BIODETERIORATION ROOT CAUSE ANALYSIS – PART 4: CLOSING THE KNOWLEDGE GAPS

In my March 2021 article, I began a discussion of root cause analysis (RCA). In that article I reviewed the importance of defining the problem clearly, precisely, and accurately; and using brainstorming tools to identify cause and effect networks or paths. Starting with my April 2021 article I used a case study to illustrate the basic RCA process steps. That post focused on defining current knowledge and defining knowledge gaps. Last month, I covered the next two steps: closing knowledge gaps and developing a failure model. In this post I’ll complete my RCA discussion – covering model testing and what to do afterwards (Figure 1).

Step 7 Test the Model

As I indicated at the end of May’s post , the data and other information that we collected during the RCA effort led to a hypothesis that dispenser slow-flow was caused by rust-particle accumulation on leak detector screens and that the particles detected on leak detector screens were primarily being delivered with the fuel (regular unleaded gasoline – RUL) supplied to the affected underground storage tanks (UST).

Commonly, during RCA efforts both actionable and non-actionable factors are discovered. An actionable factor is one over which a stakeholder has control. Conversely, a non-actionable factor is one over which a stakeholder does not have control. Within the fuel distribution channel, stakeholders at each stage have responsibility for and control of some factors but must rely on stakeholders either upstream or downstream for others.

For example, refiners are responsible for ensuring that products meet specifications as they leave the refinery tank farm (Figure 2a – whatever is needed to ensue product quality inside the refinery gate is actionable by refinery operators), they have little control over what happens to product once it is delivered to the pipeline (thus practices that ensure product quality after it leaves the refinery are non-actionable).

Pipeline operators (Figure 2b) are responsible for maintaining the lines through which product is transported and ensuring that products arrive at their intended destinations in the – typically distribution terminals in the U.S. – but are limited in what they can add to the product to protect it during transport.

Terminal operators can test incoming product to ensure it meets specifications before it is directed to designated tanks. They are also responsible for maintaining their tanks so that product integrity is preserved while it is at the terminal and remains in-specification at the rack (Figure 2c). Terminal and transport truck operators have a shared responsibility that product is in-specification when it is delivered to truck tank compartments (solid zone where Figures 2c and 2d overlap).

Tanker truck operators are also responsible for ensuring that tank compartments are clean (free of water, particulates, and residual product from previous loads). Additionally, truck operators (Figure 2d) are responsible for ensuring that tanker compartments are filled with the correct product and that correct product is delivered into retail and fleet operator tanks. They do not have any other control over product quality.

Finally, retail and fleet fueling site operators are responsible for the maintenance of their site, tanks, and dispensing equipment (Figure 2e).

Regarding dispenser slow-flow issues, typically only factors inside the retail sites’ property lines are actionable (Figure 3 – copied from May’s post).

As illustrated in Figure 3, the actions needed to prevent leak detector strainer fouling were not actionable by retail site operators. In this instance, we were fortunate in that the company whose retail sites were affected owned and operated the terminal that was supplying fuel to those sites.

A second RCA effort was undertaken to determine whether the rust particle issue at the retail sites was caused by actionable factors at the terminal. We determined that denitrifying bacteria were attacking the amine-carboxylate chemistry used as a transportation flow improver and corrosion inhibitor. This microbial activity:

Although the rust particle load in each delivery was negligible (i.e., <0.05 %), the total amount of rust delivered added up quickly. If the rust particle load was 0.025 %, 4 kg (8.8 lb) of particles would be delivered with each 26.5 m3 (7,000 gal; 19,850 kg) fuel drop. The sites received an average of two deliveries per week (some sites received one delivery per week and others received more than one delivery per day). That translates to an average of 32 kg (70 lb) of particulates per month. Corrective action at the terminal eliminated denitrification in the RUL gasoline bulk tanks and reduced particulate loads in the RUL gasoline to <0.01 %.

Step 8. Institutionalize Lessons Learned

Although the retail site operators could not control the quality of the RUL gasoline they received, there were several actionable measures they could adopt.

