Bull Environ Contam Toxicol (2015) 95:530–535 DOI 10.1007/s00128-015-1631-4
Concentrations and Toxic Equivalency of Polychlorinated Biphenyls in Polish Wastewater Treatment Plant Effluents Magdalena Urbaniak1,2 • Edyta Kiedrzyn´ska1,2
Received: 5 February 2015 / Accepted: 11 August 2015 / Published online: 18 August 2015 Ó Springer Science+Business Media New York 2015
Abstract Wastewater treatment plants (WWTPs) are widely recognized as important sources of toxic contaminants such as polychlorinated biphenyls (PCBs). An example is given in the present paper, where concentrations of 12 dioxin-like PCBs (dl-PCBs) congeners were investigated in effluents from 14 WWTPs of different sizes, using gas chromatography tandem–mass spectrometry. The results obtained demonstrate that the smallest WWTPs are characterized by the highest total dl-PCB concentration of 102.69 pg/L, roughly twice those of medium-size and large WWTPs, i.e. 41.14 and 48.29 pg/L, respectively. In all cases, the concentrations obtained were generated mostly by increased contributions of PCB-77, PCB-105 and PCB118 which constituted 48 %–59 % of the mean dl-PCB concentration. The results also reveal a predominance of mono-ortho over non-ortho PCBs. All three types of WWTP effluent were found to have similar toxic equivalency (TEQ) values, ranging from 0.31 for large to 0.37 pg TEQ/L for medium WWTPs. Keywords Wastewater treatment plant Effluents PCBs TEQ
Electronic supplementary material The online version of this article (doi:10.1007/s00128-015-1631-4) contains supplementary material, which is available to authorized users. & Magdalena Urbaniak
[email protected] 1
European Regional Centre for Ecohydrology of the Polish Academy of Sciences, Tylna 3, 90-364 Lodz, Poland
2
Department of Applied Ecology, Faculty of Biology and Environmental Protection, University of Lodz, Banacha 12/16, 90-237 Lodz, Poland
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Abbreviations WWTPs Wastewater treatment plants PCBs Polychlorinated biphenyls dl-PCBs Dioxin-like polychlorinated biphenyls TEQ Toxic equivalency TEF Toxic equivalency factor
The increased global usage of water has led to increased concern about the quality of outgoing wastewater from municipal wastewater treatment plants (WWTPs) (Bergqvist et al. 2006). To date, quantification of wastewater pollution has been restricted to monitoring traditional parameters that are easily and inexpensively analyzed and which are regulated by the European Urban Wastewater Directive (91/271/EEC), such as biochemical oxygen demand, chemical oxygen demand, nitrates, phosphates and total suspended solids (Cirja et al. 2008). Nevertheless, these routine chemical analyses cannot give a complete overview of the threat to the water environment posed by other substances released via WWTP effluent, such as dioxin-like polychlorinated biphenyls (dl-PCBs) which are toxic, carcinogenic and known endocrine disrupters posing a serious risk for living organisms (Bergqvist et al. 2006). The negative impact of dl-PCBs has also been observed in surface water, e.g. Stachel et al. (2007) demonstrated that treated wastewater containing PCBs and transported to the Elbe River, pollutes river suspended particulate matter, sediments and aquatic fauna. The toxic effect of these compounds on water ecosystems is reflected in genetic changes and a weakening of reproductive and immune processes of the aquatic organisms (Belfiore and Anderson 2001). Moreover, the consequences of exposure to dl-PCBs are revealed in the structure of river macrozoobenthos,
