ICP-OES

INTRODUCTION

The goal of the task is to analyze elements (Fe, Mg, Cu, Ca and Zn) in a sample of water with ICP-OES and determine which elements are contained in the sample and amount of these elements in water. Inductively coupled plasma optical emission spectrometry (ICP-OES), is an analytical technique used for the detection of trace metals. The sample is usually transported into the instrument as a stream of liquid sample. Inside the instrument, the liquid is converted into an aerosol through a process known as nebulization. The sample aerosol is then transported to the plasma where it is desolvated, vaporized, atomized, and excited and/or ionized by the plasma. The excited atoms and ions emit their characteristic radiation which is collected by a device that sorts the radiation by wavelength. The radiation is detected and turned into electronic signals that are converted into concentration information for the analyst. The intensity of this emission is indicative of the concentration of the element within the sample.

PLASMA

Cross section of an ICP torch and load coil depicting an ignition sequence. A - Argon gas is swirled through the torch. B - RF power is applied to the load coil. C - A spark produces some free electrons in the argon. D The free electrons are accelerated by the RF fields causing further ionization and forming plasma. E - The sample aerosol-carrying nebulizer flow punches a hole in the plasma.

The first function of the high temperature plasma is to remove the solvent from the aerosol, usually leaving the sample as microscopic salt particles. The next steps involve decomposing the salt particles into a gas of individual molecules (vaporization) that are dissociated into atoms (atomization).

The temperature varies in different areas of the plasma, being two or three times higher than those achieved in the flames of burning in the flame methods. Due to the high temperatures reached, the atomization is more complete and less chemical interference problem.

In ICP-OES, the light emitted by the excited atoms and ions in the plasma is measured to obtain information about the sample. The emission from the plasma is polychromatic, because the excited species in the plasma emit light at several different wavelengths. This polychromatic radiation must be separated into individual wavelengths so the emission from each excited species can be identified and its intensity can be measured without interference from emission at other wavelengths. The separation of light according to wavelength is generally done using a monochromator, which is used to measure light at one wavelength at a time, or a polychromator, which can be used to measure light at several different wavelengths at once.

RESULTS AND DISCUSSION

At first, we had to prepare different solutions to calibrate the instrument (then, the wavelength will be correct and we will eliminate background in the measurement). To determine limit of detection, we analyzed the blank 10 times. We prepared the calibration solution with the metals (Zn, Fe, Mg, Cu and Ca) to identificate these elements in the sample after.

Zn poly
C (mg/L) 0 0,1 1 Zn poly 19,6133 42,5477 274,300

300 y = 255.8x + 18.36 R = 0.9999

250

200 Intensity

150

100

50

0 0 0.2 0.4 0.6 C [mg/L] 0.8 1 1.2

POLY INTENSITY Sample (Zn) 24,7090

CONCENTRATION [mg/L] 0,0248

The next graph shows the confidence bands of the calibration curve.

CL = LOD (Graph) = 0,0719

We can determine the limit of detection with the confidence bands (interpolating in the graph) or we can do it with this equation:

LOD (3)

0,0042

The results are different because with the graphical method, we determine the limit of detection without background. With the 3 method limit of detection is lower than in graphical method, because in this method we determine the limit of detection with

noise; the standard deviation is the mean value of the noise, and when we multiply by 3, we are supposing that we are measuring the intensity of the sample.

Zn mono

C (mg/L) 0 0,1 1

Zn mono 7,5969 22,5047 193,2333

250 y = 187.24x + 5.789 R = 0.9997

200

Intensity

150

100

50

0 0 0.2 0.4 0.6 C [mg/L] 0.8 1 1.2

MONO INTENSITY Sample (Zn) 7,0162

CONCENTRATION [mg/L] 0,0065

LOD (Graph) LOD (3)

0,1439 0,0029

The sensitivity of a method is related to the standard deviation. So that a steeper slope of the calibration curve implies a greater sensitivity. In this case the measure is more sensitive with the polychromator, because the slope is greater.

Fe polychromator

C (mg/L) 0 0,1 1

Fe poly 2,4744 4,3334 21,1900

25 20 15 10 5 0 0 0.2 0.4 0.6 C [mg/L] 0.8 1 1.2 y = 18.721x + 2.4682 R = 1

Intensity

POLY INTENSITY Sample (Fe) 3,1545

CONCENTRATION [mg/L] 0,0388

LOD (Graph) LOD (3)

0,0715 0,0030

Fe monochromator

C (mg/L) 0 0,1 1

Fe mono 12,447 31,5753 221,2733

250 y = 209.6x + 11.579 R = 0.9999

200

150 Intensity 100 50 0 0 0.2 0.4 0.6 C [mg/L] 0.8 1 1.2

MONO INTENSITY Sample (Fe) 12,8703

CONCENTRATION [mg/L] 0,0062

LOD (Graph) LOD (3)

0.0719 0,0018

In the case of iron, the measure is more sensitive with the monochromator.

