Dr. Marianne Nyman

311 Materials and Research Center (MRC)
Rensselaer Polytechnic Institute
Troy, NY 12180

email:nymanm@rpi.edu
phone: (518) 276-2268
fax: (518) 276-2095

Publications

Nyman, M.C.; Harden, J.; Nies, L.F.; Blatchley, E.R., III. (2004) Biodegradation of 3,3’-dichlorobenzidine in freshwater lake sediments.  J. Environ. Eng. Sci., 3(2), 89-95.

N’Guessan, A.L.; Carignan, T.; and Nyman, M.C. (2004) Optimization of the Peroxy Acid Treatment of α-Methylnaphthalene and Benzo[a]pyrene in Sandy and Silty-Clay Sediments. Environ. Sci. Technol., 38(5), 1554-1560.

Drenzek, N.J.; Nyman, M.C.; Clesceri, N.L.; Block, R.C.; and Stenken, J.A. (2004) Liquid chromatographic aqueous product characterization of high-energy electron beam irradiated 2-chlorobiphenyl solutions. Chemosphere, 54 (3), 387-395.

N’Guessan, A.L.; Levitt, J.S.; and Nyman, M.C. (2004) Remediation of benzo(a)pyrene in contaminated sediments using peroxy-acid.

Levitt, J.S.; N’Guessan, A.L.; Rapp, K.L.; and Nyman, M.C. (2003) Remediation of α -methylnaphthalene-contaminated sediments using peroxy acid. Water Res., 37 (12), 3016-3022.

Nyman, M.C.; McCord, K.; Wood, W.L.; and Blatchley, E.R., III. (2003) Transport behavior of 3,3'-dichlorobenzidine in a freshwater estuary.  Environ. Toxicol. and Chem.,  22 (1),  20-25.

Petucci, C.; Nyman, M.; Guler, L.; and Kenttämaa, H. (2002) Hydrogen Atom Abstraction Reactions of Charged Polyaromatic σ-Radicals Related to the Active Intermediates of the Enediyne Antitumor Drugs.  J. Am. Chem. Soc., 124 (15), 4108 -4115.

Nyman, M.C.; Haber, K.S.; Kenttämaa, H.I.; and Blatchley, E.R., III. (2002) Photodechlorination of 3,3'-dichlorobenzidine in water.  Environ. Toxicol. and Chem.21 (3),  500-506.

Nyman, M.C.; Pérez, J.; Blatchley, E.R., III; and Kenttämaa, H.I. (1999) Determination of 3,3'-dichlorobenzidine and its degradation products in environmental samples with a small low-field Fourier transform ion cyclotron resonance mass spectrometer. J. Am. Soc. Mass Spectr., 10 (11), 1152-1156.

Lee, L.S.; Nyman, A.K.; Li, H.; Nyman, M.C.; and Jafvert, C. (1997) Initial sorption of aromatic amines to surface soils.  Environ. Toxicol. and Chem., 16 (8),  1575-1582.

Nyman, M.C.; Nyman, A.K.; Lee, L.S.; Nies, L.F.; and Blatchley, E.R., III.  (1997) 3,3'-Dichlorobenzidine Transformation Processes in Natural Sediments.  Environ. Sci. Technol., 31 (4), 1068 -1073.


Nyman, M.C.; Harden, J.; Nies, L.F.; Blatchley, E.R., III. (2004) Biodegradation of 3,3’-dichlorobenzidine in freshwater lake sediments.  J. Environ. Eng. Sci. (in press).

Abstract:

3,3’-Dichlorobenzidine (DCB) and its degradation products, 3-chlorobenzidine (MCB) and benzidine, are of environmental concern due to their toxic and carcinogenic nature.  Laboratory experiments have been conducted to elucidate the biodegradation behavior of DCB in Lake Macatawa (Holland, Michigan) sediment-water systems at 4, 24, and 30 oC incubation temperatures.  Sediment samples varied in pH (6.45 - 7.41), total organic carbon (OC) content (1.4 - 17.1), and particle size distribution (silty-clay to sandy).  Biodegradation of DCB was observed in non-autoclaved samples that were incubated at 4, 24, and 30 oC for approximately 12 months.  The dechlorination rate as a function of OC content was essentially found constant at 4 oC and 24 oC, but demonstrated a roughly linear increase at 30 oC, thereby suggesting that OC content might be correlated to dechlorination rate at 30 oC incubation temperature.  The rate as a function of particle size (e.g., <74 mm) did not demonstrate a clearly defined relationship.