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affecting from 8 % to 13 % of the observed changes (De Lange et al. 2004). Due to the harmful impact of dl-PCBs on the surface water and its threat to the biodiversity of aquatic organisms, in September 2013, European Parliament, established new priority substances and priority hazardous substances, and introduced an obligation to monitor their concentrations in water ecosystems (Directive 2013/39/EC). However, although PCBs have been identified as priority hazardous substances, no allowable concentration in inland surface waters was provided. With regard to the allowable PCB limits in treated wastewater, one of the most important Polish regulations in the field of water policy, the Water Law (OJ 2001 No. 115, item 1229, act of July 19 2001, the Water Law), prohibits the discharge of indicator PCBs (PCB 28, 52, 101, 138, 153 and 180) into river ecosystems through WWTP outlets. However, no such limit exists with respect to toxic congeners of dl-PCBs. Other Polish regulations, like the Minister of the Environment Regulation dated 24 July 2006 on the conditions to be met when discharging sewage into waters or soil, and on substances of particular adverse impact on the water environment (Journal of Laws 2006 no. 137, item 984), also prohibits the discharges of dl-PCBs with treated wastewater, but this regulation applies only to industrial WWTPs. Consequently, municipal WWTPs are not monitored as far as dl-PCB discharges are concerned. This is a vital problem, as the majority of municipal WWTPs are not efficient in removing such highly hydrophobic and persistent compounds as dl-PCBs during the conventional treatment processes (Pham et al. 1999; Blanchard et al. 2001; Katsouiannis and Samara 2005; Oleszek-Kudlak et al. 2005; Bergqvist et al. 2006; Katsouiannis and Samara 2007; Cirja et al. 2008; Deblonde et al. 2011; Jelic et al. 2011; Syakti et al. 2012). Consequently, dl-PCBs are detected not only in raw and treated wastewater, but also in rivers as it was demonstrated in our earlier study by Urbaniak et al. (2012, 2014), posing a threat to aquatic organisms. Hence, the aim of this study was to determine the occurrence, concentrations and patterns of 12 toxic congeners of PCB (dl-PCBs) in treated wastewater discharged from 14 municipal WWTPs divided into three size categories, located in one river catchment, in order to address the knowledge gap concerning priority substances in WWTP effluents.
Materials and Methods All the studied municipal WWTPs are located in the Pilica River catchment (Central Poland), with a total catchment area of 9258 km2 and an overall river length of 342 km.
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The Pilica River is the longest left-bank tributary of the largest river in Poland, the Vistula River, and is one of its most significant tributaries, entering the Vistula at 457 km along the river course (Urbaniak et al. 2012, 2014; Kiedrzyn´ska et al. 2014). Forests cover about 31 % of the catchment, however despite this, the Pilica River catchment is predominantly agricultural, with cultivated land covering 60 % of its total area. Regarding wastewater system usage, 51.3 %–70.5 % of the human population in the Pilica River catchment is connected to WWTPs, depending on the region, with a mean value for the whole catchment of 59 % (PCSO 2010; Kiedrzyn´ska et al. 2014). Of the total number of 143 WWTPs existing in the Pilica River catchment, 43.6 % are equipped with advanced nutrient removal technology (PCSO 2010; Kiedrzyn´ska et al. 2014; Urbaniak et al. 2014). The 14 municipal WWTPs selected for the present study were divided into three size categories according to the population equivalent (p.e.) (Journal of Laws 2006 no. 137, item 984), and wastewater outflow: small (p.e.: 0–1999; wastewater outflow: 100–300 m3/day); medium-sized (p.e.: 2000–9999; wastewater outflow: 300–1000 m3/day), and large (p.e.: 15,000–99,999; wastewater outflow: 1500–15,000 m3/day). Of the municipal WWTPs included in the study, 7 WTPs were classified as small, 3 as medium-sized and 4 as large (Table 1). All the studied municipal WWTPs located in the Pilica catchment utilize secondary treatment processes, with increased nutrients removal in the case of two medium WWTPs (Kiedrzyn´ska et al. 2014; Urbaniak et al. 2014). Two 5 L samples out of the treated wastewater samples were taken from each WWTP, one in May and the second in September 2010. The samples were collected directly from the wastewater outflow into the