Chemical and biological methods for the analysis and remediation of environmental contaminants frequently identified at Superfund sites

Substantial environmental contamination has occurred from coal tar creosote and pentachlorophenol (C5P) in wood preserving solutions. The present studies focused on the characterization and remediation of these contaminants. The first objective was to delineate a sequence of biological changes caused by chlorinated phenol (CP) exposure. In Clone 9 cells, short-term exposure to 10 ?M C5P decreased pH, GJIC, and GSH, and increased ROS generation. Long-term exposure caused mitochondrial membrane depolarization (25 ?M), increased intracellular Ca2+ (50 ?M), and plasma membrane depolarization (100 ?M). Cells were affected similarly by C5P or 2,3,4,5-C4P, and similarly by 2,3,5-C3P or 3,5-C2P. Endpoints were affected by dose, time, and the number of chlorine substituents on specific congeners. Thus, this information may be used to identify and quantify unknown CPs in a mixture to be remediated. Due to the toxic effects observed due to CP exposure in vitro, the objective of the second study was to develop multi-functional sorbents to remediate CPs and other components of wood preserving waste from groundwater. Cetylpyridinium-exchanged low pH montmorillonite clay (CP-LPHM) was bonded to either sand (CP-LPHM/sand) or granular activated carbon (CP-LPHM/GAC). Laboratory studies utilizing aqueous solution derived from wood preserving waste indicated that 3:2 CP-LPHM/GAC and CP-LPHM/sand were the most effective formulations. In situ elution of oil-water separator effluent indicated that both organoclay-containing composites have a high capacity for contaminants identified in wood preserving waste, in particular high molecular weight and carcinogenic PAHs. Further, GAC did not add substantial sorptive capacity to the composite formulation. Following water remediation, the final aim of this work was to explore the safety of the parent clay minerals as potential enterosorbents for contaminants ingested in water and food. Calcium montmorillonite and sodium montmorillonite clays were added to the balanced diet of Sprague-Dawley rats throughout pregnancy. Based on evaluations of toxicity and neutron activation analysis of tissues, no significant differences were observed between animals receiving clay supplements and control animals, with the exception of slightly decreased brain Rb in animals ingesting clay. Overall, the results suggest that neither clay mineral, at relatively high dietary concentrations, influences mineral uptake or utilization in the pregnant rat

Determination Of Pah Pollution And Anaerobic Pah Degradation Activity In Marmara Sea Sediments

