Determination of fluoride in air, water, soil and vegetation in the vicinity of Brick kilns area of Tehsil and District

Bhakkar. Introduction
Worldwide about 300,000 brick kilns are present and among these majorities are only present in the developing countries (CATF, 2010). These brick kilns are mostly present in the vicinity of urban areas due to high demand of bricks. These brick kilns are major contributor of atmospheric, hydrospheric, and lithospheric pollution which further contaminates the vegetation due to lack of pollution control measures. These pollutants have major impact on human health and vegetation. In these brick kilns, coal, vehicle oil and rubber tyres are used for burning purpose which results in the release of CO, SO2, NOx, and heavy metals etc. Dust emission occurs from extraction of raw clay from the soil for making bricks, high production of ash by burning coal and transportation of bricks. This dust level increases when high velocity wind passes through the loose soil of brick kiln area (NEERI, 1993; CPCB, 1996). As mostly brick kilns are present along the road sides and vehicle emissions are also contributor of environmental degradation of the brick kiln area. Fluoride presence in the vicinity of brick kilns is a major indicator of brick kiln pollution. It is released by burning of coal in the kiln which contains about 40- 295ppm of fluoride (Churchill et al. 1948). Clay used for the formation of bricks also contain large amount of fluoride which release in the environment and transferred to plants from the leaf stomata or from the water uptake by the roots. In the atmosphere Fluoride is present as silicon fluoride and hydrogen fluoride (Suttie 1980). From atmosphere particulate fluoride is transferred to soil and water and finally into the plants. In Pakistan poor quality coal is used for burning in brick kiln which result in the increasing emission of Fluoride. There are about 4000 brick kilns present only in Punjab (Awan, 2010) among these only few brick kilns are using the latest technology for the production of bricks to reduce brick kiln pollution. The residents and workers of these brick kiln areas suffer from different respiratory and dental diseases mainly due to accumulation of fluoride (CDCP, 1999).

Literature Review
In the study of Lucknow, India there was more accumulation of fluoride in the three vegetation type Mentha arvensis, Spinace aoleracea and Luffa cylindrica. Mentha arvensis had high concentration of fluoride while Luffa cylindrical had least concentration. There was more accumulation of airborne fluoride than water soluble and water reactive fluoride and soil fluoride. Total fluoride content in the study area was higher than the total fluoride content in the soil. In the area of atmospheric contaminated fluoride site, the concentration of fluoride was 1.5-950g/g. Its concentration varied at different distances depending upon the wind direction and sampling point distance from the source. Concentration of water soluble fluoride was 0.592.74ppm while CaCl2 extractable fluoride concentration was 0.69-3.18ppm (Jha, et al., 2008). The results of the 147 groundwater samples taken near brick kilns and other anthropogenic pollution source area of a village Kalalanwala, east Punjab, Pakistan had shown that there were about 75% samples that exceed the WHO limit for fluoride contamination. With the increase of depth the fluoride concentration was decreased. As Canal water contained F- concentration between 1.7-2.3mg/l, medium depth ground water contained 1.5mg/l or <1.5mg/l. and ground water at depth contain 1.5mg/l. Highly contaminated water having F- concentration 22.8mg/l was present at shallow depth of about 30m from the surface (Farooqi, et al., 2007). In the vicinity of brick kiln area of Peshawar, Pakistan there was more concentration of fluoride in the air and plants near brick kilns than at more distant sampling points. In leaves of apricot and plum, the concentration of fluoride was 63mg/kg and 46mg/kg respectively.In leaves of mango the concentration of fluoride was high. Due to fluoride contamination in plants necrosis and leaf burn was found in plants such as apricot and plum. In air HF concentration was measured for fluoride analysis and it was found that between February to May, 2008 its mean concentration was 0.22g/m3 at brick kiln site while its concentration was below the detection limit away from the brick kiln (Ahmad, et al., 2012). In Rosetta, Egypt GIS system was used to assess the air pollutant released from the brick kilns. It was found that the fluoride concentration was 0.0005587kg/sec which was higher in concentration than NOx, CO and VOC (Fouda, 2001).

