Nonylphenol (NP) and its ethoxylates are used in formulation of pesticides and detergents, production of personal care products and many industrial sectors such as textile, metal plating, plastic, paper and energy. They are also used in the formulation of household cleaning agents. Industrial uses in the production line make up 55% of the total use / whereas industrial and domestic cleaning processes constitute 30 and 15%, respectively. Since they are widely used in industry and households, NP compounds enter the environment mainly by industrial and municipal wastewater treatment plant effluents. NP is considered strongly toxic and has adverse effects even with short term exposures. Moreover, with its similarities to natural hormones, NP and its ethoxylates are considered as endocrine disrupter compounds. In studies conducted with human cells, chicken embryo, trout and mice eostrogen receptors, positive responses were observed. Due to their lipophilic and hydrophobic characteristics they accumulate in cells, tissues and organic materials such as sludge. For these reasons, fate of NP and its v ethoxylates in wastewater treatment plants and in sludge treatment processes gained importance. Nonylphenol polyethoxylates (NPnEO) are degraded in microbial media and lose their ethoxylates to nonylphenol diethoxylate (NP2EO), nonylphenol monoethoxylate (NP1EO) and NP. Moreover, nonyl phenoxycarboxylic acids (NPnEC) can be formed during some of these reactions. Because the first degradation reactions are fast, concerns and studies are focused mainly on NP2EO, NP1EO, NP, NP1EC and NP2EC. Even though these general degradation information is available, studies on sludge are very rare. In this study, treatability and toxicity of NP2EO in anaerobic batch reactors is investigated. First, with the use of Anaerobic Toxicity Assay (ATA) test, toxic doses of NP2EO which was added to the reactor as the parent component, were determined. Moreover, the degradation of these chemicals were studied in larger scale batch anaerobic digesters. The aim of this part was to observe the degradation patterns and products. Throughout the study the fate of NP and its ethoxylates was followed in aqueous and solid phases by the use of Gas Chromatography / Mass Spectrometry system (GC/MS). ATA tests showed that NP2EO was not toxic to anaerobic microorganisms at the doses investigated in this study. It was rather stimulating and caused an increase in methane production in the reactors. On the other hand the spiked NP2EO&rsquo / s at 0.5 and 2.5 mg/L concentration were completely degraded in the larger scale batch reactors. At the same time, an increase in the concentrations of NP and NP1EO was observed which supported the fact that NP2EO was degraded into NP1EO and NP under anaerobic conditions. Abiotic degradation was not observed.

This study aims to investigate the fate of polychlorinated biphenyls (PCBs) in sediments via using an anaerobic dechlorination model (ADM). PCBs are ubiquitous environmental pollutants, accumulated mostly in aquatic sediments. Significant attention was placed on the anaerobic dechlorination of PCBs since this process leads to the conversion of highly-chlorinated biphenyls to lower chlorinated ones, resulting in less toxic and more biodegradable congeners. An ADM was developed previously for the identification and quantification of anaerobic dechlorination pathways. In the present study, this model was improved and applied to laboratory and environmental sediment PCB data from Baltimore Harbor (BH), Maryland, USA, where PCB contamination has been recorded. The laboratory PCB data was from a 500 day microcosm study conducted with BH sediments which was used to validate the model, as well as to gather information on dominant dechlorination pathways affecting the sediments. ADM predicted the laboratory PCB data almost perfectly and subsequently very well predicted the environmental sediment PCB profiles. A complete identification and quantification of the anaerobic dechlorination pathways occurring in the BH sediments is achieved with this study for the first time. The significant similarity between the sediment sample PCB profiles and the model predicted profiles reveals that the BH sediments have undergone anaerobic dechlorination via a combination of previously identified dechlorination activities (N, P, M) with selective pathways. Model findings are consistent with microbial analysis of the sediments. Better understanding of anaerobic dechlorination mechanisms should aid in predicting natural attenuation of PCBs or developing bioremediation strategies for contaminated sites.