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N’Guessan, A.L.; Carignan, T.; and Nyman, M.C. (2004) Optimization of the Peroxy Acid Treatment of α-Methylnaphthalene and Benzo[a]pyrene in Sandy and Silty-Clay Sediments. Environ. Sci. Technol.

Abstract:

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 α-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 chromatog raphy 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 α-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.

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Drenzek, N.J.; Nyman, M.C.; Clesceri, N.L.; Block, R.C.; and Stenken, J.A. (2004) Liquid chromatographic aqueous product characterization of high-energy electron beam irradiated 2-chlorobiphenyl solutions. Chemosphere, 54 (3), 387-395.

Abstract:

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.

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N’Guessan, A.L.; Levitt, J.S.; and Nyman, M.C. (2004) Remediation of benzo(a)pyrene in contaminated sediments using peroxy-acid.

Abstract:

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.

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Levitt, J.S.; N’Guessan, A.L.; Rapp, K.L.; and Nyman, M.C. (2003) Remediation of α -methylnaphthalene-contaminated sediments using peroxy acid. Water Res., 37 (12), 3016-3022.

Abstract:

Laboratory experiments have been conducted to elucidate the degradation of α -methylnaphthalene in lake sediments using an advanced oxidation process (AOP) employing peroxy-acids as oxidizing agents. Abiotic degradation of α -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 3.2 m2/g (sandy sediment sample III) to 22.0 m2/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 24 h, α -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.

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Nyman, M.C.; McCord, K.; Wood, W.L.; and Blatchley, E.R., III. (2003) Transport behavior of 3,3'-dichlorobenzidine in a freshwater estuary.  Environ. Toxicol. and Chem.,  22 (1),  20-25.

Abstract:

Like many hydrophobic organic compounds, 3,3'-dichlorobenzidine (DCB) partitions preferentially to (sediment) particles in lake systems.  The behavior of DCB in these systems is substantially affected by the movement of sediments.  A field study of DCB distribution in sediments of Lake Macatawa (Holland, MI) was initiated.  The pattern of DCB distribution within the lake displayed 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.

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Petucci, C.; Nyman, M.; Guler, L.; and Kenttämaa, H. (2002) Hydrogen Atom Abstraction Reactions of Charged Polyaromatic σ-Radicals Related to the Active Intermediates of the Enediyne Antitumor Drugs.  J. Am. Chem. Soc., 124 (15), 4108 -4115.

Abstract:

Polar effects are demonstrated to play an important role in controlling the reactivity of polyaromatic σ-radicals that are structurally related to the active intermediates of the enediyne anticancer type antibiotics. This was accomplished by measuring the rate constants of hydrogen atom abstraction for novel, charged dehydroquinolines, dehydroisoquinolines, dehydrobenzenes, and dehydronaphthalenes in the gas phase by using Fourier-transform ion cyclotron resonance mass spectrometry. The reactivity trends observed for these radicals upon hydrogen atom abstraction from tetrahydrofuran and 2-methyltetrahydrofuran, simple models of deoxyribose, do not reflect differences in reaction exothermicities, radical sizes, exact location of the radical site in the ring system, or heteroatom-radical site distances. However, the reactivity trends match the trend in the calculated electron affinities of the radicals. The radicals' different electrophilicities result in variations in the reaction barrier due to different extents of polarization of the transition state. Generally, the reaction efficiencies are the greatest when the formally charged heteroatom is contained within the same ring system as the radical site. In this case, polar effects have the greatest influence on radical reactivity. Hence, insertion of a basic heteroatom (which gets protonated in biological systems) into specific locations in the polyaromatic ring system of the σ-biradicals, which ultimately cause cleavage of DNA exposed to the enediyne antitumor drugs, should allow tuning of the reactivity of these radicals.

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Nyman, M.C.; Haber, K.S.; Kenttämaa, H.I.; and Blatchley, E.R., III. (2002) Photodechlorination of 3,3'-dichlorobenzidine in water.  Environ. Toxicol. and Chem.21 (3),  500-506.

Abstract:

Laboratory experiments were 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 £ l £ 360 nm.  Analytical measurements performed by HPLC and FTIR cyclotron resonance mass spectrometry revealed that 3-chlorobenzidine 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 studied.

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Nyman, M.C.; Pérez, J.; Blatchley, E.R., III; and Kenttämaa, H.I. (1999) Determination of 3,3'-dichlorobenzidine and its degradation products in environmental samples with a small low-field Fourier transform ion cyclotron resonance mass spectrometer. J. Am. Soc. Mass Spectr., 10 (11), 1152-1156.

