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EGCSA Workshop London 30 Nov. 16 – 01 Dec 16 WASH WATER SAMPLING PROGRAMME 2 MARK WEST

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Page 1: WASH WATER SAMPLING PROGRAMME 2 - egcsa.com€¦ · wash water sampling programme 2 mark west. ... •2 eca –baltic & north ... •elemental analysis (test method en iso 11885)

EGCSA Workshop London 30 Nov. 16 – 01 Dec 16

WASH WATER SAMPLING PROGRAMME 2

MARK WEST

Page 2: WASH WATER SAMPLING PROGRAMME 2 - egcsa.com€¦ · wash water sampling programme 2 mark west. ... •2 eca –baltic & north ... •elemental analysis (test method en iso 11885)

EGCSA Workshop London 30 Nov. 16 – 01 Dec 16

• REPRISE OF FIRST SAMPLING PROGRAMME

• WHAT ARE PAH’S?

• SOME COMPARISON OF PAH ANALYSES WITH CRUDE OIL

AND PRODUCED WATER

• REVIEW OF SECOND SAMPLING PROGRAMME TO DATE

Page 3: WASH WATER SAMPLING PROGRAMME 2 - egcsa.com€¦ · wash water sampling programme 2 mark west. ... •2 eca –baltic & north ... •elemental analysis (test method en iso 11885)

EGCSA Workshop London 30 Nov. 16 – 01 Dec 16

INTRODUCTORY BRIEF PROVIDED TO THE ESSF

• UNFOUNDED CONCERNS ABOUT SCRUBBING IN EU PORTS

• LACK OF DATA ON COMPOSITION OF SCRUBBER WASH WATER DISCHARGE

• LIMITED SAMPLING AND ANALYSIS – LOW NUMBER OF INSTALLATIONS (AS OF JULY 2014)

• JOINT AGREEMENT EGCSA & EUROSHORE TO UNDERTAKE FIRST SAMPLING PROGRAMME

• IMPROVE UNDERSTANDING BY LABORATORY ANALYSIS OF WATER SAMPLES

• ANONYMITY FOR SHIP OPERATORS (& EGCSA MEMBERS)

Page 4: WASH WATER SAMPLING PROGRAMME 2 - egcsa.com€¦ · wash water sampling programme 2 mark west. ... •2 eca –baltic & north ... •elemental analysis (test method en iso 11885)

EGCSA Workshop London 30 Nov. 16 – 01 Dec 16

FIRST PROGRAMME - SAMPLING

• SAMPLES (SYSTEM DEPENDENT)

• SEAWATER/SCRUBBER INLET

• WASH WATER BEFORE TREATMENT

• OVERBOARD DISCHARGE (BEFORE pH CORRECTION)

• SCRUBBER SYSTEM & ENGINE OPERATING CONDITIONS, SHIP POSITION BEFORE & AFTER

SAMPLING

• FOR INTEGRITY ASSURANCE

• LABORATORY PREPARED SAMPLE BOTTLE PACKS

• PREPARATION - CLEANING & FLUSHING OF SAMPLING POINTS & COLLECTION GEAR

• MW SAILED WITH ALL VESSELS IN THE FIRST PROGRAMME.

Page 5: WASH WATER SAMPLING PROGRAMME 2 - egcsa.com€¦ · wash water sampling programme 2 mark west. ... •2 eca –baltic & north ... •elemental analysis (test method en iso 11885)

EGCSA Workshop London 30 Nov. 16 – 01 Dec 16

FIRST PROGRAMME - SAMPLING CONDITIONS

• PLAN AT START OF PROJECT:

• NEAR FULL ENGINE POWER AS POSSIBLE

• MULTI-INLET SCRUBBERS RUNNING AT NEAR MAXIMUM CAPACITY

• WITHIN 12 HOURS OF BERTHING IN PORT

• PRACTICAL REALITY

• FULL RANGE OF ENGINE OPERATING POWERS & SCRUBBER CAPACITIES (MANOEUVRING TO

~MCR)

• UNCERTAINTY OF SPOT MARKET SHIPS

• SCHEDULES ON REGULAR ROUTES

• VARIABLE WEATHER AND SEA CONDITIONS

• FUEL SAVING

• ENGINE (NOT SCRUBBER!) BREAKDOWNS ON THE SUBJECT SHIP AND OTHER SHIPS ON THE BERTH

Page 6: WASH WATER SAMPLING PROGRAMME 2 - egcsa.com€¦ · wash water sampling programme 2 mark west. ... •2 eca –baltic & north ... •elemental analysis (test method en iso 11885)

