doi:10.1016/j.apradiso.2006.06.0 14 Copyright © 2006 Elsevier Ltd All rights reserved. E-mail Article Export Citation Cited By Add to my Quick Links Impact of phosphate industry on the environment: A case study Save as Citation Alert , a, I. Othman and M.S. Al-Masria , Citation Feed Cited By in Scopus a Department of Protection and Safety, Atomic Energy Commission of Syria, Damascus, P.O. Box 6091, Syrian Arab Republic (2) View Record in Scopus Received 6 February 2006; revised 29 June 2006; accepted 29 June 2006. Available online 23 August 2006. Abstract This paper presents results obtained from studying the impact of the Syrian phosphate industry on the environment. This work is based on evaluating naturally occurring radionuclide concentrations in the surrounding environment at the locations of this industry, viz. mines, phosphate fertilizers factory and phosphate export platforms. Air particulates, soil, water (river, lake and sea water), biota and plant samples were collected and analyzed. Natural radionuclides (226Ra, natU, 210Po, 210Pb) were determined by means of low background gamma spectrometry and alpha spectrometry. The results showed that the distribution and enhancement of natural radionuclides in the surrounding environment in these three locations are mainly due to fallout of phosphate dust generated during loading and processing of phosphate ore. The extent of contamination was related to climate conditions. Radon gas and its daughters generated from phosphate ores were found to be the main source of enhanced concentrations of 210Po and 210Pb in soil and leafy plants. These results can be considered as baseline data and can be used to prove the effectiveness of any future pollution controls adopted. Keywords: NORM; Air particulates; Soil; Phosphate industry; Environment; Syria Article Outline 1. Introduction 2. Field and laboratory procedures 2.1. Sample collection and preparation 2.2. Radioanalytical methods 2.3. Quality control 3. Results and discussion 3.1. The impact of phosphate mining activities in the vicinity of phosphate mines and workers’ villages 3.2. The impact of phosphoric acid production plant on the environment 3.3. The impact of phosphate loading activities on the vicinity of Tartous port 4. Conclusion Acknowledgements References 1. Introduction Phosphate rocks contain relatively high concentrations of naturally occurring radioactive materials from the uranium and thorium decay series (238U and 232Th). Mining, milling, transporting of phosphate ores, manufacturing of phosphate fertilizers and using phosphate fertilizers containing uranium are ways in which the workers, public and the environment are exposed to enhanced natural radioactivity (UNSCEAR, 1993; IAEA, 2004). Most of these natural radionuclides are found in the solid waste of the phosphate fertilizer industry such as phosphogypsum, the discharged effluents such as radon gas and dust containing radioactivity. Many studies in the world have been carried out to assess the risk to humans and to the environment (Barisic et al., 1992; Carvalho, 1995; Hamam and Landsberger, 1994; Marovic and Sencar, 1995; Martinez and Garcia, 1996; Martinez et al., 1994; Bolivar et al., 1994; McCartney et al., 1992; McDonald et al., 1991; Rutherford et al., 1994; Timmrmanas and Van der Steen, 1996). Some studies (UNSCEAR, 1993; Othman et al., 1992; Othman, 1993) considered radon gas to be the most important hazard to workers and public in the mines area and the phosphate factory including phosphogypsum piles; the radiation dose due to inhalation of radon daughters can be relatively high. Air emissions (gaseous and particulates) from phosphate rock processing plant in the Thessaloniki area of northern Greece have resulted in collective dose commitment to lung tissue of 2×10−9 person Gy y−1 for 238U (Papastefanau, 2001). On the other hand, phosphogypsum is also considered to be a health hazard, and many studies (Rutherford et al., 1994; IAEA, 2004) showed that leaching of radionuclides from phosphogypsum contaminates the surrounding environment and especially the groundwater. Other studies (Barisic et al., 1992; Carvalho, 1995; Marovic and Sencar, 1995; Martinez et al., 1994; McCartney et al., 2000) showed that effluents discharges and especially into sea may enhance radioactivity in sediment, water and marine biota. McDonald et al., 1996 summarized most aspects of technologically enhanced radioactivity in the UK marine environment. Their results indicated areas of natural decay series due to discharges from the Whitehaven phosphate fertilizers plants. More recent study (Betti et al., 2004) carried out for the European Commission (Marina II) was focused on discharges of radionuclides from the Naturally Occurring Radioactive Materials (NORM) industries including the phosphate industry into north European marine waters. The collective dose rate due to such discharges was found to be 200 man Sv y−1. Another study (El-Mamoney and Khater, 2004) was conducted on the impact of phosphate mining activities in the Safaga Quusein region on the Red Sea; relatively high levels of 226Ra, 238U, 210Po and 210Pb were reported. In Syria, the main phosphate mines are situated near Palmyra Fig. 1. There are two open pit mine regions that are separated by about 25 km; more than 2000 workers are employed in this industry and live in two villages located near the mines (Othman et al., 1993). The climate is very hot and dry where strong winds may a rise. Most of the mined phosphate ore (around 2.8 million tonnes per year) has been exported for more than 20 years in large quantities via one of the main Syrian ports (Tartous) situated on the eastern part of the Mediterranean Sea (34°54′N, 35°52′E). About 300,000 tonnes of phosphate ore are transferred from the mines by train and processed at the phosphate fertilizer factory in Homs (180 km N of Damascus) since the early 1980s. During the process called “wet process” Ca3(PO4)2 ore is reacted