PERSISTENT ORGANIC CONTAMINANTS IN THE URBAN AND
PERI-URBAN AREA OF PLOIESTI CITY
Mirela Alina SANDU1,2, Ioan BICA1, Ana VIRSTA2, Mihaela PREDA3
Vasilica Silvia STAN2
1Tehnical University of Civil Engineering Bucharest, 122-124 Lacul Tei Blvd., RO 020396, District 2, Romania, Phone: +4021242.12.08, Email: [email protected], [email protected]
2University of Agronomic Sciences and Veterinary Medicine of Bucharest, 59 Marasti Blvd., Romania, Phone: +4021.318.25.64, Email: [email protected], [email protected]
3National Research and Development Institute for Soil Science, Agrochemistry and Environment - ICPA Bucharest, 61 Marasti Blvd., Romania, Phone: +4021.318.44.63,
Email: [email protected]
Corresponding author email: [email protected]
Abstract The paper presents an original research regarding the incidence of polychlorinated biphenyls compounds (PCBs) and organochlorine insecticides (HCH and DDT) on the urban area of Ploiesti. Due to the high level of toxicity, international legislation provides the list of PCBs compounds to be monitored: PCB28, 52, 101, 118, 138, 153, 180. Sample collection was made in 27 points located in ornamental garden, parks, and street intersections. The chemical analyses were conducted in the Laboratory of National Research and Development Institute for Soil Science, Agro-Chemistry and Environment of Bucharest, according to an own analytical method adapted after EPA. There were determined physical properties and chemical concentrations for humus, organic carbon, mobile phosphorus and potassium, total nitrogen, as well as the PCBs, DDT and -, - and - HCH. According to the Romanian standards, the concentrations of PCBs overcome the normal values in all sampling points and intervention threshold in seven locations. This could have a high impact on people health - especially children and old people - and some intervention measures need to be taken. Key words: polychlorinated biphenyls compounds, organochlorine insecticides, soil contamination. INTRODUCTION Persistent organic pollutants (POPs) are of worldwide concerns because of their persis-tence (Dimond and Owen, 1996), bioaccumu-lation (Nakata et al., 2002), and toxicity to human and other animal and plant lives (Jones and de Voogt, 1999). Polychlorinated biphenyls (PCBs), dichloro-diphenyltrichloroethane (DDT) and hexachlo-rocyclohexane (HCH) have been among the most widely used Persistent Organic Pollutants (POPs) throughout the world. Organochlorine insecticides were largely used in the past for medical and agricultural purposes. Technical HCH and DDT consist of about 50% of pesticide products in the 1970s (Zhang, 1996) and were heavily used for agricultural purposes.
Polychlorinated biphenyls (PCBs) were widely used in various industrial applications. Research confirmed that some PCBs congeners degrade slowly in the environment and can build up in the food chain. Commercial worldwide production ceased in 1979; however, legacy PCBs remains. PCBs may persist in the environment for periods of years and may bioconcentrate by factors of up to 70,000 fold. Humans can be exposed to POPs through diet, occupational accidents and the environment (including indoor). Exposure to POPs, either acute or chronic, can be associated with a wide range of adverse health effects, including illness and death. In Romania, research showed the presence of HCH and PCBs in human body due to indoor or outdoor exposure (Dirtu et al, 2006; Covaci et al, 2001; Cioroiu et al, 2010).
