Functionalization of chitosan with 3-nitro-4-amino benzoic acid moiety and its application to the collection/concentration of molybdenum in environmental water samples

Abstract

A chitosan resin functionalized with 3-nitro-4-amino benzoic acid moiety (CCTS-NABA resin) was newly synthesized for the collection/concentration of trace molybdenum by using cross-linked chitosan (CCTS) as base material. The carboxyl group of the moiety was chemically attached to amino group of cross-linked chitosan through amide bond formation.The adsorption behavior of molybdenum as well as other 60 elements on the resin was examined by passing the sample solutions through a mini-column packed with the resin. After the elution of the elements collected on the resin with 1 M HNO 3 , the eluates were analyzed by inductively coupled plasma-mass spectrometry (ICP-MS) and -atomic emission spectrometry (ICP-AES).The CCTS-NABA resin can adsorb several metal ions, such as vanadium, gallium, arsenic, selenium, silver, bismuth, thorium, tungsten, tin, tellurium, copper, and molybdenum at appropriate pHs. Among these metal ions, only molybdenum could be adsorbed almost completely on the resin at acidic regions. An excellent selectivity toward molybdenum could be obtained at pH 3-4. The adsorption capacity of CCTS-NABA resin for Mo (VI) was 380 mg g -1 resin. Through the column pretreatment, alkali and alkaline earth metals in river water and seawater samples were successfully removed.The CCTS-NABA resin was applied to the adsorption/collection of Molybdenum in river water and seawater samples. The Concentrations of molybdenum in river water samples were found in the range of 0.84 and 0.95 ppb (ng g -1 ), whereas molybdenum in seawater was about 9 ppb. The validation of the proposed method was carried out by determining molybdenum in the certified reference materials of SLRS-4, CASS-4, and NASS-5 after passing through the CCTS-NABA resin; the results showed good agreement with the certified values.

Pre-Concentration and Determination of Molybdenum in the Rouge River, Michigan, USA, with Graphite Furnace Atomic Absorption Spectrometry

“…Our average concentration is in line with the mean reported levels for the Aliakmonas and Pinios (Karamanis, Stamoulis, Ionndes, & Patiris, 2008), and the Thames and Great Ouse (Neal & Robson, 2000). However, our average molybdenum concentration is about three times the value reported for the Seine and more than four times that of the Marne (Elbaz-Poulichet, Seidel, Casiot, & Tusseau-Vuillemin, 2006), and Asahi and Zasu (Sabarudin, Oshima, Noguchi, & Motomizu, 2007). The average molybdenum Rouge River concentration is more than three times the values of the upper range of the Aare River (Neubert et al, 2011), and the lower range of the Chang Jiang River (Neubert et al, 2011), and it is also six times the concentrations of the lower ranges of Aare river and more than ten times the concentration of the upper range of the Kleine Emme rivers (Neubert et al, 2011).…”

“…The direct determination of molybdenum in natural water with flame atomic absorption spectrometry (FAAS), graphite furnace atomic absorption spectrometry (GFAAS) and inductively coupled plasma optical emission spectroscopy (ICP-OES) is difficult and challenging because of its low concentration and/or matrix interferences (Sabarudin, Oshima, Noguchi, & Motomizu, 2007;Ferreira, dos Santos, & Campos, 2003). Specifically, in the determination of molybdenum in natural water with GFAAS, the reproducibility of the data declines as the concentration of molybdenum reaches levels at or below 1 μg L -1 .…”

Chitosan and Its Derivatives as Highly Efficient Polymer Ligands

“…Aminoarylation is carried out using derivatives of aromatic amino acids, which enables one to consider this modification approach as an example of functionalization by aliphatic aminoacids, including standard acylation reactions ( 22N – 25N , Figure 2) [63,64,65,66]. One should mention that to form the amide group, a carbodiimide coupling reagent and pre-crosslinked chitosan are often used [63,66,67], while the less often used method here is more accessible water distillation [64,65]. In the latter case, the authors did not perform extra crosslinking.…”

Application of chitosan and its N-heterocyclic derivatives for preconcentration of noble metal ions and their determination using atomic absorption spectrometry

“…However, high affinity of chitosan and high selectivity of its chemically modified derivatives to many metal ions promote the interest to application of these materials to preconcentrate metal ions from wastewaters, natural waters, and biological and geological samples for subsequent analytical determination using atomic absorption spectrometry (ААS) (Suneetha, Kumar, Harinath, Reddy, & Seshaiah, 2012;Wan, Wang, & Qian, 2002;Wang, Li, Bao, Liu, & Liu, 2011), atomic emission spectrometry (ICP-AES) (Sabarudin, Oshima, Noguchi, & Motomizu, 2007), inductively coupled plasma-mass spectrometry (ICP-MS) (Katarina, Takayanagi, Oshima, & Motomizu, 2006;Sabarudin et al, 2007) and other techniques (Shinde et al, 2013).…”