with H2SO4 to form phosphoric acid and phosphogypsum. Phosphogypsum composed mainly of CaSO4 and contains impurities such as Al, P, F, Si, Fe, Mg as well as many trace elements, including the rare earth elements and naturally occurring radioactive materials (226Ra and 210Po). This has led to the production of tonnes of phosphogypsum, which are currently placed in a large plastic lined storage pit built nearby the factory in 1995; disposing of phosphogypsum outside this pit is currently prohibited to avoid environmental pollution. Phosphogypsum is transferred from the factory and pumped into the pit through pipes by mixing with water. The water is pumped back to the factory for re-use after filtration. Full-size image (18K) Fig. 1. Syrian phosphate industry locations. Studies on the impact of this industry on the environment were limited to the workplace near the mines, where radon concentrations in air and gamma exposure and hence radiation dose to workers have been determined (Othman et al., 1992). Uranium levels in urine, blood and hair of mine workers were also determined (Othman, 1993); Uranium concentration in the Syrian phosphate ore varies between 55 and 100 ppm (Abbas and Jubeli, 1996). Therefore, a strategy to assess the impact of emissions and discharges of this industry on the surrounding environment has been formulated. This strategy is based on evaluation of naturally occurring radionuclides concentrations in the surrounding environment in three main elements of this industry, viz. mines, phosphoric acid production plant and the phosphate export. The strategy was implemented by conducting the following measurements: (1) Enhancement of naturally occurring radionuclides in soil and air particulates in the mining areas and the workers’ villages. (2) Levels of naturally occurring radionuclides in the surrounding environment of the phosphoric acid processing plant in Homs. This study includes air particulates, surface water, agriculture crops and plants. (3) The impact of phosphogypsum piles and storage pit on the surrounding environment. (4) The impact of loading activities on the nearby marine environment of Tartous port on the Mediterranean Sea. (5) Enhancement of naturally occurring radionuclides in air particulates and soils in the Tartous port area due to phosphate loading activities into ships. The main objective of this paper is to summarize the results obtained through the implementation of this strategy. 2. Field and laboratory procedures 2.1. Sample collection and preparation Air particulates: Sampling of air particulates was carried out during March 1999 and May 1999 in the two mine areas (Knefees and Al-Sharkia) and during June 1998 and December 1998 at port Tartous. Sampling locations in the Tartous port and the Knefees mine area are shown in Fig. 2 and Fig. 3, respectively. Sampling was carried out during the year 2002 from the phosphate fertilizers site every 2 months (Fig. 4). Reference sites for the three areas were chosen far from the operations. Air particulates were collected using high volume air samplers (HVAS) (Grasby General Metal Works, USA) with EPM 2000 WHATMAN fibre glass filters (20×25 cm) with airflow of 4.2–102 m3 h−1. Sampling was performed over 4 days for each sampling campaign; two to three samplers were operated at each site simultaneously. Total suspended particulates (TSP) concentrations were determined using the weighing technique. Full-size image (67K) Fig. 2. Sampling locations at Knefees mines area. Full-size image (43K) Fig. 3. Air and soil sampling locations at Tartous port. Full-size image (58K) Fig. 4. Sampling locations around the Phosphate fertilizer area. Soil samples: Soil samples were also collected from the same locations used for air particulate sampling in addition to other sites where public and workers are expected to be present for long periods of time. Only surface soil samples (0–5 cm) were collected (about 1 kg) from each site; stones and plants were removed from the samples manually and the samples were oven-dried at 90 °C for 24 h, ground, homogenised and sieved to pass through a 560 μm sieve. Plant samples: All plant samples were collected by hand from an area of 100 m× 100 m (collective sample), placed in plastic bags and transported to the laboratory; sample volumes varied from 50 to 3000 g depending on the availability of plants in each site. The samples were taken from 20 agricultural areas around the phosphate fertilizer factory where wheat, leafy vegetables, fruits, grass and some tree leaves were collected. Samples were then cleaned manually (but not washed) to remove adhering particles and dried in the oven at 90 °C for 24 h. The samples were ground, homogenised and sieved to pass through a 560 μm sieve. Water samples: Water (30 l) samples were collected from surface water (Orontes River and Quttina Lake) near the phosphate fertilizer factory. The samples were acidified by adding concentrated hydrochloric acid (5 ml/l of water); pH value was determined to be less than 2. Marine samples: Three sampling programs were carried out; the first was executed on the 22 October 1997, while the second and the third were carried out on the 5 May 1998 and 26 June 1999 respectively. Sediments (1 kg), seawater (50 l), fish, algae and other biota samples were collected from 14 sampling sites as shown in Fig. 2. Sediment samples were taken from the surface layer at the bottom of each location by grab sampler or scuba divers. Water samples were acidified by adding concentrated hydrochloric acid. Sediment, fish, algae and crab samples were dried in the oven at 90 °C for 24–48 h. 2.2. Radioanalytical methods Determination of 210Po and 210Pb: Each air filter was cut into small pieces and digested using concentrated nitric acid for at least 24 h after addition of a known amount of 208Po (0.2 Bq) as a yield tracer for determination of 210Po and 210Pb. The filtrate was then divided into two equal portions; one for uranium determination