143
AgroLife Scientific Journal - Volume 2, Number 1, 2013
ISSN 2285-5718; ISSN CD-ROM 2285-5726; ISSN ONLINE 2286-0126; ISSN-L 2285-5718
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Figure 5. The separation of a standard mixture of organochlorine insecticides on capillary column
Figure 6. The chromatogram of a standard mixture of
PCBs
RESULTS AND DISCUSSIONS The chemical characteristics of soil sample vary greatly: the pH ranges in weak acid - weak alkali, organic matter content, mobile phosphorus, mobile potassium, total nitrogen are contrasting (Table 1). The discussions of the results were done according to Romanian regulations - MO 756/1997 regarding the content of organo-chlorine insecticides and of polychlorinated biphenyls compounds in soils. Following the evaluation of the results (Table 2) regarding the surface layer analysis (0-10 cm) it can be observed that PCB 28 is undetectable in four of the 27 sampling points. In the other samples, the PCB 28 content vary between 0.0002 mg/kg on Latina street from Ploiesti and 0.0180 mg/kg in the green space of the Hippodrome enclosure. Regarding the PCB 28 concentration, none of the studied soil samples do not range within normal limits (<0.0004 mg/kg), 30% have contents ranging between the superior threshold of normal values and the warning threshold (0.01 mg/kg), 61% exceed the warning threshold and 9% exceed the intervention threshold (0.04 mg/kg) (Figure 7).
Table 1. The chemical characteristics of soil sample of Ploiesti city
Nr. crt.
Nr. reg.
IDENTIFICATION pH Humus
(%) C organic
(%)
Total nitrogen (%)
Mobile phosphorus
(mg/kg)
Mobile potassium (mg/kg) Sampling points Comments
1 P1 Ploiesti Vest Str. Baraolt ornamental gardens 7.56 5.15 2.987 0.325 1567 356 2 P2 Billa Str. Dianei ornamental gardens 7.53 5.32 3.086 0.325 632 60 3 P3 Parcul Tineretului park 7.41 4.79 2.778 0.339 432 84 4 P4 Dero Lever ornamental gardens 7.71 5.32 3.086 0.25 1179 403 5 P5 Bd. Independentei 0.5m roadsides 7.85 2.75 1.595 0.164 477 310 6 P6 Bd. Independentei 10m 10 m to the road 7.86 2.32 1.346 0.169 494 149 7 P7 Gara de Sud roadsides 7.45 7.53 4.368 0.331 765 504 8 P8 Mihai Eminescu park 7.95 3.37 1.955 0.128 975 63 9 P9 Bd. Petrolul cu Sos. Bucure ti Roadsides 7.67 2.96 1.717 0.233 555 173
10 P10 Petrotel-Lukoil(Sos.Mihai Bravu) ornamental gardens 7.82 4.96 2.877 0.277 924 194 11 P11 Hipodrom ornamental gardens 7.77 7.55 4.379 0.451 815 59 12 P12 Bd. Democratiei ornamental gardens 8.01 3.25 1.885 0.217 1247 123 13 P13 Hotel Prahova ornamental gardens 7.70 6.98 4.049 0.303 537 218 14 P14 Feroemail SA ornamental gardens 8.07 2.43 1.140 0.199 679 148 15 P15 Liceul agricol Barcanesti Roadsides 7.77 4.05 2.349 0.295 993 519 16 P16 Petrotel-Lukoil - poarta 4 ornamental gardens 7.82 4.65 2.697 0.306 869 48 17 P17 Rafinaria Vega ornamental gardens 7.87 4.99 2.894 0.351 1106 150 18 P18 Petrom – Statia 3 Bucov ornamental gardens 8.04 3.20 1.856 0.217 616 63 19 P19 Fabrica de paine Extrapan Nord Roadsides 7.48 5.55 3.219 0.404 1713 802 20 P20 Bariera Bucov