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H2S!Takecare!|WorldBunkering

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PaulLivingston,G

Thepresenceofhydrogensulphide(H2S)inmarinefuelsposesadualdangerthroughthestorageandhandlingoffuels.Notonlymust
webeawareoftheassociatedhealthandsafetyrisksbutalsoofthedamagethatthiscorrosivegascancausetotanksandfuellines.
If we are aware of danger we can act to mitigate the risks. Historically there has been no routine test to identify this gas under
ISO8217. Instead, the policing of H2S was left with the refinery. But does the testing and indeed the specification limit adopted
downstream fully assist in quantifying the potential risk? This article aims to highlight the issues surrounding H2S and the
developmentswiththetestingofH2Sinbunkerfueloils.
JustwhatisH2S?

Hydrogen sulphide is a colourless chemical

compound that is both toxic and flammable. It is
often responsible for the foul odours of rotten
eggs in volcanic gas, stagnant water or
flatulence! Although very pungent at first, it
quickly deadens the sense of smell so that
potentialvictimsmaybeunawareofitspresence
until it is too late. This poisonous gas can attack
several different systems in the body, although
thenervoussystemismostaffected.

Itformsacomplexbondwithironblockingoxygenfrombindingandstoppingcellularrespiration.Exposuretolowerconcentrationswill
result in nausea, shortness of breath, eye irritation, sore throat and fluid in the lungs. Longterm, lowlevel exposure may result in
fatigue,lossofappetite,headaches,irritability,poormemory,anddizziness.H2Sisheavierthanairandwillsettleandaccumulateat
thebottomoftanksandpoorlyventilatedspaces.Todemonstrateitslethalabilitywecanlistthefollowingaffectsofexposure:
Oneppmisthelevelatwhichmostpeoplewilldetectthecharacteristicodour
10ppmistheoccupationalhealthexposurelimitforeightworkinghoursperday
20ppmcauseseyeirritation
200ppmparalysestheolfactorynerve:thesenseofsmelldisappears
350550ppmleadstopulmonaryoedemawiththepossibilityofdeath
5501000 ppm causes strong stimulation of the central nervous system and rapid breathing, leading eventually to loss of
breathing
800ppmisalethalconcentrationtohumanswithfiveminutesexposure
Concentrations,over1,000ppmcausesimmediatecollapsewithlossofbreathing,evenafterasinglebreath.

Howisitcreated?
Crude oil is a complex mixture of hundreds of hydrocarbons, including many which contain sulphur. Refining the crude oil includes
convertingmostofthatsulphurintogaseoushydrogensulphide.Thehydrodesulphurisationprocessliberatessulphurfrompetroleum
bytheactionofhydrogenandtheresultingH2Sisconvertedtoelementalsulphurbypartialcombustion.Rawnaturalgasalsocontains
gaseous hydrogen sulphide and mercaptans (sulphurcontaining organic chemical substances) which are removed in natural gas
processing.Thehydrogensulphideremovedintherefiningandprocessingofcrudeoilandnaturalgasissubsequentlyconvertedinto
byproductelementalsulphur.
H2Sandbunkers
H2S is undesirable in marine fuels and should not be present. However, as there are no current limits set for the accepted levels of
H2Satthepointofdeliveryofbunkers,theadoptionofanagreedlevelisbeingconsidered.Storagetanksandfuelsystemswhichuse
bunkerscontainingH2Shavebeenknowntoencounterhighlevelsofcorrosion.Sulphatereducingbacteria(SRB)intheoilhavebeen
said to cause microbial induced corrosion to the tank bottom plating. In addition, the H2S gas released from the bulk liquid during
storagewillbuildupinthetankheadspacetocreateanidealenvironmentforpyrophor(pyrophoricironsulphide).
In basic terms this means that sulphide will react with iron oxide (rust) without oxygen to create iron sulphide in an exothermic
reaction, resulting in substantial heat, which for obvious reasons is not desirable!. Wet cracking is the occurrence of blistering to
exposedsteelinanaqueousenvironmentthatcontainshydrogensulphide.Thishydrogenrelatedcorrosionresultsinblistersorblister
crackstotheplatesurfaces.FuelcontainingentrainedH2Sgaswillreleasesomeofthatgasthroughoutitsstorage.Therateatwhich
thegaswillevolvewilldependonmanyvaryingfactors,including:

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H2S!Takecare!|WorldBunkering
ThequantityofH2Sintheliquidphase
Thelengthoftimethefuelisstored
Thetemperatureoftheoil
Thewayinwhichfuelisagitated,pumpedortransferred
Biochemicaldecomposition.