and the other for 210Po and 210Pb determinations. Concentrations of 210Po and 210Pb in soil (0.5 g), plant (10 g of dry materials) and the filtrates were measured using the standard technique (the silver disc technique) (Harley, 1978). Alpha counting of 208Po (5.15 MeV) and 210Po (5.30 MeV) was done using an alpha spectrometer (Oasis, Oxford) with a passivated ion-implanted silicon detector (active area 300 mm2, 3.6 background counts per day, 100 μm minimum depletion depth and 30 keV -energy resolution at 5.30 MeV). The plating and counting were then repeated after 6 months of storage of the solution to measure the ingrowth of new 210Po from 210Pb to calculate the 210Pb concentration in the original sample. The lower limit of detection of the method used was 0.4 Bq kg−1 dry wt. For water samples, 210Pb and 210Po were precipitated from 4 l by MnO2; the precipitate being dissolved in 1.5 mol l−1 HCl and processed as described for solid samples. Determination of radium isotopes: The samples were measured by gamma spectrometers (Eurysis Systems) using high resolution (1.85 keV at 1.33 MeV), high relative efficiency (80%), low background HpGe detectors. 226Ra, 224Ra and 228Ra were determined by measuring their gamma emitter daughters, 214Pb (351.9 keV) and 214Bi (609 keV), 212Pb (238 keV) and 212 Bi (727.3 keV) and 228Ac (911.1 keV). Efficiency calibration was performed using reference samples (RGU, RGTH and RGK) provided by the International Atomic Energy Agency, IAEA. The lower limits of detection for the measured radionuclides derived from the background measurements at 100,000 s are found to be 3 Bq kg−1 for 226Ra and 228Ac. Determination of Uranium: Uranium concentrations in the filters were determined using the flourometric technique. For soil samples analysis, 0.5 g of each soil sample (duplicate) was digested using a combination of mineral acids (nitric and hydrochloric acid) for at least 24 h. Uranium was then separated from the sample using an ion exchange column (Dowex 1×4) and measured using Flourometry instrument (Jerrel-Ash 27000, Advanced Technical Services Gmbh Swiss) (Othman and Yassine, 1995). 2.3. Quality control Quality control procedures were applied using homemade control samples and reference samples provided by IAEA and EML (Environmental Monitoring Laboratory, Department of Energy, USA). In addition, all methods and laboratories used in this study are validated according to Eurachem guide and ISO17025. 3. Results and discussion 3.1. The impact of phosphate mining activities in the vicinity of phosphate mines and workers’ villages Radon exposure levels in the phosphate mines were first measured in 1990 in order to assess radiation risks to workers and their families living near the mines area (Othman et al., 1992). However, Palmyra and the mining regions (in the middle of the Syrian Badia) are considered to be in a dry area where dust is likely to occur at most times of the year, therefore, air particulates are also considered to be a health hazard; dust carrying phosphate ore particulates containing NORM being also a radiation health hazard. Total suspended particulates (TSP) in phosphate mines air have been measured to determine radioactivity content in air particulates and to evaluate the impact of mining activities on the vicinity of phosphate mines. Table 1 shows the mean values of TSP, uranium, 210Po and 210Pb concentration in air particulates collected from the Knefees mine area and the workers’ village. The highest TSP concentrations were 24,106 and 55,358 μg m−3 in Knefees mine and Al-Sharkia mine, respectively; the highest concentrations observed in the Al-Sharkia mines area are due to the fact that more milling and mining operations are carried out in this mine. However, all of the reported values of TSP are much higher than the Maximum Permissible Concentrations (120 μg m−3) (WHO, 1987). On the other hand, 210Po and 210Pb concentrations in air particulates of all sites were found to be relatively higher than the natural levels (0.47– 3.7 mBqm−3, Eisenbud and Gesell, 1997); the highest 210Po and 210Pb concentration in Knefees mine sites were 47 and 50 mBq m−3, respectively. These levels can reflect the amount of phosphate ore elevated in air and also the radon gas concentration in air. In addition, uranium concentration varied between 5 and 811 ng m−3 in Knefees mine sites, while generally lower values were observed in Al-Sharkia mines area (not more than 207 ng m−3). Moreover, lower levels of radionuclides in the Al-Sharkia workers’ village were observed. The Sharkia worker village was built after Knefees village and several considerations concerning pollution controls measures to decrease the impact of the mining activities on the worker village were taken (distance, wind direction and new equipment). However, all reported values for uranium in both mining areas are much higher than the natural levels, which is about 2.1 ng m−3 (Eisenbud and Gesell, 1997). Table 1. Mean values of uranium, 210Po and 210Pb concentration in air particulates at phosphate mines (Knefees) Site no. TSP+±1 SD (μg m−3) U±1 SD (ng m−3) 210 Po±1 SD (mBq m−3) 210 Site description 1 Administration building 3466±2523 257±155 6.3±1.3 3.1±0.7 2 Maintenance workshop 925±334 79±54 1.6±0.4 1.6±0.4 3 Workers’ village 877±371 5±0.8 1.8±0.3 1.1±0.6 4 Control room 22304±13399 670±294 47±25 50±29 5 The factory 24106±7458 811±308 42.9±13.9 34.8±11.2 6 Mine area 8317±4408 127±29 11.6±3.3 14.2±9.0 Pb±1 SD (mBq m−3) Full-size table + Two filters were collected and analyzed. Dust containing radioactivity is precipitated in the surrounding areas either as wet or dry deposition and the activity of surface soil can reflect this precipitation; fine particulates may travel for longer distances and they are more hazardous. However, radioactivity content of soil samples collected from the vicinity of the two mines areas were found to be distance and wind direction dependant; the concentrations of the