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AIR QUALITY OF PASIR MY9700833 GUDANG INDUSTRIAL ESTATE

by

Rahmalan Ahmad, Zaiton Majid, M. Rashid M. Yusoff, M. Zahari Abdullah and Abdullah Othman, University of Technology .

Abstract

The composition and distribution of anthropogenic aerosols are of interest mainly because of the health effects from atmospheric pollution to man. The Department of Environment and the Local Authority have been monitoring the levels of TSP and PM10 respectively at two different sites in Pasir Gudang for a number of years. This study was conducted to determine the concentrations of TSP and respirable air particulate matter at another station situated in the middle of the industrial zone. The particulate matter samples were collected by using high volume samplers for 24 hour periods during February to March and September to October 1993. Data included in this paper also provide information on concentrations of water soluble unions and cations and toxic metals in the air particulate.

INTRODUCTION

In the last two decades, Pasir Gudang has emerged as one of the largest industrial estates in the country. It has attracted local and foreign investor in setting up various types of industries including petrochemical, steel mill, palm oil refinery, fertilizers, cement, chemicals, shipping, offshore rigs, electronics and others.

As in most cases, industrial activity has always been associated with some environmental degradation which includes the release of particulate matter into the atmosphere. Air pollution, particularly in major towns and industrial areas, has been a matter of concern to the public and the Government. In Pasir Gudang, the Department of Environment (DOE) has been regularly monitoring the atmospheric total suspended particulate (TSP) levels for a number of years. However, only one sampling station has been established for the collection of TSP data which is situated

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in the Port Authority area. The Pasir Gudang Local Authority (PGLA) is probably the only local authority in the country which has established its air monitoring programme. The PGLA sampling station that is situated in the Pasir Gudang Town Centre has been monitoring the levels of respirable air particulate matter known as PM10 in Pasir Gudang for several years.

The concentration and composition of particulate matter from the atmospheric pollution are of interest mainly because of their effect on human health. (Wanner, H.U., 1990). There is a vast amount of data on the concentration of air particulate matter gathered by using the well-know high volume sampling method. A greater part of the data has been used to obtain a direct relationship between ambient particulate matter and its effects on man. (Federal Register, 1971). PM10 which constitutes respirable particles with diameter in the range of 10 urn or less is potentially health hazard because the small particles are able to penetrate into the human respiratory system and deposite in the lungs (Chan and Lippmann, 1980). Furthermore, the total health effect of these particles is not only governed by their physical nature, but also by their chemical composition. Various sources such as wind blown dust, construction works, fuel combustion and many others may contribute to the presence of toxic elements in the air particulate, but almost exclusively, the presence of elements in the forms of fine particles are related to high temperature processes, such as combustion, metal processing furnaces and smelting.

This paper reports the study on the composition of air particulate and their concentrations in the atmosphere of the industrial complex. The objective of the study is to evaluate the nature of respirable particles generated in this area as well as to complement the DOE and the PGLA monitoring data. It is expected that industrial activities play a major role in the formation of air particulate in this area. Contributions from the industrial emission sources around the sampling site is very likely to be felt and can be quantified.

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METHODOLOGY

Site Description

The TSP and respirable particles data in the present study were gathered from a sampling station situated in the middle of Pasir Gudang industrial complex at Jalan Timah 3, Pasir Gudang (Figure 1). The sampling site is located in an open ground covered with grass and surrounded within 50 meters to two kilometres by various types of industries: steel melting, fertilizers manufacturing, cement production, edible oil refinery, electroplating and a Tenaga National Berhad power generating plant. The nearest building to the sampling site is about 50 metres away. Among factors taken into consideration in choosing the sampling site includes accessibility of the sampling site, safety of the equipment and availability of regular electric power supply. The choice of the sampling station was suitable for purpose of the study which was to evaluate the extent of air paniculate concentrations in the middle of an industrial complex. This sampling station is situated about one kilometre north-east of the DOE TSP sampling station at the Authority and about two kilometres south-east of the Local Authority PM10 sampling station at the Pasir Gudang town centre.

