was measured in Calais (32.9) and the lowest pH (7.72) in Dover. If these values are

compared with the values at the outlet it can be seen that the salinity was slightly increased and the

temperature was raised by about 2 °C to 3 °C. The pH was lowered in all cases. The strongest

reduction was observed in the channel where the difference between inlet and outlet pH was 1.16 pH

units whereas in Calais and in Dover it was 0.66 and 0.43, respectively.

Table 31: Water temperature [°C], salinity [PSU], pH value and oxygen [mg L-1] during sampling on the “Pride of

Kent” on 24.3.2004

temp. water

[°C]

salinity

[PSU]

pH

SD1 seawater inlet Dover 10.7 34.2 7.72

SD2 seawater outlet Dover 14.8 34.6 7.29

SCH1 seawater inlet Channel 15.2 34.9 7.94

SCH2 seawater outlet Channel 17.1 35.2 6.78

SCH3 outlet from US filter 27.6 35.5 2.73

SCH4 to settling tank 28.8 35.4 2.86

SCH5 inlet to US filter 27.9 35.2 2.82

SCH6 return from Ecosilencer 28.0 35.2 2.78

SCH7 top of settling tank 27.2 33.5 2.83

SCH8 bottom of settling tank 23.0 34.9 2.83

SC1 seawater inlet Calais 9.5 32.9 8.00

SC2 seawater outlet Calais 12.8 32.9 7.34
8 Results and Discussion of environmental samplings

48

The values determined for the samples taken from the remaining seawater scrubber points show, with

the exception of the settling tank, no change in salinity. Inside the settling tank the salinity was lower

perhaps because the water remains there for a while and therefore water from different water bodies

is mixed. The remaining time of the water inside the settling tank might also be an explanation why

there the pH is higher than pH 3 as in comparison to the remaining seawater scrubber points, where it

is lower than 3. Although the effluent water had a significantly lower pH than the inflowing water, no

pH change in the harbour or close to the “Pride of Kent” was measured. Additionally there was no pH

change observable inside the harbour between the first sampling where the Ecosilencer was not

running and the second sampling.

8.2.2 Metals and Sulphate

Sulphate, transition and earth metal concentrations of the harbour and the Ecosilencer samples taken

on 23/24.03.2004 are given in Table 32. Inside the ports a copper concentration of 220 ppb in Calais

at point Cal 1 and a zinc concentration of 53 ppb at point 9 in Dover were observed. Sulphate

concentrations were highest in Dover at the Prince of Wales Pier and at Terminal 4 (back of “Pride of

Kent”, Point 9). The samples taken in the middle (point 8) and at the front (point 7) of the „Pride of

Kent“ show lower earth metal and sulphate conentents than the other samples.

Inside the seawater scrubber system the highest transition metal contents were determined for the

samples taken from the tube to the settling tank and inside the settling tank. Additionally, high copper

and zinc concentrations were found at the inlet to the US filter. Except for iron (789 ppb) no metals

could be detected directly after the Ecosilencer. This indicates that most metals are leached from the

tubing due to the low pH and do not originate from the fluegas scrubbing process itself. At the outlet of

the US filter only vanadium (183 ppb) was determined and in the SWS outlet sample taken in the

Channel and in Dover, zinc (138 ppb and 537 ppb) was detected. Inside the seawater scrubber

system highest transient metal concentrations were found at the inlet to and inside the settling tank.

This indicates that most of the metals are bound to particles or are particulates themselves and are

therefore effectively removed from the system.

Sulphate concentrations did show an increase inside the SWS directly after the Ecosilencer but this

increase was diluted to the SWS inlet sulphate level before it left the „Pride of Kent“. Inside the

harbours the sulphate concentrations are at about the same level as the effluent concentrations but

due to different salinity values they vary within a range of 1500 and 3350 ppm.
8 Results and Discussion of environmental samplings

49

Table 32: Sulphate, earth and transition metal contents determined for the samples taken in July

Cal 1 Cal 2 Cal 3 Cal 4 5 6 7 8 9 SD1 SD2 SCH2 SCH1 SCH3 SCH4 SCH5 SCH6 SCH7 SCH8 SC1 SC2

Ba ppb 18 20 22 18 23 19 18 15 19 16 17 16 21 18 34 19 19 24 26 18 19

Ca ppm 382 356 348 380 341 398 327 279 371 395 397 405 406 411 434 404 396 396 562 381 370

Cd ppb - - - - - - - - - - - - - - - - - - - - -

Co ppb - - - - - - - 8 - - - - - - - - - - - - -

Cr ppb - - - - - - - - - - - - - - 264 - - - - - -

Cu ppb 220 - - - - - - - - 129 129 - - - 7089 10978 - 273 2127 - -

Fe ppb - - - - - - - - - - - - - 1051 5283 892 789 1508 - - -

K ppm 352 345 314 366 288 398 340 297 381 397 384 428 426 434 437 422 419 405 424 388 367

Li ppb 164 158 147 165 140 178 150 128 169 188 188 187 185 185 185 183 180 175 183 172 166

Mg ppm 1154 1091 1007 1161 980 1251 1028 883 1173 1213 1202 1278 1278 1290 1289 1272 1245 1207 1255 1189 1149

Mn ppb - - - - - - - - - - 20 - - - 72 - - - 332 - -

Mo ppb - - - - - - - - - - - - - - - - - - 403 - -

Ni ppb - - - - - - - - - - - - - - 277 - - - 1076 - -

Pb ppb - - - - - - - - - - - - - - - - - - - - -

SO4 ppm 2619 2625 2307 2628 2277 2920 2342 1942 2955 2949 2962 2990 3052 3342 3380 3359 3550 3235 3419 2920 2938

Sr ppb 7220 6829 6345 7202 6160 7730 6410 5490 7308 7987 8024 8031 7953 8074 8193 7950 7830 7616 8491 7487 7151

V ppb - - - - - - - - - - - - - 183 320 - - - - - -

Zn ppb - - - - - - - - 53 - 537 - 138 - 1033 1461 655 414 98 - -

For a better visualisation and a better estimate of the SWS influence a comparison between the

sulphate, transition and earth metal concentration determined for the SWS inlet and outlet is show in

Figs. 22 to 28 comparing the inlet and outlet samples taken in March and February. Samples taken on

11.02.2004 are marked, because during this sampling the seawater scrubber was not running. During

the sampling on 24.03.2004 copper was found in inlet and outlet samples taken in Dover. In both

samples the copper concentration was the same. In Dover also manganese was found, but only in the

outlet effluent. In all outlet but not in the inlet samples except in Calais on 24.03.2004 zinc was

determined. Earth metals were all, within the accuracy of the measurements, equally concentrated in

the inlet and outlet samples, only barium seems to be slightly increased, when the SWS is running.

Copper (Cu)

Comparison between SWS Inlet and Outlet

129129

0

20

40

60

80

100

120

140

Dover 24.03.04Channel 24.03.04Calais 24.03.04Channel 11.02.04

concentration [ppb]

Inlet

Outlet

+

below

= detection

limit

IAPSO= 0 ppb

+ + + + + +

Manganese (Mn)

Comparison between SWS Inlet and Outlet

20

0

5

10

15

20

25

Dover 24.03.04Channel 24.03.04Calais 24.03.04Channel 11.02.04

concentration [ppb]

Inlet

Outlet

+

below

= detection

limit

IAPSO= 0

+ + + + + + +

Fig. 23: Left: Copper content [ppb]. Right: Manganese content [ppb] determined for Ecosilencer inlet and outlet

samples taken in Calais, Dover and the Channel on 23/24.03.2004 and on 11.02.2004. IAPSO: Atlantic

water salinity standard.
8 Results and Discussion of environmental samplings

50

Zinc (Zn)

Comparison between SWS Inlet and Outlet

537

138

143

0

100

200

300

400

500

600

Dover 24.03.04Channel 24.03.04Calais 24.03 .04Chan nel 11.02.04

concentration [ppb]

Inlet

Outlet

+

below

= detection

limit

IAPSO= 0 ppb

+ + + + +

Barium (Ba)

Comparison between SWS Inlet and Outlet

1616

1817

21

19

1312

0

5

10

15

20

25

30

35

Dover 24.03.04Channel 24.03 .04Calais 24.03 .04Chan nel 1 1.02 .04

concentration [ppb]

Inlet

Outlet

- = IAPSO

Fig. 24: Left: Zinc content [ppb]. Right: Barium content [ppb] determined for Ecosilencer inlet and outlet

samples taken in Calais, Dover and the Channel on 23/24.03.2004 and on 11.02.2004. IAPSO: Atlantic

water salinity standard.

Lithium (Li)

Comparison between SWS Inlet and Outlet

188187

172

181

18818 5

166

18 5

0

50

100

150

200

250

Dover 24.03 .04Channe l 24.0 3.04Calais 24.03.04Channel 11.02.04

concentration [ppb]

Inlet

Outlet

- = IAPSO

Strontium (Sr)

Comparison between SWS Inlet and Outlet

79 87803 1

748 7

7907

802 47 953

7151

8093

0

1000

2000

3000

4000

5000

6000

7000

8000

9000

Do ver 2 4.03 .04Channel 24.03.04Calais 24.03.04Ch anne l 11.0 2.04

concentration [ppb]

Inlet

Outlet

- = IAPSO

Fig. 25: Left: Lithium content [ppb]. Right: Strontium content [ppb] determined for Ecosilencer inlet and outlet

samples taken in Calais, Dover and the Channel on 23/24.03.2004 and on 11.02.2004. IAPSO: Atlantic

water salinity standard.

Calcium (Ca)

Comparison between SWS Inlet and Outlet

395

405

38 1

395397

4 06

3 70

401

0

50

100

150

200

250

300

350

400

450

Dover 24.03.04Channel 24.03.04Calais 24.03 .04Chan nel 11 .02.0 4

concentration [ppm]

Inlet

Outlet

- = IAPSO

Potassium (K)

Comparison between SWS Inlet and Outlet

397

428

388

357

3 84

426

367

37 6

0

50

100

150

200

250

300

350

400

450

500

Dover 24.03.04Channel 24 .03.0 4Calais 24.03.04Channel 11.02.04

concentration [ppm]

Inlet

Outlet

- = IAPSO

Fig. 26: Left: Calcium content [ppm]. Right: Potassium content [ppm] determined for Ecosilencer inlet and outlet

samples taken in Calais, Dover and the Channel on 23/24.03.2004 and on 11.02.2004. IAPSO: Atlantic

water salinity standard.
8 Results and Discussion of environmental samplings

51

Magnesium (Mg)

Comparison between SWS Inlet and Outlet

121 3

1278

118 9

12191 202

1278

11 49

1 254

0

200

400

600

800

1000

1200

1400

Dover 24.03.04Channel 24.03 .04Calais 24.03.04Channel 11.02.04

concentration [ppm]

Inlet

Outlet

- = IAPSO

Sulphate (SO4)

Comparison between SWS Inlet and Outlet

29 49

2 990

2920

2842

296 2

3052

2 938

28 74

0

500

1000

1500

2000

2500

3000

3500

Dover 24.03.04Channel 2 4.03.04Calais 24.03.04Cha nnel 1 1.02 .04

concentration [ppm]

Inlet

Outlet

- = IAPSO

Fig. 27: Left: Magnesium content [ppb]. Right: Sulphate content [ppb] determined for Ecosilencer inlet and

outlet samples taken in Calais, Dover and the Channel on 23/24.03.2004 and on 11.02.2004. IAPSO:

Atlantic water salinity standard.

8.2.3 Nutrients

Table 26 shows the nutrient and seston contents determined for the samples taken in March. In Calais

the highest seston content was observed at point Cal 2 (50.9 mg L-1) where about double the content

of the remaining points was observed. Sampling point 5 was situated at a sandy beach therefore the

seston content was higher (80.9 mg l-1) in comparison to the sample taken at the Prince of Wales pier

where the seston content was comparable to those measured in Calais. On board of the „Pride of

Kent“ the highest contents where not observed inside the settling tank as expected, but in the outlet of

the US filter (132.0 mg L-1). Inside the pipe which leads the water to the settling tank also high particle

contents where observed. Looking at the inlet and the outlet samples it can be seen, that the highest

seston contents were observed in the inlet sample taken in Calais (262.6 mg L-1). This might be an

effect of the berthing, where the screws whirl up a lot of sediment, which then might be sucked into the

ships cooling cycle. In Calais and Dover the seston contents in the outlet are lower than those

observed in the inlet. That shows that the clean-up system inside the ship (cyclones, settling tank and

US filter) worked and removed these particles. It also explains the high content measured at point

SCH4 where the removed particles pass by.

Looking at the RDP, DOP and TDP values it can be seen that they are quite the same in Dover and

Calais. Only at point Cal 3 where the algal bloom was observed nearly doubled TDP concentrations

were determined. At this point also the DIN concentrations were very high and only inside the settling

tank higher concentrations were measured. In both samples these high concentrations are due to by

high ammonia values; 33.05 μmol L-1at point Cal 3 and 76.66 μmol L-1at point SCH8 were observed,

whereas at the remaining points the concentrations varied between 1.34 and 12.81 μmol L-1. A nitrate

increase in the outlet samples in comparison to the inlet samples was only observed in Dover and

inside the Channel. In Calais the inlet sample contained more nitrate (20.47 μmol L-1) than the outlet
8 Results and Discussion of environmental samplings

52

sample (18.30 μmol L-1), but nitrite concentrations were higher in the outlet samples in Calais and the

Channel and equally high in the inlet and outlet samples in Dover.

Silicate concentrations were also highest in the sample taken from the settling tank (78.53 μmol L-1).

Inside the ports of Dover and Calais the highest concentrations were again measured at point Cal 3

and point 5. At point 5 the high concentration originates from the sand at the beach and at point Cal 3

centric diatoms were observed which are mainly built up by silicate.

Inside the seawater scrubber system high nitrate concentrations were observed, as expected, behind

the Ecosilencer (19.38 μmol L-1). At the following points the nitrate concentrations were reduced to

17.3 μmol L-1at the inlet and 14.73 μmol L-1at the outlet of the US filter. In the overboard discharge

the remaining nitrate concentration was only 8.55 μmol L-1. In contrary to the reduction of nitrate, the

reduced nitrogen compounds nitrite and ammonia increased slightly.

Table 33: Nutrient concentrations determined for the samples taken on 24.03.2004

samp.

point Seston RDP DOP TDP NO2

-

NO3

-

NH4

+

DIN Si(OH)4

[mg L-1] [μmol L-1] [μmol L-1] [μmol L-1] [μmol L-1] [μmol L

-1

] [μmol L-1] [μmol L-1] [μmol L-1]

Cal1 35.6 0.18 4.43 4.60 0.83 24.37 - - 18.41

Cal2 50.9 0.66 2.71 3.37 0.64 20.97 12.81 34.42 14.75

Cal3 23.7 2.20 4.80 7.00 1.38 18.92 33.05 53.35 25.27

Cal4 22.2 0.42 3.88 4.30 0.78 25.63 8.33 34.74 10.89

5 80.9 1.30 3.15 4.45 0.22 22.57 1.34 24.12 38.23

6 36.7 0.18 4.89 5.07 0.32 20.08 4.11 24.50 7.04

SD1 47.2 0.18 - - 0.20 14.72 - - 17.81

SD2 41.5 0.14 - - 0.20 18.67 - - 15.15

SCH1 4.6 0.08 - - 0.22 7.89 - - 4.08

SCH2 8.3 0.04 - - 2.97 8.55 - - 18.22

SCH3 132.0 1.21 - - 0.21 14.73 3.14 18.07 25.89

SCH4 118.5 0.79 - - 1.62 13.38 6.11 21.11 16.11

SCH5 25.9 0.77 - - 0.17 17.30 3.63 21.11 9.37

SCH6 55.3 0.35 - - 0.05 19.38 3.01 22.44 12.41

SCH7 23.0 0.79 - - 0.09 26.17 8.21 34.47 20.86

SCH8 39.0 0.12 - - 1.30 11.17 64.19 76.66 78.53

SC1 262.6 0.11 - - 0.60 20.47 8.55 29.62 9.29

SC2 49.9 0.19 - - 1.30 18.30 6.92 26.53 8.82

8.2.4 Polycyclic Aromatic Hydrocarbons

The total PAH contents determined for the Calais port samples are shown in Table 69. The highest

amount was measured at point Cal 3. At this point the PAH content was about double the content

observed at the other points. The high content might originate from the high amount of planktic

organisms observed at that point. PAHs might adsorb onto the surface of these organisms and thus

remain for a longer time in the water column. Also the PAHs might have been taken up actively from

the water resulting in an enrichment of PAHs in the organisms. The contents observed at the

remaining points are about as high as those determined for the first sampling. In all samples

phenanthrene was the dominating compound. High contents were also determined for pyrene and

fluoranthene.

The PAH contents determined for the samples taken in Dover are shown in Table 70. In all samples

phenanthrene was the dominating compound too. In front of the “Pride of Kent”, phenanthrene was
8 Results and Discussion of environmental samplings

53

reduced and anthracene, pyrene and fluoranthene were slightly increased. At Point 5 the particulate

PAH fraction was higher than at the other points. This is also underlined by the high seston contents

determined for that point, originating from the sandy beach. Looking at the total PAH amounts, the

lowest contents were found at point 9 (front of „Pride of Kent“) and the highest at point 6 (Prince of

Wales Pier). Close to this point is a catamaran berth. These ships blow their flue gas directly into the

screw water. Additionally at this point there are only low current speeds and hence a reduced water

exchange. The particles might remain for a longer time close to the surface and are therefore higher

contaminated with PAHs.

The results of the PAH-extraction from the Ecosilencer samples which were taken in the Channel

during normal operation mode of the „Pride of Kent“ are shown in Table 70 and Table 72. Taking the

inlet and the outlet into closer view it can be seen that the PAH content is about 10 times higher in the

outlet water than in the inlet water. The PAH composition inside the system is about the same at all

points, with phenanthrene dominating and high amounts of chrysene and pyrene also. The highest

contents were found in the tube going to the settling tank and at the bottom of the settling tank. This is

not surprising, as contaminated particles are enriched in the cyclones and transferred to the settling

tank. The samples taken before and after the US filter, which also should remove particles and oil from

the water, show that the filter system worked. The total PAH content was reduced from 15151 ng L-1to

12502 ng L-1. Within this reduction not only the particulate PAHs are included but also the dissolved

ones. The highest PAH contents were determined for the sample taken from the bottom of the settling

tank.

Origin of PAHs

Tables 34 to 37 and Fig. 28 show the calculated indices, which could be used to determine the origin

of the PAHs. A description of the basics of these indices is given in 5.4.3. Nearly all results, even

those that are not significant, show a petrogenic origin. The exceptions are for Flu/Pyr for all samples

taken in February without sample Cal 4, and for the second sampling for all samples with exception of

Cal 3. For Phe/Anth the exceptions were in February point 8 and in March point 9, and for Chr/BaA the

sample taken in February at point Cal 3 and in February at point 7.

Table 34: Indices for the determination of the origin of the PAHs (samples 11.02.04)

Feb

Cal 1

Feb

Cal 2

Feb

Cal 3

Feb

Cal 4

Feb

7

Feb

8

Feb

9

Feb

SCH1

Feb

SCH2

PHEN/ANTH 11.6 10.8 11.9 13.4 11.4 3.3 11.7 12.4 14.4

FLUA/PYR 1.2 1.5 1.7 0.5 1.4 1.3 1.1 1.1 3.8

CHRY/BaA 1.8 1.9 0.5 2.9 0.7 1.7 1.9 1.3 4.6

Table 35: Indices for the determination of the origin of the PAHs (harbour samples 24.03.04)

March

Cal 1

March

Cal 2

March

Cal 3

March

Cal 4

March

5

March

6

March

7

March

8

March

9

PHEN/ANTH 15.8 15.1 10.0 14.4 15.1 20.2 14.6 15.7 3.5

FLUA/PYR 0.5 0.8 1.5 0.8 0.4 0.5 0.8 0.6 1.1

CHRY/BaA 3.1 2.9 1.2 2.8 2.5 1.2 1.8 3.3 2.9
8 Results and Discussion of environmental samplings

54

For a better visualisation, the Phe/Anth and Flu/Pyr quotients are plotted in Fig. 28 and in a more

detailed version for the samples taken on board of the „Pride of Kent“ in Fig. 29. In these figures the

indices for coal tar and shale oil are also shown. These data underline what the indices alone already

showed. Most of the samples are to bed found in the border region between petrogenic and pyrolytic

origins. Only the Ecosilencer samples (without the samples from the inlet) are clearly of petrogenic

origin. These results are partially surprising. On the one hand no clear results were expected for the

harbour samples, because the samples were taken in harbours with high ship traffic, which would

explain the petrogenic origin. Additionally there are cities and car routes nearby, therefore also PAHs

with a pyrolytic origin, resulting in an inhomogeneous mixture of PAHs from different origins, creating

no clearly defined indices. On the other hand it is surprising, because the samples taken inside the

seawater scrubber, should clearly indicate pyrolytic origin. The reason that this is not the case might

be the incomplete combustion of the fuel and therefore the high amounts of “petrogenic” PAHs.

Table 36: Indices for the determination of the origin of the PAHs (harbour Ecosilencer samples 24.03.04)

March

SD1

March

SD2

March

SC1

March

SC2

PHEN/ANTH 16.0 34.5 14.1 37.7

FLUA/PYR 0.4 0.6 0.9 0.4

CHRY/BaA 3.7 3.5 2.0 2.7

Table 37: Indices for the determination of the origin of the PAHs (Channel of Dover Ecosilencer samples

24.03.04)

March

SCH1

March

SCH2

March

SCH3

March

SCH4

March

SCH5

March

SCH6

March

SCH7

March

SCH8

PHEN/ANTH 14.6 30.1 57.9 42.9 42.1 50.9 54.2 41.7

FLUA/PYR 0.8 0.5 0.5 0.3 0.5 0.4 0.5 0.4

CHRY/BaA 2.2 4.1 2.8 2.6 3.3 3.1 2.7 2.7

0

10

20

30

40

50

60

70

0,0 0,5 1,0 1,5 2,0 2,5 3,0 3,5 4,0

Flt/Pyr

Phe/An

Calais 110204

Calais 240304

Dover 110204

Dover 240304

on Board 110204

on board Dover 240304

on board Calais 240304

on board Channel 240304

Pyrolytic

Petrogenic

coal tar

shale oil

Fig. 28: Plot of isomeric phenanthrene/anthracene ratios against fluoranthene/pyrene ratios for all samples

taken in February and March
8 Results and Discussion of environmental samplings

55

0

10

20

30

40

50

60

70

0,0 0,5 1,0 1,5 2,0 2,5 3,0 3,5 4,0

Flt/Pyr

Phe/An

Inlet

Outlet

Pyrolytic

Petrogenic

coal tar

shale oil

Top of

Settling Tank

from Ecosilencer

Outlet

US Filter

Inlet

US Filter

Water going to

Settling Tank

Outlet Channel 110204

(Ecosilencer not running)

Bottom of

Settling Tank

Fig. 29: Plot of isomeric phenanthrene/anthracene ratios against fluoranthene/pyrene ratios for the seawater

scrubber samples taken in February and March.

To determine whether all PAHs in the samples originate from one source, a linear regression analysis

of all substances with each other was performed. If a regression coefficient of 1,000 is observed, all

points are lying on one line. That means, that in all samples the same relationship of the observed

PAH in relation to the remaining PAHs is present. If all regressions show an R2 of 1 all samples have

the same composition and this would indicate that they all originate from one source. The advantage

of this method is that the content has no influence on this calculation.

Table 38: Regression chart for the analysis of the sampling points (Sampling March). Colours are added for a

better visualisation. Yellow highly correlated, orange and red moderate or low correlation, dark red no

significant. correlation.

Cal1 Cal2 Cal3 Cal4 5 6 7 8 9 SD1 SD2 SCH1 SCH2 SCH3 SCH4 SCH5 SCH6 SCH7 SCH8 SC1 SC2

Cal1 1 0.989 0.928 0.986 0.939 0.969 0.984 0.996 0.734 0.999 0.982 0.966 0.985 0.991 0.927 0.98 0.982 0.977 0.954 0.973 0.982 Cal1

Cal2 1 0.953 0.98 0.894 0.953 0.993 0.978 0.732 0.331 0.901 0.985 0.968 0.978 0.876 0.963 0.959 0.949 0.91 0.992 0.954 Cal2

Cal3 1 0.953 0.864 0.916 0.947 0.925 0.829 0.342 0.791 0.929 0.892 0.906 0.808 0.894 0.885 0.885 0.861 0.949 0.883 Cal3

Cal4 1 0.943 0.974 0.978 0.989 0.795 0.411 0.833 0.956 0.961 0.967 0.908 0.955 0.957 0.959 0.947 0.966 0.963 Cal4

5 1 0.955 0.883 0.96 0.785 0.604 0.697 0.837 0.941 0.939 0.977 0.94 0.953 0.969 0.991 0.856 0.969 5

6 1 0.958 0.971 0.75 0.406 0.82 0.933 0.943 0.962 0.914 0.943 0.949 0.956 0.948 0.943 0.96 6

7 1 0.971 0.715 0.292 0.916 0.994 0.949 0.965 0.852 0.943 0.94 0.931 0.896 0.996 0.938 7

8 1 0.755 0.447 0.843 0.946 0.987 0.988 0.946 0.982 0.985 0.985 0.972 0.955 0.988 8

9 1 0.541 0.436 0.683 0.693 0.69 0.702 0.687 0.692 0.714 0.741 0.7 0.712 9

SD1 1 0.119 0.238 0.456 0.418 0.634 0.46 0.478 0.513 0.587 0.26 0.5 SD1

SD2 1 0.933 0.854 0.874 0.701 0.849 0.838 0.809 0.738 0.927 0.818 SD2

SCH1 1 0.923 0.943 0.806 0.915 0.911 0.897 0.852 0.996 0.906 SCH1

SCH2 1 0.995 0.956 0.998 0.998 0.993 0.967 0.936 0.993 SCH2

SCH3 1 0.945 0.996 0.995 0.99 0.961 0.954 0.992 SCH3

SCH4 1 0.957 0.969 0.979 0.99 0.824 0.978 SCH4

SCH5 1 0.998 0.994 0.967 0.931 0.993 SCH5

SCH6 1 0.998 0.977 0.925 0.998 SCH6

SCH7 1 0.988 0.913 0.999 SCH7

SCH8 1 0.87 0.986 SCH8

SC1 1 0.919 SC1

SC2 1 SC2

The results for the regressions are shown in Table 38 and Table 39. The regressions of the PAHs

among each other show a high correlation. The only two samples that show a different composition
8 Results and Discussion of environmental samplings

56

are the samples taken from the inlet inside the harbour of Dover and that one taken in Dover at the

front of the „Pride of Kent“.

Table 39: Regression of compound contents determined for the Samples taken on 24.03.04. Colours are added

for a better visualisation. Yellow - highly correlated, red - moderate or low correlation, dark red - no

significant. correlation.

