Ipek Imamoglu

Removal of cadmium from aqueous solutions using clinoptilolite: influence of pretreatment and regeneration.

In this study, Cd removal from aqueous solutions via clinoptilolite was investigated in terms of the effect of pretreatment and regeneration. Four different chemicals (NaCl, KCl, CaCl2 and HCl) were tested for this purpose. Samples treated by a total of 20 bed volume (BV) of 1M NaCl solution prepared in tap water with no pH adjustment were found to perform satisfactorily. Five exhaustion and regeneration cycles were then carried out, revealing an increasing Cd removal capacity, coupled with constant Cd elution efficiency in progressing cycles. Furthermore, the change of pH and the presence of exchangeable (Na, K, Ca and Mg) and framework cations (Si and Al) in the aqueous phase were investigated. Subsequently, these were discussed in terms of progressive conversion of clinoptilolite to its homoionic Na-form, and the presence of different Cd removal mechanisms in the system. This study emphasizes the potential of clinoptilolite to be a part of sustainable wastewater treatment technologies, enabling the recovery of both the sorbent and the metal, via demonstration of effective Cd removal and clinoptilolite recovery, besides successful concentration of metal in the regenerant solution.

PCB sources, transformations, and contributions in recent Fox River, Wisconsin sediments determined from receptor modeling

The PCB contamination in lower Fox River sediments was investigated in order to identify possible PCB sources, contributions, and transformations, using two receptor models. Congener specific sediment PCB data from sites immediately upstream of DePere dam to Green Bay that had been gathered for the Green Bay/Fox River Mass Balance Study, were used in this analysis. The first receptor model is a self training factor analysis (FA) model with non-negative constraints that was applied to identify the PCB sources and significant congener patterns. The second is a chemical mass balance model (CMB) in which published Aroclor sources, inferred from our FA model, were used to apportion these Aroclors to each sample. The FA model indicated two significant factors, the major one being Aroclor 1242 and the other, a profile dominated by low chlorinated congeners, indicating a possible PCB alteration profile. This profile had significant contributions to samples at or around sites with total PCB concentrations higher than 50 ppm, indicating a potential anaerobic dechlorination activity. It was also deduced from the FA model that very small contributions of more highly chlorinated Aroclors may be present in the system. The results from the CMB model confirmed that the system is dominated by Aroclor 1242. Its average contribution was 95%, with small amounts of Aroclor 1254 (2%) and 1260 (1%). Two of the samples, located in the vicinity of point sources, showed high contributions of Aroclor 1016 by the CMB model. This is interpreted as an altered Aroclor profile resembling the less chlorinated Aroclor 1016. Contributions obtained form the CMB and FA models show similar patterns.

Spatial distribution and source apportionment of PCBs in sediments around İzmit industrial complexes, Turkey

The spatial distribution, degree of pollution and major sources of PCBs were evaluated in surficial sediments within the heavily urbanized and industrialized İzmit Bay and its main freshwater inputs. ΣPCB concentrations range from 2.90 to 85.4ngg(-1) in marine sediments and from ND to 47.7ngg(-1) in freshwater sediments. Results suggest that high concentrations of ΣPCBs were localized around a chlor-alkali plant and an industry that handles bulk liquid, dry and drummed chemicals, and petroleum products in the Bay. Using a chemical mass balance receptor model (CMB), major sources of PCBs in the region were investigated. The CMB model identified Aroclor 1254 and 1260 to be the major PCB sources in marine sediments and the less chlorinated Aroclor 1248 and 1242 as the major PCB sources in freshwater sediments. The potential sources for the PCBs were briefly discussed in terms of their use in various industrial applications.

Evaluation of PCB dechlorination pathways in anaerobic sediment microcosms using an anaerobic dechlorination model.

