STUDY OF CONTAMINATION OF SOIL IN SURROUNDING OF ABANDONED

STUDY OF CONTAMINATION OF SOIL IN SURROUNDING OF ABANDONED PERSISTENT ORGANIC POLLUTANT (DDT) NOWSHERA FACTORY IN NORTH WEST FRONTIER PROVINCE (NWFP) PAKISTAN Project Team Dr. Mahmood A. Khwaja SUSTAINABLE DEVELOPMENT POLICY INSTITUTE (SDPI), ISLAMABAD. Dr. M. Rasul Jan and Kashif Gul INSTITUTE OF CHEMICAL SCIENCES, PESHAWAR UNIVERSITY, PESHAWAR January 2007 Table of Contents Executive Summary ................................................................................. i Acronyms ................................................................................................ iii 1. Introduction....................................................................................1 1.1 1.2 1.3 2. 2.1 2.2 2.3 3. 3.1 3.2 3.3 4. DDT Manufacturing, Supply and Use in NWFP ....................1 Reported Studies on DDT and other POPs Contaminated Environmental Samples in NWFP.........................................3 Aims and Objectives of Present Study..................................4 Soil Sampling........................................................................5 Samples Preparation and Extraction for Instrumental Analyses ...............................................................................6 Instrumental Analyses for DDT in Soil Samples ..................7 Nowshera Soil Texture........................................................17 DDT Contaminated Soil Around the Factory Area ..............17 DDT Contaminated Soil at Different Depths Around the Factory Area .......................................................................18 Conclusions and Recommendations.........................................19 National Implementation Plan (NIP) for Stockholm Convention on Persistent Organic Pollutants (POPs)…………………………… 20 References..............................................................................................21 Annexes: Annex 1: Stockholm Convention on Persistent Organic Pollutants 2001 .23 Annex 2: Details of local and smuggled DDT containing pesticides availability in district D. I. Khan market................................26 Annex 3: Concentration of DDT in water (ug/ml) around DDT Factory.....27 Annex 4: DDT Residues in Soil Samples (ug/g) around DDT Factory......28 Annex 5: Processes for Soil Decontamination and Reclamation:.............29 Results and Discussion ................................................................8 Methodology and Experimental Details.......................................5 Executive Summary Like other chemicals of persistent organic pollutant (POPs) group, DDT (dichlorodiphenyltrochloroethane), a pesticide, is also persistent in nature and does not degrade in the environment by biological, physical or chemical processes. Being non-degradable, DDT can travel to long distances and can accumulate in animal and human bodies due to its solubility in fats. Humans and Wildlife can come in contact with DDT through contaminated air, water, soil and food. Even in extremely small amounts DDT can injure human health and health of other organisms. It is harmful to stomach, intestines, liver, kidneys, can affect nervous system can cause reproductive, development defects & cancer and tumors. Women, children and infants are especially vulnerable to certain effects of DDT. In 2005 – 6, Sustainable Development Policy Institute (SDPI) & Institute of Chemical Sciences (ICS), Peshawar University, in collaboration with Environmental Protection Agency (EPA), NWFP and with support from IPEP (international POPs elimination project), South Asia, carried out a study to examine the adverse environmental and health impacts of residual DDT in and around DDT manufacturing factory, Amman Gharh, Nowshera, NWFP. During site survey and field-visits several composite samples of soil, sediments and water were collected in and around the factory area and chemically analyzed, The residual DDT levels in the studied soil samples were found to be alarmingly higher, despite the closure of the factory for many years, than the DDT standard minimum risk limit (MRL) for soil. In view of known toxicity, accumulative characteristics and adverse environmental and health impacts of DDT, its exposure in and around DDT factory in Amman Gharh may cause most serious consequences for ecosystem function, food safety and other aspects of human health. There is a dire need to carry out an extensive survey of the Amman Gharh area to examine DDT levels in different segments of its environment and likely impacts of DDT exposure on the general public, specially health of infants, children, women and other vulnerable groups. For the present study, eighty-one (81) soil samples were collected within half kilo meter distance from the gate of the factory in eight different directions. These directions, as indicated by the field-compass from the rubles of construction material, were north (N), north-west (NW), west (W), south-west (SW), south (S), south-east (SE), east (E) and north-east (NE) Soil samples were collected on clear dry days during three field-visits undertaken on December 2 (26 samples) &16 (25 samples), 2006 and January 11, 2007 (30samples). Soil samples were also collected from the soil surface, 0.15, 0.30, 0.45 & 0.60 meter depths from a single sampling point in each of the six directions. Data obtained and described in the foregoing pages indicates that 90.91% of the soil samples studied were contaminated with DDT, with 66.6% of the samples indicating residual DDT levels higher than DDT minimum risk level in soil (0.05 ug/g). It is evident from the data that in a very large area soil could be highly contaminated with DDT, despite the closure of the factory and no more production of DDT for many years. During field-visits, highly contaminated sites South West, South and South East were observed to be mostly residential areas with houses less than 200 meters away from the gate of the factory. It was also observed that the demolished factory compound had already become playing grounds for children and grazing/feeding place for stray cattle and free-range chickens. It is most strongly recommended that with immediate effect, the factory area may be declared as dangerous area and “Danger” signs in local languages be installed around it & the area be banned for any human activities. A fence/wall may be constructed, at the earliest, around the factory area, to avoid entrance of children, animals, cattle, and chickens. Advocacy campaigns for the above and awareness raising activities may be carried out at the earliest for the residents in the immediate surroundings of the factory area, especially for children/teachers in the schools of Amman Gargh. Now that the factory has been demolished, the likely sale of the land of the factory and surrounding areas for use as commercial/residential purposes, or for school, playground, park etc., is of grave concerns. The area/soil may remain contaminated with DDT for quite some time. It is most important that the land of the factory and the surrounding areas may not be sold or put to any use without prior approval of its environmental impact assessment (EIA) report by NWFP environmental protection agency, as required under section 12 of Pak Environmental Protection Act, 1997(34). High levels of DDT have been observed in soil samples from West, South West and south directions even at 550 meters from the gate of the factory and at 0.6meter depth which necessitates further examination of soil in thee area beyond 550 meters and 0.6meter depths This study has indicated most alarming situation of DDT residues in soil samples. There is a need to look into the feasibility of employing the reported processes for decontamination of DDT from the soil in and around the factory area. Pakistan needs to ratify Stockholm Convention at the earliest, so that with the incoming financial/technical support from the developed countries, as agreed under article 12(3) & 13(2) of the Convention, the activities (including rational management of POPs contaminated sites) as outlined in the National Implementation Plan (obligatory under section 7 (a) of the Convention), may be started. Details of the above investigations carried out, results achieved and recommendations for most urgent actions required to be undertaken to safeguard pubic health, specially children, are discussed and described in this report. ii Acronyms C DDT DW EIA EPA EU GC GEF GoP GTZ HCB HCl ICS IPEN IPEP MAC MIN MINFA MoE MRL NaCl ng/g NGOs NIP NWFP PCBs PCDDs PCDFs PH POPs PTS PVC SDPI ug/g ug/ml UNEP UNIDO WFPHA WHO 0 Degree centigrade Dichlorodiphenyltrichloroethane Dry Weight Environmental impact assessment Environmental protection agency European Union Gas Chromatograph Global environment facility