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Application of Nanomaterials for the Removal of Hexavalent Chromium and their Biological Implications
KTH, School of Chemical Science and Engineering (CHE), Chemical Engineering and Technology, Chemical Engineering.
2016 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

The International Agency for Research on Cancer (IARC) stated that chromium in the form of Cr(VI) has been deemed to be a class-A human carcinogen. It has been a major contaminant associated with wastewater. Moreover, the existence of heavy metals in aquatic systems is a critical concern for the environment as well as industries that manufacture or consume these particular elements. In order to remove these particular toxic metals, several well-known conventional methods including ion-exchange, filtration and adsorption are used. Amongst these methods, adsorption offers significant advantages such as the low-cost materials, ease of operation and efficiency in comparison to the other conventional methods.

The aim of this work was to develop nanomaterials (particles and fibers) to address some critical issues for the treatment of heavy metals, especially chromium in aqueous systems. Furthermore, the use of nanomaterials and how they relate to nanoscale operations at the biological level has generated considerable concerns in spite of their novel properties.

The first part of this thesis deals with the synthesis and characterizations of Fe3O4, magnetite, as nanoparticles which were further coated with surfactants bis(2,4,4-trimethylpentyl)dithiophosphinic acid, Cyanex-301, and 3-Mercaptopropionic acid with the active compound being the thiol (SH) groups, that will suffice as a viable material for Cr(VI) removal from aqueous solutions. The proposed mechanism was the complexation between the thiol group on Cyanex-301 and 3-Mercaptopropionic acid, respectively. The effect of different parameters on the adsorption including contact time, initial and final Cr(VI) ion concentration and solution pH was investigated.

The second part of this thesis encompassed the fabrication of flexible nanocomposite materials, with a large surface area and architecture for the removal of Cr(VI) in batch and continuous flow mode. A technique known as electrospinning was used to produce the nanofibers. The flexible yet functional materials architecture has been achieved by growing ZnO nanorod arrays through chemical bath deposition on synthesized electrospun poly-L-lactide nanofibers. Moreover, polyacrylonitrile nanofibers (PAN) were synthesized and adapted by the addition of hydroxylamine hydrochloride to produce amidoxime polyacrylonitrile nanofibers (A-PAN). Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) were used to identify the morphologies and particle sizes whereas Fourier-Transform Infrared spectroscopy (FT-IR) was used to identify either the presence or absence of functional groups for the formation of PAN and A-PAN nanofibers. The optimization of functionalized nanoadsorbents to adsorb Cr(VI) was also carried out to investigate the effect of experimental parameters: contact time, solution pH, initial, final and other metal ion concentration. Commercially manufactured pristine engineered (TiO2, ZnO and SiO2) nanoparticles and lab-made functionalized (Fe3O4 and CeO2) nanoparticles were studied while the powders were suspended in appropriate media by Dynamic Light Scattering (DLS) to identify their cytotoxicity effects.

Place, publisher, year, edition, pages
KTH: KTH Royal Institute of Technology, 2016. , 76 p.
Series
TRITA-CHE-Report, ISSN 1654-1081 ; 2016:4
Keyword [en]
Nanomaterials, Chromium, Biology
National Category
Engineering and Technology
Research subject
Chemical Engineering
Identifiers
URN: urn:nbn:se:kth:diva-179871ISBN: 978-91-7595-813-2 (print)OAI: oai:DiVA.org:kth-179871DiVA: diva2:890693
Public defence
2016-01-29, sal D2, Lindstedisvägen 5, KTH, Stockholm, 10:00 (English)
Opponent
Supervisors
Note

QC 20160111

Available from: 2016-01-11 Created: 2016-01-04 Last updated: 2016-01-11Bibliographically approved
List of papers
1. Surface functionalized nanofibers for the removal of chromium(VI) from aqueous solutions
Open this publication in new window or tab >>Surface functionalized nanofibers for the removal of chromium(VI) from aqueous solutions
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2014 (English)In: Chemical Engineering Journal, ISSN 1385-8947, Vol. 245, 201-209 p.Article in journal (Refereed) Published
Abstract [en]

Polyacrylonitrile (PAN) nanofibers functionalized with amine groups (PAN-NH2) were prepared using a simple one-step reaction route. The PAN-NH2 nanofibers were investigated for the removal of chromium(VI) from aqueous solutions. The adsorption and the kinetic characteristics were evaluated in batch process. The adsorption process showed pH dependence and the maximum Cr(VI) adsorption occurred at pH = 2. The Langmuir adsorption model described well the experimental adsorption data and estimated a maximum loading capacity of 156 mg/g, which is a markedly high value compared to other adsorbents reported. The kinetics studies indicated that the equilibrium was attained after 90 min and the experimental data followed a pseudo-second order model suggesting a chemisorption process as the rate limiting step. X-ray Photoelectron Spectroscopy (XPS) and Fourier transform infrared spectroscopy (FT-IR) revealed that the adsorption of Cr(VI) species on PAN-NH2 was facilitated through both electrostatic attraction and surface complexation. High desorption efficiency (> 90%) of Cr(VI) was achieved using diluted base solutions that may allow the reuse of PAN-NH2 nanofibers.