Biosorption is a phenomenon involving the mechanisms that basically mediate heavy metal tolerance of microorganisms as well as sequestration of heavy metals from environment. Different classes of microorganisms have different biosorption capacities, as a result of the differences in composition and types of functional groups found on cell surfaces. The present study was undertaken to identify the molecular mechanisms for lead [Pb(II)] biosorption in the white-rot fungus, Phanerochaete chrysosporium. The methodology involved selective blocking of the functional groups known to participate in heavy metal biosorption and allowed us to determine their relative roles in Pb (II) biosorption in this organism. The relative concentrations of the Pb (II) sorbed from the aqueous environment and Mg2+ and Ca2+ ions released to the aqueous environment were measured and compared with both native and chemically-modified biomasses by using atomic absorption spectroscopy. Fourier-Transform Infrared (FTIR) spectroscopy technique was used to monitor and analyze the molecular-level changes in both native and chemically modified cell surfaces upon Pb (II) exposure. Interactions of Pb (II) with the biomass surface was determined by observing the changes in wavenumber and absorbance of NH stretching and Amide I bands arising from the amine groups and C=O stretching band arising from the carboxyl groups. The roles of phosphate groups and lipids were also investigated. Carboxyl groups seemed to be the most important functional groups for Pb (II) biosorption in P. chrysosporium, since the biosorption capacity dramatically decreased (by 92.8 %) in carboxyl groups-blocked biomass. Amine groups were found to play a secondary and minor role in Pb (II) biosorption, only a slight decrease (6 %) in Pb (II) biosorption was detected with amine groups-blocked biomass. Blocking of phosphate groups provided a small increase in biosorptive capacity and did not appear to have much significant role in biosorption. Upon chemical treatment with acetone to extract lipids of the cell surfaces, an increase of 20.3 % in the Pb (II) biosorptive capacity was determined. It was concluded that carbonyl and carboxyl groups of chitin and glucan are the major sites and ion exchange via these groups is the main mechanism for Pb (II) biosorption in P. chrysosporium.

This study aimed at providing a thorough understanding of temporal and spatial variations of VOCs and underlying factors in different microenvironments in two different urban atmospheres, with different degrees of regulatory enforcement. The VOC data were collected in field campaigns conducted in Ankara, Turkey, and Ottawa, Canada over the years 2000-2004. Insight into the sources of VOCs in different urban atmospheres was sought by using three commonly used receptor models namely / Positive Matrix Factorization (PMF), Chemical Mass Balance (CMB) Model and Conventional Factor Analysis (CFA). Motor vehicle related source profiles were developed to use in receptor modeling. Motor vehicles are the most abundant VOC sources with about 60% and 95% contributions to ambient levels in Ankara and Ottawa, respectively. Residential heating (31%) during winter season, biogenic (9%) and architectural coating (12%) emissions during summer season and solvent use (about 12%) emissions are the next abundant VOC sources in Ankara. In addition, a new method to estimate the contribution of sources from wind sectors in urban atmosphere was developed and implemented in this study. The comparison of the results of these two cities demonstrated the influence of control measures on ambient levels and sources of VOCs observed in different urban atmospheres. VOC levels in Ankara exceed EU levels and they are about factor of two higher than that are measured in Ottawa owing to lack of implementation of emission control regulations for VOCs in Ankara compared to well adopted regulations in Ottawa.

Natural Attenuation can be an effective cleanup option for remediation of Groundwater contamination by BTEX. One of the important aspects of the methodology that has been recognized recently is that mass removal rates, the most important parameters used to determine effectiveness of the methodology, is controlled by groundwater flow regime, which to a large extent controlled by aquifer heterogeneity. Considering this recognition, the primary objective of this research is to quantitatively describe the relationship between natural attenuation rates of BTEX and aquifer heterogeneity using numerical solution techniques. To represent different levels of aquifer heterogeneity, hydraulic conductivity distributions are simulated using Turning Bands Algorithm, changing statistical parameters Coefficient of Variation (CV) and correlation length (h). Visual MODFLOW is used to model the transport of BTEX contamination, at different hydraulic conductivity fields. Degradation rates are calculated by Buscheck&amp / Alcantar and Conservative Tracer Methods. The results show that, for a given h, as CV increases, the plume slows down and stays longer at the domain, so areal extent of plume decreases. For anisotropic field, plumes are more dispersed along x and y-direction, and areal extents of the plumes are greater. During MNA feasibility studies, for the aquifer heterogeneity level of CV and h smaller than 100 % and 10 m, respectively, a minimum recommended biodegradation rate constant of 0.02 d-1 can be used, whereas for the aquifer heterogeneity level of CV and h greater than 100 % and 10 m, respectively, using a minimum biodegradation rate constant of 0.06 d-1 can be recommended.