Government of Pakistan German agency for technical cooperation Hexachlorobenzene Hyrochloric acid Institute of chemical sciences International POPs elimination network International POPs elimination project Maximum permissible limit Minute Ministry of food agriculture and livestock Ministry of environment Minimum risk level Sodium chloride nanogram per gram Non-governmental organizations National implementation plan North West Frontier Province Polychlorinated biphenyls Polychlorinated dibenzodioxins Polychlorinated dibenzofurans Hydrogen ion concentration Persistent organic pollutants Persistent toxic substances Polyvinyl chloride Sustainable Development Policy Institute Microgram per gram Microgram per milliter United nations environment program United nations industrial development organization World association of public health association World health organization iii 1. Introduction DDT (1,1,1-trichloro-2,2-bis-(p-chlorophenyl)ethane), an organo-chlorine-based pesticide, is one of the most hazardous group of chemicals called persistent organic pollutants (POPs), also known as “ The Dirty Dozen.” DDT is sold in the market under different formulator’s trade names such as Zeidane, Anofex, Dedela, Zerdane, Rukseam. etc. and has been extensively used in many country, including Pakistan, as an effective pesticide on a variety of agriculture crops and to control insects that spread diseases like malaria, dengue fever and typhus (1). However, like other chemicals of POPs group, DDT is persistent in nature and does not degrade in the environment by biological, physical or chemical processes. Being non-degradable, DDT can travel to long distances and can accumulate in animal and human bodies due to its solubility in fats. Humans and Wildlife can come in contact with DDT through contaminated air, water and food. Traces of DDT contaminations have been found to be present in the food web, in animal products-meat, fish and milk in particular, with significant hazard to those who consume these foods. Even in extremely small amounts DDT can injure human health and health of other organisms. It is harmful to stomach, intestines, liver and kidneys and can affect nervous system and can cause reproductive, development defects and cancer and tumors. Women, children and infants are especially vulnerable to certain effects of DDT (2-4). To save public health, specially the health of the children, the manufacturing and use of DDT have been banned in the world under the Stockholm Convention on Persistent Organic Pollutants (POPs), in-acted in 2001(5). A number of national governments including Pakistan have signed the Stockholm Convention and so far also ratified by 122 countries. The convention entered into force on May 17, 2004. This global convention deals with DDT and eleven other most hazardous persistent organic pollutants, which pose major and increasing threats to health and environment. Article 3 of the convention on POPs describes the measures to reduce or eliminate releases from intentional production and use of POPs and calls for specific measures to reduce/eliminate DDT (Annex B), binding each party state to eliminate the use & production of DDT except for parties that have notified the secretariat of “Restricted” production and/or use for disease vector control in accordance with the WHO recommendations and guidelines (5). Details regarding restricted use and production of DDT under the Stockholm Convention on persistent organic pollutants (POPs) are described in Annex I. 1.1. DDT Manufacturing, Supply and Use in NWFP In 1954, pesticides amounting to 254 tons were imported in the country for the first time, for the control of locust (6). However, the agricultural pesticides usage has been substantially increased from 665 tons in 1980 to 69,897 tons in 2002 (7). To meet the country pesticides need, most of these have been imported, except DDT for which a factory was established in 1963 at Amangargh , Nowshera near Peshawar, the provincial capital of North West Frontier Province, NWFP (Figure 1). The annual production of the factory when in operation was about 6000 tons. The liquid and powdered DDT products of the factory were, respectively used for malaria eradication and agricultural purposed in NWFP and also in other parts of the country. The raw material used in the production of technical DDT was (a)-Benzene: imported from abroad, (b) chlorine gas in a high-pressure cylinder, from Ittehad Chemicals, Kala Shah Kako, Lahore and (c) the source of alcohol was Mardan distillery (Mardan Sugar Mills). Waste water of the factory after lime treatment was discharged into nearby Kabul river (7). Figure 1 Site Map: DDT Factory Amangargh, Nowshera (8) In 1994 the manufacturing and the use of 21 pesticides, including DDT, were banned in Pakistan and the DDT factory, Nowshera was closed down as well. However, the factory was still in operation for many years and most surprisingly a few thousand kilograms of the chemical in worn out bags are still there on the floor of the demolished storehouse. Abandoned DDT Factory (Feb., 2005) Partly Demolished Factory (Aug., 2005) These bags are mostly worn out and the chemicals getting mixed into soil and small pools of rain water (7). 2 POPs pesticides inventory report of NWFP (9), prepared and published by environmental protection agency (EPA)-NWFP under POPs enabling activity project, has revealed the availability of smuggled DDT pesticide formulations in the open markets of district D.I. Khan, under the brand names of Methyl, Dusting Powder and 785 containing 15, 5 – 15 and 100 percent DDT, respectively (Annex 2). According to the inventory report there are approximately 49 MT of obsolete stocks of POPs pesticides (including DDT) at 32 sites in NWFP (9) 1.2. Reported Studies on DDT and other POPs Contaminated Environmental Samples in NWFP A few studies on DDT and other POPs contaminated environmental samples from NWFP carried out during 2005 – 2006 have been reported (7, 10-14). Ahad and Mohammad (10) have reported the results (total pesticides) of chemical analyses of nineteen samples of soil and water from the vicinity of POPs stores in NWFP. All of the five soil and thirteen water samples studied were found to be contaminated with varying levels of residual pesticides However, pesticides levels for water samples were found to be within the maximum permissible concentration (MAC) set by European Union (10). Studies on DDT and other POPs levels in free-range chicken eggs in Peshawar have been reported by Khwaja and Petrlik (11-12) Whereas, levels of industrial and unintended POP chemicals were within European Union prescribed limits, high levels of DDT were found in the egg samples, with measured sum equal to 2329.30 ng/g of egg fat. This DDT level in the eggs sampled nearby Peshawar waste dumpsite is four and a half time higher than the EU limit for the sum of DDT in eggs (EU limit = 500 ng/g of egg fat). Studies on POPs levels in different samples of hospital waste incineration and brickkilns residues from hospital incinerators in Peshawar, Islamabad, Lahore and brick kilns in the outskirts of Peshawar have also been carried out and reported (13-14). IPEP, South Asia: Environmental and Health Impacts of DDT Factory Sustainable Development Policy Institute (SDPI) & Institute of Chemical Sciences (ICS), Peshawar University in collaboration with Environmental Protection Agency (EPA), NWFP and with support from IPEP (international POPs elimination project), South Asia, carried out a study, in 2005 –6, to examine the adverse environmental and health impacts of residual DDT in and around DDT manufacturing factory in Amman Gharh, Nowshera, NWFP. The study was one of many activities carried out under international POPs elimination project (IPEP) in eight regions of the world, including South Asia and supervised by international POPs elimination network (IPEN). During survey and field-visits several composite samples of soil, sediments and water were collected in and around the factory area, nearby DDT stores, main factory drain leading to river Kabul and nearby villages (7). The analytical data obtained from chemical analyses of samples under study, indicated residual DDT in water. Water samples from within the vicinity of DDT factory, nearby villages and 3 drain leading to river Kabul showed little variation in DDT levels, most of the samples falling in the range 0.20+/-0.23 to 0.31+/-0.03 µg/ml. Highest and lowest DDT levels were found to be 0.40+/-0.14 and 0.07+/-0.10, respectively (Annex 3). Soil samples from within factory formulation unit showed residual DDT in the range 242.28+/- 0.81 to 573.02 +/- 0.94 µg/gm. DDT levels in the soil samples at different points outside the factory compound were found to be in the range 558.35+/-0.71 to 780.40+/-0.54 µg/gm. In the drain samples DDT levels were found in the range 388.57+/-0.48 to 1631.70+/-0.61 µg/gm. Highest DDT levels of 2822.08+/-0.88 and 2841.45+/-0.95 µg/gm were found in samples from the left-over old bags in the formulation unit and in the stores. Soil samples taken from five yards outside the stores showed 1631.70+/- 0.61 µg/gm residual DDT. However, DDT was not detected in the soil samples taken from Azakhel, ten kilometer away from DDT factory (Annex 4). The above observed DDT levels both in water and soil samples are many times higher than recommended minimum risk levels (15,16). (MRLs for water =0.008 ug/ml and for soil = 0.054 ug/gm). 