A detailed quantitative analysis of anaerobic dechlorination (AD) pathways of polychlorinated biphenyls (PCBs) in sediment microcosms was performed by applying an anaerobic dechlorination model (ADM). The purpose of ADM is to systematically analyze changes in a contaminant profile that result from microbial reductive dechlorination according to empirically determined dechlorination pathways. In contrast to prior studies that utilized modeling tools to predict dechlorination pathways, ADM also provides quantification of individual pathways. As only microbial reductive dechlorination of PCBs occurred in the modeled laboratory microcosms, extensive analysis of AD pathways was possible without the complicating effect of concurrent physico-chemical or other weathering mechanisms. The results from this study showed: (1) ninety three AD pathways are active; (2) tetra- to hepta-chlorobiphenyl (CB) congeners were common intermediates in several AD pathways, penta-CBs being the most frequently observed; (3) the highest rates of dechlorination were for penta-CB homologs during the initial 185 days; (4) the dominant terminal products of AD were PCB 32(26-4), 49(24-25), 51(24-26), 52(25-25), 72(25-35), 73(26-35) and 100(246-24), (5) potential toxicity of the sediment was reduced. ADM serves as a powerful tool not only for a thorough analysis of AD pathways, but also for providing necessary input for numerical fate models (as a degradation term) that investigate dechlorination products or outcome of natural attenuation, or bioremediation/bioaugmentation of PCB-impacted sediments.

Assessment of temporal variation and sources of PCBs in the sediments of Mediterranean Sea, Mersin Bay, Turkey

Information on temporal distribution of polychlorinated biphenyls (PCBs) in the coastal sediments of Mediterranean Sea, Mersin was compiled using data published between 1980 and 2009, and the present study. The first congener specific PCB results from the region yield concentration levels of Σ(41)PCBs in sediments ranging from 0.61 to 1.04 ng g(-1). Sediment profiles show penta-, hexa- and hepta-chlorobiphenyls, specifically, #149 and 153 as the most abundant congeners in all samples. Comparison of total PCB concentrations over time suggests no recent PCB input to the region. Using congener specific PCB data for the region, identity and contribution of PCB sources were also predicted using a chemical mass balance -based (CMB) receptor model. The CMB model identified Aroclor 1260 to be the major PCB source in coastal sediments. The potential sources for the PCBs were briefly discussed in terms of their use in various industrial applications.

Affinity of Clinoptilolite‐based Zeolites towards Removal of Cd from Aqueous Solutions

Abstract Cd removal from aqueous solutions using as‐received and pretreated forms of two different clinoptilolite samples (denoted GC and BC) was investigated and dissimilar sorption affinities were revealed. Equilibrium behavior of systems were modeled using six different adsorption isotherms. The maximum sorption capacities, as obtained from the solubility‐normalized Dubinin‐Astakhov model for as‐received samples, were determined as 0.18 meq/g and 0.12 meq/g for GC and BC, whereas 0.72 meq/g and 0.41 meq Cd/g was determined for their pretreated forms, respectively. Examination of the release of exchangeable cations into the solution at equilibrium and the change of pH were discussed in terms of varying prevalence of ion exchange, dissolution of the sorbent and adsorption.

Potential risk reduction of Aroclor 1254 by microbial dechlorination in anaerobic Grasse River sediment microcosms

Aroclor 1254 was the second most produced commercial PCB mixture and is found in soils, sediments and sewage throughout the globe. This commercial PCB mixture is considered particularly toxic because of the relatively high concentrations of congeners with dioxin-like properties. The potential for risk reduction by microbial reductive dechlorination of Aroclor 1254 (A1254) was investigated in sediment microcosms from Grasse River (GR), Massena, NY. The specificity of A1254 dechlorination was doubly- and singly-flanked chlorines in meta positions and to a less extent doubly-flanked para chlorines of 2345-substituted chlorobiphenyl rings. The average dechlorination rate of A1254 was 0.0153 Cl-/biphenyl/day, and dechlorination rates of single congeners ranged between 0.001 and 0.0074 Cl-/biphenyl/day. Potential risk associated with A1254 based on the toxic equivalency factors of the dioxin-like congeners was reduced by 83%. Additional potential risk associated with bioaccumulation in fish was reduced by 35% based on biota-sediment accumulation factor estimates for all detected congeners. Finally, the dechlorination end-products were tri- and tetra-chlorobiphenyls with unflanked chlorines, all of which are susceptible to further degradation by aerobic microorganisms. The combined results indicate that microbial reductive dechlorination has the potential for reducing risk associated with toxicity and bioaccumulation in fish in sites contaminated with A1254.