These six actions were institutionalized as standard operating procedure (SOP) at each of the region’s retail sites. Site managers received the requited supplies, training on proper performance of each test, and instruction on the required record keeping. There has been no recurrence of premature slow-flow issues at any of the retail sites originally experiencing the problem.

Wrap Up

Although I used a particular case study to illustrate the general principles of RCA, these principles can be applied whenever adverse symptoms are observed. I have used this approach to successfully address a broad range of issues across many different chemical process industries. The keys to successful RCA include carefully defining the symptoms and taking a global, open-minded, multi-disciplinary approach to defining the cause-effect paths that might be contributing to the observed symptoms. Once a well-conceived cause-effect map has been created, the task of assessing relative contributions of individual factors becomes fairly obvious, even when the amount of actual data might be limited.

Bottom line: effective RCA addresses contributing causes rather than focusing only on measures that only address symptoms temporarily. In the fuel dispenser case study, retail site operators initially assumed that slow-flow was due to dispenser filter plugging. Moreover, they never checked to confrim that replacing dispenser filters affected flow-rates. This short-sighted approach to problem solving is remarkably common across many industries. To learn more about BCA’s approach to RCA, please contact me at fredp@biodeterioration-control.com.

FUEL & FUEL SYSTEM MICROBIOLOGY PART 28 – IS THE SULFUR IN HIGH SULFUR DIESEL TOXIC?

Diesel fuel biodeterioration is not affected by the fuel’s sulfur content.

There is a broadly embraced misperception about the relationship between diesel fuel’s sulfur content and its toxicity to microorganisms. This misperception is driven by two logical flaws.

Logical argument #1:

There has been an increase in the number of microbially contaminated fuel systems since the use of ultra-low-sulfur diesel (ULSD) became mandatory.

Therefore, microbial contamination in low sulfur diesel (LSD) and high sulfur diesel must have occurred less frequently than in currently does in ULSD.

Logical argument #2:

If argument #1 is valid, then the removed sulfur must have had a biostatic (ability to prevent microbes from growing) or biocidal effect.

“Get your facts first, and then you can distort them as much as you please.”

This quote was reportedly part of a session that Samuel Clemens (Mark Twain) has with young reporters sometime in the 1890s. More recently, in one of his many books on Zen, the philosopher Alan Watts, observed that humankind is unique in our uncanny ability to make precise and accurate observations only to use them to draw erroneous conclusions. Finally, in an earlier post I quoted Daniel Kahneman’s adage: “What you see is all there is.” (WYSIATI).

Logical argument #1 fallacies:

This argument assumes that the increased incidence of reports in a particular market sector (fuel retail) is equivalent to the increased incidence of microbial contamination in diesel fuels and fuel systems. But how do we know whether stakeholders are simply more aware of something that has been going on since diesel fuels were first used? The history of marine fuel oil biodeterioration that date back to the transitions from coal to oil and from burner oils to marine diesel fuel oil (more on this, in response to argument #2). Distillate aviation fuel biodeterioration has been recognized since the Korean War.

Additionally, the argument ignores various confounding factors (in statistics, a confounding factor is an unobserved variable that affects observed variables: in our case sulfur concentration and biodeterioration are observed variables. Before concluding that removing sulfur made diesel fuel more vulnerable to biodeterioration consider these four confounding factors (there are others, but these five illustrate the concept):

