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This report is in response to your query about the levels of potentially harmful gases which might have occurred in the area of Western Massachusetts following a tanker truck spill of Fuel Oil # 6 in 2004. As detailed below, the report indicates that the area was subjected to significant vapor plumes of Hydrogen Sulfide (H2S), Naphthalene and other hydrocarbon compounds contained in Fuel Oil #6. In order to estimate the exposure levels it was necessary to generate a series of plumes or gas cloud plots based on air dispersion models. These models were developed jointly by the U.S. Environmental Protection Agency (EPA) and the National Oceanographic and Atmospheric Administration (NOAA) and are frequently used by many emergency personnel and first responders. According to the NOAA Office of Response and Restoration, Hazardous Materials and Response Division website http://response.restoration.noaa.gov/about/emergency-response-division.html “HAZMAT's most widely used computer tool for chemical spill response and planning is the Computer-Aided Management of Emergency Operations (CAMEO) system.” CAMEO consists of a suite of software programs to plan for and respond to chemical emergencies. Cameo is a chemical reference library which contains response information for approximately 6,000 chemicals including 80,000 chemical synonyms and identification numbers. All of the substances modeled in this report are contained in this database. The CAMEO suite consists of ALOHA (Aerial Locations of Hazardous Atmospheres) an air dispersion model for simulating gas plumes (or clouds of gas) from chemical release scenarios. MARPLOT (Mapping Application for Response, PLanning, and Operational Tasks) integrates the U.S. Census TIGER/Line digital map files which allows plotting of roads, rivers, boundaries, and facilities as part of the CAMEO suite. These three programs work interactively and seamlessly together to quickly display critical information and potential hazardous chemical reactions. HAZMAT states: “The ALOHA atmospheric dispersion module predicts the downwind dispersion of a chemical cloud. Graphical outputs include estimates of the plume footprint, source strength, and chemical concentration curves. The output from ALOHA can then be sent to MARPLOT, the mapping module, to display the footprint on a digitized map of the local area.” A complete analysis of this specific tanker spill requires a thorough reconstruction of the events in chronological order. Only in this way can we fully capture the magnitude and extent of the exposure of the substances involved. The time of the accident is stated in the police report as approximately 10:30 AM on October ?, 2004). The Response Action Outcome Statement reports that oral notification of the release of approximately 6000 gals of Fuel Oil #6 was made to the Massachusetts Department of Environmental Protection (MADEP) at 11:06 AM by a representative of the Fire Department. Near the time of the accident (10:54 AM), the weather station at the
Airport located approx, one half mile to the SE of the area reported weather conditions with temperature 46.9 deg F, Humidity 63% and with winds out of the East at 10.4 miles per hour. Sky conditions were mostly cloudy with precipitation of 0.01inches. The weather conditions at this time are crucial because when the accident occurred the tanker truck rolled over on its left (drivers) side) and ripped open from its impact with the paving equipment trailer leaking its contents onto the parking lot and surrounding area. While it is known that tankers carrying Fuel Oil No. 6 contain some percentage of gases such as hydrogen sulfide, naphthalene, polycyclic aromatic hydrocarbons and other hydrocarbons, the exact contents and components of the fuel spilled will probably never be known with precision because there is no known analysis of this load of fuel. Nor have any subsequent analysis of Fuel Oil No. 6 in this truck been reported either from the source station or the intended destination. This complicates any modeling simulation, but it by no means prohibits reliable analysis. Although the actual percentage of H2S may vary in the Fuel Oil No. 6 liquid, [the materials safety data sheets (MSDS) prepared by the manufacturers and distributors list a range of concentrations from trace to 1.5 percent], the percentage of H 2S in the air could still be significant. According to the Hess MSDS: “Hydrogen Sulfide (H2S) may be present in trace quantities (by weight), but may accumulate to toxic concentrations such as in tank headspace. The presence of H2S is highly variable, unpredictable and does not correlate with sulfur content. Studies with similar products have shown that 1 ppm H2S by weight in liquid may produce 100 ppm or more H2S in the vapor headspace of the storage tank.” This conclusion is supported by an article which appeared in the American Industrial Hygiene Association Journal (Slack, Donald J. 1998 vol. 49 no. 4 pg 205-206). Slack studied “Hydrogen Sulfide in Residual Fuel Oil and Storage Tank Vapor Space” and concluded liquid phase hydrogen sulfide concentrations above 8 ppm by weight can