A

T

H

Y

A

T

H

E

FLR

E

P

H

E

N

A

N

T

H

FLU

A

P

Y

R

B

a

A

C

H

RY

BbkFB

a

P

D

ahA

BghiPIN

D

E

ATHY 1 0.945 0.948 0.936 0.942 0.913 0.893 0.891 0.909 0.873 0.927 0.878 0.837 0.808

ATHE 1 0.988 0.988 0.955 0.953 0.956 0.959 0.971 0.911 0.989 0.933 0.881 0.836

FLRE 1 0.987 0.955 0.937 0.92 0.923 0.95 0.883 0.982 0.9 0.846 0.801

PHEN 1 0.975 0.966 0.952 0.949 0.967 0.925 0.984 0.937 0.897 0.857

ANTH 1 0.964 0.953 0.946 0.964 0.943 0.962 0.947 0.916 0.889

FLUA 1 0.972 0.955 0.961 0.985 0.951 0.97 0.971 0.951

PYR 1 0.995 0.989 0.976 0.964 0.994 0.964 0.936

BaA 1 0.993 0.955 0.974 0.988 0.939 0.905

CHRY 1 0.951 0.988 0.981 0.93 0.894

BbkF 1 0.918 0.984 0.997 0.986

BaP 1 0.95 0.888 0.884

DahA 1 0.977 0.955

BghiP 1 0.955

INDE 1

Additionally to the regression analysis a principal component analysis was performed. The results are

shown in Fig. 30. The feature vector is shown in Table 40. Eigenvector 1 is responsible for 70.6 % and

eigenvector 2 is responsible for 19.6 % which sums up to 90.2 % of the total variance. According to

Fig. 30 the samples can be divided into three groups. One is made up by one sample taken at point

Cal 3 and is characterized by a high positive value for eigenvector 1 and a negative value for

eigenvector 2. At Cal 3 high contents of low molecular weight PAHs were observed. This is shown by

the negative value for eigenvector 2. Eigenvector 1 mainly corresponds to the overall content and is

positive for high amounts and negative for low contents. The second group shows negative values for

eigenvector 1 and values close to zero for eigenvector 2.This group includes the samples taken in

Calais (also from the seawater scrubber inlet) and the samples taken in front of the “Pride of Kent”.

These samples are characterized by low contents of phenanthrene and high molecular weight PAH

contents. The third group contains the remaining samples taken in Dover. These samples show high

contents of those high molecular weight PAHs that are positive in the feature vector.
8 Results and Discussion of environmental samplings

57

Fig. 30: Results of the PCA of the harbour samples

Table 40: Feature vector for the PCA of the harbour samples

70.6 %

(14.0)

19.6 %

(14.0)

acenaphthylene 0.28 -0.25

acenaphthene 0.23 -0.36

fluorene 0.27 -0.31

phenanthrene 0.26 0.06

anthracene 0.27 -0.29

fluoranthene 0.30 -0.14

pyrene 0.20 0.46

benz[a]anthracene 0.30 0.22

chrysene 0.15 0.41

benzo[b]fluoranthene +

benzo[k]fluoranthene 0.30 0.08

benzo[a]pyrene 0.23 0.37

dibenz[a,h]anthracene 0.30 -0.07

benzo[ghi]perylene 0.30 0.16

indeno(1,2,3,c,d)pyrene 0.31 -0.05
8 Results and Discussion of environmental samplings

58

8.3 3

rd sampling (July)

8.3.1 pH, salinity and temperature

During this sampling additional samples to those taken on board of the “Pride of Kent” and from the

harbour walls were taken. The high and low water dates and the sampling times are given in Table 8

andTable 9. The pH, salinity and temperature data for this sampling are shown in Table 41. The air

temperatures were higher during the sampling on the boat than during the sampling from the quay

walls. The water temperature was highest at Point C5 and lowest at point Cal 3 “Quai de la Loire”. The

salinity was lower in those samples taken close to the shore than in those taken inside the harbour

and lowest at point Cal 1 and Cal 3. Both points are enclosed by harbour walls and water exchange is

only possible from one side. Therefore the water has a more brackish character. This is mainly due to

the higher buoyancy of water with lower salinity and higher temperatures compared to the cooler water

in deeper layers. Because of high temperatures and less wind this stratification is enforced in summer

and often lasts until fall. From point C5 to C700 a slight increase in pH was observed. As the salinity

also increased this might be a salinity effect. The temperature at point C5 was about 1 °C higher than

at point C50. This might be an effect of the cooling water which was approximately 3 °C higher than

the inlet water. The temperature, salinity and pH data observed in the harbour of Dover are shown in

Table 42. The air temperature was constant during the sampling as well as the water temperature and

the salinity. The pH varied between 8.30 at point D0 and maximal 8.38 at point D700.

Table 41: Temperature, salinity and pH data measured at the different sampling points in Calais harbour

point Temp [°C] air Temp [°C] water Sal [PSU] pH

Cal 1 15.0 17.0 29 7.69

Cal 2 15.2 17.1 31 8.07

Cal 3 15.8 16.5 29 8.28

Cal 4 17.3 16.9 32 8.22

C5 18.0 18.2 34 8.28

C50 18.0 17.1 34 8.29

C350 18.0 17.2 34 8.31

C700 18.0 17.5 35 8.37

Table 42: Temperature, salinity and pH data measured at the different sampling points in Dover harbour

point Temp [°C] (air) Temp [°C] water Sal [PSU] pH

D0 16.4 15.9 34 8.30

D5 16.4 15.9 34 8.35

D50 16.4 15.9 34 8.35

D350 16.4 15.9 34 8.35

D700 16.4 15.9 34 8.38

Dov 1 16.4 15.9 34 8.35

Dov 2 16.4 15.9 34 8.35

Dov 3 16.4 15.9 34 8.35

Dov 4 16.4 15.9 34 8.37

The water temperature, the salinity and the pH values for the samples taken inside the „Pride of Kent“

are shown in Table 43. Comparing the inlet and outlet samples in all cases the effluent temperature
8 Results and Discussion of environmental samplings

59

was about 3 °C higher than that of the inlet water and the pH was lower by about 1.5 pH units. The

salinity was nearly constant with 35 PSU at all points. Inside the seawater scrubber the lowest pH was

found at point SCH6 behind the Ecosilencer. At the US filter inlet and outlet the pH was already 0.14

pH units higher and in the outlet after dilution with the cooling water the pH was nearly neutral.

Table 43: Seawater scrubber temperatures, salinities and pH data

point Temp [°C] water Sal [PSU] pH

SD1 17.8 35.0 8.38

SD2 20.7 34.0 6.87

SCH1 17.4 35.0 8.44

SCH2 20.2 35.0 6.99

SCH3 36.7 34.5 3.14

SCH5 36.0 35.0 3.13

SCH6 37.0 35.0 3.09

SC1 18.2 35.0 8.16

SC2 20.9 35.0 6.82

8.3.2 Nutrients

Table 44 shows the chlorophyll, seston and nutrient data determined for the samples taken in July. In

Dover only at point D5 the chlorophyll content was high enough to be determined. In Calais the

contents varied between 11.7 μg L-1and 33.1 μg L-1. The highest content was observed at the berth in

front of the “Pride of Kent”. The seawater scrubber inlet and outlet samples taken in Calais are about

equally concentrated as those taken from the transect sampling points. The chlorophyll contents

determined for the remaining seawater scrubber samples are all within the same order of magnitude.

Nearly all seston contents laid between 50 and 65 mg L-1. Only at point C5 a higher seston content of

86.7 μg L-1 was measured. As at this point the chlorophyll content was high too the seston content

most probably originated from a high plankton abundance. Inside the seawater scrubber system the

highest seston content was measured in the outlet of the US filter. Comparing the inlet and outlet

samples only in Dover an increased seston content was observed in the outlet.

The determined RDP, DOP and TDP concentrations show no significant trend and varied between

0.33 - 5.07 μmol L-1(RDP) 0.11 - 2.41 μmol L-1(DOP) and 1.12 -2.96 μmol L-1. The highest RDP value

was measured at point Cal 3. At this point also the nitrate, nitrite, ammonium and silicate

concentrations were high. As no significantly higher seston or chlorophyll contents were determined

for that point it can be stated that at this point an algal bloom started. Comparing the determined

concentrations of both harbours it can be seen that in Calais the DIN and silicate concentrations were

generally higher than those in Dover.

Taking the seawater scrubber system samples into closer view, it can be seen that the highest nitrate

concentration was observed behind the Ecosilencer. According to the high ammonia concentration

determined for the US-filter sample the highest DIN concentration was observed at point SCH5. All
8 Results and Discussion of environmental samplings

60

outlet samples showed a higher DIN concentration than the inlet sample. This is mainly due to an

increase in NO2

-

and NO3

-

.

Table 44: Chlorophyll, seston and nutrient concentrations determined for the samples taken in July 2004

samp. point TCHL Seston RDP DOP TDP NO2

- NO3- NH4+ DIN Si(OH)4

[μg L-1] [mg L-1] [μmol L-1] [μmol L-1] [μmol L-1] [μmol L-1] [μmol L-1] [μmol L-1] [μmol L-1] [μmol L-1]

Cal1 26.7 47.9 4.60 - - 1.01 6.47 53.20 60.68 26.03

Cal2 23.5 59.3 3.13 - - 1.34 6.05 32.88 40.27 16.13

Cal3 19.3 49.4 5.07 - - 1.61 6.50 70.72 78.83 60.59

Cal4 11.7 54.8 1.37 1.12 2.49 1.12 5.29 19.29 25.70 8.84

C5 33.1 86.7 0.93 1.56 2.49 0.78 3.65 15.63 20.07 7.48

C50 26.1 63.4 0.57 1.65 2.22 0.83 3.85 16.13 20.81 7.89

C350 19.5 64.7 0.77 0.65 1.42 0.82 3.53 16.47 20.82 7.97

C700 24.3 55.8 1.12 1.06 2.18 0.80 3.48 16.42 20.70 7.85

D5 6.3 42.6 0.33 0.93 1.26 0.12 2.42 3.73 6.27 2.34

D50 - 57.2 0.33 2.43 2.76 0.16 2.47 3.73 6.36 5.84

D350 - 46.9 0.35 0.80 1.16 0.05 1.92 4.10 6.08 2.29

D700 - 54.9 0.35 0.78 1.13 0.16 2.36 3.42 5.94 1.38

Dov2 - 55.1 0.33 0.73 1.06 0.12 2.38 4.63 7.13 3.62

Dov4 - 57.8 1.98 0.11 2.09 0.05 2.34 3.42 5.81 9.12

SD1 7.7 74.3 3.04 - - 0.15 3.02 3.64 6.81 4.46

SD2 3.7 115.5 1.01 1.28 2.29 1.39 7.70 3.54 12.63 2.45

SCH1 2.1 51.4 1.83 0.35 2.18 0.04 1.33 2.88 4.25 3.82

SCH2 1.8 51.6 1.37 1.60 2.96 0.63 4.37 0.75 5.75 1.18

SCH3 2.5 145.9 1.28 1.10 2.38 0.03 17.25 5.55 22.83 9.48

SCH5 0.7 504.6 1.89 0.62 2.51 0.34 16.60 14.85 31.79 17.05

SCH6 1.7 73.2 0.42 0.70 1.12 0.33 16.83 8.60 25.75 5.34

SC1 14.7 59.8 0.35 2.41 2.76 0.42 2.79 7.20 10.42 3.60

SC2 12.4 56.7 0.33 1.82 2.15 2.99 4.05 7.17 14.21 5.19
8 Results and Discussion of environmental samplings

61

8.3.3 Polycyclic aromatic hydrocarbons

The PAH contents determined for the samples taken in Calais harbour on July 13th are shown in Table

70. Additionally the sum of the particulate and dissolved fraction is shown in Table 69. The highest

total amount was observed at Point Cal 1 (Quai en eau profonde), the lowest was determined for the

sample taken at the harbour entrance. Observed total amounts were between 46 ng L

-1

and 69 ng L

-1

and show only little variation. In all samples phenanthrene, fluoranthene and pyrene were the

dominating compounds. High molecular weight PAHs were at almost all locations below the limit of

detection.

The PAH contents determined for the samples taken in Dover are also shown in Table 70. The lowest

contents were determined for the samples taken at Point D 5 and D50 and the highest contents were

detected in the samples taken at point D 350 and point Dov 4. With exception of point D 350 almost no

PAHs bound to particles were found and therefore no high molecular weight PAHs were present. The

dominating component in all cases was phenanthrene. At some locations fluoranthene, pyrene and

chrysene also were found .

The PAH contents determined for the samples taken from the seawater scrubber system are shown in

Table 72. Comparing the inlet and outlet samples, the inlet samples always show very low contents.

These were equally concentrated in Calais and the Channel and had lower contents in Dover.

However the outlet samples show about 40 to 80 times higher total PAH contents than the inlet

samples, but nevertheless 10 times lower than inside the system before the dilution with the cooling

water. The total PAH amount behind the Ecosilencer and behind the US filter are nearly the same,

whereas the sample behind the cyclone shows a lower content. The major differences are due to the

phenanthrene, pyrene and fluoranthene contents.

Quality of measurement: Comparison 1st and 2nd extraction

Fig. 31 shows the results of the regression between the first and the second extraction. On the left the

regression of the extracted material weight is shown. For this determination the filter which was used

for the extraction of the particulate material was weighed before and after the extraction. Before the

latter the filter was dried at 100 °C. The weight thus determined is not comparable to the total

suspended material, because the filter was extracted and is therefore reduced in organic material, but

it can be used to compare the amounts of extracted material between the first and the second

extraction. On the right of Fig. 31 the regression of every single PAH compound of every single

sample determined during the first extraction was plotted against those from the second extraction.

In both regressions the slope and the R2 should be, in the best case, 1. This would show that for both

cases the amount of extracted material was the same and that in both extractions the same PAH

contents were measured. Due to the accuracy of the method (chapter 4.2) the R2 and the slope might

vary. As can be seen the difference is smaller than 4 % and therefore within the statistical range.
8 Results and Discussion of environmental samplings

62

y = 0,9847x

R

2

= 0,9785

0,000

0,005

0,010

0,015

0,020

0,025

0,030

0,035

0,040

0,000 0,005 0,010 0,015 0,020 0,025 0,030 0,035 0,040

1st extraction

2nd extrac tion

y = 1,0397x

R

2

= 0,9632

0

1000

2000

3000

4000

5000

6000

7000

8000

9000

0 1000 2000 3000 4000 5000 6000 7000 8000 9000

1st extraction

2nd extraction

Fig. 31: Regression between 1st and 2nd extraction. Left: Regression of the amount of extracted particulate

material [g]. Right: Regression of all PAHs [ng/L] (sum particulate, dissolved).

Origin of PAHs

In Fig. 32 the isomeric ratios of phenantrene/anthracene and fluoranthene/pyrene of the harbour

samples and the seawater scrubber samples are shown. The Calais harbour samples show a

behaviour similar to the harbour samples taken in February and March and are situated between a

petrogenic and a pyrolytic origin. In contrast the samples taken in Dover seem to originate from a

petrogenic pollution source.

Thehe Ecosilencer samples also show a comparable pattern. The PAHs from the sample behind the

Ecosilencer and from those before and behind the US filter have high phenanthrene to anthracene

ratios and low fluoranthene to pyrene ratios and are therefore most likely of petrogenic origin. The

PAHs in the outlet samples seem to be of petrogenic origin but not as markedly as the undiluted

samples. The inlet samples are comparable to the harbour samples.

0

10

20

30

40

50

60

70

0,0 0,2 0,4 0,6 0,8 1,0 1,2 1,4 1,6

flu/pyr

phe/ant

Calais

Dover

petrogenic

pyrolytic

coal tar

shale oil

0

10

20

30

40

50

60

70

0,0 0,2 0,4 0,6 0,8 1,0 1,2 1,4 1,6

flu/pyr

phe/ant

petrogenic

pyrolytic

coal tar

shale oil

P26 outlet ES

P23 outlet US

P25 inlet US

P12 SWS outlet Dover

P22 SWS outlet Channel

P32 SWS outlet Calais

P31 SWS inlet Calais

P21 SWS inlet

Channel P11 SWS inlet Dover

Fig. 32: Plot of isomeric phenanthrene/anthracene ratios against fluoranthene/pyrene ratios for all harbour

samples (left) and seawater scrubber samples (right).

The ratios of benz[a]anthracene and chrysene, which can also be used to determine the origin of the

PAHs in the samples are shown in Table 45. It can be seen that in most cases the contents of the two

compounds were too low and therefore this index could not be used to determine the origin. Only the
8 Results and Discussion of environmental samplings

63

contents of the outlet and the seawater scrubber samples were high enough. The quotients of these

samples are greater than one and therefore indicate pyrolytic origin.

Table 45: Quotient of benz[a]anthracene and chrysene.

sampl.

point Cal 1 Cal 2 Cal 3 Cal 4 C5 C50 C350 C700

BaA/CHRY 1.00 0.00 - - 1.00 - - -

sampl.

point Dov 2 Dov 3 Dov 4 D5 D50 D350 D700

BaA/CHRY - - - - - 0.20 -

sampl.

point SD1 SD2 SCH1 SCH2 SC1 SC2 SCH3 SCH5 SCH6

BaA/CHRY 0.00 1.89 0.00 1.47 0.00 1.86 2.63 2.46 2.26

Table 46: Regression of PAH components, yellow shows high correlation

A

T

H

Y

A

T

H

E

FLR

E

P

H

E

N

A

N

T

H

FLU

A

P

Y

R

B

a

A

C

H

RY

BbkFB

a

P

D

ahA

BghiPIN

D

E

ATHY 1 0.951 0.965 0.932 0.925 0.939 0.922 0.927 0.901 0.939 0.942 0.936 0.94 0.935

ATHE 1 0.979 0.98 0.957 0.982 0.967 0.972 0.943 0.984 0.992 0.978 0.986 0.983

FLRE 1 0.993 0.991 0.994 0.984 0.987 0.976 0.987 0.994 0.981 0.988 0.99

PHEN 1 0.99 0.999 0.996 0.998 0.99 0.991 0.993 0.979 0.988 0.976

ANTH 1 0.991 0.986 0.989 0.989 0.979 0.98 0.973 0.977 0.971

FLUA 1 0.994 0.998 0.988 0.993 0.994 0.982 0.99 0.98

PYR 1 0.995 0.994 0.977 0.981 0.959 0.972 0.959

BaA 1 0.992 0.991 0.989 0.979 0.987 0.97

CHRY 1 0.969 0.947 0.951 0.962 0.943

BbkF 1 0.996 0.996 0.999 0.986

BaP 1 0.99 0.997 0.993

DahA 1 0.998 0.988

BghiP 1 0.991

INDE 1

To examine whether the PAHs inside the harbour originate from one source the regression

coefficients for the linear regression of the compounds were calculated. These calculations might

show, whether the composition of the 16 EPA PAHs are comparable among each other. The results

are shown in Table 46. It can be seen that all compounds are highly correlated. As many PAHs had

values lower than the detection limit and some like phenanthrene appeared in high contents, the

results might only “pretend” a high correlation. Therefore the R2 was calculated for the linear

regression of each station with the remaining stations. The results are shown in Table 47. It can be

seen that sample Cal 3 does not correlate with any other sample, and that the samples taken from the

seawater scrubber are only moderately correlated with the harbour samples. However the harbour

samples and the inlet samples with exception of the Channel inlet sample also show a good

correlation aa do the SWS samples among each other. In summary it can be said that the harbour

samples and the seawater scrubber inlet samples show a similar PAH composition. The seawater
8 Results and Discussion of environmental samplings

64

scrubber samples make up another group which is not even comparable to the samples taken directly

in front of the outlet of the “Pride of Kent”. The PAH composition of point Cal 3 is totally different from

the remaining samples.

Table 47: Regression of sampling points. Colours are added for a better visualisation. Yellow - highly correlated,

orange and red moderate or low correlation, dark red - no significant correlation.

Cal 1 Cal 2 Cal 3 Cal 4 C05 C50 C350 C700 D05 D50 D350 D700 Dov2 Dov4 SD1 SD2 SCH1 SCH2 SCH3 SCH5 SCH6 SC1 SC2

Cal 1 1 0.892 0.638 0.832 0.918 0.887 0.864 0.743 0.61 0.675 0.858 0.83 0.868 0.883 0.836 0.662 0.743 0.598 0.624 0.646 0.643 0.821 0.614 Cal 1

Cal 2 1 0.506 0.877 0.916 0.912 0.951 0.877 0.77 0.788 0.895 0.889 0.891 0.953 0.875 0.713 0.807 0.657 0.663 0.685 0.682 0.897 0.641 Cal 2

Cal 3 1 0.492 0.505 0.429 0.431 0.255 0.146 0.158 0.402 0.335 0.36 0.388 0.38 0.146 0.262 0.104 0.126 0.139 0.144 0.339 0.152 Cal 3

Cal 4 1 0.759 0.791 0.85 0.789 0.733 0.746 0.713 0.845 0.909 0.864 0.723 0.644 0.804 0.584 0.604 0.621 0.613 0.752 0.557 Cal 4

C05 1 0.89 0.881 0.789 0.672 0.722 0.892 0.824 0.836 0.911 0.836 0.707 0.708 0.646 0.671 0.689 0.687 0.844 0.654 C05

C50 1 0.952 0.932 0.829 0.864 0.858 0.964 0.906 0.957 0.948 0.75 0.825 0.69 0.702 0.728 0.716 0.924 0.659 C50

C350 1 0.95 0.836 0.872 0.821 0.959 0.921 0.957 0.891 0.738 0.843 0.682 0.692 0.715 0.702 0.899 0.644 C350

C700 1 0.934 0.946 0.779 0.975 0.91 0.93 0.888 0.793 0.866 0.752 0.751 0.772 0.752 0.893 0.677 C700

D05 1 0.976 0.702 0.908 0.832 0.856 0.8 0.821 0.843 0.775 0.778 0.796 0.779 0.852 0.693 D05

D50 1 0.738 0.94 0.88 0.892 0.834 0.851 0.883 0.811 0.807 0.825 0.808 0.882 0.723 D50

D350 1 0.812 0.807 0.863 0.913 0.799 0.81 0.764 0.753 0.773 0.776 0.931 0.764 D350

D700 1 0.949 0.947 0.926 0.802 0.912 0.754 0.757 0.78 0.762 0.924 0.694 D700

Dov 2 1 0.943 0.847 0.833 0.879 0.789 0.804 0.819 0.807 0.861 0.749 Dov 2

Dov 4 1 0.881 0.778 0.822 0.714 0.731 0.752 0.743 0.903 0.676 Dov 4

SD1 1 0.781 0.897 0.751 0.726 0.752 0.746 0.977 0.715 SD1

SD2 1 0.82 0.988 0.993 0.996 0.996 0.836 0.972 SD2

SCH1 1 0.81 0.768 0.7889 0.78 0.924 0.738 SCH1

SCH2 1 0.984 0.985 0.985 0.805 0.973 SCH2

SCH3 1 0.999 0.997 0.78 0.978 SCH3

SCH5 1 0.998 0.805 0.976 SCH5

SCH6 1 0.803 0.986 SCH6

SC1 1 0.769 SC1

SC2 1 SC2

Principal component analysis

In Fig. 33 and in Table 48 the results of the PCA of all harbour samples and the SWS inlet samples

taken in July are given. In this case eigenvector 1 accounts for 33.6 % and eigenvector 2 for19.7 % of

the total variance. As both vectors only make up 52.3 % of the total variance only a part of the total

variability within these samples can be explained. According to the PCA plot the samples can be

divided into three groups. The first one is made up by C 50, C700, D 5, D 50, D 700, Dov 2, SD1 and

SC1. These samples are all in the third quadrant meaning they are negative on both axes. Looking at

the feature vector this indicates low overall concentrations and especially low anthracene, pyrene and

fluoranthene concentrations. The second group is made up by the samples Cal 2, Cal 3, Cal 4, C 350

and Dov 4. These are in the second quadrant meaning they are positively related to eigenvector 2 and

negatively related to eigenvector. As eigenvector 1 is mainly positive, this indicates, that the samples

of this group have higher contents the more they are situated on the positive side. The third group is

made up by Cal 1, C 5 and D 350. These samples also showed the highest overall concentration. The

pattern that is drawn in Fig. 33 is nearly the same, which can be observed in the regression chart

(Table 47). Cal 3, Cal 1, C5 and D350 are separated and have only low correlations with the

remaining points, whereas the remaining points are higher correlated.
8 Results and Discussion of environmental samplings

65

Fig. 33: Results of the PCA of the harbour samples

Table 48: Feature vector for the PCA of the harbour samples

33.6 %

(14.0)

19.7 %

(14.0)

acenaphthylene 0.16 0.48

acenaphthene -0.05 0.31

fluorene -0.02 0.06

phenanthrene 0.23 -0.09

anthracene 0.15 0.50

fluoranthene 0.43 0.22

pyrene 0.41 0.27

benz[a]anthracene 0.38 -0.26

chrysene 0.18 -0.26

benzo[b]fluoranthene +

benzo[k]fluoranthene 0.37 -0.09

benzo[a]pyrene 0.39 -0.11

dibenz[a,h]anthracene 0.27 -0.36

benzo[ghi]perylene 0.16 0.48

indeno(1,2,3,c,d)pyrene -0.05 0.31
8 Results and Discussion of environmental samplings

66

8.4 4

th sampling (September)

8.4.1 pH, salinity and temperature

The date and time when the samples were taken during the fourth sampling are given in Table 9. The

high and low water times are shown in Table 8. It can be seen that in Calais the samples were taken

during high tide and three hours after high tide. In Dover the samples were taken approximately one

hour after ebb tide.

The pH, salinity, air and water temperatures are shown in Table 49 (Calais), Table 50 (Dover) and in

Table 51 (seawater scrubber). The air temperatures during the sampling from the quay walls in Calais

varied between 19.0 and 19.5 °C and the water temperature between 21.5 and 22.1 °C. During the

sampling from the small boat at point C0, C5, C50, C350, C700 the air temperature was about 3 to

4 °C higher. The water temperature at point C5 and C50 was slightly increased (0.5 °C) whereas the

remaining points had about the same water temperature as the samples taken from the harbour walls.

The increase in temperature might be an effect of the seawater scrubber effluent.

Table 49: Temperature, salinity and pH data measured at the different sampling points in Calais harbour in

September

Point Temp [°C]

air

Temp [°C]

water Sal [PSU] pH

Cal 1 19.5 22.1 34.1 7.95

Cal 2 19.5 22.1 34.0 7.97

Cal 3 19.0 21.5 31.9 7.89

Cal 4 19.1 21.9 33.7 8.04

C 0 22.3 23.3 34.3 8.08

C 5 23.5 23.1 34.6 8.08

C 50 23.0 22.8 34.7 8.09

C 350 22.2 22.8 34.7 8.09

C 700 22.2 22.9 34.6 8.10

Table 50: Temperature, salinity and pH data measured at the different sampling points in Dover harbour in

September

Point Temp [°C]

air

Temp [°C]

water Sal [PSU] pH

D 5 26.9 22.8 35.1 8.07

D 50 24.4 22.3 35.2 8.04

D 350 25.1 22.1 35.0 8.05

D 700 23.6 22.1 35.0 8.04

Dov 1 23.3 22.2 35.0 8.07

Dov 2 22.6 22.2 35.1 8.08

Dov 3 22.6 21.9 35.1 8.08

Dov 4 25.0 22.2 35.2 8.08
8 Results and Discussion of environmental samplings

67

Table 31 shows that the seawater scrubber outlet water was 13 to 17 °C warmer than the inlet water.