Sampling And Analysis

The equipment used to collect the TSP was the standard high volume air sampler (HVS) model Ecotech 2000, which virtually collects all particles up to 100 um in size. Sampling of the PM10 was carried out by using the size-selective high-volume sampler (model Sierra Anderson) attached directly on to of another HVS. The PM10 sampler has cut-off diameter of 10 um (McFarland, et al., 1984). These equipments were placed one metre above ground since this is the layer of air in which man lives

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and in which suspended paniculate can have immediate and marked effect on human health. Both samplers were calibrated to operate at a rate of 70m3 per hour for 24 hour sampling period. Sampling of the TSP and PM10 was done simultaneously every other day during February-March, 1993.

During the September-October sampling period, the PM10 sampler was replaced by Sierra Anderson five stages Cascade Impactor sampler which was inserted directly into the PM10 size selective high volume sampler. This device effectively separates the respirable particles into five fractions with various sizes as shown in the Table 1. The 20.3 cm x 25.9 cm Graseby GMV P/N G8 10 glass fibre filter was used to collect the TSP and PM10 samples. The sampling system provides an area of 18 cm x 21 cm for effective collection of the air paniculate. The SAC 230 glass fibre filter with slots was used with the cascade impactor to collect the respirable particles of smaller sizes. The filter was conditioned in a dry incubator in a constant room temperature before and after each sampling event. The difference in weight of the sample filter was divided by the total volume of air sampled to give the airborne matter concentration present in the air.

SEM-EDAX Model Amray 19301 was used to study the surface morphology and elemental composition of individual particles. Each particle was irradiated for 100 sec at 20 KeV. The instrument has been previously calibrated using pure Al and Cu. Heavy metals such as Pb, Cu, Ni, Zn, Cd and Fe in the paniculate matter samples were measured by using Perkin Elmer HGA-500 coupled to the Perkin Emer Model 5000 Atomic Absorption Spectrophotometer. A section of 3 cm x 18 cm of the affected area was cut into pieces using stainless scissors and then treated with concentrated nitric acid and heated on a hot plate until the dissolution was completed. The solution was then transferred into a 50 ml volumetric flask and analysed for the heavy metals with the HGA-AAS. Water soluble anions and cations in the air paniculate were determined according to the widely used standard procedure for

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extracting water soluble inorganic ions from paniculate samples (Schulman and Ernst, 1993). A section of 2 x 18 cm of the affected filter was cut into small pieces with stainless scissor and placed in a glass beaker. The inorganic ions were then extracted from the accumulated particles during the sampling step with a 10 ml portion of ethanol-water (1:9) mixture. The filter was kept immersed in the extracting liquid overnight and then subjected to ultrasonication. After filtration through 0.45-um filter (Type HV; Millipore, Bedford, MA, USA), the extraction liquid containing water soluble ions from the collected air paniculate was immediately subjected to ion chromatographic analysis. When immediate analysis of samples was not possible, the samples were preserved by storage at freezing temperature until the time of then- injection into the ion chromatography system. The Dionex AGM 300 system with AS 4A and CS-5 columns, ion suppressor and conductivity detector was used exclusively for the anions and cations analyses.

RESULT AND DISCUSSION

Table 2 shown the daily concentration of TSP and PM10 measured during February- March, 1993 in the middle of Pasir Gudang Industrial Complex. The average concentration of TSP and PM10 as well as the PM10/TSP ratio are also given in Table 2. Both TSP and PM10 are very well correlated (r = 0.96) which suggests that the PM10 constituted the TSP concentration. The average TSP value of 139.8 ug/m3 was lower than an average value of 185.2 ug/m3. However these figures were substantially higher than the annual standard of 90 ug/m3 for TSP.