Levels and sources of polychlorinated biphenyls in Ankara creek sediments, Turkey

The spatial distribution, degree of pollution and major sources of polychlorinated biphenyls (PCBs) were evaluated in surficial sediments of Ankara Creek, located in the capital of Turkey and serving as one of the tributaries in the third largest watershed in Turkey. Sediment ΣPCB concentrations analyzed on Aroclor and congener basis (seven indicator congeners) range from 5.5 to 777.6 ng g−1 and 3.7 to 743.3 ng g−1 dw as Aroclor and congener based concentrations, respectively. High concentrations of ΣPCBs were observed in the samples located at the downstream sections of the Creek, after discharge from Ankara municipal wastewater treatment plant. Using a chemical mass balance receptor model (CMB), major sources of PCBs affecting the sediments were investigated. The CMB model identified Aroclor 1254 and 1260 to be the major PCB sources affecting sediments. The potential sources for the PCBs were briefly discussed in terms of their use in various industrial applications.

Positive Matrix Factorization dynamics in fingerprinting: A comparative study of PMF2 and EPA-PMF3 for source apportionment of sediment polychlorinated biphenyls.

Receptor models were typically used in air pollution studies and few publications are available for Positive Matrix Factorization (PMF) that consider the details of parameters and procedures in evaluating the trace organic pollutants in sediments. In this study, environmental fate and source composition of Lake Eymir sediments contaminated by polychlorinated biphenyls (PCBs) were explored by applying two PMF models, Paateros PMF2 and United States Environmental Protection Agencys (US EPA) EPA-PMF3. PMF2 and EPA-PMF3 rely on different algorithms; Paateros algorithm and multilinear engine algorithm, respectively. Here, the approaches of two PMF models were compared for the identification of PCB patterns taking into consideration the effects of various uncertainty matrices, residual matrices and goodness-of fit parameters. As a result of the study, it was understood that both models resolved five factors and indicated Clophen A60 as the source of PCBs. These results were consistent with the results resolved by Chemical Mass Balance model applied to the same data set in a previous study. However, source contributions identified by two models differed in quantity, but with similar patterns. This study indicates a way in understanding behavior, fate and global source of persistent organic pollutants in sediment by applying and comparing with a special data including high percentage of below detected value (38.2%) to understand the dynamics of PMF model parameters.

Estimation of rate constants of PCB dechlorination reactions using an anaerobic dehalogenation model.

This study aims to estimate anaerobic dechlorination rate constants (km) of reactions of individual PCB congeners using data from four laboratory microcosms set up using sediment from Baltimore Harbor. Pathway km values are estimated by modifying a previously developed model as Anaerobic Dehalogenation Model (ADM) which can be applied to any halogenated hydrophobic organic (HOC). Improvements such as handling multiple dechlorination activities (DAs) and co-elution of congeners, incorporating constraints, using new goodness of fit evaluation led to an increase in accuracy, speed and flexibility of ADM. DAs published in the literature in terms of chlorine substitutions as well as specific microorganisms and their combinations are used for identification of pathways. The best fit explaining the congener pattern changes was found for pathways of Phylotype DEH10, which has the ability to remove doubly flanked chlorines in meta and para positions, para flanked chlorines in meta position. The range of estimated km values is between 0.0001-0.133d-1, the median of which is found to be comparable to the few available published biologically confirmed rate constants. Compound specific modelling studies such as that performed by ADM can enable monitoring and prediction of concentration changes as well as toxicity during bioremediation.