1.3. Aims and Objectives of Present Study There are no national standards developed as yet or minimum risk limits (MRL) defined for DDT in Pakistan. However, when compared to other known standards (15,16), it is evident from the data given above in section 1.3 that both water and soil of the surrounding area could still be highly contaminated with DDT, despite the closure of the DDT factory over the past many years. As described in the preceding pages, DDT like other POPs chemicals is known for its persistency, transportation and accumulative characteristics, toxicity, and its adverse environmental and health impacts, even if present in extremely small amounts. Therefore DDT exposure in and around DDT factory in Amman Gharh may cause most serious consequences for ecosystem function, food safety and other aspects of human health. There is a dire need to carry out an extensive survey of the Amman Gharh area to examine DDT levels in different segments of its environment and likely impacts of DDT exposure on he general public, specially health of infants, children, women and other vulnerable groups. The study would also enable raising public awareness about health hazards caused by DDT and other POPs chemicals and in drawing government attention in taking necessary remedial measures, at the earliest, for cleaning up. The present report describes and discusses, in details, results of investigations carried out on eighty one (81) soil samples taken in six different directions up to 750 meters from the gate of the DDT factory and at a depth 75 mm. 4 2. Methodology and Experimental Details Details about the abandoned DDT factory, Amman Gargh, Nowshera and the study site have already been described in details in our last report (7). However, on our first field-visit, we found that the abandoned factory had been demolished and erased/leveled to the ground. Strong DDT odor could still be felt in the air. 2.1. Soil Sampling For the present study, eighty-one (81) soil samples were collected within half kilometer distance from the gate of the factory in eight different directions. These directions, as indicated by the field-compass from the rubles of construction material, were north (N), north-west (NW), west (W), south-west (SW), south (S), south-east (SE), east (E) and north-east (NE) Soil samples were collected on clear dry days during three field-visits undertaken on December 2 (26 samples) &16 (25 samples), 2006 and January 11, 2007 (30samples). Sampling was started around noon and completed before evening. Composite soil samples from the factory surroundings were collected at a distance of 65 meters between the two samples in the same direction and 100 meters between two samples in the adjacent directions (i.e. N & NW) from 0.15 to 0.30 meter depth (Figure 2) In the last field-visit, five samples from the soil surface, 0.15, 0.30, 0.45 & 0.60 meter depths were collected from a single sampling point in each of the six directions. Soil sampling around demolished factory Soil sampling in the factory surroundings All samples weighing one kilogram each were collected in clean polyethylene bags, employing randomized composite sampling technique and were labeled as A, AD, D, BD, B, BC, C, AC for N, NW, W, SW, S, SE, E & NE directions, respectively. Samples taken at different depth were labeled as ADD, DD, BDD, BB, BCD & CC with figures 0,1,2,3 and 4 for soil surface, 0.15, 0.30, 0.45 & 0.60 meter depths, respectively. 5 2.2. Samples Preparation and Extraction for Instrumental Analyses Samples points directions: North (N), north-west (NW), west (W), south-west (SW), south (S), south-east (SE), east (E) and north-east (NE) Distance (in meters) from gate of DDT Factory: 1 = 65; 2 = 130; 3 = 195; 4 = 260; 5 = 325; 6 = 390; 7 = 450; 8 = 520 Figure 2 Soil sampling points around DDT factory area. All the stones, pebbles and organic matter etc were removed from the sample collected. Samples were dried in the oven at 60 °C overnight, well mixed and sieved. Approximately 500 grams was taken as a laboratory sample and the remaining portion was stored. The laboratory sample (500g) was grounded to powder in a mortar and pestle and passed through a sieve. 50.00 grams analytical portion was taken out in a thimble. The extraction of each sample was carried out in triplicate. Each soil sample (50g) was taken in a thimble and placed in Soxhelt extraction apparatus. The apparatus 6 was placed on a water bath kept below 100 °C. Then the sample was extracted with 150 ml of methanol in a Soxhelt extraction apparatus for 4 hours. The volume of the sample was reduced to 20 ml in the same apparatus. A 0.25 ml portion was taken from the original sample and diluted up to 10 ml with methanol. It was transferred to well-washed, clean, dry glass vial, sealed and put in the refrigerator till analysis (1719). 2.3. Instrumental Analyses for DDT in Soil Samples Every possible care was taken to follow best laboratory practices to avoid contamination and keep reproducibility and precision of the final data.. All the extraction and clean up steps were standardized and checked for optimum behavior and quantitative recoveries. Shimadzu Gas Chromatograph model GC-14Awith electron capture detector and other accessories (as mentioned above) were used throughout the study. Operational conditions were as follows: Programming for GC: Carrier gas: Column initial temperature: Column initial time: Column program rate: Final temperature: Nitrogen 80 °C 2 min 20 min 160 °C 0 min 4 °C 250 °C 0 min 10 °C 275 °C 5 min 240 °C 280 °C Final time: Programmed rate: Final temperature: Final time: Programmed rate: Final temperature: Final time: Injector temperature: Detector temperature: DDT in the samples were identified on the basis of retention times, quantified on the basis of peak areas, and reported on the basis of sample volume or weight expressed in ug/g. 7 3. Results and Discussion DDT levels (ug/g) in 51 soil samples collected in eight directions (N, NW, W, W, S, SE, E & NE) around the factory area are described in table 1 and graphic presentations of the same are shown in figure 3 to 7. Figure 8 describes comparative DDT levels of soil in the different direction at 0.15 – 0.30meter depth and figure 9 gives comparative DDT levels of soil samples at different distances from the gate of the factory. Tables 2 & 3 and figures 11 – 15 describe DDT levels (ug/g) of 30 soil samples collected at different depths between 0.0 – 0.6 meter in six directions around the factory. Table1. DDT levels (ug/g) in soil (at 0.15-0.30 meter depth) around DDT factory Nowshera Distance in Meter A Average AD D BD B BC C AC 65 11.3 10.46 9.96 9.59 8.27 0.01 8.27±4.92 130 8.96 8.29 8.89 7.99 5.08,4.61 2.70,3.35, 2.26,2.94 8.55 7.82 0.01 7.22±3.91 195 3.06 7.7 7.86 5.96 0.03 4.79±3.29 260 0.01 7.58 5.75 6.24 0.04 3.92±3.61 325 0.02 0.01 6.53 7.43 3.87 0.02 2.98±3.45 390 0.02 0.04 6.14,6.95 & 5.51 6.28 4.14 0.01 2.70±3.01 455 0.01 0.03 5.86 0.01 1.48±2.92 520 0.01 0.01 5.19 0.01 1.31±2.59 Average 0.02±0.01 2.93±4.61 9.38±1.53 7.16±1.70 4.82±2.66 6.70±1.25 6.05±1.82 0.02±0.01 Minimum risk level (MRL) for soil = 0.05 ug/g Samples points directions from the DDT Factory gate: A = North; AD = North West; D = West; BD = South West; B = South; BC = South East; C = East; AC = North East Distance (in meters) from gate of DDT Factory: 65, 130, 195, 260, 325, 390, 450, 520 Each composite soil samples from 0.15 – 0.30meter depth. 8 BD(SOUTH WEST) 12 Conc.(ug/g) 10 8 6 4 2 0 1 2 3 4 5 6 7 8 Sample No. Figure 3: DDT levels of South-West soil samples (65–520 meters from the DDT factory) B (SOUTH) 12 10 8 6 4 2 0 1 2 3 4 5 6 7 8 Sample No. Figure 4: DDT levels of South soil samples (65–520 meters from the DDT factory) Conc.(ug/g) 9 BC (SOUTH EAST) 10 Conc.(ug/g) 8 6 4 2 0 1 2 3 4 Sample No. 5 6 7 Figure 5: DDT levels of South-East soil samples (65–520 meters from the DDT factory) C (EAST) 10 8 6 4 2 0 1 2 3 4 5 6 Sample No. Figure 6: DDT levels of East soil samples (65–520 meters from the DDT factory) Conc.(ug/g) 10 AC (NORTH EAST) 0.05 Conc.