Table 2 also indicates that PM10 constitute about 56% of the TSP concentration. This ratio is relatively low compared to such a ratio of about 75% found in the ambient air of (Mohd. Rashid, 1987). This is expected since the sampling equipment was placed one metre above ground. As the position from the ground gets higher, the ratio is expected to increase as smaller particles normally stay

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longer in the atmosphere. The PMIO value of 79.1 ug/m3 was also fairly below the daily 24 hour standard of 150 ug/m3 for the ambient air, but it was higher than the annual standard of 50 ug/m3. It is expected that the PMIO value in the middle of the industrial complex would be higher than that found in the surrounding places in Pasir Gudang. For example, it is higher than the daily 24 hour average value of 46.5 ug/m3 for the PMIO gathered by the Pasir Gudang Local Authority at the town centre (which is slightly lower than the annual standard of 50 ug/m3) (PGLA, 1994). Dilution factor of the dispersed PMIO most likely caused this difference.

The presence of such a high level of PMIO in the industrial area may implicate a long term health effect to the general workers. This is particularly a matter of concern because fine particles of various sizes may penetrate deeply into the respiratory system as depicted in Figure 2. This study has therefore gathered data on the various sizes of respirable particles for the industrial complex during September-October, 1993. This was achieved by replacing the PMIO size selective collection medium with a Sierra Anderson five stage cascade impactor. This device separates further the PMIO into five fractions of different sizes as indicated in Table 1.

Table 3 shows the daily concentrations of the respirable particles and has been compared to the TSP levels of the same daily data. Based on the PMIO concentration measured during February-March, 1993, it was assumed that respirable paniculate with particle size in the range of 0.1 - 0.5 um would constitute 17.4 % of the 179.1 ug/m3 TSP measured during Sept-Oct., 1993. It was therefore estimated that about 38.8% by weight of the TSP consists of fine particles with sizes less than 3 um and capable of penetrating deeply into the respiratory system. The coarse particles with particle sizes range 3 - 10 um constitute 30.7 ug/m3 or 17.2% of the TSP. A plot of the mass distribution (% Wt/TSP) versus the size range is shown in Figure 3. The mass-size distribution shown in this figure indicates the importance of industrial

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emissions, particularly those processes involving high energy combustion. Hot vapours released from such a process condensed in the cooler air once they were emitted and this would become the nuclei or primary particles. The primary particles in the size range of less than 0.2 um could become wetted by supersaturated water vapour and hence converted into larger particles as chain aggregates through coagulation process or to serve as further condensation centres (First, 1973 in Noller etal., 1981).

Surface Morphology And Chemical Composition Of The Air Participate

Scanning electron microscope (SEM) and the energy dispersive X-ray (EDAX) system has increasingly been used in recent years for the characterisation of individual air paniculate matter (Kasahara et. al., 1993, Dzubay and Mamane, 1989, Mamane and Noll, 1985). The SEM-EDAX systems currently available at the University of Technology Malaysia have been applied for the study of air paniculate surface morphology and elemental composition. To demonstrate the feasibility in the present study, paniculate matter collected on 3rd October 1993 at the Pasir Gudang Industrial Centre were subjected to SEM-EDAX investigation. Figure 4 shows a typical micrograph of air paniculate from the sampling site. It was apparent that the particles were characterised as spherical shape with a rough surface. The features of the particles shown in this picture indicate that these particles most probably originated from the condensation of low volatility vapours that form very fine particles. Further growth of the particles took place through coagulation which led to the formation of chain aggregates or by further condensation.

