Emirates Journal for Engineering Research, 10 (1), 89-99 (2005)

(Review Paper)

MEASUREMENT OF VOLATILE ORGANIC COMPOUNDS (VOCS) IN AMBIENT AIR IN (1997-1998)

L. Al-Awadhi, M. Ahmed and A. R. Khan Coastal and Air pollution Department, Environment and Urban Development Division, Kuwait Institute for Scientific Research, P.O Box. 24885, Safat 13109, Kuwait, E-mail [email protected]

(Received November 2004 and accepted April 2005)

ﺗﻢ اﺧﺘﻴﺎر و ﻗﻴﺎس ﻋﺪد 37 ﻣﻦ اﻟﻤﻮاد اﻟﻌﻀﻮﻳﺔ اﻟﻤﺘﻄﺎﻳﺮة ﻓﻲ اﻟﻬﻮاء اﻟﺠﻮي ﺑﺠﺎﻧﺐ ﻋﺪة ﻣﻨﺎﻃﻖ ذو آﺜﺎﻓﺔ ﻣﺮورﻳﺔ ﻋﺎﻟﻴﺔ و ﺻﻨﺎﻋﻴﺔ و ﻃﺒﻴﺔ و ﺳﻜﻨﻴﺔ. ﻓﻲ آﻞ ﻣﻨﻄﻘﺔ ﻣﻦ ﻣﻨﺎﻃﻖ اﻟﻜﻮﻳﺖ اﻟﺘﺎﺑﻌﺔ ﻟﻤﺤﺎﻓﻈﺔ اﻟﻌﺎﺻﻤﺔ ﺗﻢ اﺳﺘﺨﺪام وﻋﺎء ﺧﺎص ﻟﺠﻤﻊ اﻟﻌﻴﻨﺎت ﻟﻤﺪة ﻋﺎم واﺣﺪ وﺟﺮى اﻟﺘﺤﻠﻴﻞ اﻟﻜﻴﻤﻴﺎﺋﻲ ﻟﻬﺎ ﺑﻮاﺳﻄﺔ ﺟﻬﺎزي (GC/MS & Preconcentrator) .ﺗﻌﺪ اﻟﻜﻮﻳﺖ دوﻟﺔ ﻣﻨﺘﺠﺔ ﻟﻠﻨﻔﻂ وﻟﻜﻨﻬﺎ ﻣﺮت ﺑﻜﺎرﺛﺔ ﺑﻴﺌﻴﺔ آﺒﻴﺮة ﻣﻦ ﺟﺮاء ﺻﻨﻊ اﻹﻧﺴﺎن ﻓﻲ ﺳﻨﺔ1991 (اﻟﻐﺰو اﻟﻌﺮاﻗﻰ اﻟﻐﺎﺷﻢ -آﺎرﺛﺔ اﺣﺘﺮاق ﺁﺑﺎر اﻟﻨﻔﻂ) ﺣﻴﺚ ﺗﻢ إﺷﻌﺎل أآﺜﺮ ﻣﻦ 800 ﺑﺌﺮ ﻣﻤﺎ ﻧﺠﻢ ﻋﻨﻪ ذﻟﻚ ﺑﺤﻴﺮات ﻧﻔﻄﻴﺔ آﺒﻴﺮة ودﺧﺎن أﺳﻮد آﺜﻴﻒ ﻏﻄﻰ اﻟﻤﻨﻄﻘﺔ ﺑﺄآﻤﻠﻬﺎ ﻟﻤﺪة ﻋﺪة أﺷﻬﺮ . اﻟﻬﺪف ﻣﻦ هﺬﻩ اﻟﺪراﺳﺔ آﺎن ﺗﻘﻴﻴﻢ ﻣﺴﺘﻮي ﺗﺮاآﻴﺰ اﻟﻤﺮآﺒﺎت اﻟﻌﻀﻮﻳﺔ اﻟﻤﺘﻄﺎﻳﺮة (VOCs) اﻟﻨﺎﺗﺠﺔ ﻋﻦ ﻣﺼﺎدر ﻣﻦ أﻧﺸﻄﺔ اﻹﻧﺴﺎن ﻣﺜﻞ اﻟﺒﺤﻴﺮات اﻟﻨﻔﻄﻴﺔ- إﻧﺘﺎج اﻟﻨﻔﻂ و اﻟﺘﻜﺮﻳﺮ-ﺣﺮآﺔ اﻟﻤﺮور وأﻧﺸﻄﺔ ﺻﻨﺎﻋﻴﺔ أﺧﺮي . اﻟﺪراﺳﺔ اﻟﻤﺨﺘﺎرة ﻣﺒﻨﻴﺔ ﻋﻠﻰ ﻣﻨﺎﻃﻖ ﺻﻨﺎﻋﻴﺔ - ﺳﻜﻨﻴﺔ و ﺗﺠﺎرﻳﺔ ﻟﻤﺤﺎﻓﻈﺔ اﻟﻌﺎﺻﻤﺔ ﻓﻲ دوﻟﺔ اﻟﻜﻮﻳﺖ . ﺗﺸﻴﺮ ﻧﺘﺎﺋﺞ هﺬﻩ اﻟﺪراﺳﺔ أن ﻣﻨﻄﻘﺔ اﻟﺸﺎﻣﻴﺔ ﺗﺤﺘﻮي ﻋﻠﻰ أﻋﻠﻰ ﻧﺴﺒﺔ ﺗﻠﻮث ﺟﻮي ﺑﺎﻟﻤﻮاد اﻟﻌﻀﻮﻳﺔ اﻟﻤﺘﻄﺎﻳﺮة ﺣﻴﺚ ﻳﺘﺒﻌﻬﺎ اﻟﺸﻮﻳﺦ اﻟﺼﻨﺎﻋﻲ ﺛﻢ اﻟﺪﺳﻤﺔ و أﺧﻴﺮا اﻟﻤﻨﺼﻮرﻳﺔ ﻋﻠﻰ اﻟﺘﺮﺗﻴﺐ. اﻟﻜﻠﻮروﻓﻮرم آﺎن اآﺜﺮ اﻟﻤﻮاد اﻟﻌﻀﻮﻳﺔ اﻟﻤﺘﻄﺎﻳﺮة وﻓﺮة ﻓﻲ اﻟﻌﺎﺻﻤﺔ اﻟﺘﻌﻠﻴﻤﻴﺔ و ﻣﻨﻄﻘﺔ اﻟﺪﺳﻤﺔ، ﻳﺮﺟﻊ اﻟﺴﺒﺐ ﻓﻲ ذﻟﻚ إﻟﻲ وﺟﻮد ﻧﺴﺒﺔ آﺒﻴﺮة ﻣﻦ اﻟﻤﻴﺎﻩ اﻟﻤﻌﺎﻟﺠﺔ ﺑﺎﻟﻜﻠﻮر واﺳﺘﺨﺪام آﻠﻮر اﻟﺘﺒﻴﻴﺾ واﻟﻤﺤﺎﻟﻴﻞ اﻟﺘﻲ ﺗﺴﺘﺨﺪم ﻓﻲ اﻟﺘﻨﻈﻴﻒ اﻟﺠﺎف آﻤﺎ آﺎﻧﺖ ﻣﺎدة اﻟﺘﻠﻮﻳﻦ ﺛﺎﻧﻲ أآﺜﺮ اﻟﻤﻮاد اﻟﻌﻀﻮﻳﺔ اﻟﻤﺘﻄﺎﻳﺮة وﻓﺮة ﻓﻲ اﻟﺸﻮﻳﺦ اﻟﺼﻨﺎﻋﻲ ﻧﺴﺒﺔ ﻟﻸﻧﺸﻄﺔ اﻟﺼﻨﺎﻋﻴﺔ اﻟﻌﺪﻳﺪة و اﻟﻤﺘﻮاﺟﺪة ﻓﻲ ﺗﻠﻚ اﻟﻤﻨﻄﻘﺔ . اﻟﻤﺼﺎدر اﻟﻤﺤﺘﻤﻠﺔ ﻟﻘﻴﺎس اﻟﻤﺮآﺒﺎت اﻟﻌﻀﻮﻳﺔ اﻟﻤﺘﻄﺎﻳﺮة (VOCs) ﺗﻢ ﻣﻨﺎﻗﺸﺘﻬﺎ ﺑﺎﻟﺘﻔﺼﻴﻞ ﻓﻲ هﺬﻩ اﻟﻮرﻗﺔ . ﻓﻲ اﻟﺪراﺳﺎت اﻟﻤﺴﺘﻘﺒﻠﻴﺔ ﺳﻮف ﻳﺘﻢ اﺳﺘﺨﺪاﻣﻪ ﻟﺘﻘﻴﻴﻢ ﻧﻤﻮذج ﺗﻮازن اﻟﻜﺘﻞ اﻟﻜﻴﻤﻴﺎﺋﻴﺔ ﺑﺒﻴﺎﻧﺎت ﺗﻔﺼﻴﻠﻴﺔ أآﺜﺮ.