Tez (Yüksek Lisans) -- İstanbul Teknik Üniversitesi, Fen Bilimleri Enstitüsü, 2011Thesis (M.Sc.) -- İstanbul Technical University, Institute of Science and Technology, 2011Bu araştırma, Marmara Denizi sedimanlarındaki polisiklik aromatik hidrokarbonların (PAH) mekansal dağılımı ve kaynağıyla ilgili ilk kapsamlı çalışmayı temsil eder. Marmara Denizi’ndeki sedimanlarda PAH kirliliğinin durumunu değerlendirmek için 2 yılda 10 tortu numunesi toplanmış ve gaz kromografi – kütle spektrometrisi (GC-MS) ile 2 - 6 benzen halkalı PAH’lar analiz edilmiştir. Derişim aralığının dünya çapındaki sedimantal PAH konsantrasyonları ile karşılaştırılması sonucu Marmara Denizi’ndeki sedimanlardaki PAH kirliliğinin yüksekten son derece yüksek ve kroniğe doğru bir eğilim sergilediği gözlemlenmiştir. Marmara Denizi sedimanlarındaki PAH konsatrasyonları (17 izomerin toplamı) diğer bölgelerdeki gözlemlenenlere göre çok yüksektir. Toplam PAH’ların en yüksek konsantrasyonları Haliç ve Tuzla (1694-2154 ppm), İzmit’te (825-1081 ppm) gözlemlenmiştir. Tüm numune alma lokasyonlarında 3’ten fazla halkalı PAH’lar, düşük moleküler ağırlıklı PAH’ların yüksek biyolojik bozunma hızına sahip olmasından dolayı daha küçük halkalı PAH’lardan daha fazladır. Parmak izi analizi, sedimandaki PAH’ların gemi faaliyetlerin dolayı daha fazla petrojenik olduğunu göstermektedir; öte yandan PAH konsantrasyonlarındaki pirojenik orijin, şehirleşmiş alanlardaki yüksek yanma girdilerinden ve kentsel akıştan kaynaklanmaktadır. Biyolojik bozunma çeşitli mikrobiyal metabolik proseslerden faydalanarak aromatik kirleticilerin tam ve maliyet etkin giderilmesi sağlar. Aromatik biyolojik bozunma çevresel temizlikte önemli rol oynar ve biyolojik bozunmanın başlangıcından beri kapsamlı olarak irdelenmektedir. Bu çalışma; deniz sedimanlarında anahtar aromatik hidrokarbon biyolojik bozunma metabolic proseslerinden sorumlu bcrA fonksiyonel genlerin kapsamlı çokluğunu raporlar. Fonksiyonel gen (bcrA) mikrobiyal AnArHC process indikatörü olarak gerçek zamanlı PCR kullanılarak ölçümlenmiştir. AnArHCD organizmalarının çokluğu ve aktivitesinin, aromatik petrol hidrokarbonlarının seviyesi ve bileşimi ile ilgisi, bcrA bolluğu ve PAH derişimlerinin istatiksel olarak birbirleriyle pozitif ilişkili olmasıyla ispatlanmıştır(r=0,98, n=9,5, p<0.5). Sonuç olarak, toplam petrol HC seviyeleri; aşırı kirli deniz ortamlarıyla benzerlik göstermektedir; mikrobiyal hücre içeriği, diğer deniz ortamlarına gore çok daha yüksektir; sedimanlarda ağırlıklı olarak aktif anaerobik hidrokarbon indirgeyicileri bulunmaktadır ve bu mikroplar aktiftir. Marmara Denizi’ndeki kronik hidrokarbon kirliliğini gidermek için insanın daha az müdahale edeceği, sürdürülebilir ve maliyet etkin remidasyon stratejisi kullanılabilir. Bu amaç için en iyi seçenek; anaerobik/ anoksik koşullarda biyoremediasyondur; çünkü sedimanlarda petrolü ayrıştıran anaeroblar bol ve aktiftir.This investigation represents the first extensive study of the spatial distribution and sources of polycyclic aromatic hydrocarbons (PAHs) in marine sediments from the Marmara Sea. To assess the status of polycyclic aromatic hydrocarbon (PAH) contamination in Marmara sea sediments 10 marine sediment samples were collected in two years and analyzed for PAHs with 2–6 benzene rings by gas chromatography–mass spectrometry (GC-MS). Comparison of the concentration range with a worldwide survey of sedimentary PAH concentrations, ranked PAH contamination in Marmara sea sediments as high to extreme and chronic pollution. The concentrations of PAHs (sum of 17 isomers) in Marmara Sea sediments are high by comparison with those observed in other regions. The highest concentrations of total PAHs were observed at sites Haliç and Tuzla (1694-2154 ppm), İzmit (825-1081 ppm). In all sampling locations more than 3 rings PAHs are more abundant than smaller rings PAHs, which was due to higher biodegradation rate of low moleculer weight PAHs. Fingerprinting analysis indicates that PAHs in the sediment were mostly petrogenic in origin likely due to shipping activities, whereas pyrogenic origin was found for PAHs in some sediment probably due to the high combustion inputs and urban runoffs from urbanized areas. Biodegradation can achieve complete and cost effective elimination of aromatic pollutants through harnessing diverse microbial metabolic processes. Aromatics biodegradation plays an important role in environmental cleanup and has been extensively studied since the inception of biodegradation. This study reported the comprehensive abundance of bcrA functional genes responsible for the key aromatic hydrocarbon biodegradation metabolic processes in marine sediments. Functional gene(bcrA) was quantified using real-time PCR as the microbial AnArHC process indicators. Abundance and activity of AnArHCD organisms were related to level and composition of aromatic petroleum hydrocarbons, which were evident from a statistically significant correlation between bcrA abundance and PAH concentration (r=0,98, n=9,5, p<0.5). In conclusion, the total petroleum HC levels were similar to those from extremely polluted marine environments; the microbial cell contents were very high compared to the other marine environments; the sediments were dominated by anaerobic hydrocarbon degraders, and these microbes were active. A less human intervened, sustainable and cost effective remediation strategy can be used to overcome the chronic hydrocarbon pollution in Marmara Sea. The best candidate for this purpose is bioremediation under anaerobic/anoxic conditions, because oil-degrading anaerobes are abundant and active in the sediments.Yüksek LisansM.Sc