Objectives

To assess fluoride level in the air surrounding the brick kiln area. To assess the soil contamination from fluoride released in the vicinity of brick kiln area. To assess the land damage and top soil removal resulting from the brick making To find out the ground water contamination as a result of fluoride emission from brick kilns. To determine the accumulation of fluoride in the surrounding area vegetation of brick kilns.

Hypothesis
As the surrounding area of Brick kilns is sandy, so due to leaching there may be more accumulation of fluoride in ground water. In air there may be high accumulation of fluoride by burning of coal. Fluoride may be transferred through wind in the areas that are far from the brick kilns. In soil fluoride may be directly accumulated from the ash or it may be deposited from air through dry and wet deposition and their may be more accumulation of fluoride in top soil as compared to lower horizons. In plants fluoride may be accumulated from ground water, soil or may be directly from air through stomata. As wheat have more capacity to accumulate fluoride than brassica, so there may be more concentration of fluoride in wheat.

Material and Methods Study Area

District Bhakkar is situated in Punjab, Pakistan and is a link between Punjab Province and KPK. It lies on the left bank of Indus river and located at a geographical coordinates of 313760N and 7140E. It covers the area of 8153sq.km.It consists of four Tehsils, Mankera, Darya Khan, Kalurkot and Bhakkar (Naqvi, 2011). It has hot summers and cold dry winters. Its annual rainfall is 150-300mm Major part of Bhakkar is desert name as Thal. Tehsil Bhakkar covers the area of 2427sq.km and population of 424,488(1998) (Tehsil Municipal Administration Bhakkar, 2007). The area selected for study is present about 10km away from the Indus River. It consist of about 70-80 brick kilns which covers the area of about 400sq.km. That area is called as Bhakkar Nashaib consisting of sand. The raw clay for the bricks is obtained from the Indus River and transported to brick kilns site. The fuel used for burning in these brick kilns are mainly coal and bagasse. Crops grown in that area are wheat, brassica and chick pea (Channa). Natural vegetation includes Date trees, Acacia and some shrubs etc.

Sample Collection
Each sample will be collected from different intervals of four zones, East, West, North and South upto 10-12km. Fresh vegetation samples will be taken from the sampling area and sealed in the polyethylene bags until analysis. Soil samples will be taken upto depth of 15cm and then will be placed in the polyethylene bag before analysis in the lab. Water samples will be taken in bottles from the hand pumps fixed at brick kiln sites and then sealed. Air samples will be collected with impinger or bubbler from the surrounding sites of brick kilns.

Sample Preparation Vegetation

Each sample will be washed and rinsed with distilled water and air dried for 1 hour. After that they will be oven dried for 1day and will be grounded and sieved. Then they will be acid digested. For this purpose 0.5g of each sample and in 5cm3of conc.HNO3 will be added in a beaker and heated at 150oC until dry and NO2 gas will release. Then the solution will be cooled and 100cm3volume will be prepared by adding distilled water.

Soil
Soil samples will be oven dried and then grounded and then will be sieved through 2mm sieves to remove coarser particles. Then 10g of soil will be taken in the sealed bottle. Then 20cm3of air exposed distilled water will be added in it and stirred which will be prepared by placing it in the natural air for 48hrs and stirring it regularly after 6hrs to absorb atmospheric gases. After placing it for 6hrs then the soil sample will be filtered in 100cm 3 volumetric flasks. The remaining residue will be leached in the beaker containing the filtrate by using exposed water for 2hrs.This solution will be diluted up to the mark by using exposed water.

Groundwater
In water samples reagents will be dissolved directly and will be analyzed through UV-VIS Spectrophotometer.

Reagent Preparation for Soil, Vegetation and Water analysis Fluoride standard solution
For the preparation of standard 1.5013g of ammonium hydrogen difluoride (NH4F.HF) will be dissolved in distilled water and to make volume of about 1000cm3. Resulting solution will contain 1000mg/l of fluoride. From that solution stock solution of different ranges will be prepared e.g. 2, 4, 6, 8, 10mg/l etc.

