Next Article in Journal
On the Delayed Scaled Consensus Problems
Previous Article in Journal
Numerical Study on Dynamic Response of a Horizontal Layered-Structure Rock Slope under a Normally Incident Sv Wave
 
 
Search for Articles:
Title / Keyword
Author / Affiliation / Email
Journal
Article Type
 
 
Advanced Search
 
Section
Special Issue
Volume
Issue
Number
Page
 
Journals
Applied Sciences
Volume 7
Issue 7
10.3390/app7070715
applsci-logo
Submit to this Journal Review for this Journal Propose a Special Issue
► Article Menu

Article Menu

share Share announcement Help format_quote Cite question_answer Discuss in SciProfiles thumb_up
...
Endorse textsms
...
Comment
first_page
settings
Order Article Reprints
Font Type:
Arial Georgia Verdana
Font Size:
Aa Aa Aa
Line Spacing:
Column Width:
Background:
Article

Reduction of Hexavalent Chromium Using Sorbaria sorbifolia Aqueous Leaf Extract

by
Shashi Prabha Dubey
1,
Mika Sillanpaa
1,2 and
Rajender S. Varma
3,*
1
Laboratory of Green Chemistry, Lappeenranta University of Technology, Sammonkatu 12 (Innovation Center for Safety and Material Technology, TUMA), 50130 Mikkeli, Finland
2
Department of Civil and Environmental Engineering, Florida International University, Miami, FL 33174, USA
3
Regional Centre of Advanced Technologies and Materials (RCPTM), Faculty of Science, Palacky University, Olomouc, Šlechtitelů 11, 783 71 Olomouc, Czech Republic
*
Author to whom correspondence should be addressed.
Appl. Sci. 2017, 7(7), 715; https://doi.org/10.3390/app7070715
Submission received: 19 June 2017 / Revised: 5 July 2017 / Accepted: 6 July 2017 / Published: 11 July 2017
(This article belongs to the Section Chemical and Molecular Sciences)
Browse Figures
Versions Notes

Abstract

:
Aqueous plant leaves extract (PLE) of an abundant shrub, Sorbaria sorbifolia, was explored for the reduction of hexavalent chromium, Cr(VI), to trivalent chromium, Cr(III). The effect of contact time, pH, PLE quantity, ionic strength, hardness, temperature and effective initial Cr(VI) ion concentration were tested; Cr(VI) reduction followed the pseudo-first order rate kinetics and maximum reduction was observed at pH 2. Significantly, Cr(VI) reduction efficacies varied from 97 to 66% over the pH range of 2 to 10, which bodes well for PLE to be used for the reduction of Cr(VI) also at a higher pH. PLE-mediated Cr(VI) reduction displays considerable efficiency at various ionic strengths; however, hardness strongly affects the reduction ability. Higher temperature significantly enhances the Cr(VI) reduction. This study reveals the potential use of PLE as a green reducing agent in aqueous extract for the efficient reduction of Cr(VI) to Cr(III).

