Corrosion in Underground Storage Tanks (USTs) Storing Ultra-Low Sulfur Diesel (ULSD):
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1 Corrosion in Underground Storage Tanks (USTs) Storing Ultra-Low Sulfur Diesel (ULSD): EPA Research on Risks, Prevalence, Causes, and Next Steps Presented at the National Tanks Conference September 16, 2015 Ryan Haerer EPA Office of Underground Storage Tanks
2 Outline What is ULSD Corrosion? The problem Impacts Potential causes EPA s Research Study Overview Key Findings Conclusions What do we do with the results? Educate Address issues Update standards and practices Further research into prevention and treatment
3 Corrosion in USTs Storing ULSD Reports began around 2007 Internal metal components often STP shaft Severe and rapid onset Yet unidentified cause Extent not fully known Appearance different and impacts more severe than corrosion in sump spaces of USTs storing gasoline/ethanol blends
4 What do we know about the possible cause? Reports of corroded metal equipment in vapor space of USTs storing ULSD first in 2007 Two changes to fuel supply around same time Reduced sulfur content in diesel beginning 2006 (500ppm LSD to 15ppm ULSD) Increased production and use of ethanol and biodiesel* 2012 Hypotheses Investigation by Clean Diesel Fuel Alliance of 6 UST storing ULSD * Energy Independence and Security Act of 2007 expanded Renewable Fuel Standard, setting volumetric blending targets for renewable fuels
5 Corrosion Risks to the Environment Exposed Metals in the Vapor Space Release prevention equipment could fail to function Corrosion on flapper valves could restrict movement and allow an overfill Product level floats get stuck on corroded shafts and fail to signal a rising product level, fuel release, or water infiltration Ball float valves ball or cage may corrode Line leak detectors failing performance testing at higher rates
6 Some Observed Corrosion Examples
7 Corrosion Risks to the Environment Bottoms of Tanks Metal components could corrode completely and possibly release fuel to environment ULSD prone to collect water and sludge in bottom of tanks Some jurisdictions seeing much higher rates of bottom failures of primary walls of double-wall steel tank bottoms since ULSD Single-wall tanks possibly leaking undetected
8 Some Observed Corrosion Examples
9 Costs of Metal Corrosion for Owners Increased pace of filter changes More frequent servicing of equipment Shorter lifespan before replacement of equipment
10 Findings from Clean Diesel Fuel Alliance 2012 Hypotheses Investigation Not conclusive, but suggested microbiologically influenced corrosion (MIC) a possible cause worth further research Microbes feed on ethanol present in ULSD, creating acetic acid Ethanol possibly entering ULSD through switch-loading of trucks wherein a gasoline-ethanol load is followed by a diesel one, or by diesel and gasoline-ethanol blend UST s sharing the same vent line. Ethanol can be converted into acetic and butyric acid (and possibly into glycolic acid)
11 Could other factors be in play? Glycerol can also be converted to corrosive acids Propionic acid presence in 2012 suggests this possibility Glycerol (possibly) in biodiesel, biodiesel possibly in ULSD* Allowable concentration from production, or Out of specification biodiesel Likely that a combination of factors involved Glycerol into glyceric, lactic, and propionic acids *ASTM D975 allows biodiesel to be blended into ULSD up to 5% without being labeled biodiesel
12 Study on the Corrosion of Metal Components in USTs Storing ULSD Environmental Protection Agency Office of Underground Storage Tanks (OUST) Battelle Memorial Institute UST owner volunteers and industry partners, esp. CRC Diesel Corrosion Panel could not have made the study happen without them! Thank you! Provided critical site access for real-world data collection Provided data input on tank history and management practices Critical review of study design and draft reports
13 What did we set out to accomplish with the Research Effort? Research designed: For continuity- Build on previous research and help figure out how to address the problem Allow others to build on what we find To better understand the extent of the problem and potential risks identified in the limited reports we ve heard This research was NOT intended to: Definitively pinpoint a specific cause every UST is unique Identify specific solutions to the problem Identify correlations among UST systems with severe or minimal corrosion
14 Identify Volunteers for a Diverse UST Sample Population 10 geographic clusters 42 sites 24 fiberglass, 16 steel, 2 steel coated 8 of 10 have steel and fiberglass in cluster 8 owners Government, retail, fleet Single and multiple site Large range of fuel throughputs and suppliers Diverse USTs 1 29 years in service 5,000 to 20,000 gallons in capacity Different product storage histories Various approaches to maintenance # of USTs USTs by Capacity and Material 5,000 6,000 7,000 8,000 10,000 12,000 15,000 20,000 Tank Capacity (gallons) Steel Fiberglass
15
16 Collect Data on UST Conditions at Each Site Collect samples: Vapor Fuel Water bottom Inspect with internal tank video Collect information on maintenance, throughput, fuel supply, biocide use, etc.