Pilica River or its tributaries, placed into amber containers and transported to the laboratory in a car fridge at a temperature of 4°C, wherein they were directly analyzed. Wastewater samples of 2 L were spiked with 100 pg of 12 13C-labelled dl-PCBs (NK-LCS-G and WP-LCS respectively, obtained from Wellington Laboratories), and liquid/liquid extracted with toluene. After rotary evaporation to about 20 mL, the toluene extract was cleaned-up as follows: concentrated extract was placed in the bottom of a sealed polyethylene semipermeable membrane tube of 80 lm wall thickness and cleaned up overnight with 100 mL hexane (the outer solvent). The hexane dialysate was cleaned up on a silica gel column coated with 44 % sulphuric acid and Alumina. Determination of 12 dl-PCBs was performed by isotope dilution gas chromatography–tandem mass spectrometry on a Thermo Scientific GCQ-1100/Trace2000 system equipped with Xcalibur data acquisition and analysis
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Table 1 Characteristics of the studied WWTPs Population equivalent of WWTP
Daily average treated wastewater outflow (m3/day)
Treatment steps
Wastewater treatment plant (WWTP)
WWTP class
Spala
I
350
130
Secondary
Rozprza
I
500
107
Secondary
Koniecpol
I
600
100
Secondary
Gorzkowice
I
700
224
Secondary
Wolborz
I
800
241
Secondary
Wielgomłyny
I
1000
200
Secondary
Ujazd
I
1500
300
Secondary Secondary
Nowe Miasto
II
2583
1000
Tuszyn
II
4000
640
Secondary with advanced nutrient removal
Secondary
Sulejow
II
7500
870
Secondary
Opoczno
IV
75,000
5127
Secondary
Tomaszow Mazowiecki
IV
80,000
10,050
Secondary
Secondary
Piotrkow Trybunalski
IV
80,000
14,541
Warka
IV
99,000
9900
software. The separation was performed on a 30 m 9 0.25 mm i.d. DB5 MS J&W capillary column of 25 lm film (Aligent Technologies, Poland) and 30 m 9 0.25 mm i.d. DB17 MS J&W capillary column of 25 lm film (Aligent Technologies, Poland). A sample of 2.5 lL volume was injected into a split/splitless (SSL) injector at 260°C. The GC oven was programmed as follows: an initial temperature of 130°C held for 3 min, then a temperature ramp of 50°C/min to 180°C, then another temperature ramp of 2°C/min to 270°C. Finally, the temperature ramp was 20°C/min to 300°C and held for 5 min. The result uncertainty was expressed as extended measurement uncertainty for k = 2 at a confidence level of 95 %. Toxic equivalency (TEQ) is operationally defined as the sum of the products of the concentration of each compound multiplied by its toxic equivalency factor (TEF). The TEQ is an estimate of the 2,3,7,8-tetrachlorodibenzo-p-dioxinlike activity of the mixture (van den Berg et al. 2006). In this study, the TEQ was calculated by multiplying the concentrations of 12 dl-PCBs by their assigned TEF value (van den Berg et al. 2006; see Table 2). All analytical work was performed in the Laboratory for Trace Organic Analyses at the Krakow University of Technology in Poland. All applied analytical methods had been properly validated and the laboratory successfully accredited as part of the Circuit Interlaboratories for Dioxins organized by the Interuniversity Consortium ‘‘Chemistry for the Environment’’, in collaboration with LabService Analytica S.r.l.
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Secondary Secondary with advanced nutrient removal
Quantification was performed by the internal standard method using certified calibration standards. Each analytical batch contained a method blank, a matrix spike, and replicate samples. A reagent blank was used to assess artifacts, the precision was verified by duplicate analyses and recoveries were estimated using samples spiked with dl-PCBs. Sample spikes were used to further confirm accuracy. Recoveries and LOD through the analytical procedure were presented in the supplementary materials in Table 1S. Moreover, all glassware and bottles used in the field and laboratory were cleaned with detergent, rinsed with ultrapure water and then heated at 450°C overnight. Before use, the glassware was rinsed with acetone and hexane.