studied radionuclides decrease as the distance from the mines area increases, Table 2. The effect of mining processes is very clear near the mine area. Uranium content in soil samples collected near the Knefees village clinic was found to be 35 mg kg−1, which is much higher than the natural levels reported in Syria (2–5 mg kg−1) (Othman and Yassine, 1995). In addition, 210Po and 210Pb concentrations were also high in those samples collected near the village school; 173 and 233 Bq kg−1 being observed for 210Po and 210Pb, respectively. These high levels are due to relatively high radon concentrations in the area and not to the transport of phosphate ore dust from the mines area by wind to the village. Similar values were also found in Al-Sharkia worker village. This is in agreement with the previous study (Othman et al., 1992) where radon gas was found to be high in the village houses. The equivalent effective dose of 0.98 m Sv y−1 from radon was reported assuming 46% occupancy factor. On the other hand, there is little green cover in the area; therefore, the study was focused only on air and soil radioactivity. Table 2. Concentration of natural gamma emitters in soil samples collected from workers’ village and mines Sit Site e descriptio no n . U±1 S 226Ra±1 224Ra±1 228Ra±1 234Th±1 210Po±1 D SD SD SD SD SD (mg kg (Bq kg−1 (Bq kg−1 (Bq kg−1 (Bq kg−1 (Bq kg− −1 1 ) ) ) ) ) ) 210 Pb±1 SD (Bq kg− 1 ) 1 Administra tion building 27±3 820±25 6.0±0.5 10.7±1.5 824±100 1455±7 4 1997±1 59 2 Maintenan ce workshop 40±4 413±12 5.9±0.5 7.2±1.2 751±38 1011±8 1 3 Dryer unit 80±9 821±26 6.1±0.6 10.7±1.5 824±100 1479±7 3 2022±1 62 4 The factory 34±4 317±10 4.7±0.4 4.9±0.9 312±38 601±31 885±71 5 The mine area 72±8 510±15 6.1±0.4 7.1±0.8 510±48 760±39 1033±8 2 6 Village, main gate 94±10 820±30 5.2±0.4 14.2±2.1 750±70 1184±6 2 1557±1 24 7 Village, high school 8±1 120±5 3.4±0.2 5.1±0.3 121±12 173±10 233±19 8 Village clinic 35±4 193±6 6.0±0.4 6.6±0.5 194±23 339±17 476±38 9 Village, guest house 3.7±0. 4 85±3 11.4±0.6 14.2±0.7 84±8 148±8 211±17 Full-size table 432±56 3.2. The impact of phosphoric acid production plant on the environment The Syrian phosphate industry is considered to be one of the main sources of pollutants at the most important water resources of the middle region of Syria viz. Orontes River and Quttina Lake; the factory was built at the eastern bank of Quttina Lake. The middle region of Syria is considered to be a very important agricultural area. The impact of this industry on the Orontes River environment was first investigated in 1997, when water, particulates, sediment and plants from seven locations along the Orontes River were collected and analyzed for radioactivity (Othman et al., 1998). The results have shown a clear enhancement of natural radionuclides such as 226Ra, 238U and 210Po in those samples collected from sites close to the factory. Uranium concentration in water samples collected from Quttina Lake from a site near the factory has reached a value of 0.9±0.07 μg l−1. This enhancement was found to be due to phosphate factory discharges viz. dust and liquid effluents. In addition, an increase in the concentrations of these radionuclides was also observed in other sites where the application of phosphate fertilizers, which contain relatively high levels of 226Ra (225 Bq kg−1), 238U (444 Bq kg−1) and 210Po (220 Bq kg−1) were the main source of enhancement. Moreover, a more recent joint study with Lebanese National Council for Scientific Research (LNCSR) (Al-Oudat et al., 2003) was carried out on both parts of the Orontes River (Lebanon and Syria) and the results have shown an increase in 238U and 226Ra and 210Po concentrations in surface sediment. 226Ra concentration in surface sediment collected from Quttina Lake has increased from 15.9±2.9 Bq kg−1 (1996) to 37.2±2 Bq kg−1 (2003). This is due to the fact that effluent discharges to Quttina Lake have been increased, even though several pollution control procedures by the factory have been adopted. These pollution controls include storage of phosphogypsum piles in plastic lined disposal pits and installing new bag filter houses in the factory to reduce dust emissions. Past disposal of phosphogypsum into the surrounding environment as piles exposed to weathering processes has led to chemical and radioactive contamination (Al-Oudat and AlMasri, 1996). This is due to the fact that phosphogypsum contains a large number of harmful elements, such as trace elements and radioactive materials (226Ra and 210Po) (Rutherford et al., 1994; Conkline, 1992; Berish, 1990; Burnett et al., 1999). Studies to utilize Syrian phosphogypsum as building materials, agricultural fertilizers and as an amendment to the physical and chemical properties of soil have been performed (Othman and Mahrouka, 1994; Al-Masri et al., 1999a and Al-Masri et al., 1999b; Al-Oudat et al., 1998; Al-Oudat, 1999). Laboratory and field studies (Al-Masri et al., 1999a, Al-Masri et al., 1999b and Al-Masri et al., 2004) have been conducted to characterize the Syrian phosphogypsum and to evaluate transfer mechanisms of impurities to the surrounding environment including studies of distribution and leaching of radionuclides such as 226Ra and 210Po and trace elements. 