Pilot plant studies of ion exchange for desalination of coal seam gas produced water

This paper reports a study of ion exchange (IX) as an alternative CSG water treatment to the widely used reverse osmosis (RO) desalination process. An IX pilot plant facility has been constructed and operated using both synthetic and real CSG water samples. Application of appropriate synthetic resin technology has proved the effectiveness of IX processes.

Effect of hydrodynamics and surface roughness on the electrochemical behaviour of carbon steel in CSG produced water

The influence of fluid flow, surface roughness and immersion time on the electrochemical behaviour of carbon steel in coal seam gas produced water under static and hydrodynamic conditions has been studied. The disc electrode surface morphology before and after the corrosion test was characterized using scanning electron microscopy (SEM). The corrosion product was examined using X-ray photoelectron spectroscopy (XPS) and X-ray diffractometry (XRD).The results show that the anodic current density increased with increasing surface roughness and consequently a decrease in corrosion surface resistance. Under dynamic flow conditions, the corrosion rate increased with increasing rotating speed due to the high mass transfer coefficient and formation of non-protective akaganeite β- FeO(OH) and goethite α- FeO(OH) corrosion scale at the electrode surface.The corrosion rate was lowest at 0 rpm.The corrosion rate decreased in both static and dynamic conditions with increasing immersion time. The decrease in corrosion rate is attributed to the deposition of corrosion products on the electrode surface. SEM results revealed that the rougher surface exhibited a great tendency toward pitting corrosion.

Characterization of wood biochar and evaluation of its adsorption potential for removal of sulphate from produced water in offshore oil and gas industry

This thesis analyses the potential of wood biochar as an adsorbent in removal of sulphate from produced water. In worldwide offshore oil and gas industry, a large volume of waste water is generated as produced water. Sulphur compounds present in these produced water streams can cause environmental problems, regulatory problems and operational issues. Among the various sulphur removal technologies, the adsorption technique is considered as a suitable method since the design is simple, compact, economical and robust. Biochar has been studied as an adsorbent for removal of contaminants from water in a number of studies due to its low cost, potential availability, and adsorptive characteristics. In this study, biochar produced through fast pyrolysis of bark, hardwood sawdust, and softwood sawdust were characterized through a series of tests and were analysed for adsorbent properties. Treating produced water using biochar sourced from wood waste is a two-fold solution to environmental problems as it reduces the volume of these wastes. Batch adsorption tests were carried out to obtain adsorption capacities of each biochar sample using sodium sulphate solutions. The highest sulphur adsorption capacities obtained for hardwood char, softwood char and bark char were 11.81 mg/g, 9.44 mg/g, and 7.94 mg/g respectively at 10 °C and pH=4. The adsorption process followed the second order kinetic model and the Freundlich isotherm model. Adsorption reaction was thermodynamically favourable and exothermic. The overall analysis concludes that the wood biochar is a feasible, economical, and environmental adsorbent for removal of sulphate from produced water.

A study of methods used to analyze total oil and polycyclic aromatic hydrocarbons in produced water: steps towards the validation of molecularly imprinted polymers for use in marine environmetns