EGCSA Workshop London 30 Nov. 16 – 01 Dec 16

FIRST PROGRAMME - NUMBERS

• 10 SHIPS SAMPLED, 15 SHIP SETS OF SAMPLES LANDED, 40 SAMPLE POINTS

• 225 SAMPLE BOTTLES ANALYSED (ALL AT SGS HERTEN), ~1400 TEST RESULTS

• 12 OPEN LOOP MODE, 3 CLOSED LOOP MODE

• 7 MANUFACTURERS

• 6 HYBRID, 3 OPEN LOOP, 1 CLOSED LOOP

• 5 FERRIES, 2 CONTAINER, 2 TANKER, 1 VEHICLE CARRIER

• 8 SCRUBBERS FOR SINGLE ENGINES, 4 SCRUBBERS FOR MULTIPLE COMBUSTION UNITS

• 2 ECA – BALTIC & NORTH SEA

• 1.48 - 2.87% SULPHUR FUEL

• 90% MCR – MANOEUVRING, 52% AVERAGE

• 10 DAYS – LONGEST TIME MW ONBOARD!

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EGCSA Workshop London 30 Nov. 16 – 01 Dec 16

FIRST PROGRAMME – ANALYSES SUMMARY

• NITRATES – ALL SAMPLES (OVERBOARD – INLET) LOW & WITHIN IMO LIMITS (1.8mg/l vs. 60mg/l)

• AMEND MEPC 259.(68) SCRUBBER GUIDELINES FOR NITRATES ANALYSIS LIMITS TO: DISCHARGE –

INLET?

• POSSIBLE IMPLICATIONS OF SAMPLE AGING ON NITRATE LEVELS MEASURED BY LAB ANALYSIS

• POSSIBLE USE OF ONBOARD TESTING FOR FUTURE PROGRAMMES BECAUSE OF SHORT SAMPLE

PRESERVATION TIME (SAMPLES NEED TO BE FROZEN)

• NITRITES NOT AN ISSUE

• BTEX NOT AN ISSUE

• 11 OVERBOARD SAMPLES - BTEX NOT DETECTED, 5 OVERBOARD SAMPLES - 4ppb HIGHEST LEVEL:

2ppb BENZENE + 2ppb TOLUENE

Page 8: WASH WATER SAMPLING PROGRAMME 2 - egcsa.com€¦ · wash water sampling programme 2 mark west. ... •2 eca –baltic & north ... •elemental analysis (test method en iso 11885)

EGCSA Workshop London 30 Nov. 16 – 01 Dec 16

FIRST PROGRAMME - SUMMARY

• METALS – VERY LOW BUT SOME EVIDENCE OF MATERIALS OF CONSTRUCTION

• EGCSA STANDARD FOR SAMPLING VALVE LOCATION AND MATERIALS TO BE ESTABLISHED?

• VANADIUM?

• PAH – ALL WITHIN IMO LIMITS

• SOME EVIDENCE THAT PAH MAY BE AN INDICATOR OF OPERATION, COMBUSTION PERFORMANCE,

WWT PERFORMANCE?

• SECOND SAMPLING PROGRAMME FOCUS ON PAH & METALS (NOT MERCURY)

Page 9: WASH WATER SAMPLING PROGRAMME 2 - egcsa.com€¦ · wash water sampling programme 2 mark west. ... •2 eca –baltic & north ... •elemental analysis (test method en iso 11885)

EGCSA Workshop London 30 Nov. 16 – 01 Dec 16

SAMPLING PROGRAMME 2

• LEARNING FROM FIRST PROGRAMME

• SHIP TO TAKE SAMPLES (TIME, COST)

• REQUIRES GOOD EMAIL DIALOGUE WITH

CHIEF ENGINEER

• ESTABLISH SHIP, ENGINE, SCRUBBER DETAILS

• IDENTIFY SAMPLE POINTS

• SOME CLARIFICATION/REMINDERS

• SO FAR SO GOOD!

Page 10: WASH WATER SAMPLING PROGRAMME 2 - egcsa.com€¦ · wash water sampling programme 2 mark west. ... •2 eca –baltic & north ... •elemental analysis (test method en iso 11885)

EGCSA Workshop London 30 Nov. 16 – 01 Dec 16

SAMPLE BOTTLE PACK

• 2 BOTTLES REQUIRED PER SAMPLE POINT

• 1 x PLASTIC METALS, 1 x GLASS PAH (NO ACID PRESERVATIVE THIS TIME)

• 6 BOTTLES PER NOMINAL SAMPLE SET, 2 SAMPLE SETS PER BOX

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EGCSA Workshop London 30 Nov. 16 – 01 Dec 16

SECOND PROGRAMME – NUMBERS (EARLY DAYS!)

