Biomedical subjects

Marianne C Nyman

Publications and source records attributed to Marianne C Nyman.

12 recordsLinked to original sources

PubMed2006

Sorption and desorption behavior of benzidine in different solvent-sediment systems.

The sorption and desorption behavior of benzidine in eight solvent-sediment systems were studied using a batch method. The solvents tested included deionized water (DI), calcium chloride solution (CaCl2), sodium hydroxide solution (NaOH), acetonitrile (ACN), a mixture of acetonitrile and ammonium acetate solution (ACN-NH4OAc), methanol (MeOH), ammonium acetate solution (NH4OAc) and hydrochloric acid solution (HCl). Three sets of sorption isotherm experiments were conducted separately in these eight solvents with seven days, three weeks, and two months of contact times, respectively. The results demonstrated nonlinear benzidine sorption phenomena in all eight solvents with higher sorption affinities for sediment sites in the aqueous solvents than in the organic solvents. The results from the desorption experiments revealed that the benzidine desorption efficiencies in the solvents decreased in an order, which was approximately the reverse order of its sorption affinity. Results also suggested that hydrophobic partitioning and covalent binding processes dominated in the desorption experiments, while cation exchange process had little effect on desorption of benzidine. A three-stage model was subsequently applied to simulate the desorption data in the selected solvents of ACN, ACN-NH4OAc and NaOH, respectively. The rapidly desorbing initial fractions were about 0.13-0.20, 0.15-0.26, and 0.18-0.25 for ACN, ACN-NH4OAc and NaOH, respectively. Finally, the sorbed concentrations of benzidine in slowly and very slowly desorbing domains in the selected solvents were correlated with the maximum sorption capacities obtained from the Langmuir sorption isotherm model. The maximum sorption capacities of benzidine were found to be comparable to the amount of benzidine residing in the slowly and very slowly desorbing domains.

Adsorption↗

PubMed2006

Short-term interactions of aniline and benzidine with three soils in both natural and artificial matrices.

The fate of aromatic amines in natural systems is important to understand due to the persistence and toxicity of these chemicals. Laboratory experiments were performed to elucidate aniline and benzidine behavior in silty-clay, sandy loam, and sandy soils, and six background matrices (rainwater, 12.5 mM CaCl(2), 25 mM CaCl(2), and each passed through soil columns). The goals of this study were to test the validity of using CaCl(2) as a laboratory simulation for rainwater and to observe how short-term sorption (24 h) of aniline and benzidine changed when these solutions were passed through soil columns. Results indicated that neither CaCl(2) solution exactly predicted the sorption of these chemicals in corresponding rainwater solutions, likely due to varying soil properties that influenced the sorption mechanisms. Statistical analyses revealed that the passage of rainwater or CaCl(2) solutions through soil columns did not significantly affect the sorption of aniline or benzidine. Cation exchange and solubility plots were created to identify the sorption mechanisms taking place in the short-term batch experiments. These plots indicated that cation exchange played a role in the sorption of both aniline and benzidine under all conditions, while solubility plots showed higher correlations for benzidine, a consequence of its lower aqueous solubility.

Adsorption↗

PubMed2006

Benzidine transformation processes in natural sediments.

Aromatic amines, such as benzidine and 3,3'-dichlorobenzidine, are chemicals used in the pigment and dye processes. Release of these compounds into the environment is important because of their carcinogenic and toxic nature. In the present study, the sediment and water samples were collected from Lake Macatawa (Holland, MI, USA) and subsequently spiked with benzidine. The grain size distribution of the sediment samples investigated here ranged in composition from sandy to silty-clay sediment types. The sediment-water systems spiked with benzidine were incubated under anaerobic conditions at 4, 15, and 23 degrees C for 211 d. Degradation of benzidine was observed over the time-course analysis of the sediment-water mixtures. Three possible metabolites (aniline, 2-ethyl-1-hexanol, and 1-amino-2-hexene) were observed during this investigation as a result of gas chromatography/mass spectrometry and liquid chromatography/mass spectrometry. No metabolites were observed in autoclaved bottles, suggesting that the transformation of benzidine in the sediment-water mixtures was the result of microbial activity. From sediment-water distribution experiments, benzidine demonstrated higher sorption affinity for the different sediment phases than its degradation product, aniline. Therefore, microbially mediated transformation of benzidine to aniline is expected to yield a greater total concentration of the more mobile compound, aniline, in the water phase and a greater possibility for transport of aniline in the water phase.