Keyword
Nanofibers, Polyacrylonitrile, Adsorption, Chromium
National Category
Engineering and Technology
Identifiers
urn:nbn:se:kth:diva-138316 (URN)10.1016/j.cej.2014.02.034 (DOI)000335275200025 ()2-s2.0-84896750603 (Scopus ID)
Note

QC 20140611. Updated from submitted to published.

Available from: 2013-12-18 Created: 2013-12-18 Last updated: 2016-01-11Bibliographically approved
2. Studies on the adsorption of chromium(VI) onto 3-Mercaptopropionic acid coated superparamagnetic iron oxide nanoparticles
Open this publication in new window or tab >>Studies on the adsorption of chromium(VI) onto 3-Mercaptopropionic acid coated superparamagnetic iron oxide nanoparticles
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2014 (English)In: Journal of Colloid and Interface Science, ISSN 0021-9797, E-ISSN 1095-7103, Vol. 425, 36-43 p.Article in journal (Refereed) Published
Abstract [en]

Chromium (Cr) in the form of Cr(VI) is deemed toxic in water due to its mutagenic and carcinogenic properties. For the successful removal of Cr(VI), we demonstrate a novel adsorbent consisting of superparamagnetic iron oxide nanoparticles (SPION) functionalized with 3-Mercaptopropionic acid (3-MPA). Fourier transform infrared spectroscopy (FT-IR) confirmed the functionalization of nanoparticles and presence of sulfonate groups. Batch adsorption experiments showed that the functionalized adsorbent recovered 45 mg of Cr(VI)/g of 3-MPA coated SPION at initial concentration of 50 mg/L aqueous solution at pH 1 with less than 1% of Fe dissolution from SPION. The results from X-ray photoelectron spectroscopy confirmed that Cr(VI) chemisorbed onto the adsorbent. Hence, the XPS spectra did not indicate any reduction of Cr(VI) to Cr(III) upon adsorption. The adsorption data were better fitted for the Freundlich model. Moreover, the Cr(VI) adsorption kinetics on functionalized SPION followed a pseudo-second order rate, revealing chemisorption as the dominant mechanism. The high Cr(VI) removal, rapid adsorption kinetics and stability of adsorbent indicate that 3-MPA coated SPION could be an efficient adsorbent for the removal of Cr(VI).

Keyword
SPION, Chromium, 3-Mercaptopropionic acid, Adsorption
National Category
Other Chemistry Topics
Identifiers
urn:nbn:se:kth:diva-138311 (URN)10.1016/j.jcis.2014.03.025 (DOI)000335620500006 ()2-s2.0-84897518040 (Scopus ID)
Funder
EU, FP7, Seventh Framework Programme
Note

QC 20140609. Updated from submitted to published.

Available from: 2013-12-18 Created: 2013-12-18 Last updated: 2016-01-11Bibliographically approved
3. Removal of Chromium(VI) Using Surface Modified Superparamagnetic Iron Oxide Nanoparticles
Open this publication in new window or tab >>Removal of Chromium(VI) Using Surface Modified Superparamagnetic Iron Oxide Nanoparticles
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2013 (English)In: Separation science and technology (Print), ISSN 0149-6395, E-ISSN 1520-5754, Vol. 48, no 8, 1243-1251 p.Article in journal (Refereed) Published
Abstract [en]

