Advanced Techniques for measurement of Heavy metal concentrations from seawater

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ABSTRACT One of the major challenges in recovery of uranium from seawater was to assure quality assurance by accurate measurement of heavy metal ion concentrations from lean solutions. To address the issue, nuclear analytical techniques play a key role. Nuclear Analytical Techniques (NATs) are based on nuclear properties of the trace level isotopes and have high sensitivity and accuracy and are important tools for chemical analysis. In this paper, the application of Nuclear Analytical Techniques such as Neutron Activation Analysis (NAA) and Solid State Nuclear Track Detection (SSNTD) methods for determining the concentrations of heavy metal ions from lean solutions like seawater is presented. The procedures and time required for analysis are standardized and comparison of results with non nuclear analytical techniques is made. Keywords: Seawater; Radiation processing; Nuclear Analytical Techniques; Uranium pick up; Neutron Activation Analysis ; Nuclear Track detection;

1.0 INTRODUCTION:
The rapid growth of Industry and commerce will lead to expanding demand for energy. We have no choice but to widen our options for energy availability and develop viable strategies for energy security. India seeks international co-operation in the field of civilian nuclear energy including China [1]. Uranium is important starting material for nuclear route. In view of the anticipated exhaustion of terrestrial uranium reserve in the future, research has been directed towards the recovery of uranium and other heavy metal ions from non conventional sources such as phosphoric acid and seawater. With its lean but clean resource, oceans can serve as constant potential source of uranium and other valuable heavy metals for a long run. Uranium is one of the most valuable metals in seawater. The total volume of the oceans has been estimated to be 2x109 km3 and uranium content of oceans must be of the order 4.5x109 tonnes [2-4]. Thus the oceans are virtually limitless reservoir of dissolved uranium in a well defined chemical environment. Various inorganic and organic adsorbents have so far been synthesized and evaluated at laboratory level [46]. With the development of radiation processing technology, special adsorbents are synthesized by radiation grafting of amidoxime groups in the form of leaflets, which provides efficient contact patterns with water body in the sea. Bench scale in-field trials were initiated to develop process technology [3-6]. One of the major challenges was to assure quality assurance by accurate measurement of heavy metal ion concentrations from lean solutions [58]. To address the above issues, nuclear analytical techniques are being developed. In this paper, the application of NATs such as Neutron Activation Analysis (NAA) technique and Solid State Nuclear Track Detection (SSNTD) methods for analyzing the concentrations of heavy metal ions from lean solutions like seawater is presented [8-10]. Researchers from Japan, which is another leading country, taken active interest in this research area of uranium recovery, has adopted non nuclear analytical techniques such as ICP-AES for measurement of U +6 concentrations in feed and other solutions. Comparison of results both by nuclear analytical techniques and nonnuclear techniques are presented along with statistical analysis.

2.0 NUCLEAR ANALYTICAL TECHNIQUES:

The NATs are based on nuclear properties of the trace level isotopes and have high sensitivity and accuracy and are important tools for chemical analysis. Suitable nuclear radiations ( , , and n ) are measured to estimate the concentration of radiation emitting isotope which in turn is used to determine the elemental concentration in contrast to non nuclear techniques. Non nuclear techniques such as AAS and ICP-MS utilize the properties of the atom as a whole. Nuclear analytical techniques are broadly classified as direct methods and indirect methods. Nuclear analytical techniques are quite useful and effective in view of capability of multi element analysis in a variety of samples and with good detection limits for a number of elements. These techniques are contamination free [7-10]. Uranium and thorium are naturally occurring elements which can be judiciously exploited to produce electricity for centuries without the threat of global warming. Monazite (major naturally occurring source of Th) contains 8-9% Th, whereas uranium ores are sometimes quite less. There has been wide interest to exploit other lean but abundant sources like rock phosphate and sea water for U recovery. Thus analysis of samples of ores, minerals and seawater for U is important for prospecting these resources. NATs like Neutron Activation Analysis (NAA), Xray Fluorescence (XRF), Passive Gamma ray Spectrometry (PGS) and Solid State Nuclear Track Detectors (SSNTD) play important role for qualitative as well as quantitative estimation of U in such important samples [710]. Whereas Instrumental NAA (INAA) , XRF and PGS are non-destructive in nature and capable of measuring concentrations of U and Th in ppm range, SSNTD, on the other hand, is very sensitive technique for ultra low concentrations of uranium (in ppb range).