Mg polychromator
C (mg/L) 0 0,1 1 Mg poly 2,8645 12,3747 111,3567

120 100 80 Intensity 60 40 20 0 0 0.2 0.4 0.6 C [mg/L] 0.8 1 1.2 y = 109.08x + 2.2023 R = 0.9999

POLY Sample (Mg)

INTENSITY 872,8367

CONCENTRATION [mg/L] 7,9816

LOD (Graph) LOD (3)

0.0425 0,0004

Mg monochromator
C (mg/L) 0 0,1 1 Mg mono 79,9727 406,1767 3773,5

4000 3500 3000 Intensity 2500 2000 1500 1000 500 0 0 0.2 0.4 0.6 C [mg/L] 0.8 1 1.2 y = 3712.5x + 58.635 R = 0.9999

MONO INTENSITY CONCENTRATION [mg/L] Sample (Mg) 30174,3333 8,1120

LOD (Graph) LOD (3)

0,2391 0,0008

In this case, the measure is more sensitive with polychromator.

Cu polychromator

C (mg/L) 0 0,1 1

Cu poly 96,411 160,173333 804,363333

900 800 700 Intensity 600 500 400 300 200 100 0 0 0.2 0.4 0.6 C [mg/L] 0.8 1 1.2 y = 711.04x + 92.933 R = 0.9999

POLY Sample (Cu)

INTENSITY 123,3

CONCENTRATION [mg/L] 0,0427

LOD (Graph) LOD (3)

0,1439 0,0019

Cu monochromator
C (mg/L) 0 0,1 1 Cu mono 1,5270 2,5176 13,5373

16 14 12 Intensity 10 8 6 4 2 0 0 0.2 0.4 0.6 C [mg/L] 0.8 1 1.2 y = 12.103x + 1.423 R = 0.9997

MONO Sample (Cu)

INTENSITY 1,5367

CONCENTRATION [mg/L] 0,0094

LOD (Graph) LOD

0,1449 0,0071

The measure with polychromator has a greater slope, then this measure is more sensitive.

Ca polychromator

C (mg/L) 0 0,1 1

Ca poly 5,7311 9,1011 57,4377

70 60 50 Intensity 40 30 20 10 0 0 0.2 0.4 0.6 C [mg/L] 0.8 1 1.2 y = 52.498x + 4.8407 R = 0.9989

POLY Sample (Ca)

INTENSITY 297

CONCENTRATION [mg/L] 5,5652

LOD (Graph) LOD (3)

0,1792 0,0013

Ca monochromator

C (mg/L) 0 0,1 1

Ca mono 60,421 94,17 610,5967

700 600 Intensity 500 400 300 200 100 0 0 0.2 0.4 0.6 C [mg/L] 0.8 1 1.2 y = 559.52x + 49.904 R = 0.9987

MONO Sample (Ca)

INTENSITY 2291,031

CONCENTRATION [mg/L] 5,2565

LOD (Graph) LOD (3)

0,3649 0,0034

The slope with monochromator is greater than with polychromator. Then, the measure is more sensitive with monochromator.

CONCLUSION
Water sample "Dobr voda": Ca 5.31 mg/l Mg 7.65 mg/l

Zn POLY Sample Zn MONO Sample

INTENSITY 24,7090 INTENSITY 7,0162

CONCENTRATION [mg/L] 0,0248 CONCENTRATION [mg/L] 0,0065

The results are close to zero, then there isnt Zn in the water sample.

Fe POLY Sample

INTENSITY 3,1545

CONCENTRATION [mg/L] 0,0388

Fe MONO Sample

INTENSITY 12,8703

CONCENTRATION [mg/L] 0,0062

The results are close to zero, then there isnt Fe in the water sample.

Mg POLY Sample Mg MONO Sample

INTENSITY 872,8367

CONCENTRATION [mg/L] 7,9816

INTENSITY CONCENTRATION [mg/L] 30174,3333 8,1120

The concentration isnt close to zero, is aproximately 8,05 mg/L and the producer declared that in Dobr Voda there was 7,65 mg/L. The result is correct and the difference could be due to possible errors in calibration. We had a problem with the calibration curve, because we pressed the start button to measure the sample before to put it in the pump.

Cu POLY Sample

INTENSITY 123,3

CONCENTRATION [mg/L] 0,0427

Cu MONO Sample

INTENSITY 1,5367

CONCENTRATION [mg/L] 0,0094

The results are close to zero, then there isnt Cu in the water sample.

Ca POLY Sample Ca MONO Sample

INTENSITY 297 INTENSITY 2291,031

CONCENTRATION [mg/L] 5,5652 CONCENTRATION [mg/L] 5,2565

The concentration isnt close to zero, is aproximately 5,41 mg/L and the producer declared that in Dobr Voda there was 5,31 mg/L. So, the result is correct.

With the values obtain with ICP, we can affirm that in the sample there are Ca and Mg with concentration 5,41 mg/L and 8,05 mg/L, respectively.