Monitored natural attenuation has been particularly used at sites where petroleum hydrocarbons and chlorinated solvents have contaminated soil and groundwater. One of the important aspects of the methodology that has been recognized recently is that the mass removal rates, the most important parameter to determine effectiveness of the methodology, is controlled by the groundwater flow regime and the aquifer heterogeneity. Considering this recognition, the primary objective of this study is to quantitatively describe the relationship between the natural attenuation rates and aquifer heterogeneity using numerical simulation techniques. To represent different levels of aquifer heterogeneity, the hydraulic conductivity distribution (ln K) is statistically simulated with the numerical algorithm, Turning Bands Random Field Generator, by changing the statistical parameters, Coefficient of Variation (CV) and correlation length (h) and Visual MODFLOW and RT3D software programs are used for the simulation of groundwater flow and chlorinated solvent transport. Simulation results showed that degradation rates and the shape of the contaminant plumes show variations for different heterogeneity levels. Increasing CV resulted in the decrease in the transport of the plume and shrinkage in the areal extend. On the other hand, &ldquo / h&rdquo / determined the shape and the size of the plume through its affect on mechanical dispersion. For a given &ldquo / h&rdquo / , degradation rates increased with increasing CV, but change in &ldquo / h&rdquo / did not show a regular trend. Such findings are expected to be beneficial when assessing the effectiveness of natural attenuation process for a selected site during the feasibility studies without need for detailed site characterization.

In this study, anaerobic treatability of opium alkaloid wastewater and the effect of radiation pretreatment (gamma-rays) on anaerobic treatability were investigated. Biochemical Methane Potential (BMP) assay was performed with alkaloid wastewater having initial COD values of 2400, 6000 and 9600 mg/L with and without basal medium (BM). The highest anaerobic treatment efficiency of 77% was obtained in the BMP reactor containing alkaloid wastewater with initial COD of 9600 mg/L and BM. Co-substrate use was investigated by using BMP assay. Alkaloid wastewater having initial COD concentrations of 9000, 13000 and 18000 mg/L were used with glucose, acetate and glucose-acetate as co-substrates. Results revealed that co-substrate use did not improve alkaloid removal efficiency significantly but it abrogated the acclimation period of anaerobic bacteria to alkaloid wastewater. Continuous reactor experiments were carried out in Upflow Anaerobic Sludge Blanket (UASB) reactors. Highest overall efficiencies (above 80%) were obtained in the reactor fed with co-substrate (R2) for all initial COD concentrations. Up to 78% removal efficiency was obtained in R1 (fed with alkaloid wastewater only) at initial COD concentration of 19 g/L. Effect of radiation was sought by using BMP assay with two initial COD concentrations of 14 and 25 g/L, and two radiation doses 40 and 140 kGy. At 14 g/L COD, there was no effect of radiation on gas production for both doses. However at initial COD of 25 g/L, reactors containing wastewater dosed with 140 and 40 kGy produced gas with higher rates above certain point with respect to raw wastewater.

A conceptual site model (CSM) is simply a description of the environmental conditions at a contaminated site and surrounding area, which provides all interested parties with a vision of the site. CSM mainly identifies the source-pathway&amp / #8208 / receptor linkage to guide for effective site characterization, risk assessment and remedial investigations. Development of CSM is complicated because it is &lsquo / case specific&rsquo / and there is no single route to follow during decision making concerning the contaminated site. Moreover, type and extent of information needed varies according to size and level of contamination and site heterogeneity. The objective of this study is to develop a decision support tool that guides the site assessors during identification of possible decision routes that can be encountered / the procedure to be followed / and the information and data to be collected at each stage. This tool also introduces interactions between CSM andsampling strategies designed for various purposes. Developed decision support tool adapts to each specific contaminated site. Furthermore, a detailed review of sampling strategies is presented as a guidance for site assessors. The decision support tool is equipped with standardized tools used for CSM development, i.e. information/data collection forms, illustrative tools and exposure pathway diagram. Information on site, geology, hydrogeology, contamination source, contaminants and receptors is collected via CSM form. Illustrative tools may vary from very simple site sketches to very complex 3D drawings depending on the needs of the specific contamination cases. Exposure pathway diagram (EPD) is used to identify all transport mechanisms and potential exposure pathways. EPD is embedded into a user&amp / #8208 / friendly decision assistance tool based on Microsoft Excel and Visual Basic for Applications. The applicability and utility of the decision support tool was tested using two case studies. Case study applications indicated that the developed methodology satisfies the objectives aimed in this study.