2.1

Nuclear Activation Analysis(NAA):

This technique is based on irradiation of a sample with neutrons available from nuclear reactors and subsequent measurement of the induced radioactivity (b,g) for determination of the concentration of an element. Neutron fluxes in the range of 1011 to 1015 cm-2.s-1 are used. In NAA, the steps involved are: (i) Sampling (ii) Preparation of actual sample reference material (SRM) and control sample reference material (CRM) (iii) Preparation of the standards or single comparator (iv) Irradiation of samples and comparator in a reactor (v) Radioactive assay by high resolution -ray spectrometry (vi) Gamma spectra analysis for peak areas (vii) Evaluation of detection efficiency (for ko method) (viii) Calculation of elemental concentrations and (ix) Interpretation of the results. The koNAA method uses simultaneous irradiation of sample and a neutron flux monitor such as gold and the use of a composite nuclear constant called ko . The ko factor is defined as

k0 =

is the (n, ) cross section for thermal neutrons; is the abundance of the isotope of interest; M is the average atomic mass of the element; is the absolute gamma-ray abundance; The symbol * refers to the corresponding parameters of comparator (Au197). The concentration of element is calculated using

M * 0 M * 0 * * Where 0

1 f + Q0 ( ) * C ( g / g ) = S .D.C.W * N p / LT k0 f + Q0 ( ) S .D.C.w
*

N p / LT

Where N p - is the net counts; W and w - are masses of sample and single comparator; f-is sub cadmium to epi-

- is epi-thermal neutron flux ratio; - is efficiency of the detector; k0 , Q0 are two nuclear constants; S ( = 1 et ) - is the Saturation factor; D ( = e td ) - is the Decay factor; C ( = (1 e *CL / *LT )) - is the Correction factor; CL clock time of counting; LT live time of counting ; - is
thermal neutron flux ratio; decay constant (s-1); td is decay period; t is the duration irradiation Instrumental NAA (INAA) is a very good technique to analyze solid samples with lower mass range [910]. INAA is an isotope specific technique for simultaneous multielement determination in diverse matrices. It experiences negligible matrix effect and needs small sample size (50-100 mg) for analysis. In the present work, solid adsorbents (PAO) used for extraction of uranium from seawater were analyzed for U estimation. Three sets of solid samples (before and after elution) were analyzed by INAA using neutron irradiation at Apsara reactor at a neutron flux of 5x1011 cm-2.s-1 and radioactive assay by high resolution gamma ray spectrometry. Samples of about 100 mg mass and U-standards were packed in polythene and were irradiated for 7 hours in Apsara reactor. Radioactive assay of the daughter products of 239U (239Np, 2.27d, 106, 228 and 277 keV) were done by high-resolution gamma ray spectrometry using a 40% HPGe detector. Peak areas were determined by peak-fit software PHAST developed by Electronics Division, BARC. The relative method of INAA was used for calculation of concentration of heavy metal, the expression which is given below.

mx , sample =mx , std .

cps

x , sam ple x , std

cps

Dstd Dsample

Where mx, std and mx, sample are the masses of element,

cpsx.sample , cpsx.std are count rates and Dstd and Dsample are decay

factors of activation products of standard and sample respectively.