• 5 SHIPS SAMPLED, 7 SHIP SETS OF SAMPLES LANDED, 17 SAMPLE POINTS

• 24 SAMPLE BOTTLES ANALYSED (ALL AT SGS HERTEN), ~300 TEST RESULTS

• 4 OPEN LOOP MODE, 1 CLOSED LOOP MODE

• 2 MANUFACTURERS

• 4 HYBRID, 1 OPEN LOOP,

• 5 RORO/ROPAX

• 6 SCRUBBERS FOR SINGLE ENGINES, 1 SCRUBBER FOR MULTIPLE COMBUSTION UNITS

• 2 ECA – BALTIC & NORTH SEA

• 2.8 – 2.1% SULPHUR FUEL (IF380)

• 79% - 33%MCR, 63%% AVERAGE

Page 12: WASH WATER SAMPLING PROGRAMME 2 - egcsa.com€¦ · wash water sampling programme 2 mark west. ... •2 eca –baltic & north ... •elemental analysis (test method en iso 11885)

EGCSA Workshop London 30 Nov. 16 – 01 Dec 16

SECOND PROGRAMME - ESSF SAMPLE ANALYSIS

• ELEMENTAL ANALYSIS (TEST METHOD EN ISO 11885)

• CADMIUM (CD)

• COPPER (CU)

• NICKEL (NI)

• LEAD (PB)

• ZINC (ZN)

• ARSENIC (AS)

• CHROMIUM (CR)

• VANADIUM (V)

• ONE MONTH SAMPLE PRESERVATION TIME

Page 13: WASH WATER SAMPLING PROGRAMME 2 - egcsa.com€¦ · wash water sampling programme 2 mark west. ... •2 eca –baltic & north ... •elemental analysis (test method en iso 11885)

EGCSA Workshop London 30 Nov. 16 – 01 Dec 16

0.00

0.20

0.40

0.60

0.80

1.00

1.20

1.40

1.60

1.80

Mercury (Hg) Arsenic (As) Lead (Pb) Cadmium (Cd) Chrome (Cr) Copper (Cu) Nickel (Ni) Vanadium (V) Zinc (Zn)

mg/l

First sampling programme – overboard metals analysis (normalised to 45m3/MWh) vs. EU limits on incinerator scrubber waste water

Normalisedaverage alldischarges mg/l

Normalised Maxmg/l

Limits 2010/75/EUon industrialemissions (IPPC)mg/l

No vanadium limit

Page 14: WASH WATER SAMPLING PROGRAMME 2 - egcsa.com€¦ · wash water sampling programme 2 mark west. ... •2 eca –baltic & north ... •elemental analysis (test method en iso 11885)

EGCSA Workshop London 30 Nov. 16 – 01 Dec 16

FIRST SAMPLING PROGRAMME - METALS

• ALL AVERAGES WELL BELOW THE ILLUSTRATIVE 2010/75/EU LIMITS - NOTE NO LIMIT FOR

VANADIUM

• ONLY TWO RESULTS, LEAD(PB) ABOVE LIMIT – 0.3 & 0.29 mg/l vs. 0.2mg/l (SAME SHIP/ENGINE)

• 40 SAMPLES – LEAD FOUND IN 9: 3 SW IN, 3 BEFORE WWT, 3 OVERBOARD

• LEAD, COPPER, ZINC, CHROMIUM SEEM LIKELY FROM MATERIALS OF CONSTRUCTION EG. FROM

WWT, PIPEWORK, SAMPLE POINT ETC.

• DEPENDING ON SCRUBBER SET-UP SUGGEST FIT CLEARLY MARKED EASY TO USE NON-METALLIC

SAMPLE VALVES THAT DO NOT TRAP DEBRIS AT FOLLOWING POINTS AS STANDARD PRACTICE:

• INLET MONITORING STATION OR WHERE BACKGROUND SEAWATER SAMPLES CAN BE OBTAINED

• BEFORE WWT

• OVERBOARD DISCHARGE BEFORE pH CORRECTION - OVERBOARD MONITORING STATION

• ALSO AT SHIP SIDE IF pH CORRECTION IS USED

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EGCSA Workshop London 30 Nov. 16 – 01 Dec 16

0.00

0.50

1.00

1.50

2.00

2.50

Arsenic Lead Cadmium Chromium Copper Nickel Vanadium Zinc

mg/l

Second sampling programme – overboard metals analysis (normalised to 45m3/MWh) vs. EU limits on incinerator scrubber waste water

Normalisedaverage alldischarges mg/l

Normalised max.mg/l

Limits 2010/75/EUon industrialemissions (IPPC)mg/l

No vanadium limit

Page 16: WASH WATER SAMPLING PROGRAMME 2 - egcsa.com€¦ · wash water sampling programme 2 mark west. ... •2 eca –baltic & north ... •elemental analysis (test method en iso 11885)

EGCSA Workshop London 30 Nov. 16 – 01 Dec 16

0%

10%

20%

30%

40%

50%

60%

70%

80%

90%

100%

Av. Prog. 1 KKHT (OB) KKOL MM NNOL NNCL

First programme average vs second programme percentage of metals in each overboard sample

