COURSE OF GAS- CHROMATOGRAPHY COUPLED TO MASS … · of the “Parco delle Cave” was carried out...

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COURSE OF GAS- CHROMATOGRAPHY COUPLED TO MASS SPECTROMETRY PRELIMINARY INVESTIGATION ABOUT THE PRESENCE OF HYDROPHOBIC ORGANIC SUBSTANCES IN THE WATERS OF MILAN’S «Parco delle Cave». Davide Corso 5°A CHIMICI IIS E.TORRICELLI MILANO A.S. 2017-2018 IIS CURIE - SRAFFA in cooperation with THERMO FISHER SCIENTIFIC Analysis Coordinators: Prof. P. Protti IIS Curie Sraffa — Prof. P. Biondi UNIMI School Tutor: Prof. C. Pastorelli ISS E.Torricelli Termo Fisher Tutor : Dott. G.Giazzi Thermo Fisher Scientific

Transcript of COURSE OF GAS- CHROMATOGRAPHY COUPLED TO MASS … · of the “Parco delle Cave” was carried out...

Page 1: COURSE OF GAS- CHROMATOGRAPHY COUPLED TO MASS … · of the “Parco delle Cave” was carried out using two extraction’s techniques: The traditional SPE (solid phase extraction)

COURSE OF GAS-CHROMATOGRAPHY COUPLED TO MASS SPECTROMETRYPRELIMINARY INVESTIGATION ABOUT THE PRESENCE OF HYDROPHOBIC ORGANIC SUBSTANCES IN THE WATERS OF MILAN’S «Parco delle Cave».

Davide Corso 5°A CHIMICI IIS E.TORRICELLI MILANO A.S. 2017-2018

IIS CURIE - SRAFFA in cooperation with THERMO FISHER SCIENTIFIC

Analysis Coordinators: Prof. P. Protti IIS Curie Sraffa — Prof. P. Biondi UNIMI School Tutor: Prof. C. Pastorelli ISS E.Torricelli Termo Fisher Tutor : Dott. G.Giazzi Thermo Fisher Scientific

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MILAN’S “PARCO DELLE CAVE”.

(CASATI QUARRY, AURORA QUARRY, SWAMP, CABASSI QUARRY)

Davide Corso 5°A CHIMICI IIS E.TORRICELLI MILANO A.S. 2017-2018

Davide Corso 5°A CHIMICI IIS E.TORRICELLI MILANO A.S. 2017-2018

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INTRODUCTION

The qualitative research of hydrophobic substances into the four basins of the “Parco delle Cave” was carried out using two extraction’s techniques:

The traditional SPE (solid phase extraction) which provides the separation of the components of a mixture through a preferential adsorption process. The SPME (micro solid phase extraction) which provides the head space analysis of the sample proprerly treated and closed in a vial, and exposed to a fused silica needle, externally coated by a small amount of adsorbent stationary phase.

Davide Corso 5°A CHIMICI IIS E.TORRICELLI MILANO A.S. 2017-2018

Davide Corso 5°A CHIMICI IIS E.TORRICELLI MILANO A.S. 2017-2018

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MATERIALS, INSTRUMENTS E REAGENTS

MATERIALS

SPE • 500 mg Cartridges for SPE Supelco ENVI-18 and filtration vacuum system. • Glass test tubes with teflon cap

SPME • PDMS/DVB/CAR (polidimetilsiloxane/divinylbenzene/carboxene) fiber for SPME • 40 ml vial with teflon cap.

GC-MS • TG-5SILMS (30 m x 0,25 mm, 0,25µm) Capillary column (Thermo Scientific) with Tmax: 320/350 °C

INSTRUMENTSGC-MS • GC Termofisher “TRACE“ 1310 with PTV injector (programmable temperature

vaporizing), connected with to a ISQ LT mass spectrometer with single quadrupole

REAGENTS

BLANK TEST

• ULTRA PURE Milli-Q®water (resistivity =18 MΩ*cm)

SPE • Methanol for pesticides analysis • n-Hexane for pesticides analysis • Ethyl acetate for pesticides analysis

SPME • MgSO4

Davide Corso 5°A CHIMICI IIS E.TORRICELLI MILANO A.S. 2017-2018

Davide Corso 5°A CHIMICI IIS E.TORRICELLI MILANO A.S. 2017-2018

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Thermo Scientific

ISQ Single Quadrupole GC-MS

Advanced GC-MS system

designed for continuous high-

throughput operation

Davide Corso 5°A CHIMICI IIS E.TORRICELLI MILANO A.S. 2017-2018

Davide Corso 5°A CHIMICI IIS E.TORRICELLI MILANO A.S. 2017-2018

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OPERATING CONDITIONS (FOR GC-MS)

-Oven temperature 3 min at 50 °C then increasing of 10 °/min until 270 °C.

