Bioremediation of PAHs - Limitations and soultions

Introduction 1.1 Occurrence of polycyclic aromatic hydrocarbons (PAH) in the environment Worldwide industrial and agricultural developments have released a large number of natural and synthetic hazardous compounds into the environment due to careless waste disposal, illegal waste dumping and accidental spills. As a result, there are numerous sites in the world that require cleanup of soils and groundwater. Polycyclic aromatic hydrocarbons (PAHs) are one of the major groups of these contaminants (Da Silva et al., 2003). PAHs constitute a diverse class of organic compounds consisting of two or more aromatic rings with various structural configurations (Prabhu and Phale, 2003). Being a derivative of benzene, PAHs are thermodynamically stable. In addition, these chemicals tend to adhere to particle surfaces, such as soils, because of their low water solubility and strong hydrophobicity, and this results in greater persistence under natural conditions. This persistence coupled with their potential carcinogenicity makes PAHs problematic environmental contaminants (Cerniglia, 1992; Sutherland, 1992). PAHs are widely found in high concentrations at many industrial sites, particularly those associated with petroleum, gas production and wood preserving industries (Wilson and Jones, 1993). 1.2 Remediation technologies Conventional techniques used for the remediation of soil polluted with organic contaminants include excavation of the contaminated soil and disposal to a landfill or capping - containment - of the contaminated areas of a site. These methods have some drawbacks. The first method simply moves the contamination elsewhere and may create significant risks in the excavation, handling and transport of hazardous material. Additionally, it is very difficult and increasingly expensive to find new landfill sites for the final disposal of the material. The cap and containment method is only an interim solution since the contamination remains on site, requiring monitoring and maintenance of the isolation barriers long into the future, with all the associated costs and potential liability. A better approach than these traditional methods is to completely destroy the pollutants, if possible, or transform them into harmless substances. Some technologies that have been used are high-temperature incineration and various types of chemical decomposition (for example, base-catalyzed dechlorination, UV oxidation). However, these methods have significant disadvantages, principally their technological complexity, high cost , and the lack of public acceptance. Bioremediation, on the contrast, is a promising option for the complete removal and destruction of contaminants. 1.3 Bioremediation of PAH contaminated soil & groundwater Bioremediation is the use of living organisms, primarily microorganisms, to degrade or detoxify hazardous wastes into harmless substances such as carbon dioxide, water and cell biomass Most PAHs are biodegradable unter natural conditions (Da Silva et al., 2003; Meysami and Baheri, 2003) and bioremediation for cleanup of PAH wastes has been extensively studied at both laboratory and commercial levels- It has been implemented at a number of contaminated sites, including the cleanup of the Exxon Valdez oil spill in Prince William Sound, Alaska in 1989, the Mega Borg spill off the Texas coast in 1990 and the Burgan Oil Field, Kuwait in 1994 (Purwaningsih, 2002). Different strategies for PAH bioremediation, such as in situ , ex situ or on site bioremediation were developed in recent years. In situ bioremediation is a technique that is applied to soil and groundwater at the site without removing the contaminated soil or groundwater, based on the provision of optimum conditions for microbiological contaminant breakdown.. Ex situ bioremediation of PAHs, on the other hand, is a technique applied to soil and groundwater which has been removed from the site via excavation (soil) or pumping (water). Hazardous contaminants are converted in controlled bioreactors into harmless compounds in an efficient manner. 1.4 Bioavailability of PAH in the subsurface Frequently, PAH contamination in the environment is occurs as contaminants that are sorbed onto soilparticles rather than in phase (NAPL, non aqueous phase liquids). It is known that the biodegradation rate of most PAHs sorbed onto soil is far lower than rates measured in solution cultures of microorganisms with pure solid pollutants (Alexander and Scow, 1989; Hamaker, 1972). It is generally believed that only that fraction of PAHs dissolved in the solution can be metabolized by microorganisms in soil. The amount of contaminant that can be readily taken up and degraded by microorganisms is defined as bioavailability (Bosma et al., 1997; Maier, 2000). Two phenomena have been suggested to cause the low bioavailability of PAHs in soil (Danielsson, 2000). The first one is strong adsorption of the contaminants to the soil constituents which then leads to very slow release rates of contaminants to the aqueous phase. Sorption is often well correlated with soil organic matter content (Means, 1980) and significantly reduces biodegradation (Manilal and Alexander, 1991). The second phenomenon is slow mass transfer of pollutants, such as pore diffusion in the soil aggregates or diffusion in the organic matter in the soil. The complex set of these physical, chemical and biological processes is schematically illustrated in Figure 1. As shown in Figure 1, biodegradation processes are taking place in the soil solution while diffusion processes occur in the narrow pores in and between soil aggregates (Danielsson, 2000). Seemingly contradictory studies can be found in the literature that indicate the rate and final extent of metabolism may be either lower or higher for sorbed PAHs by soil than those for pure PAHs (Van Loosdrecht et al., 1990). These contrasting results demonstrate that the bioavailability of organic contaminants sorbed onto soil is far from being well understood. Besides bioavailability, there are several other factors influencing the rate and extent of biodegradation of PAHs in soil including microbial population characteristics, physical and chemical properties of PAHs and environmental factors (temperature, moisture, pH, degree of contamination). Figure 1: Schematic diagram showing possible rate-limiting processes during bioremediation of hydrophobic organic contaminants in a contaminated soil-water system (not to scale) (Danielsson, 2000). 1.5 Increasing the bioavailability of PAH in soil Attempts to improve the biodegradation of PAHs in soil by increasing their bioavailability include the use of surfactants , solvents or solubility enhancers.. However, introduction of synthetic surfactant may result in the addition of one more pollutant. (Wang and Brusseau, 1993).A study conducted by Mulder et al. showed that the introduction of hydropropyl-ß-cyclodextrin (HPCD), a well-known PAH solubility enhancer, significantly increased the solubilization of PAHs although it did not improve the biodegradation rate of PAHs (Mulder et al., 1998), indicating that further research is required in order to develop a feasible and efficient remediation method. Enhancing the extent of PAHs mass transfer from the soil phase to the liquid might prove an efficient and environmentally low-risk alternative way of addressing the problem of slow PAH biodegradation in soil.