Cadmium

Arsenic

Chromium

Zinc

Lead

Copper

Nickel

Vanadium

Page 17: WASH WATER SAMPLING PROGRAMME 2 - egcsa.com€¦ · wash water sampling programme 2 mark west. ... •2 eca –baltic & north ... •elemental analysis (test method en iso 11885)

EGCSA Workshop London 30 Nov. 16 – 01 Dec 16

0.00

0.50

1.00

1.50

2.00

2.50

KKHT KKOL MM NNOL NNCL

mg/

l

Metals concentration at seawater inlet (normalized 45m3/MWh)

0.00

0.50

1.00

1.50

2.00

2.50

Av. Prog. 1 KKHT (OB) KKOL MM NNOL NNCLm

g/l

Metals concentration at overboard (normalized 45m3/MWh)

Cadmium

Arsenic

Chromium

Zinc

Lead

Copper

Nickel

Vanadium

Page 18: WASH WATER SAMPLING PROGRAMME 2 - egcsa.com€¦ · wash water sampling programme 2 mark west. ... •2 eca –baltic & north ... •elemental analysis (test method en iso 11885)

EGCSA Workshop London 30 Nov. 16 – 01 Dec 16

SECOND PROGRAMME - ESSF SAMPLE ANALYSIS

• 16 EPA PRIORITY PAH:

• NAPHTHALENE

• ACENAPHTHYLENE

• ACENAPHTHENE

• FLUORENE

• PHENANTHRENE

• ANTHRACENE

• FLUORANTHENE

• PYRENE

• BENZO[A]ANTHRACENE

• CHRYSENE

• BENZO[B]FLUORANTHENE

• BENZO[K]FLUORANTHENE

• BENZO[A]PYRENE

• DIBENZ(AH)ANTHRACENE

• BENZO[GHI]PERYLENE

• INDENO[1,2,3-CD]PYRENE

POLYCYCLIC AROMATIC HYDROCARBONS (TEST METHOD EPA 8270 D)

7 DAYS SAMPLE PRESERVATION TIME

Page 19: WASH WATER SAMPLING PROGRAMME 2 - egcsa.com€¦ · wash water sampling programme 2 mark west. ... •2 eca –baltic & north ... •elemental analysis (test method en iso 11885)

EGCSA Workshop London 30 Nov. 16 – 01 Dec 16

FIRST PROGRAMME -PAH

• IMO LIMIT OF 50 ppb AT 45m3/MWh NOT

EXCEEDED BY ANY VESSEL

MEPC.259(68) limit

0

10

20

30

40

50

AA AA (C) AA (C) BB BB (B) BB (C) CC DD EE FF GG GG HH HH(A) II JJ

(µg

/l)

First programme - PAH concentration overboard (before dilution) -inlet (or clean SW) normalised to 45m3/MWh washwater flow rate

(µg/l)

Page 20: WASH WATER SAMPLING PROGRAMME 2 - egcsa.com€¦ · wash water sampling programme 2 mark west. ... •2 eca –baltic & north ... •elemental analysis (test method en iso 11885)

EGCSA Workshop London 30 Nov. 16 – 01 Dec 16

SECONDPROGRAMME -PAH

• IMO LIMIT OF 50 ppb AT 45m3/MWh ALSO

NOT EXCEEDED BY ANY VESSEL

MEPC.259(68) limit

0

10

20

30

40

50

Av. Prog. 1 KKHT (OB) KKOL MM NNOL NNCL

(µg/

l)

Second programme - PAH concentration overboard (before dilution) - inlet (or clean SW) normalised to 45m3/MWh washwater flow

rate (µg/l)

Page 21: WASH WATER SAMPLING PROGRAMME 2 - egcsa.com€¦ · wash water sampling programme 2 mark west. ... •2 eca –baltic & north ... •elemental analysis (test method en iso 11885)

EGCSA Workshop London 30 Nov. 16 – 01 Dec 16

FIRST PROGRAMME -PAH

• INCREASING MOLECULAR WEIGHT PAH ARE

AT TOP OF GRAPH

• INDICATORS EG:

• SAMPLING ISSUE

• LABORATORY ISSUE

• AREA OF OPERATION; SHALLOW WATER

SEDIMENT - CHECK SW INLET SAMPLE

• COMBUSTION PERFORMANCE

• WWT PERFORMANCE

• OTHER?

