(en)The present invention relates to a process for the detection and adsorption of arsenic from ground water and industrial waste water using lanthanide doped nanoparticles. More particularly, the present invention provides a process for the detection and adsorption arsenic in ppm level using Eu 0.05 Y 0.95 PO 4 nanoparticles.

1.ApplicationNumber: US-201515503577-A
1.PublishNumber: US-2017241970-A1
2.Date Publish: 20170824
3.Inventor: LUWANG MEITRAM NIRAJ
GHOSH DEBASISH

4.Inventor Harmonized: LUWANG MEITRAM NIRAJ(IN)
GHOSH DEBASISH(IN)

5.Country: US
6.Claims:
(en)The present invention relates to a process for the detection and adsorption of arsenic from ground water and industrial waste water using lanthanide doped nanoparticles. More particularly, the present invention provides a process for the detection and adsorption arsenic in ppm level using Eu 0.05 Y 0.95 PO 4 nanoparticles.

7.Description:
(en)FIELD OF THE INVENTION
The present invention relates to a process for the detection and adsorption of arsenic. More particularly, the present invention relates to a novel process for detection and adsorption of arsenic using lanthanide doped nanoparticles.
BACKGROUND AND PRIOR ART
Arsenic is a well-known carcinogen, and arsenic contamination of groundwater is a widespread occurrence affecting vast regions in India, Bangladesh, China, Mexico, Argentina, and the United States. According to World Health Organization (WHO), permissible limit of conc. of arsenic in water is 10 microgram per litre. Permissible limit of arsenic in industrial waste is 10 ppm. In ground water arsenic remains in two water soluble oxidation states, arsenic (III) and arsenic (V) among which Arsenic(III) is more toxic due to its soft nature. Higher conc. of arsenic in regular drinking water may cause several damages like hyperkeratosis, depigmentation, skin cancer, cancer in the lungs, bladder, liver, kidney and prostate. So detection and removal of arsenic from drinking water is very important for human health. Laboratory techniques used to detect arsenic are atomic fluorescence spectroscopy (AFS), graphite furnace atomic absorption (GFAA), inductively coupled plasma emission spectrophotometry (ICP-AES), inductively coupled plasma mass spectroscopy (ICP-MS),hydride generation atomic adsorption (HGAA), atomic absorption spectrometry (AAS) and neutron activation analysis. Although these methods can accurately measure arsenic in an environmental sample to microgram arsenic per liter concentrations, they require tedious sample preparation and pre concentration procedures, expensive instruments, and professional personnel. Moreover, they cannot be used as portable devices for on-site detection.
Article titled “Detection of trace amount of arsenic in groundwater by laser-induced breakdown spectroscopy and adsorption” by A Haider et al. published in Optics & Laser Technology, March 2014, 56, Pages 299-303 reports LIBS technique coupled with adsorption for the efficient detection of arsenic in liquid. Several adsorbents like tea leaves, bamboo slice, charcoal and zinc oxide have been used to enable sensitive detection of arsenic presence in water using LIBS. Arsenic in water at 1 ppm level reported by a combination of LIBS and adsorption by ZnO.
Article titled “Ultrasensitive mercury(II) ion detection by europium(III)-doped cadmium sulfide composite nanoparticles” by H Q Chen et al. published in Talanta, 2010, 83 (1), pp 139-144 reports Eu3+-doped cadmium sulfide composite nanoparticles synthesized through a straightforward one-pot process. The article also reports a process for the detection of trace Hg2+ in aqueous solutions.
US patent application no. 20110220577 discloses a process for the removal of arsenic and Cr(III&VI) from contaminated water using zinc peroxide nanoparticles which comprises treating the contaminated water containing arsenic and chromium with the nanoparticles of zinc peroxide in a ratio (w/v) ranging from 8:1 to 12:1 (mg/ml), having the concentration of arsenic, Cr(III&VI) contamination below 50 ppm in water, at ambient temperature, for a period of 5-10 min, followed by filtration to obtain the desired low concentrated contamination permissible drinking water.
US patent application no. 20060207945 discloses a method for removing arsenic from an aqueous feed which comprises contacting said aqueous feed with solids consisting essentially of a compound containing cerium in the +4 oxidation state to oxidize and remove said arsenic from said feed and thereby produce an aqueous fluid having a reduced arsenic concentration as compared to said aqueous feed, wherein said solids consist essentially of cerium dioxide.
U.S. Pat. No. 6,197,201 discloses a process for removing or stabilizing arsenic and/or selenium from aqueous streams or slurries is provided that includes contacting the streams or slurry with a composition containing lanthanum chloride. The lanthanum chloride composition can optionally contain various lanthanides. These lanthanide series of elements includes the elements lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium.
PCT application no. 2012040650 discloses a method for treating water and/or a water handling system with one or more rare earths to decrease deposit formation and/or to remove a deposit, wherein the deposit material can comprise one or more of fluoride, arsenite, arsenate, antimonite, bismuthate, pnictogon and the term “Rare earth” refers to one or more of yttrium, scandium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium erbium, thulium, ytterbium, and lutetium.
Article titled “Removal of arsenite and arsenate ions from aqueous solution by basic yttrium carbonate” by S A Wasay et al. published in Water Research, 1996, 30 (5), pp 1143-1148 reports a new method to remove arsenite and arsenate ions from aquatic systems by using basic yttrium carbonate (BYC). The removal by adsorption of arsenite and arsenate ions was reported to be >99% depending on initial concentration in the pH range of 9.8-10.5 and 7.5-9.0, respectively.
U.S. Pat. No. 7,338,603 discloses a process for removing oxyanions of an element using a sorbent comprising one or more rare earth compounds to remove one or more of said oxyanions, wherein the rare earth compounds are selected from lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, yttrium and scandium.
Therefore, a new highly effective, reliable, and economical technique is needed to meet the new lowered arsenic maximum contaminant level. The prior cited references indicated about the detection of Arsenic in water in the range of 1-50 ppm level by a combination of LIBS and adsorption by ZnO, Zinc peroxide, Cerium dioxide, lanthanide chloride, yttrium carbonate, etc. Compared to other known and reported techniques, the present invention of arsenic removal systems using adsorption usually do not take up a large amount of space or require additional chemicals for treatment of the water, and do not generate sludge that must be disposed of.
OBJECTIVE OF INVENTION
The main objective of the present invention is to provide a simple and rapid method for the detection and adsorption of arsenic.
Another objective of the present invention is to provide a rapid method for detection of arsenic that may be applicable on field or at the spot of contamination.
SUMMARY OF THE INVENTION
Accordingly, the present invention provides a novel process for detection and adsorption of arsenic using lanthanide doped nanoparticles.
In a preferred aspect, the present invention provides arsenic detection in ppm level using Eu 0.05 Y 0.95 PO 4 nanoparticles.



BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 : XRD patterns of Eu 3+ :YPO 4 (as prepared, water treated, arsenic adsorbed at pH=1.5 and 3.5) along with JCPDS No. 42-0082 and 11-0254.
FIG. 2 : PL spectra of arsenic YPO 4 :Eu 3+ after arsenic adsorption at pH=1.5 and 3.5 along with variation of asymmetric ratio.
FIG. 3 : PL spectra of Chlorine effect.
FIG. 4 : Life time measurements of arsenic and chloride adsorbed samples.
FIG. 5 : XPS spectra of the arsenic adsorbed sample.
FIG. 6 : TEM images of Eu 3+ :YPO 4 nanomaterials treated with As solution, SAED pattern and the lattice fringe.
FIG. 7 : SEM images and EDAX spectra of arsenic adsorbed Eu 3+ :YPO 4 nanoparticles.
FIG. 8 : Raman spectra of Eu 3+ :YPO 4 at different concentrations of As solution (a) 0, (b) 80 and (c) 100 ppm.
FIG. 9 : Schematic diagram for the interaction of As ion with the nanomaterials.



DETAILED DESCRIPTION OF THE INVENTION
The invention will now be described in detail in connection with certain preferred and optional embodiments, so that various aspects thereof may be more fully understood and appreciated.
As used herein, “adsorption” refers to the adherence of atoms, ions, molecules, polyatomic ions, or other substances of a gas or liquid to the surface of another substance, called the adsorbent. The attractive force for adsorption can be, for example, ionic forces such as covalent, or electrostatic forces, such as van der Waals and/or London's forces.
Accordingly, the inventors disclose arsenic detection in ppm level using Eu 0.05 Y 0.95 PO 4 nanoparticles.
In view of above, the present invention provides a process for flourimetric or Raman spectroscopy detection of Arsenic in water comprising lanthanide doped nanoparticles is disclosed herein, wherein the limit of detection of Arsenic is 10 ppm.
In an embodiment, the present invention provides a process for flourimetric or Raman spectroscopy detection of arsenic in water comprising:
a. Adding lanthanide doped nanomaterials to arsenic solution with >9 ppm at a pH in the range of 1 to 6; b. Analyzing the arsenic adsorbed on nanoparticles of the solution of step (a) to obtain photoluminescence effect.