Toxicity Analysis of Polycyclic Aromatic Hydrocarbon Mixtures

Polycyclic aromatic hydrocarbons (PAHs) are widely distributed in the environment and are generated by many sources. Though the potential of PAH-rich mixtures to cause health effects has been known for almost a century, there are still unanswered questions about the levels of PAHs in the environment, the potential for human exposure to PAHs, the health effects associated with exposure, and how genetic susceptibility influences the extent of health effects in individuals. The first objective of this research was to quantify concentrations of PAHs in samples of settled house dust collected from homes in Azerbaijan, China, and Texas. The trends of PAH surface loadings and percentage of carcinogenic PAHs were China > Azerbaijan > Texas, indicating that the risk of health effects from exposure to PAHs in house dust is highest in the Chinese population and lowest in the Texas population. PAHs in China and Azerbaijan were derived mainly from combustion sources; Texas PAHs were derived from unburned fossil fuels such as petroleum. The second objective of this research was to investigate the effect of pregnane X receptor (PXR) on the genotoxicity of benzo[a]pyrene (BaP). BaP treatment resulted in significantly lower DNA adduct levels in PXR-transfected HepG2 cells than in parental HepG2 cells. Total GST enzymatic activity and mRNA levels of several metabolizing enyzmes were significantly higher in cells overexpressing PXR. These results suggest that PXR protects cells against DNA damage by PAHs such as BaP, possibly through a coordinated regulation of genes involved in xenobiotic metabolism. The third objective of this research was to investigate biomarkers of exposure in house mice (Mus musculus) exposed to PAH mixtures in situ. Mice and soil were collected near homes in Sumgayit and Khizi, Azerbaijan. Mean liver adduct levels were significantly higher in Khizi than in Sumgayit. Mean lung and kidney adduct levels were similar in the two regions. The DNA lesions detected may be a combination of environmentally-induced DNA adducts and naturally-occurring I-compounds. PAHs were present at background levels in soils from both Khizi and Sumgayit. It appears that health risks posed to rodents by soil-borne PAHs are low in these two areas

Molecular and isotopic records of combustion inputs to the environment over the last 250 years

Submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy at the Massachusetts Institute of Technology and the Woods Hole Oceanographic Institution June 2004The most ubiquitous source of polycyclic aromatic hydrocarbons (PAHs) to the environment is incomplete combustion. This study generated a high-resolution historical record of pyrogenic PAH emissions since pre-industrial times from anoxic aquatic sediments, allowing for detailed comparison with energy consumption data. We show that an increase in PAH concentrations over the last decade may be due to a rise in emissions from diesel-powered vehicles. Compound-specific radiocarbon measurements demonstrated unequivocally that the proportion of PAHs derived from fossil fuel combustion has increased substantially during the 20th century. δ13C and Δ14C measurements were also used to constrain the relative importance of combustion versus in situ production as sources of perylene. In addition, a comparison of the down-core concentration and isotopic profiles of black carbon (BC) generated by a combination of chemical and/or thermal oxidation methods highlighted the limitations of these methods when applied to sedimentary matrices. Finally, parallel lead and cesium isotopic records revealed two new potential stratigraphic markers in North American sedimentary records. 206Pb/207Pb profiles show a distinct peak in the mid-19th century, while a 137Cs peak was found to coincide with the 1986 Chernobyl accident.Funding for this research was provided by the National Science Foundation (OCE-9708478 and CHE-0089172). The author also acknowledges support from the Brazilian Council for Research (CNPq)