• Hydrotreatment to remove sulfur also removes aromatic compounds – especially high molecular weight, toxic, polynuclear aromatic compounds.
• During the past three decades, the fuel distribution infrastructure has evolved from vertically integrated control (the refiner controlled all stages from refinery to retail site) to fungible (common pipelines transport products from refinery tank farms to terminals from which independent and branded retailers draw product from tanks that can that can be mixtures of product from numerous refineries – >100 refineries produce product that is stored in in New Jersey terminal tanks). Fungible product comingling means that cradle to grave product stewardship is more complex than it was historically.
• Product transport from terminals to fleet operators and retailers is typically done my third-party transport companies. Switch-loading (a given tank compartment can carry gasoline on one trip and diesel on the next) is occurring more frequently. The probability of cross-contamination between two fuel-grades is a hotly debated issue at present.
• Although the trend is beginning to reverse itself, between 1990 and 2010, total diesel storage capacity shrunk annually as product demand grew. Consequently, residence time in terminal storage tanks has decreased. Although best practice is to give water and particulates time to settle before drawing product from a tank to the fueling rack, product demand can inspire terminal operators to begin drawing product early. Consequently, any water, particulates, or both that have not settled to below the suction zone will be transported with the fuel.
• Dispensing system technology has become more sophisticated. Systems that might not have be affected historically, are now failing – primarily due to corrosion damage. As a microbiologist, I’d like to think that all fuel system corrosion is microbiologically influenced corrosion (MIC). However, if ethanol enters diesel fuel systems (either because of switch loading or vapor recovery unit vapor comingling) it can be chemically oxidized to acetic acid. Therefore, unless other low molecular weight (4 to 6-carbon) organic acids are also present, high concentrations of acetic acid in fuel-associated water is likely to be a symptom of chemical – not microbial – activity.

Logical argument #2 fallacies:

This argument is built on argument #1’s house of cards. It falls apart if the statement: “There has been an increase in the number of microbially contaminated fuel systems since the use of ultra-low-sulfur diesel (ULSD) became mandatory.” is false. As noted above, increased incidence and increased reports are two very different concepts.

To illustrate this point, consider the respiratory disease, legionellosis. The disease was given its name because the first recognized outbreak was among American Legion members attending a convention at the Bellevue-Strafford Hotel, in Philadelphia. It is beyond improbable that the bacterium that causes legionellosis – Legionella pneumophila – came into existence in 1976. However, in late July and early August 1976, after 221 American Legion convention attendees developed pneumonia-like symptoms, and 34 of the patients died, the medical establishment (physicians and epidemiologists) took note. It took a couple of years to figure out how to culture L. pneumophila, and there was wild speculation regarding the likely relationship between environmental conditions and the microorganism’s ability to grow. Forty years down the road, we know that L. pneumophila is ubiquitous – it can be found in many different environments where biofilms develop (relax – none yet recovered from fuel systems; but don’t relax too much – shower-head aerator screens tend teem with L. pneumophila). The good news is that only immunosuppressed individuals tend to develop the legionellosis.

What does this have to do with the relationship between sulfur concentration in fuel and biodeterioration risk? In both cases, the microbes causing the symptoms have been around for a long time. In the health sector, for centuries (if not millennia) L. pneumophila has caused an unknown percentage of all pneumonia cases, but it was never identified because there had never been (i.e., since the advent of modern medical microbiology, immunology, and epidemiology) such a large number of folks getting sick at the same time and place. Similarly, fuel biodeterioration was well known from the earliest days of gasoline and diesel production. However, there was no database documenting each biodeterioration event.

Prior to 2012 the upper limit for sulfur in marine diesel was 4.5 %. Before 1986, on-highway diesel typically had 0.1 % to 0.5 % (by volume) sulfur. If the sulfur in these historical fuels had been biostatic, fuel biodeterioration would have not occurred until ULSD came onto the market. Filter plugging on ships and aircraft had a more serious impact than filter plugging on dispensers, locomotives, and other land-based diesel fuel systems. However, efforts to control microbial contamination in the marine and aviation sectors were not general knowledge among fuel retailers and fleet operators. Ironically – because they ignored the biocidal effect of tetraethyl lead – folks were convinced that gasoline was too toxic to support microbial growth and that only diesel fuels and fuel systems were affected.