Graphical Abstract

1. Introduction

Chromium is a naturally occurring transition metal, found in contaminated soils, groundwater and drinking water, with the two most common oxidation states of chromium being trivalent, Cr(III) and hexavalent, Cr(VI). Cr(III) is an essential element in human nutrition and plays an important role in carbohydrate, protein and lipid metabolism [1], whereas Cr(VI) is soluble, relatively more mobile than Cr(III) [2] and toxic; Cr(VI) is a known carcinogen and mutagen [3,4]. The erosion of natural chromium deposits, oxidation of Cr(III), anthropogenic activities (dying, electroplating, leather tanning) and other industrial applications have been responsible for chromium contamination in the environment [5].
Many remediation strategies have been advanced to deal with Cr(VI) pollution, including adsorption [6], ion exchange [7], chemical precipitation [8], membrane filtration [9] and reduction [10,11,12,13,14,15,16,17], among others. The reduction of Cr(VI) is among the most widely used strategies in view of the redox activity of chromium. Reductive remediation approaches can address the toxicity of Cr(VI) by transformation into Cr(III), that can be easily removed after precipitation with alkaline substances [8]. Several synthetic and natural electron-rich compounds are capable of reducing Cr(VI): Fe(II) bearing clay minerals, zero-valent aluminum and Mn(II) have been reported as reducing, and being catalyzing agents in the reduction processes of Cr(VI) [10,11,12]. Natural organic acids including citric, oxalic, ascorbic, tartaric and formic acid have also been examined for the reduction of Cr(VI) from contaminated aqueous and soil matrices [13,14,15,16]. In general, compounds bearing aliphatic or aromatic hydroxyl groups have been found suitable for the reduction of Cr(VI) [15,17].
Most of the remediation-by-reduction strategies described in the literature entail a sharp decrease in reduction rates for a higher pH, but they are effective only at lower pH levels, which thus presents a challenge for more alkaline Cr(VI) contaminated sites [15]. Sarkar et al. report 100% Cr(VI) reduction efficiency at pH 2.25 that becomes negligible at pH > 7.5 [12]. Similarly, Lan et al. observed that montmorillonite and illite significantly catalyze the reduction of Cr(VI) by citric acid at pH < 5.0; in contrast, their effectiveness are dramatically diminished at pH 5.0 [18].
Aqueous plant extracts have been extensively utilized for the synthesis of metal nanoparticles via the reduction of noble metal ions [19,20]; the presence of multiple hydroxy and carboxylic acids groups serve as mild reduction and capping agents [21,22]. Thus, the use of an aqueous plant extract (PLE) for the reduction of Cr(VI) to Cr(III) is a viable strategy. A local abundant shrub, Sorbaria sorbifolia, was selected for this study, since it grows rapidly and contains polyhydroxy constituents in its aerial part i.e., Kaempferol 3-arabofuranoside (C20H18Ol0), Astragalin (C21H20O11), Quercetin 3-glucuronide (C21H18O13), Isorhamnetie 3-glucoside (C22H22O12), Scutellarein (C21H18O12·H2O), Chlorogenic acid (C18H18O9), Arbutin (C12H16O7) and Sorbifolin (C16H12O6) [23,24,25]. Importantly, the reductive capability of its aqueous extract for the conversion of Cr(VI) to Cr(III) has been hitherto unexplored. One of the primary objectives of the present study is to conduct the reduction of Cr(VI) over a wide-range of pH and diverse environmental settings. In this article, aqueous plant extract mediated reduction of Cr(VI) is investigated and the effects of the concentration of plant extract, pH, ionic strength, temperature, initial concentration of Cr(VI) ions and hardness are examined.

2. Materials and Methods

2.1. Reagents

Potassium dichromate (K2Cr2O7), sodium chloride (NaCl), calcium carbonate (CaCO3), sulphuric acid (H2SO4), sodium hydroxide (NaOH), 1,5-diphenylcarbazide (DPC) and acetone were purchased from Sigma-Aldrich Co., St. Louis, MO, USA. All chemicals used in the study were of reagent grade and used without further purification. All solutions were prepared using 18 MΩ·cm Milli-Q water from a Millipore system.

2.2. Preparation of PLE

Sorbaria sorbifolia’s leaves were collected locally from Mikkeli, Finland. Leaves were separated from other sections of the plant and washed three times with ultrapure water to remove any dirt. Washed plant leaves were dried at room temperature for 12 h and 75 g leaves were boiled in 250 mL ultrapure water in an Erlenmayer flask (500 mL) for 120 min. After cooling to room temperature, the solution was filtered through a Whatman filter paper (no. 40) and the filtrate was stored at −20 °C, labeled as plant leaves extract (PLE) and used as such for the reduction of Cr(VI) solutions.

2.3. Reduction and Analysis of Cr(VI)

The potential of PLE as a green reductant was assessed for Cr(VI). A 1000 mg/L stock solution of Cr(VI) was prepared from K2Cr2O7 in a 1000 mL volumetric flask and stored in a glass bottle at room temperature. PLE was added to 25 mL of freshly prepared Cr(VI) solution (10 mg/L) prepared by diluting the stock solution. Cr(VI) concentration was measured by colorimetric DPC method using a UV-Vis spectrophotometer (Perkin-Elmer Lamda-45, Waltham, MA, USA) at 540 nm [26]. DPC solution was prepared by dissolving 250 mg of DPC in 50 mL acetone and stored in a brown bottle at 4 °C. The method combines the acidification of the Cr(VI) solution by H2SO4 followed by the addition of DPC. For analysis, 0.25 mL of samples were diluted to 5 mL with ultrapure water and Cr(VI) was analyzed by DPC method after complete color development.
The effect of different parameters was examined to observe the potential of PLE for Cr(VI) reduction. Solution pH (2–10), contact time (0–90 min), PLE quantity (0.5–2.5 mL), ionic strength (0–500 mM), hardness (0.5–5 mM), temperature (278–333 K) and initial Cr(VI) concentration (5–80 mg/L), were evaluated for Cr(VI) reduction using PLE. Solution pH was adjusted with 0.1 M H2SO4 and NaOH. NaCl and CaCO3 were utilized to adjust the ionic strength and hardness. Experiments were performed in triplicate and the average value and standard deviations are presented. Functionality of PLE was measured by Fourier Transform Infrared Spectroscopy (FTIR, Nicolet 6700, Thermo Fisher, Waltham, MA, USA) using a spectral range of 4000–400 cm−1 with resolution of 4 cm−1.