2.2 Nuclear Track Detection method(NTD):

Here the uranium target with the track detector placed on it is exposed to neutron flux. Polyester pieces of 2x2 cm2 are used as nuclear track detectors for registration of fission fragment tracks. In SSNTD, fission track registration is found to be much more sensitive compared to alpha track registration due to low alpha specific activity of uranium and high thermal neutron fission cross section. Solid State Nuclear Track detectors ( SSNTDs) are insulating solids both naturally occurring and man-made. There are several types of these detectors including inorganic crystals, glasses and plastics. When a heavily ionising charged particle (alpha, fission fragment, etc) passes through such insulating solids, it leaves a narrow trail of damage about 50 in diameter along its path. This is called 'Latent Track' as it cannot be seen with the naked eye. It is possible to view this latent track with an electron microscope. The exact nature of the physical and chemical changes occurring at the damage site depends on the charge (Z) and velocity ( = /c, where is the particle velocity and c is the velocity of light) of the particle, on the chemical structure of the detector material and also on the environmental conditions like temperature and pressure. These latent tracks can be enlarged / developed so that they can be viewed under an optical microscope by etching with some chemicals such as sodium hydroxide and hydrofluoric acid. The Pneumatic Carrier facility of Dhruva was standardized for the estimation of uranium in uranyl nitrate solution samples in ppb range by using solid state nuclear track detection method [7,8]. For this purpose, uranyl nitrate solutions in the concentration range ~10-1000 ppb were prepared from uranium SRM standard. The standard uranium solutions taken in polypropylene tubes along with the Lexan track detectors inside them were irradiated in the Pneumatic Carrier Facility (PCF) of Dhruva, research reactor at BARC Mumbai for 1 min. A blank of 2M HNO3 was also irradiated along with the uranium solutions. The irradiated detectors were then etched in 6N NaOH at 60 o C for 1 hr to reveal fission tracks. The fission tracks were counted under an optical microscope to get track density. A linear curve obtained between the track density and uranium concentration indicates the possibility of using this facility for the estimation of uranium in ppb range by track method. It has been found that this facility can

be used for the uranium estimation upto 5 ppb for 1 min irradiation time. The detection limit of uranium can be further lowered if the irradiation time is increased. The standardized method was then applied to the feed and elutes samples for uranium estimation. For the U estimation in the feed and elute samples, a U standard was always irradiated along with the samples and the U concentration was calculated with respect to the standard. The track density obtained by scanning a small representative detector area is related to concentration C (g/cc) of the element by equation

K wet CXN t where K wet is defined as the track registration efficiency in solution and is A expressed in cm; is the neutron flux in reactor and is the thermal neutron cross section. When simultaneous Td =
irradiation of a standard and sample is carried out, then only track densities and concentrations of standard and sample come into picture as shown in equation below:

Td ( sample ) Td ( s tan dard )

Csample Cs tan dard

The above method makes error independent arising due to small variations in the flux. The PCF facility of Dhruva was standardized for the estimation of uranium in uranyl nitrate solution in ppb levels using SSNTD for the first time [7]. The standardized method was then applied to the feed and elute samples of RUSWapp facility, routinely generated from Desalination Division for uranium estimation.

3. APPLICATION FOR MEASUREMENT OF URANIUM IN SEAWATER: Analysis of feed and elute samples:
During lab-scale experiments, many types of fiber cross sections and geometry were evaluated for their efficacy for grafting purposes. Polyester and polypropylene fiber materials were short listed for further experiments. Finally experiments are done using polypropylene fiber of 1.5 denier cross section as stem material in non-woven felt form. Electron Beam Radiation induced grafting of acrylonitrile on the stem fibre was carried out at ILU-6 to optimize the parameters for maximized % grafting. The solution viscosity and temperature were also found to be important factors during conversion of grafted acrylonitrile into amidoxime. Irradiation of substrate sheets was carried out using departmentally available 20 kW ILU-6 accelerators under the following conditions: Beam energy = 1.8 MeV, current = 1.06 mA and variable conveyor speed. Initial trails were carried out on bench scale and semi pilot scale at Trombay estuary to establish the process and material parameters under actual marine conditions. The submerged samples are retrieved from sea and defouling is done before carrying out elution operation. Analysis of feed and elute samples were carried out by solid state nuclear track detection method and results are shown in Table-1 below. The concentration factors of up to 100 have been achieved. Table-1 Analysis of Liquid samples by SSNTD technique
Sl. no 1 2 3 4 Token size 100 mm x 100mm do do 1000mm x 1000 mm Avg. Grafting level 50% Do do 102% Duration of submergence 360 hrs Do Do 410 hrs Location of submergence Cirus jetty Do Do Do Type elution Lab scale Do Do Pilot scale of U pick up (RChD lab) 30 ppb 32 ppb 42 ppb 386 ppb Remarks/ Method/ Technique SSNTD Do Do do

