Update on wash water sampling programme paper & standards for PAH monitoring MARK WEST - RENAISSANCE HOTEL, LONDON, 09-10 OCTOBER 18 Paper submitted to IMO MEPC 73 MEPC 73/INF.5 key points: • 238 samples • 20 vessels in Baltic and North Sea ECAs, 2 vessels in the Mediterranean (11 RO-RO) • IF380 - 0.96%S to 3.14%S (2.38%S average) • Manoeuvring to full power (59% MCR average)

• Two sampling programmes, two laboratories • US EPA 16 Polycyclic Aromatic Hydrocarbons (PAH) • Metals (Hg in Programme 1 only) • BTEX (in Programme 1 only) • Nitrates/nitrites (in Programme 1 only)

EGCSA Workshop Renaissance Hotel, London 9-10 Oct 2018 2 EGCS type & mode of operation

• Complete anonymity – ships and EGCS Number scrubber vendors Hybrid 16 • EGCS configurations – market representative Open loop 5 • Multiple and single entry units Closed 1 • Multiple and single units on a ship • ‘U’, ‘inline’, cyclonic, packed bed, open tower Hybrid system sampling • Main engines, auxiliary engines and boilers 13 open loop only 2 open & closed loop 1 closed loop only

EGCSA Workshop Renaissance Hotel, London 9-10 Oct 2018 3 Analysis results key points Concentrations of EPA 16 PAH normalized at 45m3/MWh washwater flow rate: • Below 43μg/l in the discharges from all 22 vessels • Average normalized concentration less than 12μg/l Most prevalent PAH species • Naphthalene (average 47%) • Phenanthrene (average 25%) B(a)P – World Health Organization marker for drinking water quality • WHO guideline limit of 0.7μg/l • Normalized concentrations below in all but one sample (0.74μg/l) • Average normalized B(a)P concentration 0.06μg/l • Unnormalized concentrations all below the WHO limit

EGCSA Workshop Renaissance Hotel, London 9-10 Oct 2018 4 Analysis results key points

BTEX • Maximum concentration of 4μg/l in one sample • Below limits of detectability in 11 of 15 overboard samples • Concentrations in the other four samples below WHO guideline limits for drinking water

- - Nitrates (NO3 ) & Nitrites (NO2 ) • Current EGCS systems not designed to scrub NOx • All normalized nitrate levels at overboard discharge below Scrubber Guidelines’ limit of 60mg/l • Concentrations of nitrite negligible • Nitrate in the clean seawater supply to open loop scrubbers contributed significantly to nitrate at the discharge. • Max normalized concentration of 7mg/l was found by deducting the concentration at system inlet from overboard. • Suggest if needed for compliance, this an option is allowed in Scrubber Guidelines • Alternatively, consider removing the need for nitrate testing for current scrubber designs

EGCSA Workshop Renaissance Hotel, London 9-10 Oct 2018 5 Analysis results key points

• Vanadium most prevalent metal • Arsenic, Cadmium Mercury below limits of detectability in most samples – where detected concentrations sub parts per billion • As no limits in Scrubber Guidelines, concentrations of chromium, copper, lead, nickel and zinc compared with EU limits for discharges of waste water from cleaning of waste gases from incineration plant. • Of 195 individual test results, three (two lead and one zinc) were found to be above the EU limits on two ships. • First ship - lead below detectable limits at a later sampling • Second ship - high zinc at sea water inlet to the scrubber system • Evidence of contribution of zinc and copper probably from anodic protection and marine growth inhibition systems. • Likely to be seen on many ships regardless of whether scrubbers are installed

EGCSA Workshop Renaissance Hotel, London 9-10 Oct 2018 6 Practicality vital

http://www.egcsa.com/wp- http://www.egcsa.com/wp content/uploads/EGCSA- -content/uploads/EGCSA- Euroshore-scrubber-water- Scrubber-Water-Sampling- sampling-Ship-Guide-2016_17.pdf Point-Specification-v1.pdf

EGCSA Workshop Renaissance Hotel, London 9-10 Oct 2018 7 Why monitor PAH? • PAH is monitored in scrubber discharges due to the lack of instrumentation capable of directly monitoring the very low concentrations of oil. • Oil in scrubber discharges is well below detection capabilities of marine 15 or 5 ppm oil-in- water monitors. • Oil contains PAHs which fluoresce when the molecules are exposed to and absorb ultra violet light energy • Detection possible at very low ppb concentrations • Instruments are calibrated using phenanthrene, but in service other PAH’s in the discharge water fluoresce and are detected at the same wavelength as phenanthrene