3. Results

3.1. Reduction Efficacies of PLE

3.1.1. Effects of Contact Time and Rate Kinetics

The reduction of Cr(VI) by PLE over varying contact times is presented in Figure 1a. A sharp increase in Cr(VI) reduction efficiency was observed with increasing contact time and more than 90% reduction efficiency was discerned in the first 20 min. Thereafter, the reduction efficiency reached 97% in 60 min, with no further increase in reduction efficiency by increasing contact time. Hence, 60 min contact time was optimized for all other experiments. Pseudo first-order rate kinetics for PLE mediated Cr(VI) reduction was determined. ln(C/C0) was plotted against time and the rate constant was determined from the linear part using regression analysis (Figure 1b). A high correlation coefficient (R2 = 0.957) signifies that the reduction of Cr(VI) by PLE follows pseudo-first order kinetics. The rate constant was obtained from the regression equation and was found to be 0.0835 min−1.

3.1.2. Effects of pH

The effects of varying pH on Cr(VI) reduction efficiency is shown in Figure 2. As indicated, pH plays a crucial role on Cr(VI) using PLE. At pH 2, 97% was Cr(VI) was reduced to Cr(III) in 60 min, which decreased to 77% at pH 4. From pH 6 to 10, Cr(VI) reduction efficacies varied from 69 to 66%, which is an important finding and PLE can also be utilized to reduce Cr(VI) in an alkaline medium. The reduction of Cr(VI) under varying solution pH has been studied previously and most of the reductants have either too low or no ability to reduce Cr(VI) in alkaline media [27,28]. In contrast, PLE could be used as a green reductant to successfully remediate Cr(VI) across a wider range of pH; acidic solution has the maximum reduction efficiency when compared to neutral and alkaline solutions.

3.1.3. Effects of PLE Quantity

A quantitative range of PLEs were examined to reduce Cr(VI) and the ensuing results are presented in Figure 3; Cr(VI) reduction efficiency increases with increasing PLE quantity. In lower PLE amounts (0.5 mL), 54% of Cr(VI) is converted to Cr(III) within 5 min contact time, which increases to a maximum of 63% in 60 min. Increasing PLE quantity to 1.5 mL, efficiency enhancement varies from 79–97% in 5–60 min, respectively. Further increasing the PLE quantity to the maximum value of 2.5 mL, increases the value to 90%, but reduction efficiency at 60 min is virtually unchanged and remains similar to the maximum value (97%) attained using 1.5 mL of PLE; 1.5 mL of PLE is subsequently used in the other set of experiments.

3.1.4. Effects of Ionic Strength

It is imperative to explore the relationship between varying ionic strength and PLE mediated Cr(VI) reduction, as several ionic species may be present in natural water systems. Ionic strength was adjusted by addition of NaCl to acquire the desired ionic strength. Cr(VI) reduction using our green reductant was tested at different ionic strength and contact time. The obtained results presented in Figure 4 reveal that Cr(VI) reduction ability decreased (96–88%) with increasing ionic strength (10–500 mM) but had less effect (~8%) at a wide range of ionic strength solutions and hence, PLE can be utilized for remediation of Cr(VI) from different aqueous sources, including fresh water (~8 to 10 mM) to sea water (~400 mM) content.

3.1.5. Effects of Hardness

Effect of hardness was also examined for the potential of PLE to affect Cr(VI) reduction. Hardness was adjusted by CaCO3 addition to Cr(VI) solutions to acquire the varying hardness levels (0.5–5 mM). The obtained results presented in Figure 5 reveal that Cr(VI) reduction efficiency decreased sharply with increasing hardness of the solution; 92% reduction efficiency is obtainable at 2 mM hardness level which decreases to 68% at 5 mM. Similar observations have been recorded in the literature which indicate that presence of Ca2+ hardness with carbonate has resulted in a substantial drop in Cr(VI) reduction efficiency [29,30]. It is important to emphasize that the divalent cation (Ca2+) has a more significant effect on Cr(VI) reduction efficiency than monovalent cations (Na+).