produce atmospheres immediately dangerous to life or health in residual fuel oil storage tanks and ship and barge holds. His research showed the highest concentrations on day 1 after a product transfer showing more than 900 ppm H2S (by volume) in the vapor phase related to nearly 11 ppm (by weight) in the liquid phase. It is therefore reasonable that H2S in the head space of the tanker truck would have been at a concentration to be dangerous to life or health at the time the tanker was pierced. Furthermore, since the density of H2S is heavier than air [as virtually every fireman and first responder is taught in training,] any H2S which escaped from the tanker truck would have remained close to the ground. However, it may not have been obvious by smell. The Hess MSDS states: “Hydrogen sulfide (H2S) has a rotten egg “sulfurous” odor. This odor should not be used as a warning property of toxic levels because H2S can overwhelm and deaden the sense of smell. Also, the odor of H2S in heavy oils can easily be masked by the petroleum-like odor of the oil. Therefore, the smell of H2S should not be used as an indicator of a hazardous condition - a H2S meter or colorimetric indicating tubes are typically used to determine the concentration of H2S” As mentioned previously, the tanker overturned on its left side and was torn open on what was (before the accident) the left top of the tank (Source Point) now lying close to
the ground. This tear was then directly facing the back door of the structure (the Threat Point) as gases and fuel oil escaped at a distance of approximately 15 feet across the gravel parking lot. While there is no assertion that anyone was inside the building at the precise time of the collision, there would have been ample opportunity for any escaping H2S gas to seep under the doors and through any openings available in the moments after the collision. This would have raised the levels of H2S in the building to potentially dangerous levels which could have persisted for days especially in corners and low lying or protected areas in the back of the kitchen. To calculate this exposure it is necessary to input the initial weight and concentrations of H2S (given the estimated dimensions of the tanker and headspace volume) and then model the air dispersion as a result of the weather conditions at the time. Table I shows the input data for the ALOHA Model and summarizes the concentration data for hydrogen sulfide. Note that weather conditions are as previously reported and the source strength is conservatively estimated as 30 cu ft of gas. This represents less than 5% of the tank volume if it were entirely filled with gas instead of the 6000 gallons of fuel oil. The ALOHA model estimates an initial outdoor maximum concentration of 3470 ppm at the Threat Point 15 feet to the west and 5 feet to the north of the leaking tank truck. At this distance, the model predicts a maximum indoor concentration of nearly 40 ppm. In addition, the heavy gas model calculates three different threat zones based on the following criteria: The Emergency Response Planning Guidelines (ERPGs) were developed as planning guidelines, to anticipate human adverse health effects caused by exposure to toxic chemicals. ERPGs are public exposure guidelines: they are intended to predict how members of the general public could be affected if exposed to a particular hazardous chemical. Typically, public guidelines are used for tasks like toxic gas dispersion modeling and other kinds of consequence analysis, when the goal is to assess the severity of a hazard to the general public. Like AEGLs and TEELs, ERPGs do not incorporate safety margins. Also, hypersensitive people would suffer adverse reactions to concentrations far below those suggested in the guidelines. ERPG-3 is "the maximum airborne concentration below which it is believed that nearly all individuals could be exposed for up to 1 hour without experiencing or developing life-threatening health effects." ERPG-2 is "the maximum airborne concentration below which it is believed that nearly all individuals could be exposed for up to 1 hour without experiencing or developing irreversible or other serious health effects or symptoms which could impair an individual's ability to take protective action." ERPG-1 is "the maximum airborne concentration below which it is believed that nearly all individuals could be exposed for up to 1 hour without experiencing other than mild transient health effects or perceiving a clearly defined, objectionable odor." http://response.restoration.noaa.gov/erpgs TABLE I – SUMMARY OF HYDROGEN SULFIDE DATA SITE DATA:
Location: W. MASSACHUSETTS Building Air Exchanges Per Hour: 0.74 (sheltered single storied) Time: October ?, 2004 1050 hours EDT (user specified) CHEMICAL DATA: Chemical Name: HYDROGEN SULFIDE Molecular Weight: 34.08 g/mol ERPG-1: 0.1 ppm ERPG-2: 30 ppm ERPG-3: 100 ppm IDLH: 100 ppm LEL: 43000 ppm UEL: 455000 ppm Ambient Boiling Point: -78.0° F Vapor Pressure at Ambient Temperature: greater than 1 atm Ambient Saturation Concentration: 1,000,000 ppm or 100.0% ATMOSPHERIC DATA: (MANUAL INPUT OF DATA) Wind: 10 miles/hour from E at 3 meters Ground Roughness: urban or forest Cloud Cover: 7 tenths Air Temperature: 47° F Stability Class: D No Inversion Height Relative Humidity: 63% SOURCE STRENGTH: Direct Source: 30 cubic feet Source Height: 0 Source State: Gas Source Temperature: equal to ambient Source Pressure: equal to ambient Release Duration: 1 minute Release Rate: 0.0445 pounds/sec Total Amount Released: 2.67 pounds Note: This chemical may flash boil and/or result in two phase flow. THREAT ZONE: (HEAVY GAS SELECTED) Model Run: Heavy Gas Red : 63 yards --- (100 ppm = ERPG-3) Orange: 119 yards --- (30 ppm = ERPG-2) Yellow: 1.3 miles --- (0.1 ppm = ERPG-1) THREAT AT POINT: Concentration Estimates at the point: West: 15 feet North: 5 feet Max Concentration: Outdoor: 3,470 ppm Indoor: 39.5 ppm
FIG. 1 - HYDROGEN SULFIDE PLUME MODEL
FIG. 2 - CLOSE-UP OF HYDROGEN SULFIDE PLUME MODEL
FIG. 3- MAP OF HYDROGEN SULFIDE CONCENTRATIONS The ALOHA model automatically calculates the size of these threat zones based on the Chemical Database in CAMEO and draws their extent as shown in Figure 1 with a zoomed in area shown in Figure 2. Note that ERPG 3 (Red Zone) corresponds to 100 ppm H2S out to a distance of 63 yards from the source of the gas. ERPG-2 (Orange Zone) corresponds to 30 ppm H2S and extends out 119 yards and ERPG -3 (Yellow Zone) corresponds to 0.1ppm and extends 1.3 miles from the source in the first hour. As noted above, this model cannot accurately predict concentrations of H2S or exposures of longer duration than one hour. However, the plaintiff (according to her testimony) would have been repeatedly exposed to concentrations of H2S which persisted in the building for up to 3 days and she may have even been exposed to higher concentrations when she frequently went outdoors. Figure 3 plots the results of the model on a map view of the area using MARPLOT and considering the prevailing wind direction and wind speed. Another substance that was present at the spill site was naphthalene. Naphthalene is listed on three separate MSDS as ranging between 0- 3% in Fuel Oil # 6. It was also found in the soil analysis of the containment pit as high as 40 ppm with 10 samples recording more than 20 ppm as shown in the Response Action Statement. This is 5 times the Massachusetts Department of Environmental Protection exceedance value for MCP Method 1 GW-1/S-1 Soil standards set for Naphthalene as a volatile petroleum hydrocarbon shown in that report.
For Naphthalene, the CAMEO chemical library does not supply the ERPG values, but rather it generates the equivalent threat zones described in detail below:
Temporary Emergency Exposure Limits (TEELs) are temporary Toxic Levels of Concern similar to ERPGs, and defined by the U.S. Department of Energy for use when ERPGs aren't available. Unlike AEGLs and ERPGs, TEELs are not peer-reviewed, and are intended as temporary guidance. AEGLs, ERPGs, and TEELs do not incorporate safety factors. Rather, they are designed to represent the predicted response of members of the general public to different concentrations of a chemical during an incident. There are three TEEL levels that are important for responders to consider: TEEL-1: Maximum concentration in air below which it is believed nearly all individuals could be exposed without experiencing other than mild transient health effects or perceiving a clearly defined objectionable odor. TEEL-2: Maximum concentration in air below which it is believed nearly all individuals could be exposed without experiencing or developing irreversible or other serious health effects or symptoms that could impair their abilities to take protective action. TEEL-3: Maximum concentration in air below which it is believed nearly all individuals could be exposed without experiencing or developing life-threatening health effects. The TEEL methodology, which uses more widely available data than is required for the ERPG, can be used to derive a LOC for a broad range of chemicals -more chemicals than AEGLs or ERPGs at this time. The power of TEELs is not as substantial as AEGLs or ERPGs, but TEELs can provide a useful reference when no other LOC is available.http://www.atlintl.com/DOE/teels/teel/teeldef.html The ALOHA model treats these threat zones in a similar fashion to the ERPGs. The total volume of Naphthalene on the input sheets (Table II) was estimated as 1% of the fuel oil spilled or 60 gallons based on the median value of the three material safety data sheets. The ALOHA Model calculates that the Red Zone (250 ppm = TEEL-3) extends out to 22 yards. The output notes that this threat zone was not drawn because effects of near-field patchiness make dispersion predictions less reliable for short distances. Figure 4 shows that the Orange Zone (35 ppm = TEEL-2) reaches to 60 yards and the Yellow Zone (15 ppm = TEEL-1) extends 92 yards from the source. The Threat at Point estimates a maximum outdoor concentration of 2,870 ppm and an indoor maximum of approximately 36 ppm in the first hour. Figure 5 is the MARPLOT map view of the naphthalene concentrations. Since naphthalene vapor is also heavier than air, it is likely that some of these gases would have persisted in the vicinity of the Building for many hours if not days.