Thirty-seven volatile organic compounds (VOCs) were selected and quantified in areas impacted by traffic sources as well as industrial, commercial and residential areas in . In each sector of Kuwait city, especially the Capital, Al-Asema governorate monitoring was performed using Summa – passivated canisters during a 1-year period. Analysis of samples was performed by means of a pre-concentrator, followed by gas chromatography/mass spectrometry (GC/MS). Kuwait, being an oil producing country, has experienced the world largest manmade environmental disaster in 1991, whereby ignition of over 800 wellheads resulted into huge oil lakes and also covered the entire area by a thick black smoke for a period of some months. The focus of this study was to assess the range of concentrations of VOCs resulting from anthropogenic sources such as oil lakes, oil production and refining, road traffic and other industrial activities. The selected study area is based on industrial sectors, residential and commercial districts of capital governorate. Results of this study indicate that the Al- sector has the highest ambient VOCs, followed by industrial , Al-, and Al- Mansouria sectors, respectively. Chloroform, the most abundant VOC in Al-Madena and Al- Dasma sectors, was mainly related to chlorinated water, bleach, and dry cleaning and solvents. The next abundant VOC in industrial Shuwaikh was toluene that is attributed to the multifaceted industrial activities in this area. The probable sources of measured VOCs are discussed in detail in the following sections. In future work, chemical mass balance model (CMB) with more extensive data will be used to assess the contributions of traffic, oil production, and oil refining industries to the VOCs concentrations in the ambient air.

1. INTRODUCTION VOCs were compared to outdoor levels and the carcinogenic nature of different VOCs were discussed Volatile Organic Compounds (VOCs) are constituents in detail. The monitoring of ambient levels of VOCs in often found to be present in the air that we breathe, the atmosphere has been the focus of recent work and affecting adversely health and welfare. Many VOCs was reported in a number of publications3,4,5,6. are toxic or carcinogenic for humans and animals 1 Identification and quantification of VOCs in the above certain dosage level . The most comprehensive atmosphere is becoming increasingly important due to work on of VOCs in the air have been reported by 2 concerns of their participation in oxidant formation Wallace , in which high indoor concentrations of (mainly ozone), VOCs potential toxicity, and their