Evaluation of contaminated sites based on human health and environmental hazards is an essential task for the proper management of the contaminated sites. A large number of contaminated sites have been waiting for remediation all over the World. However, contaminated site remediation is generally a difficult, time consuming and very expensive process. Ranking systems for contaminated sites are useful tools to determine the remedial priority and to manage the available remediation budget in the most efficient way before the costly remedial actions are taken. To be able to have a reliable ranking result, accurate and sufficient amount of data on the nature of contamination and site characteristics are needed, which are usually not available at the early identification phases of contaminated sites, and the available data is mostly limited and vague in nature. If the available data are inaccurate or vague, the corresponding remedial ranking results can be questionable, as well. Most of the current ranking methodologies overlook the vagueness in the parameter values. The main objective of this study is to develop a remedial priority ranking system for contaminated sites by taking vagueness in parameter values into account. Within this context, development of the new Remedial Priority Ranking System, RPRS, aims to define and evaluate the current and possible environmental risks by using sufficiently comprehensive readily available parameters describing the fate and transport of contaminants in the environment and considering vagueness in those parameter values. The consideration of vagueness in parameter values was included in remedial prioritization of contaminated sites by means of fuzzy set theory. A fuzzy expert system was built up for the evaluation of contaminated sites and it was developed in Microsoft Office Excel 2007 platform, with the intention of making the evaluation fast and user friendly. Hypothetical and real case study applications are presented to test ease of use and validity of the results of the developed methodology. Results of case study applications revealed that the developed RPRS can serve as an alternative method for remedial priority ranking of contaminated sites.

Chemical composition of particles and rain water at three sites in Turkey were extensively compared to determine if there is a relationship between aerosol and rain composition. If such relationship exists, it can allow one to construct rain water composition using aerosol data. This is important because, rain composition data is scarce as sampling and analysis of very low concentrations of elements and ions in rain water is more difficult compared to sampling and analysis of atmospheric aerosol. Results showed that aerosol composition can be closely reflected in composition of rain water if below cloud processes dominate over the incloud processes. This is clearly observed for crustal elements in all stations and for most of the elements in urban Ankara station. However, in rural stations there were differences in rain and aerosol that is attributed to significant contribution from in cloud processes. Seasonal patterns and enrichment factors observed in aerosol composition showed general agreement with corresponding temporal variations observed in rain water concentrations of elements, but short term variations became visible only if data is averaged over a long period of time. These observations suggest that certain features of rain water composition can be constructed from if concentration data is available for aerosols. However it should be noted that there are also significant differences between stations and between elements or element groups, indicating that composition of rain water constructed from aerosol data can only be a crude one. Similarities between rain and aerosol compositions is more pronounced in urban Ankara station compared to rural stations used in this study. Factor analysis performed to aerosol and rain water data sets showed that source types affecting chemical composition of rain and particles are generally the same, bur contribution of each source type to rain and aerosol composition shows differences. Similarly, the source regions, defined by potential source contribution function, affecting aerosol and rain compositions are not identical. In Antalya station Source regions affecting chemical composition of rain water are more local compared to source regions affecting composition of aerosol. Same difference is not observed in Amasra station. Scavenging ratios is found to be a suitable tool to construct rain water composition using aerosol data. Scavenging ratios calculated using paired daily data are more variable both between stations and within a station. Long-term averaged data was found to be more reliable for calculating SRs of elements and ions at all stations.