roadsides with DN 1B 7.89 4.12 2.390 0.276 582 270 21 P21 Gara de Nord ornamental gardens 7.75 2.75 1.595 0.242 932 536 22 P22 Spitalul Boldescu Roadsides 8.04 4.29 2.488 0.27 957 99 23 P23 Muzeul Nichita Stanescu ornamental gardens 7.84 3.05 1.769 0.178 699 128 24 P24 Mihai Viteazu Roadsides 7.84 4.43 2.570 0.358 1371 529 25 P25 A. Muresan si Sos. Nordului Roadsides 7.72 3.75 2.175 0.246 550 257 26 P26 Str. Scolii ornamental gardens 7.76 3.84 2.227 0.253 951 437 27 P27 Str. Latina Roadsides 7.83 3.62 2.100 0.25 931 465
146
Table 2. Polychlorinated biphenyls compounds in the Ploiesti city
Nr. crt. SAMPLING POINTS PCB 28
mg/kg PCB 52 mg/kg
PCB 101 mg/kg
PCB 138 mg/kg
PCB 153 mg/kg
PCB 180 mg/kg
Total PCB mg/kg
1 Ploiesti Vest Str. Baraolt 0.0085 nd. nd. 0.0253 0.0245 0.0233 0.0816 2 Billa Str. Dianei 0.0013 nd. nd. 0.0008 0.0008 0.0011 0.0040 3 Parcul Tineretului 0.0037 nd. nd. 0.0266 0.0278 0.0425 0.1006 4 Dero Lever 0.0042 0.0023 0.0048 0.0558 0.0520 0.0695 0.1886 5 Bd. Independentei 0.5m 0.0074 0.0025 0.0063 0.0853 0.0585 0.0945 0.2546 6 Bd. Independentei 10m 0.0024 0.0015 0.0009 0.0594 0.0564 0.0632 0.1838 7 Gara de Sud nd. nd. nd. 0.0555 0.0675 0.0682 0.1912 8 Mihai Eminescu 0.0156 0.0032 0.0193 0.0163 0.0156 0.0208 0.0908 9 Bd. Petrolul cu Sos. Bucure ti 0.0031 nd. nd. 0.0223 0.0222 0.0429 0.0905
10 Petrotel-Lukoil(Sos.Mihai Bravu) 0.0059 nd. nd. 0.0220 0.0233 0.0485 0.0977 11 Hipodrom 0.0180 nd. nd. 0.0018 0.0026 0.0033 0.0257 12 Bd. Democratiei nd. nd. nd. 0.0086 0.0053 0.0144 0.0283 13 Hotel Prahova 0.0028 nd. nd. 0.0410 0.0418 0.0613 0.1469 14 Feroemail SA nd. nd. nd. 0.0004 0.0006 0.0010 0.0020 15 Liceul agricol Barcanesti 0.0021 nd. nd. 0.0009 0.0016 0.0022 0.0066 16 Petrotel-Lukoil - poarta 4 0.0028 nd. nd. 0.0123 0.0128 0.0253 0.0532 17 Rafinaria Vega 0.0022 nd. nd. 0.0018 0.0020 0.0031 0.0087 18 Petrom – Statia 3 Bucov 0.0007 nd. nd. 0.0055 0.0109 0.0112 0.0283 19 Fabrica de paine Extrapan Nord 0.0005 nd. nd. 0.0005 0.0005 0.0027 0.0042 20 Bariera Bucov 0.0030 nd. 0.0079 0.1026 0.0989 0.1201 0.3325 21 Gara de Nord 0.0014 nd. nd. 0.0048 0.0040 0.0071 0.0173 22 Spitalul Boldescu 0.0014 nd. nd. 0.0043 0.0050 0.0083 0.0190 23 Muzeul Nichita Stanescu 0.0031 nd. nd. 0.0052 0.0045 0.0059 0.0187 24 Mihai Viteazu 0.0012 nd. nd. 0.0012 0.0015 0.0020 0.0059 25 A. Muresan si Sos. Nordului nd. nd. nd. 0.0012 0.0018 0.0024 0.0054 26 Str. Scolii 0.0021 nd. nd. 0.0006 0.0009 0.0014 0.0050 27 Str. Latina 0.0002 nd. nd. 0.0013 0.0017 0.0022 0.0054
nd – not detected MO 756/1997 Normal values <0.0001 <0.0001 <0.0004 <0.0004 <0.0004 <0.0004 <0.01 Warning threshold 0.002 0.002 0.01 0.01 0.01 0.01 0.25 Intervention threshold 0.01 0.01 0.04 0.04 0.04 0.04 1
Figure 7. Distribution of soil samples collected by the
charge of PCBs compounds
Polychlorinated biphenyls PCB 52 and PCB 101 are detectable in four, five respectively of the analyzed samples (Table 2), recording values over the normal ones (<0.000 4 mg/kg) in five sampling points and four concentrations that exceed the warning threshold of 0.01 mg/kg.