Screening, quantitative Analyse und Toxikologie organischer Verbindungen in Sedimenten und Schwebstoffen der Saar und des Rheins (Deutschland)

River sediments and suspended particulate matter (SPM) are sinks as well as secondary sources for nonpolar organic compounds that might pose a risk to aquatic ecosystems’ goods and services. Sources of these pollutants are for example wastewater treatment plants effluents or direct discharges as well as dry and wet atmospheric deposition. Surface run-off of contaminated soils and dust from streets are other important origins. The particularly bound substances with different physical and chemical properties are constrained to partitioning processes between the solids and the water phase. Hence, they might get bioavailable and thus pose an ecotoxicological risk for water organisms. During flood events, contaminated sediments could be remobilized and transported to riparian lands. Consequently, there are concerns regarding risks for terrestrial ecosystems’ goods and services. In the first part of this thesis, sediments and SPM samples of the Saar and the Rhine were investigated regarding organic compounds using target, suspect and nontarget screening analysis with gas chromatography – mass spectrometry (GC-MS). Sediment core and suspended particulate matter samples were collected at representative sampling sites along the both rivers. This study was conducted, among other things, to improve information regarding nonprioritized organic compounds in sediments and suspended particulate matter of the Saar and the Rhine. In the second part, the extractability and potential toxicity of particularly bound organic compounds was investigated. Sediment samples from the Saar as well as the Elbe and the Bílina in Czech Republic was extracted with different exhaustive and biomimetic extraction approaches. Soxhlet, ultrasonic and accelerated solvent extraction as well as membrane dialysis extraction were used as exhaustive methods. Extractions with Tenax®-TA as well as mixtures of water with methanol or 2-hydroxypropyl-β-cyclodextrin were applied as biomimetic approaches. The main objective of these investigations was the generation of comprehensive knowledge concerning the relationship between the physical-chemical properties of compounds and sediments as well as extractability and resulting toxicity. Recommendations for the integrated risk assessment of sediments including exhaustive extraction as well as biomimetic methods and dosing were compiled. In the third part, potentially adverse effects of contaminated sediments and SPM for riparian lands were investigated. A main aim was the investigation of two exposition pathways in the contact tests – native sediment versus acetonic extract. Effect-directed analysis was used to examine selected soil and SPM samples regarding effect potentials in vitro and to unravel responsible compound classes or substances, respectively.Fluviale Sedimente und Schwebstoffe bilden sowohl eine Senke als auch eine sekundäre Quelle für hydrophobe organische Verbindungen mit ökotoxikologischem Potential. Der Eintrag dieser Substanzen in die Gewässer erfolgt beispielsweise durch Klär- und Direkteinleitung, trockene und nasse atmosphärische Deposition, oder den Eintrag von Bodenpartikeln und Oberflächenabfluss bei Niederschlagsereignissen. Die partikulär gebundenen Stoffe mit unterschiedlichen physiko-chemischen Eigenschaften können aufgrund von Verteilungsprozessen zwischen Sediment bzw. Schwebstoff und der Wasserphase für Wasserorganismen verfügbar werden und bilden damit ein ökotoxikologisches Gefährdungspotential. Während Flutereignissen besteht die Gefahr, dass belastete Sedimente remobilisiert und diese in Auengebiete eingetragen werden, somit die Besorgnis einer Gefährdung terrestrischer Schutzgüter besteht. Der erste Teil der vorliegenden Arbeit befasst sich mit der chemischen Analyse und Identifizierung von organischen Verbindungen in Sedimenten und Schwebstoffen des Rheins und der Saar. An verschiedenen repräsentativen Standorten des Rheins und der Saar wurden Sedimentkerne mit einem Gefrierkernverfahren bzw. einem Kernstechverfahren sowie Schwebstoffe gewonnen. Diese Studie wurde unter anderem durchgeführt, um die Datenlage hinsichtlich nichtregulierter organischer Substanzen in Sedimenten und Schwebstoffen der Saar und des Rheins zu verbessern. Der zweite Teil dieser Arbeit umfasste die Frage nach der Extrahierbarkeit und potentiellen Toxizität partikulär gebundener organischer Verbindungen. Sedimentproben wurden mit unterschiedlichen erschöpfenden und nichterschöpfenden Extraktionsverfahren (Soxhlet-, Ultraschall- und Beschleunigte Lösungsmittelextraktion, Membran- Dialyse-Extraktion sowie Extraktion mit dem Polymer TENAX®-TA und Methanol- bzw. 2-Hydroxypropyl-β-Cyclodextrin-Wassergemischen). Das Ziel dieser Untersuchung war es unter der Anwendung chemischer und bioanalytischer Methoden neue Erkenntnisse zum Zusammenhang zwischen Extrahierbarkeit, Stoff- und Sedimenteigenschaften und resultierender Sedimenttoxizität zu erlangen. Aus den Ergebnissen wurden Empfehlungen für eine umfassende Risikobewertung von Sedimenten unter der Berücksichtigung von Verfahren zur Bestimmung des bioverfügbaren Anteils abgeleitet sowie weiterer Forschungsbedarf aufgezeigt. Der dritte Teil dieser Abhandlung untersucht potentielle adverse Effekte des Eintrages von Schwebstoffen und remobilierten Sedimenten des Rheins in ein Auengebiet am Oberrhein. Ein wichtiger Aspekt war die Untersuchung unterschiedlicher Expositionspfade in Sediment- bzw. Bodenkontakttests (natives Sediment versus acetonischer Extrakt). Desweiteren wurden ausgewählte Proben einer wirkungsorientierten Analytik unterzogen um biologische Effekte in vitro zu untersuchen sowie für die Effekte verantwortlichen Substanzklassen bzw. Verbindungen zu identifizieren