-Temperature (MS), (ionisation chamber and transfer line)

280 °C

-Energy ionisation with electronic impact

E = 70 eV

- Injector planning PTV splitless, for 3 min at 50°C

- Injection volume 1 microliter

Davide Corso 5°A CHIMICI IIS E.TORRICELLI MILANO A.S. 2017-2018

Davide Corso 5°A CHIMICI IIS E.TORRICELLI MILANO A.S. 2017-2018

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SAMPLE TREATMENT

We used amber glass bottles for withdrawal in deep water. Two 500 ml bottles of each quarry water have been collected.

The samples have been stored in a fridge.

PRELIMINARY WASH OF ANY GLASSWARE: The bottles were filled with 5% HNO3 solution for a week, and then rinsed with ULTRA PURE Milli-Q®

water and acetone. Finally the bottles have been kept overnight at 300 °C.

Davide Corso 5°A CHIMICI IIS E.TORRICELLI MILANO A.S. 2017-2018

Davide Corso 5°A CHIMICI IIS E.TORRICELLI MILANO A.S. 2017-2018

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SEPARATION TECHNIQUE Davide Corso 5°A CHIMICI IIS E.TORRICELLI MILANO A.S. 2017-2018

SPE

SPE cartridges were placed over a chamber connected to a vacuum pump.

This technique requires five main steps: -conditioning with 5 ml of methanol -equilibration with 5 ml of Milli-Q® ULTRA PURE water -sample loading (250 ml of sample water) -washing with 5 ml of Milli-Q® ULTRA PURE water and 5 ml of ethyl acetate - first elution with 5 ml of ethyl acetate - second elution (control) with 5 ml of n-hexane

The eluate was analyzed by GC / MS

Davide Corso 5°A CHIMICI IIS E.TORRICELLI MILANO A.S. 2017-2018

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SEPARATION TECHNIQUE Davide Corso 5°A CHIMICI IIS E.TORRICELLI MILANO A.S. 2017-2018

SPMEA fiber (PDMS / DVB / CAR) was used to analyze the headspace.

Using a vial, 20 ml of sample water are added with 6 g of MgSO4 to promote the release of the most volatile compounds.

The vials have been keeped in a sand bath at 50 ° C for 30 minutes.

Then the fiber has been put in contact to the headspace through a special syringe (see photos)

To desorb the sample, the fiber has been inserted in the GC injector at 280 ° C using the same syringe.

Davide Corso 5°A CHIMICI IIS E.TORRICELLI MILANO A.S. 2017-2018

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The search of the substances has been compared with the mass spectra which are present in the NIST (National Institute for Standards and Technology) library and not with the related standard solutions.

Davide Corso 5°A CHIMICI IIS E.TORRICELLI MILANO A.S. 2017-2018

Davide Corso 5°A CHIMICI IIS E.TORRICELLI MILANO A.S. 2017-2018

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RESULTS Davide Corso 5°A CHIMICI IIS E.TORRICELLI MILANO A.S. 2017-2018

Cabassi quarry - Ethyl Acetate

(SPE first elution)Recognised substances

through GC-MS TR (min)

Size of peak

(small/medium/large)

Toluene 3,7 lDodecene 13,84 mDiisobutyl

phthalate (DIBP) 19,32 l

Butyl-phthalate 20,28 sEicosenoic Acid 23,41 s

Squalene 27,72 l

Davide Corso 5°A CHIMICI IIS E.TORRICELLI MILANO A.S. 2017-2018

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DIBP FAMILY

Diisobutylphthalate (DIBP) is a solvent that is used in the paper recycling process, to remove inks and dyes. In April 2006, it was surprisingly discovered in pizza cartons by an analysis laboratory.

DIBP is an odorless plasticizer and has excellent heat and light stability.

-USES: nitrocellulose plastics, nail polish removers, explosive materials, enamelling and joint use with methyl methacrylate.

Davide Corso 5°A CHIMICI IIS E.TORRICELLI MILANO A.S. 2017-2018

Davide Corso 5°A CHIMICI IIS E.TORRICELLI MILANO A.S. 2017-2018

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RESULTS Davide Corso 5°A CHIMICI IIS E.TORRICELLI MILANO A.S. 2017-2018

Aurora quarry - Ethyl Acetate

(SPE first elution)

Recognised substances through GC-MS

TR (min)

Size of peak

(small/medium/large)

Limonene 8,36 sDi-isopropylnaphthalene 17,32 s

Butyl-phthalate 19,32 sEicosenoic Acid 23,41 s

Squalene 27,72 s

Davide Corso 5°A CHIMICI IIS E.TORRICELLI MILANO A.S. 2017-2018

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LIMONENE

Limonene is a chiral molecule: the two enantiomers have identical chemical properties but different fragrances. Limonene is uncoloured at room temperature and has a strong smell of oranges or lemons according to his chiral composition. (+)- Limonene is the isomer that is found in oranges and of course it smells of oranges. The smell of (-)-limonene is similar to turpentine, although some people suggest it has a lemon like aroma.