This difference is more than 10 °C higher than those observed during the first three samples. An

increased temperature was also observed at the first and second points in Dover in a distance of 5

and 50 m away from the outlet. At point D 5 the temperature was 0.7 °C higher than at the remaining

points inside the harbour, with the exception of point Dov 3 in the middle of the port, where the

temperature was the lowest (21.9 °C). Inside the seawater scrubber system the highest temperatures

were measured directly after the Ecosilencer, in front of and behind the US-filter. Here the

temperatures were 45.1, 45.3 and 46.2 °C, respectively. The water in the seawater scrubber outlet still

had a temperature of 35.7, 37.1 and 37.6 °C. The pH inside the harbour was nearly constant for all

samples with exception of the samples taken from the quay walls in Calais. Inside the seawater

scrubber system the lowest pH (3.05) was determined in the pipe leading to the settling tank and also

behind the US filter. The outlet water in Dover, the Channel and Calais showed a pH of 6.2, 6.4 and

6.15, respectively. It was about 1.7 pH units lower in comparison to the inlet water. The samples taken

inside the Channel had a salinity of about 37 whereas in Calais and Dover the salinity varied between

34 and 35. At point Cal 3 a salinity of only 31.9 was observed due to the enclosed situation of that

sampling point.

Table 51: Temperature, salinity and pH data measured at the different sampling points in the seawater scrubber

in September

Point Temp [°C]

water Sal [PSU] pH

SD1 24.0 34.4 7.99

SD2 37.6 35.7 6.20

SCH1 23.0 36.0 8.08

SCH2 37.1 36.0 6.40

SCH3 45.3 36.8 3.14

SCH4 42.5 36.6 3.05

SCH5 46.2 36.8 3.05

SCH6 45.1 36.4 3.13

SCH7 38.5 37.0 3.04

SC1 20.7 34.5 7.88

SC2 37.6 34.7 6.15
8 Results and Discussion of environmental samplings

68

8.4.2 Nutrients

The chlorophyll, seston and nutrient concentrations determined for the samples taken in September

are shown in Table 52. It can be seen that in Dover the chlorophyll concentration was generally lower

than in Calais. The highest chlorophyll content was measured at point Cal 3 (181.9 μg L-1). At this

point also the highest seston, silicate, ammonium and RDP concentrations ws determined, whereas

the nitrate concentration was the lowest observed in all samples. This shows that there was an algal

bloom at this point. The nitrate concentration was reduced because it is used as an important nitrogen

supply. Ammonium is the first degradation product of nitrogen-containing organic material. Hence the

higher concentrations in the harbour waters of Calais indicate that somde degradation already had

taken place. At the remaining points in Calais the chlorophyll concentrations varied between 5.1 and

48.4 μg L-1. The lowest value was observed at point Cal 1 and the highest at C350. In Dover

Chlorophyll concentration between 4.2 (Dov 4) and 12.8 μg L-1(D350) were observed. The RDP,

DOP, TDP, seston and silicate values were all within the same range as in Calais, whereas the nitrate

concentrations were increased and the ammonium concentrations were lower in Dover. Taking a look

at the first transect samples D5 and C5 it can be seen that the nitrate concentrations are slightly

increased in comparison to the other points. This could be an effect of the seawater scrubber but also

of eutrophication due to the enclosed area and the ship traffic.

Table 52: Chlorophyll, seston and nutrient concentrations determined for the samples taken in September 2004

samp.

point TCHL Seston RDP DOP TDP NO3

- NH4+ DIN Si(OH)4

[μg L-1] [mg L-1] [μmol L1] [μmol L -

1

] [μmol L1] [μmol L1] [μmol L -

1

] [μmol L1] [μmol L1]

Cal1 5.1 54.8 0.87 0.13 1.00 4.05 12.60 17.29 7.82

Cal2 16.2 56.7 0.97 0.07 1.04 3.76 14.20 18.60 8.57

Cal3 181.9 100.8 4.50 0.31 4.81 0.75 41.93 43.19 14.73

Cal4 22.9 64.0 0.65 0.31 0.96 3.52 9.28 13.36 6.92

C0 23.2 86.0 0.47 0.52 0.99 2.79 8.28 11.59 6.83

C5 35.3 76.2 0.39 0.61 0.99 3.58 9.95 14.02 6.84

C50 43.2 89.2 0.37 0.56 0.94 2.78 7.93 11.19 6.64

C350 48.4 76.5 0.37 0.19 0.56 2.52 9.02 12.02 5.04

C700 44.9 67.3 0.23 0.50 0.73 2.86 8.14 11.47 4.15

D5 7.2 59.5 0.55 0.35 0.90 2.86 0.63 3.80 6.78

D50 10.5 59.7 0.65 0.06 0.70 2.50 1.50 4.31 6.46

D350 12.8 58.8 0.23 0.24 0.47 2.58 1.44 4.31 4.94

D700 10.0 72.6 0.19 0.13 0.32 4.33 0.34 5.06 5.00

Dov1 5.9 74.8 0.55 0.23 0.78 7.37 1.22 9.07 6.02

Dov2 9.9 61.3 0.44 0.09 0.53 5.43 1.38 7.29 5.00

Dov3 7.6 65.6 0.44 0.08 0.52 5.32 1.41 7.19 6.49

Dov4 4.2 66.0 0.21 0.03 0.24 4.27 1.78 6.35 6.02

SD1 16.5 62.1 0.23 0.09 0.32 3.63 1.43 5.39 6.81

SD2 9.6 69.9 0.22 0.08 0.30 7.66 2.42 10.79 6.00

SCH1 5.7 57.8 0.20 0.09 0.29 3.96 2.26 6.63 3.89

SCH2 6.1 55.0 0.20 0.03 0.23 3.77 2.08 6.27 3.15

SCH3 10.2 54.1 0.78 0.29 1.07 19.21 4.33 23.61 7.58

SCH4 9.6 70.6 1.35 0.23 1.59 21.58 8.40 30.61 12.31

SCH5 6.7 61.1 0.83 0.10 0.93 18.27 3.67 22.01 6.95

SCH6 4.6 57.6 0.99 0.09 1.08 17.85 3.40 21.32 10.04

SCH7 7.4 99.1 1.54 0.08 1.62 21.05 4.90 26.10 12.28

SC1 49.1 61.8 0.64 0.15 0.79 3.76 8.33 12.63 8.70

SC2 32.0 64.2 0.42 0.23 0.65 5.52 7.37 13.54 7.60

Looking at the seawater scrubber inlet and outlet samples it can be seen that the nitrate

concentrations are higher in the outlet, in Calais they even doubled. On board, the highest nitrate

concentrations were not observed directly behind the Ecosilencer but at point SCH4, the pipe leading
8 Results and Discussion of environmental samplings

69

to the settling tank, and at point SCH7, the settling tank. These points also show high TDP, silicate

and seston values. As silicate is the main substance of which diatom tests are built up it is not

surprising that it is enriched by the cyclones in the seawater scrubber system. Comparing the inlet and

outlet samples it can be seen that the nitrate concentration due to the formation of nitric acid in the

Ecosilencer is increased. Additionally the seston content is higher in the outlet samples. This might

result from remaining soot particles originating from the scrubbing process.

8.4.3 Metals and Sulphate

Table 53 shows the sulphate, earth and transition metal concentrations determined for the samples

taken in Dover and Calais directly in front of the seawater scrubber outlet and inside the seawater

scrubber system. It can be seen that As, Ba, Cd, Co, Cr, Cu, Mn, Mo, Ni, Pb could not be detected. Fe

was only found inside the seawater scrubber system but not in the inlet and the outlet. The highest

iron content (4513 ppb) was found at point SCH4 in the pipe leading to the settling tank. One reason is

the very low pH measured at this point which increases the solubility of iron. Another reason is that all

particles collected in the seawater scrubber system, which also contain rust, are concentrated in the

cyclones and pass this pipe, and a third aspect might be an overflow pipe from the funnel which flows

into the settling tank pipe shortly before point SCH4 and which might contain particles and rust from

the funnel. The same reasons might be responsible for the high vanadium concentration measured at

point SCH4. However K, Li and Mg have nearly constantly contents in all samples, whereas the

strontium concentration is higher in Calais than in Dover.

Table 53: Sulphate, earth and transition metals determined for the samples taken in September ( - below

detection limit)

SD 1 SD2 SCH1 SCH2 SCH3 SCH4 SCH5 SCH6 SC2 SC 1

As ppb - - - - - - - - - -

Ba ppb - - - - - - - - - -

Ca ppm 393 397 383 386 404 407 404 411 411 389

Cd ppb - - - - - - - - - -

Co ppb - - - - - - - - - -

Cr ppb - - - - - - - - - -

Cu ppb - - - - - - - - - -

Fe ppb - - - - 803 4513 687 680 - -

K ppm 380 380 390 340 360 400 400 380 370 330

Li ppb 180 180 170 180 180 180 180 180 180 180

Mg ppm 1235 1230 1205 1205 1260 1265 1255 1290 1265 1220

Mn ppb - - - - - - - - - -

Mo ppb - - - - - - - - - -

Ni ppb - - - - - - - - - -

Pb ppb - - - - - - - - - -

SO4 ppm 2670 2710 2590 2600 2940 2940 2990 2980 2870 2590

Sr ppb 7680 7760 7515 7705 7915 7915 8020 8055 8035 7620

V ppb - - - - 155 420 240 170 - -

Zn ppb - 290 - - 455 - 395 360 - -

Zinc was only determined in the outlet sample in Dover and at points SCH3, SCH5 and SCH6, but not

in the pipe going to the settling tank and in no other outlet sample. The source for this contamination
8 Results and Discussion of environmental samplings

70

might be the valves used during the sampling which might contain zinc. Otherwise if zinc would

originate from the system itself it should also have been detected at point SCH4 and in the outlet

water.

As expected the sulphate concentration was increased inside the seawater scrubber due to the

formation of sulphuric acid, but comparing the in and outlet sample taken in the Channel no increase

was observed.

Summarising the data of Table 53 it can be said that no increase in the metal or sulphate

concentration was observed outside the “Pride of Kent” and that the increased Fe and V

concentrations were only observed inside the pipe leading to the settling tank. As the water and the

particles from the settling tank will be treated in a special way (deposition or burning), and as Fe and V

are not toxic, no negative effect is to be expected.

8.4.4 Polycyclic aromatic hydrocarbons

The concentrations of the determined dissolved and particle bound PAHs are shown in Table 70 and

Table 72.The total amounts of all EPA PAHs (without naphthalene) are given in Table 69. Comparing

the total amounts with the samplings in February, March and July, it can be seen that the contents in

September were especially in Calais about 100 ng L-1higher than in July, but the overall

concentrations where not as high as in March or February. All analysed concentrations were situated

between 44 and 248 ng L-1 with exception of the outlet samples where concentrations of 3422, 3263

and 3577 ng L-1 were determined. Taking a closer view at the single compounds it can be seen that

almost no acenaphthene, acenaphthylene, anthracene, benzo[b+k]fluoranthene, benz[a]pyrene,

dibenz[a,h]anthracene, benzo[ghi]perylene or indeno[1,2,3,c,d]pyrene were present. In all samples

phenanthrene, fluoranthene and pyrene dominated. These three compounds as well as fluorene were

also the dominating compounds in the seawater scrubber effluent, where phenanthrene

concentrations of 1400 ng L-1 were detected. No increased contents of high molecular weight PAHs

were found in the outlet samples.

Looking at the PAH concentration determined 5, 50, 350 and 700 m away from the seawater scrubber

outlet no increase was observed. In contrary the transect samples taken in Calais show lower PAH

concentrations than the samples taken from the quay walls. Additionally the blank sample taken

before the “Pride of Kent” arrived showed a higher PAH concentration (133 ng L

-1

) than the sample

taken at point C 5 (109 ng L

-1

). In Dover the sample taken 5 m away from the outlet had a content

similar to the sample from the middle port at point Dov 2. All these observations show that the

seawater scrubber effluent does not seem to increase the PAH concentration.

Inside the seawater scrubber all four- and five-ring compounds with the exception of fluoranthene and

pyrene were nearly completely found bound to the particulate fraction. Phenanthrene which partially

made up about 50 % of the total amount of all measured PAHs was also found in high concentrations
8 Results and Discussion of environmental samplings

71

in the particulate fraction. This shows that most of the PAHs are bound to soot particles, and that an

effective remove of these particles is able to lower these concentrations significantly.

Quality of measurement: Comparison 1st and 2nd extraction

Fig. 34 shows the regression of the extracted and dried filters and of the determined PAHs (chapter

8.3.3). In both cases high correlation coefficients and slopes close to one were observed. Therefore

the results of the first and the second extraction are very similar.

y = 1,0323x

R

2

= 0,9702

0,000

0,005

0,010

0,015

0,000 0,005 0,010 0,015

1

st extraction

2

nd

extraction

y = 0,9533x

R

2

= 0,9707

0

2000

4000

6000

8000

10000

0 5000 10000

1

st extraction

2

nd

extraction

Fig. 34: Regression between 1st and 2nd extraction left: Regression between the amount of extracted particulate

material [g]. Right: Regression of all determined PAH concentrations [ng/l] (sum, particulate,

dissolved).

Origin of PAHS

To determine the origin of the PAHs a regression of the compound concentrations among each other

and a regression of the concentrations determined at the single sampling points was performed. The

results are shown in Table 55 and Table 54.

The correlation coefficients of Table 54 show high correlation coefficients for nearly all compounds.

When a high correlation between for example fluoranthene and pyrene was found this meant that at all

points where high concentrations of fluoranthene were measured, also high concentrations of

phenanthrene were measured. If the relative relations of all compounds were the same at all points,

and differences only appear in the concentration itself, high correlation coefficients would be observed

for all compounds. As the anthracene concentrations were often close to or lower than the detection

limit, the R2 for the correlation with this compound is low. The same reason can be given for the low R2

observed for the correlations with dibenz[ah]anthracene and acenaphthylene. As this method of

regression analysis is not very specific and gives no information about the similarity of single sampling

points, a regression of the observed PAH concentrations of the sampling points was also performed.
8 Results and Discussion of environmental samplings

72

Table 54: Regression of compounds. Colours are added for a better visualisation. Yellow - highly correlated, dark

red - no significant correlation.

A

T

H

Y

A

T

H

E

FLR

E

P

H

E

N

A

N

T

H

FLUAP

Y

R

B

a

A

C

H

R

Y

BbkFB

a

P

D

ahA

BghiPIN

D

E

ATHY 1 0.787 0.819 0.851 0.619 0.876 0.874 0.851 0.891 0.93 0.759 0.921 0.941 0.934

ATHE 1 0.994 0.988 0.927 0.976 0.978 0.974 0.966 0.7 0.948 0.824 0.753 0.815

FLRE 1 0.997 0.918 0.99 0.991 0.987 0.982 0.74 0.959 0.851 0.79 0.843

PHEN 1 0.895 0.996 0.998 0.991 0.992 0.778 0.952 0.878 0.823 0.872

ANTH 1 0.872 0.873 0.9 0.855 0.487 0.952 0.608 0.548 0.601

FLUA 1 0.999 0.989 0.996 0.815 0.942 0.899 0.856 0.896

PYR 1 0.991 0.997 0.811 0.943 0.898 0.852 0.894

BaA 1 0.993 0.769 0.974 0.848 0.805 0.843

CHRY 1 0.831 0.943 0.902 0.863 0.899

BbkF 1 0.645 0.956 0.99 0.965

BaP 1 0.728 0.689 0.722

DahA 1 0.97 0.997

BghiP 1 0.981

INDE 1

Table 55: Regression of sampling points. Colours are added for a better visualisation. Yellow highly correlated,

orange and red moderate or low correlation, dark red no significant correlation.

Cal1 Cal2 Cal3 Cal4 C0 C5 C50 C350 C700 D5 D50 D350 D700 Dov2 Dov3 Dov4 SD1 SD2 SCH1 SCH2 SCH3 SCH4 SCH5 SCH6 SC1 SC2

Cal1 1 0,926 0,837 0,835 0,914 0,957 0,893 0,942 0,935 0,791 0,918 0,675 0,628 0,982 0,801 0,715 0,929 0,785 0,769 0,743 0,761 0,731 0,752 0,771 0,811 0,768 Cal1

Cal2 1 0,745 0,824 0,878 0,940 0,839 0,934 0,859 0,782 0,840 0,575 0,502 0,893 0,753 0,599 0,827 0,754 0,683 0,701 0,733 0,738 0,727 0,731 0,727 0,740 Cal2

Cal3 1 0,852 0,889 0,815 0,936 0,758 0,781 0,877 0,896 0,865 0,843 0,830 0,881 0,931 0,886 0,893 0,931 0,882 0,882 0,837 0,868 0,898 0,917 0,884 Cal3

Cal4 1 0,968 0,817 0,958 0,757 0,778 0,977 0,795 0,866 0,769 0,802 0,975 0,822 0,896 0,947 0,908 0,919 0,941 0,930 0,945 0,936 0,950 0,943 Cal4

C0 1 0,904 0,974 0,856 0,879 0,932 0,855 0,818 0,740 0,872 0,946 0,816 0,915 0,900 0,877 0,865 0,882 0,858 0,880 0,889 0,930 0,892 C0

C5 1 0,858 0,972 0,945 0,775 0,914 0,616 0,585 0,905 0,770 0,650 0,834 0,765 0,735 0,719 0,737 0,712 0,730 0,749 0,779 0,745 C5

C50 1 0,811 0,877 0,948 0,879 0,886 0,810 0,882 0,971 0,900 0,943 0,938 0,935 0,913 0,917 0,882 0,924 0,931 0,958 0,930 C50

C350 1 0,917 0,690 0,895 0,520 0,472 0,896 0,697 0,568 0,785 0,675 0,657 0,619 0,645 0,621 0,631 0,654 0,690 0,649 C350

C700 1 0,753 0,943 0,679 0,683 0,909 0,783 0,746 0,841 0,766 0,775 0,734 0,743 0,705 0,729 0,758 0,804 0,747 C700

D5 1 0,784 0,919 0,929 0,770 0,978 0,878 0,889 0,982 0,944 0,970 0,977 0,964 0,985 0,978 0,970 0,986 D5

D50 1 0,711 0,708 0,917 0,795 0,768 0,868 0,827 0,843 0,797 0,801 0,752 0,777 0,819 0,823 0,800 D50

D350 1 0,962 0,681 0,939 0,970 0,844 0,937 0,963 0,955 0,936 0,893 0,946 0,949 0,963 0,945 D350

D700 1 0,638 0,861 0,947 0,782 0,886 0,925 0,917 0,891 0,841 0,890 0,905 0,917 0,892 D700

Dov2 1 0,786 0,733 0,949 0,782 0,768 0,745 0,755 0,721 0,747 0,770 0,793 0,765 Dov2

Dov3 1 0,903 0,901 0,966 0,953 0,953 0,953 0,923 0,968 0,963 0,983 0,965 Dov3

Dov4 1 0,861 0,904 0,953 0,919 0,897 0,847 0,901 0,919 0,937 0,908 Dov4

SD1 1 0,896 0,884 0,874 0,877 0,841 0,879 0,891 0,910 0,890 SD1

SD2 1 0,972 0,995 0,991 0,965 0,995 0,999 0,973 0,998 SD2

SCH1 1 0,974 0,963 0,913 0,959 0,978 0,979 0,966 SCH1

SCH2 1 0,990 0,962 0,994 0,998 0,969 0,996 SCH2

SCH3 1 0,988 0,990 0,992 0,966 0,992 SCH3

SCH4 1 0,971 0,964 0,928 0,970 SCH4

SCH5 1 0,995 0,970 0,999 SCH5

SCH6 1 0,976 0,998 SCH6

SC1 1 0,972 SC1

SC2 1 SC2

Taking Table 55 into closer view, it can be seen that most of the sampling points are highly correlated.

Especially the correlation between the seawater scrubber samples among each other and the Calais

samples among each other showed high R2 values indicating that the PAH composition of these

samples is similar. In contrary the correlation of the samples taken from the harbour in Dover seem to

be different in their composition from the samples taken in Calais. They show only moderate

correlation coefficients for these regressions, but high correlation coefficients when compared with the

seawater scrubber samples. The samples taken from the Calais transect are only moderately

correlated with the samples taken from the seawater scrubber. Summarising can be said, that all

Dover samples show a comparable composition while the Calais samples are not comparable to the

seawater scrubber samples. Therefore the composition of the Dover and Calais samples is different

too.
8 Results and Discussion of environmental samplings

73

Additionally to the regression analysis a principal component analysis (Fig. 36, Table 57) and an

analysis of the isomeric ratios of phenanthrene to anthracene, fluoranthene to pyrene (Fig. 35) and

benz[a]anthracene to chrysene (Table 55) was performed. The plot of the phen/anth ratios against the

flua/pyr ratios indicates that the seawater scrubber samples seem to originate from a petrogenic

source. This would underline the results of the previous samplings. The same holds for the isomeric

ratios of benz[a]anthracene and chrysene which are all smaller than one and therefore indicate a

pyrolytic origin too.

0

10

20

30

40

50

60

70

80

90

100

0,0 0,5 1,0 1,5 2,0 2,5

phenanthrene / anthracene

fluorathene / pyrene

Dover

Calais

SWS

outlet

petrogenic

pyrolytic

D 350

Fig. 35: Plot of isomeric phenanthrene/anthracene ratios against fluoranthene/pyrene ratios for all samples

The phenanthrene to anthracene ratios of the harbour samples are close to ten and the fluoranthene

to pyrene and the benz[a]anthracene to chrysene ratios are close to one. This might have the same

reasons as those mentioned in the discussion of the February, March and July samplings. The explicit

petrogenic character of the sample D 350, which shows nearly the same isomeric ratios as the outlet

samples cannot be explained. Perhaps a thin oil film flowing on top of the water contaminated this

sample.

The principal component analysis underlines and specifies the results of the regression analysis. From

this the samples can be divided into three different groups. The first group is made up by only one

sample: Cal 2. This sample is characterised by relative high anthracene, fluoranthene and pyrene

contents. As point Cal 2 is situated close to the place where the service boats anchor, these might

originate from the lighter petroleum used for these boats.

Table 56: The quotient of benz[a]anthracene to chrysene can be used as marker for the origin of a sample

sampl. point Cal 1 Cal 2 Cal 3 Cal 4 C0 C5 C50 C350 C700

BaA/CHRY 0,2 0,9 0,8 0,6 0,6 0,0 1,2 1,0 1,0

sampl. point Dov 2 Dov 3 Dov 4 D0 D5 D50 D350 D700

BaA/CHRY 0,7 0,8 1,0 0,6 0,7 0,4

sampl. point SD1 SD2 SCH1 SCH2 SC1 SC2 SCH3 SCH4 SCH5 SCH6

BaA/CHRY 0,6 0,6 0,6 0,5 0,5 0,5 0,5 0,5 0,6 0,5
8 Results and Discussion of environmental samplings

74

Fig. 36: Results of the PCA of the harbour samples

Table 57: Feature vector for the PCA of the harbour samples

42.2 %

(14.0)

17.9 %

(14.0)

acenaphthylene 0.14 0.20

acenaphthene 0.28 0.19

fluorene 0.13 0.18

phenanthrene 0.30 -0.08

anthracene 0.15 -0.34

fluoranthene 0.32 -0.41

pyrene 0.39 -0.22

benz[a]anthracene 0.24 0.51

chrysene 0.20 0.52

benzo[b]fluoranthene +

benzo[k]fluoranthene 0.40 0.02

benzo[a]pyrene 0.36 -0.12

dibenz[a,h]anthracene

benzo[ghi]perylene 0.36 -0.03

indeno(1,2,3,c,d)pyrene 0.14 0.20

The second group is made up by the samples D 50, Dov 2, C 350, C 5, Cal 1, C 700 and SD1. For

these samples both eigenvectors are negative. The second eigenvector which is plotted on the y-axis

mainly shows high chrysene, benz[a]anthracene and indeno(1,2,3,c,d)pyrene concentrations. All the

samples of this group were taken close to the entrances of the ports of Dover and Calais. These

points were influenced from the channel water which was not influenced by port activities and

therefore contained less petroleum-derived PAHs.

The third group is made up from the samples inside the harbour and it makes no difference whether

they were taken from the transect or not. Therefore it can be stated, that the samples are quite similar

within their composition and that the seawater scrubber obviously does not change this composition

significantly.
8 Results and Discussion of environmental samplings

75

8.5 5

th sampling (November)

8.5.1 pH, salinity and temperature

The sampling dates as well as the high and low water times are shown in Table 8 and Table 9. The

samples in Calais were taken during low tide and the samples in Dover during high tide.

The air and water temperatures, the pH and the salinity determined for the samples taken in Calais,

Dover and inside the “Pride of Kent” are shown in Table 58,Table 59 and Table 60. The air

temperature in Calais was 13 °C at all points. The water temperature was a little bit lower and varied

between 11.1 and 11.6 °C. A temperature increase in front of the outlet of the seawater scrubber at

point C 5 as it was observed during the sampling in July and September could not be detected this

time.

As mentioned before, the samples from point C0 and C5 were not taken from the same position. C0

was taken before the arrival of the “Pride of Kent” but at a parallel quay farer inside the port. That is

why the pH was lower than at point C5 and closer related to the pH observed at point Cal 2. The

lowest pH was measured, comparable to the sampling before, at point Cal 3. This point also showed a

lower salinity (30.7) than the remaining points. The reason might be the enclosed position of this point.

The floodgate which can be seen in the map in Table 6 is only opened twice a day and therefore there

is only little water exchange and the water is getting more brackish at the surface and stratification is

enforced. At the remaining points the salinity was nearly constant and varied between 32.8 and 33.0

with exception of point Cal 2 where a salinity of only 23.5 was observed.

In Dover the pH range was smaller than in Calais. The lowest pH (8.15) was observed at point Dov 3

and the highest (8.26) at point D50. Within the transect samples no significant decrease or increase in

pH was observed. The water and the air temperature was nearly constant at all points and also the

salinity varied only between 34.2 and 34.3

Table 58: Temperature, salinity and pH data measured at the different sampling points in Calais harbour in

November 2004

Point Temp [°C]

air

Temp [°C]

water pH Sal [PSU]

Cal 1 13.0 11.6 7.95 32.5

Cal 2 13.0 11.4 7.76 23.5

Cal 3 13.0 11.1 7.92 30.7

Cal 4 13.0 11.5 8.18 32.9

C 0 13.0 11.5 7.86 32.9

C 5 13.0 11.6 8.12 32.8

C 50 13.0 11.6 8.11 32.8

C 350 13.0 11.6 8.12 32.8

C 750 13.0 11.5 8.12 33.0
8 Results and Discussion of environmental samplings

76

Table 59: Temperature, salinity and pH data measured at the different sampling points in Dover harbour in

November 2004

Point Temp [°C]

air

Temp [°C]

water pH Sal [PSU]

D 0 13.0 11.7 8.23 34.2

D 5 13.0 11.6 8.24 34.2

D 50 13.0 11.6 8.26 34.3

D 350 13.0 11.7 8.25 34.3

D 750 13.0 11.6 8.17 34.3

Dov 1 13.0 11.6 8.21 34.4

Dov 2 13.0 11.6 8.18 34.4

Dov 3 13.0 11.5 8.15 34.3

Dov 4 13.0 11.5 8.19 34.3

Table 60: Temperature, salinity and pH data measured at the different sampling points in the seawater scrubber

harbour in November 2004

Point Temp [°C]

water pH Sal [PSU]

SD1 13.2 8.32 33.9

SD2 27.4 6.47 34.8

SCH1 14.0 8.28 34.3

SCH2 26.2 6.66 35.0

SCH3 35.5 3.35 35.7

SCH4 34.1 2.67 35.9

SCH5 35.4 3.34 35.6

SCH6 36.9 3.30 35.8

SCH8 24.1 3.79 35.0

SC1 13.6 7.81 33.0

SC2 25.5 6.33 33.5

Inside the seawater scrubber system the water temperature was highly variable. The lowest

temperatures (13.2, 14.0 and 13.6 °C) were measured in the inlet samples. In the outlet the

temperature was about 12 to 14 °C higher. The highest temperature was measured at point SCH6

(36.9 °C) directly behind the seawater scrubber. It slightly decreased at points SCH3 and SCH5 to

35.5 °C. The salinity inside the channel was slightly higher than inside the ports of Dover and Calais.