3.1.6. Effects of Temperature and Initial Cr(VI) Concentration

Effect of temperature (278–333 K) on Cr(VI) reduction was discerned and the result is presented in Figure 6. Initial Cr(VI) concentration of 30 mg/L was admixed with 1.5 mL of PLE and the mixture was kept at 278–333 K for 60 min. At 278 K, 71% reduction efficiency was observed whereas a significantly higher value of 97% could be attained at 333 K temperature.
The effect of initial Cr(VI) concentration on Cr(VI) reduction efficiency by PLE was examined by varying initial Cr(VI) concentration (5–80 mg/L); more than 92% of reduction efficiency was obtained, which decreased to 56% with increasing Cr(VI) concentration to 80 mg/L (Figure 7).

3.2. Comparison of the Present Study with Other Reductants

Our study demonstrates that reduction efficiency of PLE to convert Cr(VI) to Cr(III) is significant (97–66%) under a wide-ranging pH (2–10) conditions and occurs in an expeditious manner (short time, 60 min) when compared to other reductants documented in the literature (Table 1).

3.3. Possible Mechanism for Reduction Efficiency of PLE

The FTIR spectra of PLE sample is recorded in Figure 8d, which clearly shows absorption band at 3307, 1636, 1040 and 612 cm−1, suggesting the presence of –OH group [32], C=O group [33], C–O group [34], stretching C–H group bending frequencies.
The plant extracts usually contain sugars, glycosides, phenolics and even vitamins. Hydroxyl groups from sugars and phenolics can affect the reduction of metal salts including also vitamins [35,36,37,38,39,40,41,42]. Aerial parts of Sorbaria sorbifolia are known to contain a variety of polyphenols, flavonoids and glycosides [23,24,25]; glycosides are non-reducing sugars, but polyphenols and flavonoids are known antioxidants that serve as reducing agents [36,37,38,39] and are thus most likely responsible for the reduction of Cr(VI) to Cr(III) using ‘greener’ PLE as a reductant. A schematic presentation delineates the reduction mechanism (Figure 8a–c); captured image for the gradual conversion of carcinogenic Cr(VI) into nontoxic Cr(III) is shown in Figure 8e.

4. Conclusions

An aqueous plant leaf extract of Sorbaria sorbifolia was prepared and utilized as a green reductant for reduction of Cr(VI); reduction follows pseudo first order rate kinetics and 97% of Cr(VI) reduced in 60 min contact time. Cr(VI) reduction occurs over a wide pH range (pH 2–10) with maximum reduction efficiency at acidic pH (pH 2). PLE can be utilized for a wide variety of water sources, including fresh to sea water, with a moderate reduction efficiency for Cr(VI); a reduction in efficiency, however, occurs at increasing hardness in PLE mediated reduction. FTIR spectra of crude PLE indicates the presence of hydroxyl and carboxy compounds (polyphenols and flavonoids) in the aqueous extract may reduce Cr(VI) to Cr(III). The ensuing results suggest that PLE can be successfully utilized as a greener strategy for the reductive remediation of Cr(VI) in aqueous matrices.

Author Contributions

S.P.D. and M.S. conceived and designed the experiments; S.P.D. performed the experiments; M.S. and R.S.V. analyzed the data; all authors (S.P.D., M.S. and R.S.V.) wrote the paper.

Conflicts of Interest

The authors declare no conflict of interest.