The main chemical compound present in nature and the most important compound used in the food industries and merchandise field is (+)- Limonene.

The name is coming from the lemon fruit, because the lemon peel contains large quantities of this chemical compound, which is largely responsible for the characteristic smell.

-USES: Limonene is commonly used in the production of cosmetic products, toothpastes, detergents as a flavoring agent, in the food industry as a flavour and in botany as an insecticide.

Davide Corso 5°A CHIMICI IIS E.TORRICELLI MILANO A.S. 2017-2018

Davide Corso 5°A CHIMICI IIS E.TORRICELLI MILANO A.S. 2017-2018

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Davide Corso 5°A CHIMICI IIS E.TORRICELLI MILANO A.S. 2017-2018

Swamp - Ethyl Acetate

(SPE first elution)Recognised substances

through GC-MS TR (min)

Size of peak (small/

medium/large)

Toluene 3,9 sDi-isobutyl phthalate 19,32 s

Palmitoleic acid 20,09 sPalmitic acid 20,29 s

Squalene 27,72 m

Davide Corso 5°A CHIMICI IIS E.TORRICELLI MILANO A.S. 2017-2018

RESULTS

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SQUALENE

Squalene is a triterpene present in fish and other animals liver, but also in some plants such as amaranth seeds, rice bran and olives.

All higher organisms produce squalene, including humans.

Thanks to its chemical nature, the squalene is less dense in comparison to the water. Squalene is the biochemical precursor of steroids and triterpenes.

It is generally used in vaccines

Davide Corso 5°A CHIMICI IIS E.TORRICELLI MILANO A.S. 2017-2018

Davide Corso 5°A CHIMICI IIS E.TORRICELLI MILANO A.S. 2017-2018

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RESULTS Davide Corso 5°A CHIMICI IIS E.TORRICELLI MILANO A.S. 2017-2018

Casati quarry Ethyl Acetate

(SPE first elution)Recognised

substances through GC-MS

TR (min)Size of peak

(small/medium/

large)

Di-isopropylnaphthalene (isomers)

17.32 - 17.41 - 17.85 -

17.91 - 17.98 s

Diisooctyl phthalate 25.36 s

Squalene 27.71 s

Caffeine 19,18 s4-tert-butyl-2-(2-methylbutan-2-yl)phenol 15,31 s

Davide Corso 5°A CHIMICI IIS E.TORRICELLI MILANO A.S. 2017-2018

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CAFFEINE

Caffeine is present in leaves, seeds and fruits of Coffea plant and others different plants, such as guarana, tea, cola or yerba mate, where it acts as a natural insecticide, having a toxic effect or by paralyzing the insects or other arthropods that eat them.

USES: It is commonly consumed as an infusion of seeds and leaves, as well as introduced as flavour in many foods and beverages.

Davide Corso 5°A CHIMICI IIS E.TORRICELLI MILANO A.S. 2017-2018

Davide Corso 5°A CHIMICI IIS E.TORRICELLI MILANO A.S. 2017-2018

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RESULTS

Cabassi Quarry n-hexane

SPE second elution (control)Recognised substances

through GC-MS TR (min)

Size of peak

(small/medium/

large)

Diisopropyl naphthalene

(isomers)17,43 - 17,87 s

Erucic Acid 23,44 s

Davide Corso 5°A CHIMICI IIS E.TORRICELLI MILANO A.S. 2017-2018

Davide Corso 5°A CHIMICI IIS E.TORRICELLI MILANO A.S. 2017-2018

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ERUCIC ACID

Erucic acid is a carboxylic acid belonging to the class of the monounsaturated aliphatic fatty acids. It is insoluble in water, but soluble in methanol and ethanol. Canola seed oil and mustard oil contain up to 50% of Its glyceric ester

-USES: It is used in the production of emollients and surfactants and, in the form of erucamide, in the synthesis of plastic films. It is also used for the polymerization of Nylon-13.13. Finally, it is an integral part of biodiesel oils. -NUTRITION: Erucic acid is toxic for the human organism. The law forbids its presence, indicating as maximum limit 50 g/kg in fat oils and food and 10 g/kg in infant formulas.