226Ra and210Po mean activity concentrations in the Syrian phosphogypsum are 310±60 and 471±67 Bq kg−1, respectively (Al-Masri and Al-Bich, 2002a). On the other hand, even though phosphogypsum was collected in a lined pit, radon gas is emanated to the surrounding villages that are only at 500–1500 m distances from the pit. Therefore, a study was carried out to assess radon concentration in houses (Othman et al., 1997); radon concentration in most houses has increased by 22 Bq m−3 since the base line measurements of natural radioactivity carried out before 1995 (Othman and Yassine, 1995). The fertilizer production company strategy is to compact the phosphogypsum and add one meter clean soil cover when the pit is completely filled. This will reduce dust and radon emanation Air particulates emissions are also one of the potential health hazards of processing phosphate ores. Dust is generated in the drying during offloading of phosphate ores, and in the granulation and packaging of the produced phosphate fertilizers; installing bag filters reduces these emissions to the surrounding environment (UNEP, 1998). However, uranium and 210Po and 210Pb levels in air particulates collected from different sites surrounding the phosphate fertilizers factory in Homs have been determined. Mean total air particulates concentration ranged from 31 μg m−3 in site no. 5 and 514 μg m−3 in site no. 7, Table 3. Uranium concentration in air particulates was relatively high in those samples collected from site no. 1 and other sites situated north east of the factory (Table 4); as high as 5.9 ng m−3 in site no. 1, which is 2.5 times higher than the natural levels (2.1 ng m−3) (Eisenbud and Gesell, 1997). In addition, lower values of all studied radionuclides were observed in July and they are due to partial shutdown of the factory. Moreover, air particulates were collected in the studied sites at four seasons in the year to assess the impact of washout on air activity. It was found that uranium content has decreased from 5.9 ng m−3 in spring period to 1.7 ng m−3 in winter. However, this can not only reflect the impact of washout by rainwater, but also the pollution controls that are being implemented and the low production rates at the time of measurement. 210 Pb and 210Pb analysis of air particulates have shown low levels of these two isotopes in comparison to the mines area; a value of 2 mBq m−3 has not been exceeded (Table 4). Therefore, air emissions from the factory containing radioactive materials are relatively low. This is due to strict control procedures on transport and loading processes of phosphate in addition to the high efficiency of filters used for air emissions from the phosphate fertilizers factory during the study period (2002). Table 3. Mean values of TSP concentration in air at the vicinity of Phosphate fertilizer factory Site no. Sampling location Distance from factory TSP±1 SD (μg m−3) January 2002 April 2002 July 2002 October 2002 1 South of factory 50 m South 91±42 276±87 184±19 225±80 2 Quttina town 1000 m South 50±26 128±15 113±18 180±46 3 AlMumbarkia 2.6 km East 64±23 93±21 120±39 151±54 4 Tal Al Shoor 4 km North West 51±10 115±11 152±12 442±160 5 Apel 6.5 km East 31±8 101±48 213±33 151±126 6 Al-mushahida 2.7 km North West 67±28 89±18 NM NM 7 Kerbet al-teen 12 km North 65±25 86±18 113±26 514±53 Full-size table Table 4. Mean values of uranium, 210Po and 210Pb concentration in air at the vicinity of Phosphate fertilizer factory S it e n o. U±1 SD (ng m−3) 210 Pb±1 SD (mBq m−3) Po±1 SD (mBq m−3) 210 Jan uary 2002 Apri l 2002 July 2002 Octo Janua ber ry200 2002 2 Apri l 2002 July 2002 Octo Jan ber uary 2002 2002 Apri l 2002 July 2002 Octo ber 2002 1 1.7± 1.2 5.9± 1.1 0.52 ±0.2 5 1.7± 0.06 0.3±0. 0 0.61 ±0.0 1 0.9± 0.04 0.89 ±0.0 6 0.4± 0.3 0.54 ±0.1 5 0.29 ±0.0 8 0.26 ±0.0 3 2 0.9± 0.6 0.6± 0.3 0.36 ±0.2 4 0.1± 0.0 0.46 0.12±0 ±0.0 .02 2 1.10 ±0.0 4 1.16 ±0.0 8 0.17 ±0.1 2 0.40 ±0.0 7 0.48 ±0.2 9 0.23 ±0.0 2 3 0.70 ±0.0 3 0.3± 0.2 0.84 ±0.8 8 0.1± 0.0 0.27 0.73±0 ±0.0 .03 1 0.83 ±0.0 5 0.74 ±0.0 5 1.0± 0.5 0.40 ±0.0 9 0.32 ±0.0 8 0.17 ±0.0 2 4 0.20 ±0.1 7 0.2± 0.1 0.88 ±0.8 9 0.13 ±0.0 6 0.65 0.17±0 ±0.0 .01 4 0.96 ±0.0 3 0.92 ±0.0 7 0.20 ±0.0 1 0.31 ±0.0 4 0.39 ±0.1 5 0.17 ±0.0 2 5 0.30 ±0.2 9 0.3± 0.2 0.75 ±0.3 5 0.12 ±0.0 1 0.37 0.18±0 ±0.0 .01 4 0.74 ±0.0 5 0.76 ±0.0 5 0.35 ±0.2 9 0.30 ±0.0 8 0.37 ±0.1 9 0.17 ±0.0 2 6 0.20 ±0.1 5 0.21 ±0.0 2 NM NM 0.52 0.52±0 ±0.0 .03 4 NM NM 0.52 ±0.0 3 0.41 ±0.0 8 NM NM 7 0.11 ±0.0 8 0.1± 0.01 1.31 ±0.9 8 0.11 ±0.0 0.46 0.77±0 ±0.0 .03 3 0.85 ±0.0 5 1.99 ±0.1 3 1.2± 0.9 0.61 ±0.0 6 0.37 ±0.0 7 0.31 ±0.0 1 Full-size table Since the surrounding areas of the phosphate fertilizer factory are considered to be an important agricultural region, levels of naturally occurring radionuclides in crops and soils have been determined. The analytical results have shown relatively high concentrations of uranium, 226Ra, 210Po and 210Pb in those samples collected from sites close to the eastern side of the fertilizer factory where Quttina and AlMumbarkia fields are located (Table 5). Wind direction at the studied area is western and northwestern. The highest 226Ra concentration was found to 56 Bq kg−1 in site no. 6. This is due to fallout of phosphate ore dust generated during dry processes. In addition, most values of the measured radionuclides in agricultural crops were within the natural levels reported in the Syrian Environment (Othman and Yassine, 1995), except for some relatively high levels of 210Po and 210Pb in leafy vegetables; an activity concentration of 109 and 30.5 Bq kg−1 dry wt for 210Pb and 210Po, respectively, has been observed. These levels are due to either fallout of phosphate ores or decay of radon gas emanated from both the phosphate ore and fertilizers stored before processing and dispatch, or come from the phosphogypsum pit. Table 5. Natural radioactivity concentration in soil samples collected from the vicinity of phosphate fertilizer factory Site no. Sampling location Distance from factory U±1 SD (mg kg−1) 226 Ra±1 SD (Bq kg−1) 210 Po±1 SD (Bq kg−1) 210 1 Al-ryhania (reference site) 19.3 (km) North West 0.84±0.08 8±1 40.2±6 34.2±1.4 2 Gzila 15 (km) North West 0.57±0.00 27±2 36.6±6 23.8±1.5 3 Al-Khansaa 14 (km) West 1.51±0.06 17±1 17.8±0.7 17.6±0.9 5 AlMumbarkia 2.6 (km) East 1.15±0.05 30±2 49.1±2.0 34.1±2.8 6 East of factory 0.2 (km) East 3.03±0.48 56±3 39.7±0.5 60.6±6.0 8 Al-mushahida 2.7 (km) North West 1.11±0.05 26±1 34.3±1.7 40.4±5.4 9 Al-fyzia 4.5 (km) North 1.16±0.19 17±1 75.2±1.1 57.3±5.6 10 Papa omar 7.7 (km) North East 1.04±0.17 15±1 47.5±0.9 30.6±2.1 11 Kefir aya 4.5 (km) North East 0.74±0.03 27±2 56.4±1.7 41.5±2.2 12 Apel 6.5 (km) East 1.41±0.04 