Grantee Research Project Results

Final Report: The Use of Nitrate for the Control of Sulfide Formation in Oklahoma Oil Fields

EPA Grant Number: R827015C008
Subproject: this is subproject number 008 , established and managed by the Center Director under grant R827015
(EPA does not fund or establish subprojects; EPA awards and manages the overall grant for this center).
Center: HSRC (1989) - Northeast HSRC
Center Director: Sidhu, Sukh S.
Title: The Use of Nitrate for the Control of Sulfide Formation in Oklahoma Oil Fields
Investigators: Suflita, Joseph , Davidova, Irene A.
Institution: University of Oklahoma
EPA Project Officer: Aja, Hayley
Project Period: July 1, 1999 through June 30, 2000 (Extended to June 30, 2001)
RFA: Integrated Petroleum Environmental Consortium (IPEC) (1999) RFA Text |  Recipients Lists
Research Category: Hazardous Waste/Remediation , Targeted Research

Objective:

In this project we investigated, how relevant is the use of nitrate as a preferred electron acceptor to control the metabolic activity of sulfate reducing bacteria to selected oil fields in Oklahoma.

Summary/Accomplishments (Outputs/Outcomes):

The final stage of the project was devoted to data integratio and generalization and preparing a manuscript.

The produced waters at the selected site (Bebee-Konawa oil field) were highly reduced, devoid of nitrate and contained relatively high level of dissolved sulfide ( 3.6 mM), while sulfate concentrations were relatively low (0.58 mM) (Table 1). These chemical characteristics were consistent with the prospect of sulfate reduction occurring in the formation. In consistent fashion, we detected sulfate reduction in samples from the Oklahoma field wellheads and from the oil-water separator. The rates of sulfate reduction varied from 0.05 to 0.16 µM S d^-1 at the wellheads, but were about an order of magnitude higher in the sample from the oil-water separator (Table 2). These data led to the hypothesis that the majority of the sulfide produced at this facility occurred after the oil was pumped aboveground. The potential for nitrate-reducing activity was also higher in samples taken from oil-water separator than from other produced waters (Table 2). For example, in the Bebee-Konawa field, the nitrate-reducing activity in the wellhead samples were 0.016 and 0.012 mmol L^-1 d^-1, whereas the activity in the sample from the oil-water separator was 0.06 mmol L^-1 d^-1. We detected both sulfate reducing bacteria (SRB) and nitrate-reducing bacteria (NRB) in the oil field, which indicated a sufficient biodiversity for implementation of nitrate technique.

However in oil-water separator SRB were more numerous and exceeded NRB in two orders of magnitude (Table 2).

We focused our laboratory experiments on the produced waters as possible targets for nitrate amendment to control sulfide production aboveground. Figure 1A shows the sulfide concentrations in laboratory incubations that contained produced water from the oil-water separator. This water contained a relatively low sulfate concentration (0.35 mM, Table 1), and little sulfide production occurred in the unsupplemented sample. Substantially more sulfide was evident when 5 mM sulfate was added to the incubation mixture, which was further increased when sulfate and oil were added together (Figure IA). These results suggested that the activity of SRB was limited, in part, by the availability of both a terminal electron acceptor and suitable electron donors.

Produced water from the oil-water separator at the Oklahoma field was used to determine the nitrate-reducing potentials in the presence and absence of the Bebee-Konawa oil. In both cases, the potential was 0.06 mmol L^-1 d^-1. Thus, the presence of a separate oil phase did not stimulate the rate of nitrate reduction and dissolved components in the produced water provided an adequate supply of electron donors for the this process.

When produced water samples from the oil-water separator in the Bebee-Konawa field were amended with nitrate (5 mM), approximately half of the amendment was consumed during a 14-wk incubation (Figure 1B). Over the same period, the sulfide concentration was reduced to near undetectable levels in the nonsterile incubations. There was little change in these components in the sterile controls (Figure 1B).

Lower initial nitrate concentrations (1 or 2 mM) in to the produced waters yields only a temporary effect. That is, sulfide was incompletely removed and sulfate reduction resumed after nitrate was depleted.

All of the produced water samples we examined harbored NRB (Table 2). Thus, nitrate treatment in this oil field would be expected to stimulate nitrate-reducing activity and the use of an inoculant would be unnecessary. However, it is not known if our findings will prove generating for other oil field waters.