References

  1. Xu, H.J.; Huang, R.L.; Li, T.J.; Kong, X.F.; Yin, Y.L. Nutritional and physiological functions of chromium. Nat. Prod. Res. Dev. 2010, 3, 531–534. [Google Scholar]
  2. Faybishenko, B.; Hazen, T.C.; Long, P.E.; Brodie, E.L.; Conrad, M.E.; Hubbard, S.S.; Christensen, J.N.; Joyner, D.; Borglin, S.E.; Chakraborty, R.; et al. Tokunaga, long-term reductive bioimmobilization of Cr(VI) in groundwater using hydrogen release compound. Environ. Sci. Technol. 2008, 42, 8478–8485. [Google Scholar] [CrossRef] [PubMed]
  3. Cheng, L.; Sonntag, D.M.; Boer, J.D.; Dixon, K. Chromium (VI)-induced mutagenesis in the lungs of big blue TM transgenic mice. J. Environ. Pathol. Toxicol. Oncol. 2000, 19, 239–249. [Google Scholar] [PubMed]
  4. Cohen, M.D.; Kargacin, B.; Klein, C.B.; Costa, M. Mechanisms of chromium carcinogenicity and toxicity. Crit. Rev. Toxicol. 1993, 23, 255–281. [Google Scholar] [CrossRef] [PubMed]
  5. Altundogan, H.S. Cr(VI) removal from aqueous solution by iron(III) hydroxide-loaded sugar beet pulp. Process Biochem. 2005, 40, 1443–1452. [Google Scholar] [CrossRef]
  6. Dubey, S.P.; Gopal, K. Adsorption of chromium (VI) on low cost adsorbents derived from agricultural waste material: A comparative study. J. Hazard. Mater. 2007, 145, 465–470. [Google Scholar] [CrossRef] [PubMed]
  7. Dharnaik, A.S.; Ghosh, P.K. Hexavalent chromium [Cr(VI)] removal by the electrochemical ion-exchange process. Environ. Technol. 2014, 35, 2272–2279. [Google Scholar] [CrossRef] [PubMed]
  8. Karale, R.S.; Wadkar, D.V.; Nangare, P.B. Removal and recovery of hexavalent chromium from industrial waste water by precipitation with due consideration to cost optimization. J. Environ. Res. Dev. 2007, 2, 209–216. [Google Scholar]
  9. Muthumareeswaran, M.R.; Alhoshan, M.; Agarwal, G.P. Ultrafiltration membrane for effective removal of chromium ions from potable water. Sci. Rep. 2017, 7, 41423. [Google Scholar] [CrossRef] [PubMed]
  10. Bishop, M.E.; Glasser, P.; Dong, H.; Arey, B.; Kovarik, L. Reduction and immobilization of hexavalent chromium by microbially reduced Fe-bearing clay minerals. Geochim. Cosmochim. Acta 2014, 133, 186–203. [Google Scholar] [CrossRef]
  11. Treviño, P.; Ibanez, J.G.; Vasquez-Medrano, R. Chromium(VI) reduction kinetics by zero-valent aluminum. Int. J. Electrochem. Sci. 2014, 9, 2556–2564. [Google Scholar]
  12. Sarkar, B.; Naidu, R.; Krishnamurti, G.S.R.; Meghara, M. Manganese(II)-catalyzed and clay-minerals-mediated reduction of chromium(VI) by citrate. Environ. Sci. Technol. 2013, 47, 13629–13636. [Google Scholar] [CrossRef] [PubMed]
  13. Xu, Z.; Bai, S.; Liang, J.; Zhou, L.; Lan, Y. Photocatalytic reduction of Cr(VI) by citric and oxalic acids over biogenetic jarosite. Mater. Sci. Eng. C 2013, 33, 2192–2196. [Google Scholar] [CrossRef] [PubMed]
  14. Xu, X.R.; Li, H.B.; Li, X.Y.; Gu, J.D. Reduction of hexavalent chromium by ascorbic acid in aqueous solutions. Chemosphere 2004, 57, 609–613. [Google Scholar] [CrossRef] [PubMed]
  15. Brose, D.A.; James, B.R. Hexavalent chromium reduction by tartaric acid and isopropyl alcohol in mid-atlantic soils and the role of Mn(III, IV)(hydr)oxides. Environ. Sci. Technol. 2013, 47, 12985–12991. [Google Scholar] [CrossRef] [PubMed]
  16. Yadav, M.; Xu, Q. Catalytic chromium reduction using formic acid and metal nanoparticles immobilized in a metal-organic framework. Chem. Commun. 2013, 49, 3327–3329. [Google Scholar] [CrossRef] [PubMed]