In preferred embodiment, the lanthanide doped nanoparticle comprises europium and ytterbium.
In another preferred embodiment, the lanthanide doped nanoparticle is Eu 0.05 Y 0.95 PO 4 .
In another preferred embodiment, the size of lanthanide doped nanoparticle is 1-2 μm in length and 20 nm in width.
The arsenic containing water is selected from hard or soft ground water, effluent, domestic or potable water.
The process of the present invention can detects arsenic at a concentration greater than 9 ppm.
In one embodiment, the present invention provides Eu 3+ (5%) doped hexagonal YPO 4 nanoparticles prepared by co-precipitation method and are used for arsenic detection.
In another preferred embodiment the present invention provides Eu 3+ (5%) doped hexagonal YPO 4 nanoparticles which are stable in acidic medium.
Adsorption of arsenic on the surface of lanthanide doped nanoparticles reduces the luminescence intensity of the doped lanthanide ions. This change in luminescence property may be used to detect arsenic in ground water and the lanthanide doped nanomaterials are also a good adsorbent. In the emission spectra of Eu 3+ , intensity ratio of magnetic transition (591 nm) and the electrical transition (617 nm) is influenced by the environment around the lanthanide ion.
In yet another preferred embodiment, the invention provides a process of detection of Arsenic wherein the process detects arsenic at a concentration greater than 9 ppm.
In another aspect, the present invention provides using the luminescence enhancement and quenching properties of the nanoparticles for the detection of both arsenic and arsenous acid in the industrial waste.
In still another aspect, the lanthanide doped Eu 0.05 Y 0.95 PO 4 nanoparticles may be synthesized by methods known in the art.
In an embodiment of the invention, the present invention provides a process, which detects arsenic at a concentration greater than 9 ppm, producing visual change in luminescence.
In a preferred embodiment, the nanoparticles are synthesized by co-precipitation method.
Amount of arsenic adsorbed by the nanoparticles are measured by inductively coupled plasma atomic emission spectroscopy (ICP-AES). (Table 2)
The following examples, which include preferred embodiments, will serve to illustrate the practice of this invention, it being understood that the particulars shown are by way of example and for purpose of illustrative discussion of preferred embodiments of the invention.
EXAMPLES
Reagents and Materials:
Yttrium(III) nitrate hexahydrate, Y(NO 3 ) 3 , 6H 2 O (99.9%), ammonium dihydrogen phosphate, (NH 4 )H 2 PO 4 (99.999%), polyethylene glycol (PEG) from Sigma-Aldrich. Arsenic(III) oxide, As 2 O 3 sodium hydroxide, hydrochloric acid, Glycerol from Merck was used without further purification. Deionized water was used throughout the experiment.
Example 1
Synthesis of YPO 4 :Eu 3+ Nanorods
Eu 0.05 Y 0.95 PO 4 nanoparticles were synthesised by co-precipitation method. Stoichoimetric amounts of Y(NO 3 ) 3 .6H 2 O (1.582 g), Eu(NO 3 ) 3 .5H 2 O (0.093 g), and 3 g of PEG were dissolved in a mixture of 40 ml of water and 60 ml of ethylene glycol (EG). The mixture was stirred at 80° C. for half an hour. Then a solution of 0.5 g of (NH 4 )H 2 PO 4 in 10 ml of deionised water was added slowly to the reaction mixture and refluxed at 140° C. for three hour in a 250 ml round bottom flask fitted with a condenser under water circulation. The resulting white precipitate was collected by centrifuging at 10,000 rpm after washing with water and methanol. The precipitate was dried in an oven at 100° C. temperature and used as sensing material for arsenic. ( FIG. 1 )
Example 2
Preparation of 100 ppm Arsenic (III) Solution: (FIG. 2 , 3 )


At pH=1.5


132 mg of As 2 O 3 was dissolved in 10 ml 1(N) NaOH solution. 2 ml conc. HCl was added and diluted with deionised water to 100 ml. This solution was further diluted with 2% (V/V) HCl solution to 1000 ml to get an arsenic solution of 100 ppm strength. pH of this arsenic solution is 1.5.
At pH=3.5