The pH values in the inlet were 8.32 in Dover, 8.28 in the Channel and 7.81 in Calais. These values

are comparable to the values measured outside the “Pride of Kent”. The lowest pH was measured at

point SCH4. An explanation might be an overflow valve from the funnel reaching the pipe shortly

before the sampling point. The pH values at points SCH6, SCH5 and SCH3 were nearly constant with

3.30, 3.34 and 3.35. The outflowing water showed a pH between 6.33 and 6.66. It can be seen that

the dilution with cooling water increased the pH and directly in front of the outlet no decrease in pH

was measured.
8 Results and Discussion of environmental samplings

77

8.5.2 Metals and Sulphate

The sulphate, earth and transition metal contents are shown in Table 61. It can be seen that

chromium, manganese and molybdenum could only be determined in the settling tank and in the pipe

leading to the settling tank. The reason for this might be, as explained before, the low pH and the

concentration of particles in the cyclones and the settling tank.

Copper was measured at all points with the exception of point SCH1. An increase of the copper

content due to the seawater scrubber cannot be stated for sure especially as during the sampling in

September no copper could be determined. During the sampling in March high copper concentrations

were also detected inside the settling tank. With respect to the inlet and outlet samples, copper is even

decreasing in Calais.

The iron contents were again highest inside the settling tank. Here values up to 70 times higher than

those at the remaining seawater scrubber points were observed. In the outlet water only in Dover an

increased iron content was measured. Molybdenum, vanadium and nickel, also contents of ship steel,

were found especially in the seawater scrubber system. Tin concentrations varied in the system but

were higher in the outlet samples in comparison to the inlet samples. At point SCH4 no tin was found

and inside the settling tank no increased tin content was observed. This again shows that the

determined tin most probably originates from the sampling procedure. Potassium, lithium and

magnesium had equal contents in all samples. These earth metals are conservative due to their

reactivity and their concentration only depends on salinity.

Table 61: Sulphate, earth and transition metals determined for the samples taken in November 2004

SC1 SC2 C 5 SCH1 SCH2 SCH3 SCH4 SCH5 SCH6 SCH8 SD1 SD2 D 5

Ca ppm 397 402 384 368 400 400 407 406 406 405 385 388 388

Cr ppb - - - - - - 74 - - 362 - - -

Cu ppb 119 48 35 32 74 40 60 100 1138 37 48 46

Fe ppb - - 74 - - 750 5292 481 585 33479 62 93 79

K ppm 388 392 353 352 386 382 386 378 381 379 359 355 361

Li ppm 178 180 163 168 184 181 183 184 183 183 170 170 167

Mg ppm 1238 1251 1186 1157 1256 1255 1272 1263 1270 1251 1198 1185 1239

Mn ppb - - - - - - - - - 148 - - -

Mo ppb - - - - - - - - - 13 - - 12

Ni ppb - 34 - - - 68 150 59 64 583 - - -

Pb ppb 31 24 - - 18 - - - - - - 34 -

SO4 ppm 2699 2864 2578 2685 2805 3008 3140 3055 3061 3038 2587 2644 2669

Sr ppm 8008 8054 7489 7693 8278 8087 8118 8264 8183 8203 7821 7731 7496

V ppb - - - - - 197 304 201 208 2676 - 29 -

Zn ppb - 229 - - 96 426 - 266 454 465 31 147 -
8 Results and Discussion of environmental samplings

78

8.5.3 Nutrients

The seston and nutrient concentrations determined for the samples taken in November 2004 are

shown in Table 62. In Calais the mean seston contents were about 100 mg L-1higher than those

observed in Dover. The highest concentrations were observed at points Cal 3 and Cal 4. The lowest

were determined for point Dov 3. Inside the seawater scrubber system a significant increase was only

measured at point SCH8. Comparing the inlet and outlet it can be seen that the concentrations in the

inlet samples are comparable to those measured inside the harbours. In Dover the outlet water

contained more suspended material than the inlet water. In Calais and in the Channel it was the

reverse case. In Calais the concentration was even the half the concentration of the inlet sample.

Table 62: Seston and nutrient concentrations determined for the samples taken in November 2004

samp.

point Seston RDP DOP TDP NO2

- NO3- NH4+ DIN Si(OH)4

[mg L-1] [μmol L-1] [μmol L-1] [μmol L-1] [μmol L-1] [μmol L-1] [μmol L-1] [μmol L-1] [μmol L-1]

Cal1 148.9 0.70 4.89 5.59 0.82 14.51 10.72 26.05 22.23

Cal2 122.1 12.97 2.25 10.73 3.32 44.86 27.10 75.27 124.14

Cal3 181.1 1.21 0.66 1.87 2.29 26.71 14.75 43.75 32.22

Cal4 184.9 0.59 2.75 3.35 0.89 14.41 9.48 24.78 20.81

C0 101.6 0.86 5.81 6.67 0.76 12.26 9.79 22.81 18.16

C5 93.1 0.15 1.52 1.67 1.50 17.15 50.27 68.92 22.28

C50 131.5 0.51 3.35 3.85 0.96 13.43 10.55 24.95 18.18

C350 126.3 0.59 2.07 2.67 0.87 13.35 10.68 24.90 18.18

C700 63.7 0.57 5.09 5.66 0.72 11.67 9.64 22.03 15.55

D0 25.4 0.64 6.32 6.96 1.09 16.46 1.56 19.10 6.99

D5 26.9 0.68 6.17 6.85 1.14 16.47 1.56 19.16 7.14

D50 70.3 0.70 3.72 4.43 1.10 16.40 1.62 19.12 5.95

D350 33.1 0.73 5.24 5.97 1.28 14.67 1.28 17.23 9.47

D700 23.6 0.70 5.09 5.79 1.16 14.66 2.30 18.13 24.15

Dov2 34.0 0.79 5.22 6.01 1.20 13.89 1.50 16.58 11.56

Dov3 15.9 0.64 4.52 5.15 1.10 12.34 1.25 14.68 7.98

Dov4 51.6 0.64 4.23 4.87 1.17 14.26 2.12 17.55 29.47

SD1 28.8 0.62 - - 0.82 13.79 0.37 14.98 7.01

SD2 86.5 - - - 2.36 19.47 2.75 24.57 6.19

SCH1 23.2 0.37 - - 1.39 11.09 0.56 13.04 5.06

SCH2 16.1 0.22 - - 2.57 11.83 2.09 16.49 4.92

SCH3 67.7 1.21 - - 0.03 24.45 2.76 27.24 8.94

SCH4 66.9 1.21 - - 0.41 26.76 5.16 32.33 10.39

SCH5 18.7 0.81 - - 0.03 18.36 0.94 19.33 7.52

SCH6 18.7 0.84 - - 0.02 18.24 0.91 19.17 7.74

SCH8 407.4 0.42 - - 0.70 14.37 6.32 21.38 28.92

SC1 140.0 0.29 - - 0.74 10.78 5.56 17.08 15.65

SC2 73.7 0.26 - - 1.45 13.18 7.93 22.56 15.81

Looking at the phosphorus compounds in the ports it can be seen that the RDP concentration was

highest at point Cal 2 (12.97) whereas at the remaining points the concentrations varied between 0.15

(C5) and 1.21 μmol L-1(C3). At point Cal 2 also high silicate, nitrate nitrite and ammonium

concentrations were observed. As this point is situated at the service quay in an enclosed position at

the eastern end of the harbour this point is easily eutrophicated. Inside the harbour of Calais the

nitrate, silicate and ammonium concentrations were slightly increased in comparison to the samples

taken in Dover, whereas in Dover the nitrite concentrations were increased. The reason therefore

might be the architecture of the ports. Dover has one big “basin” open at two sides and no freshwater

inflow. During each ebb and flow the water is flowing through the port and enables a marked water
8 Results and Discussion of environmental samplings

79

exchange. Additionally a great part of the harbour cannot be reached from the public areas. The

opposite holds for Calais. The port has many enclosed arms and areas. Water exchange is only

possible through the relatively small gate in the west of the port. Additionally the city Calais was built

around the harbour and therefore the anthropogenic influence is greater than in Dover.

Inside the seawater scrubber system the RDP concentrations were only higher at points SCH3 and

SCH4. At the remaining points the determined concentrations were within the range observed inside

the harbour. Comparing the inlet and outlet samples an increase in nitrate, nitrite and ammonium can

be seen. In contrast inside the system especially the NO2

-

and NH4

+

values are low and even lower

than those observed in the outlet. Only the nitrate concentrations are slightly increased inside the

seawater scrubber due to the NOx remove from the fluegas.

8.5.4 Polycyclic Aromatic Hydrocarbons

The PAH concentrations determined for the samples taken in November are shown in Table 69,,Table

70 and Table 72. From the PAH concentrations measured in the samples taken in Calais it can be

seen that the lowest total amount was determined for point Cal 2 (225 ng L-1) and the highest for

C 350 (625 ng L-1). In Dover the lowest concentration was measured at point D 0 (106 ng L-1) and the

highest at point Dov 3 (569 ng L-1). The transect samples taken in Dover and Calais indicate a specific

trend. In Dover the samples taken 50 m away from the outlet showed the highest concentration and in

Calais that one 350 m away from the outlet. Compared to the previous samplings, the highest

concentrations were observed.

Taking a look at the seawater scrubber samples the highest amount was again determined inside the

settling tank. Here high concentrations of phenanthrene, fluoranthene, pyrene, chrysene and

benz[a]anthracene were measured. Also high concentrations of high molecular weight PAHs were

observed, whereas two-ring compounds were not enriched. As these compounds have a high

solubility and do not adsorb to surfaces, they are not removed by the cyclones. The concentrations in

the seawater scrubber outlet are within the same range as observed during the other samplings.
8 Results and Discussion of environmental samplings

80

Quality of measurement: Comparison 1st and 2nd extraction

The regressions of the filter weights and the regression of all PAH concentrations determined for the

first and the second extraction of the samples are shown in Fig. 37. It can be seen that both values are

close to one and no outlyers are obvious.

y = 0,9964x

R

2

= 0,966

0,00

0,01

0,02

0,03

0,04

0,00 0,01 0,02 0,03 0,04

1st extraction

2nd extraction

y = 0,9698x

R

2

= 0,9967

0

2000

4000

6000

0 2000 4000 6000 8000

1

st extraction

2

nd

extraction

Fig. 37: Regression between the first and the second extraction. Left: filter weights, right: PAH concentrations.

Origin of PAHs

To determine the relationships between the different sampling points and to determine the origin of the

PAHs a regression analysis of the compounds (Table 63) and of the sampling points (Table 64) was

performed. Additionally a principle component analysis was carried out (Table 66 and Fig. 39) and a

plot of the isomeric ratios Phen/Anth and Flua/Pyr (Fig. 38) and BaA/Chry (Table 65) was drawn.

Looking at Table 63 it can be seen that nearly all compounds are highly correlated. Only anthracene

and acenaphthene show moderate R2 values. To obtain a better resolution and to prevent

mathematical errors a look at Table 64 is necessary. From this it can be stated that all Calais samples

with the exception of Cal 2 show the same distribution of PAHs. Also the seawater scrubber samples

(without the inlet samples) are highly correlated with each other. Additionally the points Dov 4 and D50

seem to show different PAH patterns in comparison to the remaining samples taken in Dover. No

correlation was observed between the samples taken from the seawater scrubber and those taken in

Calais, between the seawater scrubber samples and those taken in Dover, and also between most

samples taken in Dover and Calais. In summary it can be said, that the PAH composition inside the

harbours was different from that in the seawater scrubber system with one exception: point D5 which

was taken directly in front of the seawater scrubber outlet is highly correlated with the seawater

scrubber samples. A comparably high correlation was not observed in Calais or at the remaining

transect points in Dover.
8 Results and Discussion of environmental samplings

81

Table 63: Regression of PAH compounds. Colours are added for a better visualisation. Yellow - highly correlated,

orange and red - moderate or low correlation, dark red - no significant correlation.

A

T

H

Y

A

T

H

E

FLR

E

P

H

E

N

A

N

T

H

FLUAP

Y

R

B

a

A

C

H

R

Y

BbkFB

a

P

D

ahA

BghiPIN

D

E

ATHY 1 0.865 0.926 0.906 0.93 0.868 0.913 0.92 0.899 0.903 0.928 0.813 0.82 0.757

ATHE 1 0.724 0.696 0.831 0.684 0.718 0.78 0.729 0.781 0.761 0.601 0.615 0.557

FLRE 1 0.996 0.906 0.976 0.993 0.969 0.984 0.968 0.985 0.952 0.961 0.908

PHEN 1 0.874 0.967 0.986 0.974 0.989 0.965 0.989 0.962 0.956 0.894

ANTH 1 0.897 0.926 0.876 0.869 0.892 0.89 0.786 0.848 0.831

FLUA 1 0.984 0.939 0.968 0.967 0.949 0.964 0.991 0.968

PYR 1 0.961 0.977 0.966 0.976 0.947 0.965 0.926

BaA 1 0.991 0.987 0.99 0.937 0.915 0.842

CHRY 1 0.988 0.989 0.97 0.955 0.893

BbkF 1 0.979 0.946 0.945 0.89

BaP 1 0.934 0.925 0.853

DahA 1 0.973 0.929

BghiP 1 0.983

INDE 1

Table 64: Regression of sampling points. Colours are added for a better visualisation. Yellow - highly correlated,

orange and red - moderate or low correlation, dark red - no significant correlation.

Cal1 Cal2 Cal3 Cal4 C0 C5 C50 C350 C700 D5 D50 D350 D700 Dov2 Dov3 Dov4 D0 SD1 SD2 SCH1 SCH2 SCH3 SCH4 SCH5 SCH6 SCH8 SC1 SC2

Cal1 1 0.196 0.878 0.956 0.892 0.927 0.954 0.77 0.968 0.507 0.895 0.542 0.438 0.72 0.556 0.752 0.393 0.913 0.468 0.928 0.367 0.334 0.382 0.359 0.355 0.373 0.951 0.421 Cal1

Cal2 1 0.306 0.246 0.261 0.232 0.239 0.272 0.264 0.466 0.223 0.531 0.616 0.513 0.315 0.201 0.689 0.251 0.243 0.144 0.245 0.239 0.23 0.241 0.239 0.24 0.285 0.252 Cal2

Cal3 1 0.929 0.928 0.96 0.96 0.965 0.907 0.717 0.916 0.78 0.654 0.887 0.836 0.823 0.605 0.855 0.653 0.737 0.573 0.546 0.589 0.573 0.562 0.604 0.925 0.632 Cal3

Cal4 1 0.945 0.914 0.946 0.841 0.986 0.608 0.845 0.618 0.532 0.781 0.632 0.692 0.502 0.94 0.543 0.89 0.448 0.414 0.463 0.433 0.43 0.45 0.96 0.488 Cal4

C0 1 0.891 0.905 0.853 0.938 0.765 0.816 0.735 0.663 0.865 0.737 0.659 0.601 0.963 0.753 0.85 0.663 0.628 0.678 0.647 0.646 0.657 0.974 0.695 C0

C5 1 0.991 0.925 0.892 0.615 0.98 0.698 0.539 0.823 0.775 0.909 0.474 0.833 0.575 0.761 0.486 0.46 0.499 0.494 0.482 0.52 0.919 0.567 C5

C50 1 0.901 0.928 0.603 0.97 0.669 0.527 0.814 0.723 0.871 0.472 0.873 0.551 0.802 0.46 0.431 0.472 0.462 0.451 0.484 0.944 0.532 C50

C350 1 0.792 0.714 0.876 0.78 0.628 0.843 0.909 0.835 0.572 0.734 0.656 0.594 0.592 0.575 0.608 0.602 0.588 0.644 0.818 0.661 C350

C700 1 0.589 0.831 0.607 0.533 0.776 0.589 0.667 0.507 0.951 0.528 0.934 0.429 0.393 0.446 0.412 0.411 0.426 0.969 0.464 C700

D5 1 0.548 0.903 0.924 0.893 0.807 0.454 0.853 0.691 0.904 0.434 0.896 0.88 0.887 0.884 0.883 0.888 0.698 0.896 D5

D50 1 0.662 0.49 0.784 0.739 0.956 0.42 0.767 0.513 0.701 0.43 0.405 0.439 0.444 0.429 0.468 0.872 0.52 D50

D350 1 0.943 0.943 0.897 0.618 0.896 0.793 0.783 0.427 0.768 0.755 0.756 0.776 0.766 0.79 0.707 0.813 D350

D700 1 0.89 0.76 0.416 0.963 0.591 0.78 0.374 0.782 0.768 0.765 0.773 0.771 0.774 0.627 0.783 D700

Dov2 1 0.861 0.695 0.82 0.801 0.793 0.601 0.742 0.72 0.74 0.742 0.735 0.753 0.859 0.789 Dov2

Dov3 1 0.741 0.672 0.58 0.78 0.396 0.757 0.755 0.763 0.782 0.765 0.819 0.674 0.826 Dov3

Dov4 1 0.348 0.577 0.419 0.519 0.354 0.339 0.36 0.381 0.361 0.41 0.7152 0.458 Dov4

D0 1 0.538 0.65 0.347 0.652 0.636 0.636 0.637 0.636 0.641 0.572 0.645 D0

SD1 1 0.66 0.908 0.563 0.522 0.575 0.537 0.54 0.539 0.975 0.583 SD1

SD2 1 0.429 0.988 0.978 0.991 0.982 0.984 0.977 0.655 0.982 SD2

SCH1 1 0.327 0.291 0.345 0.307 0.31 0.31 0.892 0.35 SCH1

SCH2 1 0.998 0.997 0.996 0.998 0.99 0.559 0.985 SCH2

SCH3 1 0.995 0.997 0.999 0.991 0.522 0.983 SCH3

SCH4 1 0.993 0.995 0.99 0.57 0.981 SCH4

SCH5 1 0.999 0.996 0.546 0.993 SCH5

SCH6 1 0.993 0.543 0.989 SCH6

SCH8 1 0.554 0.991 SCH8

SC1 1 0.603 SC1

SC2 1 SC2

Table 65: Isomeric ratios of benz[a]anthracene and chrysene

sampl.

point Cal 1 Cal 2 Cal 3 Cal 4 C0 C5 C50 C350 C700

BaA/CHRY 0.9 0.8 0.7 1.0 0.9 1.3 0.8 0.8 0.9

sampl.

point Dov 2 Dov 3 Dov 4 D0 D5 D50 D350 D700

BaA/CHRY 0.8 0.8 0.8 0.8 0.8 0.7 0.9 0.9

sampl.

point SD1 SD2 SCH1 SCH2 SC1 SC2 SCH3 SCH4 SCH5 SCH6 SCH8

BaA/CHRY 1.7 1.9 1.0 0.5 0.8 0.6 0.5 0.5 0.5 0.6 0.5
8 Results and Discussion of environmental samplings

82

0

10

20

30

40

50

60

70

80

90

100

0,0 0,5 1,0 1,5 2,0

phenanthrene / anthracene

fluoranthene / pyrene

Dover

Calais

SWS

outlet

petrogenic

pyrolytic

Fig. 38: Plot of isomeric phenanthrene/anthracene ratios against fluoranthene/pyrene ratios for all samples

Taking a look at the BaA/Chry ratios (Table 65) it can be seen that all values, with exception of SD1,

SD2 and D5 are <1 and therefore indicate a pyrolytic origin. In Fig. 38 where the

phenanthrene/anthracene and fluoranthene/pyrene ratios are plotted, only the samples taken from the

seawater scrubber outlet and the seawater scrubber system itself show petrogenic character. The

remaining samples, especially those taken in Calais, seem to originate from combustion processes.

As the samples were taken in fall when the heating season starts, these PAHs are most probably

PAHs produced by burning wood, heating oil and gas.

The principal component plot shows the similar separation of the samples as the regression chart

already did. Sample Cal 2 is an outlyer, showing only low concentrations. Dov 2 is correlated with

C700, C350 and C005 and these samples are also located in one group in the PCA plot. Additionally

D50, SD1 and Cal1 are within this group. All these samples show negative values for eigenvector 2

which is positive for low molecular weight and negative for high molecular weight PAHs. The samples

show a similar distribution but as eigenvector 2 is only responsible for 20 % of the total variance it is

not significant. According to their distribution along eigenvector 2 the samples can partially be divided

into PAHs originating from petrogenic (negative) or pyrolytic (positive) pollution sources. Thereafter

D50 has the most petrogenic and Cal 4 and C 700 the most pyrolytic character. This can easily be

explained by the positions of these points. Cal 4 and C 700 are the most eastern points in the port

Calais and are situated at the entrance. These points are therefore influenced by North Sea water

reaching the harbour. There the main pollution source is the atmosphere, which carries especially

PAHs from pyrolytic processes. Inside the port the influence of the shipping activities is greater and

this direct pollution is of petrogenic origin.
8 Results and Discussion of environmental samplings

83

Fig. 39: Results of the PCA of the harbour samples

Table 66: Feature vector for the PCA of the harbour samples

39.6 %

(14.0)

22.3 %

(14.0)

acenaphthylene 0.13 0.38

acenaphthene -0.13 0.42

fluorene -0.09 0.54

phenanthrene 0.23 0.36

anthracene 0.28 0.35

fluoranthene 0.32 0.18

pyrene 0.32 0.11

benz[a]anthracene 0.36 -0.14

chrysene 0.38 -0.14

benzo[b]fluoranthene +

benzo[k]fluoranthene 0.41 -0.12

benzo[a]pyrene 0.40 -0.14

dibenz[a,h]anthracene 0.14 -0.06

benzo[ghi]perylene 0.02 -0.11

indeno(1,2,3,c,d)pyrene 0.13 0.38
9 Results and discussion of the toxicity and accumulation tests

84

8.6 Annual circle

8.6.1 pH, salinity and temperature

In this chapter the temperature, salinity and pH values determined during all samplings are shown.

Inside the “Pride of Kent“ not at all points samples were taken during every sampling. In February the

seawater scrubber was not active and therefore only samples from the inlet and outlet were taken.

During the sampling in July sampling points 4, 7 and 8 were closed and in September and November

the settling tank was not full enough to take a sample from point 7. For samples taken inside the

harbour of Calais (Fig. 40, ,Fig. 41) values for all samplings are available. It can be seen that the

highest temperatures were measured in late summer during the sampling in September. Here the

water temperature was about 22 °C and thus about 15 °C higher than during the sampling in February.

The salinity at point Cal 4 was relative stable and higher than at point Cal 1 to Cal 3. This point is

situated close to the harbour entrance and is therefore influenced by the North Sea where the salinity

is relatively stable. The farer inside the sampling point was located in the harbour the higher the

variability was. At point Cal 2 at the eastern end of a long sidearm the salinity varied within a wide

range (18.3 to 34.0). As the pH in brackish and fresh water is lower than in salt water, the pH was also

very variable at this point (7.76 - 8.50).

Cal 1: Quai en eau profonde

7,97 7,95 8,42 7,95 7,69

32,5

7,4 8,5

17,0

11,6

27,0

34,1

29,0

31,2

22,1

0

2

4

6

8

10

11.02.0424.03.0414.07.0408.09.0416.11.04

sampling date

pH

0

5

10

15

20

25

30

35

40

salinity [pSU]

temperature [°C]

pH

Sal

Temp

Cal 2: Quai de service

7,81 8,07 7,76

8,5 7,97

23,5

7,3 8,5

17,1

11,4

31,7 31,0

34,0

18,3

22,1

0

2

4

6

8

10

11.02.0424.03.0414.07.0408.09.0416.11.04

sampling date

pH

0

5

10

15

20

25

30

35

40

salinity [pSU]

temperature [°C]

pH

Sal

Temp

Fig. 40: Salinity, temperature, and pH measured at points Cal 1 and Cal 2

Cal 3: Quai de la Loire

8,28

9,35 7,89

8,04 7,92

7,3 7,7

16,5

11,1

27,5 29,6 29,0 31,9 30,7

21,5

0

2

4

6

8

10

11.02.0424.03.0414.07.0408.09.0416.11.04

sampling date

pH

0

5

10

15

20

25

30

35

salinity [pSU]

temperature [°C]

pH

Sal

Temp

Cal 4: Jetee ouest

8,02 8,22 8,04 8,18 8,63

32,9

7,4 8,5

16,9

11,5

31,0

33,7 31,5 32,0

21,9

0

2

4

6

8

10

11.02.0424.03.0414.07.0408.09.0416.11.04

sampling date

pH

0

5

10

15

20

25

30

35

40

salinity [pSU]

temperature [°C]

pH

Sal

Temp

Fig. 41: Salinity, temperature, and pH measured at points Cal 3 and Cal 4

Samples from the transect points in Calais were only taken in July, September and November. The

annual course is shown in Fig. 43 and Fig. 44. As these points were situated inside the harbour the
9 Results and discussion of the toxicity and accumulation tests

85

variability in salinity and pH was lower than in the samples taken closer to the shore. The latter are

characterised by lower water depths and reduced water exchange and therefore by higher possibilities

for the formation and longer duration of a stratified water body. The temperature at the transect points

was also highest in September and decreased towards November. Only during the sampling in July an

increase in pH from point C5 to C700 was observed. During that sampling also a salinity increase was

observed.

C 5: 5 m from outlet

8,28 8,08 8,12

18,2

23,1

11,6

34,0 32,8 34,6

0

2

4

6

8

10

14.07.0408.09.0416.11.04

sampling date

pH

0

5

10

15

20

25

30

35

40

salinity [pSU]

temperature [°C]

pH

Sal

Temp

C 50: 50 m from outlet

8,29 8,09 8,11

17,1

22,8

11,6

34,0 32,8 34,7

0

2

4

6

8

10

14.07.0408.09.0416.11.04

sampling date

pH

0

5

10

15

20

25

30

35

40

salinity [pSU]

temperature [°C]

pH

Sal

Temp

Fig. 42: Salinity, temperature, and pH measured at points C5 and C50

C 350: 350 m from outlet

8,31 8,09 8,12

17,2

22,8

11,6

34,0 32,8 34,7

0

2

4

6

8

10

14.07.0408.09.0416.11.04

sampling date

pH

0

5

10

15

20

25

30

35

40

salinity [pSU]

temperature [°C]

pH

Sal

Temp

C 700: 700 m from outlet

8,37 8,10 8,12

17,5

22,9

11,5

35,0 33,0 34,6

0

2

4

6

8

10

14.07.0408.09.0416.11.04

sampling date

pH

0

5

10

15

20

25

30

35

40

salinity [pSU]

temperature [°C]

pH

Sal

Temp

Fig. 43: Salinity, temperature, and pH measured at points C350 and C750

The results of the pH, salinity and temperature measurements of Dover are shown in Fig. 44 and Fig.