(ug/g) 0.04 0.03 0.02 0.01 0 1 2 3 4 5 6 7 8 Sample No. Figure 7: DDT levels of North-East soil samples (65–520 meters from the DDT factory) combine bargraph 10.00 Average Conc. 8.00 6.00 4.00 2.00 0.00 1 2 3 4 5 6 7 8 No. of sides Figure 8: Comparative DDT levels (in soil at o.15 – 30 meter) in all directions from the DDT factory gate: 1 = North; 2 = North West; 3 = West; 4 = South West; 5 = South; 6 = South East; 7 = East; 8 = North East 11 Average Conc. (ug/g) 10 8 6 4 2 0 65 130 195 260 325 390 455 520 Distance in meter Figure 9: Comparative DDT levels of soil samples (at 0.15 – 30 meter) at different distances (meters) from the DDT factory gate. Table 2. DDT levels (ug/g) of soil between 0.0 – 0.6 meter depths around DDT factory Nowshera. CONC. 9.95 8.18 7.03 3.74 0.01 10.62 6.30 3.91 3.02 0.58 1.73 1.77 0.05 0 0 2.14 2.14 0.85 0 0 8.31 4.50 Ave. 5.78±3.94 SAMPLE NAME ADD0 ADD1 ADD2 ADD3 ADD4 DD0 DD1 DD2 DD3 DD4 BDD0 BDD1 BDD2 BDD3 BDD4 BCD0 BCD1 BCD2 BCD3 BCD4 BB0 BB1 4.88±3.80 0.71±0.95 1.03±1.08 12 BB2 BB3 BB4 CC0 CC1 CC2 CC3 CC4 1.28 0 0 4.94 3.90 0.02 0 0 2.82±3.58 1.77±2.45 Samples points directions from the DDT Factory gate: ADD = North West; DD = West; BDD = South West; BB = South; BCD = South East; CC = East Soil Samples from depth (meters): 0 = Soil surface; 1 = 0.15; 2 = 0.30; 3 = 0.45 & 4 = 0.60 7 6 5 4 3 2 1 0 Average Conc. North West South South South East West West East Dire ction MRL Figure 10. DDT levels (ug/g) of soil between 0.0 – 0.6 meter depths around DDT factory. Table 3. DDT levels (ug/g) of soil at different depths (meter) around DDT factory Nowshera. Samples points directions from the DDT Factory gate: ADD = North West; DD = West; BDD = South West; BB = South; BCD = South East; CC = East Depths (meters) ADD DD BDD BB BCD CC Averages Soil surface 9.95 10.62 1.73 8.31 2.14 4.94 6.28±3.90 4.47±2.46 0.15 8.18 6.30 1.77 4.50 2.14 3.90 2.19±2.77 0.30 7.03 3.91 0.05 1.28 0.85 0.02 13 0.45 3.74 3.02 0 0 0 0 1.13±1.76 0.60 0.01 0.58 0 0 0 0 0.10±0.22 Average Conc. (ug/g) 9 8 7 6 5 4 3 2 1 0 W es W es W es So u Ea s Ea s th th So u Direction Figure 11: DDT levels of surface soil samples around DDT factory area Average Conc.(ug/g) 12 10 8 6 4 2 0 W es W es W es Ea s So u Ea s M R L t t th t t t th th So u Direction Figure 12: DDT levels of soil at 0.15 meter around DDT factory area Average Conc. (ug/g) 8 7 6 5 4 3 2 1 0 Figure 13: DDT levels of soil at 0.30 meter around DDT factory area So u N or th So u N or th W es t W es W es So u Ea s Ea s th th So u Direction 14 So u N or th M R L t th t t t M R L t t th t t t Average Conc. (ug/g) 4 3.5 3 2.5 2 1.5 1 0.5 0 W es t W es W es So u Ea s Ea s Ea s t th th Direction Figure 14: DDT levels of soil at 0.45 meter around DDT factory area Average Conc. (ug/g) 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0 W es W es W es So u Ea s M R L t t th t t th th th So u So u N or th M R L t th t t t Direction Figure 15: DDT levels of soil at 0.60 meter around DDT factory area So u So u N or 15 7 6 5 4 3 2 1 0 1 2 3 Depths (metres) Figure 16: Comparative DDT levels at different depths (meter) around the factory (1 = surface soil; 2 = 0.15; 3 = 0.30; 4 = 0.45 and 5 = 0.60) DDT Conc . 4 5 Figure 10 describes the comparative DDT levels of composite soil samples between 0.0 – 0.6 meter in six directions around the factory. Comparative DDT levels at different depths are given in Figure 16. Increase in the amount of organochlorine compounds (OC) such as DDTs in the global environment has been observed over the last many year as a consequence of their extensive use since the industrial revolution (20-23). In the seventies, concern over their potential toxicity and high persistence, led to the implementation of many regulations for their restricted use or phase out. Scientific interest has also been focused on the study of historic inputs in soil/sediments for the evaluation of the success of these international environmental policies (24-27). However, evaluation of long-term changes in/around chemically contaminated remote sites has been barely considered. POPs contamination of environmental segments may be related to point sources or more frequently, to diffuse sources which are the major pathway for the transfer of these persistent organic chemicals to remote sites. However, soils and sediments possess different micro environmental conditions affecting air and water exchange and post-depositional processes. Comparison of the accumulation patterns of POPs in these two environmental compartments is therefore a pre-condition for an integrated understanding of the pollution load of these compounds in remote sites. Although the use of many POPs has been restricted or even banned in many countries, these chemicals continue to be found widespread in the environment especially in biological matrices (28-29). Under UNEP program of regionally based assessment of persistent toxic substances (PTS), levels of DDT and other persistent organic pollutants (POPs) have been monitored in samples from different environmental segments as well as food items in 12 regions of the world, including South East Asia and South Pacific (18-19). DDT 16 has been reported in sediment samples from rivers and lakes. Reported concentration values range from not detected to thousands of µg/kg.dw. DDT concentrations have been observed to be usually higher at places where DDT is still used. Sediment samples from Indian rivers showed the highest values. High levels of DDT have also been reported in East Asian region and in the former USSR (18). DDT residues in the soil of areas surrounding a DDT manufacturing factory in Dehli have been reported by Yadav et al and Saxena et al (30-31). The reported data clearly indicates an upward trend residual DDT in the soil of the surrounding DDT manufacturing factory from a mean value 034+/-0.49 ppm of total DDT in 1974 to 1.43+/-1.16 and 1.67+/-1.16 in 1978 and 1983, respectively (30). The results also indicated an increase in highest DDT level of 7.27 ppm in 1983 compared to 2.61 ppm in 1974. In the studied soil samples around the DDT factory, residual DDT decreased with the increasing distance from the factory. Soil samples from agricultural land also indicated less total DDT residue as compared to samples from urban soils (31). 3.1. Nowshera Soil Texture The soil of Nowshera district is generally described as sandy (8). Soil characteristics of village Gundhari, district Nowshera have been reported as a recent river alluvium, sandy loam to clay loam in texture and slightly to highly saline (32). Employing standard method (33) for soil texture examination, the soil samples around DDT factory site was found to belong to texture class Sandy Loam, with clay, silt and sand contents to be 1.6, 48.0 and 50.4 %, respectively. 3.2. DDT Contaminated Soil Around the Factory Area Eight representative soil samples could not be taken in each of the 8 directions around the DDT factory area as planned (Figure 2), due to obstructions like protected fences, shops, factory & residential buildings, tar roads and railway lines. In the West direction only two soil samples (within 65 - 130 meters), in the South three samples (within 65 – 195 meters) and in the North four samples (between 325 – 520 meters) could be taken. All the 51 soil samples taken at a depth of 0.15 – 0.30 meter showed the presence of residual DDT (Table 1). Only soil samples examined in the North East (AC) indicated residual DDT level (average 0.02 +/- 0.01) below the minimum risk level (MRL) of 0.05 ug/g. Soil samples collected between 325 – 520 meters in the North and North West directions also indicated residual DDT levels, below MRL, between 0.01 to 0.04ug/g. Highest residual DDT level (11.30 ug/g) was found at 65 meters from the factory gate in the North West direction. However, soil in the South East direction appeared to be most contaminated (average 6.70 +/- 1.25 ug/g), showing the highest level of DDT (5.19 ug/g) in soil sample collected as far as at 520 meters from the gate of the DDT factory. Soil in the South direction also appeared highly contaminated, with an average DDT residual level of 7.16 +/- 1.70 ug/g between 65 – 390 meter away from the factory (Table 1). In all directions, except NE, around the factory area, residual DDT levels in soil samples generally showed a decrease with increasing distance from the factory 17 (Figures 3 – 7). However, soil samples collected in North East direction indicated higher DDT levels between 195 – 325 meters compared to soil samples collected from 65 – 130 and 455 – 520 meters. A comparison of average DDT levels of soil samples in all directions (Figure 8) indicated higher levels towards the West (9.38 +/1.53 ug/g) and South West (7.16 +/- 1.70 ug/g) directions. Figure 9 describes average DDT levels of soil samples in all directions at different distances from the gate of the factory, indicating a decreasing trend of DDT levels with increasing distance. Highest (8.27 +/- 4.9 ug/g) and lowest DDT levels (1.31 +/2.5 ug/g) were indicated in soil samples, respectively, at 65 and 520 meters from the gate of the factory (Figure 9). 