Update-Chemical Contaminants in Fuels from ARA Region
Update-Chemical Contaminants in Fuels from ARA Region
FINDINGS & INSIGHTS
Since the last alert (BF202207-01) dated on 05-July-2022 on Chemical Contaminants in Fuels from ARA Region (Amsterdam, Rotterdam & Antwerp), CTI-Maritec has kept a close watch on the fuel quality in the region. More recently, several VLSFOs delivered in this region are still observed with the presence of chemical contaminants. These VLSFOs also indicated elevated potassium content and acid number.
Forensic analysis by Gas Chromatography and Mass Spectrometry techniques, specifically ASTM D7845 GC/MS and Solid Phase Extraction (SPE) GC/MS, on some of the samples revealed the presence of the following compound groups at abnormally high concentrations
- Fatty Acids and Monoglycerides (>1000ppm)
- Alkylresorcinols (>2000ppm)
- Phenolic compounds (>1000ppm)
It is difficult to determine a safe concentration level suitable for marine diesel engine usage or the baseline wherein machinery problems may occur. Due to the severity of the Machinery problems faced, we urge vessel operators to continue pre-emptively testing the fuels bunkered in the region by accredited test methods to detect these contaminants assessing the risk each bunker stem has on the vessel machinery.
Recommendation by CTI-Maritec:
- Obtain quality assurance and test proof from suppliers on the absence of contaminants in the intended stem prior bunker delivery (This will require testing beyond the scope of standard ASTM D7845-20 test method)
- Plan your bunkers well in advance to keep the incoming fuel segregated and reduce the risk of comingling.
- Ensure sampling procedure during bunkering is witnessed by both supplier and receiver and sample bottles are counter-sealed and same recorded in the Bunker Delivery Note.
- Be aware of your bunker supply contract and the notification time limit stipulated to flag potentially problematic fuels to the supplier.
- Look for signs of abnormally high potassium content (>110ppm) and/or high total acid number (>1.5mgkoh/g) and pre-emptively analyze the bunker fuel by Gas Chromatography and Mass Spectrometry (GC-MS) that can reveal the presence of undesirable compounds in the fuel thus safeguarding vessel operations.
- Where chemical compounds have been detected, gather sufficient evidence to support further investigation. Proceed to conduct joint analysis in agreement with the supplier by an independent laboratory capable of detecting the compounds to determine the compliance with ISO8217 clause 5 – General Requirements.
This document however does not reflect on the overall quality of fuel being supplied at ARA region.
Maritec Pte Ltd can assist you in with further information on quality of bunkers tested in different regions. If you require any other information or assistance do not hesitate to contact us
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Contaminated VLSFO in US-Gulf Region
Contaminated VLSFO in US-Gulf Region
FINDINGS & INSIGHTS
Recently MARITEC has investigated 5 VLSFO samples that were bunkered in the US-Gulf region between June to July 2022. Operational Feedback was received from 2 vessels that had used these fuels indicating issues such as excessive wear of fuel pump plungers, barrels, and fuel injectors.
Further investigation through forensic analysis by ASTM D7845 Direct Injection and Solid Phase Extraction GCMS methods, has indicated these fuels to have an uncharacteristic detection of chemical species, specifically:
- Tetrachloroethylene (Chlorinated Organic Compound) at concentration less than 100ppm
- FAME at concentrations 300 to 400ppm
- Fatty Acids at concentrations between 50-2000ppm
Though there is insufficient literature that the presence of these compounds especially at these concentration levels causing issues as mentioned above, it remains a cause of concern as they are not natural products of a refinery stream.
Through experience and feedback from vessel usage, these compounds primarily affect the fuel service system resulting in excessive wear of injection components.
It may not always be possible to get a thorough GCMS analysis along with the supplier’s Certificate of Quality prior bunkering. If you are planning to bunker in this region, we recommend ensuring correct sampling procedure and proper documentation is carried out onboard to ensure true representation of the bunkered fuel. Record any event and document evidence indicating any operational issues faced onboard by the vessel during the fuel usage.
