Y.V. Rami Reddy* et al. /International Journal Of Pharmacy&Technology ISSN: 0975-766X CODEN: IJPTFI Available Online through www.ijptonline.com Research Article DETERMINATION OF ARSENIC, NICKEL & LEAD CONTENTS IN AMBIENT AIR REPAIRABLE SUSPENDED PARTICULATE MATTER (P.M10) IN AND AROUND TIRUPATI, CHITTOOR DISTRICT, ANDHRA PRADESH, INDIA P.M.N.Prasad, R.Chenna Krishna Reddy, V Hanuman Reddy, M Tirupal Reddy, Y.V. Rami Reddy* Enviro-Analytical Laboratory, Department of Chemistry, S.V.University, Tirupati -517502. Email: dryvrsvu@gmail.com Received on 24-12-2011 Accepted on 10-01-2012 Abstracts Ministry of Environment and Forests (MoEF), Govt of India was introduced limits for Ambient Air Quality (AAQ) for new environmental pollutants like P.M.2.5, O3, NH3, As, Ni, Pb, Benzene and Benzo (a) Pyrene in NAAQS, November 2009. In this study we made an attempt to study the three trace carcinogenic metals concentration levels in AAQ in Tirupati. The Arsenic, Nickel and Lead are summarized in results and discussion. For this study we were identified 5 sampling locations in Tirupati. Sampling was carried out 24 hourly and twice a week for P.M.10 in the month of February 2011. Totally 15 P.M10 samples were collected. The samples were digested and subjected to analysis for Arsenic, Lead and Nickel using Inductively Coupled Plasma -Mass Spectrometer (ICP-MS) based on USEPA Compendium method IO 3.5. ICP-MS is one of the best analytical techniques for the determination of metals in different matrices. By using ICP-MS we can able to determine the Arsenic minimum 0.03 ng/m3, Nickel minimum 0.02 ng/m3 and Lead minimum 0.01 ng/m3. The concentration levels of Arsenic, Nickel and Lead in different areas of Tirupati are summarized in results and discussion. These metals were compared with NAAQS amended by MoEF. The observed results of Pb, As and Ni were found lesser than NAAQS. Keywords: Tirupati – AAQ-Trace Metals (As, Ni, Pb)-NAAQS-MoEF. Introduction Owing to the up growing population, industrialization and urbanization, the air pollution problem has been assuming objectionable proportion. Rapidly growing industrialization has aggrevated the problem through industrial operations. Due to the growing pollution problems Central Pollution IJPT | April-2012 | Vol. 4 | Issue No.1 | 3802-3810 Control Board (CPCB) & Page 3802 Y.V. Rami Reddy* et al. /International Journal Of Pharmacy&Technology Ministry of Environment and Forestry (MoEF), Govt. of India amended the limits for new parameters in November 2009. Air pollution can arise from many sources. Most of the sources are man-made. Rapidly growing vehicular population as well as pollutants emitted by them generate harmful that have marked effects on pedestrians as well as near-by residents. Atmospheric particles are generated through a variety of physical and chemical mechanisms, and are emitted into the atmosphere from numerous sources, by combustion, industrial and natural processes. They are involved in many atmospheric processes, and play an important role in reducing visibility, acid deposition, and the balance of radiation in the atmosphere, both directly and indirectly through cloud formation (1). The effects of atmospheric particulate matters on environment and human health have been of great global concern. Atmospheric aerosol found in urban areas represent a mixture of primary particles emitted from various sources and secondary particles from aerosols formed by chemical reactions. The morphology and composition of these particles may change through several processes, including vapour condensation, evaporation and coagulation. The final ‘products’ usually vary according to origin, chemical composition and physical properties, leading to particular deposition patterns in the human respiratory system. (2) The high influx of population to urban areas, increase in consumption patterns and unplanned urban and industrial development has led to the problem of air pollution. (3) Pb, As and Ni are known carcinogenic pollutants in Air. In November 2009, CPCB and MoEF was amended the NAAQS and included maximum permissible limit for pollutants like Lead, Arsenic, Nickel, Benzene, Benzo (a) Pyrene, Ammonia and Ozone. Present Study Tirupati is one of the most popular pilgrim city in Andhra Pradesh, India and daily lakhs of pilgrims will visit and therefore rapidly growing vehicular population pollutant levels may also increases. In view of the air pollution effects on human health, we made an attempt to study the