The PCB 138 concentration ranges between 0.0005 mg/kg in Extrapan Nord bread factory area and 0.1026 mg/kg in the sample collected in front of the Bariera Bucov from Ploiesti. Practically, it can be observed a low charging level in the residential area and high concentrations, even over the intervention threshold, in industrial areas. Therefore, it may be stated that the charging level of PCB 138 is high, the most polluted areas being situated in the city industrial area (Petrotel-Lukoil and Dero), and in high road traffic areas (Bulevardul Independen ei, Gara de Sud, Hotel Prahova, Bariera Bucov). From the distribution by PCB 153 charge degrees in figure 8, it is shown that none of the twenty seven studied sampling points is characterized by normal values of concentration, 52% of the soil samples recording concentrations ranging between of the normal values and warning threshold, 26% record values exceeding warning threshold and 22% exceed intervention threshold. The PCB 180 content, the highest chlorinated of the six under study, ranges between 0.010
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mg/kg in Feroemail SA area and 0.1201 mg/kg Bariera Bucov, therefore a variation on a large spectrum of values. In this study case, 52% of the analyzed samples have concentrations between normal values and the warning threshold, 15% exceed warning threshold and the remaining 33% have values exceeding intervention threshold (Figure 8). It can be observed that, the higher is the chlorination degree, more samples have a concentration exceeding intervention threshold. Also, the charging level is higher in the same points for each isomer, the crowded areas respectively (Bariera Bucov, Bulevardul Independentei, Gara de Sud, Bd. Petrolului, Hotel Prahova) and in the industrial areas (Petrotel-Lukoil, Dero). In regard to all content of PCBs compounds, this varies between 0.0042 mg/kg in the residential area of the city and 0.3325 mg/kg in the area of Bariera Bucov. Around 33% of the analyzed samples show concentration values between normal limits (<0.01 mg/kg), 59% show concentrations between normal values and the warning threshold (0.25 mg/kg), and 8% exceed the warning threshold (1 mg/kg) (Figure 8).
Figure 8. Distribution of soil samples collected by the
charge of PCBs compounds The most polluted samples are the ones collected from Petrotel-Lukoil area, Dero factory, high traffic areas from Independen ei Blvd. and South Station, Prahova Hotel (Figure 9). The organochlorine insecticides had been used in our country since 1948 and were prohibited
in 1985, their half-life period being two years for HCH and tens of years for DDT.
Figure 9. The presence of PCBs (mg/kg)
in the Ploiesti city
The data provided by the research studies on organochlorine insecticides from the analyzed soil show that the recorded values were normal in all specified samples (DDT<0.05 mg/kg, HCH<0.001 mg/kg) or little above them, however not exceeding the warning threshold (DDT - 0.25 mg/kg and HCH - 0.1 mg/kg), which leads us to the conclusion that they have not been used anymore after their prohibition. The resulted organochlorine insecticides concentrations are presented in Table 3 and Figure 10. From the distribution of organochlorine insecticides charge degrees in Figure 11, it is shown that all of the sample points have concentrations between normal values and the warning threshold (0.005-0.25 mg/kg) of HCH, 78% are normal values for total DDT and 22% of the soil samples record concentrations ranging between the normal values and warning threshold.