Alternatively, CTI-Maritec advises to pre-emptively conduct GCMS by D7845 and Solid Phase Extract to look out for such deleterious material and check whether the fuel supplied to the vessel contravenes stipulations of the MARPOL Annex VI Regulation 18.3 & ISO 8217 Clause 5 both of which mentions that marine fuels supplied to the ships should be free from chemical waste or added substances at quantities that may jeopardize the safety or adversely affects the performance of the machinery.
This document however does not reflect on the overall quality of fuel being supplied at US Gulf region, it is however advised to take the necessary precautions as indicated above.
Maritec Pte Ltd can assist you in with further information on quality of bunkers tested in different regions. If you require any other information or assistance do not hesitate to contact us.
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Chemical Contaminants in Fuels from ARA Region
Chemical Contaminants in Fuel from ARA Region
FINDINGS & INSIGHTS
Maritec has tested several VLSFOs delivered in the ARA region to be observed with the presence of chemical contaminants in the recent months. These VLSFOs also indicated elevated potassium content and acid number.
From these samples, CTI-Maritec has obtained feedback from vessels encountering rapid and excessive wear on fuel pumps on main propulsion engines and a tendency for increased deposit formation in the exhaust system.
Figure 1: Exhaust grid fouling
Figure 2: Turbocharger Nozzle Ring fouling
Figure 3: Fuel Pump Plunger wear down
Forensic analysis by Gas Chromatography and Mass Spectrometry techniques, specifically ASTM D7845 GC/MS and Solid Phase Extraction (SPE) GC/MS, on some of the samples revealed the presence of the following compound groups at abnormally high concentrations
- Fatty Acids and Monoglycerides (>1000ppm)
- Alkylresorcinols (>2000ppm)
- Phenolic compounds (>1000ppm)
Fatty acids and Monoglycerides are acidic compounds commonly found in fuels where the FAME content has broken down in the presence of water and have known to cause costly accelerated wear in fuel oil injection pumps. The presence of these compounds can also suggest an inclusion of substandard Bio-fuels into the blend. This also explains the high potassium content in the fuel as Potassium Hydroxide (KOH) is one of the possible catalysts used in the production of bio-diesel. The separation of the spent catalyst out from the final product is a complicated and expensive process. The increased potassium can also contribute towards the total ash forming tendency of the fuel leading to abnormal deposit formation in post combustion exhaust system components.
The presence of Alkylresorcinols and phenolic compounds suggests the inclusion of shale oil which is allowed as per the definition of ‘petroleum fuel’ in ISO 8217 standards. CTI-Maritec’s experience however has shown that the presence of these compounds tends to cause fuel instability leading to issues like filter blockages and purifier bowl overloading. This is despite the Total Sediment potential tests being within specification. Any sludge not capable of being removed by the fuel treatment system can cause combustion issues in the main engine.
If your vessel is expected to bunker in the ARA region; CTI Maritec advises to check the pre-bunkering certificate of quality or Manifold sample test results for signs of abnormally high potassium content (>110ppm) and/or high total acid number (>1.5mgkoh/g) and pre-emptively analyze the bunker fuels by Gas Chromatography and Mass Spectrometry (GC-MS) that can reveal the presence of undesirable compounds in the fuel thus safeguarding vessel operations.
In every case, CTI Maritec urges bunker fuel receivers to ensure thorough attention is given to the witnessing of correct sampling procedures during bunkering, counter-sealing and recording of seals in the bunker delivery note and any other documentation required to ensure correct representative samples are obtained during the bunkering process.
Collecting objective evidence on the storage, treatment and usage of the fuel is to be always given a high priority in the event an operational problem occurs to determine if the fuel used was one of the root causes for a machinery failure.
This document however does not reflect on the overall quality of fuel being supplied at ARA region.
Maritec Pte Ltd can assist you in with further information on quality of bunkers tested in different regions. If you require any other information or assistance, please do not hesitate to contact us
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Low Flashpoint VLSFO Bunkers in Singapore
Low Flashpoint VLSFO Bunkers in Singapore
FINDINGS & INSIGHTS
Maritec Pte Ltd has tested five samples representing VLSFO deliveries in Singapore with flashpoint as low as 50°C for the period of 12th June 2022 to 24th June 2022 from various suppliers.