  17. Basu, A.; Saha, R.; Mandal, J.; Ghosh, S.; Saha, B. Removal of hexavalent chromium by an aromatic alcohol. J. Biomed. Sci. Eng. 2010, 3, 735–741. [Google Scholar] [CrossRef]
  18. Yeqing, L.; Chen, L.; Jingdong, M.; Jun, S. Influence of clay minerals on the reduction of Cr6+ by citric acid. Chemosphere 2008, 71, 781–787. [Google Scholar]
  19. Dubey, S.P.; Dwivedi, A.D.; Lahtinen, M.; Lee, C.; Kwon, Y.N.; Sillanpää, M. Protocol for development of various plants leaves extract in single-pot synthesis of metal nanoparticles. Spectrochim. Acta A 2013, 103, 134–142. [Google Scholar] [CrossRef] [PubMed]
  20. Dubey, S.P.; Lahtinen, M.; Sillanpää, M. Tansy fruit mediated greener synthesis of silver and gold nanoparticles. Process Biochem. 2010, 45, 1065–1071. [Google Scholar] [CrossRef]
  21. Nadagouda, M.N.; Varma, R.S. Green synthesis of silver and palladium nanoparticles at room temperature using coffee and tea extract. Green Chem. 2008, 10, 859–862. [Google Scholar] [CrossRef]
  22. Nadagouda, M.N.; Hoag, G.E.; Collins, J.B.; Varma, R.S. Green synthesis of Au nanostructures at room temperature using biodegradable plant surfactants. Cryst. Growth Des. 2009, 9, 4979–4983. [Google Scholar] [CrossRef]
  23. Zaitsev, V.G.; Makarova, G.V.; Komissarenko, N.F. Phenolic compounds of Sorbaria sorbifolia. Chem. Nat. Compd. 1969, 5, 598. [Google Scholar] [CrossRef]
  24. Zaitsev, V.G.; Makarova, G.V.; Komissarenko, N.F. Sorbifolin—A new flavone glycoside from Sorbaria sorbifolia. Chem. Nat. Compd. 1969, 5, 504–507. [Google Scholar] [CrossRef]
  25. Kim, D.K.; Zee, O.P. A new cyanogenic glycoside from Sorbaria sorbifolia var. stellipila. Chem. Pharm. Bull. 2000, 48, 1766–1767. [Google Scholar] [CrossRef] [PubMed]
  26. Eaton, A.D.; Clesceri, L.S.; Greenberg, A.E. Standard Methods for the Examination of Water and Wastewater, 19th ed.; APHA: Washington, DC, USA, 1995. [Google Scholar]
  27. Pettine, M.; Campanella, L.; Millero, F.J. Reduction of hexavalent chromium by H2O2 in acidic solutions. Environ. Sci. Technol. 2002, 36, 901–907. [Google Scholar] [CrossRef] [PubMed]
  28. Yurkow, E.J.; Hong, J.; Min, S.; Wang, S. Photochemical reduction of hexavalent chromium in glycerol-containing solutions. Environ. Pollut. 2002, 117, 1–3. [Google Scholar] [CrossRef]
  29. Lo, I.M.C.; Lam, C.S.C.; Lai, K.C.K. Hardness and carbonate effects on the reactivity of zero-valent iron for Cr(VI) removal. Water Res. 2006, 40, 595–605. [Google Scholar] [CrossRef] [PubMed]
  30. Karvonen, A. Cation effects on chromium removal in permeable reactive walls. J. Environ. Eng. 2004, 130, 863–866. [Google Scholar] [CrossRef]
  31. Mystrioti, C.; Sparis, D.; Papassiopi, N.; Xenidis, A.; Dermatas, D.; Chrysochoou, M. Assessment of polyphenol coated nano zero valent iron for hexavalent chromium removal from contaminated waters. Bull. Environ. Contam. Toxicol. 2015, 94, 302–307. [Google Scholar] [CrossRef] [PubMed]
  32. Yar, M.S.; Siddiqui, A.A.; Ali, M.A. Synthesis and antimycobacterial activity of novel heterocycles. J. Serb. Chem. Soc. 2007, 72, 5–11. [Google Scholar] [CrossRef]
  33. Rajarajan, K.; Anbarasan, K.; Solomon, J.S.; Madhurambal, G. XRD and FT-IR studies on lead (II) nitrate doped histidine picrate crystal: A nonlinear optical material. J. Chem. Pharm. Res. 2012, 4, 4060–4065. [Google Scholar]