Physico-chemical speciation and ocean fluxes of Polycyclic Aromatic Hydrocarbons

Thesis (Ph. D.)--Joint Program in Oceanography, Massachusetts Institute of Technology/Woods Hole Oceanographic Institution, 1997.Includes bibliographical references.by Örjan Gustafsson.Ph.D

Molecular and isotopic records of the combustion inputs to the environment over the last 250 yrs

Thesis (Ph. D.)--Joint Program in Oceanography (Massachusetts Institute of Technology, Dept. of Earth, Atmospheric, and Planetary Sciences; and, the Woods Hole Oceanographic Institution), 2004.Includes bibliographical references.The most ubiquitous source of polycyclic aromatic hydrocarbons (PAHs) to the environment is incomplete combustion. This study generated a high-resolution historical record of pyrogenic PAH emissions since pre-industrial times from anoxic aquatic sediments, allowing for detailed comparison with energy consumption data. We show that an increase in PAH concentrations over the last decade may be due to a rise in emissions from diesel-powered vehicles. Compound-specific radiocarbon measurements demonstrated unequivocally that the proportion of PAHs derived from fossil fuel combustion has increased substantially during the 20th century. [delta]¹³C and [delta]¹⁴C measurements were also used to constrain the relative importance of combustion versus in situ production as sources of perylene. In addition, a comparison of the down-core concentration and isotopic profiles of black carbon (BC) generated by a combination of chemical and/or thermal oxidation methods highlighted the limitations of these methods when applied to sedimentary matrices. Finally, parallel lead and cesium isotopic records revealed two new potential stratigraphic markers in North American sedimentary records. ²⁰⁶Pb/²⁰⁷Pb profiles show a distinct peak in the mid-19th century, while a ¹³⁷Cs peak was found to coincide with the 1986 Chernobyl accident.by Anna Lúcia Cessel de Lima.Ph.D