3.3. DDT Contaminated Soil at Different Depths Around the Factory Area For examining soil contamination at different depths around the factory area, samples were collected in only six directions (NW, W, SW, S, SE & E), excluding North & North East, as DDT levels (0.02 +/- 0.01 ug/g) in soil samples at 0.15 – 0.30 meter depth from N & NE directions were already found to be below minimum risk level (MRL) of 0.05 ug/g (Table 1). For soil between surface and 0.60meter depth, highest residual DDT level (5.78 +/- 3.94 ug/g) was observed in samples from NW direction (Table 2 ), followed by samples from the West direction (4.88 +/- 3.80 ug/g). The lowest residual DDT level (0.71 +/- 0.95 ug/g) was observed for soil samples in the South West direction. Except for NW & W directions, soil samples from other directions did not show residual DDT beyond 0.45 meter. Even at 0.60meter depth in the West direction, alarmingly high level (0.58 ug/g) of residual DDT was observed (Table 3), compared to MRL (0.05 ug/g) for soil. A comparison (Figure 10) of average DDT levels in the six directions did not show any increasing or decreasing trends of residual DDT in soil, from soil surface to 0.6meter depth, around DDT factory. Figures 11 to 15 show comparative residual DDT levels in six directions for soil samples from surface and at 0.15, 0.30, 0.45, 0.6meter depths. At all different depths (soil surface to 0.60 meter) studied, higher residual DDT levels were found in soil samples from North West (9.95 – 0.01 ug/g) and West (10.62 – 0.58 ug/g) directions. No increasing or decreasing trends in residual DDT levels at any depth were observed for soil samples from the six directions around the factory area. It was observed that in all soil samples, there was decrease in level of residual DDT as one goes from top (surface soil) to bottom (0.60 meter), indicating not much leaching into the soil. This could be attributed to the soil texture with a silt content of 48% (section 3.1). In most of the soil samples, the level of residual DDT dropped to below detection level on reaching 0.45meter depth (Table 3). A comparison of average residual DDT levels at different depths (Figure 16) also indicated a similar decreasing trend in residual DDT from 6.28 +/- 3.90 to 0.10 +/- 0.22 with increasing depth from surface to 0.60meter of the soil around the demolished factory area. 18 4. Conclusions and Recommendations Data described in Tables 1 and 2 indicates that 90.91% of the soil samples studied were contaminated with DDT, with 66.6% of the samples indicating residual DDT levels higher than DDT minimum risk level in soil (0.05 ug/g). It is evident from the data that soil of the area is still highly contaminated with DDT, despite the closure of the factory and no more production of DDT for many years. During field-visits, highly contaminated sites South West, South and South East were observed to be mostly residential areas with houses less than 200 meters distance from the gate of the factory. It was also observed that the demolished factory compound had already become playing grounds for children and grazing/feeding place for stray cattle and free range chickens. Sport by children nearby DDT factory Cattle around the factory compound As also briefly described in the preceding pages (section 1), the toxicity, persistency, accumulative nature, transportation and adverse environmental & health impacts of DDT even if present in extremely small amounts, are well established and known. DDT contamination in and around the abolished DDT factory areas in Amman Gharh may cause most serious consequences for ecosystem function, food safety and other aspects of human health. It is, therefore, most strongly recommended that with immediate effect, the factory area may be declared as dangerous area, “Danger” signs in local languages be installed around it and the area be banned for any human activities. Accordingly, advocacy compaignes for the above and awareness raising activities may be carried out at the earliest for the residents in the immediate surroundings of the factory area, specially for children/teachers in the schools of Amman Gargh. A fence/wall may be constructed, at the earliest, around the factory area, to avoid entrance of children, animals, cattle, and chickens. High levels of DDT have been observed in soil samples from West, South West and south directions even at 550 meters and 0.6meter depth (Table 1 & 2) which necessitates further examination of soil in thee area beyond 550 meters and 0.6meter depths 19 The exposure’s potential risk to human health posed by hazardous wastes like DDT is known to be enhanced by a general lack of vegetation in the affected soil, therefore, as an immediate measure excessive vegetation may be grown in the area for effective minimization of the risk. In order to evaluate the risk associated with the DDT-contaminated site, studies using bio indicators like eggs, adipose tissues, milk, fish, birds, endocrine disruption and cholinesterase levels etc should be initiated in these areas. Earlier reports have indicated high DDT levels in the eggs sampled near Peshawar, NWFP (11-12) The presence of high level of DDT in the soil samples indicates the persistence of DDT in this high temperature zone of Pakistan, though there were earlier reports (18, 35, 36) that DDT may not be persistent in this part of the world. The present study necessitates a fresh look into those findings. There is also a dire need to identify similar DDT and other POP hot-spots in the country and study the level of health threats to local population in this and all other areas in Pakistan, where the formulation storage and application of DDT was practiced. Further work is also needed to see if other degradation products like DDE are present in the vicinity of the demolished DDT factory. This study has indicated most alarming situation of DDT residues in soil samples. There is a need to look into the feasibility of employing the reported processes for decontamination of DDT from the soil in and around the factory area. A number of soil decontamination processes have been developed and reported (37). Some of these are referred to in Annex V. Pakistan National Implementation Plan (NIP) for the Stockholm Convention NIP (obligatory under article 7 of the Stockholm Convention) elaborates current situation on POPs, including DDT and states commitment and actions that it intends to undertake in the management and control of POPs for the duration of 15 years starting from 2007 (5,38). Among challenges in management of POPs, NIP identifies lack of facilities for sound disposal of wastes (consisting of containing or contaminated with POPs) and very limited and financial and technical resources for remediation of contaminated sites. Details of activities for rational management of POPs pesticides obsolete stocks/contaminated sites by 2010 has also been described in the NIP. Pakistan needs to ratify Stockholm Convention at the earliest, so that with the incoming financial/technical support from the developed countries, as agreed in article 12 (3) & 13 (2) of the Convention, the activities outlined in NIP may be started (5,38). 