Results and Discussion The results obtained in the present study confirmed that WWTPs release dl-PCBs as all the studied congeners were detected in the effluents. The smallest concentration of 1.73 pg/L (±0.98) was observed for PCB-189 while the highest value of 32.49 pg/L (±68.84) was noted for PCB118. In regard to the size of WWTPs, the highest variance of the congeners concentration was observed in small WWTPs being between 2.45 pg/L (±1.35) and 32.49 pg/L (±68.49). Much smaller divergence was observed in medium-sized WWTPs wherein the concentrations ranged between 2.43 pg/L (±1.58) and 4.93 pg/L (±2.71). In the case of large WWTPs the values ranged from 1.73 pg/L (±0.98) to 12.16 pg/L (±13.72) (Table 2).
1.43 27.85
2.49 25.12 14.15
0.0003
0.1
0.03
0.00003
0.00003
0.00003
0.00003
0.00003
0.00003
0.00003
0.00003
PCB-81
PCB-126
PCB-169 P Non-ortho PCBs
PCB-105
PCB-114
PCB-118
PCB-123
PCB-156
PCB-157
PCB-167
PCB-189 P Mono-ortho PCBs P dl-PCBs TEQ
4.10
33.60 53.80 0.32
121.58 130.44 0.14
77.57 102.69 0.33
3.40
3.40
2.65
3.90
7.20
4.40
4.25
16.75
1.95
2.45
3.65
2.55
4.42
2.43
13.90
3.30
68.84
3.35
28.42
1.35
6.79
27.76
1.00
2.67
5.01
4.34
7.75
5.67
32.49
5.49
2.45
6.02
14.16
0.0001
PCB-77
508.30 0.59
463.90
4.20
19.00
10.60
51.80
12.80
251.00
14.90
106.00
112.05
5.46
5.10
26.70
105.00
Max
26.70 0.13
22.00
0.90
1.30
1.30
1.33
1.90
2.10
1.50
2.40
4.70
0.90
0.70
0.88
1.20
Min 2.53
41.14 0.37
27.99
2.43
3.36
3.18
2.47
4.20
4.93
4.25
3.18
13.15
3.51
2.65
4.46
17.66 0.19
13.84
1.58
1.87
1.74
1.27
2.10
2.71
2.27
1.57
5.41
2.56
1.73
2.29
0.92
SD
38.40 0.29
25.10
2.05
3.15
3.25
2.10
4.25
4.45
4.30
3.00
12.55
2.45
2.30
5.20
2.70
Median
Mean
Median
Mean
SD
Medium-sized (n = 6)
Small (n = 14)
TEF
Congener
Table 2 PCB concentrations in wastewater effluents from three size categories of WTPs (pg/L)
65.75 0.67
44.60
4.38
5.90
5.04
4.40
6.90
9.70
6.60
5.70
22.53
7.77
5.10
6.77
3.68
Max
16.89 0.19
8.34
0.31
0.46
0.41
0.85
0.68
2.20
0.53
1.10
7.50
1.40
0.71
0.88
1.40
Min
48.29 0.31
35.24
1.73
3.06
2.82
2.86
3.62
12.16
3.05
5.94
13.05
2.07
2.47
3.36
5.16
Mean
27.26 0.18
22.64
0.98
1.75
1.84
2.13
2.21
13.72
2.02
5.43
6.60
1.56
1.82
2.09
7.36
SD
Large (n = 8)
44.40 0.28
33.35
1.43
2.55
2.19
2.00
2.90
8.10
2.29
4.10
12.50
1.85
2.15
2.65
2.55
Median
111.00 0.60
84.30
3.20
6.10
5.80
7.50
6.60
45.50
6.70
17.90
26.70
5.34
5.40
6.24
23.10
Max
22.50 0.09
15.50
0.50
0.90
0.60
1.27
0.80
2.90
0.70
1.70
4.90
0.20
0.30
1.20
1.10
Min
Bull Environ Contam Toxicol (2015) 95:530–535 533
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In the case of total concentrations, the highest value of 102.69 pg/L (±130.44) was demonstrated by the smallest WWTPs; while the total dl-PCBs levels noted for the medium-sized and large WWTPs were less than half this value (41.14 pg/L (±17.66) and 48.29 pg/L (±27.26), respectively) (Table 2, Fig. 1S). This is probably related to the insufficient treatment of wastewater in small WWTPs, which in turn is due to the limited volume and short retention time of wastewater in the WWTP, but also in some cases, the use of outdated technology, as demonstrated in our earlier study by Kiedrzyn´ska et al. (2014) and Urbaniak et al. (2014). Also, the maximum total dl-PCB concentration of 508.30 pg/L was observed in small WWTPs, while the lowest mean, median, maximum and minimum concentrations were observed in medium-sized WWTPs (Table 2, Fig. 1S). The very high total concentration of dl-PCBs noted for