45. The results of the transect samples are shown in Fig. 46 and Fig. 47. In Dover the variability in pH

and salinity was lower than in Calais. As mentioned before, this is mainly due to the differences in the

architecture of the two ports. Calais is an enclosed harbour with three separated arms and only one

entrance. The harbour is situated parallel to the stream which enables a water exchange mainly in that

part of the harbour close to the entrance. In the remaining part of the harbour, especially at the end of

the three arms ebb and flow are the only forces allowing a water exchange inside the port. Opposite to

Calais, the port of Dover is relatively open. There are two entrances, one in the north-west and one in

the north-east. The stream, which is flowing parallel to the harbour, has the chance to flow partially

through the harbour. Therefore a high water exchange is possible and the influence of the North Sea

is greater here than in Calais. The lowest measured salinity was 34 PSU. Temperature was highest in

September and about 14 °C higher than in February. During all samplings the temperatures in Dover

were about 1 °C higher than in Calais. The values determined at the transect sampling points are

within the same range as the samples taken at the remaining points.
9 Results and discussion of the toxicity and accumulation tests

86

Dov 1: eastern entrance

8,10 8,35 8,07 8,21

8,4

15,9

22,2

11,6

34,0 34,0 35,0 34,4

0

2

4

6

8

10

11.02.0414.07.0408.09.0416.11.04

sampling date

pH

0

5

10

15

20

25

30

35

40

salinity [pSU]

temperature [°C]

pH

Sal

Temp

Dov 2: east entrance

8,35 8,08 8,18

15,9

22,2

11,6

34,0 35,1 34,4

0

2

4

6

8

10

14.07.0408.09.0416.11.04

sampling date

pH

0

5

10

15

20

25

30

35

40

salinity [pSU]

temperature [°C]

pH

Sal

Temp

Fig. 44: Salinity, temperature, and pH measured at points Dov 1 and Dov 2

Dov 3: middle port

8,35 8,08 8,15

15,9

21,9

11,5

34,0 35,1 34,3

0

2

4

6

8

10

14.07.0408.09.0416.11.04

sampling date

pH

0

5

10

15

20

25

30

35

40

salinity [pSU]

temperature [°C]

pH

Sal

Temp

Dov 4: western port

8,37 8,08 8,19

15,9

22,2

11,5

34,0 35,2 34,3

0

2

4

6

8

10

14.07.0408.09.0416.11.04

sampling date

pH

0

5

10

15

20

25

30

35

40

salinity [pSU]

temperature [°C]

pH

Sal

Temp

Fig. 45: Salinity, temperature, and pH measured at points Dov 3 and Dov 4

D 5: 5 m from outlet

7,95 8,35 8,07 8,24

8,8

15,9

22,8

11,6

34,4 34,0 35,1 34,2

0

2

4

6

8

10

24.03.0414.07.0408.09.0416.11.04

sampling date

pH

0

5

10

15

20

25

30

35

40

salinity [pSU]

temperature [°C]

pH

Sal

Temp

D 50: 50 m from outlet

8,00 8,35 8,04 8,26

8,8

15,9

22,3

11,6

34,4 34,3 35,2 34,0

0

2

4

6

8

10

24.03.0414.07.0408.09.0416.11.04

sampling date

pH

0

5

10

15

20

25

30

35

40

salinity [pSU]

temperature [°C]

pH

Sal

Temp

Fig. 46: Salinity, temperature, and pH measured at points D5 and D50

D 350: 350 m from outlet

8,35 8,25 8,05

15,9

22,1

11,7

34,0 35,0 34,3

0

2

4

6

8

10

14.07.0408.09.0416.11.04

sampling date

pH

0

5

10

15

20

25

30

35

40

salinity [pSU]

temperature [°C]

pH

Sal

Temp

D 700: west entrance

8,10 8,38 8,04 8,17

8,5

15,9

22,1

11,6

34,1 34,0 35,0 34,3

0

2

4

6

8

10

11.02.0414.07.0408.09.0416.11.04

sampling date

pH

0

5

10

15

20

25

30

35

40

salinity [pSU]

temperature [°C]

pH

Sal

Temp

Fig. 47: Salinity, temperature, and pH measured at points D350 and D700
9 Results and discussion of the toxicity and accumulation tests

87

Table 67: Differences between the inlet and outlet samples taken from the seawater scrubber system in Calais,

Dover and the Channel. Left: pH difference. Right: temperature difference

pH March July Sept. Nov. Temp [°C] March July Sept. Nov.

Dover 0.43 1.51 1.79 1.85 Dover 4.1 2.9 13.6 14.2

Channel 1.16 1.45 1.68 1.62 Channel 1.9 2.8 14.1 12.2

Calais 0.66 1.34 1.73 1.48 Calais 3.3 2.7 16.9 11.9

The annual course of the salinity, pH and temperature of the inlet and outlet samples is shown in Fig.

48 (Dover), Fig. 49 (Calais) and Fig. 50 (Channel). The pH, the temperature and the salinity of the inlet

samples taken in Dover and Calais are within the same range as the samples taken in the ports. Only

the sample taken in Calais in September shows a relatively low pH, but this is comparable to the

sample taken at point Cal 2 (Table 49). As the samples from point SC1 were not taken at the same

time and not directly at the pier but during entering the harbour, small variations are possible.

Therefore it can be said, that the values are comparable and an influence of the outlet water onto the

inlet water can be mainly excluded. Looking at the outlet samples, also an annual influence onto the

temperature is obvious. The temperature of the outlet is strongly dependent of the inlet temperature.

but as the difference between the inlet and outlet temperatures was greater in September and

November than during the samplings in February, March and July (Table 67) the main influence is by

the seawater scrubber.

The lowest pH in the outlet was measured in September as well. The reason therefore might also be

differences in the efficiency of the Ecosilencer. Another reason could be the relatively high

temperature of the effluent, because the pH is also temperature dependent. To determine this

dependency a small test was performed. 500 mL seawater (Jade Bay, Table 1) were heated and

cooled down again and the pH was measured continuously. It can be seen that the higher the

temperature was, the lower the pH was. The different ascent between heating and cooling is a

physical effect called hysteresis. If calcium carbonate is dissolved in water the following reaction

occurs:

CaCO3 + H2O + CO2 Ca(HCO3)2

An increase in the temperature shifts the equilibrium towards the left side. Therefore more CO2 is

introduced and carbonic acid is built according to:

CO2 + H2O H2CO3 H

+

+ HCO3

-

2 H++ CO3

2-

This reduces the pH. When the water is cooled down again the CO2 solubility increases and carbonic

acid concentration is reduced, resulting in a pH increase. As during the heating process the CO2 has

to leave the water this step takes more time in comparison to the increase in solubility.
9 Results and discussion of the toxicity and accumulation tests

88

SD1: Dover inlet

7,72 7,99 8,38 8,32

10,7

17,8

24,0

13,2

34,2 34,4 33,9 35,0

0

2

4

6

8

10

24.03.0414.07.0408.09.0416.11.04

sampling date

pH

0

5

10

15

20

25

30

35

40

salinity [pSU]

temperature [°C]

pH

Sal

Temp

SD2: Dover outlet

7,29

6,20

6,87 6,47

14,8

20,7

34,0

35,7

34,6 34,8

37,6 27,4

0

2

4

6

8

10

24.03.0414.07.0408.09.0416.11.04

sampling date

pH

0

5

10

15

20

25

30

35

40

salinity [pSU]

temperature [°C]

pH

Sal

Temp

Fig. 48: Salinity, temperature, and pH measured at points SD1 and SD2

SC1: Calais inlet

8,00 7,88 8,16 7,81

18,2

13,6

35,0 34,5 32,9 33,0

9,5

20,7

0

2

4

6

8

10

24.03.0414.07.0408.09.0416.11.04

sampling date

pH

0

5

10

15

20

25

30

35

40

salinity [pS

U]

temperature [°C]

pH

Sal

Temp

SC2: Calais outlet

7,34

6,15 6,33 6,82

20,9

32,9 33,5

34,7

35,0 37,6

12,8

25,5

0

2

4

6

8

10

24.03.0414.07.0408.09.0416.11.04

sampling date

pH

0

5

10

15

20

25

30

35

40

salinity [pSU]

temperature [°C]

pH

Sal

Temp

Fig. 49: Salinity, temperature, and pH measured at points SC1 and SC2

SCH1: Channel inlet

8,06 8,44 8,28 7,94 8,08

34,3

9,2

15,2

23,0

14,0

34,9 35,0 36,0 34,3

17,4

0

2

4

6

8

10

11.02.0424.03.0414.07.0408.09.0416.11.04

sampling date

pH

0

5

10

15

20

25

30

35

40

salinity [pSU]

temperature [°C]

pH

Sal

Temp

SCH2: Channel outlet

7,99

6,99 6,66 6,40 6,78

35,0

22,3

17,1

34,9 35,2 35,0 36,0

37,1 26,2

20,2

0

2

4

6

8

10

11.02.0424.03.0414.07.0408.09.0416.11.04

sampling date

pH

0

5

10

15

20

25

30

35

40

salinity [pSU]

temperature [°C]

pH

Sal

Temp

Fig. 50: Salinity, temperature, and pH measured at points SCH1 and SCH2

y = -0,0037x + 8,0609

R

2

= 0,7122

y = -0,0085x + 8,4243

R

2

= 0,8147

7,7

7,8

7,9

8,0

8,1

8,2

8,3

8,4

15 25 35 45 55 65

temperatur [°C]

pH-va lue

heating

cooling

Fig. 51: Temperature dependency of pH. The red line shows the course of the pH when the sample was heated

and the blue line shows the course of the pH when the sample was cooled down again.
9 Results and discussion of the toxicity and accumulation tests

89

The comparison of all samples taken at the points SCH3, SCH5 and SCH6 are shown in Fig. 52 and

Fig. 53. The salinity in these samples was always relatively high in comparison to the samples taken

inside the harbours and was highest in September. In September also the highest temperature was

measured. The lowest pH was determined in the samples taken during the second sampling. As the

system was not working completely in March the reason could be a slower flow speed of the water

through the Ecosilencer and therefore a higher saturation with sulphuric and nitric acid.

SCH3: Channel outlet US-filter

2,73 3,14 3,14 3,35

36,7 35,5

34,5 36,8 35,7

35,5

45,3

27,6

0

2

4

6

8

10

24.03.0414.07.0408.09.0416.11.04

sampling date

pH

0

10

20

30

40

50

salinity [pSU]

temperature [°C]

pH

Sal

Temp

SCH5: Channel inlet US-filter

2,82 3,13 3,05 3,34

36,0 35,4

35,0 36,8 35,6

35,2

27,9

46,2

0

2

4

6

8

10

24.03.0414.07.0408.09.0416.11.04

sampling date

pH

0

10

20

30

40

50

salinity [pSU]

temperature [°C]

pH

Sal

Temp

Fig. 52: Salinity, temperature, and pH measured at points SCH3 and SCH5

SCH6: Channel outlet Ecosilencer

2,78 3,13 3,30 3,09

35,2 37,0 36,9

35,0 36,4 35,8

45,1

28,0

0

2

4

6

8

10

24.03.0414.07.0408.09.0416.11.04

sampling date

pH

0

10

20

30

40

50

salinity [pSU]

temperature [°C]

pH

Sal

Temp

Fig. 53: Salinity, temperature, and pH measured at point SCH6

A plot of all pH values observed during all sampling is shown in Fig. 54 and Fig. 55. The error bars

show the maximum allowed pH change caused by effluents outside the initial mixing zone (US-EPA

1986). In both graphs it can be seen that the natural pH range is greater than the pH change within the

sample suite taken at the transect points. The same can be seen in Fig. 56. During no sampling a pH

decrease from the first transect point towards the harbour entrance was observed.

From Fig. 58 where all the measured temperatures of all sampling points (without seawater scrubber

system) are shown, it can be seen that the highest temperature differences were observed inside the

ports in March. The temperatures measured at the transect points in July were partially higher than

those measured at the remaining points inside the harbour. In detail this is shown in Fig. 57. It can be

seen that during the sampling in July and September the temperatures were higher at the first transect

point in comparison to the remaining points. During the sampling in September the difference between

the inlet and the outlet temperature was also very high (Table 67). In July the difference was over
9 Results and discussion of the toxicity and accumulation tests

90

10 °C lower and the same effect was observed whereas in November high temperature differences did

not increase the values at points C5 and D5. Due to the buoyancy of the warmer effluent it will initially

have an effect on the upper water column. In summer the density stratification is more stable than in

winter or fall. Therefore the influenced water volume is smaller in summer than in winter and the

temperature can be influenced more easily. As this temperature increase made up only 1 °C and was

only measured close to the ship, no negative effects are to be expected.

7.5

7.75

8

8.25

8.5

33.5 34 34.5 35 35.5

salinity [PSU]

p

H

Dover harbour

Dover transect

Fig. 54: pH and salinity in the harbour of Dover. Triangles represent the natural variability during all samplings

in 2004. Diamonds represent the values of the transect samples.

7.5

8

8.5

9

9.5

16 21 26 31 36

salinity [PSU]

p

H

Calais harbour

Calais transect

Fig. 55: pH and salinity in the harbour of Calais. Triangles represent the natural variability during all samplings

in 2004. Diamonds represent the transect values.
9 Results and discussion of the toxicity and accumulation tests

91

6,8

7

7,2

7,4

7,6

7,8

8

8,2

8,4

8,6

8,8

0 200 400 600

distance from oulet [m]

pH

Calais 14.07.2004

Calais 08.09.2004

Calais 16.11.2004

Dover 14.07.2004

Dover 08.09.2004

Dover 16.11.2004

Fig. 56: pH impact of SWS effluents on the receiving harbour water in Dover and Calais at three sampling (July,

Sept. and Nov.)

0

5

10

15

20

25

0 200 400 600

distance from outlet [m]

temperature [°C]

Calais 14.07.2004

Calais 08.09.2004

Calais 16.11.2004

Dover 14.07.2004

Dover 08.09.2004

Dover 16.11.2004

Fig. 57: Temperature [°C] impact of SWS effluents on the receiving harbour water in Dover and Calais at three

sampling (July, Sept. and Nov.)

0

5

10

15

20

25

Jan. 04Mrz. 04Apr. 04Jun. 04

Aug. 04Sep. 04Nov. 04

Dez. 04

sampling date

tem

perature [°C]

harbour

transect

Fig. 58: Temperatures [°C] of harbour and transect samples.
9 Results and discussion of the toxicity and accumulation tests

92

8.6.2 Nitrate and sulphate

Nitrate

In Fig. 59 the nitrate concentrations determined in the ports and for the inlet and outlet samples are

shown. It can be seen that in summer the concentrations were lower than in winter and fall. Because

nitrogen is an essential compound for marine primary production it is depleted in summer when the

phytoplankton production is high and nitrogen availability is a limiting factor. In winter when the

plankton production is generally close to zero the nitrogen is remineralised and its concentration

increases. Additionally in Fig. 59 the nitrate concentrations of the inlet and the outlet water are shown.

It can be seen that in Calais the outlet concentration was within the natural range whereas in Dover it

was slightly higher. The transect points did not show a nitrate concentration increase during any

sampling and were all within the natural range.

0

10

20

30

40

50

60

70

80

Feb. Mar. Jul. Sep. Nov.

sampling date

N

O3- concentration [μmol l-1]

Cal1

Cal2

Cal3

Cal4

C5

C50

C350

C700

SC1

SC2

0

10

20

30

40

50

60

70

80

Feb. Mar. Jul. Sep. Nov.

sampling date

N

O3- concentration [μmol l-1]

Dov2

Dov4

D5

D50

D350

D700

SD1

SD2

Fig. 59: Nitrate concentrations [μmol l-1] observed during all samplings. Left: Port of Calais. Right: Port of Dover

The sulphate concentrations determined in the inlet and outlet of the seawater scrubber samples are

shown in Table 68. Calculating the sulphate increase between the inlet and the outlet it can be seen

that the greatest difference was observed during the sampling in November in Dover. This increase of

165 pm corresponds to a concentration change of 6.1 %. This value lies within the accuracy of the

measurement and within the natural variability.

Table 68: Comparison of sulphate inlet and outlet concentrations [ppm]

Feb. Mar. Sep. Nov.

SD1 n.d. 2949 n.d. 2699

SD2 n.d. 2962 2710 2864

SCH1 2842 2990 2590 2685

SCH2 2874 3052 2600 2805

SC1 n.d. 2920 n.d. 2587

SC2 n.d. 2938 2870 2644
9 Results and discussion of the toxicity and accumulation tests

93

8.6.3 Polycyclic aromatic hydrocarbons

Within this chapter the PAH concentrations determined during all samplings will be discussed. Table

69 shows the total PAH amounts, Table 70 the particulate and dissolved fractions of the harbour

samples and Table 72 the bound and unbound PAHs of the seawater scrubber samples. Looking at

the total amounts which are calculated as the sum of the 16 EPA PAHs without naphthalene, it can be

seen that the lowest concentrations were measured in July and the highest in November. This is an

effect of fossil fuel and wood burning in the cities around the ports. Parallel to this seasonal effect

there are also great differences between the two harbours and within harbours themselves. As an

effect of the harbour structure as explained above in Dover generally lower concentrations than in

Calais were observed. Water from outside the harbour, which is normally less contaminated and less

subjected to anthropogenic influence, can easier reach the port of Dover than the port of Calais.

Besides physical processes such as water exchange rates chemical and biological processes control

the PAH contents in natural waters. Phytoplankton and seston adsorb PAHs and thus become

passively enriched. Additionally, organisms can take up the PAHs and change their structure or

destroy specific structures leading to an enrichment of some structures whereas others are depleted.

Additionally organisms that have taken up PAHs are removing the PAHs from the water after death

when they are sedimenting or when they are consumed by heterotrophic organisms.

With respect to the outlet samples, the contents are always around 3000 ng L-1and the lowest PAH

contents were in almost all cases measured in the Channel. The reason for this might be that the

cleaning efficiency of the SWS is higher when the machines are running at full speed. Within the

seawater scrubber system the highest concentrations were always measured inside the settling tank

and at point SCH4. This shows that the cyclones effectively remove particles and hence particlebound PAHs from the water. In contrary the US filter did not work in all cases. During the sampling in

July and September the PAH concentration increased behind the US filter.

Table 69: Sum of all 16 EPA-PAHs (particulate and dissolved, excluding naphthalene) concentrations in ng l-1for

all samplings (n.d. = not determined).

Cal 1 Cal 2 Cal 3 Cal 4 C0 C5 C50 C350 C700 Dov 2 Dov 3 Dov 4 D0 D5 D50 D350 D700 Dover

inlet

Dover

outlet

Channel

inlet

Channel

outlet

Calais

inlet

Calais

outlet

11.02.2004 268 353 209 420 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. 246 4055 n.d. n.d.

24.03.2004 361 334 765 342 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. 473 2921 306 3400 282 2380

14.07.2004 99 69 58 46 n.d. 63 46 51 28 41 75 n.d. 26 23 72 39 35 2852 58 2459 60 3395

08.09.2004 117 248 187 134 133 109 65 86 69 130 101 50 n.d. 129 156 70 44 133 3422 72 3263 115 3577

16.11.2004 516 225 327 419 619 622 521 625 428 536 569 419 106 274 345 200 198 432 2870 593 2029 445 3407

SCH3 SCH4 SCH5 SCH6 SCH7 SCH8

11.02.2004 n.d. n.d. n.d. n.d. n.d. n.d.

24.03.2004 12502 19187 15151 15019 17320 24714

14.07.2004 20354 n.d. 16491 19854 n.d. n.d.

08.09.2004 16649 23868 14732 15901 n.d. n.d.

16.11.2004 11879 13486 12465 10334 n.d. 21211

Table 70: PAH concentrations in ng L-1. Listed are the concentrations of the single PAH compounds in all

samples. Concentrations are given as dissolved/particulate PAH. Dashes indicate concentrations

below the limit of detection. (n.d. = not determined)
9 Results and discussion of the toxicity and accumulation tests

94

compound Date Cal 1 Cal 2 Cal 3 Cal 4 Dov 2 Dov 3 Dov 4 C0 C5 C50 C350 C700 D0 D5 D50 D350 D700 SD1 SD2 SCH1 SCH2 SC1 SC2

ATHY 11.02.04 1/- 4/- 2/- 1/- n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. 1/- -/25 n.d. n.d.

24.03.04 2/- 4/- 23/2 8/- n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. 1/- 7/- 1/- 9/1 2/- 10/-

14.07.04 8/- 3/- 9/- 8/- 4/- n.d. 2/- -/- -/- 1/- -/- -/- -/- -/- 2/- -/- 6/- 6/- -/- -/- 4/-

08.09.04 1/- 1/- -/- 1/- -/- -/- -/- 4/- -/- -/- -/- -/- -/- -/- -/- -/- -/- 2/- -/- 7/- -/- 3/-

16.11.04 9/- 8/- 11/- 12/- 28/- 12/- 9/- 9/- 14/- 14/- 12/- 13/- 7/- 8/- 8/- 11/- 10/- 13/- 14/- 8/- 13/- 13/- 23/1

ATHE 11.02.04 7/- 16/- 5/- 6/- n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. 5/- -/120 n.d. n.d.

24.03.04 7/- 8/- 15/1 7/- n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. 6/- 30/1 5/- 43/3 8/- 32/1

14.07.04 -/- 8/- 4/- 4/- 2/- n.d. 5/- n.d. 3/- 2/- 4/- 3/- 3/- 1/- 2/- 2/- 1/- 28/- 1/- 1/- 2/- 2/-

08.09.04 5/- 6/- 7/- 3/- 3/- 3/- 3/- 4/- 3/- 2/- 3/- 3/- 3/- 1/- 4/- 2/- 4/- 23/1 3/- 34/1 5/- 45/2

16.11.04 17/- 72/1 14/- 16/- 45/- 20/- 18/- 19/- 20/- 19/- 21/- 20/- 12/- 18/- 13/- 16/- 19/- 16/- 37/1 12/- 27/1 19/- 60/2

FLRE 11.02.04 25/- 35/- 21/- 25/- n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. 25/- -/518 n.d. n.d.

24.03.04 26/- 30/- 74/6 22/- n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. 28/- 132/2 30/- 193/12 23/- 126/4

14.07.04 5/- 2/- 4/- 1/- 3/- n.d. 2/- n.d. 1/- 6/- 5/- 3/- n.d. 2/- 2/- 3/- 5/- 5/- 113/2 7/- 135/2 6/- 128/3

08.09.04 5/- 5/- 27/1 6/- 6/- 5/- 6/1 9/- 5/- 8/- 3/- 4/- n.d. 7/- 7/- 6/- 4/- 9/- 144/5 5/- 147/4 7/- 163/6

16.11.04 19/- 38/1 14/- 15/- 46/- 31/1 15/- 17/- 20/- 18/- 20/- 18/- 14/- 21/- 13/- 19/- 28/1 17/- 126/4 13/- 108/3 19/- 153/6

PHEN 11.02.04 143/5 184/6 105/6 150/4 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. 139/3 415/2185 n.d. n.d.

24.03.04 152/5 147/5 207/62 134/5 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. 173/8 964/77 159/6 1039/404 133/4 845/98

14.07.04 27/1 22/1 3/- 16/- 16/- n.d. 32/1 n.d. 18/1 18/1 18/- 12/- n.d. 16/- 14/- 22/1 17/- 13/- 1135/71 23/- 967/68 24/- 1105/121

08.09.04 36/- 59/3 59/19 43/2 43/1 37/2 15/7 41/2 34/2 23/1 26/1 23/6 n.d. 42/3 73/3 30/1 24/1 45/1 1197/217 33/2 1249/151 47/2 1201/222

16.11.04 36/2 31/1 43/2 42/3 98/6 127/8 29/2 106/7 59/8 46/4 84/10 41/2 23/2 68/5 29/2 43/3 48/4 63/3 954/140 51/3 760/99 57/5 1087/220

ANTH 11.02.04 12/- 17/1 9/- 11/- n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. 11/- 29/152 n.d. n.d.

24.03.04 10/- 10/- 21/6 9/- n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. 11/1 28/2 11/- 35/13 9/- 22/3

14.07.04 3/- 3/- 4/- 2/- 1/- n.d. 1/- n.d. 2/- -/- 4/- 1/- n.d. -/- 1/- -/- 1/- -/- 26/2 3/- 30/2 2/- 41/4

08.09.04 9/- 9/1 -/- -/- 16/- -/- -/- -/- -/- 1/- 1/- -/- n.d. -/- 4/- 1/0 -/- 15/- 30/6 -/- 29/4 -/- 38/7

16.11.04 16/1 19/1 13/1 17/1 21/1 25/2 14/1 25/2 21/3 20/2 22/3 17/1 12/1 15/1 12/1 17/1 15/1 15/1 24/4 20/1 29/4 20/2 56/11

FLUA 11.02.04 28/1 39/1 20/1 35/1 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. 25/1 72,378 n.d. n.d.

24.03.04 29/1 31/1 84/25 41/1 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. 45/2 163/13 30/1 173/67 29/1 142/17

14.07.04 18/1 11/- 11/- 6/- 6/- n.d. 13/- n.d. 10/- 7/- 7/- 3/- n.d. -/- 1/- 9/- 4/- 4/- 121/8 3/- 105/7 5/- 130/14

08.09.04 27/1 50/3 20/7 16/1 28/1 11/1 -/4 22/1 28/2 9/- 25/1 14/6 n.d. 11/- 35/1 3/0 3/- 19/- 238/43 5/- 188/23 12/- 227/42

16.11.04 41/2 14/1 46/2 45/3 43/3 97/6 56/3 55/4 67/9 53/5 102/12 41/2 9/3 19/1 36/2 20/1 14/1 20/1 165/24 32/2 119/16 28/2 203/41

PYR 11.02.04 15/10 15/13 6/7 52/17 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. 17/6 94,25 n.d. n.d.

24.03.04 35/22 28/14 29/46 36/20 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. 37/46 232/279 26/16 122/372 22/11 146/262

14.07.04 12/14 9/7 13/10 5/4 4/2 n.d. 13/5 n.d. 8/7 6/6 6/4 3/2 n.d. 3/2 3/1 9/7 6/2 5/3 213/186 7/2 149/105 10/4 248/236

08.09.04 20/1 46/3 18/6 23/1 20/1 14/1 -/3 21/1 21/1 9/- 20/1 9/- n.d. 18/2 29/1 5/0 -/- 12/6 103/383 10/- 348/42 14/- 389/72

16.11.04 70/4 10/- 44/2 38/2 68/4 103/6 113/7 62/3 103/14 79/8 88/10 38/2 5/7 22/2 73/5 27/2 15/1 18/18 121/246 48/3 225/29 50/4 477/97

BaA 11.02.04 2/1 2/1 6/7 10/3 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. 3/1 5/1 n.d. n.d.