  34. Oh, T.; Lee, K.-M.; Kim, K.S.; Choi, C.K. Comparison of the Nano-Structure due to C=O and C=C double bond. J. Korean Phys. Soc. 2004, 45, 705–708. [Google Scholar]
  35. Nadagouda, M.N.; Varma, R.S. Microwave-assisted shape-controlled bulk synthesis of noble nanocrystals and their catalytic properties. Cryst. Growth Des. 2007, 7, 686–690. [Google Scholar]
  36. Markova, Z.; Novak, P.; Kaslik, J.; Plachtova, P.; Brazdova, M.; Jancula, D.; Siskova, K.M.; Machala, L.; Marsalek, B.; Zboril, R.; et al. Iron(II,III)–polyphenol complex nanoparticles derived from green tea with remarkable ecotoxicological impact. ACS Sustain. Chem. Eng. 2014, 2, 1674–1680. [Google Scholar] [CrossRef]
  37. Stephen, A.; Seethalakshmi, S. Phytochemical synthesis and preliminary characterization of silver nanoparticles using hesperidin. J. Nanosci. 2013, 2013, 126564. [Google Scholar] [CrossRef]
  38. Hoag, G.E.; Collins, J.B.; Holcomb, J.L.; Hoag, J.R.; Nadagouda, M.N.; Varma, R.S. Degradation of bromothymol blue by ‘greener’ nano-scale zerovalent iron synthesized using tea polyphenols. J. Mater. Chem. 2009, 19, 8671–8677. [Google Scholar] [CrossRef]
  39. Nadagouda, M.N.; Castle, A.; Murdock, R.C.; Hussain, S.M.; Varma, R.S. In vitro biocompatibility of nanoscale zerovalent iron particles (nzvi) synthesized using tea polyphenols. Green Chem. 2010, 12, 114–122. [Google Scholar] [CrossRef]
  40. Nadagouda, M.N.; Varma, R.S. Green and controlled synthesis of gold and platinum nanomaterials using vitamin B2: Density-assisted self-assembly of nanospheres, wires and rods. Green Chem. 2006, 8, 516–518. [Google Scholar] [CrossRef]
  41. Nadagouda, M.N.; Varma, R.S. A greener synthesis of core (Fe, Cu)-shell (Au, Pt, Pd and Ag) nanocrystals using aqueous vitamin C. Cryst. Growth Des. 2007, 7, 2582–2587. [Google Scholar] [CrossRef]
  42. Nadagouda, M.N.; Polshettiwar, V.; Varma, R.S. Self-assembly of palladium nanoparticles: Synthesis of nanobelts, nanoplates and nanotrees using vitamin B1 and their application in carbon-carbon coupling reactions. J. Mater. Chem. 2009, 19, 2026–2031. [Google Scholar] [CrossRef]
Applsci 07 00715 g001 550
Figure 1. (a) Effects of contact time, [Cr(VI)]0 = 10 mg·L−1, Cr(VI) volume = 25 mL, contact time = 0–80 min, pH = 2, plant leaves extract (PLE) quantity = 1.5 mL; (b) Pseudo first order rate kinetics of Cr(VI) reduction.
Figure 1. (a) Effects of contact time, [Cr(VI)]0 = 10 mg·L−1, Cr(VI) volume = 25 mL, contact time = 0–80 min, pH = 2, plant leaves extract (PLE) quantity = 1.5 mL; (b) Pseudo first order rate kinetics of Cr(VI) reduction.
Applsci 07 00715 g001
Applsci 07 00715 g002 550
Figure 2. Effects of pH: [Cr(VI)]0 = 10 mg·L−1, Cr(VI) volume = 25 mL, contact time = 60 min, pH = 2–10, PLE quantity = 1.5 mL.
Figure 2. Effects of pH: [Cr(VI)]0 = 10 mg·L−1, Cr(VI) volume = 25 mL, contact time = 60 min, pH = 2–10, PLE quantity = 1.5 mL.
Applsci 07 00715 g002
Applsci 07 00715 g003 550
Figure 3. Effects of PLE quantity: [Cr(VI)]0 = 10 mg·L−1, Cr(VI) volume = 25 mL, contact time = 60 min, pH = 2, PLE quantity = 0.5–2.5 mL.
Figure 3. Effects of PLE quantity: [Cr(VI)]0 = 10 mg·L−1, Cr(VI) volume = 25 mL, contact time = 60 min, pH = 2, PLE quantity = 0.5–2.5 mL.
Applsci 07 00715 g003
Applsci 07 00715 g004 550
Figure 4. Effects of ionic strength: [Cr(VI)]0 = 10 mg·L−1, Cr(VI) volume = 25 mL, contact time = 60 min, pH = 2, PLE quantity = 1.5 mL, ionic strength = 10–500 mM.