This study describes the removal of Chromium(VI) from aqueous solutions using surface tailored superparamagnetic iron oxide nanoparticles (SPION) coated with bis(2,4,4-trimethylpentyl)dithiophosphinic acid (Cyanex-301). The synthesized Cyanex-301 coated SPION has been characterized by Transmission Electron Microscopy (TEM), Fourier-Transfer Infrared Spectroscopy (FT-IR), X-ray Photonic Spectroscopy (XPS), and Thermogravimetric Analysis (TGA). The adsorption mechanism was proposed to be via complexation between the thiol group on Cyanex-301 and Cr(VI) ions based on the XPS and FTIR analysis. It has been found that the equilibrium can be attained in less than 2hr. The adsorption behavior of Cr(VI) on the Cyanex-301 coated SPION can be well described by the Langmuir model and the maximum adsorption capacity for Cr(VI) was estimated to be 30.8mg/g. The selectivity of the Cyanex-301 coated SPION adsorbent towards Cr(VI) ions was found to be high and the maximum loading capacity obtained is up to an order of magnitude higher than that of other adsorbents reported in the literature. The desorption studies showed that more than 70% of Cr(VI) can be recovered using HNO3 as eluting solution. Our findings suggest a high potential of the designed adsorbent material for the treatment of industrial wastewater containing Cr(VI).

Keyword
adsorption, Chromium(VI), Cyanex-301, SPION
National Category
Engineering and Technology
Identifiers
urn:nbn:se:kth:diva-123435 (URN)10.1080/01496395.2012.734364 (DOI)000318293700013 ()2-s2.0-84877284511 (Scopus ID)
Funder
EU, FP7, Seventh Framework Programme
Note

QC 20130614

Available from: 2013-06-14 Created: 2013-06-10 Last updated: 2016-01-11Bibliographically approved
4. Microsomal Glutathione Transferase 1 Protects Against Toxicity Induced by Silica Nanoparticles but Not by Zinc Oxide Nanoparticles
Open this publication in new window or tab >>Microsomal Glutathione Transferase 1 Protects Against Toxicity Induced by Silica Nanoparticles but Not by Zinc Oxide Nanoparticles
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2012 (English)In: ACS Nano, ISSN 1936-0851, Vol. 6, no 3, 1925-1938 p.Article in journal (Refereed) Published
Abstract [en]

Microsomal glutathione transferase 1 (MGST1) is an antioxidant enzyme located predominantly in the mitochondrial er membrane and endoplasmk reticulum and has been shown to protect cells from lipid peroxidation induced by a variety of cytostatic drugs and pro-oxidant stimuli. We hypothesized that MGST1 may also protect against nanomaterial-induced cytotoxicity through a specific effect on lipid peroxidation. We evaluated the induction of cytotoxicity and oxidative stress by TiO2, CeO2, SiO2, and ZnO in the human MCF-7 cell line with or without overexpression of MGST1. SiO2 and ZnO nanoparticles caused dose- and time-dependent toxicity, whereas no obvious cytotoxic effects were induced by nanoparticles of TiO2 and CeO2. We also noted pronounced cytotoxicity for three out of four additional SiO2 nanoparticles tested. Overexpression of MGST1 reversed the cytotoxicity of the main SiO2 nanoparticles tested and for one of the supplementary SiO2 nanoparticles but did not protect cells against ZnO-induced cytotoxic effects. The data point toward a role of lipid peroxidation In SiO2 nanoparticle-induced cell death. For ZnO nanoparticles, rapid dissolution was observed, and the subsequent interaction of Zn2+ with cellular targets is likely to contribute to the cytotoxic effects. A direct inhibition of MGST1 by Zn2+ could provide a possible explanation for the lack of protection against ZnO nanoparticles in this model. Our data also showed that SiO2 nanoparticle-induced cytotoxicity is mitigated in the presence of serum, potentially through masking of reactive surface groups by serum proteins, whereas ZnO nanoparticles were cytotoxic both In the presence and in the absence of serum.

Keyword
engineered nanoparticles, oxidative stress, lipid peroxidation, microsomal glutathione transferase 1
National Category
Other Materials Engineering
Identifiers
urn:nbn:se:kth:diva-93650 (URN)10.1021/nn2021056 (DOI)000301945900006 ()2-s2.0-84859147188 (Scopus ID)
Funder
EU, European Research Council, NMP-SL-2008-214281Swedish Research Council
Note
QC 20120423Available from: 2012-04-23 Created: 2012-04-23 Last updated: 2016-01-11Bibliographically approved
5. Oxidative Stress and Dermal Toxicity of Iron Oxide Nanoparticles In Vitro
Open this publication in new window or tab >>Oxidative Stress and Dermal Toxicity of Iron Oxide Nanoparticles In Vitro
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2013 (English)In: Cell Biochemistry and Biophysics, ISSN 1085-9195, E-ISSN 1559-0283, Vol. 67, no 2, 461-476 p.Article in journal (Refereed) Published
Abstract [en]