132 mg of As 2 O 3 was dissolved in 10 ml 1(N) NaOH solution. 1 ml conc. HCl was added and diluted with deionised water to 100 ml. This solution was further diluted with 1% (V/V) HCl solution to 1000 ml to get an arsenic solution of 100 ppm strength. pH of this arsenic solution is 3.5. These standard arsenic solutions were further diluted with 2% and 1% of HCl solutions respectively to get solutions of different concentrations. Only freshly prepared arsenic solutions were used for surface adsorption reactions to prevent arial oxidation of arsenic.
Example 3
Adsorption of Arsenic on YPO 4 :Eu 3+ Surface
To each 50 ml solution of arsenic of different conc. (100 ppm, 80 ppm, 60 ppm, 40 ppm, 20 ppm, 10 ppm), 0.15 g of Eu 0.05 Y 0.95 PO 4 nanoparticles were added and stirred at room temperature for three hours. Then the arsenic adsorbed nanoparticles were collected by centrifuging at 10000 rpm and washing with methanol. These collected nanoparticles were dried at 150° C. temperature and their corresponding analyses were performed. ( FIG. 4-9 )
Example 4
Photoluminescence Study
Photoluminescence study of pure nanoparticles and arsenic adsorbed nanoparticles were performed. On excitation at 375 nm and 395 nm Eu 3+ showed its characteristic red light emission. The experimental study indicates that on arsenic adsorption, luminescence intensity is much reduced. This decrease in luminescence intensity due to adsorption (surface complex formation and non-radiative thermal quenching) may be used to detect arsenic conc. in ground water. (Table 1)
At pH=1.5 the electronic predominates over magnetic transition with increase in the arsenic concentration which we observed in the increasing asymmetric ratio (I AS ). At pH=3.5 electronic transition and magnetic transitions are almost equal or magnetic transition predominating.
To determine the amount of arsenic adsorbed by the nanoparticles inductively coupled plasma mass spectroscopy was performed with mother and the filtrate arsenic solutions. The ICP-AES analysis shows that some definite quantity of the arsenic species is adsorbed by the nanoparticles. Amount of adsorption is higher at higher concentration of arsenic and it is low at lower concentration. This analysis support the interaction of arsenic with the nanoparticles and the enhancement trend observed in the luminescence spectra. (Table 2)





TABLE 1



Relation between arsenic concentration and asymmetric ratio (I).






Area of peak








Electric
Magnetic









Arsenic
transitions
transitions
Asymmetric

Sl.
Concentration
( 5 D 0 → 7 F 2 )
( 5 D 0 → 7 F 1 )
ratio

No.
(ppm)
(A e )
(A m )
(I = A e /A m )










1
pH = 1.5
0
112374.21938
119382.59727
0.94

2

10
143034.95019
143748.94145
0.99

3

20
144614.91105
141406.28489
1.02

4

60
178697.97057
173600.00968
1.03

5

100
191237.05734
165359.29374
1.15

6
pH = 3.5
0
216934.30064
229095.76553
0.94

7

10
119028.93677
209459.68526
0.56

8

40
111569.8393
185278.86541
0.60

9

60
99067.39673
174811.64582
0.56

10

80
83159.20339
91497.84235
0.90

11

100
70293.04284
74149.92192
0.94

















































TABLE 2



ICP-AES data showing percentage change in As concentration.








Mother
Filtrate
Change in


Sl.
solution
solution
concentration
%

no.
(ppm)
(ppm)
(ppm)
change









1
67.022
61.265
5.757
8.58

2
53.655
50.05
3.605
6.72

3
39.45
38.205
1.245
3.15

4
26.165
24.89
1.275
4.87

5
12.265
12.055
0.21
1.71

6
6.405
6.355
0.05
0.78































Results
The photoluminescence study of pure nanoparticles and arsenic adsorbed nanoparticles are performed. On excitation at 375 nm and 395 nm Eu 3+ showed its characteristic red light emission. The experimental study indicates that on arsenic adsorption, luminescence intensity is much reduced. This decrease in luminescence intensity due to adsorption (surface complex formation and non-radiative thermal quenching) may be used to detect arsenic conc. in ground water. (Table 1) At pH=1.5 the electronic predominates over magnetic transition with increase in the arsenic concentration which is observed in the increasing asymmetric ratio (I AS ). At pH=3.5 electronic transition and magnetic transitions are almost equal or magnetic transition predominating. To determine the amount of arsenic adsorbed by the nanoparticles inductively coupled plasma mass spectroscopy are performed with mother and the filtrate arsenic solutions. The ICP-AES analysis shows that some definite quantity of the arsenic species is adsorbed by the nanoparticles. Amount of adsorption is higher at higher concentration of arsenic and it is low at lower concentration. This analysis support the interaction of arsenic with the nanoparticles and the enhancement trend observed in the luminescence spectra. (Table 2).
Advantages of Invention:
Detects very low concentration of As
Avoids expensive analytical instruments
Portable kits may be made, making detection on site easy
Works for analyte that may be hard or soft ground water, effluent, domestic or potable.