Benzidines↗

PubMed2005

Concentrations and distribution of 3,3'-dichlorobenzidine and its congeners in environmental samples from Lake Macatawa.

Release of 3,3'-dichlorobenzidine (DCB), an intermediate in dye manufacturing processes, is of environmental concern due to its carcinogenic nature. An 11-year field study has been conducted to elucidate the fate and behavior of DCB and its congeners in the Lake Macatawa (Holland, MI, USA) sediment-water system. The sediments were variable in composition, ranging from sandy sediments with 1-8.7% total organic carbon (OC) to silty-clay sediments with 7.5-20.6% total OC. The pH ranged from 6.3 to 7.4. The findings from this field study confirmed that DCB and its congener, benzidine, are transported over long distances. The concentration of DCB in the water phase was found to be from non-detectable to approximately 1300 times greater than the water quality criteria established for DCB (0.021 microg/l). Its congener, benzidine, which is substantially more toxic for humans than its parent compound has been found up to approximately 12300 times higher levels than the EPA guidelines suggest (0.000086 microg/l). Both DCB and benzidine were found in the sediment phase. DCB was observed at almost 70 mg/kg in a sample collected in 1993. The concentrations in both phases have declined in recent years. To assess the threat of the released pollutants, it is necessary to understand how pollutants tend to behave in various media. Therefore, it is crucial to identify and quantify all sources of the chemical and its congeners in order to meaningfully predict the fate (and transport) of a hydrophobic organic compound (HOC) in the environment.

3,3'-Dichlorobenzidine↗

PubMed2005

Sorption of benzidine and 3,3'-dichlorobenzidine to lake sediments. 1. Conceptualization and development of a multiparameter model.

Aromatic amines, such as benzidine and 3,3'-dichlorobenzidine (DCB), are part of the dyes and pigments manufacturing process. The prolonged use of these carcinogenic chemicals in the past generation has introduced a significant amount of contamination to the environment. Their persistency in several mediums has sparked a number of studies in an attempt to develop predictive tools of their fate and transport in the environment. In this study, benzidine and DCB batch isotherms were developed and evaluated. The sediment samples were variable in composition, ranging from sandy to silty-clay sediment samples. The batch isotherms were then analyzed using high-performance liquid chromatography. Subsequently, a multiparameter model (MPM) that accounted for partitioning, covalent bonding, and cation exchange was developed and tested in an effort to understand the various mechanisms. Results proved the proposed model to be effective in predicting sorption of aromatic amines to lake sediments. The findings suggest that the MPM can provide a better understanding of the sorption process of aromatic amines than more conventional models.

3,3'-Dichlorobenzidine↗

PubMed2005

Slow desorption behavior of one highly resistant aromatic amine in Lake Macatawa, Michigan, USA, sediment.