levels of trace metals like Arsenic, Nickel and Lead. Recently Ministry of Environment and Forestry adopted maximum permissible limits for these pollutants in National Ambient Air Quality Standards (India) – Amended in November 2009. IJPT | April-2012 | Vol. 4 | Issue No.1 | 3802-3810 Page 3803 Y.V. Rami Reddy* et al. /International Journal Of Pharmacy&Technology The prime objective of the air monitoring is to evaluate the existing air quality of the Tirupati area with respect to the As, Ni and Pb levels. For this study we selected five sampling locations which are having more vehicle moment. Ambient air quality monitoring has been carried out with a frequency of alternative days in week at each location. At each of these locations, sampling stations were operated for 24 hours. In this regard we collected fifteen RSPM (PM10) samples in five selected locations. These samples are collected both working days and holidays period in the month of February 2011. Particles with an aerodynamic diameter smaller than 10 µm (PM10) were collected on 8’x10’ cellulose membrane filters exposed for 24 hours using Repairable Dust Samplers (Envirotech), at the average flow rate of 1.2 m3 /min. Filters were pre-weighed and then dried in a desiccators for at least 24 hours after being exposed to air. The samples are collected at the following locations in and around the Tirupati area: S.V.University Main Gate • Gandhi Road • Near RTC Bus stand • K.T.Road • Alipiri Bypass road The details of sampling locations with date and time and total volume of air collected is given in below table. Table–1: Details of Ambient Air Quality Monitoring Locations. Sample Code AAQ1 AAQ2 AAQ3 AAQ4 AAQ5 AAQ6 AAQ7 AAQ8 AAQ9 AAQ10 AAQ11 AAQ12 AAQ13 AAQ14 AAQ15 Location S.V.U Main Gate S.V.U Main Gate S.V.U Main Gate Gandhi Road Gandhi Road Gandhi Road Near RTC Bus stand Near RTC Bus stand Near RTC Bus stand K.T.Road K.T.Road K.T.Road Alipiri Bypass road Alipiri Bypass road Alipiri Bypass road Date and Time of Sampling Started 02-02-2011 & 6:30 a.m 04-02-2011 & 6:10 a.m 06-02-2011 & 6:45 a.m 02-02-2011 & 7:30 a.m 04-02-2011 & 6:45 a.m 06-02-2011 & 7:12 a.m 02-02-2011 & 8:10 a.m 04-02-2011 & 7:12 a.m 06-02-2011 & 7:35 a.m 02-02-2011 & 8:55 a.m 04-02-2011 & 7:40 a.m 06-02-2011 & 7:58 a.m 02-02-2011 & 9:40 a.m 04-02-2011 & 8:05 a.m 06-02-2011 & 8:25 a.m IJPT | April-2012 | Vol. 4 | Issue No.1 | 3802-3810 Date and Time of Sampling Started 03-02-2011 & 7:20 a.m 05-02-2011 & 6:50 a.m 07-02-2011 & 7:15 a.m 03-02-2011 & 8:15 a.m 05-02-2011 & 7:20 a.m 07-02-2011 & 7:35 a.m 03-02-2011 & 9:04 a.m 05-02-2011 & 7:45 a.m 07-02-2011 & 7:55 a.m 03-02-2011 & 9:50 a.m 05-02-2011 & 8:10 a.m 07-02-2011 & 8:30 a.m 03-02-2011 & 10:35 a.m 05-02-2011 & 8:30 a.m 07-02-2011 & 8:55 a.m Volume of Air Sampled 1624 1682 1596 1684 1632 1588 1627 1646 1602 1672 1613 1583 1628 1672 1601 Page 3804 Y.V. Rami Reddy* et al. /International Journal Of Pharmacy&Technology Table-2: Techniques used for ambient air quality monitoring. Sr. No. Parameter Technique Technical Protocol 1 Arsenic, Nikel & Lead ICP-MS USEPA COMPENDIUM METHOD IO – 3.5 Minimum Detectable Limit (µ µg/m3) 0.001 Analytical Methodology After completion of the sampling cut the filter paper and transfer the pieces into a clean beaker washed with detergent, rinsed with distilled water, soaked in 1+1 HNO3 rinse in distilled water. Added sufficient amount of conc. HNO3 and conc. HCl. to cover the sample. Covered the beaker with a watch glass and heated on hot plate in a fume hood. Did not allowed the sample to evaporate to dryness and added 5 ml of conc. HNO3 two times. Treat the unexposed glass fiber filter paper in a similar way to prepare the blank solution. After dissolution, cool the contents by adding the distilled water and filter using the 42 no. wahtmann filter paper. Wash the filter with sufficient distilled water to make it free of acid. Make up the filtrate to 50ml or 100 ml in standard flask. Adjust the operating parameters of ICP-MS as per the operating manual. Set the wavelength at the proper value and aspirate the blank and sample solution one after the other into the instrument. To the extent possible, all determinations shall be replicate analyses. In order to eliminate the interference from the filter paper, a blank sample treated and analyzed exactly in a similar way as that of sample filter paper. The PM10 filter paper is divided into 1 x 8 “ strip equalling parts from the exposed filter. A part of filter strip is placed in an