**2.1 Preparation of standard solutions**

Dilution for Endosulfan (EN) was carried out on pure standard (SIGMA-ALDRICH, Product: 45852, EN solution 100 ng μL−1 in n-hexane, PESTANAL®). As a standard for PAHs, Dr. Ehrenstorfer 2095009 product PAH-mix 9 was used. In the standard, there are mixtures of 16 polycyclic aromatic hydrocarbons (PAHs); naphthalene (NAP), acenaphthalene (ACE), acenaphtylene (ACY), fluorene (FLU), phenantherene (PHN), anthracene (ANT), fluoranthene (FLR), pyrene (PYR), benz(a)anthracene (BaA), chrysene (CRY), benzo(b)fluoranthene (BbF), benzo(k)fluoranthene (BkF), benzo(a)pyrene (BaP), dibenz(a,h)anthracene (DahA), benzo(g,h,i)perylene (BghiP) and indeno(1,2,3,c,d)pyrene (IcdP). Optimum conditions of EN and PAHs were shown in **Tables 1** and **2**. According to the mass spectra of the chromatograms of the EN and PAH pesticides, column retention times and ion inputs were studied in SIM mode. Pesticide standards were prepared (0.1, 0.25, 0.5, 1, 2, 2.5, 5, 7.5, 10, 25, 50, 100, 250, 500, 750 and 1000 μg L−1) and measurements were taken. PAH-mix 9 of 16 polycyclic aromatic hydrocarbon compounds in standard contented NAP, ACE, ACY, FLU, PHN, ANT, FLR, PYR, BaA, CRY, BbF, BkF, BaP, DahA, BghiP and IcdP, and the dilution made out of from standard mixture was prepared standards of 1, 5, 10, and 25 μg L−1. The methods applied in GC–MS for EN and PAHs are given in **Tables 1** and **2**, respectively.

The retention times (RT), SIM fragmentation ions, chromatogram programming times of PAHs are given in **Table 3**. The TICs of EN and PAHs were shown in **Figures 3** and **4**.


**271**

**Table 3.**

**Table 2.**

*Determination of Concentration for Some Priority Substances in Paddy Fields of Ergene River…*

**Column oven temperature program MS information**

10 120 1 MS source

time (min)

70 (initial) 1 EM voltage obtained 2329

300 (post run) 3 Scanned mass range 100–279

Rate (°C/min) Temperature (°C) Standby

**Applied method** Splitless **Injection volume** 1 μL **Inlet temperature** 70°C **He gas flow rate** 1 mL/min **Total flow rate** 64 mL/min **Septum cleaning flow** 3 mL/min **Temperature program** 300 °C for 1 min **Cleaning flow for split vent** 60 mL/min throughout 2.0 min **Transfer line temperature program** 150°C for 0 min, runtime 42.43 min

*DOI: http://dx.doi.org/10.5772/intechopen.93383*

**GC injection conditions**

**Pesticides RT** 

*Optimum GC-MS conditions for PAHs.*

**(min)**

**Target ion**

7 270 13 MS Quad (°C) 150

Naphthalene (NAP) 7.584 128.00 129.00 — 6.00 Acenaphthalene (ACE) 12.394 152.00 153.00 — 8.00 Acenaphtylene (ACY) 13.017 153.00 154.00 — 12.67 Fluorene (FLU) 14.694 166.00 165.00 — 13.50 Phenantherene (PHN) 17.846 178.00 176.00 179.00 15.00 Anthracene (ANT) 17.994 178.00 176.00 179.00 17.91 Fluoranthene (FLR) 21.850 202.00 200.00 203.00 18.10 Pyrene (PYR) 22.556 202.00 200.00 203.00 22.15 Benz(a)anthracene (BaA) 26.650 228.00 226.00 229.00 23.00 Chrysene (CRY) 26.879 228.00 226.00 229.00 26.71 Benzo(b)fluoranthene (BbF) 30.281 252.00 250.00 253.00 26.90 Benzo(k)fluoranthene (BkF) 30.376 252.00 250.00 253.00 30.33 Benzo(a)pyrene (BaP) 37.713 252.00 250.00 253.00 35.65 Benzo(g,h,i)perylene (BghiP) 31.539 276.00 138.00 277.00 31.70 Dibenz(a,h)anthracene (DahA) 38.082 276.00 278.00 279.00 37.95 Indeno(1,2,3,c,d)pyrene (IcdP) 39.436 276.00 274.00 277.00 38.50

*The retention times (RT), SIM fragmentation ions, and chromatogram programming times of PAHs.*

**Ion 1 Ion 2 Programming** 

280°C for 0 min, runtime 41.43 min

temperature (°C)

**Collection mode Scan**

Solvent delay (min) 0.00 Gain factor 5.00

**time (min)**

230

**Table 1.**

*The optimum GC-MS conditions applied for endosulfan.*

*Determination of Concentration for Some Priority Substances in Paddy Fields of Ergene River… DOI: http://dx.doi.org/10.5772/intechopen.93383*



#### **Table 2.**

*Emerging Contaminants*

respectively.