TABLE II – SUMMARY OF NAPHTHALENE DATA
SITE DATA: Location: W, MASSACHUSETTS Building Air Exchanges Per Hour: 0.74 (sheltered single storied) Time: October ?, 2004 1050 hours EDT (user specified) CHEMICAL DATA: Chemical Name: NAPHTHALENE TEEL-1: 15 ppm TEEL-2: 35 ppm IDLH: 250 ppm LEL: 8800 ppm Carcinogenic risk - see CAMEO Ambient Boiling Point: 420.7° F Freezing Point: 176.5° F
Molecular Weight: 128.17 g/mol TEEL-3: 250 ppm UEL: 59000 ppm
ATMOSPHERIC DATA: (MANUAL INPUT OF DATA) Wind: 10 miles/hour from E at 3 meters Ground Roughness: urban or forest Cloud Cover: 7 tenths Air Temperature: 47° F Stability Class: D No Inversion Height Relative Humidity: 63% SOURCE STRENGTH: Direct Source: 60 gallons Source Height: 0 Source State: Gas Source Temperature: equal to ambient Source Pressure: equal to ambient Release Duration: 1 minute Release Rate: 0.0508 pounds/sec Total Amount Released: 3.05 pounds THREAT ZONE: (HEAVY GAS SELECTED) Model Run: Heavy Gas Red : 22 yards --- (250 ppm = TEEL-3) Note: Threat zone was not drawn because effects of near-field patchiness make dispersion predictions less reliable for short distances. Orange: 60 yards --- (35 ppm = TEEL-2) Yellow: 92 yards --- (15 ppm = TEEL-1) THREAT AT POINT: Concentration Estimates at the point: West: 15 feet North: 5 feet Max Concentration: Outdoor: 2,870 ppm Indoor: 35.9 ppm
FIG. 4 – NAPHTHALENE PLUME MODEL
FIG. 5– MAP OF NAPHTHALENE CONCENTRATIONS
Fuel Oil #6 is a complex and variable mixture of relatively high molecular weight compounds which is difficult to characterize in its entirety. However, when the CAMEO chemical library is augmented by the thermodynamic properties of Bunker C Fuel oil (a synonymous product) based on the oil catalog produced by Environment Canada, most of the input parameters for the ALOHA model are available. The critical input is the amount of the material released into the atmosphere based on the evaporation rate. Fortunately there is another software program created by NOAA specifically for this purpose. The Automated Data Inquiry for Oil Spills (ADIOS2) model is designed to calculate the oil budget or percentage evaporation over a maximum of 5 days. Fuel Oil # 6 has been selected from the included oils. Figure 6 shows the continuous rate of evaporation under the previously specified weather conditions calculated by ADIOS2. Note that nearly 8% or more than 460 gallons of fuel oil is evaporated into the air in the first 5 days. Placing sheeting over 6000 gallons of Fuel Oil #6, (even temporarily) will not prevent this evaporation unless it is claimed that the cover is air tight and never lifted for remediation and removal of the spilled fuel. Figure 7 illustrates the oil budget with the number of gallons evaporated, dispersed and remaining and Figure 8 is a chart of that process on an hourly basis. The ADIOS 2 evaporation model predicts an initial evaporation rate of 40 gal. per hour and this value was applied to the ALOHA air dispersion model.