• Hence the term phenanthrene equivalents – PAHphe is used in the Scrubber Guidelines

• PAHphe concentration limits at various flow rates in the Scrubber Guidelines are for control of the amount of oil in scrubber water discharges

EGCSA Workshop Renaissance Hotel, London 9-10 Oct 2018 8 Phenanthrene excitation & detection

Output proportional to compound concentration

Detector Wavelengths specific to Phenanthrene compound Phenanthrene absorbance – UV fluorescence - light source detection Emission filter & lenses

Excitation filter Wavelengths Light source & lenses emitted by compound & stray light

Many Specific Sample cell wavelengths of wavelengths of (absorbance & excitation light light of compound)

EGCSA Workshop Renaissance Hotel, London 9-10 Oct 2018 9 Why monitor PAH – the history MEPC 55/4/5, 7 July 2006: 7.2 It has been demonstrated that the monitoring of PAH provides a direct surrogate to the monitoring of oil content in the wash water. Further the instruments available to monitor PAH have resolutions to parts per billion (ppb), levels and are insensitive to interference from the varying nature of sea water. Max concentration of oil Several assessments of currently available technology for wash water treatment suggest that it is reasonable to set the maximum content of oil in the wash water at 1 ppm (parts per million). Relating the oil content to PAH, leads to a recommendation to set maximum continuous PAH concentration at 30 ppb

MEPC.259(68) 2015 GUIDELINES FOR EXHAUST GAS CLEANING SYSTEMS 10.2 Washwater monitoring 10.2.1 pH, oil content (as measured by PAH levels), and turbidity should be continuously monitored and recorded as recommended in section 7 of these guidelines…

EGCSA Workshop Renaissance Hotel, London 9-10 Oct 2018 10 However… Questions: • What is meant by phenanthrene equivalence/equivalents? • Not helped by Appendix 3 of scrubber guidelines, which requests PAH and oil (detailed GC-MS analysis) of discharge water, to inform possible future changes to discharge limits; and • Separately from IMO but referencing scrubber guidelines, US EPA VGP, which requires annual analysis of discharge water for EPA16 Unintended consequences: • Shift a focus from monitoring oil to the monitoring of PAH itself

• Attempts at comparison of PAHphe online results with EPA 16 by laboratory analysis EGCSA has therefore convened a PAH monitor supplier working group • Coincides with IMO undertaking a review of the Scrubber Guidelines MEPC.259(68) by Correspondence Group reporting to PPR6 in February 2019 • CG brief includes clarification of the term PAH (polycyclic aromatic hydrocarbons) monitoring

EGCSA Workshop Renaissance Hotel, London 9-10 Oct 2018 11 Set standards & answer questions • Opportunity - important contribution to IMO review by the experts to bring clarity • What does the term phenanthrene equivalents really mean? • Agree a common definition for a PAH monitor, so same readings reported for same oil (hydrocarbon mix) • Monitoring both open and for closed loop systems • Measurement performance requirements/qualification criteria • Initial calibration methods • Onboard calibration & in-service verification procedures • Installation standards

• How does online PAHphe relate to “oil” and EPA16 at the laboratory • Understandable by persons with little or no specialist knowledge e.g. regulators, surveyors (& me!) • Product neutral standards / guidelines will allow suppliers and technologies to enter the market on a level playing field, while preserving proper standards • Address concerns regarding reliability and what is actually being reported • Buyers able to make decisions based on factors such as availability, price, relationship, etc.

EGCSA Workshop Renaissance Hotel, London 9-10 Oct 2018 12 June meeting welcome • The forecast growth in sales of EGCS is said to be in the region of 10,000 ships by 2025. • The EGCS technology is likely to advance in the future to include particulate removal. • We need to assure the integrity of EGCS so that they become accepted and main stream. • We need to assure integrity of the performance monitoring systems. • The work on PAH measurement needs to be scientifically founded. • We need to ensure that the parameters that are relevant to repeatable and accurate measurement are standardized. • We need to have completed the work before the revised EGCS guidelines go to MEPC 74 for adoption. • Remember we are protecting against oil discharge and not PAH. • The long term intention is that EGCSA members agree as part of the membership criteria observe the EGCSA standards, which may include PAH measurement standard. • The benefit for instrument manufacturers is a level playing field in terms of the technology performance specification.