20 References 1. Peter Orris, Lin Kaatz Chary, Karen Perry and Joe Asbury, “Persistent Organic Pollutants (POPs) and Human Health,” World Federation of Public Health Association’s POPs Project, WFPHA, May 2000. Karen Arms, “Environmental Science,” Saunders College Publishing, London, 1989 J.C. Hansen, Int. J Circumpolar Health, 57, 280 1998 WWW.POPS.INT International POPs Elimination Network (IPEN), 2006 “Stockholm Convention on Persistent Organic Pollutants (POPs), United Nations Environment Program UNEP/CHEMICALS, France October 2001 Tahir Hasnain, SDPI Working Paper Series # 42 1999 Mahmood A. Khwaja, M. Rasul Jan and Kashif Gul, “Physical Verification and Study of Contamination of Soil and Water in and Surrounding Areas of Abandoned Persistent Organic Pollutant (DDT) Factory in North West Frontier Province (NWFP), Pakistan”, Sustainable Development Policy Institute, Islamabad May, 2005 “1998 District Census Report of Nowshera,” Population Consensus Organization, Statistics Division, Government of Pakistan, Islamabad, Pakistan, December, 1999. Noor ul Hadi, “Inventory of POPs in NWFP,” POPs Enabling Activity Project, Pak-EPA and UNDP, NWFP Environmental Protection Agency, Peshawar, Pakistan, December 2005. Karam Ahad and Ashiq Mohammad, “POPs (Pesticides) in Water and Soil Samples collected from Obsolete Pesticides Stores in NWFP and Punjab,” –ibid-,Pakistan Environmental Protection Agency (Pak-EPA), Islamabad, Pakistan, October, 2005 Mahmood A. Khwaja and Jindrich Petrlik, “ Study on Contamination of Chicken Eggs by Persistent Organic Pollutants (POPs) in Peshawar, NWFP, Pakistan,” Paper presented at 11th International Conference of the Pacific Basin Consortium (PBC) for Environment and Health Sciences, East – West Center, Hawaii, USA. September 4 - 6, 2005 Mahmood A. Khwaja, “Contamination of Chicken Eggs by Highly Toxic Chemicals,” Research and News Bulletin, Sustainable Development Policy Institute (SDPI), Islamabad, Pakistan 12(2), March-April, 2005 Jindrich Petrlik and Mahmood A. Khwaja, Hot Spot Report: “POPs in Different Samples of Waste Incineration residues in Pakistan,” Arnika – Prague, Czech Republic and SDPI Islamabad, Pakistan, April, 2006 (www.IPEN.org) Mahmood A. Khwaja and Jindrich Petrlik, “Study of Persistent Organic Pollutants in Different Samples of Hospitals Waste Incineration and Brick Kilns Residues in Pakistan,” Arnika-SDPI, Sustainable Development Policy Institute (SDPI), Islamabad, Pakistan, May, 2006. www.epa.gov/Region5/reraca/edq110-4-99.PDF (Accessed March, 2007) www.atsdr.cdc.gov/HAC/PHA/helena/hel_p2.html (Accessed March, 2007) Hussain A, M.R.Asi and Z.Iqbal, “Desipation and degredation of C14 –DDT in tandojam (sindh) soil under field condition,” Pak.J.Anal.Chem, 2 (1), 14-18, 2001 UNEP “Regionally Based Assessment of Persistent Toxic Substances,” Global Report 2003 –ibid, South East Asia and South Pacific Regional Report, December, 2001 Eisenreich, S.J.; Capel, P.D.; Robbins, J.A.; Bourbonniere, R. Environ. Sci. Technol.1989, 23, 1116. Alcock, R.E.; Johnston, A.E.; McGrath, S.P.; Berrow M.L.; Jones, K.C.; Environ. Sci. Technol. 1993, 27,1918. Sanders, G.; Jones, K.C.; Hamilton-Taylor, J. Chemosphere1994, 29, 2201. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13. 14. 15. 16. 17. 18. 19. 20. 21. 22. 21 23. 24. 25. Oliver, B.G.; Charlton, M.N.; Durham, R.W.; Environ. Sci. Technol. 1989, 23, 208. G. Sanders, K.C. Jones and J. Hamilton-Taylor, PCB and PAH fluxes to a dated UK peat core. Environ. Pollut. 89 (1995), pp. 17–25. C.S. Wong, G. Sanders, D.R. Engstrom, D.T. Long, D.L. Swackhamer and S.J. Eisenreich, Accumulation, inventory and diagenesis of chlorinated hydrocarbons in Lake Ontario sediments. Environ. Sci. Technol. 29 (1995), pp. 2661–2672. D.C.G. Muir, A. Omelchenko, N.P. Grift, D.A. Savoie, W.L. Lockhart, P. Wilkinson and G.J. Brunskill, Spatial trends and historical deposition of polychlorinated biphenyls in Canadian mid latitude and Arctic Lake sediments. Environ. Sci. Technol. 30 (1996), pp. 3609–3617. M. Krauss, W. Wilcke and W. Zech, Polycyclic aromatic hydrocarbons and polychlorinated biphenyls in forest soils: depth distribution as indicator of different fate. Environ. Pollut. 110 (2000), pp. 79–88. F. Wania and D. Mackay. Environ. Sci. Technol. 30 (1996), p. 390A. M. Biziuk, A. Przyjazny, J. Czerwinski and M. Wiergowski. J. Chromatogr. A 754 (1996), p. 103. D.V. Yadav, P.K. Mittal, H.C. Agarwal and M.K.K. Pillai, “Organochlorine Insecticide Residues in Soil and Earthworms in the Delhi Area, India August – October, 1974,” Pestic Monit J., 15:80-85, 1974 S.P. Saxena, C.Khare, K.Murugesan, A.Farooq, T.D.Dogra and J.Chandra, “DDT Residues in Soil of Areas Surrounding a DDT Manufacturing Factory in Delhi, India,”Bull. Environ.Contam.Toxicol, 38: 388-391 Global Report 1987 M.J. Khan, H. Rashid, A. Rashid and R. Ali, “Intra-varietal Variability in Wheat Grown under Saline Conditions,” Pak. J. Biological Sciences, 2(3), 693 1999 M. Rasul Jan, “ Micronutrient Status of Soil of Peshawar and Mardan,” M.Phil, Thesis, Institute of Chemical Sciences, University of Peshawar 1979. Pakistan Environmental Protection Act, 1997 A.Hussain, M.R.Asi and Zafar Iqbal, “ Studies on Dissipation and Degradation of C14 –DDT and C14 DDE in Pakistan Soil under Field Conditions,” J.Env.Sci.Health B29 (1,1-15) 1994 –ibid-, "Dissipation and Degradation of C14-DDT in Potohar Area, Islamabad Soil under field conditions," Pak.J.Anal.Chem,.3, 48-51 (2002) Mahmood A. Khwaja and Jindrich Petrlik “ Alternatives for Persistent Organic Pollutants (POPs) Disposal,” IPEN Fact Sheet, 2nd Revised Edition, Arnika – Prague, Czech Republic and SDPI - Islamabad, Pakistan, (2005) Mahmood A. Khwaja, Member, Drafting Team, “National Implementation Plan (NIP) for the Stockholm Convention on Persistent Organic Pollutants (POPs) in Pakistan,” POPs Enabling Activity, Pakistan Environmental Protection Agency, Ministry of Environment, GoP, October, 2006 26. 27. 28. 29. 30. 31. 32. 33. 34. 35. 36. 37. 38. 22 Annex I: Stockholm Convention on Persistent Organic Pollutants 2001 Annex B of Stockholm Convention on Persistent Organic Pollutants Restriction Part I Chemical Activity Acceptable purpose (or) Specific exemption Production Acceptable purpose: Disease vector control use in accordance with Part II of this Annex Specific exemption: Intermediate in production of dicofol Intermediate DDT (1,1,1- trichloro- 2,2bis (4-chlorophenyl) ethane) CAS No: 50-29-3 Acceptable purpose: Disease vector control in accordance with Part II of this Annex Specific exemption: Production of dicofol Intermediate Use Notes: (i) Except as otherwise specified in this Convention, quantities of a chemical occurring as unintentional trace contaminants in products and articles shall not be considered to be listed in this Annex; This note shall not be considered as a production and use acceptable purpose or specific exemption for purposes of paragraph 2 of Article 3. Quantities of a chemical occurring as constituents of articles manufactured or already in use before or on the date of entry into force of the relevant obligation with respect to that chemical, shall not be considered as listed in this Annex, provided that a Party has notified the Secretariat that a particular type of article remains in use within that Party. The Secretariat shall make such notifications publicly available; This note shall not be considered as a production and use specific exemption for purposes of paragraph 2 of Article 3. Given that no significant quantities of the chemical are expected to reach humans and the environment during the production and use of a closedsystem site-limited intermediate, a Party, upon notification to the Secretariat, may allow the production and use of quantities of a chemical listed in this Annex as a closed-system site-limited intermediate that is chemically transformed in the manufacture of other (ii) (iii) 23 chemicals that, taking into consideration the criteria in paragraph 1 of Annex D, do not exhibit the characteristics of persistent organic pollutants. This notification shall include information on total production and use of such chemical or a reasonable estimate of such information and information regarding the nature of the closed-system site-limited process including the amount of any non-transformed and unintentional trace contamination of the persistent organic pollutant-starting material in the final product. This procedure applies except as otherwise specified in this Annex. The Secretariat shall make such notifications available to the Conference of the Parties and to the public. Such production or use shall not be considered a production or use specific exemption. Such production and use shall cease after a ten-year period) unless the Party concerned submits a new notification to the Secretariat) in which case the period will be extended for an additional ten years unless the Conference of the Parties) after a review of the production and use decides otherwise. The notification procedure can be repeated; (iv) All the specific exemptions in this Annex may be exercised by Parties that have registered in respect of them in accordance with Article 4. Part II DDT (1,1,1-trichloro-2,2-bis(4-chlorophenyl)ethane) 1. The production and use of DDT shall be eliminated except for Parties that have notified the Secretariat of their intention to produce and/or use it. A DDT Register is hereby established and shall be available to the public. The Secretariat shall maintain the DDT Register. 2. Each Party that produces and/or uses DDT shall restrict such production and/or use for disease vector control in accordance with the World Health Organization recommendations and guidelines on the use of DDT and when locally safe) effective and affordable alternatives are not available to the Party in question. 3. In the event that a Party not listed in the DDT Register determines that it requires DDT for disease vector control, it shall notify the Secretariat as soon as possible in order to have its name added forthwith to the DDT Register. It shall at the same time notify the World Health Organization. 