28±2 55.1±1.8 29.0±2.8 14 Shinshar 11.5 (km) South East 0.77±0.02 19±1 49.5±1.7 29.0±4.2 15 East boida 10.6 (km) East 1.09±0.11 15±1 41.8±1.5 29.9±1.8 16 Zydel 16.7 (km) North East <0.5 NM 65.8±4.0 27.5±4.1 17 Fieroza 14.3 (km) 0.98±0.07 16±3 47.7±1.9 30.2±2.9 Pb±1 SD (Bq kg−1) Site no. Sampling location Distance from factory U±1 SD (mg kg−1) 226 Ra±1 SD (Bq kg−1) 210 Po±1 SD (Bq kg−1) 210 Pb±1 SD (Bq kg−1) North East Full-size table 3.3. The impact of phosphate loading activities on the vicinity of Tartous port Syrian phosphate ore is exported in large amounts (2.3 million tonnes per year) via one of the main ports at the Mediterranean Sea (Tartous port) using mechanical conveyers where large amount of phosphate ores are thrown in the air and dust is transferred to the surrounding environment. Previous studies of the marine environment along the Syrian coast (Othman et al., 1994) have reported high concentrations of 210Po in sediment collected from Tartous shore; phosphate loading activities were considered to be the main source of these high levels. Another study supported by IAEA, EML (Environmental Marine Laboratory) in Monaco has been conducted to evaluate the impact of loading activities on the near marine environment (Al-Masri et al., 2002b). The results have shown that dust, during loading cargoes of phosphate ores into ships has polluted the nearby surface seawater and sediment marine environment; a significant enhancement of 210Po, 210Pb and other natural radionuclides in sediment and surface water inside the port area has been observed. The highest 210Po and 210 Pb concentrations observed in sediment were found to be 170 and 64 Bq kg−1, respectively, while 210Pb and 210Po concentrations in surface water ranged from 5 to 20 mBq l−1 and 0.93 to 3.23 mBq l−1. These high levels were found to be mainly related to wind direction, with air particulates carrying radioactivity either being blown to land or sea. In addition, another study on radioactivity in air particulates and surface soil has been conducted. Table 6 shows the results of total suspended particulates and the mean values of uranium, 210Po and 210Pb concentration in air particulates collected from the Tartous port area. The results have been compared with those obtained for the reference site No. 8, which is 7 km south of the affected area (wind direction in the port area is mainly northwestern). Total Suspended Particulates (TSP) concentrations were found to vary between 136 and 2269 μg m−3 at the loading platform. All values for other locations situated outside the loading platform were also higher than the reference site value (110 μg m−3) and higher than the maximum permissible levels (120 μg m−3) (WHO, 1987); this is a very large fluctuation in the measured values that is due to distribution pattern of the sampling points (at the four directions). It is clear that dust has spread only in an area with 500 m radius; this may be due to the fact that large particulates may be formed because of the high humidity in air at the coast, therefore the possibility of longer distance travel no particle size distribution being determined in this study. However, small air particulates may still be carried to by wind to reach Tartous City (around 2 km). On the other hand, uranium concentrations have reached a maximum value of 2010 ng m−3 at the loading platform, which is much higher than the natural levels (2.1 ng m−3) (Eisenbud and Gesell, 1997); uranium concentrations in the other six locations were found to vary between 2.5 and 80 ng m−3. In addition, 210Po in particulates ranged from 1.0 mBq m−3 (Tartous City) to 305 mBq m−3 at the loading platforms; natural levels being between 0.47 and 3.7 mBq m−3. A similar variation was observed for 210Pb at the same locations. The highest concentration of 210 Pb was 160 mBq m−3, which is 43 times higher than the average natural levels (3.7 mBq m−3). Overall, the highest concentrations were found to be within a 500 m circle around the loading platform; wind direction in the area may affect this distribution and air particulates carrying radioactivity can reach other areas situated several kilometers north of the port. Furthermore, soils collected near the loading platform were found to contain high levels of uranium, 210Po, 210Pb and other gamma emitters at almost phosphate ore levels (Table 7). In addition, the activity concentrations of U and 226Ra vary very widely, while 210Po and 210Pb concentrations were found to be relatively high in all other sites (even at the reference site) varying between 73 and 1175 Bq kg−1 and 73 and 925 Bq kg−1 for 210Po and 210 Pb, respectively. These high levels in soil may be due to high radon concentrations in the area, and hence high 210Pb and 210Po fluxes, and it is not due to transport of phosphate dust generated during loading and unloading operations. Therefore, radon gas, which is generated from the phosphate piles stored near the platform in large quantities before exporting, can be considered the main hazard in these sites; a radon study is currently progressing. Table 6. Mean values of uranium, 210Po and 210Pb concentration in air particulates in the vicinity of Tartous port area U±1 SD (ng m−3) 210 Po±1 SD (mBq m−3) 210 2010 305±39 160±9 1779±963 80±9 45±0.7 3.7±0.2 450 m North East 1221±973 20±1 10.5±2.6 2.6±0.2 4 De-Loading Station (400 m South East) 2269±1708 19±10 13±11 1.9±0.5 5 Al-Maxer Area (1100 m South East) 179±27 4±1 1.7±0.01 1.8±0.2 6 Maintenance workshop (1000 m North East) 136±57 2.5±0.1 2±0.1 1.70±0.03 7 Tartous city center (2 km South East) 171±38 2.5±0.5 1.0±0.6 0.8±0.1 8 Tartous beach cabins 110±15 (ref. site), 8 km South 2.1±2 1.6±0.4 1.6±0.2 Site no. Site description 1 Loading platform 2 400 m North East 3 TSP+±1SD (μg m−3) 2263 Pb±1 SD (mBq m−3) Full-size table + Only one measurement. Two filters were collected and analyzed. Table 7. Natural radioactivity concentration in soil samples collected from the vicinity of Tartous port Sit e no. Site description U±1 SD (mg kg− 1 ) 226 Ra±1 S D (Bq kg−1) 228 224 210 D (Bq kg−1) D (Bq kg−1) D (Bq kg−1) Ra±1 S Ra±1 S Po±1 S 210 Pb±1 S D (Bq kg−1) Sit e no. U±1 SD (mg kg− 1 ) 226 Site description 228 224 210 D (Bq kg−1) D (Bq kg−1) D (Bq kg−1) D (Bq kg−1) Pb±1 S D (Bq kg−1) 1 Weather forecast center, 1200 m North East 1.3±0.1 19±1 19.6±2.2 17.1±1.9 73±6 75±1 2 Port custom building 1, 1100 North East 3.7±0.3 41±3 9.4±1.0 6.3±0.7 109±6 121±6 3 Administrati on building, 1000 North east 52.2±4. 