Produced water is a by-product of offshore oil and gas production, and is released in large volumes when platforms are actively processing crude oil. Some pollutants are not typically removed by conventional oil/water separation methods and are discharged with produced water. Oil and grease can be found dispersed in produced water in the form of tiny droplets, and polycyclic aromatic hydrocarbons (PAHs) are commonly found dissolved in produced water. Both can have acute and chronic toxic effects in marine environments even at low exposure levels. The analysis of the dissolved and dispersed phases are a priority, but effort is required to meet the necessary detection limits. There are several methods for the analysis of produced water for dispersed oil and dissolved PAHs, all of which have advantages and disadvantages. In this work, EPA Method 1664 and APHA Method 5520 C for the determination of oil and grease will be examined and compared. For the detection of PAHs, EPA Method 525 and PAH MIPs will be compared, and results evaluated. APHA Method 5520 C Partition-Infrared Method is a liquid-liquid extraction procedure with IR determination of oil and grease. For analysis on spiked samples of artificial seawater, extraction efficiency ranged from 85 – 97%. Linearity was achieved in the range of 5 – 500 mg/L. This is a single-wavelength method and is unsuitable for quantification of aromatics and other compounds that lack sp³-hybridized carbon atoms. EPA Method 1664 is the liquid-liquid extraction of oil and grease from water samples followed by gravimetric determination. When distilled water spiked with reference oil was extracted by this procedure, extraction efficiency ranged from 28.4 – 86.2%, and %RSD ranged from 7.68 – 38.0%. EPA Method 525 uses solid phase extraction with analysis by GC-MS, and was performed on distilled water and water from St. John’s Harbour, all spiked with naphthalene, fluorene, phenanthrene, and pyrene. The limits of detection in harbour water were 0.144, 3.82, 0.119, and 0.153 g/L respectively. Linearity was obtained in the range of 0.5-10 g/L, and %RSD ranged from 0.36% (fluorene) to 46% (pyrene). Molecularly imprinted polymers (MIPs) are sorbent materials made selective by polymerizing functional monomers and crosslinkers in the presence of a template molecule, usually the analytes of interest or related compounds. They can adsorb and concentrate PAHs from aqueous environments and are combined with methods of analysis including GC-MS, LC-UV-Vis, and desorption electrospray ionization (DESI)- MS. This work examines MIP-based methods as well as those methods previously mentioned which are currently used by the oil and gas industry and government environmental agencies. MIPs are shown to give results consistent with other methods, and are a low-cost alternative improving ease, throughput, and sensitivity. PAH MIPs were used to determine naphthalene spiked into ASTM artificial seawater, as well as produced water from an offshore oil and gas operation. Linearity was achieved in the range studied (0.5 – 5 mg/L) for both matrices, with R² = 0.936 for seawater and R² = 0.819 for produced water. The %RSD for seawater ranged from 6.58 – 50.5% and for produced water, from 8.19 – 79.6%.

Phase and partitioning behavior of phenols and polycyclic aromatic hydrocarbons in offshore oil and gas produced water

Produced water constitutes the largest volume of waste from offshore oil and gas operations and is composed of a wide range of organic and inorganic compounds. Although treatment processes have to meet strict oil in water regulations, the definition of “oil” is a function of the analysis process and may include aliphatic hydrocarbons which have limited environmental impact due to degradability whilst ignoring problematic dissolved petroleum species. This thesis presents the partitioning behavior of oil in produced water as a function of temperature and salinity to identify compounds of environmental concern. Phenol, p-cresol, and 4-tert-butylphenol were studied because of their xenoestrogenic power; other compounds studied are polycyclic aromatic hydrocarbon PAHs which include naphthalene, fluorene, phenanthrene, and pyrene. Partitioning experiments were carried out in an Innova incubator for 48 hours, temperature was varied from 4ﾟC to 70ﾟC, and two salinity levels of 46.8‰ and 66.8‰ were studied. Results obtained showed that the dispersed oil concentration in the water reduces with settling time and equilibrium was attained at 48 h settling time. Polycyclic aromatic hydrocarbons (PAHs) partitions based on dispersed oil concentration whereas phenols are not significantly affected by dispersed oil concentration. Higher temperature favors partitioning of PAHs into the water phase. Salinity has negligible effect on partitioning pattern of phenols and PAHs studied. Simulation results obtained from the Aspen HYSYS model shows that temperature and oil droplet distribution greatly influences the efficiency of produced water treatment system.

Assessment of Geogenic Contaminants in Water Co-Produced with Coal Seam Gas Extraction in Queensland, Australia : Implications for Human Health Risk