The desorption behavior of benzidine from Lake Macatawa (Holland, MI, USA) sediment was investigated in this study using batch solvent extraction method. Seven solvents were tested as the extracting reagents: Deionized water (DI), calcium chloride in DI (CaCl2), sodium hydroxide in DI (NaOH), acetonitrile (ACN), a mixture of acetonitrile and ammonium acetate in DI (ACN-NH4OAc), methanol (MeOH), and hydrochloric acid in DI (HCl). These solvents are proposed to react with sediment-associated benzidine by different mechanisms (e.g., cation exchange, hydrophobic partitioning, and covalent binding). Three sets of sorption isotherm experiments were conducted separately in these seven solvents with a 7-d, three-week, and two-month contact time. The results demonstrated nonlinear isotherms with Freundlich 1/n values varying from 0.25 to 0.52. The desorption behavior of benzidine in the solvents was evaluated after the sorption of benzidine onto the sediment with same contact times of 7 d, three weeks, and two months. A two-stage model subsequently was applied to simulate the experimental data. The rapidly desorbing rate constants were on the order of one to two per day for ACN, ACN-NH4OAc, and NaOH solvents, and the slowly desorbing rate constants were on the order of 10(-5) to 10(-4)/d. Sequential desorption experiment demonstrated low total extraction efficiency of less than 40%. Both the observed sorption and desorption phenomena suggested that hysteresis and/or mass-transfer limited diffusion may result in the slow desorption behavior observed in this study.

Acetates↗

PubMed2004

Optimization of the peroxy acid treatment of alpha-methylnaphthalene and benzo[a]pyrene in sandy and silty-clay sediments.

The majority of polycyclic aromatic hydrocarbons (PAHs) released to the environment come from anthropogenic sources involving the incomplete combustion of organic compounds. Several techniques are available for the degradation of PAHs. Among the abiotic/biotic processes used to degrade PAHs, an alternative strategy utilizing a primary chemical oxidative step to be combined with a biological was created. The degradation of alpha-methylnaphthalene and benzo[a]pyrene using an advanced oxidation process was optimized over a period of 24 h by varying the ratio of acetic acid to hydrogen peroxide, the compounds that form peroxy acids. The optimization process was performed using sandy and silty-clay sediment types. Gas chromatography equipped with a flame ionization detector was used to determine the varied rates of degradation depending on acetic acid:hydrogen peroxide ratios and the characteristics of the sediment sample. Reduction of 20-90% of alpha-methylnaphthalene and benzo[a]pyrene was observed when 2-5 mL of hydrogen peroxide was used, respectively. A peracetic acid solution (e.g., a commercial form of acetic acid and hydrogen peroxide) was used to compare the results from the peroxy acid experiments. In all the experiments, peracetic acid was more reactive than the combination of acetic acid and hydrogen peroxide. Acetic acid, deionized water, and hydrogen peroxide served as controls and demonstrated minimal degradation over the time course study. Therefore, the use of a peroxy acid process to target electron dense pollutants may have a great utility.

Aluminum Silicates↗

PubMed2004

Remediation of benzo(a)pyrene in contaminated sediments using peroxy-acid.

Release of benzo(a)pyrene is of an environmental concern due to its toxic nature. To elucidate the degradation of benzo(a)pyrene in lake sediments an advanced oxidation process (AOP) employing peroxy-acids as oxidizing agents was investigated. The sediments used in this study were collected from Lake Macatawa (Holland, MI) throughout the eastern basin and ranged in composition from sandy to silty-clay. Laboratory experiments were made by exposing spiked sediment samples to a 1:1:1 v/v/v mixture of hydrogen peroxide/acetic acid/deionized (DI) water solution. Analytical measurements were performed using gas chromatography equipped with a flame ionization detector. From the AOP experiments, transformation of benzo(a)pyrene was observed in both sediment types over a period of 24-h. The disappearance of the parent compound seemed more rapid with the use of propionic acid than with acetic acid, a behavior that is not yet well understood. The organic acid, DI water, and hydrogen peroxide controls did not demonstrate applicable degradation, suggesting that the disappearance of the parent compound was related to the peroxy-acid process.

Acetic Acid↗

PubMed2004

Liquid chromatographic aqueous product characterization of high-energy electron beam irradiated 2-chlorobiphenyl solutions.