24.03.04 7/4 6/3 11/18 7/4 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. 7/9 59/70 3/2 29/88 4/2 40/72

14.07.04 -/2 -/- -/- -/- -/2 n.d. -/- n.d. -/2 -/- -/- -/- n.d. -/- -/- -/2 -/- -/- 234/210 -/- 242/170 -/- 355/338

08.09.04 1/1 7/6 2/7 7/6 3/2 6/6 5/- 5/6 -/- 5/2 1/1 2/- n.d. 5/7 -/- 4/4 2/1 5/3 57/205 3/2 96/146 5/4 64/216

16.11.04 49/56 7/5 20/21 29/49 24/36 20/26 21/28 53/56 26/70 27/52 21/48 34/49 4/28 10/13 20/26 7/11 6/11 39/40 95/194 68/97 46/102 28/49 69/201

CHRY 11.02.04 4/3 3/3 3/4 31/10 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. 4/1 23/6 n.d. n.d.

24.03.04 22/13 17/9 13/21 18/10 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. 25/31 242/290 7/4 118/361 8/4 109/196

14.07.04 -/2 2/2 -/- -/- -/- n.d. -/- n.d. -/2 -/- -/- -/- n.d. -/- -/- 3/7 -/- 2/2 124/111 4/2 165/116 4/3 191/182

08.09.04 5/4 8/7 3/8 12/9 4/3 8/8 5/- 8/10 3/5 4/2 1/1 2/- n.d. 8/11 -/- 5/6 5/3 9/5 101/369 5/4 187/283 10/8 118/403

16.11.04 54/61 9/6 28/29 30/51 29/44 24/31 26/34 60/64 28/44 32/63 26/59 39/56 5/34 13/17 27/35 7/13 7/13 47/- 153/- 72/101 87/194 34/59 108/315

BbkF 11.02.04 1/1 1/2 1/2 4/7 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. -/1 1/- n.d. n.d.

24.03.04 1/3 1/2 6/17 2/3 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. -/6 4/37 -/- 3/32 2/3 3/26

14.07.04 -/3 -/- -/- -/- -/- n.d. -/- n.d. -/4 -/- -/- -/- n.d. -/- -/- -/- -/- -/- -/47 -/- 7/39 -/- -/56

08.09.04 -/- 2/11 1/2 1/3 -/- -/- -/- -/- -/- -/- -/- -/- n.d. 1/3 -/- -/- -/- -/- 4/95 -/- 17/81 -/- 15/103

16.11.04 8/32 -/- 4/17 9/29 3/21 4/16 5/18 8/36 3/38 5/37 4/36 4/29 -/18 2/8 3/20 -/3 -/2 6/29 10/72 5/31 7/41 4/27 7/74

BaP 11.02.04 1/3 1/4 1/3 15/25 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. 1/2 5/- n.d. n.d.

24.03.04 3/8 4/8 7/21 3/6 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. 1/27 18/153 1/2 19/183 3/4 16/131

14.07.04 -/4 -/- -/- -/- -/- n.d. -/- n.d. -/- -/- -/- -/- n.d. -/- -/- -/3 -/- -/- -/115 -/- 10/63 -/- 13/99

08.09.04 -/- 2/12 -/- -/- -/- -/- -/- -/- -/4 -/- -/- -/- n.d. 1/4 -/- -/- -/- -/- 6/143 -/- 27/132 -/- 23/152

16.11.04 6/23 -/- 3/13 7/22 2/12 2/9 4/15 6/27 3/32 4/30 3/30 3/17 -/15 2/9 2/16 -/- -/- 5/24 14/100 3/20 11/64 3/20 11/125

DahA 11.02.04 -/- -/1 -/- -/- n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. -/- -/- n.d. n.d.

24.03.04 1/2 -/- 4/11 -/1 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. -/3 4/37 -/- 2/23 1/1 3/25

14.07.04 -/- -/- -/- -/- -/- n.d. -/- n.d. -/- -/- -/- -/- n.d. n.d. -/- -/- -/- -/- -/34 -/- -/23 -/- -/42

08.09.04 -/- -/- -/- -/- -/- -/- -/- -/- -/- -/- -/- -/- n.d. n.d. -/- -/- -/- -/- -/3 -/- 2/7 -/- -/-

16.11.04 -/- -/- -/- -/- -/- -/- -/- -/- -/- -/- -/- -/- -/- -/- -/- -/- -/- -/- 1/7 -/- -/- -/- -/3

BghiP 11.02.04 -/1 1/2 -/- 3/5 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. -/- -/- n.d. n.d.

24.03.04 1/4 1/2 5/14 1/2 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. -/6 5/46 -/1 4/34 1/1 4/31

14.07.04 -/- -/- -/- -/- -/- n.d. -/- n.d. -/4 -/- -/- -/- n.d. -/- -/- -/3 -/- -/- -/49 -/- -/40 -/- -/62

08.09.04 -/- 1/4 -/- -/- -/- -/- -/- -/- -/- -/- -/- -/- n.d. -/3 -/- -/- -/- -/- 1/27 -/- 6/29 -/- 9/43

16.11.04 1/3 -/- -/- -/- -/- -/- -/- -/- 1/6 -/3 1/8 -/- -/- 2/8 -/- -/- -/- 1/3 5/33 -/- 5/27 -/- 3/35

INDE 11.02.04 -/1 -/1 -/- 2/3 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. -/- -/- n.d. n.d.

24.03.04 1/2 -/1 4/13 1/1 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. -/2 3/23 -/- 2/16 1/1 2/13

14.07.04 -/- -/- -/- -/- -/- n.d. -/- n.d. -/- -/- -/- -/- n.d. -/- -/- -/- -/- -/- -/16 -/- -/13 -/- -/22

08.09.04 -/- 1/3 -/- -/- -/- -/- -/- -/- -/- -/- -/- -/- n.d. -/- -/- -/- -/- -/- 1/17 -/- 4/20 -/- -/12

16.11.04 1/3 -/- -/- -/- -/- -/- -/- -/- -/- -/- -/4 -/- -/- 2/7 -/- -/- -/- 1/3 2/14 -/- 2/11 -/- 1/17

The PAH composition is dominated in all samples by fluorene, phenanthrene and pyrene. Only in a

few samples acenaphthene, fluoranthene, chrysene and benz[a]anthracene could not be detected.

High molecular weight PAHs such as indeno(1,2,3,c,d)pyrene, benzo[ghi]perylene and

dibenz[a,h]anthracene were below the detection level. Benzo[a]pyrene and the sum of

benzo[b]fluoranthene and benzo[k]fluoranthene were mainly found in low contents.

As the high molecular weight PAHs are generally more harmful than the low molecular weight PAHs

and as the former are more easily degraded by microorganisms it can be stated that the ports of

Dover and Calais are not seriously polluted. According to the World Health Organisation the maximum

permissible concentration of PAHs in drinking water is 200 ng L

-1

calculated as the sum of BbF, BghiP,
9 Results and discussion of the toxicity and accumulation tests

95

BkF, BaP, Flua, Ind in carbon weight. The sums of these compounds are shown in Table 71. It can be

seen that in no harbour sample the concentration was higher than the maximum permissible content.

Only the PAH concentrations determined directly in the outlet show higher values, but already directly

in front of the outlet no increase was observed and values were still below the threshold of 200 ng L

-1

.

Table 71: Sum of BbF, BghiP, BkF, BaP, Flua, and Inde calculated as carbon weight (n.d. - not determined)

[ng l-1] Feb. Mar. Jul. Sep. Nov.

Cal 1 35 50 25 27 114

Cal 2 49 49 10 85 14

Cal 3 27 187 10 29 81

Cal 4 95 58 6 20 109

Dov 2 n.d. n.d. 6 28 80

Dov 3 n.d. n.d. n.d. 11 127

Dov 4 n.d. n.d. 12 4 96

C0 n.d. n.d. n.d. 22 129

C5 n.d. n.d. 17 32 151

C50 n.d. n.d. 7 9 130

C350 n.d. n.d. 7 25 190

C700 n.d. n.d. 3 19 91

D0 n.d. n.d. n.d. n.d. 43

D5 n.d. n.d. 0 22 57

D50 n.d. n.d. 1 34 75

D350 n.d. n.d. 14 3 23

D700 n.d. n.d. 4 3 16

SD1 n.d. 85 4 18 89

SD2 n.d. 443 339 547 418

SCH1 29 33 3 5 89

SCH2 433 507 270 502 289

SC1 0 44 5 11 80

SC2 0 367 377 596 492

The PAH composition established in the outlet samples was also found in the seawater scrubber

samples. Phenanthrene, fluoranthene and pyrene had the highest contents in all samples. Chrysene

and benz[a]anthracene were found with contents >2000 ng L

-1

. The high molecular weight PAHs

benzo[ghi]perylene, indeno(1,2,3,c,d)pyrene and dibenz[a,h]anthracene were almost completely

bound to particles and therefore found in highest contents in the settling tank. The low molecular

weight PAHs were found almost with equal contents inside the seawater scrubber during all

samplings. The variance of the high molecular weight PAH concentrations was however higher. The

reason for this might be the particle load of the water entering the seawater scrubber. This was

highest in July when also the PAH concentrations were highest.

Table 72: PAH concentrations in ng L-1determined for the seawater scrubber samples. Listed are the

concentrations of the single PAH compounds in all samples. Contents are given as

dissolved/particulate PAH. Dashes indicate concentrations below the limit of detection. (n.d. = not

determined)
9 Results and discussion of the toxicity and accumulation tests

96

compound Date SCH3 SCH4 SCH5 SCH6 SCH7 SCH8

ATHY 11.02.04 n.d. n.d. n.d. n.d. n.d. n.d.

24.03.04 33/3 39/3 35/4 38/4 34/6 44/9

14.07.04 41/5 n.d. 32/4 33/4 n.d. n.d.

08.09.04 11/1 18/8 8/1 5/1 n.d. n.d.

16.11.04 35/3 27/4 38/3 30/3 n.d. 37/9

ATHE 11.02.04 n.d. n.d. n.d. n.d. n.d. n.d.

24.03.04 166/17 208/17 153/16 170/20 191/33 208/44

14.07.04 171/22 n.d. 143/17 143/17 n.d. n.d.

08.09.04 166/23 143/54 136/20 156/34 n.d. n.d.

16.11.04 157/13 107/17 172/13 140/12 n.d. 182/45

FLRE 11.02.04 n.d. n.d. n.d. n.d. n.d. n.d.

24.03.04 712/75 774/65 809/84 763/88 764/132 815/171

14.07.04 718/92 n.d. 663/80 648/79 n.d. n.d.

08.09.04 650/89 665/250 570/85 553/249 n.d. n.d.

16.11.04 596/50 544/86 601/44 493/42 n.d. 880/219

PHEN 11.02.04 n.d. n.d. n.d. n.d. n.d. n.d.

24.03.04 3972/1445 5052/1423 4644/1594 4382/1757 4469/2229 5308/3276

14.07.04 7034/1182 n.d. 4766/1907 7122/901 n.d. n.d.

08.09.04 4075/2665 3768/4914 3732/2099 3116/3570 n.d. n.d.

16.11.04 3666/1599 3334/2374 3798/1503 3139/1341 n.d. 3997/4584

ANTH 11.02.04 n.d. n.d. n.d. n.d. n.d. n.d.

24.03.04 69/25 118/33 110/38 86/34 82/41 127/79

14.07.04 138/22 n.d. 98/39 134/17 n.d. n.d.

08.09.04 58/38 44/54 85/48 66/89 n.d. n.d.

16.11.04 76/33 38/28 115/5 72/31 n.d. 113/129

FLUA 11.02.04 n.d. n.d. n.d. n.d. n.d. n.d.

24.03.04 619/225 853/240 777/267 691/277 852/425 1269/783

14.07.04 781/132 n.d. 532/213 769/95 n.d. n.d.

08.09.04 743/486 757/991 683/383 200/1005 n.d. n.d.

16.11.04 606/264 626/446 647/255 492/210 n.d. 957/1098

PYR 11.02.04 n.d. n.d. n.d. n.d. n.d. n.d.

24.03.04 491/1358 1176/2553 452/1618 424/1885 700/2119 1179/3490

14.07.04 861/1592 n.d. 467/1669 1076/1681 n.d. n.d.

08.09.04 1313/859 1304/1700 1201/674 263/1816 n.d. n.d.

16.11.04 1088/474 960/684 1343/530 1021/436 n.d. 1489/1707

BaA 11.02.04 n.d. n.d. n.d. n.d. n.d. n.d.

24.03.04 132/364 364/790 138/492 120/534 212/643 312/925

14.07.04 1298/2397 n.d. 626/2182 1402/2191 n.d. n.d.

08.09.04 149/967 155/1480 212/1067 23/1140 n.d. n.d.

16.11.04 189/618 168/865 228/618 161/604 n.d. 184/1095

CHRY 11.02.04 n.d. n.d. n.d. n.d. n.d. n.d.

24.03.04 370/1024 951/2064 448/1603 374/1661 566/1714 835/2472

14.07.04 492/912 n.d. 249/892 622/970 n.d. n.d.

08.09.04 325/2110 335/3271 385/1933 46/2172 n.d. n.d.

16.11.04 346/1134 331/1699 423/1162 281/1054 n.d. 385/2294

BbkF 11.02.04 n.d. n.d. n.d. n.d. n.d. n.d.

24.03.04 21/131 20/243 18/185 9/178 31/201 55/430

14.07.04 118/354 n.d. 53/284 94/282 n.d. n.d.

08.09.04 -/1052 -/2421 39/464 -/456 n.d. n.d.

16.11.04 29/223 23/304 34/208 25/187 n.d. 24/441

BaP 11.02.04 n.d. n.d. n.d. n.d. n.d. n.d.

24.03.04 111/697 102/1221 94/980 48/930 159/1029 155/1207

14.07.04 255/764 n.d. 211/634 214/643 n.d. n.d.

08.09.04 -/442 -/730 58/685 -/690 n.d. n.d.

16.11.04 48/372 31/409 59/363 39/291 n.d. 32/575

DahA 11.02.04 n.d. n.d. n.d. n.d. n.d. n.d.

24.03.04 23/146 29/342 20/212 10/201 35/225 56/436

14.07.04 47/245 n.d. 31/172 27/176 n.d. n.d.

08.09.04 -/62 -/98 2/21 -/38 n.d. n.d.

16.11.04 3/26 4/49 4/27 4/28 n.d. 4/67

BghiP 11.02.04 n.d. n.d. n.d. n.d. n.d. n.d.

24.03.04 27/169 28/330 22/229 12/225 41/264 80/618

14.07.04 129/386 n.d. 59/320 98/295 n.d. n.d.

08.09.04 -/215 -/465 7/80 -/129 n.d. n.d.

16.11.04 19/145 16/209 22/134 16/123 n.d. 22/400

INDE 11.02.04 n.d. n.d. n.d. n.d. n.d. n.d.

24.03.04 11/67 11/136 9/98 5/94 17/107 38/292

14.07.04 27/139 n.d. 23/125 18/105 n.d. n.d.

08.09.04 -/152 -/243 4/49 -/84 n.d. n.d.

16.11.04 8/59 7/93 10/64 7/54 n.d. 13/230

In Table 73 the mean PAH content differences between the inlet and the outlet, their standard

deviations, their minima and their maxima are shown. The greatest differences were observed for

phenanthrene, pyrene, chrysene and benz[a]anthracene. Almost no changes were observed for

acenaphthylene and the six ring compounds

Table 73: Differences [ng L-1] between inlet and outlet samples taken in March, July, September and November

in Dover, Calais and the Channel. Shown are the mean, the standard deviation and the minimum and

maximum values.

[ng l-1] mean std min max

ATHY 5 4 -6 9
9 Results and discussion of the toxicity and accumulation tests

97

ATHE 24 14 0 41

FLRE 129 24 97 175

PHEN 1128 218 805 1278

ANTH 28 13 11 37

FLUA 170 57 101 210

PYR 392 94 203 452

BaA 253 190 -17 113

CHRY 361 120 108 476

BbkF 55 33 12 36

BaP 126 43 52 199

DahA 18 15 0 38

BghiP 41 10 28 46

INDE 17 5 12 24

Origin of PAHS

To determine the origin of the PAHs and to compare all samples again a plot of the isomeric ratios of

phenanthrene/anthracene and fluoranthene/pyrene is used. It can be seen that all outlet samples

clearly showa petrogenic character, whereas the remaining samples cannot clearly be assigned to one

specific source. Only the samples taken in November are all characterized by low

phenanthrene/anthracene ratios and only two samples show comparable ratios to the outlet samples:

Dov 4 (July) and D 350 (September). As the samples taken from points C5 and D5 directly in front of

the seawater scrubber outlet do not show such a pattern it is most probable that Dov 4 and D350

were not influenced by the seawater scrubber and that these ratios, even though they are similar, do

not relate to a PAH input from the “Pride of Kent”.

0

10

20

30

40

50

60

0,0 0,5 1,0 1,5 2,0 2,5

fluoranthene / pyrene

phenanthrene / anthracene

11.02.04

24.03.04

14.07.04

08.09.04

16.11.04

Petrogenic

Pyrolytic

outlet samples

Dov 4

D350

Fig. 60: Isomeric ratios of Phe/Anth vs. Flu/Pyr for all sampling dates.

For a further classification of the harbour samples a principal component analysis was performed

including all samples taken inside the ports of Dover and Calais and from the inlet of the seawater

scrubber. The results are shown in Table 74 and Fig. 61. Both eigenvectors together make up 72.4 %

of the total variance within the samples. For eigenvector 1 the values are all within the same order of

magnitude and therefore the samples are separated according to their distribution along the x-axis.

The November and the March samples all have positive x-value while the September and July
9 Results and discussion of the toxicity and accumulation tests

98

samples are all located on the left part of the diagram. These samples also show only a low variability

in eigenvector 2. They are all situated in a range of ± 1, whereas the March samples show negative

and the November samples positive y-values. From Table 74 it can be seen that eigenvector 2 is

positive especially for chrysene, benz[a]anthracene and benzo[b]fluoranthene plus

benzo[k]fluoranthene while it is negative for fluorene, phenanthrene, dibenz[a,h]anthracene,

benzo[ghi]perylene and indeno(1,2,3,c,d)pyrene. The lower the y-value for the specific sample is the

more the samples contains of the latter compounds and the higher the y-value the more the more they

contain of the first group of compounds. Therefore the samples taken in November contained more

chrysene and benz[a]anthracene whereas the samples taken in March contained more phenanthrene

and more high molecular weight compounds. As in March the heating period was still going on the

water was enriched in high molecular weight PAHs whereas in November the heating period just

started and therefore the pyrolytic influence was not as strong.

Fig. 61: Results of the PCA of all harbour samples taken in February (F), March (M), July (J), November (N)

and September (S)

Table 74: Feature vector for the PCA of all harbour samples taken in February, March, July, November and

September

52.4 %

(14.0)

20.0 %

(14.0)

acenaphthylene 0.28 0.14

acenaphthene 0.20 0.18
9 Results and discussion of the toxicity and accumulation tests

99

fluorene 0.27 -0.26

phenanthrene 0.21 -0.38

anthracene 0.30 0.03

fluoranthene 0.32 -0.05

pyrene 0.31 0.02

benz[a]anthracene 0.27 0.36

chrysene 0.29 0.32

benzo[b]fluoranthene +

benzo[k]fluoranthene 0.31 0.28

benzo[a]pyrene 0.33 0.06

dibenz[a,h]anthracene 0.15 -0.38

benzo[ghi]perylene 0.23 -0.36

indeno(1,2,3,c,d)pyrene 0.21 -0.38
9 Results and discussion of the toxicity and accumulation tests

100

8.6.4 Plankton samples

In March all samples with the exception of point Cal 3 (Calais: Quai de la Loire) were dominated by

diatoms. Most of them were single cells, but colonies were also observed. The sample from point

Cal 3 was dominated centric diatoms (Coscinodiscus sp.). During these sampling the samples were

only analysed qualitatively. During the sampling in July, September and November plankton cells were

counted quantitatively and concentrations were calculated as cells per mL. The results are shown in

Table 75.

Table 75: Results of plankton cell counting. Concentrations are given in cells per mL.

July July July July Sept. Sept. Sept. Sept. Nov. Nov. Nov. Nov.

C 5 C700 D 5 D700 C 5 C700 D 5 D700 C 5 C700 D 5 D700

water volume

[mL] 2900 2880 2595 2950 3390 3440 3290 3390 5000 4950 4370 4550

concentrated

volume [mL] 71 58 63 53 51 59 55 56 50 50 50 47

examined

volume [mL] 5 5 5 5 5 1 5 5 1,0 1 1 1

examined

fields 30 30 30 30 25 30 30 30 50 40 50 50

Amphora 8

Anomoneoneis 0 1 4

Biddulphia 3 5 1 8 8 1 3 1 1

Chaetocerus 3 7 10

Coscinodiscus 0 1 1 3 6 30 1 13 22 5 5

Ditylum 1 1 1 2 2

Eucampia 3 63 10 18

Gymnodiunium 1 4

Gyrodinium 2

Lauderia 16 62

Melosira 5 6 38 58 79 20 31

Metromonas 1

Navicula 1 3 1 2 2 1

Nitzschia 12 10 8 6 53 165 3 7 13 19

Olotrychales 50

Peridium 1

Pleurosigma 1 2 1 1 3 2 1

Porosira 1

Rhaphoneis 2 12 16 1 1 2 2

Rhizosolenia 2 4 3 1 6 3 1 25 69 1 1

Schroederella 5

Scenedesmus 8

Skeletonema 5

Stauroneis 1 1

Tetraedron 19 3

Tetraselmis 1

Thallasionema 13 5 14 2 15

Thallasiosira 6 1 4 5 1

Triceratium 1 5 1

Ulothrix 32 25 9 50

Calanoid 1 1 1

Polychaeten

Larve 1

Sum 34 25 14 27 136 398 20 13 247 316 30 59
9 Results and discussion of the toxicity and accumulation tests

101

The highest cell contents were determined for sample C 700 taken in September, but also for the

samples taken at points C 5 and C 700 in November. The samples taken in Calais contained more

cells than those taken in Dover. This may be the result of the higher nutrient concentrations measured

inside the port of Calais. Because of its enclosed architecture, this harbour becomes more easily

eutrophicated and therefore more plankton can potentially grow. In all samples diatoms were

dominating. The species observed the most often was Nitzschia spec. Zooplanktan like copepods

were only detected rarely.

As no plankton data from the past are available for the ports it cannot be said whether the observed

plankton contents were higher or lower than in the past. Even when the concentrations were different

from those in the years before a direct influence of the seawater scrubber cannot be assumed a priori

as the variability can also be due to natural reasons like weather, nutrient availability and predation.

The potential effect of the SWS can, however, be theoretically estimated. The samples taken in July,

September and November contained more dissolved inorganic nitrogen (DIN) in the outlet water than

the inlet water (Table 76). The greatest difference was observed for the sample taken in Dover in

November. Marine organic material of phytoplankton origin has a specific ratio of different elements.

This is termed the Redfield ratio and describes the (C, N, P, O, H)-composition as C106H263O110N16P1.

It can be assumed that C, H, O and P are not production limiting as C, N, O and H are ubiquitous and

P was found in all samples in sufficiently high concentrations. Thus, the phytoplankton growth only

depends on the concentrations of inorganic N-compounds.

Nevertheles, the calculations presented in the following must remain highly speculative as e.g. no data

on overall water exchange rates are available. In addition, the volume of the water body into which the

cooling water disperses during one stay in the port is not known. Similarly the short-term variability of

nutrients over the investigation period is unknown as is the variability in light.

One mole of a Redfield molecule weighs 3550 g and contains 224 g N. One mole N weighs 14 g.

Taking the highest DIN difference from Table 76 and assuming that all DIN added from the SWS is

converted to biomass, than 9.59 μmol L-1 would produce 2.13 mg biomass L-1. Due to the large in-port

and seasonal variations it is difficult to relate this value to actual ambient DIN values. Taking 10 μmol

L

-1

as low and 60 μmol L-1as high ambient concentrations then from these 2.2 and 13.3

mg biomass L

-1

, respectively, could be produced.

This calculation does, however, not take into account duration of input or mixing processes. During

one hour the seawater scrubber/cooling system produces 70 t of outlet water. Normally the „Pride of

Kent“ stays 45 minutes inside the harbour and therefore approximately 52.5 m3 or 525,000 L effluent

pass the cooling system. The additional DIN from the SWS/cooling system would thus produce 1.12

kg planktonic biomass during each visit. With five vists of the “Pride of Kent” per day this would a total

of 5.59 kg additional biomass/d.

Assuming that the volume affected by the discharge of 52.5 m3 SWS/cooling water is 6,000 m3 (area

20 * 50 m area to a depth of 6 m), then this relates to a volume dilution of 114. At the same time, in the

6000 m3 5.04 kg biomass could be produced from ambient 10 μmol DIN L-1. A dilution of the 1.12 kg
9 Results and discussion of the toxicity and accumulation tests

102

biomass produced from the excess DIN added (see above) by a factor 114 gives 9.77 * 10-3kg. Thus

even at the lowest ambient DIN concentrations an effect of the SWS nitrogen input is negligible.

The port of Dover has a total water volume of 2.538 km3.

Table 76: DIN differences between inlet and outlet samples taken in Dover, Calais and the Channel.

[μmol L-1] Jul. Sep. Nov.

Dover 5,82 5,40 9,59

Channel 1,50 -0,36 3,45

Calais 3,79 0,91 5,48

8.7 Results of mussel analysis

During the last sampling (November) mussels were taken from the quay wall at point C0. These

mussels were analysed for to their PAH contamination to have the possibility to compare the results of

the accumulation test. Also there is more literature available that deals with PAH in mussels than with

seawater contents. The results of the analyses are presented in Table 77 and are arranged according

to mussel size. It can be seen that the highest total concentration (all 16 EPA PAHs without

naphthalene) was determined in the largest size class (40-50 mm). In this class the dominating

compounds were phenanthrene, acenaphthylene, fluoranthene and pyrene. Within the medium size

class (30-40 mm) the major compounds were fluoranthene, chrysene and benz[a]anthracene. In the

smallest size class (20-30 mm) the same order was observed. Dibenz[a,h]anthracene and

indeno(1,2,3,c,d)pyrene were not detected. The differences in the PAH concentrations might have two

reasons. The larger the mussels are, the older they are. These mussels have lived for a longer time in

contaminated water and therefore had a longer time to accumulate contaminants. Another reason

might be the metabolic rates of the mussels. As these organisms were taken from the littoral (zone

influenced from tides) they are not as large as mussels taken from the sublittoral. The mussels in the

size class 40-50 mm are therefore relatively old and the older and the bigger they are, the more

energy is needed for metabolic processes and the less energy can be used for gamete production. As

this production is the major indirect process for the mussel to reduce lipid-soluble pollutants the

pollutants become enriched in the older mussels.

Table 77: PAH concentrations [ng g- 1] measured in mussels taken from the quay walls at sampling point C0 and

Bio Concentration Factors (BCF).

size class [mm] 20-30 30-40 40-50 20-30 30-40 40-50

mean size [mm] 25.7 34.8 43.1 BCF BCF BCF

ATHY - 10 231 - 1.4 31.4

ATHE 5 8 43 0.4 0.6 3.4

FLRE 11 28 154 0.8 2.0 10.9

PHEN 50 58 343 2.0 2.4 14.0

ANTH 4 8 65 0.3 0.6 5.0

FLUA 83 89 178 8.4 9.0 17.9

PYR 58 65 173 11.7 13.1 34.8

BaA 60 70 110 6.9 8.1 12.7

CHRY 75 84 121 7.1 8.0 11.5

BbkF 23 25 33 - - -
9 Results and discussion of the toxicity and accumulation tests

103

BaP 14 15 36 - - -

DahA - - - - - -

BghiP 4 3 14 - - -

INDE - - 3 - - -

sum 389 462 1505 3.7 4.4 14.3

This increase can also be seen in the Bio Concentration Factors (BCFs, Table 77). BCFs are

calculated as the quotient of the concentration observed in the mussel and the concentration

measured in the water. If the BCF is 1 there is no bioaccumulation of the observed pollutant. If the

BCF is smaller than one, the organism uses regulatory processes to reduce its pollutant concentration.