Organic compounds in Australian coal seam gas produced water (CSG water) are poorly understood despite their environmental contamination potential. In this study, the presence of some organic substances is identified from government-held CSG water-quality data from the Bowen and Surat Basins, Queensland. These records revealed the presence of polycyclic aromatic hydrocarbons (PAHs) in 27% of samples of CSG water from the Walloon Coal Measures at concentrations <1 µg/L, and it is likely these compounds leached from in situ coals. PAHs identified from wells include naphthalene, phenanthrene, chrysene and dibenz[a,h]anthracene. In addition, the likelihood of coal-derived organic compounds leaching to groundwater is assessed by undertaking toxicity leaching experiments using coal rank and water chemistry as variables. These tests suggest higher molecular weight PAHs (including benzo[a]pyrene) leach from higher rank coals, whereas lower molecular weight PAHs leach at greater concentrations from lower rank coal. Some of the identified organic compounds have carcinogenic or health risk potential, but they are unlikely to be acutely toxic at the observed concentrations which are almost negligible (largely due to the hydrophobicity of such compounds). Hence, this study will be useful to practitioners assessing CSG water related environmental and health risk.

Field evaluation of a suite of biomarkers in an Australian Tropical Reef Species, Stripey Seaperch (Lutjanus carponotatus) : Assessment of Produced Formation water from the Harriet A Platform

There is paucity of data regarding hydrocarbon exposure of tropical fish species inhabiting the waters near oil and gas platforms on the Northwest Shelf of Australia. A comprehensive field study assessed the exposure and potential effects associated with the produced water (PW) plume from the Harriet A production platform on the northwest shelf in a local reef species, Stripey seaperch (Lutjanus carponotatus). This field study was a continuation of an earlier pilot study which concluded that there were “warning signs” of potential biological effects on fish populations exposed to PW. A 10-day field caging study was conducted deploying 15 individual fish into 6 separate steel cages set 1-m subsurface at 3 stations in a concentration gradient moving away from the platform. A battery of biomarkers were evaluated including hepatosomatic index (HSI), total cytochrome P450, bile metabolites, CYP1A-, CYP2K- and CYP2M-like proteins, cholinesterase (ChE) activity, and histopathology of liver and gill tissues. Water column and PW effluent samples was also collected. Results confirmed that PAH metabolites in bile, CYP1A-, CYP2K-, and CYP2M-like proteins and liver histopathology provided evidence of significant exposure and effects after 10 days at the near-field site (~200 m off the Harriet A platform). Hepatosomatic index, total cytochrome P450, and ChE did not provide site-specific differences by day 10 of exposure to PW. CYP proteins were shown by principal component analysis (PCA) to be the best diagnostic tool for determining exposure and associated biological effects of PW on L. carponotatus. Using a suite of biomarkers has been widely advocated as a vital component in environmental risk assessments worldwide. This study demonstrates the usefulness of biomarkers for assessing the Harriet A PW discharge into Australian waters with broader applications for other PW discharges. This approach has merit as a valuable addition to environmental management strategies for protecting Australia’s tropical environment and its rich biodiversity.

Evaluation of electrocoagulation for the pre-treatment of coal seam water

This work explored the applicability of electrocoagulation (EC) using aluminium electrodes for the removal of contaminants which can scale and foul reverse osmosis membranes from a coal seam (CS) water sample, predominantly comprising sodium chloride, and sodium bicarbonate. In general, the removal efficiency of species responsible for scaling and fouling was enhanced by increasing the applied current density/voltage and contact times (30–60 s) in the EC chamber. High removal efficiencies of species potentially responsible for scale formation in reverse osmosis units such as calcium (100%), magnesium (87.9%), strontium (99.3%), barium (100%) and silicates (98.3%) were achieved. Boron was more difficult to eliminate (13.3%) and this was postulated to be due to the elevated solution pH. Similarly, fluoride removal from solution (44%) was also inhibited by the presence of hydroxide ions in the pH range 9–10. Analysis of produced flocs suggested the dominant presence of relatively amorphous boehmite (AlOOH), albeit the formation of Al(OH)3 was not ruled out as the drying process employed may have converted aluminium hydroxide to aluminium oxyhydroxide species. Evidence for adsorption of contaminants on floc surface sites was determined from FTIR studies. The quantity of aluminium released during the electrocoagulation process was higher than the Faradaic amount which suggested that the high salt concentrations in the coal seam water had chemically reacted with the aluminium electrodes.