FIG 6 - ADIOS2 EVAPORATION MODEL
FIG.7 - OIL BUDGET CHART
FIG. 8 - OIL BUDGET TABLE
Since ERPG or TEEL have not yet been established for Fuel Oil #6, (Fuel Oil is currently under review) the flammable area of the vapor cloud was used to establish the spread of the gases. The ALOHA model instructions define these threat zones as follows: The LEL [Lower Explosive Limit] is the level above which a gas can combust -that is, catch on fire or explode (depending on the conditions). When a flammable vapor cloud is dispersing, the concentration of fuel in the air is not uniform. Near the release source, the fuel-air concentration will be very high. The concentration will decrease as the cloud travels further away from the source and mixes with the air. You might expect that the LEL could be used as the LOC [Levels of Concern] to determine the areas in which a fire might occur. However, the concentration levels estimated by ALOHA are time-averaged concentrations. In an actual vapor cloud, there will be areas where the concentration is higher than the average and areas where the concentration is lower than the average. This is called concentration patchiness. Because of concentration patchiness, there will be areas, called pockets, where the chemical is in the flammable range even though the average concentration has fallen below the LEL. (ALOHA uses a shorter averaging time when estimating the flammable areas, to help compensate for this effect, but it cannot completely compensate for this effect.) Some experiments have shown that flame pockets can occur in places where the average concentration is above 60% of the LEL. ALOHA uses 60% of the LEL as the default LOC for the red threat zone. Another common threat level used by responders is 10% of the LEL. ALOHA uses this concentration as the default LOC for the yellow threat zone. For this tanker truck spill, Table III shows the data summary for Fuel Oil # 6. The ALOHA plume model (Figure 9) calculates that the Red Zone (6,000 ppm = 60% LEL = Flame Pockets) extends to 26 yards but the “threat zone was not drawn because effects of near-field patchiness make dispersion predictions less reliable for short distances.” The Yellow Zone (1,000 ppm = 10% LEL) is shown to extend 65 yards from the source. Also note that because much of the fuel oil during this timeframe is believed to be confined to the sump pit area as shown on the Map, the source has been adjusted slightly to the northeast in relation to the initial tank rupture point to reflect the pit as the source. The maximum concentration of Fuel Oil #6 at the Threat Point) is 4,440 ppm. Figure 10 shows the extent of the Yellow Zone on the MARPLOT map of the building area. Clearly the Threat at Point is engulfed by the plume. Figure 11 shows the effects of the continuous evaporation of Fuel oil #6 at 40 gals per hour. While the outdoor concentration rises rapidly to over 4000 ppm and remains constant through the first hour, the indoor concentration is estimated to rise slowly as the vapors accumulate. The ALOHA model estimates that the indoor concentration at the Threat at Point would exceed the Yellow Zone minimum (1000 ppm) after 20 minutes and rise to nearly 3000 ppm after the first hour.
Table III- DATA SUMMARY FOR FUEL OIL # 6 SITE DATA: Location: W, MASSACHUSETTS Building Air Exchanges Per Hour: 0.74 (sheltered single storied) Time: October ?, 2004 1050 hours EDT (user specified) CHEMICAL DATA: Chemical Name: FUEL OIL #6 Molecular Weight: 800.00 g/mol LEL: 10000 ppm UEL: 50000 ppm Ambient Boiling Point: 411.8° F Vapor Pressure at Ambient Temperature: 0 atm Ambient Saturation Concentration: 1.41e-004 ppm or 1.41e-008% Note: Not enough chemical data to use Heavy Gas option ATMOSPHERIC DATA: (MANUAL INPUT OF DATA) Wind: 10 miles/hour from E at 3 meters Ground Roughness: urban or forest Cloud Cover: 7 tenths Air Temperature: 47° F Stability Class: D No Inversion Height Relative Humidity: 63% SOURCE STRENGTH: Direct Source: 40 gallons/hr Source Height: 0 Source State: Liquid Source Temperature: equal to ambient Release Duration: 60 minutes Release Rate: 1,270 pounds/min Total Amount Released: 75,985 pounds THREAT ZONE: (GAUSSIAN SELECTED) Threat Modeled: Flammable Area of Vapor Cloud Model Run: Gaussian Red : 26 yards --- (6,000 ppm = 60% LEL = Flame Pockets) Note: Threat zone was not drawn because effects of near-field patchiness make dispersion predictions less reliable for short distances. Yellow: 65 yards --- (1,000 ppm = 10% LEL) THREAT AT POINT: Concentration Estimates at the point: West: 20 feet North: 2 feet Max Concentration: Outdoor: 4,440 ppm
FIG. 9 - FUEL OIL #6 PLUME MODEL
FIG. 10– MAP OF FUEL OIL #6 DISPERSION MODEL
FIG. 11- CONCENTRATION AT THREAT POINT OVER 1 HR These air dispersion models show a consistent pattern of vapor spread from the fuel oil source to the Building. This is not surprising since the Map shows the extent of the oil spill in the parking lot spanning two sides of the building. With this amount of fuel oil spilled even a small percentage of gases evaporated or released amount to significant threat zones in the immediate proximity of the spill. David Lincoln Greenlite Consultants
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