Department-store education: an acount of the training methods developed at the Boston School of Salemanship under the direction of Lucinda Wyman Prince

by Helen Rich Norton.

Notebook of James Lovell, 1757-1760

Marbled paper-covered handwritten notebook of James Lovell. The volume contains three texts written in Latin, “Praecellentissime Domine,” dated 1757, an untitled text beginning, “Cogitanti mihi et superiorum revolti…” dated 1759, and Lovell’s funeral oration for Tutor Henry Flynt titled “Oratio funebris” dated 1760. The Latin texts are followed by blank pages and the volume ends with an untitled English text about orators that begins, “Ridiculous certainly is that Practice of some...” The last page of the text includes the marginal notes: “John Winthrop Esqr. Hollisian Professor” and, “For T.H. of Carolina.” There are verses attributed to the London Magazine written on the inside front cover.

John Warren's copy of votes from a meeting of the Boston Medical Society, 1784 May 3

This document lists the eleven votes cast at a meeting of the Boston Medical Society on May 3, 1784. It was authorized as a "true coppy" by Thomas Kast, the Secretary of the Society. The following members of the Society were present at the meeting, all of them doctors: James Pecker, James Lloyd, Joseph Gardner, Samuel Danforth, Isaac Rand, Jr., Charles Jarvis, Thomas Kast, Benjamin Curtis, Thomas Welsh, Nathaniel Walker Appleton, and doctors whose last names were Adams, Townsend, Eustis, Homans, and Whitwell. The document indicates that a meeting had been held the previous evening, as well (May 2, 1784), at which the topics on which votes were taken had been discussed. The votes, eleven in total, were all related to the doctors' concerns about John Warren and his involvement with the emerging medical school (now Harvard Medical School), that school's relation to almshouses, the medical care of the poor, and other related matters. The tone and content of these votes reveals anger on the part of the members of the Boston Medical Society towards Warren. This anger appears to have stemmed from the perceived threat of Warren to their own practices, exacerbated by a vote of the Harvard Corporation on April 19, 1784. This vote authorized Warren to apply to the Overseers of the Poor for the town of Boston, requesting that students in the newly-established Harvard medical program, where Warren was Professor of Anatomy and Surgery, be allowed to visit the hospital of the almshouse with their professors for the purpose of clinical instruction. Although Warren believed that the students would learn far more from these visits, in regards to surgical experience, than they could possibly learn in Cambridge, the proposal provoked great distrust from the members of the Boston Medical Society, who accused Warren of an "attempt to direct the public medical business from its usual channels" for his own financial and professional gain.

Small Pocks, 1775-1779 (inclusive)

Ledger containing accounts of smallpox inoculation by Dr. John Jeffries (1745-1819) at Rainsford Island Hospital in Boston, Massachusetts, from June to July 1775; at a West Boston smallpox hospital in July 1775; and in Halifax, Nova Scotia, between 1776 and 1779. The accounts include dates, names, ages and physical condition of patients, and details regarding the method of delivery. Among the patients he inoculated was his son, John, at Rainsford Island Hospital on 14 June 1775.

Student lectures notes on chemistry and materia medica, and medical recipes, of Lyman Spalding, 1795-1799 (inclusive)

Contains notes taken by Harvard student Lyman Spalding during eleven chemistry lectures delivered by Harvard Professor Aaron Dexter (1750-1829) in the fall of 1795 and recipes prepared and used by Spalding in his medical practice in 1797. The recipes include elixir vitriol, containing liquor, Jamaica pepper, cinnamon, and ginger, and an electuary for a cough, containing oxymel squills (sea onion in honey), licorice, antimonium tartaricum potash (a compound of the chemical element antimony and a potassium-containing salt), and opium. The volume also contains writings about chemistry by Spalding, some of which appear transcribed from published sources, in undated entries, and a diary entry from 1799 regarding an experiment with water.