Polychlorinated biphenyls (PCBs) are of environmental concern due to their toxic nature. Ionizing radiation has been suggested as a means to remediate PCB-contaminated samples in complex matrices. A set of experiments was performed to qualitatively and quantitatively determine the aromatic degradation products of 2-monochlorobiphenyl (2-MCB) in an aqueous system exposed to ionizing radiation. The degradation of 2-MCB was observed in aqueous samples that were exposed to radiation from a linear accelerator electron beam source. Analytical measurements performed by liquid chromatography (LC) equipped with an ultraviolet (UV) detector revealed that biphenyl, o-hydroxybiphenyl, p-hydroxybiphenyl, phenol, chlorobenzene, and other unidentified products were created after 2-MCB irradiation. These results suggest that sensitive and selective analytical methods will be required to account for all degradation products during ionizing radiation of aqueous PCB-contaminated samples.

Biphenyl Compounds↗

PubMed2003

Remediation of alpha-methylnaphthalene-contaminated sediments using peroxy acid.

Laboratory experiments have been conducted to elucidate the degradation of alpha-methylnaphthalene in lake sediments using an advanced oxidation process (AOP) employing peroxy-acids as oxidizing agents. Abiotic degradation of alpha-methylnaphthalene was observed in sediment samples exposed to a 1:1:1 v/v/v mixture of water/organic acid/hydrogen peroxide solution. Sediment samples were collected from Lake Macatawa (Holland, MI) and ranged in total organic carbon content from 2.1% (sandy sediment sample III) to 12.8% (silty-clay sediment sample I) and surface area, which ranged from 3.2m(2)/g (sandy sediment sample III) to 22.0m(2)/g (silty-clay sediment sample I). Analytical measurements performed by gas chromatography revealed varied rates of degradation, depending on the type of acid and the characteristics of the sediment sample. Within 24h, alpha-methylnaphthalene was reduced to 70% and 100% of its original concentration when propionic acid and acetic acid were used as the organic acids, respectively. The formation of products was explored using a gas chromatograph equipped with a mass spectrometer and indicated mainly the formation of lower molecular weight compounds, such as alkyl chains. This AOP method of PAH degradation in sediment/liquid slurry was fast acting and products were most likely biodegradable.

Aluminum Silicates↗

PubMed2003

Transport behavior of 3,3'-dichlorobenzidine in a freshwater estuary.

Like many hydrophobic organic compounds, 3,3'-dichlorobenzidine (DCB) partitions preferentially to (sediment) particles in lake systems. As such, the behavior of DCB in these systems is substantially affected by the movement of sediments. A field investigation of DCB distribution in sediments of Lake Macatawa (Holland, MI, USA) was initiated. The pattern of DCB distribution within the lake was found to display an oscillatory pattern that was consistent with a wind-driven mechanism of sediment transport. Numerical modeling of seiching behavior supported the hypothesized importance of this mechanism of sediment transport and redistribution. The dynamic behavior of sediment-associated DCB within Lake Macatawa seems to be strongly influenced by phenomena that are common to many freshwater estuaries. As such, the behavior of this system is expected to represent a reasonable model of the dynamic behavior of hydrophobic contaminants in other freshwater estuaries.

3,3'-Dichlorobenzidine↗

PubMed2002

Photodechlorination of 3,3'-dichlorobenzidine in water.

Laboratory experiments have been conducted to elucidate the photochemical behavior of 3,3'-dichlorobenzidine (DCB) and its congeners in aquatic systems. Photodechlorination of DCB was observed in aqueous samples that were irradiated with monochromatic radiation from a variable-wavelength laser at several wavelengths in the range 300 nm < or = lambda < or = 360 nm. Analytical measurements performed by high-performance liquid chromatography (HPLC) and Fourier-transform ion cyclotron resonance (FT-ICR) mass spectrometry revealed that 3-chlorobenzidine (MCB) was produced as a transient intermediate in the photodechlorination process, with subsequent photodechlorination to yield benzidine as a stable photoproduct. Data obtained from these measurements also suggest the existence of other (unidentified) reaction pathways and products. The time-course measurements of chlorobenzidine congener concentrations and irradiance history were combined with a simple reaction model to develop estimates of reaction kinetics. Model predictions were consistent with results obtained for all wavelengths investigated.

3,3'-Dichlorobenzidine↗