SOLAS Chapter II-2, Part B, Reg. 4. Clause 2.1.1 states
“The following limitations shall apply to the use of oil as fuel, except as otherwise permitted by this paragraph, no oil fuel with a flashpoint of less than 60°C shall be used.”
If your vessel has bunkered a low flashpoint fuel it is prudent to observe the below precautions.
- Flame screens on tank vents should be maintained in good condition and there should be no sources of ignition in the vicinity of the vents. This will assist in safe natural ventilation of volatile components in the fuel.
- No Smoking, No naked flame and No hot work must be allowed at any areas near to tank air vents.
- Send additional tank(s) samples upon arrival in port to check the fuel properties and flash point results especially if there has been co-mingling of fuels in bunker tanks
- If the vessel is out at sea it may be possible to obtain dispensation from your Flag State Administration up to next arrival port
- Put the supplier on notice promptly and notify your P&I club.
ISO 4259 interpretation for tested flashpoint temperature is not taken into consideration here as the safety of onboard crew and vessel is of higher precedence.
This document however does not reflect on the overall quality of fuel being supplied at Singapore, if you intend to bunker at this region please request for a Certificate of Quality prior to loading.
Maritec Pte Ltd can assist you in with further information on quality of bunkers tested in different regions. If you require any other information or assistance do not hesitate to contact us
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Organic Chlorinated Compounds from Singapore Region
Organic Chlorinated Compounds from Singapore Region
FINDINGS & INSIGHTS
Updates to detection levels and effects on machinery encountered
Issued on 20 April 2022
Since the last alert (BF202203-02) dated 15-March-2022 on High Sulphur Bunker fuels contaminated with chlorinated organic compounds, CTI-Maritec has kept a close watch on the fuel quality in the region and collated further feedback on the fuel’s usage. The summary data on samples from Q1 2022 shows the contaminants mainly have a detrimental effect on the fuel injection system and to a certain extent on the fuel treatment and filtration system.
The damages reported have affected both conventional and electronic engines and not limited to any Engine maker and type. This has led to failure of prime movers for the vessels affected by the contaminated fuel.
Our investigation thus far confirmed high concentration level with an average value of 3419ppm on 1,2-Dichloroethane (CAS no.107-06-2) as the main compound detected. This compound in its pure form is considered hazardous to personnel by OSHA causing irritation to eyes, respiratory system and skin depending on the exposure concertation and time. As with any marine fuel it is advised to ensure sufficient ventilation in the machinery spaces, particularly in the fuel treatment room. It is also advised to minimize personnel exposure to fuel tank vent heads as these chlorinated organic compounds have low boiling points that can be below the heating temperature of settling and service tanks.
It is difficult to determine a safe concentration level suitable for marine diesel engine usage or the baseline wherein machinery problems may occur. Due to the severity of the Machinery problems faced, we urge vessel operators to continue pre-emptively testing the fuels bunkered in the region by accredited test methods to detect these contaminants assessing the risk each bunker stem has on the vessel machinery.
It should be further noted that the compounds in question are not listed in the component table of the test method ASTM D7845-20 comprising of 29 commonly detected compounds and therefore can be missed by the quality control process in the supply side.
Maritec offers ASTM D7845-20 GCMS analysis & in addition extra 22 compounds calibrated with external standards for accurate quantification which includes organic chlorides.
The percentage of High Sulphur fuels detected with Chlorinated Organic Compounds by CTI-Maritec in Singapore bunker stems in 2022 is given below, a decreasing trend in the detection is observed for April 2022. Nevertheless, CTI-Maritec advises vessel owners to be vigilant and continue to pre-emptively test their fuel samples obtained from the receiving manifold.
Recommendation by CTI-Maritec:
- Obtain quality assurance and test proof from suppliers on the absence of chlorinated organic compounds in the intended stem prior bunker delivery (This will require testing beyond the scope of standard ASTM D7845-20 test method)
- Plan your bunkers well in advance to keep the incoming fuel segregated and reduce the risk of comingling.