extraction tube. 20 ml of the 4% Nitric acid is added into the extraction tube with the filter. The extraction tube is closed with Cap and sonicated for 3 hours at 69 °C in sonication bath. The filter was occasionally checked during sonication period and used a clean pyrex or quartz glass rod to adjust the filter to the bottom of the tube without getting any floats out of the acid. After sonication, the sample is allowed to cool to room temperature and is filtered using Watman numbered 42 filter paper. The final volume of the sample is made up to 50 ml in volumetric flask with double distilled water. Transfered the sample extract to a polypropylene bottle then the sample was ready for analysis. IJPT | April-2012 | Vol. 4 | Issue No.1 | 3802-3810 Page 3805 Y.V. Rami Reddy* et al. /International Journal Of Pharmacy&Technology ICP-MS is one of the most sensitive technique for determination of trace metals in air, water, soil, drug and other matrices. By using ICP-MS technique we can able to determine minimum 1.0 µg/L concentration of trace metals in aqueous solutions. As per USEPA Compendium method IO-3.5, the Minimum Detection Limits of Arsenic is 0.3 ng/m3, Nickel is 0.02 ng/m3 & Lead is 0.01 ng/m3. Multi elements standard was used to determine all the three metal concentrations in single aspiration. Seven different working standards were prepared and made standard curve using the standards in ICP-MS. The correlation coefficient is observed greater than 0.999 for each of the element. After the completion of standard curve preparation, one standard check and one QC check was analyzed. Trace metals were analysed using ICPMS (Agilent 7300) Standard reference material of 1,000 mg/L (Multi elements- Merck). Seven different linear concentration standards were prepared, ranging from 0.001 mg/L–0.1 mg/L. Before conducting sample analysis, different concentrations of standards were analysed and linear curve was prepared. All metals having good linear graph with correlation coefficients of > 0.999 were observed in the preparation of standard curves. Results and Discussion: ICP-MS or AAS-GFA is the most useful technique for the determination of trace metals upto parts per trillion levels. Since, AAS-GFA is a single element analyser, it takes more time to analyse multiple elements. ICP-MS is a very useful technique to determine trace levels of metals in a single aspiration. Arsenic: In environment there are many arsenic compounds includes both organic and inorganic. Inorganic arsenic can have acute, sub acute and chronic effects, which may be either local or systemic. Some studies also show that populations near emission sources of inorganic arsenic, such as smelters, have a moderately elevated risk of lung cancer The arsenic concentration of different sampling areas in different days is ranging from 1.7 ng/m3 to 4.1 ng/m3. The maximum concentration of Arsenic is observed near RTC Bus stand area, particularly in Sunday (holiday time). And the minimum concentration of Arsenic is observed near S.V.University main gate. In holidays the vehicle movement is more in bus stand area and vehicle movement is less near S.V.University main gate. The NAAQ standard limit for Arsenic is 6.0 ng/m3. Therefore the observed results of Arsenic are less than that of NAAQ standard limit. IJPT | April-2012 | Vol. 4 | Issue No.1 | 3802-3810 Page 3806 Y.V. Rami Reddy* et al. /International Journal Of Pharmacy&Technology Figure -1: Trends of Arsenic in Different Aaq Locations in Different Days Nickel Nickel presents in nature and enter into air and water both from natural sources and human activity. In nonsmokers, about 99% of the estimated daily nickel absorption stems from food and water; for smokers the figure is about 75%. Allergic skin reactions are the most common health effect of nickel, affecting about 2% of the male and 11% of the female population. Nickel content in consumer products and possibly in food and water causes dermatological diseases. The respiratory tract is also a target organ for allergic manifestations of occupational nickel exposure. Work-related exposure in the nickel-refining industry has been documented to cause an increased risk of lung and nasal cancers. Inhalation of a mixture of oxidic, sulfidic and soluble nickel compounds at concentrations higher than 0.5 mg/m3, often considerably higher, for many years has been reported. Nickel has a strong and prevalent allergenic potency. 