4. Every three years) each Party that uses DDT shall provide to the Secretariat and the World Health Organization information on the amount used, the conditions of such use and its relevance to that Party’s disease management strategy, in a format to be decided by the Conference of the Parties in consultation with the World Health Organization. 5. With the goal of reducing and ultimately eliminating the use of DDT, the Conference of the Parties shall encourage: a. Each Party using DDT to develop and implement an action plan as part of the implementation plan specified in Article 7. That action plan shall include: i. Development of regulatory and other mechanisms to ensure that DDT use is restricted to disease vector control; ii. Implementation of suitable alternative products, methods and strategies, including resistance management strategies to ensure the continuing effectiveness of these alternatives; 24 iii. Measures to strengthen health care and to reduce the incidence of the disease. b. The Parties, within their capabilities, to promote research and development of safe alternative chemical and non-chemical products, methods and strategies for Parties using DDT, relevant to the conditions of those countries and with the goal of decreasing the human and economic burden of disease. Factors to be promoted when considering alternatives or combinations of alternatives shall include the human health risks and environmental implications of such alternatives. Viable alternatives to DDT shall pose less risk to human health and the environment, be suitable for disease control based on conditions in the Parties in question and be supported with monitoring data. 6. Commencing at its first meeting, and at least every three years thereafter, the Conference of the Parties shall, in consultation with the World Health Organization, evaluate the continued need for DDT for disease vector control on the basis of available scientific, technical, environmental and economic information, including: a. The production and use of DDT and the conditions set out in paragraph 2; b. The availability, suitability and implementation of the alternatives to DDT; and c. Progress in strengthening the capacity of countries to transfer safely to reliance on such alternatives. 7. A Party may, at any time, withdraw its name from the DDT Registry upon written notification to the Secretariat. The withdrawal shall take effect on the date specified in the notification. 25 Annex 2: Details of local and smuggled DDT containing pesticides availability in district DI Khan market Sr. No 1 2 3 Name Item Methyle Dusting po Wder 785 100 Irani multipurpose Dispatched in bulk Multan, Lahore, Bannu, Local 15 5-15 of DDT% Place of origin Irani Local Multipurpose sugarcane etc) For ant control (domestic) 100-150 Kg D I khan, Bannu (cotton, 100-150 Kg D I Khan, Bannu Purpose of use Annual turnover/shop Area of use Source: Noor ul Hadi, “Inventory of POPs in NWFP,” POPs Enabling Activity Project, Pak-EPA and UNDP, NWFP Environmental Protection Agency, Peshawar, Pakistan, December 2005 26 Annex 3: Concentration of DDT in water ug/ml S.No. 1. 2. 3. 4. 5. 6. 7. 8. 9. Sample Name Sample was taken from the mosque near the DDT factory Sample was taken from the petrol pump on the G.T Road side in Amangarh Sample was taken from the tape of the mosque of Gharib Abad area This sample was taken at the end of the drain 10 yards away from the bank of the Kabul River This sample was taken at the end of the drain 10 yards away from the bank of the Kabul River KRDW3 (Kabul River drainage water 3) KRDW4 (Kabul River drainage water 4) Well water 1 Well water 3 Concentration (ug/ml) 0.22 ± 0.01 0.40 ± 0.14 0.31 ± 0.11 0.31 ± 0.03 0.20 ± 0.23 0.07 ± 0.10 0.22 ± 0.02 0.21 ± 0.04 0.30 ± 0.21 Source: Mahmood A. Khwaja, M. Rasul Jan and Kashif Gul, “Physical Verification and Study of Contamination of Soil and Water in and Surrounding Areas of Abandoned Persistent Organic Pollutant (DDT) Factory in North West Frontier Province (NWFP), Pakistan”, Sustainable Development Policy Institute, Islamabad May, 2005 27 Annex 4: DDT Residues in Soil Samples (ug/g) S. No. 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13. 14. 15. 16. Sample Name Sample was taken from the inner side of the wall of formulation unit. Sample was taken from bags present in the formulation unit Sample was taken from within the factory (formulation unit) Sample was taken from within the factory (formulation unit) Sample was taken from within the factory (formulation unit) Sample taken from outside the factory at a depth of 3 inches Sample taken from outside the factory at a depth of 3 inches Sample taken from end of the drainage near the factory wall Sample taken from material from left over bags from store house1 and 2 Sample taken from material from left over bags from store house1 and 2 Sample taken 5 yards away from old store house D4 start of the drain towards Kabul River; depth 7 inches D3 ends of the drain towards Kabul River D2 ends of the drain towards Kabul River D1 ends of the drain towards Kabul River Control soil sample taken from Azakhel near petrol pump Concentration (ug/g) 242.28 ± 0.81 2822.08 ± 0.88 399.216 ± 0.90 573.02 ± 0.94 327.59 ± 0.63 780.40 ± 0.54 599.21 ± 0.98 558.35 ± 0.71 7.504.00 ± 0.11 2841.45 ± 0.95 1858.02 ± 0.78 1631.70 ± 0.61 629.04 ± 0.18 388.57 ± 0.48 1039.34 ± 0.75 Not detected Source: Mahmood A. Khwaja, M. Rasul Jan and Kashif Gul, “Physical Verification and Study of Contamination of Soil and Water in and Surrounding Areas of Abandoned Persistent Organic Pollutant (DDT) Factory in North West Frontier Province (NWFP), Pakistan”, Sustainable Development Policy Institute, Islamabad May, 2005 28 Annex 5. Processes for Soil Decontamination and Reclamation: 1. E. Smith, J. Smith, R. Naidu and A. L. Juhasz. Desorption of DDT from a Contaminated Soil using Cosolvent and Surfactant Washing in Batch Experiments Water, Air, and Soil Pollution Issue: Volume 151, Numbers 1-4 Date: January 2004 Pages: 71 – 86 1,1-bis(p-chlorophenyl)-2,2,2-trichloroethane (p,p-DDT) is a recalcitrant organic compound that is difficult to remove from contaminated soil due to its low solubility. In this study we investigated the effectiveness of both co-solvents and surfactants in enhancing the solubility of p,p-DDT from a soil that has been contaminated with DDT for nearly 40 yr. The presence of selected surfactants removed less than 1 to 11% of p,p-DDT compared to cosolvents, which removed less than 1 to 77% of p,p-DDT from the same soil. The low solubility of p,pDDT in the presence of surfactants was attributed to the decreased surfactant concentration to below critical micelle concentration following sorption by soil surfaces. Enhanced solubility of p,p-DDT was achieved with the use of cosolvents that released up to 77% of p,p-DDT from a contaminated soil. Increasing the solution concentration and hydrophobicity of the cosolvent increased the amount of p,p-DDT desorbed. For example, the amount of p,p-DDT desorbed increased in the order 5% 1-propanol << 50% ethanol << 50% 1-propanol. Repeated washing of the soil with various cosolvents, in all but two cases, markedly increased the total amount of p,p-DDT desorbed from the soil. For example, repeated washing of the soil with 50% ethanol increased the amount of p,p-DDT removed by 42% while repeated washings of the soil with 50% 1-propanol had little effect on the amount of p,p-DDT desorbed. Increasing the soil-solution ratio from 1:2 to 1:10 in the presence of 40% 1-propanol increased the amount of p,p-DDT desorbed by 100%; suggesting that the soilsolution ratio was an important parameterin controlling the amount of p,p-DDT desorbed. 2. Douglas E. Morrison, Boakai K. Robertson, and Martin Alexander. Bioavailability to Earthworms of Aged DDT, DDE, DDD, and Dieldrin in Soil. Environ. Sci. Technol., 34 (4), 709 -713, 2000. 10.1021/es9909879 S0013-936X(99)00987-6. A study was conducted to determine the bioavailability of several pesticides that have persisted for various periods in soils in the field and the laboratory. Based on the concentrations or the percentages of the compound in soil samples that were found in the earthworm Eisenia foetida, ca. 30, 12, 34, and 20% of DDT, DDE, DDD, and a total of the three compounds were bioavailable in a soil treated in the field with DDT 49 years earlier. Only 28 or 43% of dieldrin aged for 49 years was bioavailable based on concentrations in E. foetida or percentages of the compound assimilated by the worms, respectively. Comparably low percentages of DDT, DDE, and DDD but not dieldrin were assimilated by the worms from samples of soil from a waste-disposal site receiving the insecticide ca. 30 years earlier. Aging for 190 days in Kendaia loam in the laboratory markedly reduced the availability to E. 29 foetida of DDT and DDE but not DDD. The amounts of aged or unaged DDT, DDE, and DDD but not dieldrin that were removed from the soils by solid-phase extraction with Tenax TA beads were generally greater with increasing amounts assimilated by the earthworms. The results show that aging markedly reduces the bioavailability of these compounds. 