- Ensure sampling procedure during bunkering is witnessed by both supplier and receiver and sample bottles are counter-sealed and same recorded in the Bunker Delivery Note.
- Pre-emptively test vessel manifold samples by accredited GCMS test methods capable of identifying the chlorinated organic compounds – preferably quantitative methods to identify the concertation levels of the detected compounds.
- Pre-emptively conduct stability analysis outside the scope of ISO8217 involving the referee TSP method.
- It is noted that the recent samples with the high levels of chlorinated organic compounds tested poorly for fuel stability when subject to Manual P-value by SMS1600 test method.
- Be aware of your bunker supply contract and the notification time limit stipulated to flag potentially problematic fuels to the supplier.
- Where chlorinated organic compounds have been detected, gather sufficient evidence to support further investigation. Proceed to conduct joint analysis in agreement with the supplier by an independent laboratory capable of detecting the compounds to determine the compliance with ISO8217 clause 5 – General Requirements.
This document however does not reflect on the overall quality of the fuel being supplied in Singapore. If you intend to bunker at this region, CTI-Maritec can assist you with further information of the bunker quality in the region.
If you require any other information or assistance do not hesitate to contact us
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GS/MS Analysis as a Complementary to ISO 8217 table 1 and table 2 specification testing to detect and quantify deleterious materials within the purview of ISO 8217 - Clause 5
GS/MS Analysis as a Complementary to ISO 8217 table 1 and table 2 specification testing to detect and quantify deleterious materials within the purview of ISO 8217 - Clause 5
Table of Contents
- Table of Contents
- INTRODUCTION
- THE SUPPLY CHAIN
- THE SPECIFICATION
- GAS CHROMATOGRAPHY–MASS SPECTROMETRY (GCMS) ANALYSIS
- GCMS AND PRE-TREATMENT
- GCMS BY ASTM D7845
- GCMS BY SPE (SOLID PHASE EXTRACTION)
- FINDINGS
- CHLORINATED ORGANIC COMPOUNDS
- BY-PRODUCT OR PROCESSED PRODUCT DERIVED FROM BIO-BASED OR PLANT-BASED SOURCES AND BY-PRODUCT FROM CHEMICAL INDUSTRY
- CASHEW NUTSHELL LIQUID
- ESTONIAN SHALE OIL
- GCMS ANALYSIS AS A COMPLEMENTARY TEST SOLUTION
- ACCREDITED GC/MS TEST PACKAGE AND ASSOCIATED DETECTIONS
- MOVING FORWARD
Issue of chemical contamination had plagued the bunkering industry for years, and the risk of receiving contaminated bunker fuels is likely to persist. The importance of buying from reputable suppliers with robust quality control procedures cannot be over empathised. However, the complexity of the bunker supplier chain as well as unregulated use of cutter stocks would mean that any quality control process, no matter how robust, is likely to only minimise and not fully eliminate risk of such contaminations. It is therefore important for bunker buyers and operators have their own control measures in place.
The test scope stated in table 1 & 2 of ISO 8217 is limited and insufficient to cover the requirement for detection of deleterious materials in marine bunker fuels. Marine fuel testing laboratories had successfully addressed the limitation of ASTM D7845, the only standard GCMS test method, and is able to apply it as an effective chemical screening tool to complement the table 1 & 2 test scope. As demonstrated in the case of Chlorinated Organic Compound (COC) contamination in 2022, most fuel laboratories had successfully identified COC, using ASTM D7845 test method, as the main contaminants causing the damages. Findings had been proven to be consistent across laboratories using the same method and was well accepted by the industry and port authorities.
Over the years, GC/MS analysis has proven to be a practical technique to employ for detection and quantification of deleterious materials, or chemical contaminants present in bunker fuels. This technique been widely used and accepted across the marine industry for marine fuel forensic testing. Chemical screening of bunker fuel is a critical element of successful onboard fuel management, and GC/MS analysis can be employed as a complement to the routine test scope, specifically to cover the detection and quantification of deleterious materials which otherwise cannot be detected by the table 1 and 2 parameters.
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