89 L. Al-Awadhi, M. Ahmed and A. R. Khan

Figure 1. Sampling locations in Capital Governorates. chemical changes based upon their reactivity in the production and distribution, chemical manufacturing, atmosphere7,8. Fujita et al9 have used chemical mass industrial and commercial organic solvent use and balance receptor model to nonmethane organic gases, food processing. In 1991, the detonation of more than NMOG, in California's San Joaquin Valley and San 800 oil well heads by the retreating army resulted in a Francisco Bay area. They concluded that 70-75% of catastrophic incident that had produced thick black NMOG were due to vehicle emission in urban areas clouds of particulate matter, soot, unburned during 8:00-10:00 and 12:00-14:00 compared to daily hydrocarbon and huge oil lakes near oil production emission inventory 44%. The rest NMOG emissions facilities. The contribution of this incident to the were due to oil production facilities. Qin et al10 environmental pollution has been the subject of this compared weekend emissions with weekdays for investigation and the measurements were restricted to ozone, NOx, CO, VOCs, PM10 and light scatting in the urban area. The study area in Kuwait city is known southern California. Weekdays, large activities and as Capital (Al-Asema Governorate). The measured mainly traffic resulted into high NOx, CO and VOCs values of VOCs in ambient air were mainly attributed concentrations resulting into low ozone concentration to the regular emissions from traffic, commercial, while weekend ozone was reported higher than industrial, residential and oil related activities. weekdays. The VOCs sensitivity to ozone formation The 37 VOCs were selected and their and low concentrations of NOx are main reason for concentrations in the ambient air were quantified the weekend effect. Lin et al11 have measured VOCs during the year 1997 from different selected locations. concentration in ambient air of Kaohsiung Petroleum Ambient air samples were taken for the period of 24 Refinery in Taiwan. Benzene and toluene were the hours using Summa passive-sampling canisters during highest and the concentrations were 18 to 20 fold than a one-year monitoring period. Analysis of samples in downtown due to the close proximity to the source was performed by pre-concentrator followed by gas and well dispersed in the city center. chromatography / mass spectrometry (GC/MS). This study mainly assesses the range of concentrations of VOCs resulting from anthropogenic 2. SAMPLING sources of VOCs that are related directly or indirectly to oil production, refining, utilization and other human 2.1 Sampling Location activities in Kuwait City. VOC concentrations in the Among the six governorates in the state of Kuwait, the air are related to the fuel used, vehicle types and Capital (Al-Asema), which is located adjacent of engines, flow rates and traffic speed as well as road Kuwait, bay was selected for this study, shown in and environmental conditions in the city12. There is a Figure 1 and Table 1. The population in 1997/98 was wide variety of natural and anthropogenic sources of about 182,800 (baseline information from ministry of VOCs in ambient air7. Anthropogenic sources include transportation, petroleum refining, oil and gas

90 Emirates Journal for Engineering Research, Vol. 10, No.1, 2005 Measurement of Volatile Organic Compounds (VOCs) in Ambient Air in Kuwait (1997-1998)

Table 1. Selected Sampling Locations in the Al-Asema Governorate Capital Sampling Sites Governorate Name of residential Population First Site Second Site Third Site complex Kuwait Society for Studies and Al-Madina 27365 Ministry of education Capital Governorate Building Specialized Research. Al Mansouria Co-op School for Girls-Al- Al-Zubair Bin Al-Awam Mosque, Al-Mansouria Kinder Garden Street 13 Al-Mansouria 4278 Mansouria Street Street 26,Block 2 Block 1 Dental Bnied Al-Gar Center Al-Muhalla Bnied Al-Gar 12503 Mosque in the Bursyed street Park Street

Al-Emam Ebin Taimia Mosque Abu Buker Al-Sadique Mosque, Al- Gulf Arab State Educational Research Al-Shamiya 6612 Al-Huda Street Huda Street Center Al-Shamiya Street Al-Abbas Bin Abdu Al-Mutalab, Abdullah Salem 9900 Al-Mutair Mosque Block 4 Quoraish Sakhar Kinder Garden, Block 1 Block 2 Durrah Bint Abi Salama Elementary Solaibikhat 15617 Al-Luluah Kinder Garden School for Girls Garnata 1345 Khalid Bin Sayed mosque General Park under the Al-Shaikh Bin Abdullah Al-Faris Mosque Al-Shaheed Hassan Hussain Al-Zaabe Al-Faiha 1073 responsibility of Municipality Al- Al-Faha Street,Block 2 Park, Al-Shuhaba Street,Block 6 Shuhaba street, Block 4 Al-Nozha Youth center, Quoraish Abdulla Bin Al-Zubair, Akka Street Ozama Bin Ezit Mosque Quoraish Street Al-Nozha 6641 Street,Block1 Block 3 Block 2 Residential Elementary School for Boys Al-Mansour Post Office-Society Service Al-Shuwaikh Junior High School for Boys- 2264 Showaikh Street,Block 1 Center.Street 23, Block 2 Shuwaikh Street, Block 5 Omir Bin Al-Hamam Mosque, Othman Bin Arfan Mosque, Kiefan Street Kiefan 1497 Al-Adsani Mosque Arafat Street Block 4 Ammar Bin Yasser Street Block6 Block3 Moaath Bin Jabal Mosque,Al Sayed Al-Khaldia Co-educational School Al-Kaldia 7615 Fatat Sports Club Oruba Street Block 2 Omar Kindergarden School Street for Girls,Qaza Street,Block1 42,Block 4 College of Administrative Sciences Kuwait Al-Odailia Secondary School for Qrenada Co-educational Girls School Al-Odailia 8391 University Al-Kulaib Street Block 1 Girls Block 2 Block 3 Al-Sheikh Mohamed Al-Khalaf Al-Emam Ali Bin Abi Talib Mosque Al-Qadesia 9865 Al-Qadesia Youth Center Block 22 Mosque,Bader Street,Block 8 Street 98,Block 9 Al-Daia Co-educational School for Al-Daia Youth center,Al-Bohari Abdullah Al- Farag Kinder Garden School Al-Daia 7494 Girls,Rashid Bin Ahmed Al-Rumi Street Street Abu Thamam Street Al-Furat Kinder Garden School Al-Furat Kuwait Teachers Society Khadma Amna Elementary School for Girls Al- Al-Desma 8449 Street, Block 6 Street Street Block1 Mirshid Mohammed Al- Sulaiman Eben Al-Qaem Al-Jouzia Mosque, Al-Rawda 1444 Al-Quoz Kinder Garden,Street 22,Block 2 Mosque,Street 45,Block 4 Al-Musoodi Street, Block 5 Medical Area 2636 Kuwait Institute for Scientif Research Maternity Hospital Mosque Al-Razi Hospital Ibrahim Ali Abdul Rahman Al- Hawal Industrial Shuwaikh 5139 Ali-Al Yaqoud Mosque Mosque Al emam Ahmed Bin Hambel Kinder Al-Doha Elementary School for Al-Doha 18167 Garden Block3 Boys, Block 1 Mirshid Mohammed Al- Sulaiman Eben Al-Qaem Al-Jouzia Mosque, Al-Rawda 1444 Al-Quoz Kinder Garden,Street 22,Block 2 Mosque,Street 45,Block 4 Al-Musoodi Street, Block 5 Medical Area 2636 Kuwait Institute for Scientif Research Maternity Hospital Mosque Al-Razi Hospital Ibrahim Ali Abdul Rahman Al- Hawal Industrial Shuwaikh 5139 Ali-Al Yaqoud Mosque Mosque Al Emam Ahmed Bin Hambel Kinder Al-Doha Elementary School for Al-Doha 18167 Garden Block3 Boys, Block 1