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Table 3. Organochlorine insecticides in the Ploiesti city Nr
crt Sampling points HCH
mg/kg HCH
mg/kg HCH
mg/kg
HCH total
mg/kg
pp' DDE
mg/kg
op' DDD mg/kg
op'DDT mg/kg
pp' DDD mg/kg
pp' DDT
mg/kg
DDT total
mg/kg
Total organo-chlorin-
insecticid 1 Ploiesti Vest 0.044 0.048 0.013 0.105 0.003 nd 0.003 0.008 0.043 0.056 0.206 2 Billa Str. Dianei 0.048 0.013 0.003 0.063 0.003 0.001 0.001 0.001 0.007 0.012 0.075 3 Parcul Tineretului 0.089 0.042 0.009 0.140 0.012 0.001 0.006 0.007 0.050 0.076 0.216 4 Dero Lever 0.017 0.039 0.006 0.061 0.020 0.002 0.014 0.003 0.141 0.179 0.240 5 Bd. Independ. 0.5m 0.044 0.020 0.002 0.066 0.004 0.001 0.003 0.001 0.009 0.017 0.083 6 Bd. Independ. 10m 0.011 0.005 nd 0.016 0.005 0.001 0.003 0.002 0.002 0.012 0.028 7 Gara de Sud 0.016 0.009 nd 0.025 0.008 0.002 0.004 0.003 0.013 0.029 0.054 8 Mihai Eminescu 0.029 0.012 0.002 0.044 0.037 0.013 0.007 0.019 0.103 0.179 0.223 9 Bd. Petrolul 0.083 0.034 0.009 0.125 0.009 0.001 0.005 0.003 0.038 0.057 0.182
10 Petrotel-Lukoil 0.037 0.007 nd 0.044 0.007 0.003 0.009 0.002 0.074 0.095 0.139 11 Hipodrom 0.119 0.012 0.013 0.144 0.005 0.001 0.003 0.006 0.015 0.031 0.175 12 Bd. Democratiei 0.026 0.010 nd 0.036 0.006 nd 0.002 0.003 0.002 0.013 0.049 13 Hotel Prahova 0.004 0.002 nd 0.006 nd 0.001 nd 0.002 0.001 0.003 0.009 14 Feroemail SA 0.017 0.005 nd 0.022 0.002 nd 0.001 nd 0.002 0.005 0.027 15 Liceul Barcanesti 0.016 0.006 nd 0.023 0.003 0.002 0.005 0.003 0.019 0.032 0.055 16 Petrotel poarta 4 0.016 0.004 nd 0.020 0.015 0.001 0.010 0.001 0.052 0.078 0.098 17 Rafinaria Vega 0.044 0.036 0.007 0.087 0.005 0.004 0.006 0.002 0.012 0.028 0.115 18 Petrom – Statia 3 0.010 0.001 nd 0.011 0.014 0.001 0.004 0.002 0.020 0.039 0.050 19 Extrapan Nord 0.009 0.002 nd 0.011 0.009 0.001 0.008 0.001 0.034 0.053 0.064 20 Bariera Bucov 0.018 0.008 nd 0.026 0.023 0.002 0.009 0.002 0.045 0.081 0.107 21 Gara de Nord 0.015 0.004 nd 0.019 0.010 0.001 0.004 0.004 0.023 0.042 0.061 22 Spitalul Boldescu 0.024 0.005 nd 0.029 0.033 0.005 0.026 0.009 0.173 0.245 0.274 23 Muzeul N. Stanescu 0.021 0.009 0.002 0.032 0.012 0.001 0.006 0.004 0.013 0.036 0.068 24 Mihai Viteazu 0.013 0.091 nd 0.104 0.017 0.004 0.011 0.004 0.034 0.070 0.174 25 A. Muresan 0.006 0.002 0.002 0.010 0.005 0.001 0.003 0.002 0.004 0.015 0.025 26 Str. Scolii 0.023 0.011 0.002 0.036 0.010 0.002 0.006 0.003 0.008 0.029 0.065 27 Str. Latina 0.027 0.006 0.003 0.036 0.013 0.002 0.005 0.002 0.011 0.033 0.069 nd – not detected Normal values <0.002 <0.001 <0.001 <0.005 < 0.05 < 0.05 < 0.05 < 0.05 < 0.05 < 0.15 0.2 Warning threshold 0.1 0.05 0.02 0.25 0.25 0.25 0.25 0.25 0.25 0.5 1 Intervention threshold 0.2 0.1 0.05 0.5 0.5 0.5 0.5 0.5 0.5 1 2
Figure 10. The concentration of HCH and DDT (mg/kg)
in the Ploiesti city
In this study case, from total organochlorine insecticides, 19% of the analyzed samples have concentrations between normal values and the warning threshold, and the remaining 81% are normal values.