To ensure repeatability and reproducibility of results, the sample of pilot scale elution is evaluated by various techniques as listed in Table-2 below and the data shows an average value of 555 ppb and standard deviation of 115. Table-2 Comparison of sample analysis by various techniques

Laboratory name U (ppb) ACD/BARC EAD/BARC HPD/BARC IDD/BARC RChD/BARC REDS/BARC Statstics 771.7 511 543.22 499 437.5 570 555.4 115.06

Remarks/Method/Technique adopted

ICP-MS Anodic splitting voltametry Do Alpha-spectrometry Solid state nuclear track detection Avg of two readings (386 & 489) ICP-AES Avg. value Std.deviation

Analysis of solid sample

In order to evaluate the elution efficiency, the solid samples were analysed by Instrumental Neutron Activation Analysis technique and results are as shown in Table-3 below. The solid sorbent samples were analysed before and after elution. Elution was carried out using 0.5M Hydrochloric acid at temperature of 60C for a duration of four hours. Based on concentration values observed elution efficiency of around 80% is observed for bench scale operations.
Table-3 Neutron Activation Analysis of RUSWapp adsorbent samples (correlation of solid and liquid samples)

Sample id PAO-1 PAO-2

Concentratio n (mg/kg) 3 2.2

Avg value (mg/g)

Quantity of adsorbent taken for elution (gms)

Volume of initial elution solution (ml)

Volume of final elution solution (ml)

Total U on solid adsorbent (mg)

Expected uranium concentratio n (mg/l)

Remarks

PAO-3 PAO-4 PAO-5 PAO-6

2.9 0.78 0.64 0.48

2.7

94.69

1900

1500

0.2556

0.10299

Reported value for the solution is 0.016 mg/l

0.6333

94.69

0.0599

4.0 CONCLUSIONS:
Nuclear Analytical Techniques such as Neutron Activation Analysis (NAA) technique and Solid State Nuclear Track Detection (SSNTD) methods for analyzing the concentrations of heavy metal ions from lean solutions like seawater is established and standardized. These techniques are found quite useful and effective in view of capability of multi elemental analysis in a variety of samples. It has given good detection limits for a number of elements. The relative standard deviation of the SSNTD method for the Uranium concentration in the range ~ 5 to 40 ppb is 25%. The Minimum Detection Limit (MDL) for this method is 5 ppb of uranium at 3 level. Efforts are underway for further improvement of MDL with longer time irradiation and usage of supra pure solutions. Time required to estimate has been reduced from hours to minutes. Both solid samples and eluted liquid samples have been analysed by nuclear analytical techniques and comparison of results both by nuclear analytical techniques and non-nuclear techniques are satisfactory and lies within the accuracy limits described by IAEA. Acknowledgemtns The authors wish to thank Sri. SK Ghosh Director Chemical Engg Group for giving constant encouragement to the programme. Thanks are also due to AChD, HPhD, IDD, REDS and EAD divisions of BARC for their technical support in sample analysis. We acknowledge the support received from RUSWapp team and Staff of CIRUS/Dhruva reactors.

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