Emirates Journal for Engineering Research, Vol. 10, No.1, 2005 91 L. Al-Awadhi, M. Ahmed and A. R. Khan

Pressure gauge Cryogenic trap PC

1 2 6

3 5 4 Liq N2 He 6 port MS valve

Pump Canister Chromatograph

Figure 2. Schematic diagram for the analysis setup using GC/MS

planning) in this governorate. The capital, Al-Asema Table 2. Chromatographic conditions is the center of all the major activities in the State, consisting of all ministries, commercial centers, Chromatography university, colleges, hospitals, professional Column: Hewlett-Packard VOC column-fused associations' centers and cottage industries. The silica capillary column (60m x 0.2mm ID, 1.1µm film thickness) Carrier gas: Helium (1.0 cm3/min at 250oC) comprehensive list of the selected sampling locations Injection Volume: Constant (1-3µl) is tabulated in Table 1, including, site, location and Injection mode: Splitless population in the corresponding sector. There are about 425 small cottage industries and Temperature Program Initial Column Temperature: 35oC companies in the Capital Governorate that produce Initial Hold Time: 3 min different types of products. Most of the industries are Program: 35oC iso, 2min; 15oC/min to 95oC; located in the and a few of 2.5oC/min to 105oC; 5oC/min to them in other areas too. There are about eight hospitals 205oC; 205o iso, 5min in this governorate where diesel is used as a fuel for Final Hold Time: 15min standby generators. Furthermore, there are about 5 Mass spectrometer garages belonging to the Kuwait Public Transport Mass Range: 10 to 250amu Company. Also there are 14 fuel dispensing-stations Scan Time: 1s/scan distributed in this selected area. The sampling sites EI Condition: 70eV were chosen according to activities listed above. These Mass Scan: Per manufacture’s instruction for sites consisted of 24 mosque, 23 schools, 5 office selecting mass selective detector buildings, 5 recreational facilities and 2 hospitals. and SIM mode Detector mode: Multiple ion detection 2.2 Sampling System GC = Gas Chromatography, MS=Mass spectrometer, ID= internal diameter, SIM= selected ion Monitoring. Samples were collected in SUMMATM passive 6-liter stainless steel canisters as per the method recommended by EPA. Pump-less canisters were used 2.3 Sample Collection and Duration for sample collection which were cleaned and Sampling was conducted for 24 hour periods in evacuated in accordance with US EPA method 13 residential, industrial areas and high traffic density TO-14 using Entech Instrument 3100 smart lab areas and then sampled canisters were properly sealed canister cleaning system. Vacuum level for each and analyzed within following 24 hrs in the canister was set at 6.65Pa (50 µm Hg). An electronic laboratory. Number of selected samples was 4 at each mass flow controller is equipped on the canisters, site and the sampling was taken during the spring and which ensures the entry of ambient air into the canister autum periods. There were limitd numbers of canisters at constant rate during the specified period. After and a sampling strategy was deviced to collect four sample collection the canister was sent back to the samples in a day from the close sites in specific areas. laboratory.

92 Emirates Journal for Engineering Research, Vol. 10, No.1, 2005 Measurement of Volatile Organic Compounds (VOCs) in Ambient Air in Kuwait (1997-1998)

) 1400.00

3. ANALYTICAL METHOD 3 1200.00

The air sample from the canister was drawn into the 1000.00 preconcentrator and analyzed by GC/MS, Hewlett 800.00 Packard G1800A (Figure 2), under the conditions 600.00 given in Table 2. The analysis followed the procedures 400.00 13 described in EPA method TO-15 . The organic 200.00 0.00 compounds were identified qualitatively by a (µg/m Concentration Wiley138 software library and quantitatively

estimated by comparing the chromatograms of the Avg. Avg. Al-Doha Avg. Avg. Al-Da`ia Avg. Avg. Al- Avg. Avg. Gharnata Avg. Al-Odailia Avg. Avg. Al-Rawda Avg. Shuwaikh Avg. Al-Dasma Avg. Avg. Al-Khaldia Avg. Avg. Al-Faiha`a Avg. Al-Shamia Avg. Avg. Al-Medina Al-Medina Avg. Avg. Avg. unknown with the retention time and area of the Avg. Al-Qadesia Avg. Medical Area Medical Avg. Avg. Al-Mansouria Avg. reference compound having known concentrations Al-Gar Bneid Avg. Avg. Abdullah Al-Salem Avg. Industrial Shuwaikh (standards). GC/MS was calibrated every alternate day Locations with standard sample of 37 organic compounds of known concentrations of 50 ppbv. Quality control and Figure 3. Total concentrations of volatile organic compounds at quality assurance was maintained throughout the different sectors in Capital Governorate. program.