Abstract:

3,3'-Dichlorobenzidine (DCB) and its degradation products, 3-chlorobenzidine (MCB) and benzidine, are of environmental concern because of their carcinogenic nature. The suitability of a small Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometer for the analysis of these environmental contaminants in different types of matrices was explored. All the measurements were carried out by depositing the sample solution directly on a disk that was introduced into the mass spectrometer. This approach is very fast and simple because it requires no prior chromatographic separation or derivatization. Calibration curves determined by collecting 70-eV electron ionization mass spectra of neat samples yielded lower limits of detection of 29 and 17 pg (total amount on the solids probe) for DCB and benzidine, respectively (based on a signal to noise ratio of > 2:1), while chemical ionization with ammonia resulted in lower limits of detection of 21 pg for DCB and 9 pg for benzidine (total amount on the solids probe). FT-ICR analysis of sediments collected from Lake Macatawa (Holland, MI) verified the presence of DCB in this complex, environmentally significant sample matrix. Laboratory experiments designed to probe biodegradation and photodegradation pathways showed that DCB undergoes sequential dehalogenation to yield MCB and then benzidine under exposure to microorganisms and under simulated tropospheric solar radiation. The ability of the FT-ICR to determine elemental compositions of compounds introduced as described above was demonstrated for one of the degradation products.

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Lee, L.S.; Nyman, A.K.; Li, H.; Nyman, M.C.; and Jafvert, C. (1997) Initial sorption of aromatic amines to surface soils.  Environ. Toxicol. and Chem., 16 (8),  1575-1582.

Abstract:

Sorption of aniline, a -naphthylamine, and benzidine to three silty clay loams was measured from CaCl2 electrolyte solutions. in single and binary solute systems after a 1-day residence time.  Soils varied in pH (4.4-7.2), cation-exchange capacity (CEC, 10-30 cmolc/kg), and org. carbon content (OC, 1-3%).  Plots of sorbed amine concentrations vs. aqueous amine concentrations exhibited nonlinearity in the concentration range investigated.  Sorption increased with decreasing soil-solution pH for all solutes.  Decreases in sorption with increasing CaCl2 concentrations were greatest at low pH.  In binary solute experiments, a -naphthylamine depressed the sorption of aniline and this depression increased with decreasing pH.  Normalizing sorption to the cation-exchange capacity of the protonated species compensated for most of the differences observed between soils at different pH values, suggesting that cation exchange is the primary process occurring during initial contact times.  Sorbed aromatic amines were extracted from soils with different solvents after a 1-day incubation.  At low initial concentrations (<0.01 mM), only a few percent of each amine was extractable; whereas 85% to 98% was recoverable at higher initial concentrations (1 mM).  Although initial sorption appears to be to cation-exchange sites, the inability to recover all of the sorbed amine suggests early covalent bond formation on highly reactive sites and/or sorption to high-energy sites on clays or other soil constituents.

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Nyman, M.C.; Nyman, A.K.; Lee, L.S.; Nies, L.F.; and Blatchley, E.R., III.  (1997) 3,3'-Dichlorobenzidine Transformation Processes in Natural Sediments.  Environ. Sci. Technol., 31 (4), 1068 -1073.

Abstract:

Release of 3,3'-dichlorobenzidine (DCB), an intermediate in dye manufacturing, and its congeners are of environmental concern due to their carcinogenic nature. To elucidate the fate of these compounds in sediment/water systems, sediment/water mixtures were spiked with DCB and incubated at 20 °C for 12 months under anaerobic conditions. The sediments used in this study were collected from Lake Macatawa (Holland, MI) and ranged in composition from silty-clay to sandy. Dehalogenation of DCB to benzidine appeared to take place through a transient intermediate, 3-monochlorobenzidine, which was observed in time-course analyses of the sediment/water mixtures. No metabolites were observed in autoclaved samples, sug gesting that dehalogenation of DCB in anaerobic sediment/water systems was mediated by microbial activity. The product of dehalogenation (benzidine) is more toxic to humans than the parent compound, DCB. From sediment/water distribution experiments, DCB showed greater affinity for the sediment phase than its non-chlorinated derivative, benzidine. Therefore, progressive dehalogenation of DCB in anaerobic lake sediments is expected to yield a greater total concentration of aromatic amines in the solution phase, a shift to a more toxic form, and greater potential for transport in the environment.

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