17 Fuel Analysis Methods Method Identifier Determination of Water in Petroleum Products, Lubricating Oils, and Additives by Coulometric Karl Fischer Titration (Procedure B) ASTM D Determination of Density, Relative Density, and API Gravity of Liquids by Digital Density Meter Acid Number of Petroleum Products by Potentiometric Titration Determining Corrosive Properties of Cargoes in Petroleum Product Pipelines Particulate Contamination in Middle Distillate Fuels by Laboratory Filtration Determination of Biodiesel (FAME) Content in Diesel Fuel Oil Using Mid Infrared Spectroscopy (FITR-ATR- PLS Method) ASTM D ASTM D NACE TM ASTM D ASTM D FUEL Water Content Density Total Acid Number Corrosion Rating Particulates Biodiesel Content Flash Point by Pensky-Martens Closed Cup Tester ASTM D93 15 Flashpoint Determination of Free and Total Glycerin in Biodiesel Blends by Anion Exchange ASTM D Free and Total Glycerin Chromatography GC-MS Full Scan Lab In-House Method Unknowns of Interest Determination of Total Sulfur in Light Hydrocarbons, Spark Ignition Engine Fuel, Diesel Engine Fuel, and Engine Oil by Ultraviolet Fluorescence Electrical Conductivity of Aviation and Distillate Fuels Determination of Short Chain Fatty Acids by Gas Chromatography-Mass Spectrometry (GC-MS) ASTM D ASTM D FUEL Lab In-House Method Sulfur Content Conductivity Acetate, Formate, Propionate, Lactate, Glycerate Sample Analyses WATER Water Bottom Analysis Methods Method Identifier Determination of Ion Chromatography (IC) for short chain fatty acids Modified EPA 300 Acetic, Formic, Propionic, Lactic Acids IC Test for Free Glycerin Lab In-House Method Glycerin Determination of Dissolved Alkali and Alkaline Earth Cations and Ammonium in Water and Wastewater by Ion Chromatography ASTM D Cations (Sodium, Calcium, Magnesium, Potassium, Ammonium) and Anions (Chloride, Sulfate, Nitrate and Fluoride) ph (Electric) EPA ph Conductance (Specific Conductance, umhos at 25 C) EPA Conductivity Nonhalogenated Organics Using GC/FID SW B 22 Ethanol and Methanol VAPOR Vapor Analysis Methods Method Identifier Determination of Ullage % Relative Humidity Hygrometer used per manufacturer instructions % relative humidity Carboxylic Acids in Ambient Air Using GC-MS Determination of Lactic Acid in Ambient Air ALS Method 102 Modified NIOSH 7903 Acetic, Formic, Propionic, and Butyric Acids Lactic Acid
18 Assess and Categorize Corrosion Coverage Based on protocol developed by CRC Diesel Performance Group Corrosion Panel 3 assessments of coverage on STP shaft Minimal as < 5% Moderate from > 5% to < 50% Severe as > 50% If in unanimous agreement, UST was categorized If not in agreement, discussed and considered overall condition of UST equipment and categorized by panel vote
19 Observed Corrosion Examples Example Of An UST System with a Fiberglass Tank With Minimal Corrosion Coverage (Installed 2003 And Age Of Filter < 1 Month). Example Of An UST System with a Fiberglass Tank With Severe Corrosion Coverage (Installed 1986)
20 Observed Corrosion Examples Example Of An UST System with a Steel Tank With Minimal Corrosion Coverage Example (Installed 1994) Example Of An UST System with a Steel Tank With Severe Corrosion Coverage (Installed 1992).
21 More Corrosion Examples STP Shafts Drop Tubes Tank Walls Ball float cages ATG floats/shafts
22 Looking at the Data USTs by Corrosion Category and Material Minimal Moderate Severe Steel Fiberglass Analyzed data according to corrosion category Identify potential predictive characteristics Identify any trends with respect to corrosion development
23 A note about findings: Please do not cite. This is preliminary data from the report which has not yet completed peer-review. This is presented only to share what we initially observed. Only the final peer-reviewed paper should be cited as an official source of information from the study.
24 Key Findings Corrosion appears to be very common. 35 of 42 USTs judged as moderately or severely corroded. Likely affecting same or higher proportion of total ULSD UST population emergency generators and owners of single UST systems were not represented in this sample. Corrosion could pose a serious risk to integrity or functionality of metal UST system components. No smoking gun correlation among corroded tanks identified. Gasoline found in all 42 samples, and ethanol in 38 of the samples.
25 Assumptions Microbiologically influenced corrosion (MIC) likely responsible for the corrosion. Food sources (ethanol or glycerol) were present All water bottoms found acids that could result from microbial consumption of ethanol or glycerol Conditions good for microbial growth Eliminating water is recognized as a key factor in preventing this corrosion.
26 From ASTM D975: X6 MICROBIAL CONTAMINATION X6.1 Uncontrolled microbial contamination in fuel systems can cause or contribute to a variety of problems, including increased corrosivity and decreased stability, filterability, and caloric value. Microbial processes in fuel systems can also cause or contribute to system damage. X6.2 Because the microbes contributing to the problems listed in X6.1 are not necessarily present in the fuel itself, no microbial quality criterion for fuels is recommended. However, it is important that personnel responsible for fuel quality understand how uncontrolled microbial contamination can affect fuel quality. X6.3 Guide D6469 provides personnel with limited microbiological background an understanding of the symptoms, occurrences, and consequences of microbial contamination. Guide D6469 also suggests means for detecting and controlling microbial contamination in fuels and fuel systems. Good housekeeping, especially keeping fuel dry, is critical.
27 Next steps Educate owners about the risks. Use available treatments or preventions if your system is affected Remove water, conduct testing, tank lining, oxygen displacement, biocides, corrosion inhibitors, others. Explore changes to technical standards and operating procedures Support continued research on causes and solutions
28 Thank You for Listening! Please reach out to EPA to share input, ideas, information or with any questions. Ryan Haerer EPA Office of Underground Storage Tanks Thanks to: Anne Marie Gregg, Battelle For her efforts on the study and materials for this presentation
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