A number of commercially available metal/metal oxide nanoparticles (NPs) such as superparamagnetic iron oxide (SPION) are utilized by the medical field for a wide variety of applications. These NPs may able to induce dermal toxicity via their physical nature and reactive surface properties. We hypothesize that SPION may be toxic to skin via the ability of particles to be internalized and thereby initiate oxidative stress, inducing redox-sensitive transcription factors affecting/leading to inflammation. Due to the skin's susceptibility to UV radiation, it is also of importance to address the combined effect of UVB and NPs co-exposure. To test this hypothesis, the effects of dextran-coated SPION of different sizes (15-50 nm) and manufacturers (MicroMod, Rostock-Warnemunde, Germany and KTH-Royal Institute of Technology, Stockholm, Sweden) were evaluated in two cell lines: normal human epidermal keratinocytes (HEK) and murine epidermal cells (JB6 P+). HEK cells exposed to 20 nm (KTH and MicroMod) had a decrease in viability, while the 15 and 50 nm particles were not cytotoxic. HEK cells were also capable of internalizing the KTH particles (15 and 20 nm) but not the MicroMod SPION (20 and 50 nm). IL-8 and IL-6 were also elevated in HEK cells following exposure to SPION. Exposure of JB6 P+ cells to all SPIONs evaluated resulted in activation of AP-1. Exposure to SPION alone was not sufficient to induce NF-kappa B activation; however, co-exposure with UVB resulted in significant NF-kappa B induction in cells exposed to 15 and 20 nm KTH SPION and 50 nm MicroMod particles. Pre-exposure of JB6 P+ cells to UVB followed by NPs induced a significant depletion of glutathione, release of cytokines, and cell damage as assessed by release of lactate dehydrogenase. Altogether, these data indicate that co-exposure to UVB and SPIONs was associated with induction of oxidative stress and release of inflammatory mediators. These results verify the need to thoroughly evaluate the adverse effects of UVB when evaluating dermal toxicity of engineered NPs on skin.

Keyword
Nanoparticles, Skin exposure, Ultraviolet radiation, Iron oxide
National Category
Biochemistry and Molecular Biology Cell Biology
Identifiers
urn:nbn:se:kth:diva-134729 (URN)10.1007/s12013-012-9367-9 (DOI)000326282900024 ()2-s2.0-84886583005 (Scopus ID)
Funder
EU, FP7, Seventh Framework Programme, EC-FP-7-NANOMMUNE-214281
Note

QC 20131129

Available from: 2013-11-29 Created: 2013-11-28 Last updated: 2016-01-11Bibliographically approved
6. ZnO-PLLA Nanofiber Nanocomposite for Continuous Flow Mode Purification of Water from Cr(VI)
Open this publication in new window or tab >>ZnO-PLLA Nanofiber Nanocomposite for Continuous Flow Mode Purification of Water from Cr(VI)
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2015 (English)In: Journal of Environmental and Public health, ISSN 1687-9805, E-ISSN 1687-9813, Vol. 2015, 687094Article in journal (Refereed) Published
Abstract [en]

Nanomaterials of ZnO-PLLA nanofibers have been used for the adsorption of Cr(VI) as a prime step for the purification of water.The fabrication and application of the flexible ZnO-PLLA nanofiber nanocomposite as functional materials in this well-developedarchitecture have been achieved by growing ZnO nanorod arrays by chemical bath deposition on synthesized electrospun poly-Llactidenanofibers. The nanocomposite material has been tested for the removal and regeneration of Cr(IV) in aqueous solutionunder a “continuous flow mode” by studying the effects of pH, contact time, and desorption steps.Theadsorption of Cr(VI) speciesin solution was greatly dependent upon pH. SEM micrographs confirmed the successful fabrication of the ZnO-PLLA nanofibernanocomposite.Theadsorption and desorption of Cr(VI) species were more likely due to the electrostatic interaction between ZnOand Cr(VI) ions as a function of pH.The adsorption and desorption experiments utilizing the ZnO-PLLAnanofiber nanocompositehave appeared to be an effective nanocomposite in the removal and regeneration of Cr(VI) species.

Place, publisher, year, edition, pages
Hindawi Publishing Corporation, 2015
Keyword
Chromium, nanofibers, water purification
National Category
Materials Chemistry
Research subject
Chemical Engineering
Identifiers
urn:nbn:se:kth:diva-179870 (URN)10.1155/2015/687094 (DOI)26681961 (PubMedID)2-s2.0-84949238526 (Scopus ID)
Note

QC 20160111

Available from: 2016-01-04 Created: 2016-01-04 Last updated: 2016-11-01Bibliographically approved

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