 

The amendment of 5 mM nitrate stopped sulfide production in the produced water samples. However, in other oil fields this value could be different. We reconunend that each oil field should be assessed to, determine whether NRB are present and the nitrate concentration required to suppress sulfide production.

Petroleum industry efforts to control sulfide production using either biocides or nitrate injection are largely focused on injecting these control agents into a suitable reservoir. However, our work suggested that reservoirs may not be the only, or even the major, source of sulfide production problems in oil field operations. In our study, the majority of sulfide production and sulfate-reducing activity was evident in aboveground facilities. Enumeration data and activity profiles showed that aboveground facilities could be effective targets for sulfide control measures with nitrate.

The manuscript "The influence of nitrate on microbial processes in oil industry production waters" was submitted to the Journal of Industrial Microbiology & Biotechnology.

 

Table 1. Geochemical characteristics of the samples from the Bebee-Konawa oil field.

Oil Field	Sample	pH	Temp (°C)	Chloride (mM)	Sulfide (mM)	Sulfate (mM)
Bebee-Konawa	Well 1	7.8	25	137	3.6	0.38
Oklahomaa
	Well 2	8.0	27	95	3.6	0.52
	Oil-water separator	7.9	23	100	3.9	0.35

 

Table 2. Biogeochemical characteristics of the samples from the Bebee-Konawa oil field.

Oil Field	Sample	Sulfate-reducing activity (µM S d-1)	Potential nitrate reducing activity (mmol L-1 d-1)	SRB (MPN mL-1)	NRB (MPN mL-1)
Bebee-Konawa,	Well 1	0.16 ± 0.04	0.016 ± 0.004	2.5 x 103	2.5 x 102
Oklahoma
	Well 2	0.05 ± 0.016	0.012 ± 0.0005	4.5 x 102	2.5 x 105
	Oil-water separator	1.8 ± 0.27	0.06 ± 0.02	2.5 x 103	15

 

 

Figure 1. Sulfide and nitrate concentrations in laboratory incubations that contained produced water from the oil-water separator at the Bebee-Konawa field. (A) No nitrate added, (B) amended with 5 mM nitrate.

Journal Articles on this Report : 1 Displayed | Download in RIS Format

Publications Views

Other subproject views:	All 1 publications	1 publications in selected types	All 1 journal articles
Other center views:	All 120 publications	19 publications in selected types	All 16 journal articles

Publications

Type	Citation	Sub Project	Document Sources
Journal Article	Davidova I, Hicks MS, Fedorak PM, Suflita JM. The influence of nitrate on microbial processes in oil industry production waters. Journal of Industrial Microbiology and Biotechnology 2001;27(2):80-86.	R827015C008 (2000) R827015C008 (Final)	Abstract from PubMed Abstract: Springer Exit

Supplemental Keywords:

Sulfate reduction, nitrate reducing bacteria, microbial processes, biogeochemical, oil-water separator, oxidation, electron acceptor., RFA, Scientific Discipline, INTERNATIONAL COOPERATION, Waste, Water, Geographic Area, Contaminated Sediments, Remediation, Chemistry, State, Civil/Environmental Engineering, Hazardous Waste, Oil Spills, Bioremediation, Engineering, Environmental Engineering, Hazardous, dentrification, microbial degradation, sulfate reducing bacteria, sulfate reducing bacterium, contaminated sediment, sulfide formation, contaminated soil, oil spill, soils, nitrate compounds, soil, treatment, contaminants in soil, bioremediation of soils, Hydrogen sulfide, hazardous waste cleanup, nitrate, Oklahoma (OK), dentrifying bacteria, leachate, bacterial degradation

Progress and Final Reports:

Original Abstract

2000 Progress Report

Main Center Abstract and Reports:

R827015    HSRC (1989) - Northeast HSRC

Subprojects under this Center: (EPA does not fund or establish subprojects; EPA awards and manages the overall grant for this center).
R827015C001 Evaluation of Road Base Material Derived from Tank Bottom Sludges
R827015C002 Passive Sampling Devices (PSDs) for Bioavailability Screening of Soils Containing Petrochemicals
R827015C003 Demonstration of a Subsurface Drainage System for the Remediation of Brine-Impacted Soil
R827015C004 Anaerobic Intrinsic Bioremediation of Whole Gasoline
R827015C005 Microflora Involved in Phytoremediation of Polyaromatic Hydrocarbons
R827015C006 Microbial Treatment of Naturally Occurring Radioactive Material (NORM)
R827015C007 Using Plants to Remediate Petroleum-Contaminated Soil
R827015C008 The Use of Nitrate for the Control of Sulfide Formation in Oklahoma Oil Fields
R827015C009 Surfactant-Enhanced Treatment of Oil-Contaminated Soils and Oil-Based Drill Cuttings
R827015C010 Novel Materials for Facile Separation of Petroleum Products from Aqueous Mixtures Via Magnetic Filtration
R827015C011 Development of Relevant Ecological Screening Criteria (RESC) for Petroleum Hydrocarbon-Contaminated Exploration and Production Sites
R827015C012 Humate-Induced Remediation of Petroleum Contaminated Surface Soils
R827015C013 New Process for Plugging Abandoned Wells
R827015C014 Enhancement of Microbial Sulfate Reduction for the Remediation of Hydrocarbon Contaminated Aquifers - A Laboratory and Field Scale Demonstration
R827015C015 Locating Oil-Water Interfaces in Process Vessels
R827015C016 Remediation of Brine Spills with Hay
R827015C017 Continuation of an Investigation into the Anaerobic Intrinsic Bioremediation of Whole Gasoline
R827015C018 Using Plants to Remediate Petroleum-Contaminated Soil
R827015C019 Biodegradation of Petroleum Hydrocarbons in Salt-Impacted Soil by Native Halophiles or Halotolerants and Strategies for Enhanced Degradation
R827015C020 Anaerobic Intrinsic Bioremediation of MTBE
R827015C021 Evaluation of Commercial, Microbial-Based Products to Treat Paraffin Deposition in Tank Bottoms and Oil Production Equipment
R827015C022 A Continuation: Humate-Induced Remediation of Petroleum Contaminated Surface Soils
R827015C023 Data for Design of Vapor Recovery Units for Crude Oil Stock Tank Emissions
R827015C024 Development of an Environmentally Friendly and Economical Process for Plugging Abandoned Wells
R827015C025 A Continuation of Remediation of Brine Spills with Hay
R827015C026 Identifying the Signature of the Natural Attenuation of MTBE in Goundwater Using Molecular Methods and "Bug Traps"
R827015C027 Identifying the Signature of Natural Attenuation in the Microbial Ecology of Hydrocarbon Contaminated Groundwater Using Molecular Methods and "Bug Traps"
R827015C028 Using Plants to Remediate Petroleum-Contaminated Soil: Project Continuation
R827015C030 Effective Stormwater and Sediment Control During Pipeline Construction Using a New Filter Fence Concept
R827015C031 Evaluation of Sub-micellar Synthetic Surfactants versus Biosurfactants for Enhanced LNAPL Recovery
R827015C032 Utilization of the Carbon and Hydrogen Isotopic Composition of Individual Compounds in Refined Hydrocarbon Products To Monitor Their Fate in the Environment
R830633 Integrated Petroleum Environmental Consortium (IPEC)
R830633C001 Development of an Environmentally Friendly and Economical Process for Plugging Abandoned Wells (Phase II)
R830633C002 A Continuation of Remediation of Brine Spills with Hay
R830633C003 Effective Stormwater and Sediment Control During Pipeline Construction Using a New Filter Fence Concept
R830633C004 Evaluation of Sub-micellar Synthetic Surfactants versus Biosurfactants for Enhanced LNAPL Recovery
R830633C005 Utilization of the Carbon and Hydrogen Isotopic Composition of Individual Compounds in Refined Hydrocarbon Products To Monitor Their Fate in the Environment
R830633C006 Evaluation of Commercial, Microbial-Based Products to Treat Paraffin Deposition in Tank Bottoms and Oil Production Equipment
R830633C007 Identifying the Signature of the Natural Attenuation in the Microbial Ecology of Hydrocarbon Contaminated Groundwater Using Molecular Methods and “Bug Traps”
R830633C008 Using Plants to Remediate Petroleum-Contaminated Soil: Project Continuation
R830633C009 Use of Earthworms to Accelerate the Restoration of Oil and Brine Impacted Sites