Despite all of this, isn’t it fair to say that ULSD biodeterioration is more pervasive than that of diesel grades with greater sulfur concentrations? My answer is: Not necessarily. There are no hard statistics on the average number of ULSD biodeterioration incidents per year since 1986 and there are certainly no reliable statistics for the decades before the switch to ULSD (or in off-highway systems using low or high sulfur diesel). The assessment that the incidence rate has increased since ULSD replaced other fuel grades for on-highway use is purely subjective. One more time: increased awareness (as in the case of legionellosis) is not the same as increased incidence. The switch to ULSD and biodiesel blends was highly visible to the industry. From the outset, stakeholders wanted to know what the change might do to their systems. Consequently, they now notice damage more quickly than they had in the past. Okay, this is an optimistic statement. In two recent fuel quality surveys, sites originally identified as control sites (no reported problems) had more microbial contamination and corrosion than he problem sites. In the more recent, US EPA-sponsored study, operators were unaware of any problems at 87 % of the moderately to heavily corroded sites.

The Science:

There is no question that some organosulfur compounds are biocidal. For example, two of the few fuel-treatment biocides are mixtures of organosulfur compounds:

CIT/MIT (also referred to as CMIT): 5-Chloro-2-methyl-3(2H)-isothiazolone + 2-methyl-3(2H)-isothiazolone (isothiazolinones are ring structured molecules with the chemical formula: C₃H₃NOS).

MECT: 2-(Thiocyanomethylthio)benzothiazole + Methylene bis(thiocyanate) (the thio in each molecule’s name indicates that they are organosulfur compounds)

However, sulfur is one of the five primary elements (the other four are: carbon, hydrogen, nitrogen, and oxygen) on which all life depends.

Studies on fuel biodegradability have shown that the aromatic content, rather than the sulfur content is a primary factor affecting diesel biodegradability. Regardless of sulfur concentration, fuels with higher aromatic concentrations or more complex aromatic compounds biodegrade more slowly than more severely hydrotreated fuels from which aromatics have been substantially removed. The same hydrotreating process that removes sulfur also reduces fuel’s aromatic content. Note that although there are no aromatic biocides approved for fuel treatment, there are numerous aromatic biocides approved for other applications.

Bottom line:

If ULSD fuels are more susceptible than higher sulfur content fuels are to biodeterioration, it is due to the reduced concentration of complex, toxic polynuclear aromatic compounds – not because of sulfur’s inherent toxicity.

FUEL & FUEL SYSTEM MICROBIOLOGY PART 24 – PETROLEUM EQUIPMENT INSTITUTE’S 2018 CONVENTION

The Petroleum Equipment Institute (PEI) held its 2018 convention at the Las Vegas Convention Center from 07 to 10 October 2018. As usual, the PEI convention was held in conjunction with the much larger National Association of Convenience Store (NACS) convention. Today, I’ll focus on a few items that are particularly relevant to fuel and fuel system microbiology. I’m not going to attempt to provide anything approaching an overview of the entire convention. Instead I’ll report and discuss a few statements I heard from speakers during PEI’s Tuesday 09 October education sessions.

Regulatory issues

EPA Regulatory Update – Carolyn Hoskinson, Director of EPA’s Office of Underground Storage Tanks (OUST) and several members of her staff spoke to the current state of affairs regarding UST regulations. Tony Raia reported that with the 13 October 2018 compliance deadline looming, 32 states had updated their UST regulations to harmonize them with the 2015 updated US EPA regulations. Tony identified five state categories:
1. State Program Approval (SPA) States that have completed their updates and which are now in full compliance
2. Non-SPA States that have completed their updates to comply with the 2015 regulations
3. SPA States that have delayed revising their state regulations
4. SPA States that have updates in progress
5. Non-SPA States that have not yet updated their regulations per the US EPA 2015 regulations.
Bottom line is that we are entering a period during which there will be some confusion over compliance.