0%

10%

20%

30%

40%

50%

60%

70%

80%

90%

100%

First programme - percentage of PAH species at overboard

Indeno(1,2,3-c,d)pyrene

Benzo(g,h,i)perylene

Dibenzo(a,h)anthracene

Benzo(a)pyrene

Benzo(k)fluoranthene

Benzo(b)fluoranthene

Chrysene

Benz(a)anthracene

Pyrene

Fluoranthene

Anthracene

Acenaphthene

Acenaphthylene

Fluorene

Phenanthrene

Naphthalene

Page 22: WASH WATER SAMPLING PROGRAMME 2 - egcsa.com€¦ · wash water sampling programme 2 mark west. ... •2 eca –baltic & north ... •elemental analysis (test method en iso 11885)

EGCSA Workshop London 30 Nov. 16 – 01 Dec 16

WHAT ARE PAH’S?

• OCCUR NATURALLY IN CRUDE OIL, ALSO PRODUCED AS BY-PRODUCTS OF FUEL COMBUSTION

• ENGINES & BOILERS DESIGNED TO OPTIMISE THE FUEL OIL COMBUSTION

• HOWEVER EXHAUST GASES CONTAIN:

• INCOMPLETELY COMBUSTED AND UNBURNED MATERIAL

• GASEOUS HYDROCARBON AND PARTICULATE EMISSIONS FROM SIMPLE METHANE TO VERY LARGE

COMPLEX MOLECULES

• PROPORTION OF WHICH INCLUDES POLYCYCLIC AROMATIC HYDROCARBONS.

• LOW MOLECULAR WEIGHT PAHS FOUND MAINLY UNBOUND IN THE GASEOUS PHASE EXHAUST

• HEAVIER MOLECULAR WEIGHT PAHS PART OF A GROUP OF SUBSTANCES THAT ARE BOUND ONTO

SOOT DURING COMBUSTION

Page 23: WASH WATER SAMPLING PROGRAMME 2 - egcsa.com€¦ · wash water sampling programme 2 mark west. ... •2 eca –baltic & north ... •elemental analysis (test method en iso 11885)

EGCSA Workshop London 30 Nov. 16 – 01 Dec 16

WHAT ARE PAH’S?

• PAHS ARE AROMATIC COMPOUNDS CONTAINING FROM 2 TO 8 [BENZENE] RING SYSTEMS

• PAHS PRESENT IN THE MARINE ENVIRONMENT IN RELEVANT CONCENTRATIONS TYPICALLY

DIVIDED INTO 2 GROUPS DEPENDING ON THEIR ORIGIN:

• PYROGENIC

• INCOMPLETE COMBUSTION OF ORGANIC MATERIAL E.G. FOSSIL FUEL OILS

• PETROGENIC

• OIL AND OIL PRODUCTS

• TYPICALLY PYROGENIC COMPOSED OF LARGER RING SYSTEMS THAN PETROGENIC

• TYPICALLY PYROGENIC MORE TOXIC AND PERSISTENT THAN PETROGENIC

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EGCSA Workshop London 30 Nov. 16 – 01 Dec 16

Page 25: WASH WATER SAMPLING PROGRAMME 2 - egcsa.com€¦ · wash water sampling programme 2 mark west. ... •2 eca –baltic & north ... •elemental analysis (test method en iso 11885)

EGCSA Workshop London 30 Nov. 16 – 01 Dec 16

FATE OF PAH’S

• PAHS ENTER ECOSYSTEMS VIA UNSCRUBBED ENGINE AND BOILER EMISSIONS

• SCRUBBERS REMOVE PARTICULATE MATTER, HENCE HEAVIER WEIGHT GENERALLY MORE

HARMFUL PAHS

• LOWER WEIGHT UNBOUND PAHS DISSOLVED INTO THE WASH WATER.

• SCRUBBER OVERBOARD DISCHARGES REQUIRED TO BE MONITORED FOR PAH AND

TURBIDITY FOR PARTICULATE CONTENT.

Page 26: WASH WATER SAMPLING PROGRAMME 2 - egcsa.com€¦ · wash water sampling programme 2 mark west. ... •2 eca –baltic & north ... •elemental analysis (test method en iso 11885)

EGCSA Workshop London 30 Nov. 16 – 01 Dec 16

FATE OF PAH’S

PETROGENIC

• LOWER MOLECULAR WEIGHT

• GREATER SOLUBILITY

• DEGRADATION BY A GREATER NUMBER OF

BIOGEOCHEMICAL PROCESSES:

• VOLATILIZATION, DISSOLUTION,

PHOTOCHEMICAL OXIDATION, MICROBIAL

BREAKDOWN

PYROGENIC

• HIGHER MOLECULAR WEIGHT

• REDUCED SOLUBILITY

• RESISTANT TO VARIOUS FORMS OF

MICROBIAL AND ENVIRONMENTAL

DEGRADATION:

• PAHS ADSORBED TO SOOT CARBON SHOW

LITTLE PHOTOCHEMICAL OXIDATION

• REMOVAL MAINLY BY SEDIMENTATION

Page 27: WASH WATER SAMPLING PROGRAMME 2 - egcsa.com€¦ · wash water sampling programme 2 mark west. ... •2 eca –baltic & north ... •elemental analysis (test method en iso 11885)