4. RESULTS AND DISCUSSION Table 3. Average Concentrations of Selected Hydrocarbons measured at the seven locations in Al-Asema Governorate (µg m-3) This study indicated that in Capital Governorate (Al- Asema), VOCs having the highest concentrations were Pollutant Locations Mean Range released by many anthropogenic sources, such as 1 ------small cottage industries, automobiles, burning of fossil p-xylene 3 24.9 nd-74.6 fuels ( gas, oil) oil production and refining facilities, 4 31.4 nd-94.1 power generating stations, incinerators, construction 6 77.3 nd-309.2 and decoration of buildings, air conditioning units, 8 114.6 nd-252.7 laundries and extensive use of aerosols. The 13 0.4 nd-0.7 concentrations of chloroform and toluene were the 16 0.04 nd-0.4 highest among all the VOCs pollutants measured in 16 100.6 1.7-199.5 ambient air samples. The total average VOCs o-xylene 1 - - concentration was interpreted in terms of benzene and 3 25.1 nd-75.3 it was measured 1195 µg m-3 equivalent to benzene 4 31.6 nd-94.6 concentrations of 370 ppb at Al-Shamiya location and 6 78.1 nd-312.1 919 µg m-3 (316 ppb equivalent benzene) at industrial 8 117.0 nd-258.2 Shuwaikh locations. The measured values were above 13 0.2 nd-0.5 the specified standard limits of benzene by NIOSH 16 0.04 nd-0.3 specified as stated. “The recommended airborne m-xylene 1 - - 3 24.8 nd-74.4 exposure limit is 100 ppb averaged over a 10- hour 4 31.1 nd-93.1 work shift and 1 ppm, not to be exceeded during any 6 74.2 nd-296.7 15 minute work period” (NJ.US 1994). 8 42.6 nd-91.8 Total concentrations of VOCs are directly related 13 0.4 nd-0.6 to fugitive sources originating from automobiles, gas 16 0.04 nd-0.4 dispersing stations, paper mill, food industries, Ethyl benzene 1 - - incinerators, power stations, plastic molding, 3 15.7 nd-47.1 laundries, solvent and paints mentioned in proceeding 4 19.6 nd-58.7 paragraph. Figure 3 shows total concentrations of 6 58.0 nd-232.1 -3 VOCs in µgm for Capital Governorate from 8 41.2 33.9-83.8 downtown (Medina). Some of these high 13 0.3 nd-0.7 concentrations were directly related to nearby sources 16 0.02 nd-0.04 with the exception of Al-Shamiya. Total VOCs 1 471.0 11.8-1502 Al-Shamiya measurements for total VOCs is 3 723.8 12.5-1083.5 around 1195 µg m-3, followed by the Shuwaikh 4 519.1 12.3-1369.1 industrial area and Al-Dasma. However, it is found 6 1195.3 33.9-4503.5 that the Al- Shamiya total VOCs concentrations have a 8 919.2 nd-2007.8 wider variation in day-to-day samples. The total 13 289.3 22.6-816.1 16 142.3 39-456.2

Emirates Journal for Engineering Research, Vol. 10, No.1, 2005 93 L. Al-Awadhi, M. Ahmed and A. R. Khan reported value is an average of several readings for Chloroform concentrations in Al-Madina, Al- many different periods and some of those Dasma and Kaifan were found to be high as indicated measurements yielded high concentration due to local in Figures 5 and 6. Al-Medina showed the highest activities during sampling time. As an example, value of all, about 380 µg m-3 followed by Al-Dasma measurements over one period showed 76.54 µg m-3 320 µg m-3 and finally Kaifan 247 µg m-3. -3 cyclohexane, 13.03 µg m 3-methylhexane, 177.2 µg The measured values of CHCl3 concentrations are m-3 n-heptane as compared to another period of 0.13 the average for a period of one year. Anthropogenic µg m-3 cyclohexane, 1.76 µg m-3 3- methylhexane and sources contributed to the baseline concentration of -3 0.53 µg m n-heptane, which is evidently a large CHCl3 in three sampling sites. Meteorological factors variation in readings. This is mainly attributed to the have minimal affect, and the baseline average steady metrological conditions, transporting VOCs from oil state concentrations are due to complete dispersion. production and refining activities (source) to the The sources that contributed to higher levels of sampling site. The other most probable source may be halogenated hydrocarbon likely include evaporation of sample contamination from major road repair chlorinated water coming from many sources, cooling asphalting or heavy construction machines, like towers, heavy industrial and residential area having a concrete mixtures and lifting cranes, which normally substantial use of chlorinated water, dancing fountains are left running all day long even during the worker’s (ornamental) located at recreational parks, amusement lunch break. A convoy of moving trucks that passed in centers shopping mall and commercial buildings, and almost 20 minutes by the sampling site had car wash centers. Concentrations of chloroform were contributed to the high recorded values of VOCs. One recorded higher than the other hydrocarbon pollutants high reading strongly influences the results and yields near Al-Dasma and Al-Medina areas. Al-Medina has a high average concentration. There were 4 samples several new and old buildings. Large complexes, such taken for the period of the study, which provided equal as shopping malls, the Ministries Complex, the Kuwait weight to each measured value dependent on place, Market, high rise buildings are equipped with large time, and duration of the sample. With limited air-conditioning system comprising of chillers and samples, it was decided not to ignore any cooling towers. Most of the old buildings that are measurements based on low or high concentration. spread all over Al-Medina use old window type air Table 3 summarizes the results (average values) of conditioning units. These units still operate on old various VOCs measured concentrations in seven refrigeration media where Freon 12 is released during locations in Al-Asema governorate. It is noticed that operation and maintenance of these units. aromatic hydrocarbons have high concentration at Al-Medina area has many paint stores where industrial Shuwaikh sector location (5). halogenated hydrocarbons are a major source (solvent) These values are compared with various reported of painting material. Halogenated hydrocarbons are VOCs concentrations in other urban centers in Table major constituent of lacquers, and solvent for gums, 4. It is obvious that VOCs concentrations measured in greases, waxes, adhesives, oils and rubber. Other this work are much higher than the reported values in sources at the highly populated areas of Al-Medina, the literature due to oil related activities. Kaifan, and Al-Dasma are dry-cleaning laundry shops In Kuwait, northwestern wind prevails over 50% that use solvents and other chemicals in the process of of the time as shown in Figure 4. The major sources of dry- cleaning garments. Furthermore, almost all fire VOCs are from oil production and refining facilities, extinguishing materials are sold mainly in Al-Medina. which are mainly located in the south of the country, Al-Dasma, as small as it is, has some major institutes with the exception of a few power plants and northern and firms such as teachers’- society, Al-Dasma oil fields. These northern sources represent a very National Theatre, two major fitness clubs (having small portion of the total emissions. The prevailing large chlorinated swimming pools). A few of these wind facilitates good dispersion and most of the VOCs establishments use chillers with cooling towers where spread further down to Saudi Arabia and Arabian chlorinated water is used to keep the circulation Gulf. system clean from bio-growth. There are various types of dusty events, (Severe Dust Halogenated hydrocarbons are used as aerosols Storm SDS, Mild Dust Storm MDS, Mild Rising Dust and paint propellant solvents. Al-Dasma and Al- MRD, Severe Rising Dust SRD, Thick Suspend Dust Medina areas are adjacent to Kuwait’s oldest industrial TSD, Mild Suspended Dust MSD and Haze) that have and repair area; in particular, air conditioning where occurred during the year and have strongly influenced CFC's (Freon 12, Freon 113 etc.) are used in refilling the pollutants distribution. air conditioning system. Car body repair shops use Chloroform concentrations in Al-Madina, Al- different solvents (hydrocarbon mix) and paint sprays Dasma and Kaifan were found to be high as indicated that contribute to a variety of pollutants in the ambient in Figures 5 and 6. Al-Medina showed the highest air. Al- has high concentrations of cyclo- value of all, about 380 µg m-3 followed by Al-Dasma hexane in residential areas due to its use as a solvent in 320 µg m-3 and finally Kaifan 247 µg m-3. domestic and industrial cleaning agents, oil based paint, varnishes furniture polisher and the dry