Higher concentrations reflect that no such processes are available or that these processes work

inefficiently only. Mussels are organisms that have very few possibilities to reduce their pollutant

contents. That is why they are often used in monitoring studies. In Table 77 it can be seen that the

mussels of the size classes 20-30 mm and 30-40 mm show similar BCFs whereas the BCFs in the

bigger mussels are higher. This supports the explanations given before.

In the literature several biomonitoring studies employing mussels are available. In South Shetland

mussels Webster et al (1997) determined phenanthrene concentrations comparable to those

measured in Calais but Flua, Pyr, BaA and Chry concentrations one order of magnitude lower. In the

southern Baltic mussels contained total PAH amounts (ΣEPA) between 8.6 and 29.2 ng g-1(Potrykus

et al 2003). As these samples were taken at sites away from anthropogenic influence the mussels

have lower contamination levels whereas Stella et al. (2002) determined PAH concentrations in Italian

mussels comparable to those observed in the size classes 20-30 mm and 30- 40 mm.
9 Results and discussion of the toxicity and accumulation tests

104

8.8 Results of sediment analysis

Sediment samples were taken during the samplings in July, September and November. During all

samplings attempts were made to obtain samples from points C5, D5, C700 and D700. Due to

currents and due to the state of the bottom surface this was not always possible with the van Veen

grab. Therefore samples were obtained at the points shown in Table 78. The sediment samples were

taken to clarify whether the composition of the PAHs measured in the water samples at point C5 or D5

is identical with the PAH composition of the sediment. If so an increase in the PAH water

concentration might be the result of resuspended sediment, because sediments are generally higher

polluted than water samples. Another reason for taking the sediment samples was to check whether

the composition of the sediment taken at points C5 and D5 is the same as observed at point C700 and

D700. This could give information about the influence of the shipping activities on the sediment, i.e. is

the impact is higher at the positions where the ships are berthing or is the contaminated water

spreading over the whole harbour before the polluted particles settle down. In the latter case the

content and the composition should be similar at both points. If this is the case it can be expected that

the effluent water of the seawater scrubber gets highly diluted and the influence onto the harbour

would be smaller.

Table 78: PAH concentrations determined for sediment samples taken in July, September and November

date Jul. Jul. Nov. Jul. Sep. Nov. Jul. Sep. Nov. Sep.

point Cal 1 C 5 C 5 C 700 C 700 C 700 D 5 D 5 D 5 D 700

ATHY - - - - - - - - - -

ATHE 15 3 993 2 - 11 15 3 10 2

FLRE 21 7 790 3 7 11 18 6 11 6

PHEN 173 81 8805 20 20 60 102 34 61 38

ANTH 45 18 1177 6 2 15 36 8 20 7

FLUA 564 248 9763 46 16 104 182 114 209 186

PYR 378 170 6948 30 12 70 135 88 166 146

BaA 171 80 5487 25 8 56 107 54 104 73

CHRY 79 26 2562 11 4 22 36 23 40 30

BbkF 138 28 2676 26 6 52 92 28 63 37

BaP 180 42 4520 34 8 72 147 33 94 52

DahA 41 6 702 5 2 10 17 7 15 10

BghiP 123 20 2044 22 8 50 89 27 62 36

INDE 169 24 2272 29 4 55 96 29 69 35

Sum 2098 754 48737 259 97 588 1071 453 925 657

From Table 78 it can be seen that the sediment PAH contents measured at point C5 in November

were significantly higher than those measured at the remaining points. A reason for this cannot be

given. Perhaps the sample was contaminated with tar or oil. Taking a look at the remaining stations it

can be seen that at point Cal 1 higher concentrations were found than at the remaining points. This

sample was taken from the harbour wall at a point where there is no berthing activity and where the

currents are very slow. This allows fine particles to settle down. As fine particles have a greater
9 Results and discussion of the toxicity and accumulation tests

105

surface than coarse ones, more PAHs can adsorb to them. At point C 700 the total PAH load was

different during the three samplings, with highest contents measured in November and lowest

measured in September. This partially corresponds to the water contents which were also highest in

November. In Dover at point D5 the lowest overall concentration was also measured in September

and the highest in November. The September sample taken form the harbour entrance was higher

contaminated than the one taken at the berth. So far no clear trend is visible but it seems that in Dover

there is no difference between samples taken at the berth or at the port entrance, whereas in Calais

the berth samples seem to be higher contaminated. This would also underline the observations made

before. Dover with its relatively open structure and the faster water exchange allows pollutants to be

transported over a longer distance, whereas in Calais with its enclosed structure the PAHs mainly

remain close to the point where they were released.

From Table 79 it can be seen that the relative PAH compositions are comparable. Only the sample

taken in July at point C5 shows in relation to the other samples a higher pyrene and

benz[a]anthracene value.

Table 79: PAH composition of the sediment samples taken in Calais and Dover in July, September and November

in percent.

date Jul. Jul. Nov. Jul. Sep. Nov. Jul. Sep. Nov. Sep.

point Cal 1 C 5 C 5 C 700 C 700 C 700 D 5 D 5 D 5 D 700

ATHE 0 0 0 0 0 0 0 0 0 0

FLRE 1 0 2 1 0 2 1 1 1 0

PHEN 1 1 2 1 7 2 2 1 1 1

ANTH 8 11 18 8 21 10 10 8 7 6

FLUA 2 2 2 2 2 3 3 2 2 1

PYR 27 33 20 18 16 18 17 25 23 28

BaA 18 23 14 12 13 12 13 19 18 22

CHRY 8 11 11 10 9 10 10 12 11 11

BbkF 4 4 5 4 4 4 3 5 4 5

BaP 7 4 5 10 6 9 9 6 7 6

DahA 9 6 9 13 8 12 14 7 10 8

BghiP 2 1 1 2 2 2 2 2 2 1

INDE 6 3 4 8 8 9 8 6 7 5

Plotting the isomeric ratios of PHEN/ANTH against FLUA/PYR it can be seen that in all sediments with

exception of C700 the PAH composition indicates a pyrolytic origin. In contrary to the sediment, the

composition of the PAHs in the water samples often did not clearly indicate the source. This difference

might be the result of the faster degradation of PAHs originating from petrogenic sources (see

Introduction). Therefore mainly PAHs from pyrolytic processes enter the sediment.
9 Results and discussion of the toxicity and accumulation tests

106

0

2

4

6

8

10

12

0,0 0,5 1,0 1,5 2,0

fluoranthene/pyrene

p

h

e

n

a

nthre

n

e/a

nthra

c

e

n

e

petrogenic

pyrolytic

C700 (Nov.)

Fig. 62: Plot of isomeric phenanthrene/anthracene and fluoranthene/pyrene ratios of all sediment samples taken

in Dover and Calais in July, September and November.

To compare the sediment samples, the water samples and the mussel samples taken in Dover and

Calais a principal component analysis was performed. The results are shown in Table 80 and Fig. 63.

Eigenvector 1 was responsible for 47.6 % and eigenvector 2 for 18.2 % of the total variance.

Eigenvector 1 was mainly positive for the high molecular weight and negative for the low molecular

weight PAHs. Eigenvector 2 refers mainly to chrysene, benz[a]anthracene and the sum of

benz[b]fluoranthene and benz[b]fluoranthene. These compounds are partially soluble in water. The

PCA plot shows that all sediment samples had high values for eigenvector 1 and therefore they show

a higher content of high molecular weight PAHs. As this indicates a pyrolytic origin as observed in the

plot of the isomeric ratios it can be assumed that the sediment samples were mainly influenced from

atmospheric input. The samples of the small and medium sized mussels were taken close to stations

C5 and C0. The water samples taken in July are situated at the bottom of the graph whereas the

samples taken in November are situated at the top of the graph. This shows that the four and five ring

compounds make up a lower percentage of the total concentration in the July samples than in

November. In Fig. 63 it can also be seen that the water samples even those taken close to the “Pride

of Kent” do not show a PAH pattern similar to the sediment samples. This shows that the sediment

which was resuspended by the ship screws does not influence the water samples.
9 Results and discussion of the toxicity and accumulation tests

107

Fig. 63: Principal component analysis of the relative PAH concentrations (percentages) of the water, sediment

and mussel samples taken in Dover and Calais in July, September and November. First letter:

W=water sample, S=sediment sample, M=mussel sample (SMAL=small 20-30mm, MEDI=medium 30-

40mm, LARG=large 40-50 mm). Second letter: J=July, S=September, N=November. Last four letters:

sampling point.

Table 80: Feature vector for the PCA of the water, sediment and mussel samples taken in Dover and Calais in

July, September and November

compound EV1 EV2

ATHY -0.16 0.16

ATHE -0.30 -0.08

FLRE -0.34 -0.00

PHEN -0.30 -0.30

ANTH -0.11 0.25

FLUA 0.25 -0.13

PYR 0.12 -0.31

BaA 0.15 0.54

CHRY -0.10 0.55

BbkF 0.33 0.24

BaP 0.35 0.07

DahA 0.34 -0.13

BghiP 0.33 -0.13

INDE 0.33 -0.10

Soclo et al (2000) examined sediments in a French harbour (Cotonou). Here the total PAH content,

with a comparable PAH composition to that one analysed in this project, had a maximum value of

1411 ng g

-1

. Inside the harbours of Rotterdam and Amsterdam (The ) sediments were analysed by de

Boer et al. (2001). In this case the total contents of about 4000 ng g-1 were higher than in Calais.
9 Results and discussion of the toxicity and accumulation tests

108
9 Results and discussion of the toxicity and accumulation tests

109

9 Results and discussion of the toxicity and accumulation tests

9.1 Lumistox test

The results of the Lumistox test are shown in Fig. 64. For this experiment three independent inlet and

outlet samples were taken at points SCH1 and SCH2. All three samples were tested twice for their

overall toxicity. The pH values of the outlet and inlet samples are shown in Fig. 64. The inlet samples

all had a pH of 8.07. The basic luminescence measured at the beginning of the first test (pH 6.86) was

3478 that one of the second test (pH 7.02 and pH 6.84) was 4206. The figure shows the differences in

inhibition between inlet and outlet water. These determined against a 3 % NaCl solution control. Due

to the nutrients in the natural seawater which are missing in the NaCl solution also negative values for

the luminescence inhibition were determined. It can be seen that all results and also the results plus

the determined variance were below 20 % inhibition. As these values were obtained with undiluted

samples these results represent the highest values which can be expected. Therefore there is no

possibility to calculate the EC20 (effective concentration where 20 % luminescence inhibition is

observed) and the samples can be regarded as non-toxic. As the Lumistox test corresponds to

microbial toxicity it can be said that the effluent of the seawater scrubber has no determinable

negative effect on the microbial system of the harbours.

0

5

10

15

20

25

30

pH 6.86 pH 7.02 pH 6.84

in

hibitio

n

of lu

min

e

s

c

e

n

c

e [%]

Fig. 64: Results of Lumistox test. Shown are the differences between seawater scrubber inlet and outlet water

taken during the sampling in September. The pH shown was the pH of the outlet sample
9 Results and discussion of the toxicity and accumulation tests

110

9.2 Brine shrimp test

Table 81 and Table 82 show the results of the acute and the chronic toxicity determined with the brine

shrimp test. The results for the test performed with juvenile Artemia salina are shown in Table 81

those for the test with adults are shown in Table 82. The pH of the outlet water varied between 6.83

and 7.07, that of the inlet water between 8.12 and 8.15. The samples taken for the brine shrimp test

were independent from those taken for the Lumistox test. For the test with the juvenile Artemia

between 34 and 75 individuals and for the adult test 22 to 35 individuals were randomly chosen and

put in petri dishes. As can be seen no adult or juvenile Artemia salina died during the test, neither after

6 h nor after 24 h. Therefore no toxicity of the outlet water towards A. salina could be observed. As the

test was performed over a time span of 24 h also no chronic toxicity could be observed. A. salina is

regarded as key representative for plankton organisms. Therefore it can be stated that the seawater

scrubber effluent has no negative effects on plankton organisms.

Table 81: Results of the brine shrimp test performed with 24 h old juvenile Artemia salina

juveniles 30 min 6 h 24 h

pH alive dead alive dead alive dead

inlet Probe 1 8,13 34 0 34 0 34 0

inlet Probe 2 8,12 37 0 37 0 37 0

inlet Probe 3 8,15 62 0 62 0 62 0

outlet Probe 1 7,07 67 0 67 0 67 0

outlet Probe 2 6,87 75 0 75 0 75 0

outlet Probe 3 6,83 68 0 68 0 68 0

Table 82: Results of the brine shrimp test performed with 4 weeks old juvenile Artemia salina

adult 30 min 6 h 24 h

pH alive dead alive dead alive dead

inlet Probe 1 8,13 23 0 23 0 23 0

inlet Probe 2 8,12 22 0 22 0 22 0

inlet Probe 3 8,15 27 0 27 0 27 0

outlet Probe 1 7,07 27 0 27 0 27 0

outlet Probe 2 6,87 24 0 24 0 24 0

outlet Probe 3 6,83 35 0 35 0 35 0
9 Results and discussion of the toxicity and accumulation tests

111

9.3 Accumulation test

9.3.1 Mussel analyses: size, weight, condition index, fat content

In this chapter the results of the combined accumulation and toxicity test, performed with the mussel

Mytilus edulis, are presented. In Fig. 65 the proportions of the dry tissue, the shell weight and the

water content are shown. The sizes of the single mussels are shown in Table 83. “Control 2”

contained in comparison to “control 5” and “control 8” more individuals greater than 60 mm whereas in

“control 5” and “control 8” there were more individuals smaller than 50 mm. The water content and the

dry tissue weight of the latter two are with 26.9 %, 27.2 % and 4.5 %, 5.1%, respectively, higher than

in “control 2” with 23.7 % water content and 3.2 % dry tissue weight. A similar behaviour can be

observed for the tests “part 01”, “part 04” and “part 07”. In test “part 01” 11 mussels were greater than

or equal 60 mm, in “part 04” only 4 and in “part 07” none of the mussels was greater than 60 mm. For

the tests “diss 03”, “diss 06” and “diss 09” the size distributions were similar to those of the particulate

trial and the controls, with relatively more long mussels in trial “diss 03” and fewer in trial “diss 06” and

“diss 09”. In this case the observed relations of water, shell and dry tissue weight are only reflected in

the water content. On the right side of Fig. 65 the mean percentages of the water content, the dry

tissue and the shell weight of all size classes, are given. It can be seen that increasing mussel size is

paralleled by an increase in shell weight and a decrease in relative water content.
9 Results and discussion of the toxicity and accumulation tests

112

Table 83: length [mm] of all mussels employed for the accumulation test. The colours separate the table in the

main classes used for the PAH determination. The first class smaller than 50 mm and the second class

between 50 mm and 60 mm

control external

basin part 01 cont 02 diss 03 part 04 cont 05 diss 06 part 07 cont 08 diss 09

15.2 36.2 36.1 31.1 40.2 41.8 35.6 40.1 38.8 43.4

15.8 38.4 36.1 36.8 41.7 44.8 42.5 42.9 41.4 43.7

22.4 39.4 36.7 38.9 42.2 45 43.3 44 41.8 46.7

24.7 40.1 38.2 40.8 43.2 45.4 43.4 44 42.7 49.1

28.2 41 39.3 43.8 43.8 46 43.9 44.1 43.7 49.2

33 44.8 47.8 46.9 43.9 46.4 44.1 45.6 45.5 49.9

33.3 45.8 47.8 49.2 44.7 46.7 44.5 45.6 46.1 50.3

39.1 51.5 49.5 50.4 45.7 47.2 46.1 46.1 46.4 50.9

45.3 52 53.2 52.9 46.1 47.4 46.5 46.3 47.2 52.1

45.3 53.5 53.4 53.3 46.3 47.8 47.3 47.4 47.6 52.8

46.4 54.1 54.9 53.9 47.2 47.9 47.4 47.8 47.8 53

47.1 54.5 55.1 54.1 48.8 48.3 48.2 49.5 48.7 53.2

47.6 55.8 56 55.9 50.1 48.4 48.2 49.6 48.8 53.3

48.2 56.5 56.5 57.1 50.3 48.6 48.6 49.6 49 54.2

48.4 57.5 56.7 58 50.8 49.2 49 50.2 49.7 54.4

49.8 57.6 57.2 58.5 51.4 49.2 49.2 51.2 49.7 55

50 59.8 58.2 59.2 51.6 49.2 49.2 51.3 49.8 55.3

50.2 59.9 58.5 61.1 52.4 50 49.9 51.7 50.4 56.3

50.3 60 59 61.3 52.7 50.7 50.7 52.1 50.7 56.7

50.8 60.1 59.1 61.3 55.2 51.5 51 52.3 51.8 56.8

51.6 61.2 59.2 61.5 55.2 52.1 51.5 52.5 52.3 57

52.6 61.2 59.9 61.7 55.7 52.6 51.6 52.8 52.8 57.7

52.6 62 60.1 62.1 55.8 53.7 51.7 53.4 53.3 58.7

52.6 63.5 61.5 62.8 59.7 54.5 52.5 53.4 53.8 59.1

53.2 66 62 63 59.8 55.8 52.7 53.5 55.1 59.4

53.6 66.5 65.8 63.8 59.9 55.9 53.3 50 55.8 59.9

53.8 67.5 66.8 63.9 60.5 56.1 53.8 54.9 56.6 60.6

54.7 69.7 67.7 64.3 62.5 56.2 54.8 57.1 56.9 61

56.3 70.2 69.6 63 59.4 56.3 59 60.8 62.2

56.5 68.9 70 56.7 62.8

56.6

56.8

57.7

58.4

62.8

64

70.7

0%

10%

20%

30%

40%

50%

60%

70%

80%

90%

100%

17,0 25,6 35,7 45,8 54,5 63,3

mean length [mm]

percentage

water

dry tissue

shell

Fig. 65: Mean percentages of shell, dry and wet tissue weight for all mussels used in the accumulation test. Left:

percentages for each test, right: mean for all tests.
9 Results and discussion of the toxicity and accumulation tests

113

0

10

20

30

40

50

60

70

0 50 100

length [mm]

whole wet weight [g]

0

10

20

30

40

50

60

70

0 50 100

length [mm]

shell weight [g]

Fig. 66: Correlation plots. Left: whole wet weight against length. Right: shell weight against length. In both cases

the red line shows the nonlinear model and the black lines the 95 % confidence interval

0

2

4

6

8

10

12

0 50 100

length [mm]

tissue wet weight [g]

0

0,5

1

1,5

2

2,5

3

3,5

0 50 100

length [mm]

dry tissue [g]

0

0,2

0,4

0,6

0,8

1

1,2

1,4

1,6

1,8

0 5 10 15

wet tissue [mm]

dry tissue [g]

Fig. 67: Correlation plots: Left: wet tissue weight against length. Middle: dry tissue weight against length. Right:

dry tissue weight against wet tissue weight. In both cases the red line shows the nonlinear model and

the black lines the 95 % confidence interval

In Fig. 66 and Fig. 67 the correlation plots of total wet weight, shell weight, dry tissue weight, and wet

tissue weight against shell length and dry tissue against wet tissue weight are shown. The used model

functions, their parameters, the 95 % confidence intervals of the parameters and the correlation

coefficient R2 are shown in Table 84. It can be seen that the dependencies between length and shell

weight, wet weight and total weight show good correlations, whereas the scatter of the dry tissue

weight is much higher.

Table 84: Results of linear and nonlinear regression

dependent variable weight

total [g]

weight

shell [g]

weight

wet tissue [g]

weight

dry tissue [g]

weight

dry tissue [g]

independent variable length [mm] length [mm] length [mm] length [mm] weight

dry tissue [g]

function b

y ax

b

y a x

b

y ax

b

y ax y a x

Parameter a 6.732E-05 1.206E-05 2.332E-04 2.564E-04 0.1488

min 95 % 4.700E-05 7.115E-07 1.200E-04 1.490E-05 0.1450

max 95 % 8.800E-05 2.341E-05 3.465E-04 4.980E-04 0.1530

Parameter b 3.062 3.363 2.412 1.910

min 95 % 2.886 3.131 2.291 1.675

max 95 % 3.238 3.595 2.533 2.145

R2 0.826 0.767 0.874 0.551 0.753
9 Results and discussion of the toxicity and accumulation tests

114

9.3.2 Mussel analyses: PAH content, accumulation, mortality

In Fig. 68 the results of the standardized mussel tissue extraction and the R2 values for the calibration

lines are shown. The error bars for the mussel tissue are the errors given by the manufacturer. The

error bars of the determined values are calculated by aid of the GC-MS accuracy according to the

values given in Table 17 (25 μg l-1). It can be seen that all values were determined within the given

error range and accuracy with the exception of fluorene. In this case the determined concentration

was 11.3 ± 0.2 ng g-1 whereas the given value was 10.2 ± 0.4 ng g-1. It has to be considered, that only

the accuracy of the GC-MS measurement was stated and not the accuracy of the whole method,

which would be somewhat higher. For the mussel extraction the accuracy of the method was not

determined like for the extraction of the water samples, because a standardised reference material as

control was available.

All determined PAH concentrations are shown in Table 85. The compounds added permanently during

the test are indicated in italics. The contents of these compounds are also visualised in Fig. 69. The

“background” concentrations of those compounds that were not added during the test are shown in

Fig. 70. These contents can be regarded as negative control. In the latter graph it can be seen that

acenaphthylene, acenaphthene and dibenz[a,h]anthracene are equally concentrated in all mussels,

benzo[a]pyrene, benzo[ghi]perylene and indeno(1,2,3,c,d)pyrene are slightly increased and fluorene,

benz[a]anthracene and benzo[b]fluoranthene plus benzo[k]fluoranthene are nearly doubled in the

controls from the external basin. It can also be seen that within the external controls the PAH contents

are slightly increased in those mussels greater than 50 mm. For the mussels used in the test an

inverse distribution was observed. In most cases the concentration is lower in the mussels smaller

than 50 mm. Fig. 69 also shows a quite similar distribution of PAHs in the controls from the external

basin and from the controls in the test. The PAH concentrations of those compounds added

permanently are increased clearly in the mussels from the particulate and the dissolved test in

comparison to the controls and those mussels from the external basin. Comparing the results from the

dissolved and the particulate test there is no difference recognizable. To check this observation

statistically, a t-test was performed. The test was performed in two different ways: I) to check whether

there is a significant difference between the two size classes and II) to check whether there is a

significant difference between the dissolved and the particulate tests. The used test was the t-test for

testing the equality of the variances of two dependent random samples and was calculated according

to

1

2

2

2  2

2

2

2

1

4 1

2

s s R

n

t s s

  

   

where s1 and s2 are the standard deviations of two samples, n is the number of compared rows and R2

is the correlation coefficient. The reference value can be taken from a significance chart (degrees of

freedom = 8, α= 5 %; t (8/0.05) = 2.31). In both cases the calculated t-value was below 2.31, therefore it

can be said that the observed differences in variability are coincidental. A measure for the correlation

can be given by the R2 which is 0.9763 for the comparison of the PAH concentrations in the mussels
9 Results and discussion of the toxicity and accumulation tests

115

smaller and greater than 50 mm, and 0.9877 for the comparison of the PAH concentrations in the

mussels from the dissolved and the particulate test. This shows a high correlation between the results.

0

10

20

30

40

50

60

70

80

90

FLRE

PHENFLU

A

PY

R

BaA

BbkF

BaP

DahA

BghiP

IN

DE

PAH compound

concentration [ng g

-1

]

determined

concentration

concentration in

standard mussel tissue

compound steepness section R2

naphthalene 0,0046 -0,0045 0,9998

acenaphthylene 0,0035 -0,0034 0,9988

acenaphthene 0,0024 -0,0027 0,9987

acenaphthene-D10 0,0025 -0,0027 0,9995

fluoren 0,0027 -0,0027 0,9981

phenanthrene-D10 0,0041 -0,0043 0,9985

phenanthrene 0,0046 0,0000 0,9974

anthracene 0,0033 -0,0047 0,9947

fluoranthene 0,0043 0,0008 0,9905

pyrene 0,0043 0,0000 0,9895

benz[a]anthracene 0,0044 0,0000 0,9990

chrysene-D12 0,0044 0,0000 0,9979

chrysene 0,0044 0,0197 0,9962

benzo[b]fluoranthene +

benzo[k]fluoranthene 0,0067 -0,0047 0,9988

benzo[a]pyrene 0,0025 -0,0028 0,9987

perylen-D12 0,0026 -0,0042 0,9978

dibenz[a,h]anthracene 0,0019 0,0000 0,9938

benzo[ghi]perylene 0,0030 -0,0037 0,9978

indeno(1,2,3,c,d)pyrene 0,0024 -0,0029 0,9963

Fig. 68: Left: Comparison of PAH concentrations determined in the standard mussel tissue and the original

concentrations. Right: correlation coefficients, steepness and section of the external reference lines

Table 85: PAH concentrations [ng g-1] determined for the mussels in the accumulation test. Compounds indicated

in italics are those added daily. ext are the mussels taken from the external basin, 02, 05 and 08 are

the controls, 03, 06 and 09 are the mussels from the dissolved test and 01, 04 and 07 are the mussels

from the particulate test.

test length ATHY ATHE FLRE PHEN ANTH FLUA PYR BaA CHRY BbkF BaP DahA BghiP INDE

ext < 50 3 5 31 92 23 218 152 17 7 16 9 1 10 9

ext > 50 3 4 27 106 32 223 159 20 10 19 10 3 11 10

02 < 50 3 4 8 45 16 119 223 7 1 10 8 0 10 9

02 > 50 3 4 8 39 12 69 171 9 1 10 7 2 8 7

05 < 50 2 4 24 65 16 99 195 6 0 10 6 0 9 6

05 > 50 3 4 26 84 27 124 219 7 0 7 6 1 7 5

08 < 50 3 4 7 46 16 84 160 5 0 11 8 0 8 7

08 > 50 3 5 11 61 21 116 226 5 0 8 6 0 8 6

03 < 50 3 4 6 612 460 1218 851 6 219 9 7 0 8 7

03 > 50 3 4 7 594 434 1171 846 6 199 10 8 1 10 8

06 < 50 3 3 19 786 619 1759 1186 6 299 8 6 1 7 5

06 > 50 3 4 9 833 286 1729 1115 7 214 5 4 0 6 4

09 < 50 3 4 16 267 162 641 484 11 214 15 10 4 13 10

09 > 50 3 3 6 271 147 782 587 7 207 11 6 0 8 6

01 < 50 3 4 7 430 297 1141 818 9 254 10 7 0 8 8

01 > 50 3 4 7 393 231 1039 764 8 214 10 7 0 8 7

04 < 50 3 4 7 591 308 1205 861 6 270 12 7 0 9 7

04 > 50 2 4 29 709 437 1168 832 7 162 10 7 2 9 7

07 < 50 3 3 19 478 317 985 710 5 205 10 7 0 8 7

07 > 50 3 3 6 665 247 1354 916 6 211 7 5 0 7 5
9 Results and discussion of the toxicity and accumulation tests

116

0

200

400

600

800

1000

1200

1400

P

H

E

N

A

NT

H

F

L

U

A

P

Y

R

C

H

R

Y

compound

c

o

n

c

e

ntratio

n [n

g

g

-1

]

ext < 50

ext > 50

cont < 50

cont > 50

diss < 50

diss > 50

part < 50

part > 50

Fig. 69: Mean concentrations of the added PAHs, determined for the different accumulation tests.