Davide Corso 5°A CHIMICI IIS E.TORRICELLI MILANO A.S. 2017-2018

Davide Corso 5°A CHIMICI IIS E.TORRICELLI MILANO A.S. 2017-2018

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Davide Corso 5°A CHIMICI IIS E.TORRICELLI MILANO A.S. 2017-2018

Aurora quarry n-hexane

SPE second elution (control)

Recognised substances through GC-MS TR (min)

Size of peak (small/

medium/large)

2-Hydroxy-2-octylsebacic acid 9,43 sDodecanoic acid, 3-hydroxy 11,2 s

Tetradecane 13,97 sbutylhydroxytoluene (BHT) 15,32 m

Tetradecane trimethyl (isomers) 16,47 - 18,11 s

Di-isopropylnaphthalene (isomers) 17,33 - 17,42 - 17,86 - 17,93 - 17,99 - 17,51 m

1-Eicosene 18,64 sNonadecane 18,71 m

2-Hexadecanol 19,07 sPhthalic acid, butyl undecyl ester 19,34 s

tridecyl phthalate 20,3 mIsopropyl palmitate 20,94 s

2-Hexadecanol 21,09 sErucic Acid 23,43 m

Oleic acid, 3-(octadecyloxy)propyl ester 25,38 s

Squalene 27,5 sDavide Corso 5°A CHIMICI IIS E.TORRICELLI MILANO A.S. 2017-2018

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BHT FAMILY

BHT (butylhydroxytoluene) is an alkylated phenol. At room temperature it appears as a white crystalline powder, slightly soluble in water, soluble in common organic solvents (ethanol).

-USES: It is used as an antioxidant, both in polymers and foods, in which it has a preservative function. It prevents the oxidation of fatty substances, and of the other organoleptic qualities of the products which it is added to. Both BHT and BHA are also used as antioxidants in the cosmetics industry, especially for creams and lipsticks, and in the pharmaceutical industry.

Davide Corso 5°A CHIMICI IIS E.TORRICELLI MILANO A.S. 2017-2018

Davide Corso 5°A CHIMICI IIS E.TORRICELLI MILANO A.S. 2017-2018

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Davide Corso 5°A CHIMICI IIS E.TORRICELLI MILANO A.S. 2017-2018

Swamp

n-hexane SPE second elution (control)

Recognised substances through GC-MS TR (min)

Size of peak

(small/medium/

large)

Butane, 1-propoxy- 3,04 sPentane, 2,3,4-trimethyl- 3,19 lHexane, 2,3-dimethyl- 3,33 m1-Heptanol, 2-propyl- 8,39 sNonadecane 9,1 sDecanal 11,19 mbutylhydroxytoluene (BHT) 14,72 sphenol, 4-(1,1-dimethylethyl)-2-(1,1-dimethylpropyl) 15,31 mBenzofuran-2-one, 4-amino-2,3-dihydro- 15,54 sTrimethyl-Tetradecane, isomers 15,66 - 16,46 sNaphthalene di-iso-propyl (isomers) 17,32 - 17,41 mTetradecanoic acid 18,21 mPalmitoleic acid 20,09 sn-Hexadecanoic acid 20,31 lOctadecane, 3-ethyl-5-(2-ethylbutyl)- 26,64 s

Davide Corso 5°A CHIMICI IIS E.TORRICELLI MILANO A.S. 2017-2018

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RESULTS Davide Corso 5°A CHIMICI IIS E.TORRICELLI MILANO A.S. 2017-2018

Casati quarry n-hexane

SPE second elution (control)

Recognised substances through GC-MS TR (min)

Size of peak (small/

medium/large)

Di-isopropylnaphthalene, isomers

17.34 - 17.86-17.42 - 17.93 - 17.99 s - m - m

2-Hexadecanol 21.55 sSqualene 27.50 l

Davide Corso 5°A CHIMICI IIS E.TORRICELLI MILANO A.S. 2017-2018

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CONCLUSIONS

The presence of several natural substances such as carboxylic acids, alcohols and long chain hydrocarbons, saturated and unsaturated, have been detected in all quarries

Besides, some traces of substances of industrial origin such as diisopropylnaphthalene (DIPN), phenolic antioxidants of the BHT family (butylhydroxytoluene) and phthalates (such as diisobutyl phthalate) have been even detected. These substances are generally present in plastics or into the receipts paper (DIPN).

Anyway, the presence of all compounds in the samples has to be validated by a more accurate analysis by using proper standard solution followed by the determination of the real concentration of each compound.

The analysis carried out with the SPME method were not taken into account because was not found an effective protocol for the complete cleaning of the fibers, contaminated by previous analytes: the results obtained with this method are then unconsistent.

Davide Corso 5°A CHIMICI IIS E.TORRICELLI MILANO A.S. 2017-2018

Davide Corso 5°A CHIMICI IIS E.TORRICELLI MILANO A.S. 2017-2018

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Davide Corso 5°A CHIMICI IIS E.TORRICELLI MILANO A.S. 2017-2018

Thanks for your attention!

[email protected]

Davide Corso 5°A CHIMICI IIS E.TORRICELLI MILANO A.S. 2017-2018