94 Emirates Journal for Engineering Research, Vol. 10, No.1, 2005 Measurement of Volatile Organic Compounds (VOCs) in Ambient Air in Kuwait (1997-1998)

North North

20% 16% 20% 16% 12%

8% 12% 8% 4% West 4% East West East Wind Speed (m/s) Wind Speed (m/s) >10.8 8.8-10.8 >10.8 5.7-8.88.8-10.8 3.6-5.7 5.7-8.8 2.1-3.6 3.6-5.7 0.5-2.1 2.1-3.6 South 0.5-2.1 South

Figure 4. Wind rose for year 1998 indicating the wind direction based on metrological data from Kuwait Institute for Scientific Research Station Shuwaikh.

Table 4. Aromatic hydrocarbons in Al-Asema Governorate (Kuwait) and other urban centers (ppbv) (m + p)- o-x xylene Site Period Benzene Toluene Ethylbenzene References xylene ylene (Total) Sydney 1982 2.6 8.9 1.3 3.9 1.5 Nelson and Quigley 14 Milan 1992 6.7-18 Guerra et al 15 Rome 1992-1993 10.9 25.9 4 12.3 5.7 Brocco et al 16 Osaka 1992 5.1 31.1 3.8 7.7 2.8 Tsujino and Kuwata 17 Athens 1993 0.8-18.7 0.4-8.2 0.6-8.1 2.6-29.8 1.4-6.4 Moschonas and Glavas 18 Grenoble May 1995 0.5-3 1-3.5 0.2-1.5 0.5-3 0.2-1.5 Ferrari et al 19 Bangkok 1995 5.6 48.5 8.3 18.4 6.6 Gee and Sollars 20 Manila 1995 3.9 43.8 5.0 12.6 3.8 Gee and Sollars 20 Changchun 1997-1998 13.5 20.5 4.3 5.3 Al-Asema 1997-1998 9.7 80.7 9.5 36.9 26.9 63.1 (Kuwait) * * The highest mean concentration found in Industrial Shuwaikh sector (Al-Asema)

Emirates Journal for Engineering Research, Vol. 10, No.1, 2005 95 L. Al-Awadhi, M. Ahmed and A. R. Khan

400.00

Avg. Al-Medina 350.00 Avg. Bneid Al-Gar Avg. Al-Da`ia 300.00 Avg. Al-Dasma

250.00

200.00

150.00 concentration(ug/m3)

100.00

50.00

0.00 ethanol toluene p-xylene benzene n-butane o-xylene m-xylene n-decane n-pentane n-heptane 2-propane Freon 113 1,4dioxane Chloroform 2-butanone n-dodecane cyclohexane cyclopentane ethylbenzene 2-methylbutane 3 methylheptane 3-metthylhexane 2-metthylpentane methylenechloride methylcyclohexane carbontetrachloride 2,4-dimethylhexane Methylcyclopentane 1,2,3-trimethylbenzene 1,3,5-trimethylbenzene 1,2,4-trimethylbenzene 1-ethyl-2-methylbenzene 1-ethyl-4-methylbenzene VOCs

Figure 5. Concentrations of VOCs at Al-Madina, Bneid Al-Gar, Al Da'ia and Al-Dasma sector.

300.00

250.00 Avg. Kaifan Avg. Al-Khaldia Avg. Al-Faiha`a 200.00 Avg. Al-Nuzha

150.00

concentration(ug/m3) 100.00

50.00

0.00 toluene ethanol p-xylene benzene n-butane o-xylene m-xylene n-decane n-heptane n-pentane 2-propane Freon 113 Freon 1,4dioxane Chloroform 2-butanone n-dodecane cyclohexane cyclopentane ethylbenzene 2-methylbutane 3 methylheptane 3-metthylhexane 2-metthylpentane methylenechloride methylcyclohexane carbontetrachloride 2,4-dimethylhexane Methylcyclopentane 1,2,3-trimethylbenzene 1,3,5-trimethylbenzene 1,2,4-trimethylbenzene 1-ethyl-2-methylbenzene 1-ethyl-4-methylbenzene VOCs

Figure 6. Concentration of VOCs at Al-Mansouria, Al-Qadesia, Al-Shamiya and Abdulla Al-Salem sectors.