Dot-mapping of the particle is shown in Figure 5. This picture shows that the surface morphology of the particle is characterised by a heterogeneous distribution of the elements. Elements with higher atomic number, e.g. mercury, copper and iron

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were found on the upper region of the particle while lighter elements, i.e. sodium, sulphur and chlorine were found at the lower region. Elemental compositions at two points on the particle surface were significantly different as indicated in Table 4. The overall health effect from the air particulates is not only governed by the physical nature of the particles but also by their chemical compositions. Certain heavy metals such as lead, cadmium, copper, nickel and iron were expected to be present in the air paniculate from the industria area. It was found that the average values of lead, cadmium, nickel and iron respectively, were higher in the PMIO gathered in the town centre during the same period of February-March, 1993 (Figure 6). It was found also that most of the heavy metal concentrations in PMIO were higher than those in the TSP (Figure 7). These results agree with the above findings which indicate that significant portions of the heavy metals were present in the smaller particles originated from the surrounding industrial activities. The average values of the heavy metals concentrations in the TSP at the industrial centre were comparable to similar data gathered by the DOE at the Johore Port Authority during the same period of Feb-Mar, 1993 (Table 5). Higher values of lead in the Port Authority area could be attributed to the higher traffic volume in this area.

Water soluble anions and cations in the TSP and PMIO samples were analysed to determine their concentrations in the air of the industrial area. Figure 8 and 9 indicate that the concentrations of phosphate, sulphate, nitrate, chloride and sodium were significantly high in the air particulates. The presence of phosphate in the TSP was probably due to fertilizer manufacturing activities. As expected, sulphate was also high in the air particulates. Studies by Mamane and Noll (1985) indicated some evidence on the association of larger particles as carriers for sulphates in the atmosphere. Thus, the TSP sulphate concentrations tend to be slightly higher than its concentration in the PMIO. The presence of high levels of sodium chloride in the air particulates could be attributed to the sea spray as well as from the industrial origin.

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CONCLUSION

The study described here is part of the effort to characterise air particulates in the industrial, urban and residential areas in Southern Johor. We have used a powerful scanning electron microscopy technique equipped with an X-ray energy dispersive analyser to study the surface morphology and elemental distribution in the individual particulate. The main points brought out in this paper may be summarised as follows:-

a) In the industrial complex area studied here the air particulate levels, as expected, are relatively high and over 50% by mass consists of respirable particles PM10. The potentially health hazardous fine particles with size range of less than 3 um was estimated to represent 38.8% weigh of the total particulate matter.

b) The mass-size distribution as well as scanning electron micrograph of the air particulates revealed the overwhelming evidence of the high energy combustion contributions to the formation of the air particulates in the industrial areas. c) The presence of high phosphate levels in the TSP could be attributable to fertiliser manufacturing activities, while sea spray was probably one of the major contributors to the presence of sodium chloride in the air particulate matter. which enabled the study to be undertaken as well as the Universiti Teknologi Malaysia for their research management through the Research and Development Unit. The authors would like also to express gratitude and appreciation to the Department of Environment, MST&E Head Office as well as the Johore Branch Office, the Pasir

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Gudang Local Authority and PERSTIM for their support and co-operation during the study. The authors would like to acknowledge the technical assistance from Pn. Liha bte Husrin for her skilful handling of the SEM-EDAX system. The authors also thank Associate Professors Dr. Alias Mohd. Yusoff and Dr. Mohd. Marsin Sanagi for valuable comments and suggestions.

Although data gathered by the Department of Environment and the Pasir Gudang Local Authority have been quoted in several occasions throughout this paper, they are subject to the agencies review and do not necessarily reflect the views of the agencies and therefore no official endorsement should be inferred.

The finding in the present study indicates the needs of further research in particular into the transportation and distribution of the air pollutants released from the industrial areas to the surrounding residential and agricultural areas. There is also a need to study on the bioavailability of toxic elements in the particulates and the effects of air particulates on human health, in particular on the correlation between the concentrations of toxic elements, sulphates and nitrates in the respirable paniculate and the occurrence of chronic disorders of the respiratory tracts.

ACKNOWLEDGEMENT

The authors would like to acknowledge the financial support from the Ministry of Science, Technology and the Environment (MST&E) through the IRPA mechanism

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REFERENCE

Chan, T.L. and Lippmann, M. (1980), "Experimental Measurements and Empirical Modelling of the Regional Deposition of Inhaled Particles in Humans", Am. Ind. Hyg. Assoc. J. 41 p 399.