EGCSA Workshop London 30 Nov. 16 – 01 Dec 16

Page 28: WASH WATER SAMPLING PROGRAMME 2 - egcsa.com€¦ · wash water sampling programme 2 mark west. ... •2 eca –baltic & north ... •elemental analysis (test method en iso 11885)

EGCSA Workshop London 30 Nov. 16 – 01 Dec 16

0%

10%

20%

30%

40%

50%

60%

70%

80%

90%

100%

Av. Prog. 1 KKHT (OB) KKOL MM NNOL NNCL

%

Second programme - percentage of PAH species at overboard vs. first programme average

Indeno(1,2,3-c,d)pyrene

Benzo(g,h,i)perylene

Dibenzo(a,h)anthracene

Benzo(a)pyrene

Benzo(k)fluoranthene

Benzo(b)fluoranthene

Chrysene

Benz(a)anthracene

Pyrene

Fluoranthene

Anthracene

Acenaphthene

Acenaphthylene

Fluorene

Phenanthrene

Naphthalene

Page 29: WASH WATER SAMPLING PROGRAMME 2 - egcsa.com€¦ · wash water sampling programme 2 mark west. ... •2 eca –baltic & north ... •elemental analysis (test method en iso 11885)

EGCSA Workshop London 30 Nov. 16 – 01 Dec 16

0%

10%

20%

30%

40%

50%

60%

70%

80%

90%

100%

48 different crude oils mean mg/kg oil ESSF sampling programme 1

Percentage of PAH in 48 crude oils vs. percentage in overboard samples first programme

Indeno[1,2,3-cd]pyrene

Benzo[g,h,j]perylene

Dibenz[a,h]anthracene

Benzo[a]pyrene

Benzo[k]fluoranthene

Benzo[b]fluoranthene

Benzo[a]anthracene

Pyrene

Fluoranthene

Anthracene

Acenaphthene

Acenaphthylene

Chrysene

Fluorene

Phenanthrene

Naphthalene

Page 30: WASH WATER SAMPLING PROGRAMME 2 - egcsa.com€¦ · wash water sampling programme 2 mark west. ... •2 eca –baltic & north ... •elemental analysis (test method en iso 11885)

EGCSA Workshop London 30 Nov. 16 – 01 Dec 16

0%

10%

20%

30%

40%

50%

60%

70%

80%

90%

100%

48 different crude oils mean mg/kg oil ESSF sampling programme 2

Percentage of PAH in 48 crude oils vs percentage in overboard samples second programme

Indeno[1,2,3-cd]pyrene

Benzo[g,h,j]perylene

Dibenz[a,h]anthracene

Benzo[a]pyrene

Benzo[k]fluoranthene

Benzo[b]fluoranthene

Benzo[a]anthracene

Pyrene

Fluoranthene

Anthracene

Acenaphthene

Acenaphthylene

Chrysene

Fluorene

Phenanthrene

Naphthalene

Page 31: WASH WATER SAMPLING PROGRAMME 2 - egcsa.com€¦ · wash water sampling programme 2 mark west. ... •2 eca –baltic & north ... •elemental analysis (test method en iso 11885)

EGCSA Workshop London 30 Nov. 16 – 01 Dec 16

COMPARISON WITH O&G PRODUCED WATERS

0

20

40

60

80

100

120

140

160

Oil installation Gas installation Unspecified installation ESSF samplingprogramme 2

ESSF samplingprogramme 1

µg/

l

PAH concentration in produced water from oil & gas installations vs. scrubber discharges

Naphthalene

Phenanthrene

Fluorene

Page 32: WASH WATER SAMPLING PROGRAMME 2 - egcsa.com€¦ · wash water sampling programme 2 mark west. ... •2 eca –baltic & north ... •elemental analysis (test method en iso 11885)

EGCSA Workshop London 30 Nov. 16 – 01 Dec 16

0.00

5.00

10.00

15.00

20.00

25.00

30.00

35.00

Oil : pr1 Gas : pr1 Unspec : pr1 Oil : pr2 Gas : pr2 Unspec : pr2

O&

G P

W :

Scru

bb

er d

isch

.