96 Emirates Journal for Engineering Research, Vol. 10, No.1, 2005 Emirates Journal for Engineering Research, 10 (1), 89-99 (2005)

(Review Paper) cleaning of garments. The Kuwait University is Shuwaikh. Total VOCs concentration in Al-Shamiya located in Khaldiya and the cyclohexane is also found to be 3361.6µg m-3. These high values could extensively used in laboratories for extraction. be attributed to the fact that Al-Asema is the center of As stated above, VOCs are directly related to the country, rich in both industrial and commercial some type of indeterminate sources and that is why activities. The influence of one of the largest they are labeled as fugitive emissions. Some of these manmade environmental disasters of 1991 is still fugitive emissions are related to nearby small cottage lingering over the horizon of Kuwait for years to industries. A typical example is the Shuwaikh come, resulting in high concentrations of VOCs from industrial area where the emissions originate from oil lakes. Other activities, such as road traffic, power heavy traffic, repair shops involving solvents, paints, generation, oil production and oil refining and air conditioning agents, light duty industries such as petrochemical industrial complexes are also major Kuwait Flour mill electrical panel board sources of VOCs. The measured VOCs manufacturing plants.Aluminum molding shops use concentrations were the highest in the cold month of cheap used engine oil as fuel for Aluminium smelting January and were the least in the summer month of for making staircase rails and grills used in domestic July. In winter, succinct atmospheric inversions, low and industrial buildings. This can be seen by the high temperature and dense air result into localized high concentrations of toluene, Figure 7. pollutant concentrations. In July, the temperature Another set of high concentration values at Al- most often approaches 50C, and high wind speeds Mansoria is for ethyl benzene, p-xylene, o-xylene, m- facilitate atmospheric dispersion and mixing process. xylene and other derivatives of Aromatic Hydro- The dusty events (high concentrations of PM10) as carbons mainly due to major petrol-filling station, the shown in Figure 4, in summer months not only largest in Al-Asema Governorate. The most obvious reduce the solar radiations but adsorb most of the sources of these aromatic hydrocarbons are road VOCs naturally balancing the organic load in the traffic and gas dispensing stations. Additionally, a ambient air. large sports stadium, Al Arabi, is a hub of social and In future work, Chemical mass balance model sports activities that entices a large number of with more extensive measurement data will be used participants and spectators resulting into a large to assess the contributions of the most probable increase in the traffic density. sources of VOCs, like road traffic, oil production, oil Kaifan, a residential area not far from the refining, petrochemical and other industries using Shuwaikh industrial area, houses the Kuwait organic solvents to the VOCs concentrations in the University, Al-Kaifan Stadium, telecommunication ambient air. Photo-oxidation model will be used to tower and other professional societies. The elevated plan pollution abating strategies to keep clean and levels of halogenated hydrocarbons in Al-Kaifan are healthy environment in Kuwait. attributed to the air-conditioning and dry-cleaning activities in this area, specifically to the use of REFERENCES chemicals and solvents. In Doha, there is a large power generation plant 1. Ashford, N.A. and Miller, C.S., 1998, Low-Level Chemical exposures: A challenge for science and that burns heavy fuel oil resulting into high release of policy. Environmental Science and Technology VOCs, NOx and SO2, the ozone precursor 32(21): 508A-509A. compounds, as shown in Figure 8. 2. Wallace, L.A. 2001. Assessing Human Exposure to The location of this plant is such that emissions Volatile Organic Compounds, Chapter 33 in Indoor are predominantly directed towards the residential Air Quality Handbook, by Spengler, J.D., Samet, J.M., area due to most commonly prevailing northwestern and McCarthy, J.F., eds., McGraw-Hill, NY USA. winds. 3. Pellizzari, E. D., 1982, Analysis for organic vapor emissions near industrial and chemical waste disposal sites, Environ Science and Technology 16, 781-785. 4. CONCLUSION 4. Harkov, R., Kebbekus, B., Bozzelli, J. W., and Lioy, This study summarizes the average VOCs P. J., Measurement of selected volatile organic concentrations in the most populated Capital compounds at three locations in new jersey during the Governorate, Al-Asema, which is a part of one year summer season, j. air pollution control assoc. 33, 1177-1183. monitoring of VOCs released by many anthropogenic 5. Wathne B. M., 1983, Measurement of benzene, sources in all the six Governorates of Kuwait State. toluene and xylenes in urban air, Atmospheric The average values of VOCs were found to be Environment 17, 1713-1722. maximum at Al-Shamiya (around 1195 µg m-3), 6. Sexton, K., and Westberg, H., 1984, non-methane followed by Industrial Shuwaikh and Al-Dasma hydrocarbon composition of urban and rural respectively. Al-Madina showed the highest reading atmospheres, Atmospheric Environment 18, 1125- of halogenated hydrocarbons (380 µg m-3) and 1132. 7. Wark, K., Warner, C. F., and Davis, W. T., 1998, Air finally Kaifan (247 µg m-3). Toluene is the next rd abundant VOC which is found in Industrial pollution its origin and Control, 3 Edn., Addison- Wesely Longman, Inc. Menlo Park California USA.

97 L. Al-Awadhi, M. Ahmed and A. R. Khan

25.00

Avg. Al-Odailia Avg. Al-Rawda Avg. Medical Area 20.00 Avg. Gharnata

15.00

10.00

5.00

0.00 toluene ethanol p-xylene benzene n-butane o-xylene m-xylene n-decane n-pentane n-heptane Freon 113 2-propane 1,4dioxane Chloroform 2-butanone n-dodecane cyclohexane cyclopentane ethylbenzene 2-methylbutane 3 methylheptane 3-metthylhexane 2-metthylpentane methylenechloride methylcyclohexane carbontetrachloride 2,4-dimethylhexane Methylcyclopentane 1,2,3-trimethylbenzene 1,3,5-trimethylbenzene 1,2,4-trimethylbenzene 1-ethyl-2-methylbenzene 1-ethyl-4-methylbenzene

Figure 7. Average concentrations of volatile organic compounds at Al-Odailia, Al-Rawda, Medical Area and Gharnata sectors.