3. RONALD C. WESTER, HOWARD I. MAIBACH, DANIEL A. W. BUCKS, LENA SEDIK, JOSEPH MELENDRES, CHENG LIAO and STEPHEN DIZIO. Percutaneous Absorption of [14C]DDT and [14C]Benzo[a]pyrene from Soil. Oxford Journals -Life Sciences-Toxicological Sciences-Volume 15, Number 3 -Pp. 510-516. Received January 22, 1990; accepted May 24, 1990. Percutaneous Absorption of [14C]DDT and [14C]Benzo[a]pyrene from Soil. WESTER, R. C, MAIBACH, H. I., BUCKS, D. A. W., SEDIK, L., MELENDRES, J., LIAO, C, AND DIZIO, S. (1990). Fundam. Appl. Toxicol. 15, 510–516. The objective was to determine percutaneous absorption of DDT and benzo[a]pyrene in vitro and in vivo from soil into and through skin. Soil (Yolo County 65-California-57-8; 26% sand, 26% clay, 48% silt) was passed through 10-, 20-, and 48-mesh sieves. Soil then retained by 80-mesh was mixed with [14C]-labeled chemical at 10 ppm. Acetone solutions at 10 ppm were prepared for comparative analysis. Human cadaver skin was dermatomed to 500 µm and used in glass diffusion cells with human plasma as the receptor fluid (3 ml/hr flow rate) for a 24-hr skin application time. With acetone vehicle, DDT (18.1 ± 13.4%) readily penetrated into human skin. Significantly less DDT (1.0 ± 0.7%) penetrated into human skin from soil. DDT would not partition from human skin into human plasma in the receptor phase (<0.1%). With acetone vehicle, benzo[a]pyrene (23.7 ± 9.7%) readily penetrated into human skin. Significantly less benzo[a]pyrene (1.4 ± 0.9%) penetrated into human skin from soil. Benzo[a]pyrene would not partition from human skin into human plasma in the receptor phase (<0.1 %). Substantivity (skin retention) was investigated by applying 14 C-labeled chemical to human skin in vitro for only 25 min. After soap and water wash, 16.7 ± 13.2% of DDT applied in acetone remained absorbed to skin. With soil only 0.25 ±0.11% of DDT remained absorbed to skin. After soap and water wash 5.1 ±2.1% of benzo[a]pyrene applied in acetone remained absorbed to skin. With soil only 0.14 ±0.13% of benzo[a]pyrene remained absorbed to skin. In vivo percutaneous absorption of DDT in rhesus monkey was significantly less (p < 0.02) from soil (3.3 ± 0.5%) than from acetone solution (18.9 ± 9.4%). DDT in vitro skin penetration values into human skin were similar to in vivo absorption values in the rhesus monkey. In vivo absorption in the rhesus was not statistically different 30 from published in vivo absorption in man (10.4 ± 3.6%). In vivo percutaneous absorption of benzo[a]pyrene in rhesus monkey was significantly less (p < 0.015) from soil (13.2 ± 3.4%) than from acetone solution (51.0 ± 13.2%). Thus, with in vitro and animal in vivo systems relevant to man, skin absorption of DDT and benzo[a]pyrene from soil was significantly less than when the chemicals were applied to skin in acetone Solvent. 4. Albert L. Juhasz , Euan Smith, Julie Smith and Ravendra Naidu Development of a Two-Phase Cosolvent Washing-Fungal Biosorption Process for the Remediation of DDT-Contaminated Soil Issue: Volume 146, Numbers 1-4 Date: June 2003 Pages: 111 - 126 A bench scale, two-phase soil washing-biosorption process was developed for the remediation of p,p -DDT-contaminated soil (containing 990 and 7750 mg kg-1 of p,p -DDT). Removal of p,p -DDT from contaminated soil was achieved by washing the soil with low molecular weight primary alcohols (ethanol or 1-propanol). An improved efficiency of p,p DDT removal was observed with increasing C-chain length of the co-solvent and by increasing the co-solvent volume fraction. When 40 or 80% 1-propanol were used, greater than 93% of p,p -DDT was desorbed from the respective soils. p,p -DDT was partitioned from the co-solvent solutions using biomass of Cladosporium sp. strain AJR318,501 as the sorptive matrix. When studies were conducted using a co-solvent-recycling regime (with 80% 1-propanol) greater than 95% of p,p -DDT was removed from Soil A (990 mg kg-1 p,p DDT) and Soil B (7750 mg kg-1 p,p -DDT) with the majority of the desorbed organochlorine repartitioning onto the fungal biomass. Less than 2.4 g mL-1 p,p -DDT was detected in the co-solvent wash solution of Soil A after 80 hr: potentially the co-solvent could be further reused to treat other soil. A higher concentration of p,p -DDT was detected in the co-solvent wash solution of soil B after 120 hr (13.3 g mL-1) indicating that the p,p -DDT sorption sites on the fungal biomass were fully saturated. 5. W. Chu , C.Y. Kwan. Remediation of contaminated soil by a solvent/surfactant system. Chemosphere, 53 (2003) 9–15. Received 15 October 2002; received in revised form 5 March 2003; accepted 1 April 2003. This study investigates a new approach using a solvent/surfactant-aided soil-washing process to improve the performance of conventional surfactant-aided soil remediation. Three surfactants (Brij 35, Tween 80, and SDS) and three organic solvents (acetone, triethylamine, and squalane) were used to evaluate the desorption performances of 4,40- dichlorobiphenyl (DCB) out of three soils with different sorption characteristics. The performance improvement is likely due to better dissolution of the hydrophobic contaminants from the soil 31 assisted by the solvent, and the formation of solvent-incorporated surfactant micelles, which increases both the size (i.e. capacity) and affinity of micelles for more effective contaminant extraction. The foc of soils were found to be important in determining the performance of a solvent/surfactant-aided soil-washing process. Judging from the experimental data and as verified by the two constants in the proposed soil-washing model, as the organic solvent is coexisting with the surfactant micelles, both the marginal soil-washing performance (right after the use of a very small amount of solvent compared to that of none) and the final soilwashing capacity are increased compared to those of a pure surfactant-aided washing process. 6. ANITESCU G.; TAVLARIDES L. L. Supercritical extraction of contaminants from soils and sediments. The Journal of supercritical fluids (J. supercrit. fluids), ISSN 0896-8446 Source / Source.2006, vol. 38, no2, pp. 167-180 [14 page(s) (article)] This paper summarizes representative developments in the field of polluted soil/sediment decontamination by supercritical extraction (SCE). The broad accomplishments of SCE through sustained research and its applications as a remedial technology are outlined. This technology basically employs green supercritical fluids (SCFs) such as carbon dioxide (SCCD) and water (SCW) for the extraction of volatile organic compounds (VOCs) and persistent organic pollutants (POPs), which include polychlorinated biphenyls (PCBs), polycyclic aromatic hydrocarbons (PAHs), and various pesticides from environmental matrices. Comprehensive data on solute solubilities in SCFs, partition equilibrium of solutes between a solid matrix and SCFs, solute desorption from the matrix, and solute separation from the SCF provide a solid basis to develop models regarding a SCE process. Significant experimental results and various proposed models to interpret the extraction phenomena from soils/sediments are presented. SCE has been developed to be applied as an environmental remedial technology after its successful use in analytical chemistry. This development has occurred because of a need for a rapid, safe and cheap cleanup method. Conventional techniques for the extraction of environmental matrices (e.g. liquid solvent extraction, thermal desorption) are time and solvent/energy consuming. The review attempts to summarize the representative studies about SCE of organic contaminants, advantages and the drawbacks of SCE compared to other remedial technologies, and economic aspects. A short section on the future direction for research in this field and general trends toward commercial applications are also included. This review is also intended as a guide for conducting a 32 remediation study in a systematic and stepwise fashion for determination of the effectiveness of SCE technology in conjunction with other cleanup technologies. Systematically conducted and well-documented remedial studies are important in the investigation/feasibility and design processes. The applicability and inherent limitations of SCE technology to determine its specific suitability are also discussed. 33