Figure 4. Effects of ionic strength: [Cr(VI)]0 = 10 mg·L−1, Cr(VI) volume = 25 mL, contact time = 60 min, pH = 2, PLE quantity = 1.5 mL, ionic strength = 10–500 mM.
Applsci 07 00715 g004
Applsci 07 00715 g005 550
Figure 5. Effects of hardness: [Cr(VI)]0 = 10 mg·L−1, Cr(VI) volume = 25 mL, contact time = 60 min, pH = 2, PLE quantity = 1.5 mL, hardness = 0.5–5 mM.
Figure 5. Effects of hardness: [Cr(VI)]0 = 10 mg·L−1, Cr(VI) volume = 25 mL, contact time = 60 min, pH = 2, PLE quantity = 1.5 mL, hardness = 0.5–5 mM.
Applsci 07 00715 g005
Applsci 07 00715 g006 550
Figure 6. Effects of temperature: [Cr(VI)]0 = 30 mg·L−1, Cr(VI) volume = 25 mL, contact time = 60 min, pH = 2, PLE quantity = 1.5 mL, temperature = 278–333 K.
Figure 6. Effects of temperature: [Cr(VI)]0 = 30 mg·L−1, Cr(VI) volume = 25 mL, contact time = 60 min, pH = 2, PLE quantity = 1.5 mL, temperature = 278–333 K.
Applsci 07 00715 g006
Applsci 07 00715 g007 550
Figure 7. Effects of initial Cr(VI) concentration: [Cr(VI)]0 = 5–80 mg·L−1, Cr(VI) volume = 25 mL, contact time = 60 min, pH = 2, PLE quantity = 1.5 mL.
Figure 7. Effects of initial Cr(VI) concentration: [Cr(VI)]0 = 5–80 mg·L−1, Cr(VI) volume = 25 mL, contact time = 60 min, pH = 2, PLE quantity = 1.5 mL.
Applsci 07 00715 g007
Applsci 07 00715 g008 550
Figure 8. (a–c): Schematics describing reduction mechanism of Cr(VI) using polyphenols and flavonoids; (d) Fourier Transform Infrared Spectroscopy (FTIR) spectra of native PLE sample; and (e) Gradual conversion of carcinogenic Cr(VI) into nontoxic Cr(III).
Figure 8. (a–c): Schematics describing reduction mechanism of Cr(VI) using polyphenols and flavonoids; (d) Fourier Transform Infrared Spectroscopy (FTIR) spectra of native PLE sample; and (e) Gradual conversion of carcinogenic Cr(VI) into nontoxic Cr(III).
Applsci 07 00715 g008
Table
Table 1. Comparison of results using various reductants.
Table 1. Comparison of results using various reductants.
ReductantsInitial Cr(VI) Concentration pHContact TimeReduction EfficiencyReferences
Ferrous chloride (300 μM)50 μM7.2120 min100%[10]
Citrate (10 mM)192.32 μM2.2524 h12%[12]
Citrate (10 mM) + Mn(II) (182.02 μM)192.32 μM2.2524 h52%
Citrate (10 mM) + clay (3% (w/v))192.32 μM2.2524 h84%
Citrate (10 mM) + clay (3% (w/v)) + Mn(II) (182.02 μM)192.32 μM2.256 h100%
Oxalic acid (300 μM)50 μM320 min100%[13]
Ascorbic acid (300 μM)100 μM7120 min100%[14]
Tartaric acid (12 mM) + Isopropyl alcohol (0.29 M)2.0 mM499 h19%[15]
Russett soil (5 g)2.0 mM499 h25%
Russett soil (5 g) + Tartaric acid (12 mM) + Isopropyl alcohol (0.29 M)2.0 mM499 h99%
Punica granatum-nZVI (Fe(0) (1.53 mM))50 mg/L2.732 days96%[31]
PLE (1.5 mL)10 mg/L2–1060 min99–66%Present study

Share and Cite

MDPI and ACS Style

Dubey, S.P.; Sillanpaa, M.; Varma, R.S. Reduction of Hexavalent Chromium Using Sorbaria sorbifolia Aqueous Leaf Extract. Appl. Sci. 2017, 7, 715. https://doi.org/10.3390/app7070715

AMA Style

Dubey SP, Sillanpaa M, Varma RS. Reduction of Hexavalent Chromium Using Sorbaria sorbifolia Aqueous Leaf Extract. Applied Sciences. 2017; 7(7):715. https://doi.org/10.3390/app7070715

Chicago/Turabian Style

Dubey, Shashi Prabha, Mika Sillanpaa, and Rajender S. Varma. 2017. "Reduction of Hexavalent Chromium Using Sorbaria sorbifolia Aqueous Leaf Extract" Applied Sciences 7, no. 7: 715. https://doi.org/10.3390/app7070715

Note that from the first issue of 2016, this journal uses article numbers instead of page numbers. See further details here.

Article Metrics

Back to TopTop