7 530±37 7.3±0.8 5.3±0.6 828±15 688±96 4 Civil construction building 800 m East 2.4±0.2 28±2 11±1 9±1 105±2 73±12 5 Loading platform 70.5±6. 3 656±45 10±1 4.3±0.5 1175±13 874±55 6 400 South 48.5±4. East Loading 4 Platform 297±20 7.7±0.8 6.3±0.7 657±68 620±40 7 Port custom building 2, 800 m North East 3.4±0.3 20.7±1.4 5.1±0.6 4.5±0.5 201±31 146±16 8 Tartous beach cabins (ref. site), 8 km South 2.8±0.3 23.6±1.7 7.7±0.8 7.1±0.8 81±7 73±6 9 Arwad island ( 3 km west) 0.9±0.1 8.4±0.6 4.3±0.5 4.0±0.5 26±0.3 31±2 10 1000 East loading platform 30.7±2. 8 580±40 NM 6.1±0.7 1030±128 925±70 11 Tartous city 2 (2 km South East ) 12.8±1. 1 144±10 4.3±0.5 1.9±0.2 224±1 238±5 12 800 m North East 38.5±3. 5 415±30 5.3±0.5 4.9±0.5 641±41 455±50 Ra±1 S Ra±1 S Ra±1 S Po±1 S 210 Full-size table 4. Conclusion The Syrian phosphate industry is considered to be a main source of enhancement of naturally occurring radionuclides in the Syrian Environment. This was investigated by determining uranium, radium isotopes, 210Po and 210Pb in air particulates, soil, sediment, plants, and water and biota samples collected from different areas around the three regions of this industry. Elevated levels of radioactivity were found to be generally located around the workplaces in the mines areas, phosphate fertilizer factory and the export platforms, with phosphate dust containing radioactivity being the most important risk. In addition, relatively high concentrations of 210Po and 210Pb in soils, plant and surface water are mainly due to decay of radon gas generated from the phosphate ores. However, a risk assessment study can be carried out using the obtained data in order to determine the dose received by the critical groups at the three locations of this industry (workers and public living near the area). Acknowledgment The authors would like to thank all staff members of the Environment Protection Division for their time spent for collecting and analyzing the related samples. References Abbas and Jubeli, 1996 M. Abbas and Y. Jubeli, Phosphate in Syria, Alam Al-Zarra 43 (1996), pp. 70–83. Al-Masri et al., 1999a M.S. Al-Masri, A. Ali, M. Keitou and Z. Al-Hares, Leaching of 226Ra from Syrian phosphogypsum. In: W.A. Newton, Editor, Environmental Radiochemical Analysis, Royal Society of Chemistry, UK (1999). Al-Masri et al., 1999b M.S. Al-Masri, F.A. Ali, M. Keitou and Z. Al-Hares, Leaching of Ra226 from Syrian phosphogypsum. In: G.W.A. Newton, Editor, Environmental Radiochemical Analysis, Royal Society of Chemistry, UK (1999), p. 21. Al-Masri and Al-Bich, 2002a M.S. Al-Masri and F. Al-Bich, Distribution of polonium-210 in Syrian phosphogypsum, J. Radioanal. Nucl. Chem. 251 (2002) (3), pp. 431–435. Full Text via CrossRef | View Record in Scopus | Cited By in Scopus (2) Al-Masri et al., 2002b M.S. Al-Masri, S. Mamish and Y. Budeir, The impact of phosphate loading activities on near marine environment: the Syrian coast, J. Environ. Radioact. 58 (2002), pp. 95–104. Al-Masri et al., 2004 M.S. Al-Masri, Y. Amin, S. Ibrahim and F. Al-Bich, Distribution of some trace metals in the Syrian phosphogypsum, Geochemistry 19 (2004), pp. 747–753. Article | PDF (274 K) | View Record in Scopus | Cited By in Scopus (6) Al-Oudat and Al-Masri, 1996 M. Al-Oudat and Al-Masri, The phosphate and the environment, Alam Al-Zarra 43 (1996), pp. 121–130. Al-Oudat et al., 2003 Al-Oudat, M., Kattan, Z., Al-Masri, M. S., Al-Nimeh, El-Samad, O., Saad, Z., Slim, K., 2003. Study of Orontes River environment in Syria and Lebanon. Atomic Energy Commission of Syria, AECS-PR. Al-Oudat et al., 1998 M. Al-Oudat, A. Arslan and S. Kanacri, Physical and chemical properties, plant growth and radionuclides accumulations effect from mixing phosphogypsum with some soil, Common. Soil. Sci. Plant Anal. 29 (1998) (15-16), pp. 2515–2528. View Record in Scopus | Cited By in Scopus (4) Al-Oudat, 1999 Al-Oudat, M., 1999. The effect of adding phosphogypsum to cracking soil on plant growth and radionuclides accumulation, Atomic Energy Commission of Syria, AECSPR/FRSR205. Barisic et al., 1992 D. Barisic, S. Lulic and P. Milatic, Radium and uranium in phosphate fertilizers and their impact on the radioactivity of water, Water Res. 26 (1992), pp. 607–611. Abstract | View Record in Scopus | Cited By in Scopus (23) Berish, 1990 Berish, C.W., 1990. Potential environmental hazards of phosphogypsum storage in central Florida, In: Proceedings of the Third International Symposium on Phosphogypsum, Orlando, pp. 1–29. Betti et al., 2004 M.A. Betti, L. Aldare las Heras, A. Janssons, E. Herich, G. Hunter, M. Gerchikov, M. Dutton and A.W. Van Weers, Results of the European commission marina II, study part II. Effect of discharges of naturally occurring radioactive materials, J. Environ. Radioact. 74 (2004) (1-3), pp. 255–277. Article | PDF (811 K) | View Record in Scopus | Cited By in Scopus (3) Bolivar et al., 1994 Bolivar, J.P., Garcia, T. R., Garcia, L. N., 1994. Fluxes and distribution of natural radionuclides in the production and use of fertilizer. Sixth-International Symposium on Radiation Physics. Rabat, 2pp. Burnett et al., 1999 W.C. Burnett, G. Schaefer and M.K. Schultz, Fractionation of 226Ra in Florida phosphogypsum. In: G.W.A. Newton, Editor, Environmental Radiochemical Analysis, Royal Society of Chemistry, UK (1999), pp. 1–20. Carvalho, 1995 F.P. Carvalho, 210Pb and 210Po in sediments and suspended matter in Tagus estuaries Portugal, local enhancement of natural levels by wastes from phosphate ore processing industry, Sci. Total Environ. 