3 3 The Nickel concentration of different sampling areas in different days is ranging from 6.4 ng/m to 14.7 ng/m . The maximum concentration of Nickel is observed near RTC Bus stand area that to in Sunday (holiday time). And the minimum concentration of Arsenic is observed near S.V.University main gate. In holidays the vehicle movement is more in bus stand area and vehicle movement is less near S.V.University main gate. The NAAQ standard limit for Nickel is 20 ng/m3. However the observed results of Nickel are less than that of NAAQ standard limit. IJPT | April-2012 | Vol. 4 | Issue No.1 | 3802-3810 Page 3807 Y.V. Rami Reddy* et al. /International Journal Of Pharmacy&Technology Figure -2: Trends of Nickel In Different Aaq Locations In Different Days. Lead The relationship between air lead exposure and blood lead has been shown to exhibit downward curvilinearity if the range of exposure is sufficiently large. At lower levels of exposure, the deviation from linearity is negligible and linear models of the relationship between intake and blood lead are satisfactory approximations. 3 3 The Lead concentration of different sampling areas with different days is ranging from 0.055 µg/m to 0.47 µg/m . The maximum concentration of Lead is observed near RTC Bus stand area that to in Sunday (holiday time) and the minimum concentration of Lead is observed near S.V.University main gate. In holidays the vehicle movement is more in bus stand area and vehicle movement is less near S.V.University main gate. The NAAQ standard limit for Lead is 1.0 µg/m3. Therefore the observed results of Lead are less than that of NAAQ standard limit. Figure -3: Trends of Lead In Different Aaq Locations In Different Days. IJPT | April-2012 | Vol. 4 | Issue No.1 | 3802-3810 Page 3808 Y.V. Rami Reddy* et al. /International Journal Of Pharmacy&Technology Table-3: Concentrations of Lead, Arsenic & Nickel In Different Aaq Locations Sampled In Different Week Days. Sample Code Location Date and Time of Sampling Started Lead as Pb (µg/m3) 0.082 AAQ1 S.V.U Main Gate Arsenic as Nickel as As Ni (ng/m3) (ng/m3) 02-02-2011 & 6:30 a.m 2.6 10.8 AAQ2 AAQ3 AAQ4 S.V.U Main Gate S.V.U Main Gate Gandhi Road 04-02-2011 & 6:10 a.m 06-02-2011 & 6:45 a.m 02-02-2011 & 7:30 a.m 3.8 1.7 3.1 11.6 7.4 10.6 0.097 0.055 0.26 AAQ5 AAQ6 AAQ7 AAQ8 AAQ9 AAQ10 AAQ11 AAQ12 AAQ13 AAQ14 AAQ15 Gandhi Road Gandhi Road Near RTC Bus stand Near RTC Bus stand Near RTC Bus stand K.T.Road K.T.Road K.T.Road Alipiri Bypass road Alipiri Bypass road Alipiri Bypass road 04-02-2011 & 6:45 a.m 06-02-2011 & 7:12 a.m 02-02-2011 & 8:10 a.m 04-02-2011 & 7:12 a.m 06-02-2011 & 7:35 a.m 02-02-2011 & 8:55 a.m 04-02-2011 & 7:40 a.m 06-02-2011 & 7:58 a.m 02-02-2011 & 9:40 a.m 04-02-2011 & 8:05 a.m 06-02-2011 & 8:25 a.m 2.9 3.4 3.1 3.6 4.1 2.1 3.3 2.1 3.4 2.9 3.8 9.7 8.2 8.8 7.6 13.9 7.6 9.6 6.4 8.1 9.3 14.7 0.18 0.29 0.32 0.27 0.47 0.24 0.27 0.18 0.22 0.29 0.43 Conclusion This study concluds that the observed concentration levels of trace carcinogenic metals like Lead, Nickel and Arsenic in Ambient Air Quality of Tirupati area is less than that of NAAQS amended on 16th November 2009, published by Ministry of Environment and Forestry, Govt.of India. This study has given an awareness of concentration levels of trace carcinogenic metals (Pb, Ni & As) in Ambient air Quality of Tirupati. References 1. Tursic J, et al. determination of trace elements in aerosols arh hig rada toksikol 2008;59:111-116. 2. The Malaysian Journal of Analytical Sciences Vol. 12 No. 1 (2008.) 3. CPCB (2000c) Air Quality status and trends in India, National Ambient Air Quality Monitoring Series: NAAQMS/14/1999-2000. Delhi: Central Pollution Control Board. 4. ISO 9855: Ambient Air – Determination of the particulate lead content of aerosols Collected on filters – Atomic absorption spectrometric method, 1993. IJPT | April-2012 | Vol. 4 | Issue No.1 | 3802-3810 Page 3809 Y.V. Rami Reddy* et al. /International Journal Of Pharmacy&Technology 5. Pekar, M., Gusev A. and L. Erdman: Modelling of long-range transport of lead and Cadmium from European sources in 1996. EMEP MSC-E Report 25/98. Meteorological Synthesizing Centre - East of EMEP, Moscow, Russia (1998). 6. Wong, J.L., J. Qian and C.H. Chen; „Nickel speciation of fly ash by phase extraction“, Anal. Chim. Acta 349, 121-129 (1997). 7. World health Organization Regional Office for Europe Copenhagen (WHO regional publications. European series; No. 91). Corresponding Author: Y.V.Rami Reddy*, Email: dryvrsvu@gmail.com IJPT | April-2012 | Vol. 4 | Issue No.1 | 3802-3810 Page 3810