EGCSA Workshop Renaissance Hotel, London 9-10 Oct 2018 13 “Oil”, PAHphe & EPA16 PAH

Many species & sub-species Complex mix!

Great range of concentrations & ratios

Standard Handbook Oil Spill Environmental Forensics: Fingerprinting and Source Identification - Scott Stout, Zhendi Wang 2016, P656 &657

EGCSA Workshop Renaissance Hotel, London 9-10 Oct 2018 14 “Oil”, PAHphe & EPA16 PAH Oil • Firstly using mean concentrations total of all PAH listed for IF380 analysed: • 27ppb PAH = 1 ppm oil

PAHphe • Instruments are calibrated using phenanthrene, but in service other PAHs in the discharge water fluoresce and are detected at the same wavelength as phenanthrene • There are many species and sub-species of PAH in oil EPA 16 PAH • Literature widely reports that the concentration of the EPA 16 PAHs and other PAHs, and the ratios between the various PAH differ from oil to oil • Great variation of the content of the various PAHs in crude oil from different sites

The concentration of EPA 16 from sample analysis by laboratory therefore cannot be compared with the PAHphe concentration reported by online monitors

EGCSA Workshop Renaissance Hotel, London 9-10 Oct 2018 15 Tomorrow AM - Working Group focus on • Definition of phenanthrene equivalents, excitation & detection – wavelength, bandwidth, tolerances • Effect of turbidity & gas bubbles, (clarifying related Scrubber Guidelines paragraph) • Closed loop monitoring PM - Feedback to members

EGCSA Workshop Renaissance Hotel, London 9-10 Oct 2018 16 Thank you

Q&A

EGCSA Workshop Renaissance Hotel, London 9-10 Oct 2018 17 PS – EGCSA.com

EGCSA Workshop Renaissance Hotel, London 9-10 Oct 2018 18 SOx scrubbing Scrubber wash water removes and converts sulphur oxides from the exhaust gases so they are discharged in the wash water as harmless sulphate. After sodium and chloride, sulphate is the most common ion in seawater. If all the sulphur in the world’s oceans were to be removed it would form a layer on the earth’s surface about 1.7m deep All the sulphur in all of the world’s oil reserves would add 10µm (10 x 10-6m)

EGCSA Workshop Renaissance Hotel, London 9-10 Oct 2018 19 EGCSA Workshop Renaissance Hotel, London 9-10 Oct 2018 20 References

• Mörtberg, M. (2015). Alstom Environmental Control Solutions, An Overview. [online] Network.bellona.org. Available at: http://network.bellona.org/content/uploads/sites/3/2016/05/1_Forum_Ene rgyClimate-Dialogue_Alstom_Presentation_ukr.pdf.

• Pampanin, D. and Sydnes, M. (2013). Polycyclic Aromatic Hydrocarbons a Constituent of Petroleum: Presence and Influence in the Aquatic Environment. INTECH Open Access Publisher, p.85.

• Stout, S. and Wang, Z. (2016). Standard handbook oil spill environmental forensics. 2nd ed. Academic Press, pp.656, 657.

EGCSA Workshop Renaissance Hotel, London 9-10 Oct 2018 21 MARK WEST

Mark West is a consultant and project manager with over 35 years experience in the marine industry; much of his work over the last 14 years has been associated with exhaust gas cleaning systems and instrumentation and technologies related to MARPOL Annex VI air pollution regulations, marine fuels and lubricants for 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. His work has included the EC funded DEECON project to develop an advanced scrubbing unit for SOx and particulate emission control. He has also managed ‘washwater’ sampling programmes on behalf of EGCSA for the European Sustainable Shipping Forum and has sailed on ships with scrubbers from several manufacturers for this project. Mark 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 SIBCON. Before taking up consultancy, 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] Tel +44 (0) 7785 916113

EGCSA Workshop Renaissance Hotel, London 9-10 Oct 2018 22 All information contained in this presentation, is for illustrative purposes only. It is non-binding and not guaranteed in any way. The Project Business and the presenter of this material hereby exclude all liabilities to the extent permitted by law for any errors or omissions in the presentation and for any loss, damage or expense (whether direct or indirect) suffered by a third party relying on information contained in the presentation. If you have any questions or need further information, please don’t hesitate to contact. Mark West, E: [email protected] T: +44 (0) 7785 916113

EGCSA Workshop Renaissance Hotel, London 9-10 Oct 2018 23