159 (1995), pp. 201–214. Article | PDF (1886 K) | View Record in Scopus | Cited By in Scopus (22) Conkline, 1992 Conkline, C., 1992. Potential uses of phosphogypsum and associated risks. Background Information Document, EPA 402-R 92-002. Eisenbud and Gesell, 1997 M. Eisenbud and T. Gesell, Environ. Radioact. (fourth ed.), Academic Press, New York (1997). El-Mamoney and Khater, 2004 M.H. El-Mamoney and A.E.M. Khater, Environmental characterization of radioecological impacts of non-nuclear industries on the Red Sea coast, J. Environmental Radioactivity 73 (2004) (2), pp. 151–168. Article | PDF (205 K) | View Record in Scopus | Cited By in Scopus (7) Hamam and Landsberger, 1994 H. Hamam and S. Landsberger, Studies of radioactivity and heavy metals in phosphate fertilizer, J. Radioanal. Nucl. Chemistry, 194 (1994), pp. 331–336. Harley, 1978 Harley J. H., 1978. Manual of standard procedures, Environmental Measurement Laboratory, Department of Energy. USAEC Report HASL-300. New York. International Atomic Energy Agency, 2004 International Atomic Energy Agency, 2004. Extent of environmental contamination by naturally occurring radioactive materials (NORM) and technological options for mitigation. Technical Report No. 419. Vienna. Marovic and Sencar, 1995 G. Marovic and J. Sencar, 226Ra and possible water contamination due to phosphate fertilizer production, J. Radioanal. Nucl. Chem. 200 (1995), pp. 9–18. Full Text via CrossRef | View Record in Scopus | Cited By in Scopus (3) Martinez et al., 1994 A.A. Martinez, L.M. Garcia and M. Ivanovich, The distribution of U, Th, and 226Ra derived from the phosphate fertilizer industries on an estuarine system in south west Spain, J. Environ. Radioact. 22 (1994), pp. 155–177. Martinez and Garcia, 1996 A. Martinez and L.M. Garcia, Anthropogenic emissions of 210Po, 210 Pb, 226Ra in an estuarine environment, J. Radioanal. Nucl. Chem. 207 (1996), pp. 357–367. McCartney et al., 1992 M. McCartney, P.J. Kershaw, D.J. Allingtu, A.K. Young and D. Turner, Industrial sources of naturally occurring radionuclides in the eastern Irish Sea, Radiat. Prot. Dosim. 45 (1992), pp. 711–714. View Record in Scopus | Cited By in Scopus (8) McCartney et al., 2000 M. McCartney, C.M. Davidson, S.E. Howe and G.E. Keating, Temporal changes in the distribution of natural radionuclides along the Cumbrian coast following the reduction of discharges from a phosphoric acid production plant, J. Environ. Radioact. 49 (2000) (3), pp. 279–291. Article | PDF (558 K) | View Record in Scopus | Cited By in Scopus (8) McDonald et al., 1991 P. McDonald, G.T. Cook and M.S. Baxter, Natural and artificial radioactivity in coastal regions of the UK. In: P.J. Kershaw and D.S. Woodhead, Editors, Radionuclides in the Study of Marine Processes, Elsevier Applied Science, London (1991), pp. 329–339. McDonald et al., 1996 P. McDonald, M.S. Baxter and E.M. Scott, Technological enhancement of natural radionuclides in the marine environment, J. Environ. Radioact. 32 (1996), pp. 67–90. Article | PDF (1289 K) | View Record in Scopus | Cited By in Scopus (9) Othman et al., 1992 I. Othman, M. Al-Hushari and G. Raja, Radiation exposure levels in phosphate mining activities, Radiat. Prot. Dosim. 45 (1992), pp. 197–201. View Record in Scopus | Cited By in Scopus (6) Othman, 1993 I. Othman, The relation between uranium and the number of working years in the Syrian phosphate mines, Environ. Radioact. 18 (1993), pp. 151–161. Abstract | View Record in Scopus | Cited By in Scopus (1) Othman and Mahrouka, 1994 I. Othman and M. Mahrouka, Radionuclide content in some building materials in Syria and their indoor gamma dose rate, Radiat. Protect. Dosim. 55 (1994) (4), pp. 299–304. View Record in Scopus | Cited By in Scopus (10) Othman et al., 1994 I. Othman, T. Yassine and I. Bhat, Measurements of some radionuclides in the marine coastal environment of Syria, Sci. Total Environ. 153 (1994), pp. 57–60. Abstract | View Record in Scopus | Cited By in Scopus (12) Othman and Yassine, 1995 I. Othman and T. Yassine, Natural radioactivity in the Syrian environment, Sci. Total Environ. 170 (1995), pp. 119–124. Article | PDF (422 K) | View Record in Scopus | Cited By in Scopus (8) Othman et al., 1998 Othman, I., Al-Masri, M. S., Al-Oudat, M., Aba, A., Al-Hushari, M., Berakdar, E., 1998. Radioactivity in Orontes River environment, Atomic Energy Commission of Syria, AECS-PR. Othman et al., 1993 Othman I, Al-Hushari M, Raja, G., Sawaf., A. M., 1993. Effect of phosphogypsum on workers and population's radiation exposure in the vicinities of phosphogypsum waste burial site. Atomic Energy Commission of Syria, AECS-POR. Papastefanau, 2001 C. Papastefanau, Radiological impact from atmospheric release of 238U and 226Ra from phosphate rock processing plants, J. Environ. Radioact. 54 (2001) (1), pp. 75– 85. Rutherford et al., 1994 P.M. Rutherford, M.J. Dudas and R.A. Samek, Environmental impacts of phosphogypsum, Sci. the Total Environ. 149 (1994), pp. 1–38. Abstract | View Record in Scopus | Cited By in Scopus (50) Timmrmanas and Van der Steen, 1996 C.W. Timmrmanas and J. Van der Steen, Environmental and occupational impacts of natural radioactivity from some non-nuclear industries in the Netherlands, J. Environ. Radioact. 32 (1996), pp. 97–104. United Nations Scientific Committee on the Effects of Atomic Radiation (UNSCEAR), 1993 United Nations Scientific Committee on the Effects of Atomic Radiation (UNSCEAR). Sources and Effects of Ionizing Radiation. United Nations, New York, 1993. United Nations Environment Program (NUEP), 1998 United Nations Environment Program (NUEP), 1998. Mineral Fertilizers and the Environment. The fertilizer industry's manufacturing process and the environment. Technical Report no. 26, part1. New York. World Health Organization (WHO), 1987 World Health Organization (WHO), 1987. Air quality guidelines for Europe. WHO Regional Publications, European Series No. 23.