**Figures 3** and **4**.

**GC injection conditions**

**2.1 Preparation of standard solutions**

Dilution for Endosulfan (EN) was carried out on pure standard (SIGMA-ALDRICH, Product: 45852, EN solution 100 ng μL−1 in n-hexane, PESTANAL®). As a standard for PAHs, Dr. Ehrenstorfer 2095009 product PAH-mix 9 was used. In the standard, there are mixtures of 16 polycyclic aromatic hydrocarbons (PAHs); naphthalene (NAP), acenaphthalene (ACE), acenaphtylene (ACY), fluorene (FLU), phenantherene (PHN), anthracene (ANT), fluoranthene (FLR), pyrene (PYR), benz(a)anthracene (BaA), chrysene (CRY), benzo(b)fluoranthene (BbF), benzo(k)fluoranthene (BkF), benzo(a)pyrene (BaP), dibenz(a,h)anthracene (DahA), benzo(g,h,i)perylene (BghiP) and indeno(1,2,3,c,d)pyrene (IcdP). Optimum conditions of EN and PAHs were shown in **Tables 1** and **2**. According to the mass spectra of the chromatograms of the EN and PAH pesticides, column retention times and ion inputs were studied in SIM mode. Pesticide standards were prepared (0.1, 0.25, 0.5, 1, 2, 2.5, 5, 7.5, 10, 25, 50, 100, 250, 500, 750 and 1000 μg L−1) and measurements were taken. PAH-mix 9 of 16 polycyclic aromatic hydrocarbon compounds in standard contented NAP, ACE, ACY, FLU, PHN, ANT, FLR, PYR, BaA, CRY, BbF, BkF, BaP, DahA, BghiP and IcdP, and the dilution made out of from standard mixture was prepared standards of 1, 5, 10, and 25 μg L−1. The methods applied in GC–MS for EN and PAHs are given in **Tables 1** and **2**,

The retention times (RT), SIM fragmentation ions, chromatogram programming times of PAHs are given in **Table 3**. The TICs of EN and PAHs were shown in

280°C for 0 min, runtime 30 min

temperature (°C)

**Collection mode Scan**

Solvent delay (min) 10.00 Gain factor 5.00

230

**Applied method** Splitless **Injection volume** 1 μL **Temperature** 250°C **He gas flow rate** 1 mL/min **Total flow rate** 64 mL/min **Septum cleaning flow** 3 mL/min **Temperature program** 250°C for 1 min **Cleaning flow for split vent** 60 mL/min throughout 2.5 min **Transfer line temperature program** 150°C for 0 min, runtime 30 min

**Column oven temperature program MS information**

4 220 0 MS Quad (°C) 150

21 150 5 MS source

time (min)

45 (initial) 1 EM voltage obtained 2271

300 (post run) 3 Scanned mass range 100–279

Rate (°C/min) Temperature (°C) Standby

*The optimum GC-MS conditions applied for endosulfan.*

**270**

**Table 1.**

*Optimum GC-MS conditions for PAHs.*


#### **Table 3.**

*The retention times (RT), SIM fragmentation ions, and chromatogram programming times of PAHs.*

**Figure 3.** *GC chromatograms of Endosulfan compound.*

**Figure 4.** *GC chromatograms of PAH compounds.*

The standards (EN and PAHs) were prepared in certain concentrations and readings were made in the device and the calibration graphs were plotted to calculate the amounts in the actual samples (**Figures 5** and **6**).

The linear regression, correlation coefficient, the detection limit (LOD) indicating the performance of the method in the method validation [14], the determination limit (LOQ ), relative standard deviation percentage (RSD) and recovery calculations of the pesticides analyzed by GC-MS were shown in **Table 4**.

## **2.2 Collection of samples and preparation for analysis**

For each point determined, twice samples were sampled in the months of July (sowing period) and September (harvesting period) in the periods of paddy sowing

**273**

**Figure 6.**

**Figure 5.**

are given in **Table 5**.

*The calibration graphs of PAHs compounds.*

*Determination of Concentration for Some Priority Substances in Paddy Fields of Ergene River…*

and harvesting. In the paddy pan, selected for sampling, three points were determined to represent each of the ceilings and pan water, soil and plant samples were made from these points. Since there were no paddy in the sowing period, only in the harvesting period of soil and water "at the latest 5 days before the harvest" were done every triple sampling. The pan water, sediment samples, rice grains and rice husk samples from the paddy samples were coded with the abbreviation "w," "sd," "r," and "rh," respectively. The coordinates of the locations, code and sampling dates

Water samples prepared for analysis of EN and PAHs are enriched in the solid phase extraction system and prepared for analysis by GC-MS. Plant and sediment

*DOI: http://dx.doi.org/10.5772/intechopen.93383*

*The calibration graph of Endosulfan compound.*

*Determination of Concentration for Some Priority Substances in Paddy Fields of Ergene River… DOI: http://dx.doi.org/10.5772/intechopen.93383*