Strategies for the management and treatment of coal seam gas associated water

Coal seam gas (CSG) is a growing industry in Queensland and represents a potential major employer and deliverer of financial prosperity for years to come. CSG is a natural gas composed primarily of methane and is found trapped underground in coal beds. During the gas extraction process, significant volumes of associated water are also produced. This associated water could be a valuable resource, however, the associated water comprises of various salt constituents that make it problematic for beneficial use. Consequently, there is a need to implement various water treatment strategies to purify the associated water to comply with Queensland’s strict guidelines and to mitigate environmental risks. The resultant brine is also of importance as ultimately it also has to be dealt with in an economical manner. In some ways it can be considered that the CSG industry does not face a water problem, as this has inherent value to society, but rather has a “salt issue” to solve. This study analyzes the options involved in both the water treatment and salt recovery processes. A brief overview of the constituents present in Queensland CS water is made to illustrate the challenges involved and a range of treatment technologies discussed. Water treatment technologies examined include clarification (ballasted flocculation, dissolved air flotation, electrocoagulation), membrane filtration (ultrafiltration), ion exchange softening and desalination (ion exchange, reverse osmosis desalination and capacitance deionization). In terms of brine management we highlighted reinjection, brine concentration ponds, membrane techniques (membrane distillation, forward osmosis), thermal methods, electrodialysis, electrodialysis reversal, bipolar membrane electrodialysis, wind assisted intensive evaporation, membrane crystallization, eutectic freeze crystallization and vapor compression. As an entirety this investigation is designed to be an important tool in developing CS water treatment management strategies for effective management in Queensland and worldwide.

Novel photocatalytic reactor development for removal of hydrocarbons from water

Hydrocarbons contamination of the marine environment generated by the offshore oil and gas industry is generated from a number of sources including oil contaminated drill cuttings and produced waters. The removal of hydrocarbons from both these sources is one of the most significant challenges facing this sector as it moves towards zero emissions. The application of a number of techniques which have been used to successfully destroy hydrocarbons in produced water and waste water effluents has previously been reported. This paper reports the application of semiconductor photocatalysis as a final polishing step for the removal of hydrocarbons from two waste effluent sources. Two reactor concepts were considered: a simple flat plate immobilised film unit, and a new rotating drum photocatalytic reactor. Both units proved to be effective in removing residual hydrocarbons from the effluent with the drum reactor reducing the hydrocarbon content by 90% under 10 minutes. 

Geochemical and Strontium Isotope Characterization of Produced Waters from Marcellus Shale Natural Gas Extraction

Extraction of natural gas by hydraulic fracturing of the Middle Devonian Marcellus Shale, a major gas-bearing unit in the Appalachian Basin, results in significant quantities of produced water containing high total dissolved solids (TDS). We carried out a strontium (Sr) isotope investigation to determine the utility of Sr isotopes in identifying and quantifying the interaction of Marcellus Formation produced waters with other waters in the Appalachian Basin in the event of an accidental release, and to provide information about the source of the dissolved solids. Strontium isotopic ratios of Marcellus produced waters collected over a geographic range of ∼375 km from southwestern to northeastern Pennsylvania define a relatively narrow set of values (εSr SW = +13.8 to +41.6, where εSr SW is the deviation of the 87Sr/86Sr ratio from that of seawater in parts per 104); this isotopic range falls above that of Middle Devonian seawater, and is distinct from most western Pennsylvania acid mine drainage and Upper Devonian Venango Group oil and gas brines. The uniformity of the isotope ratios suggests a basin-wide source of dissolved solids with a component that is more radiogenic than seawater. Mixing models indicate that Sr isotope ratios can be used to sensitively differentiate between Marcellus Formation produced water and other potential sources of TDS into ground or surface waters.