Ratio of PAH in produced water from oil & gas installations to scrubber discharges

Naphthalene

Phenanthrene

Fluorene

COMPARISON WITH O&G PRODUCED WATERS

Concentration of the 3 most prevalent lighter weight PAH

species in scrubber discharges between 6 and 30 times less

than in produced waters from oil & gas production facilities

Page 33: WASH WATER SAMPLING PROGRAMME 2 - egcsa.com€¦ · wash water sampling programme 2 mark west. ... •2 eca –baltic & north ... •elemental analysis (test method en iso 11885)

EGCSA Workshop London 30 Nov. 16 – 01 Dec 16

0.00

0.20

0.40

0.60

0.80

1.00

1.20

1.40

1.60

Benzo(k)fluoranthene Benzo(a)pyrene Dibenzo(a,h)anthracene Indeno(1,2,3-c,d)pyrene

kg/y

r

Indicator species

Second programme vs. Scottish Environment Protection AgencyPollution Release Inventory (worst case scenarios)

Average (kg/yr)

Maximum (kg/yr)

Emission to WaterReporting Threshold(kg/yr)

Calculated by concentration at flow rate at time of sampling if discharged 24 hours per day 365 days per year

Page 34: WASH WATER SAMPLING PROGRAMME 2 - egcsa.com€¦ · wash water sampling programme 2 mark west. ... •2 eca –baltic & north ... •elemental analysis (test method en iso 11885)

EGCSA Workshop London 30 Nov. 16 – 01 Dec 16

BENZO[A]PYRENE

• 4TH EDITION OF WORLD HEALTH ORGANISATION DRINKING WATER GUIDELINES

• BENZO[A]PYRENE GUIDELINE VALUE OF 0.7 ppb

• “GUIDELINE VALUE NORMALLY REPRESENTS THE CONCENTRATION OF A CONSTITUENT THAT

DOES NOT RESULT IN ANY SIGNIFICANT RISK TO HEALTH OVER A LIFETIME OF CONSUMPTION.”

• HIGHEST CONCENTRATION OF BENZO[A]PYRENE RECORDED DURING THE SCRUBBER

WATER SAMPLING PROGRAMME TO DATE IS 0.35ppb

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EGCSA Workshop London 30 Nov. 16 – 01 Dec 16

IN CONCLUSION

• METALS – VERY LOW CONCENTRATIONS

• ALL AVERAGES WELL BELOW THE ILLUSTRATIVE 2010/75/EU LIMITS

• PROGRAMME 2: EVIDENCE OF MATERIALS OF CONSTRUCTION CONTINUES

• EGCSA STANDARD FOR SAMPLING VALVE LOCATION AND MATERIALS TO BE ESTABLISHED?

• PROGRAMME 2: OTHER THAN MATERIALS OF CONSTRUCTION VANADIUM MOST

PREVALENT

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EGCSA Workshop London 30 Nov. 16 – 01 Dec 16

IN CONCLUSION - PAH

• IMO LIMIT OF 50 ppb AT 45m3/MWh NOT EXCEEDED BY ANY VESSEL IN EITHER PROGRAMME TO DATE

• PROGRAMME 2: LIGHTER WEIGHT NAPHTHALENE, PHENANTHRENE, FLUORENE CONTINUE AS MOST

PREVALENT SPECIES (TYPICALLY PETROGENIC ORIGIN)

• PROGRAMME 2: NO SAMPLES WITH SIMILAR PROFILE OF HEAVIER MOLECULAR WEIGHT SPECIES AS SEEN IN

PROGRAMME 1 (TYPICALLY PYROGENIC ORIGIN)

• NAPHTHALENE, PHENANTHRENE, FLUORENE COMPARISON:

• ~ 90% IN 48 CRUDE OILS

• ~ 75% IN PROGRAMME 1

• ~ 90% IN PROGRAMME 2

• ALTHOUGH NOT SEEN IN PROGRAMME 2 TO SAME EXTENT AS PROGRAMME 1: HIGHER PROPORTION OF

PYROGENIC SPECIES NOT UNEXPECTED FOR SAMPLES RELATED TO AN ENGINE EXHAUST (LIKELY TO BE

BOUND TO SOOT RATHER THAN DISSOLVED/DISPERSED)

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EGCSA Workshop London 30 Nov. 16 – 01 Dec 16

IN CONCLUSION - PAH

• CONCENTRATION OF THE 3 MOST PREVALENT LIGHTER WEIGHT PAH SPECIES IN SCRUBBER

DISCHARGES BETWEEN 6 AND 30 TIMES LESS THAN IN PRODUCED WATERS FROM OIL &

GAS PRODUCTION FACILITIES

• WORST CASE SCENARIO FOR ANNUAL DISCHARGE QUANTITIES OF 4 HEAVIER MOLECULAR

WEIGHT INDICATOR SPECIES WELL BELOW ILLUSTRATIVE SEPA LIMITS

• HIGHEST CONCENTRATION OF BENZO[A]PYRENE RECORDED HALF THAT OF WHO

DRINKING WATER GUIDELINES LIMITS

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EGCSA Workshop London 30 Nov. 16 – 01 Dec 16

Q&A WASH WATER SAMPLING PROGRAMME 2

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EGCSA Workshop London 30 Nov. 16 – 01 Dec 16

REFERENCES

• BURGESS, R.M., AHRENS, M.J. & HICKEY, C.W. (2003). GEOCHEMISTRY OF PAHS IN AQUATIC ENVIRONMENTS: SOURCE, PERSISTENCE

AND DISTRIBUTION. IN: DOUBEN, P.E.T. ED. PAHS: AN ECOTOXICOLOGICAL PERSPECTIVE. CHICHESTER: WILEY, PP.39-45.