Figure 11. Distribution of soil samples collected by the charge of organochlorine insecticides compounds
CONCLUSIONS The performed research work indicate the presence of POPs, namely PCBs, DDT and HCH in Ploiesti city.
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The concentration values of organochlorine insecticides were below normal values accepted by standards and in accordance with other research showing lower values in urban areas and bigger on agricultural lands due to previous use of these compounds as a pesticide. The results regarding the high concentrations of PCBs are not surprising, since Ploiesti has a major industrial activity inside the city. Generally, concentrations of PCBs in Ploiesti is high (maximum value of 0.3325 mg/kg for
PCBs), compared to other urban areas. The variability of the results might be not only a result of the proximity to sources, source type, age of sites, but also a result of the soil retention capacity as well. The presence of PCBs in almost all investigated points, the concentrations being over the warning threshold in some locations, arises concernment reasons for the exposed population - especially children - because according to the International Agency of Research on Cancer (IARC) PCBs belong to a group of probable carcinogens for man. Further research will focused on risk contamination and soil decontamination technologies for high risk identified areas. ACKNOWLEDGEMENTS This study has been carried out under the frame of Sectoral Operational Programme Human Resources (POSDRU) 2007-2013, the Project PhD Scholarships in Environmental Engineering Building, ID 76896 and under the "Platform for Geoinformation in Support of Disaster Management (GEODIM)" scientific project financed by the Executive Agency for Higher Education, Research, Development and Innovation Funding. GEODIM (ID PN-II-PT-PCCA-2011-3.2-0575). The support of the Department of National Research and Development Institute for Soil Science, Agro-chemistry and Environment - ICPA Bucharest is gratefully acknowledged.
REFERENCES Cioroiu M., Tarcau D., Mocanu R., Cucu-man S.,
Nechita B., Luca M., 2010. Organochlorine pesticides in colostrums in case of normal and preterm labor (Iasi, Romania). Science of The Total Environment, Vol. 408, Issue 13, p. 2639-2645.
Covaci A., 2001. Selected persistent organochlorine pollutants in Romania. Science of The Total Environment. Vol. 280, Issues 1-3, p. 143-152.
Dimond J.B., Owen R.B., 1996. Long-term residue of DDT compounds in forest soils in Maine. Environment Pollutans 92, p. 1122-1130.
Dirtu A.C., 2006. Organohalogenated pollutants in human serum from Iassy, Romania and their relation with age and gender. Environment International, Vol. 32, Issue 6, p. 797-803.
Jones K.C., de Voogt P., 1999. Persistent organic pollutants (POPs): state of the science. Environment Pollut. 100, p. 209-221.
MO 756/1997. Nakata H., Kawazoe M., Arizono K., Abe S., Kitano
T., Shimada, H., Li W., Ding X., 2002. Organochlorine pesticides and polychlorinated biphenyl residues in foodstuffs and human tissues from China: status of contamination, historical trend, and human dietary exposure. Arch. Environ. Contaminant Toxicol. 43, p. 473-480.
Zhang Z.M., 1996. The development of Chinese pesticide industry. Pesticides 35, p. 12-14.
National Environmental Protection Agency (ANPM), 2010. Environmental Status in Romania.
STAS 7184/1-75 SR ISO 11074 - 2:2001. US EPA Method 8270, 1998.
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