Department of Environment (DOE) Ministry of Science, Technology and the Environment, (1994), personal communications.

Dzubay, T.G. and Mamane, Y., (1989), "Use of Electron Microscopy Data in Receptor Models for PM10", Atmospheric Environment, Vol. 23, No. 2, pp 467 - 476.

Federal Register, (1971) 36:8191, "Reference Method for the Determination of Suspended Particulates in the Atmosphere (High Volume Method)".

First, M.W., (1973), Arch. Intern. Med., Vol. 131, p. 24.

Kasahara, M., Shinoda, K., Yoshida, K. and Takahashi, K, (1993) "Characterization of Atmospheric Aerosol Based on SEM-EDX Analysis of Individual Particle-Preprint.

Mamane, Y. and Noll, K.E., (1985), "Characterization If Large Particles at Rural Site In The Eastern United States: Mass Distribution and Individual Particle Analysis", Atmospheric Environment, Vol. 19, No.4, pp 611-622.

McFarland, A>R., Ortiz, C.A. and Beth, R.W., (1984), "A 10 urn Cutpoint Size Selective Inlet for Hi-Vol. Sampler", J. Air Pollit. Contr. Vol. 34, pg 544.

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Mohd. Rashid Mohd. Yusoff, (1987), "An Investigation of PMIO Concentrations At One Site Kuala Lumpur", 3rd, Symphosium, Malaysian Chemical Engineers, 15-16 June, UTM, Kuala Lumpur.

Pasir Gudang Local Authority (PGLA), (1994), personal communications.

Schumann, H. and Ernst, M. (1993), "Monitoring of Ionic Concentrations in airborne Particles and Rain Water In an urban Area of Central Germany", Journal of Chromatography, Vol. 640, pp 241-249.

Wanner, H.U., (1990), "Effects of Atmospheric Pollution On Man", Aerosol Science, Vol. 21, pp. S389-S396.

Whiby, K.T., (1977), National Bureau of Standards Special Publication 464, pi66, in Noller, B.N., Bloom, H. and Arnold, A.P., (1981), Prog. Analyt. Spectrosc. Vol 4 pp 81-189.

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Table 1 : Five Stages Cascade Impactor Particle Size Range Collection

STAGE SIZE RANGE (um) 1 7.2- 10 2 3.0-7.2 3 1.5-3.0 4 0.95 - 1.5 5 0.49- 0.95

Table 2 : The TSP And PM10 Concentrations (ug/m3) At The Middle Of Industrial Complex, Pasir Gudang, 1993

DATE PM10 TSP PM10/TSP 9-Feb 117.5 196.3 0.60 14-Feb 85.0 156.6 0.54 17-Feb 94.4 175.1 0.54 21-Feb 83.5 145.5 0.57 23-Feb 74.2 130.4 0.57 25-Feb 76.1 140.1 0.54 28-Feb 23.8 51.4 0.46 2-Mar 80.4 134.3 0.60 5-Mar 89.1 167.6 0.53 7-Mar 60.7 97.9 0.62 10-Mar 85.9 143.1 0.60 Mean 79.1 139.8 0.56 Std. Dev. 23.2 39.0 0.05

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Table 3: Concentration of Respirable Particles in the Industrial Complex of Pasir Gudang in 1993

RESPIRABLE PARTICLES (ug/m3) SAMPLING TSP DATE (um/m1) State 1 State 2 State 3 State 4 StateS 7.2 urn 3.0 um 1.5 um 1.0 um 0.5 um