• GUIDELINES FOR DRINKING-WATER QUALITY. 4TH ED. (2011). SWITZERLAND: WORLD HEALTH ORGANISATION. AVAILABLE AT:

HTTP://WWW.WHO.INT/WATER_SANITATION_HEALTH/PUBLICATIONS/2011/DWQ_GUIDELINES/EN/

• HATZIANESTIS, I. & SKLIVAGOU, E. (2002). DISSOLVED AND SUSPENDED POLYCYCLIC AROMATIC HYDROCARBONS (PAH) IN THE NORTH

AEGEAN SEA. MEDITERRANEAN MARINE SCIENCE, VOL. 3/1, 2002, PP. 89-98.

• HUFNAGL, M., LIEBEZEIT, G. & BEHRENDS, B. (2005). EFFECTS OF SEA WATER SCRUBBING FINAL REPORT. SUNBURY: BP MARINE.

• NAGDAL, N. (1993). AMBIENT WATER QUALITY CRITERIA FOR POLYCYCLIC AROMATIC HYDROCARBONS (PAHS) [ONLINE]. PROVINCE OF

BRITISH COLUMBIA: MINISTRY OF ENVIRONMENT, LANDS AND PARKS. AVAILABLE AT:

HTTP://WWW.ENV.GOV.BC.CA/WAT/WQ/BCGUIDELINES/PAHS/

• PAMPANIN, D.M. & SYDNES, M.O. (2013) POLYCYCLIC AROMATIC HYDROCARBONS A CONSTITUENT OF PETROLEUM: PRESENCE AND

INFLUENCE IN THE AQUATIC ENVIRONMENT. IN: KUTCHEROV, V. ED. HYDROCARBON. INTECH, DOI: 10.5772/48176. AVAILABLE AT:

HTTP://WWW.INTECHOPEN.COM/BOOKS/HYDROCARBON/POLYCYCLIC-AROMATIC-HYDROCARBONS-A-CONSTITUENT-OF-

PETROLEUM-PRESENCE-AND-INFLUENCE-IN-THE-AQUATIC-EN

• POLYCYCLIC AROMATIC HYDROCARBONS (PAHS) (FOUR INDICATOR COMPOUNDS OF LRTAP) [ONLINE]. (UNDATED). SCOTTISH

POLLUTION RELEASE INVENTORY: SCOTTISH ENVIRONMENT PROTECTION AGENCY. AVAILABLE AT:

HTTP://APPS.SEPA.ORG.UK/SPRIPA/PAGES/SUBSTANCEINFORMATION.ASPX?PID=128

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EGCSA Workshop London 30 Nov. 16 – 01 Dec 16

MARK WEST

MARK WEST IS A SELF-EMPLOYED CONSULTANT AND PROJECT MANAGER WITH OVER 30 YEARS EXPERIENCE IN

THE MARINE INDUSTRY; MUCH OF HIS WORK OVER THE LAST 12 YEARS HAS BEEN ASSOCIATED WITH MARPOL

ANNEX VI AND TRIALS OF EQUIPMENT FOR THE CONTROL AND MONITORING OF EXHAUST EMISSIONS FROM

SHIPS.

HE WAS BP’S REPRESENTATIVE ON TRIALS OF TWO LARGE SEAWATER SCRUBBER SYSTEMS ON PASSENGER

VESSELS, INCLUDING THE FERRY PRIDE OF KENT FROM 2003 AND AN INDUSTRY REPRESENTATIVE ON THE IMO

DRAFTING GROUPS FOR THE FIRST ITERATION OF THE EXHAUST GAS CLEANING SYSTEM GUIDELINES. HE HAS

WRITTEN AND EDITED THE EGCSA GUIDE TO EXHAUST GAS CLEANING SYSTEMS AND CO-AUTHORED A SNAME

PAPER ON SOX EMISSIONS. MARK HAS PRESENTED AT EGCSA TRAINING COURSES AND WAS A SPEAKER AND

TECHNOLOGY PANEL HOST AT THE SIBCON 2014 SESSION ON SCRUBBERS.

BEFORE STARTING HIS OWN BUSINESS IN 2003, MARK HELD VARIOUS TECHNICAL MANAGEMENT ROLES IN

CASTROL MARINE LUBRICANTS AND WAS A SEAGOING ENGINEER FOR 11 YEARS. HE HAS A UK CLASS 1

CERTIFICATE OF COMPETENCY - CHIEF MARINE ENGINEER OFFICER.

CONTACT: [email protected]