Solution Preparation of Alizarin Red

To make 1000cm3of alizarin solution 0.73g of alizarin red will be dissolved in distilled water in a volumetric flask

Zirconyl Acid Solution Preparation

In 800cm3 of distilled water about 0.345g of zirconyl chloride will be dissolved. After that about 33.30cm3 of conc.H2SO4 will be added slowly and stirred continuously. Finally about 101cm3HCl will be added and stirred and volume of 1000cm3 will be prepared.

Fluoride analysis by using UV-Vis Spectroscopy

5cm3 of alizarin red and zirconyl acid solution will be dissolved in 100cm3 of standard solution and samples and will be kept for 1hr for development of color. The absorbance measurements will be taken at 520nm and concentrations will be find out from calibration curve which will be prepared from plot of absorbance verses concentration of standard solution. For appropriate results the concentrations will be multiplied with dilution factor (Paul, et al., 2011).

Air Analysis
Air collected by the air sampler will be dissolved in alkaline solution. After that it will be titrated with thorium nitrate by using Chrome Azurol S as an indicator. Then its concentration will be measured using UV-Vis Spectrophotometer (Revinson & Harley, 1953).

References
(2007). Retrieved March 8, 2012, from Tehsil Municipal Administration Bhakkar: http://www.tmabhakkar.com/ Ahmad, M. N., Berg, L. J., Shah, H. U., Masood, T., Buker, P., Emberson, L., et al. (2012). Hydrogen fluoride damage to vegetation from peri-urban brick kilns in Asia: A growing but unrecognised problem? Environmental Pollution , 162, 319-324. CDCP (Centers for Disease Control and Prevention) (1999). Achievements in public health, 19001999: fluoridation of drinking water to prevent dental caries. Morbidity and Mortality Weekly Report 48, 933940. Churchill, H. V., Rowley, R. J. & Martin, L. N. (1948). Fluorine content of certain vegetation in Western Pennsylvania area. Anal Chem, 20(1), 6971. CPCB (1996). Comprehensive industry document with standards/guidelines for pollution control in brick kiln. CPCB Comprehensive Industry Document Series: COINDS/16/1995-96, Central Pollution Control Board, New Delhi, India. Edelstein, B. L., Cottrel, D., Sullivan, D. O., &Tinanoff, N. (1992). Comparison of colorimeter and electrode analysis of water fluoride. Pediatric Dentistry , 14 (1), 47-49. Farooqi, A., Masuda, H., Kusakabe, M., Naseem, M., &Firdous, N. (2007). Distribution of highly arsenic and fluoride contaminated groundwater from east Punjab, Pakistan, and the controlling role of anthropogenic pollutants in the natural hydrological cycle. Geochemical Journal , 41, 213-234. Fouda, Y. E. (2001). A GIS for environmental assessment of air pollution impacts on urban clusters and natural landscape at Rosetta City and region, Egypt. Urban Ecosystems , 5, 525. Jha, S. K., Nayak, A. K., Sharma, Y. K., Mishra, V. K., & Sharma, D. K. (2008). Fluoride accumulation in soil and vegetation in the vicinity of brick kiln fields. Bull Environ ContamToxicol , 80, 369373. Naqvi, S. S. (2011). Retrieved March 7, 2012, from Welcome to the Bhakkar City: http://bhakkar.webs.com/

NEERI (1993). Air pollution studies to redefine Taj Trapezium co-ordinates. NEERI, Nagpur, India. NEERI (1993). Carrying capacity based development planning for Doon Valley. NEERI, Nagpur, India. Paul, E. D., Gimba, C. E., Kagbu, J. A., Ndukwe, G. I., &Okibe, F. G. (2011). Spectrometric Determination of Fluoride in Water, Soil and vegetables from the Precinct of River Basawa, Zaria, Nigeria. Journal of Basic and Applied Chemistry, 1(6), 33-38. Revinson, D., & Harley, J. H. (1953). Spectrophotometric determination of fluoride ion with Chrome Azurol S. Anaytical Chemistry , 25 (5), 794797. Suttie, J. E., (1980). Performance of a dairy cattle herd in close proximity to an industrial fluoride emitting source. Paper presented at the Jine annual meeting of the A.P.C.A, 23.