7-Sep. 192.7 9.58 39.34 4.82 11.01 17.20

9-Sep. 259.6 12.62 17.56 8.75 7.92 32.56

11-Sep. 197.1 5.42 22.20 14.46 16.19 16.37

13-Sep. 199.1 9.82 21.67 12.98 16.31 19.88

15-Sep. 236.1 18.57 31.49 16.37 15.71 19.11

17-Sep. 173.0 10.06 22.86 7.86 7.62 10.36

19-Sep. 91.6 4.40 10.00 8.39 7.44 10.71

21-Sep. 77.6 7.44 17.20 9.52 12.56 17.20

23-Sep. 130.1 7.38 14.28 5.06 6.43 8.33

26-Sep. 131.1 4.76 11.90 6.73 11.96 17.14

28-Sep. 201.2 12.68 21.07 9.40 11.96 15.36

30-Sep. 205.2 11.49 23.15 12.74 13.87 19.46

2-Oct. 174.6 6.55 16.49 6.73 9.46 9.58

4-Oct. 232.3 13.09 28.75 13.15 17.92 25.42

6-Oct. 218.9 11.19 17.80 8.39 9.88 14.17

Mean 179.1 9.67 21.05 9.69 11.75 16.86

%TSP 100 5.4 11.8 5.4 6.6 9.4

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Figure 4: Elemental Composition at Two Points on the Surface of a Particle From Industrial Complex, Pasir Gudang, 3rd. October, 1993

CONCENTRATION (%Wt.) ELEMENT ATOMIC NUMBER Point 1 Point 2 Na 11 17.0 - AI 13 0.8 - P 15 - 1.2 S 16 15.7 - CI 17 20.3 - K 19 1.1 0.6 Ca 20 19.8 94.1 Fe 26 4.7 - Cu 29 12.3 4.2 Hg 80 8.3 - TOTAL 100 100

Table 5: Comparison of Heavy Metal Concentrations in the TSP from the Industrial Centre and The Johor Port Authority Area, during February-March, 1993

INDUSTRIAL CENTRE (ug/m3) PORT AREA (ug/m3)* METAL Average Maximum Minimum Average Maximum Minimum Pb 0.024 0.14 0 0.095 0.32 0 Cd 0.001 0.005 0 0.001 0.01 0 Cu 0.029 0.067 0.002 0.456 1.41 0.13 Ni 0.022 0.034 0.01 0.006 0.02 0 Fe 0.957 1.293 0.399 1.555 6.39 0.26

Note: a. *DOE, 1994 b. Value of "0" indicates below detection limits of the analytical methods employed.

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Seiat.

li Saxaoiia?; Sites ot AeTSF and. 2.M1G iit Zaair Gudans.

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Stage: 1 T-11 micmns:

Stage ZT 4.7-Trmctoaa: Stage! -4& microns.

2H -33 microns: Stage 5 1.1 - 2.1 microns

Stages 0.43 - 0J5S microns:

Sixuaiaied- Human: Respirotorj Systear by Set Stages Cisade anpacor [NolIersdL. 1981 ]

Q_

Parftde Size (urn)

r Mass-Size Distribuiioaof Respi In :he Tadastrial Complex of Pasir Gud&ng-, Septeainer-OctoberL993.

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Figure 4: Scanning Electron Micrograph of Air Suspended Particulates from Pasir Gudang Industrial Complex 3rd. October 1993.

Figure 5: SEM Dot Map or an Air Suspended Particulates from Pasir Gudang Industrial Complex 3rd. October 1993.

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0.1 - 0.09- • - 0.08-•- _ o.or - ^ O.0S -

0J131

Cu Figure 6: Heavy Metal Concentrations in -fte PM10 Industrial Centre and Town Centre. Fefamary-Marck 1993

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0J31

0 Pb Cd Cii FexfC

Ff gura 7: Heavy Md»l Concentraiions in TSP and PM10 of Pasir Gudang IndastriaL Complet. Febrcary-Marcit 1993~

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2 •rrap aPMia

3- 5

2: 1 0 ^ PB a 8r NC3 SO4-- Figure 8: Aaion Cca

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u Na NH4 Ffgur»9: Canioo Cooceafcrationa m TSP and PMtO of Pasir Gudang Industrial Com pie*. Febraary-Mardi L993-

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