Radiological aspects of petroleum exploration and production in the sultanate of Oman

This thesis is a study of naturally occurring radioactive materials (NORM) activity concentration, gamma dose rate and radon (222Rn) exhalation from the waste streams of large-scale onshore petroleum operations. Types of activities covered included; sludge recovery from separation tanks, sludge farming, NORM storage, scaling in oil tubulars, scaling in gas production and sedimentation in produced water evaporation ponds. Field work was conducted in the arid desert terrain of an operational oil exploration and production region in the Sultanate of Oman. The main radionuclides found were 226Ra and 210Pb (238U - series), 228Ra and 228Th (232Th - series), and 227Ac (235U - series), along with 40K. All activity concentrations were higher than the ambient soil level and varied over several orders of magnitude. The range of gamma dose rates at a 1 m height above ground for the farm treated sludge had a range of 0.06 0.43 µSv h 1, and an average close to the ambient soil mean of 0.086 ± 0.014 µSv h 1, whereas the untreated sludge gamma dose rates had a range of 0.07 1.78 µSv h 1, and a mean of 0.456 ± 0.303 µSv h 1. The geometric mean of ambient soil 222Rn exhalation rate for area surrounding the sludge was mBq m 2 s 1. Radon exhalation rates reported in oil waste products were all higher than the ambient soil value and varied over three orders of magnitude. This study resulted in some unique findings including: (i) detection of radiotoxic 227Ac in the oil scales and sludge, (ii) need of a new empirical relation between petroleum sludge activity concentrations and gamma dose rates, and (iii) assessment of exhalation of 222Rn from oil sludge. Additionally the study investigated a method to determine oil scale and sludge age by the use of inherent behaviour of radionuclides as 228Ra:226Ra and 228Th:228Ra activity ratios.

Australia and New Zealand CBNG development and environmental implications

Following the success of Coalbed Natural Gas (CBNG) operations in the United States, companies in Australia and New Zealand have been actively exploring and developing this technology for the last two decades. In particular, the Bowen and Surat basins in Queensland, Australia, have undergone extensive CBNG development. Unfortunately, awareness of potential environmental problems associated with CBNG abstraction has not been widespread and legislation has at times struggled to keep up with rapid development. In Australia, the combined CBNG resource for both the Bowen and Surat basins has been estimated at approximately 10,500 PJ with gas content as high as 10 m3/tonne of coal. There are no official estimates for the magnitude of the CBNG resource in New Zealand but initial estimates suggest this could be up to 1,300 PJ with gas content ranging from 1 to 5 m3/tonne of coal. In Queensland, depressurization of the Walloon Coal Measures to recover CBNG has the potential to induce drawdown in adjacent deep aquifer systems through intraformational groundwater flow. In addition, CBNG operators have been disposing their co-produced water by using large unlined ponds, which is not the best practice for managing co-produced water. CBNG waters in Queensland have the typical geochemical signature associated with CBNG waters (Van Voast, 2003) and thus have the potential to impair soils and plant growth where land disposal is considered. Water quality from exploration wells in New Zealand exhibit the same characteristics although full scale production has not yet begun. In general, the environmental impacts that could arise from CBNG water extraction depend on the aquifer system, the quantity and quality of produced water, and on the method of treatment and disposal being used. Understanding these impacts is necessary to adequately manage CBNG waters so that environmental effects are minimized; if properly managed, CBNG waters can be used for beneficial applications and can become a valuable resource to stakeholders.

Regulating coal seam gas in Queensland : lessons in an adaptive environmental management approach?

The current regulatory approach to coal seam gas projects in Queensland is based on the philosophy of adaptive environmental management. This method of “learning by doing” is implemented in Queensland primarily through the imposition of layered monitoring and reporting duties on the coal seam gas operator alongside obligations to compensate and “make good” harm caused. The purpose of this article is to provide a critical review of the Queensland regulatory approach to the approval and minimisation of adverse impacts from coal seam gas activities. Following an overview of the hallmarks of an effective adaptive management approach, this article begins by addressing the mosaic of approval processes and impact assessment regimes that may apply to coal seam gas projects. This includes recent Strategic Cropping Land reforms. This article then turns to consider the preconditions for land access in Queensland and the emerging issues for landholders relating to the negotiation of access and compensation agreements. This article then undertakes a critical review of the environmental duties imposed on coal seam gas operators relating to hydraulic fracturing, well head leaks, groundwater management and the disposal and beneficial use of produced water. Finally, conclusions are drawn regarding the overall effectiveness of the Queensland framework and the lessons that may be drawn from Queensland’s adaptive environmental management approach.