Student lecture notes on the Theory & Practice of Physic, and patient case histories, of Lyman Spalding, 1795-1799 (inclusive)

Contains notes taken by Harvard student Lyman Spalding from lectures delivered by Hersey Professor of the Theory and Practice of Physic Benjamin Waterhouse (1754-1846) in 1795. The notes cover the history of medicine, theories of contemporary physicians like Herman Boerhaave, William Cullen, and John Brown, and topics like fetal growth, digestion, and circulation. The volume also contains six pages of patient case notes from Spalding’s medical practice in Walpole, New Hampshire, in 1799, which detail the patients’ symptoms and course of treatment he pursued. In the case of a young man who complained of pain in his breast following a wrestling match, Spalding bled him and prescribed a cathartic of soap and aloes. Spalding also operated on a man who cut off part of his ankle with an ax.

Student lecture notes on anatomy and surgery, and medical notes, of Lyman Spalding, 1795

Contains notes taken by Harvard student Lyman Spalding (1775-1821) from lectures on anatomy and surgery delivered by Harvard Professor John Warren (1753-1815) in 1795, as well a section entitled “Medical Observations,” which includes entries on “Vernal Debility,” or diseases occurring in the spring, and lung function. It is unclear if these are Spalding’s own writings or transcriptions from a published work. There is also text transcribed from “Elementa Medicinae,” published in 1780 by Scottish physician John Brown.

Account book of David Townsend, 1774-1791

Account book kept by Dr. David Townsend (1753-1829) that records patients treated, illnesses, and fees charged in Boston, Massachusetts, and neighboring towns from 1774 to 1791. His patients included a number of soldiers and sailors, as well as figures like the French-American writer John Hector St. John (1735-1813). Townsend's treatments typically consisted of delivering cathartics or emetics. For the family of Samuel Appleton, Townsend administered smallpox inoculation in 1776, charging him 4 pounds, 4 shillings. Townsend sometimes recorded the occupation or race of the patient. For example, he attended the delivery of a child of Sappho Henshaw, "black girl," in 1786; in 1787 he attended to an unnamed "black man at [who lived at the] corner of Board Alley" in the North End of Boston. Other patients included John Hancock (1736-1793) and members of Hancock's household, as well as Federalist publisher John Fenno (1751-1798).

Receipt book of Francis Kittredge, 1780

Contains instructions for preparing and administering medicine for adults and children, and generalized uses for certain ingredients, written by Dr. Francis Kittredge. Preparations include ointment for scurvy, bone ointment, nerve ointments, procedures to soothe a sore mouth and to stop excessive bleeding, and treatment to kill worms. The materials used to prepare bone ointment include fresh butter, hog fat, chamomile, garlic, and night shade, among other ingredients. The recipe for “simple nerve ointment” instructs the preparer to simmer half a pint of neet foot oil, a pint of rum, and one jell of oil of turpentine over a “gentle fire.” Kittredge writes that oil of St. John’s Wort is effective in treating swelling of the legs, for cold and aches, and for burning and scalds, while oil of Elderflower is indicated for belly aches. The manuscript is housed in a binding created by the Harvard Medical School library. Tipped into the binding is one letter from Frederick O. West, M.D., Harvard Medical School, Boston, Massachusetts, that accompanied his donation of the Kittredge receipt book to the library in 1919. There is also one letter of unknown provenance enclosed with the receipt book, which contains an inventory of the estate of Antipas Brigham, of Grafton, Massachusetts, signed by Worcester County Judge Joseph Wilder on 7 November 1749. It is unclear if this letter has any connection to Frederick O. West or Francis Kittredge.

Kine Pox, 1775-1802 (inclusive)

Ledger containing lists and charts of smallpox inoculation cases and patient case histories of Boston physician John Jeffries (1745-1819), recorded from November 1775 to June 1802. Descriptions include patients’ names, ages, and physical condition, method of inoculation and symptoms. The entries dated 1800-1802 are not in chronological order.

Student notebook of Benjamin Waterhouse: 1776

Volume containing notes taken in 1776 by Benjamin Waterhouse (1754-1846) on medical lectures given in Scotland by University of Edinburgh Professor Andrew Duncan (1744-1828). The lectures focused on pathology, with attention given to secretion, absorption, nutrition, excretion, circulation, and respiration. There are also notes on common medicines and their indications and contraindications, such as emetics, cathartics, diaphoretics, and diuretics.

Argument of Charles F. Choate, esq., in behalf of the Northern (N.H.) railroad, against the consolidation of the Boston & Lowell and Fitchburg railroads, before the railway committee of the Massachusetts legislature, February 26, 1873.

Mode of access: Internet.

The Boston Cooking School magazine of culinary science and domestic economics.

Description based on: v. 3, no. 3 (Oct./Nov. 1898)

Boston College's first Boston Brahmin friends /

Title from cover.