Combustion of Bio-oil and Heavy Fuel Oil

The use of combustion parameters to predict what happens to fuel during burning and its effect on living systems is important. This work is directed towards understanding the fundamental chemistry of soot generated from burning biomass-pyrolysis liquid fuels and its mechanism of formation. In this study, fuels such as eugenol, anisole, furfural and some hydrocarbon fuels are subjected to combustion using a wick burner which allowed the burning rate, smoke point and emission factor to be investigated. Reaction zone analysis of flames by direct photography and by using optical filters for further investigation of C2* and CH* species, was conducted. Additionally, detailed characterization of the soot generated was performed, and comparisons were made with soot from petroleum products and from biomass combustion system. The key aim was to generate experimental data and to capture detailed information regarding sooting tendencies with a view to utilize the information which would eventually allow the formation of a comprehensive bio-oil combustion model. This could provide accurate predictions of the combustion characteristics and pollutant formation. Studies are reported on the significant role of high temperature pyrolysis products in soot formation and acquiring further mechanistic insight. This work has been extended to consider heavy petroleum fuel oils (residual oil) during combustion and the effect of composition on combustion products and on the effect on health and the global environment. Heavy fuel oil, such as Bunker C and vacuum residue, are commonly used as fuel for industrial boilers, power generation, and as transport fuels in, for example, in large marine engines. The combustion of these fuels gives rise to carbonaceous particulate emissions including fine soot (Black Carbon or BC) which, along with associated polynuclear aromatic hydrocarbons (PAH): The structure and thermal reactions of petroleum asphaltene have been studied by analytical pyrolysis. Additionally, related combustion characteristics of the asphaltene extracted from bio-oil have been investigated by pyrolysis gas chromatography-mass spectrometry. The results showed the difference between bio-asphaltene and the petroleum asphaltene and the different tendency to form smoke. They also showed the presence of markers for the bio-asphaltene structure

Application of attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy to measure sub-lethal effects of potential mutagens

Techniques employed in vibrational spectroscopy monitor the vibrational modes of functional groups within biomolecules and enable a correlation between chemical information and histological structures. Interrogation of biological samples using infrared (IR) techniques generates spectrum with wavenumber-absorbance intensities specific to biomolecules within the sample. Methods are relatively non-destructive, and so samples can subsequently be analyzed by more conventional approaches. Analyses can be carried out ex vivo or in situ in living tissue, where a reference range of a designated normal state can be derived, and anything lying outside this range is potentially atypical. Computational approaches allow one to minimize within-category confounding factors. The application of vibrational spectroscopy in contaminant biomonitoring is a welcome development which has enabled the investigation of realtime contaminant exposure effects in the tissues of sentinels. IR techniques such as attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy, was able to detect changes in various tissue samples exposed to varying levels of polycyclic aromatic hydrocarbons (PAHs). This technique discriminated between spatial and temporal variations in the interrogated tissues. Multivariate analysis was able to relate the alterations at various regions of the fingerprint, to PAH exposure and was able to detect PAH exposure in tissues from sites with no documented knowledge of contamination. ATR-FTIR detected PAH-induced changes in isolated nuclei of cultured cell populations in G0/G1 and S- phases of the cell cycle. Findings from the various projects affirm, that techniques involved in IR spectroscopy are highly sensitive to minimal changes in cell molecules. The ability to generate rapid results in real-time is valuable and the wide variety of sample types which can be interrogated using IR techniques makes it a suitable technique for environment biomonitoring