Settinglimits
ISGOTT(InternationalSafetyGuideforOilTankersandTerminals)statesinitsguidelinesforcrewenteringpumproomsandenclosed
spaces, a limit of 10ppm TLV (Threshold Limiting Value) and OSHA (Occupational Health & Safety Administration) has guidelines for
H2Sexposurealsosetat10ppm.Thecruxofthematterisunderstandingthepotentialriskthatthisgasposes.Overexposurecankill.
So what limit should we apply? And should the limit be applied to H2S in the vapour phase or the liquid phase? From a health and
safetyperspective,itisthegasphasewhichismostimportant,assignificantconcentrationsofthegasareknowntoaccumulateinthe
headspaceofstoragetanks.
From an operational perspective, the liquid phase is considered more important. However, the concentration of gas in the vapour
phase can only be measured at a given moment of time, whereas the measurement of H2S in the liquid phase gives a total
concentration and therefore indicates the potential of the fuel to emit the gas in the vapour phase. Unfortunately, the correlation
betweenH2Sintheliquidphaseandinthevapourphaseisfarfromsimple.Theamountofgasemittedbyaliquidtotheatmosphere
dependslargelyonapartitioncoefficient.Insimpleterms,thisistheamountofgasthatisentrainedinaliquidphasethatwouldbe
expectedtobereleasedtotheatmosphere(theequilibriumpoint).
The problem with marine bunker fuel is that it is not a pure distillate or pure chemical, and as such each batch could have a
different chemical makeup and therefore a different coefficient. Various studies have been carried out in an effort to determine the
partitioncoefficientofresidualoil.Dependinguponwhichstudyis referred to, the findings vary. However, in general, it is estimated
thatevery1mg/kgH2Sinliquidphaserepresentsanythingbetween80and400ppminthevapourphase.
Testmethods
HistoricallytheindustryhasreliedontwoestablishedtestmethodsforthedetectionofH2S,butbothneedtobeputintothecontextof
the appropriate application. To measure H2S in the liquid phase of the oil (by IP 399) we use a traditional wet chemistry test which
involveslengthypreparation.Thisisconsideredacomplextestandmeasuresthetrapped(entrained)gasintheliquidwhichcanbe
releasedovertime.Thetest,oncecomplete,willquotearesultinmilligramsperkilogramme(mg/kgorppm).Refinery(downstream)
specificationsmayvarybutgenerallyalimitofbetween2to3mg/kgisappliedpriortothesalesofthestock.
TomeasureH2Sinthevapourphaserequiresthemeasurementofevolvedgasintotheheadspaceofasamplecontainer.Thistestis
carriedoutusinggasdetectiontubes.Thelaboratorytest(ASTMD5705)involvesheatingaknownquantityofoilinanenclosedvessel
for a set period of time, after which a gas detection tube in the inert head space measures the H2S in the gas phase. Additionally,
thesegasdetectiontubescanbeusedtocheckH2Slevelsintanktopsorworncontinuouslybybargeorvesselcrewtocalculate the
exposureovertime.
This onboard vapour phase test is best suited for use to quantify and assess occupational health
risks.Inrealitytheonlysemiaccuratewayofmeasuringtheevolvedgasistocarryoutonboard
measurements in the tank tops or the affected confined working areas. These onboard tests will
give a snap shot of the level of H2S at that given time. However, the onboard test is not a
standard test method, it is simply a means to measure the levels of exposure, if you remember
ISGOTT recommend exposure be limited to 10ppm TLV (Threshold Limiting value) Reports of
increased cases of H2S in bunker fuels has prompted the ISO working group to add a new test
and specification limit to the proposed (draft) of the ISO8217, expected to be finalised and
publishedin2010.
The new test method (IP 570) has been adopted by ISO in an attempt to make routine analysis
faster and more accessible. But there are problems. Due to poor historical data on the
occurrencesofH2Sinbunkerfuels,theinclusionoftheparameterhasbeendelayeduntil2012to
allowtimefordatatobecollatedandanappropriatespecificationtobeconcluded.
Thewayforward
ItisclearthatthepresenceofH2Sinmarinefuelisundesirable.Defininganacceptablelimitwithinthespecificationissomethingthat
we believe will require considerably more debate. The limit of 2 mg/kg put forward by the ISO working group has been questioned
because an acceptable level of 2 mg/kg in the liquid phase could give rise to as much as 800 ppm in the vapour phase a lethal
concentrationwithfiveminutesexposureandwellinexcessoftheoccupationalhealthrecommendationof10ppmvalue
ThefactthattheISOworkinggrouphaveaddedH2StothelatestdraftofISO8217isinouropinionaverypositivestepasitservesto
heighten the profile of what is a very important debate. Currently there is little research on H2S in marine fuels and it seems that
thereissomewaytogobeforeanacceptablelevelwillbeagreed.

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