U.S. EPA UST Enforcement – Mark Barolo – the US EPA OUST official responsible for enforcement – noted that in nearly all cases, individual States were responsible for enforcement. Recognizing the confusion, Mark opined that inspectors were going to address violations on a case-by-case basis. Generally speaking, retailers who had been incompliance, had the required documentation, and demonstrated that they were making good-faith efforts to ensure that they remained in compliance, would experience less enforcement grief than those who have not. Mark’s colleague, Cho Yi Risher noted that the regulations do not prescribe the time permitted for site owners to repair or replace non-compliant equipment. Moreover, the inspections required by the 2015 regulations identify non-compliant equipment. There is no incentive for owners to institute predictive maintenance programs (see my 16 January 2017 post) that would detect failure trends before equipment became non-compliant.

Failure to detect uncontrolled microbial contamination and biodeterioration before they cause valves to seize or tanks and lines to leak is a false economy. A few pennies saved during regulation-mandated inspections can lead to remediation expenses in excess of $0.5 million.
Although for some of us, it’s hard to believe that the UST installed in 1987 – in compliance with the original UST regulations – are now beyond their 30-year warranty life. Discussion during the session’s question and answer period indicated that all stakeholders shared a common interest in ensuring that sites with tanks that were more than 30-years old would be able to continue to operate. I anticipate seeing articles to this issue in PEI Journal in the coming months.

Fuel Quality and Corrosion
Scott Boorse – PEI’s Technical Program Manager; recently retired from a major fuel retailer – made several observations that validated much of what I’ve been discussing in Fuel Microbiology What’s New posts. He suggested that in his experience, 100 % of all retail site fuel systems had some corrosion. He attributed much of this corrosion to the bacterial genus Acetobacter converting ethanol to acetic acid. I am convinced that most of the headspace and spill containment well acid production comes form chemical oxidation of ethanol to acetic acid. Microbes are involved in an estimated 50 % of all system corrosion issues, but – as I’ve written previously – microbes produce a variety of organic acids. These acids can react with chloride, sulfate, and nitrate in fuel-associated water to form organic bases (or salts) and strong, highly corrosive, inorganic acids – hydrochloric, sulfuric, and nitric acids, respectively. Still, Scott was on spot suggesting that UST system corrosion was much more wide-spread than most stakeholders realize.

Rebbeca Moore – GM and chair of the automotive industry’s Top Tier Detergent Gasoline and Diesel Fuel consortia – discussed the importance of fuel quality on engine performance. Top Tier is an auto industry sponsored compliance program intended to go beyond ASTM product specifications typically cited in state regulations. I’ll steer clear of the perennial debates between engine manufactures and petroleum producers that enliven our semi-annual ASTM D02 (Petroleum Products) subcommittee A (Gasoline and Oxygenated Fuels) and E (Burner, Diesel, Non-Aviation Gas Turbine, and Marine Fuels), but Rebbeca made an important point. ASTM specifications are often misused. They are meant to indicate whether a product (i.e., fuel) is fit for use at a single point and place in time (i.e., when and where the sample was collected). The petroleum industry’s infrastructure is vast and complex. Moreover, product ages (if it didn’t it wouldn’t combust so well in engines). Specification tests provide little information about how the product will age during storage.
Rebbeca illustrated the dilemma by listing the typical components of 7,500 gal of in-specification ULSD delivered to UST:
• 1 cup of dirt
• 1 to 2 gallons of water
• Up to 325 gallons of FAME (B5 ULSD is now included in ASTM Specification D975 Diesel Fuel Oils)
• 1 gallon of glycerin
• 5 to 40 gallons of additives
At sites that receive frequent deliveries, these trace amounts of dirt and water add up! Not surprisingly, along with measures that are outside the retail site or fleet owner’s control, Rebecca recommended more aggressive water removal and better dispenser filtration (there is an ongoing debate among stakeholders with some recommending that all dispensers have 5.0 µm, water absorbing filters and others arguing for 100 µm particulate filters). I share Rebecca’s view that all dispensers should have 5.0 µm, water absorbing filters. Marketers who are focused only on low rates and not product quality have argued for eliminating the filtration requirement completely.