0

5

10

15

20

25

30

35

AT

H

Y

A

T

H

E

F

L

R

E

B

a

A

B

b

k

F

B

a

P

D

a

h

A

B

g

hiP

IN

D

E

compound

c

o

n

c

e

ntratio

n [n

g

g

-1

]

ext < 50

ext > 50

cont < 50

cont > 50

diss < 50

diss > 50

part < 50

part > 50

Fig. 70: Mean concentrations of the PAHs which were not added during the test, determined for the different

accumulation tests.

Table 86: expected PAH concentrations in the mussels if all added PAHs would have been accumulated
9 Results and discussion of the toxicity and accumulation tests

117

PHEN ANTH FLUA PYR CHRY

particulate 01 <50 47926 20036 18668 8141 1399

>50 47926 20036 18668 8141 1399

particulate 04 <50 47652 19921 18561 8095 1391

>50 47652 19921 18561 8095 1391

particulate 07 <50 47199 19731 18385 8018 1378

>50 47199 19731 18385 8018 1378

diss 03 <50 35501 14841 13828 6031 1037

>50 35501 14841 13828 6031 1037

diss 06 <50 43475 18175 16934 7385 1269

>50 43475 18175 16934 7385 1269

diss 09 <50 53405 22326 20802 9072 1559

>50 53405 22326 20802 9072 1559

Table 87: Percentage of accumulated PAHs, calculated as quotient of expected and observed PAH contents in

the mussels.

PHEN ANTH FLUA PYR CHRY

particulate 01 <50 0.9 1.5 6.1 10.0 18.2

>50 0.8 1.2 5.6 9.4 15.3

particulate 04 <50 1.2 1.5 6.5 10.6 19.4

>50 1.5 2.2 6.3 10.3 11.6

particulate 07 <50 1.0 1.6 5.4 8.9 14.9

>50 1.4 1.3 7.4 11.4 15.3

diss 03 <50 1.7 3.1 8.8 14.1 21.1

>50 1.7 2.9 8.5 14.0 19.2

diss 06 <50 1.9 1.6 10.2 15.1 16.8

>50 1.9 1.6 10.2 15.1 16.8

diss 09 <50 0.5 0.7 3.8 6.5 13.2

>50 0.5 0.7 3.8 6.5 13.2

During the whole test (30 days) the mussels in the dissolved and particulate trials were fed with the

following absolute PAH amounts:

 phenanthrene = 640475 ng

 anthracene = 267750 ng

 fluoranthene = 249475 ng

 pyrene = 108800 ng

 chrysene = 18700 ng

Y

If the mussels would have accumulated the total amount of the added PAHs the concentration shown in Table 86

would have to be expected. The values were calculated as the quotients of the total amount of the PAH

compounds and the sum of the dry tissue weight of all mussels used in the concerning test. Comparing

these values with the actually determined compound concentrations, the accumulation rate can be

calculated, as quotient of the observed concentration and the expected concentration in percent. The

results are shown in

Table 87. It can be seen that from the added phenanthrene 0.5 % to 1.9 %, the anthracene 0.7 % to

3.1 %, fluoranthene 3.8 % to 10.2 %, the pyrene 6.5 % to 10.6 % and the chrysene 11.6 % to 21.1 %

were accumulated.
9 Results and discussion of the toxicity and accumulation tests

118

control - phenanthrene

0

50

100

150

200

250

300

begin end

concentration [ng l-1]

dissolved - phenanthrene

0

50

100

150

200

250

300

begin end

concentration [ng l-1]

particulate - phenanthrene

0

50

100

150

200

250

300

begin end

concentration [ng l-1]

control - anthracene

0

50

100

150

200

250

300

350

400

450

begin end

concentration [ng l-1]

2.7 2.2

dissolved - anthracene

0

50

100

150

200

250

300

350

400

450

begin end

concentration [ng l-1]

11.4 22.5

particulate - anthracene

0

50

100

150

200

250

300

350

400

450

begin end

concentration [ng l-1]

9.6

control - fluoranthene

0

200

400

600

800

1000

begin end

concentration [ng l-1]

dissolved - fluoranthene

0

200

400

600

800

1000

begin end

concentration [ng l-1]

particulatel - fluoranthene

0

200

400

600

800

1000

begin end

concentration [ng l-1]

control - pyrene

0

200

400

600

800

1000

1200

begin end

concentration [ng l-1]

dissolved - pyrene

0

200

400

600

800

1000

1200

begin end

concentration [ng l-1]

particulate - pyrene

0

200

400

600

800

1000

1200

begin end

concentration [ng l-1]

control - chrysene

0

100

200

300

400

500

600

begin end

concentration [ng l-1]

dissolved - chrysene

0

100

200

300

400

500

600

begin end

concentration [ng l-1]

particulate - chrysene

0

100

200

300

400

500

600

begin end

concentration [ng l-1]

particulate

dissol

Fig. 71: Concentrations of phenanthrene, anthracene, fluoranthene, pyrene and chrysene [ng l-1] measured in the

aquaria of the controls, the particulate and the dissolved test one hour after a water exchange and right

before the following water exchange (3 days). Contents are separated into dissolved and particulate

fractions.
9 Results and discussion of the toxicity and accumulation tests

119

During the accumulation test the contents of the added PAH compounds phenanthrene, anthracene,

fluoranthene, pyrene and chrysene in the water of the aquarium were determined half an hour after a

water exchange and directly before the following water exchange after three days. The results are

shown in Fig. 71. The pH, salinity and the water temperature are shown in Table 88. Within the water

samples of the controls the phenanthrene and anthracene contents were equally low in the beginning

and at the end of the three day period whereas the pyrene, chrysene and fluoranthene increased

during that time. The same was observed in the samples from the aquaria of the dissolved test. Also

the contents were quite similar. In contrary to the increase of dissolved pyrene, chrysene, and

fluoranthene, the contents observed in the particulate test showed another distribution: the

phenanthrene content in the beginning was 259 ng l-1and in the end 15 ng l-1, the anthracene contents

were 427 ng l-1and 10 ng l-1the fluoranthene contents 727 ng l

-1

and 174 ng l-1, the pyrene contetnts

609 ng l-1and 203 ng l

-1

and the chrysene contents 448 ng l-1and 400 ng l-1, respectively. The

observed differences between the PAH contents of the particulate and the dissolved tests and the

increase of fluoranthene cannot be explained. One reason might be that the water of the aquarium

was not mixed thoroughly enough before taking the samples. This was difficult as stirring was not

possible because of the mussels in the aquarium. This would also explain why mainly dissolved PAHs

were determined whereas the particulate PAH fraction was low. The reason for the latter aspect could

also be that the samples were not taken directly after the PAH addition, but about half an hour later.

As blue mussels are able to filter about 1 l seawater per hour and 30 mussels were inside the

aquarium half an hour would be sufficient to filter the whole water volume of 17 l.

Table 88: pH, salinity and temperature determined in the aquariums during the test

pH Sal Temp [°C]

1 7.91 31.5 18.5

2 8.06 31.5 18.5

3 7.83 31.5 18.5

4 7.92 31.5 18.3

5 8.01 31.5 18.5

6 7.94 31.5 18.4

7 7.94 31.5 18.5

8 8.02 31.5 18.5

9 7.93 31.5 18.5

From Table 77 where the PAH concentrations determined for the mussels taken in Calais are shown.

It can be seen that the total amount of the mussels smaller than 40 mm in Calais is about the same as

those concentrations observed in the external basin and the controls, but the composition is different.

The mussels taken in Calais contain higher concentrations of phenanthrene and fluoranthene whereas

the mussel taken from the Jade Bay show higher concentrations of high molecular weight PAHs. Due

to their life history the mussels are not directly comparable concerning to their PAH concentrations.

The mussels in Calais were growing inside an enclosed harbour with high shipping activities. The PAH

composition of this harbour has been discussed before. The mussels taken from the Jade Bay were

mainly influenced from PAHs reaching them through the atmosphere. Therefore they contain mainly

high molecular weight PAHs.
9 Results and discussion of the toxicity and accumulation tests

120

Although the PAH compositions of the mussels cannot be compared directly, the accumulation rates will be

similar. The „Pride of Kent“ discharges about 52.5 m3 of mixed colling water/seawater scrubber

effluents during each visit (see 8.6.4 on page 100) in the ports of Dover and Calais, 5 times a day.

During one day 252.5 m3 of outlet water would be introduced into each port. Taking the mean PAH

differences of Table 73 this would sum up to a total PAH introduction and to a concentration increase

of the values shown in Table 89. As only the water volume of the port of Dover was available this

calculation was exemplary carroied out with this volume (2.538 km2). In this calculation losses due to

biological or chemical degradation (UV, micro organisms, translocation processes) and physical

processes (currents, adsorption and settling) are not included. Assuming that one mussel filters about

1 l seawater per hour and using the dry weight calculated according to Table 84 and a mean

accumulation rate from

Table 87 then the contents given in Table 90 would be the result after one year of accumulation for

one mussel. As inside a harbour there is not only one mussel and as the accumulated PAHs would

have to be subtracted from the available PAHs in the water body the real value makes up only a very

small fraction of the values in shown in Table 90.

Table 89: Total PAH amounts [mg] that will be theoretically introduced during one day into the ports of Dover and

Calais and theoretical concentration increase [pg l-1]

total amount [mg]

released in 1 day

concentration increase

[pg l-1] per day

ATHY 1 1

ATHE 6 3

FLRE 34 13

PHEN 296 117

ANTH 7 3

FLUA 45 18

PYR 103 41

BaA 66 26

CHRY 95 37

BbkF 15 6

BaP 33 13

DahA 5 2

BghiP 11 4

INDE 4 2

Table 90: Mean accumulation rate, total accumulation per day and year and resulting contamination after one

year for a 20 mm mussel.

mean acc

rate [%]

accumulation

per day [pg]

accumulation

per year [ng]

concentration in a 20 mm

mussel after 1 year [ng g-1]

1.3 35 12.8 163

1.7 1 0.4 5

6.9 29 10.6 136

11.0 107 39.1 499

16.3 102 37.2 475

Mortality

This test was also performed as a toxicity test. Therefore the mortality of the mussels was also

observed. During the whole test 4 of the 270 employed mussels died. Two mussels of the aquarium

“diss 3” after three and after 21 days, one of test “part 7” after seven days and one in aquarium “part

1” after 10 days. As the mussels of the particulate and the dissolved test were equally contaminated

with PAHs this mortality can be assumed for all mussels in the tests. Four mussels of the 180 mussels
9 Results and discussion of the toxicity and accumulation tests

121

died, this gives a mortality of 2.2 %. When the tests are considered separately than the mortalities in

the particulate test would be 3.3 %, 0 % and 3.3 %. For the dissolved tests the result would be 6.6 %,

0 % and 0 %. These values are within the natural variability. Therefore it can be stated that the PAHs

had no toxic effect on the mussels. As this test was performed over a time span of 30 days it can also

be stated that the PAH composition of the effluent has no chronic toxic effect on the mussels.

To check the constitution of the mussels, the fat and the shell index (SI) were determined. The results

are given in Table 91. The higher the fat content and the higher the SI is, the better the conditions of

the mussels were. It can be seen that the SI for the mussels taken in Calais was about double the SI

determined for the mussels used in the test. The reason for this might be that the mussels for the test

were stored in the external basin where no additional food than the seston and plankton collected

together with the mussels was available. The mussels of Calais were collected directly inside the

harbour. Harbours are characterized by eutrophication and high bioproduction and therefore enough

food for the mussels was available.

Low fat and SI values were only determined for “part 1”. In this test the mean shell length was

55.4 mm whereas in the remaining particulate tests the shell length was shorter. Bigger mussels need

more food and therefore they faster suffer starvation. This could also be a reason why some of the

mussels died during the test.

Table 91: Mean shell index and fat content determined for the mussels of the accumulation test and for the

mussels taken in Calais

test SI fat content [%]

Calais 13.1 n.d.

ext basin 7.4 2.2

cont 2 5.0 5.6

cont 5 6.8 6.1

cont 8 7.7 5.3

part 1 4.4 3.3

part 4 7.6 3.4

part 7 6.9 5.9

diss 3 7.6 3.9

diss 6 7.5 5.9

diss 9 6.9 5.9
10 Conclusions

122

10 Conclusions

During this project the environmental impact of a seawater scrubber has been analysed for the

harbours of Calais and Dover. Five sampling campaigns were organised during which samples were

taken inside the ports, from the seawater scrubber system and within a transect leading 700 m away

from the seawater scrubber outlet. The seawater scrubber, the so-called “Ecosilencer”, was installed

in the funnel of the channel ferry “Pride of Kent” to reduce her SOx emissions. As seawater scrubbing

is a wet fluegas desulphurisation process not only SOxis dissolved but also NOx, volatile organic

compounds, and hydrochloric acid. The dissolved SOx and NOxform sulphuric and nitric acids and

reduce together with the HCl the pH of the scrubbing effluent significantly. The samples taken from the

seawater scrubber system partially showed pH values lower than pH 3. Because of the buffering

capacity of seawater due to the bicarbonate system the pH increases again after an initial acidification.

This could be shown in several experiments. From these it could also be shown that a mixture

containing 40 % of seawater acidified to a pH of 4, i.e. comparable to that what happens in a seawater

scrubber, only changes its pH about 0.2 units. To reach this equilibrium several hours were needed

but the largest changes were observable already a short time after mixing. On board of the „Pride of

Kent“ the seawater scrubber effluent was mixed with seawater from the cooling cycle of the vessel.

Thus a significant pH increase could be obtained but the pH was still lower in comparison to the inlet

and the surrounding waters. The lowest pH measured in the overboard discharge was 6.2. As many

organisms are only able to survive when environmental conditions are stable adecrease in pH might

be a risk for those organisms. That is why the United States Environmental Protection Agency has

passed a guideline concerning the introduction of acids which states that within the initial mixing zone

the pH change is not allowed to be higher than 0.2 units. In the case of the Ecosilencer the initial

mixing zone is directly in front of the overboard discharge of the „Pride of Kent“. To check whether

there is an observable pH change, samples were taken directly in front of the outlet (1 to 5 m distance)

and 50 m, 350 and 700 m away from the outlet. In no sample taken at the first point of this transect a

pH decrease was observed. In Calais the natural pH variability was much higher than the variability

measured in the transect. This shows that the bicarbonate system in the seawater effectively buffers

the acids added by the operation of the Ecosilencer.

Additionally to the acidification the dissolved SOxincreases the sulphate concentration in the effluent.

The samples taken behind the Ecosilencer showed a sulphate increase between 14.0 and 18.7 %. In

fresh water lakes sulphate might be a limiting factor but in sea water sulphate is a common and

conservative component. The inlet samples taken in the Channel can be considered as blank sample,

because the inlet water was not influenced by the outlet water and in the Channel the water current is

high enough so that an influence of the previous passing of the „Pride of Kent“ can be neglected. In

these samples sulphate concentrations between 2590 and 2990 ppm were observed. In the outlet

samples values between 2600 and 3052 ppm were determined which accounts for an increase of 0.4

to 4.5 %. As the method to determine this concentration already had an error of 6 % a sulphate

increase in the outlet samples cannot be stated for sure. Even if there would be a slight increase the
10 Conclusions

123

influence of the seawater scrubber on the sulphate concentrations in the harbours and therefore on

the marine environment would be very low. Additionally it has to be mentioned that in Calais a wide

range of sulphate concentrations, between 1479 and 2628 ppm, was observed.

Another nutrient that might be influenced by the seawater scrubber is nitrate. It is formed in the

scrubbing process when NOx is dissolved in water. It is an important nutrient in the sea. In the samples

taken after the Ecosilencer in the Channel, the nitrate concentrations were about two to thirteen times

higher than in the seawater inlet samples. The cleanup processes on board (cyclones and US filter)

did not reduce these concentrations. The only reduction was observed after dilution of the effluent

water with the cooling water. In the effluent samples the nitrate was only twice the inlet concentration.

To determine the influence of this additionally added nitrogen a calculation was made to determine the

amount of additional biomass production. This showed that an increase in primary production in a

given year would be less than the actual primary production during one sunny day per square metre.

Another indirect influence of the seawater scrubber that has to be considered is that the reduced pH in

the effluent influences the solubility of metal ions. To check this, samples were taken from the

seawater scrubber system and analysed for their metal contents. The highest values for all samplings

were determined for the samples taken from the settling tank and the pipe leading to the settling tank.

This water contains the particles filtered from the water by the cyclones. The high concentrations

showed that the cyclones effectively remove contaminated particles. The highest metal contents were

determined for iron. As iron is the major compound of ship steel this result is not surprising. In the

outlet samples beside iron also copper, nickel and lead were found. These were only detected during

two samplings and here also in the inlet samples. The copper might originate from ship coatings that

contain copper as antifouling biocide while nickel is like iron a compound of ship steel. With respect to

the metals it can be said that the seawater scrubbing process itself has no influence on their contents,

but that due to the reduced pH metals are leached from the steel, the tubing and the funnel. If the

metals are present in particulate form they are filtered out of the water and retained in the settling tank.

The sludge is removed separately and therefore no harm on the marine environment is expected.

Another group of compounds that is enriched in the seawater scrubber effluent are polycyclic aromatic

hydrocarbons. These are either dissolved or bound to soot particles which are formed during

incomplete combustion processes. The low molecular weight PAHs such as the two and three ring

compounds are soluble in water whereas the higher molecular weight PAHs with four rings and more

are mainly bound to particles. Therefore not all PAHs can be removed from the water with the US filter

and the cyclones which remove only particulates. This is the reason why there were still relatively high

amounts of PAHs in the outlet samples. However, in front of the seawater scrubber outlet no

increased PAH contents could be determined. In Dover high PAH concentrations were most often

found close to the middle or in the western part of the port where the water is shallower. At this point

the current speeds are lower and therefore pollutants might be enriched. Close to the berth and at the

eastern entrance of the harbour low PAH contents were measured most probably originating from

North Sea water, which is lower contaminated with PAHs, and is flowing into the port at this point.
10 Conclusions

124

In Calais the PAH contents were mostly equal at all points. Only during the sampling in March very

high contents were observed at point Cal 3. Here a total PAH content of 765 ng l-1 was measured

which was the highest value determined in all harbour samples. This high concentration was the result

of an algal bloom occurring at that point. The plankton cells might have enriched the PAHs by different

pathways: the PAHs might have adsorbed to the surface of the cells or the organism itself produced

the PAHs or took them up and accumulated them that way. This shows that there are also very high

natural variations. Seasonal variations were also observed. In summer the concentrations were close

to the detection limit and high molecular weight PAHs were not found at any point. In contrary in late

fall and early spring the PAH contents were higher. This variability is the result of fossil fuel burning

which is increased during the heating period. This is also the reason why in fall higher amounts of high

molecular weight PAHs were measured.

To determine the origin of the PAHs and to exclude the seawater scrubber as probable source

regression and principle component analyses were performed and different indices based on isomeric

ratios were applied. The latter indicated that the PAHs determined in the seawater scrubber samples

originated from a petrogenic source. This was surprising because it can be expected that in a funnel

only PAHs of pyrolytic origin should occur. The reason could be that the fuel is not completely

combusted. The indices calculated for the harbour samples did not clearly differentiate between a

pyrolytic or a petrogenic origin possibly due to the different PAH sources that influence the harbour.

On one hand there are big cities close to the ports introducing a high amount of PAHs originating from

a pyrolytic origin (shipping, car traffic, heating) and on the other hand there are the shipping activities

inside the port that introduce PAHs originating from petrogenic sources. With the linear regression and

the principle component analyses it could be shown that the composition of the seawater scrubber

samples was different from those observed in the harbours. A change of the signal due to the dilution

with the cooling water could be rejected because the PAHs in the outlet samples showed the same

distribution as those in the system itself. As data on seawater samples are rarely available in the

literature sediment and mussel samples were also taken inside the ports of Dover and Calais. The

PAH load of the sediments was comparable to concentrations measured in another French harbour

and were lower than in the ports with high shipping activities like Rotterdam and Amsterdam. The

mussels were higher contaminated than mussels collected at the Shetlands or in the Baltic.

With respect to temperature, nutrients and PAHs, the two ports showed differences. One reason might

be the different architecture. In Calais the harbour is enclosed by walls and is made up of three arms.

One arm is separated by a flood gate which is only opened during high tide. The city of Calais and

local industry are located next to the harbour and therefore the anthropogenic influence is relatively

high. A water exchange is only possible through a relatively small entrance in the north-west of the

harbour. In contrary the harbour of Dover possesses two entrances, one in the south and one in the

west. This enables a higher water exchange and therefore the water remains inside the harbour for a

shorter time. This port has no side arms where water can be retained, as the harbour walls are built

around a large basin. Due to this architecture the city of Dover touches the port only at the north side.

Because of these differences the environmental parameters determined in the ports were also

different. In Dover the salinity was higher and the water temperature was lower in the most cases than
10 Conclusions

125

in Calais. Also the phosphate and nitrogen concentrationsn and in most cases also concentrations of

polycyclic aromatic hydrocarbons were lower. The nitrate concentrations determined for the two ports

showed a distinct seasonal behaviour. In summer low concentrations were measured, whereas in

February and November relatively high concentrations were observed. Nitrate is a limiting nutrient for

marine organisms and therefore it is depleted in summer when plankton bioproduction is high. In fall

and winter organic nitrogen compounds are remineralised and hence the nitrate concentrations

increase.

Additionally to the observations inside the ports and board of the „Pride of Kent“, toxicity tests were

performed to determine the overall toxicity of the outlet water. The tests covered inhibition of bacterial

luminescence, mortality of brine shrimps and accumulation of PAH by blue mussels (Mytilus edulis).

None of all this tests did reveal an increased toxicity of the effluent, neither acute nor chronic.

Summarizing the results it can be said that in the effluent the pH was decreased by a maximum of two

pH units, the sulphate content was slightly increased and the nitrate concentration was doubled. Close

to the seawater outlet in the ambient warters no decrease in pH, no higher nitrate or sulphate values,

and no increased PAH or metal contents were determined. Also no toxicity towards bacteria,

zooplankton or mussels was determined for the outlet samples. Although the PAHs are increased in

the outlet water these would have reached the North Sea anyway by atmospheric deposition after

release by combustion. In this case the PAH amounts would have been higher as in the seawater

scrubber system a part was collected by the cyclones. Improvement of the cylone efficiency would

help to minimise the problem of particulate PAH introduction to the marine environment

Additionally it has to be stated that when the seawater scrubber is to be be used in areas with brackish

or fresh waters, the effects might be different. Fresh waters have for example less pH buffering

capacitiy – unless the water drains a carbonaceous area - and therefore the critical load for acidity

might be reached very fast.
References

126

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Appendix

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Appendix

Matlab Source Code for Principal component analysis

close all;

clear all;

load alle_harbour.txt;

M = alle_harbour;

num_row = size(M,1);

num_col = size(M,2);

fid = fopen('txt_alle_harbour_neu.txt','r');

ind=1;

while feof(fid) == 0

h(ind) = fscanf(fid,'%c \n',1);

ind=ind+1;

end

fclose (fid);

stand1 = 1; %Standardize values by mean and standard deviation

stand2 = 0; %Standardize values only by mean

cov1 = 0; %varialbes for the calcualtion of the covariance

cov2 = 0; %varialbes for the calcualtion of the covariance

for i = 1:num_col

A1(i) = mean(M(1:num_row,i));

B1(i) = std(M(1:num_row,i));

end

% Standardize values

if stand1

for i = 1:num_row

for j = 1:num_col

M_std(i,j) = (M(i,j)-A1(j))/B1(j);

end

end

end

if stand2

for i = 1:num_row

for j = 1:num_col

M_std(i,j) = M(i,j)-A1(j);

end

end

end

% Calculating covariance matrix

for j = 1:num_col

A2(j) = mean(M_std(1:num_row,j));

end

for j1=1:num_col

for j2=1:num_col

for i = 1:num_row

cov1 = (M_std(i,j1)-A2(j1))*(M_std(i,j2)-A2(j2));

cov2 = cov2 + cov1;

cov1 = 0;

end

cov(j1,j2) = cov2/(num_row-1);

cov2=0;

end

end

% Computing eigenvalues and eigenvectors

[V,D] = eig(cov);

d = eig(cov);

V = V*(-1);

%Finding max eigenvector values

[VALUE,INDEX] = sort(d);

Index1 = INDEX(num_col);

Value1 = VALUE(num_col);

Index2 = INDEX(num_col-1);

Value2 = VALUE(num_col-1);

if num_col > 3

Index3 = INDEX(num_col-2);

Value3 = VALUE(num_col-2);

end

total_var = sum(d);

Val1_var = (Value1/total_var)*100;

Val2_var = (Value2/total_var)*100;

Val3_var = (Value3/total_var)*100;

disp(sprintf ('\n\n\n'))

disp(sprintf ('Value1 (%2.3f) gives account for %2.1f %% of the total variance (%2.1f) ',Value1,Val1_var,total_var))

disp(sprintf ('Value2 (%2.3f) gives account for %2.1f %% of the total variance (%2.1f) ',Value2,Val2_var,total_var))
Appendix

131

if num_col > 3

disp(sprintf ('Value3 (%2.3f) gives account for %2.1f %% of the total variance (%2.1f) \n\n\',Value3,Val3_var,total_var))

end

% Creating feature vector

feat_V (1:num_col,1) = V(1:num_col,Index1);

feat_V (1:num_col,2) = V(1:num_col,Index2);

feat_V = feat_V';

disp(sprintf ('The feature vector for deriving the new data set is \n'))

for i = 1:size(feat_V,2)

disp(sprintf ('\t %2.2f \t%2.2f',-feat_V(1,i), feat_V(2,i)))

end

% Deriving the new data set

M_std=M_std';

Final_Data = feat_V*M_std;

Final_Data = Final_Data';

% plotting final data

x = Final_Data(1:num_row,1);

y = Final_Data(1:num_row,2);

plot(x,y,'ok')

title('Principal component ananlysis, al harbour samples from all samplings')

xlabel(sprintf ('eigenvector 1 (%2.1f %% of variance)',Val1_var))

ylabel(sprintf ('eigenvector 2 (%2.1f %% of variance)',Val2_var))

str_ind=1;

for i=1:size(x,1)

text(x(i),y(i),h(str_ind:str_ind+4),'HorizontalAlignment','right','VerticalAlignment','bottom','FontSize',6,'Rotation',270)

str_ind=str_ind+5;

end

Systat source code for linear regression analysis

REGRESS

use 'D:\ECOSILENCER_DATEN\Daten\Pn5_161104\reg_5\punkte.syd'

PRINT = LONG

MODEL P02 = P01

ESTIMATE

PLOT P01*P02 / SMOOTH=LINEAR CONFI=0.9500