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%.

Design construction and testing of a heat loop for study of fouling and its interrelationship to corrosion in heat exchanger tubes

A heat loop suitable for the study of thermal fouling and its relationship to corrosion processes was designed, constructed and tested. The design adopted was an improvement over those used by such investigators as Hopkins and the Heat Transfer Research Institute in that very low levels of fouling could be detected accurately, the heat transfer surface could be readily removed for examination and the chemistry of the environment could be carefully monitored and controlled. In addition, an indirect method of electrical heating of the heat transfer surface was employed to eliminate magnetic and electric effects which result when direct resistance heating is employed to a test section. The testing of the loop was done using a 316 stainless steel test section and a suspension of ferric oxide and water in an attempt to duplicate the results obtained by Hopkins. Two types of thermal ·fouling resistance versus time curves were obtained . (i) Asymptotic type fouling curve, similar to the fouling behaviour described by Kern and Seaton and other investigators, was the most frequent type of fouling curve obtained. Thermal fouling occurred at a steadily decreasing rate before reaching a final asymptotic value. (ii) If an asymptotically fouled tube was cooled with rapid cir- ·culation for periods up to eight hours at zero heat flux, and heating restarted, fouling recommenced at a high linear rate. The fouling results obtained were observed to be similar and 1n agreement with the fouling behaviour reported previously by Hopkins and it was possible to duplicate quite closely the previous results . This supports the contention of Hopkins that the fouling results obtained were due to a crevice corrosion process and not an artifact of that heat loop which might have caused electrical and magnetic effects influencing the fouling. The effects of Reynolds number and heat flux on the asymptotic fouling resistance have been determined. A single experiment to study the effect of oxygen concentration has been carried out. The ferric oxide concentration for most of the fouling trials was standardized at 2400 ppM and the range of Reynolds number and heat flux for the study was 11000-29500 and 89-121 KW/M², respectively.

The mermaid series of Elizabethan and Jacobean dramatists (1887-1909): a literary and critical history

The Mermaid Series (1887-1909) edited by Havelock Ellis was a major watershed in appreciation of Elizabethan and Jacobean drama. Before it appeared plays were available to general readers in scattered anthologies, large expensive collected editions or in expurgated selections which included only the more lyrical speeches and memorable scenes. Criticism of the drama followed suit; the majority of critics concentrated on the sections which appealed to the romantic and sentimental tastes of nineteenthcentury readers. The two men who conceived the Mermaid Series, John Addington Symonds and Havelock Ellis, approached the drama differently from their contemporaries; Symonds studied a play as a whole work of art and Ellis concentrated on its view of life. Both were unsatisfied with the "select beauties", fragmented approach and wanted readers to have the best plays in their entirety easily available in handy, inexpensive editions. Symonds's awareness of the drama as theatre was combined with a historical perspective allowing him to judge the drama in relation to its own time. He made a lasting but hitherto underestimated contribution to study of Beaumont and Fletcher, Dekker, Marlowe, and Ford. Ellis's work on the drama is overshadowed today by his studies of sex but his concentration on ideas and appreciation of unconventional behaviour enabled him to formulate new views on Ford, Middleton and Chapman. The two other major editors to work on the series, A. C. Swinburne and Arthur Symons had more conventional nineteenth-century approaches. Both were impressionistic critics who were most attracted to the l~nguage of the drama. Swinburne, however, occasionally transcended his fragmented approach and offered significant interpretations of Tourneur, Massinger; 'The .Changeling, Heywood. Symons's range was more limited but his form of impressionism was valuable for its concentration on the aesthetic experience at the heart of a work of art. His most important contributions were the study of Middleton and Massinger. Besides these four major critics numerous lesser writers worked on the series. Their editorial work was valuable and some, notably Ernest Rhys, c. H. Herford and Thomas Dickinson offered criticism of enduring importance. In my first chapter I consider the general availability of texts of the Elizabethan and Jacobean drama in the nineteenth century, the general attitudes towards the drama, and the critical approaches of each of the editors. The subsequent chapters are organized around the volumes of the series. I consider the climate of opinion in which each appeared, assess its critical and editorial contribution and evaluate the work of the other Mermaid editors on the dramatist included in the volume. My study shows that the concept of the Mermaid Series and the work of its editors helped to revolutionize study of the Elizabethan and Jacobean dramatists by providing good texts and by pointing the way to our present view of the plays as whole works of art.