350.00

Avg. Sulaibikhat Avg. Al-Doha 300.00 Avg. Shuwaikh Avg. Industrial Shuwaikh

250.00

200.00

150.00

100.00

50.00

0.00 toluene ethanol p-xylene benzene n-butane o-xylene m-xylene n-decane n-heptane n-pentane 2-propane Freon 113 1,4dioxane Chloroform 2-butanone n-dodecane cyclohexane cyclopentane ethylbenzene 2-methylbutane 3 methylheptane 3-metthylhexane 2-metthylpentane methylenechloride methylcyclohexane carbontetrachloride 2,4-dimethylhexane Methylcyclopentane 1,2,3-trimethylbenzene 1,3,5-trimethylbenzene 1,2,4-trimethylbenzene 1-ethyl-2-methylbenzene 1-ethyl-4-methylbenzene

Figure 8. Average concentrations of volatile organic compounds at Al-Solaibikhat, Al-Doha, Shuwaikh and Industrial Shuwaikh sectors.

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8. Arriaga-Colina, J. L., West, J. J., Sosa, G., Escalona, S. 18. Moschonas, N., and Glavas, S., 1996, C3-C10 S., Ordunez, R. M., and Cervantes, A. D. M., 2004, hydrocarbons in the atmosphere of Athens, Greece, Measurements of VOCs in Mexico City (1992-2001) Atmospheric Environment 30, 2769-2772. and evaluation of VOCs and CO in the emissions 19. Ferrari, C. P., Kaluzny, P., Roche, A., Jacob, V., and inventory, Atmospheric Environment 38, 2523-2533. Foster, P., 1998, Aromatic hydrocarbons and aldehydes 9. Fujita, E. M., Watson, J. G., and Chow, J. C., 1995, in the atmosphere of Grenoble France, .Chemosphere Receptor model and emission inventory sources 37, 1587-1601 apportionments of non-methane organic gases in 20. Gee, I. L., and Sollars, C. J., 1998, Ambient air levels California San Joaquin valley and San Francisco bay of volatile organic compounds in Latin American and area, Atmospheric Environment 29, 3019-3035. Asian cities, Chemosphere 36, 2497-2506. 10. Qin, Y., Tonnesen, G. S., and Wang, Z., 2004, 21. Agency for Toxic Substances and Disease Registry, Weekend/Weekdays difference of ozone, NOx, CO, January 1989, (Chloroform) http://www.cla.sc.edu/ VOCs, PM10 and light scatter during ozone season in geog/hrl/sctrap/toxfaqs/chlorofo.htm South California, Atmospheric Environment 38, 3069- 22. Aysen M., Odabasi, M., and Onat, L., 2001, Volatile 3087. organic compounds in the air of Izmir, Turkey. 11. Lin, T-Y., Sree, U., Tseng, S-H., Chiu, K. H., Wu, C- Atmospheric Environment 35, 753-760. H., and Lo, J-G., 2004, Volatile Organic Compound 23. Duce, R. A., Mohnen, V. A., Zimmerman, P. R., concentrations in ambient air of Kaohsiung Petroleum Grosjean, D., Cautreel, W., Chatfield, R., Jaenicke, R., Refinery in Taiwan, Atmospheric Environment 38, Ogren, J. A., Pellizzari, E. D., and Wallace, G. T., 4111-4122. 1983, Organic materials in the global troposphere, Rev. 12. Paul, J., 1997, Improved air quality on Turkish roads: Geophys. Space, Phys. 21, 921-952 fuels and exhaust gas treatment. Environmental 24. Environmental indicator of the month for september Research Forum 7-8, 145-152. 2003, Careful where you breathe-pollutants in indoor 13. USEPA 1988, The Determination of Volatile Organic air, http://www.pca.state.mn.us/programs/indicators/ Compounds (VOCs) in Air Collected in Specially- iom-0903.html Prepared canisters and Analyzed by Gas 25. Hazardous Substance Fact Sheet, New Jersey Chromatograph/Mass spectrometer, http://www. Department of Health and Senior Services, November epa.gov/region9/lab/sops312.html 1994, (Benzene). http://www.state.nj.us/health/eoh/ 14. Nelson, P.F., and Quigley, S. M., 1982, Non-Methane rtkhsfs.htm hydrocarbons in the atmosphere of Sydney, Australia. 26. Issa, A., Al-Sudairawi, M., Yafaoui, H., Al-Awadhi, L., Environmental Science and Technology 16, 650-655. Al-Otaibi, Y., Al-Shammari, A., and Rashad, M., 15. Guerra, G., Lemma, A., Lerda, D., Martines, C., Salvi, 1998, Assessing the impact of Volatile Organic M., and Tamponi, M., 1995, Benzene emissions from Compounds emitted from anthropogenic sources on the vehicle traffic in the urban area of Milan: hypothesis of ambient Air Quality of Kuwait. Final Report, health impact assessment. Atmospheric Environment KISR5239, Kuwait Institute for Scientific Research 29, 3559-3569. Kuwait. 16. Brocco, D., Fratarcangelli, R., Lepore, L., Petrcca, M., 27. Liu, C., Xu, Z., Du, Y., and Guo, H., 2000, Analysis of and Ventrone, I., 1997. Determination of aromatic volatile organic compounds concentrations and hydrocarbons in urban air of Rome. Atmospheric variation trends in the air of Changchun, the northeast Environment 31, 557-566. of China. Atmospheric Environment 34, 4459-4466. 17. Tsujino, Y., and Kuwata, K., 1993, Sensitive flame 28. Staff Report, September 1990, Proposed Identification ionization detector for the determination of trace of of Chloroform as a toxic air contaminant, State of atmospheric hydrocarbons by capillary gas California, Air Resources Board, Stationary Source chromatography, Journal of Chromatography 642, 383- Division, California USA. 388.

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