Ryan Haerer – of US EPA’s OUST (https://www.epa.gov/ust) – wrapped up the session, sharing a few notable points. First, Ryan reminded attendees that UST regulations apply only to system components that are in contact with the soil. The US EPA does not regulate the condition of internal components that are not in direct contact with the soil (for example, submerged turbine pumps – STP – and their associated hardware). He also explained that under the UST regulations, there is a requirement that system components be compatible with the substance stored. This is likely to become interesting as new products (for example, E15 gasoline or substitution of ethanol with isobutyl alcohol) are introduced into the commercial fuel infrastructure – here I’m using interesting – in the same way it is used in of the phrase: “May you live in interesting times.” (Austen Chamberlain – British Foreign Secretary, 1924 to 1929 wrote that he had been told that this was an ancient Chinese curse, but his claim has never been verified).

Bringing it home

At this point we are enjoying an interesting paradox. Regulators, insurers, and an increasing number of retailers recognize that waiting until fuel systems fail is a problem. However, the system largely provides incentives for site owners to wait until failures have occurred. After failure, insurance covers component replacement costs. In many states, superfund monies cover remediation costs. When site owners invest in predictive maintenance, they only see the costs. Although there are benefits – not the least of which is customer satisfaction and a positive corporate image – they are intangible. How do we break the paradox?

Please share your thoughts on this issue with me at fredp@biodeterioration-control.com. I’ll compile comments and post them anonymously as a future What’s New column.

FUEL & FUEL SYSTEM MICROBIOLOGY PART 20 – PREVENTING MICROBIAL DAMAGE TO FUEL SYSTEMS PART 2; WATER BITS

Water, water everywhere…

Samuel Coleridge’s infamous mariner paid dearly for having killed an albatross (figure 1). Do fuel quality managers and personnel responsible for fuel system integrity pay dearly for underestimating the ability of small (<1 oz; 30 mL) pools of fuel-associated-water left behind after water has been nominally purged from a fuel tank? A water bit is any small volume of water that remains in a fuel tank after dewatering (my personal, technical definition).
In Part 20, I wrote: “No water means no bugs. Is it as easy as all that?” I also explained why the short answer to the question was: “No.” For emphasis, I’ll again share figure 3 from Part 20 (figure 2, here):

A – a 6’6” tall man standing at the base of Mt. Kilimanjaro; B- a bacterial cell “standing” in a pool of water that is >2 mm deep; the ratios between the height of Mt. Kilimanjaro and the man in A, and between the depth of the pool of water and the bacterial cell in B are the approximately the same.

What can we do about these traces of water?
I confess that I am not a big fan of dispersants. When water dispersants are used routinely as fuel additives, the dispersed water can act as a corrosive agent; damaging engine components. However, when used to complete the job started by draining or vacuuming most of the free-water out of a tank, dispersants can be quite effective.
Figure 3 illustrates how dispersants work. Most dispersants are organic molecules that have a polar (charged; water-soluble) head and a non-polar (non-charged; fuel-soluble) tail. When added to fuel over water (figure 3b), they move towards anywhere where fuel contacts water (figure 3c) and trap tiny (typically <1 µm; 0.0004 in dia) fuel droplets. The fuel “sees” only the dispersant’s non-polar tails, so the droplets disperse uniformly throughout the fuel (figure 3d). The dispersed droplets (micelles) get transported with the fuel and evaporate during combustion in the engine cylinder.

Fig 3. Dispersant action: a) fuel over bottoms-water; b) dispersant added to fuel – inset shows dispersant molecule with polar head and non-polar tail; c) dispersant heads and tails align in water an fuel phases, respectively; d) dispersants form micelles with water droplet trapped in center; typical droplet size is < 1 μm dia.

Disclaimer:
Microbes are ubiquitous. There are extraordinarily few habitats on earth where thriving, microbial communities have not been detected. In practical terms, this means that it is unlikely that operators will ever have a completely sterile fuel system or that they will reduce their fuel system biodeterioration risk to zero. Biodeterioration can still occur in the best maintained fuel systems. However, the risk of it occurring in an inadequately maintained system is much more likely.