small WWTPs was mainly generated by the increased concentrations of three congeners, PCB-77, PCB-105 and PCB-118, which constituted 91 % of the maximum and 59 % of the mean dl-PCB concentration (Table 2). In the case of medium-sized WWTPs, no such predominance was observed, while the large WWTPs showed, similarly to small WWTPs, increased values for the same three congeners which contributed 78 % and 48 % of the maximum and mean dl-PCB concentrations (Table 2, Fig. 1S). With regard to the contribution of the non-ortho and mono-ortho PCBs to total dl-PCB concentration, monoortho PCBs were found to predominate in all cases with the greatest proportion being found in the small WWTPs (76 %), followed closely by the large WWTPs (73 %), and then the medium-sized WWTPs (68 %). The above contribution of non-ortho and mono-ortho PCBs was reflected in TEQ concentrations, as the non-ortho PCBs are characterized by higher TEF values and thus contribute more strongly to the TEQ than the mono-ortho congeners (van den Berg et al. 2006). As the highest TEF value is expressed by the PCB-126 congener, it is this concentration which has the greatest influence on the increase of TEQ concentration; thus the medium-sized WTPs are characterised by the highest TEQ concentration and the lowest mean total PCB concentration (Table 2, Fig. 2S and 3S). With reference to results obtained worldwide, only a few publications refer to the concentrations of PCBs in WWTP effluents. Katsoyiannis and Samara (2004, 2005) demonstrated that the mean occurrence of the sum of seven P indicator PCBs ( 7PCBs) fell from 1000,000 pg/L in raw urban wastewater to 631,000 pg/L after primary treatment and to 250,000 pg/L after secondary treatment. Chevreuil P et al. (1990) also demonstrated a very high 7PCBs concentration of 280,000 pg/L at the outlet from a
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secondary settling basin. Another study conducted by Blanchard et al. (2001) in the outflow from the Montreal WWTP (Canada) revealed much lower concentrations, measured as the sum of 13 PCB congeners, ranging from 20 to 860 pg/L with a mean valuePof 310 pg/L, whereas Pham and Prolux (1997) report the 13PCB concentration in treated wastewater from the same WWTP to be 1400 pg/ P L. Higher 7PCB concentrations ranging from 1000 to 6000 pg/L were found by Bergqvist et al. (2006) in WWTPs in Umea (Sweden) and in Siauliai (Lithuania). P The authors also demonstrated a rapid increase of 7PCB values during the treatment process ranging from 300 to 1000 pg/L in the case of Umea, and from 1000 to 6000 pg/ L in Siauliai WWTP. Very high values were also noted in the study of Durrel and Lizotte (1998) – the PCBs concentration in the effluents ranged from 1000 pg/L up to 10,000 pg/L. The authors also observed that each plant had a different PCB congener distribution pattern related to its location and pollutants’ sources. Vogeslang et al. (2006) in turn demonstrated the PCBs concentration in WWTP effluent to be between 500 and 4100 pg/L. The above data suggest that WWTPs are insufficient in the removal of PCBs. The earliest study by Shannon et al. (1977), conducted in the Canadian lower Great Lakes, demonstrated that the average PCBs removal efficiency in a secondary treatment was 66 % and occurs mainly as a result of PCBs settling in sludge. Other author suggests that treatment processes such as sorption to the sludge remove up to 70 % of PCBs, whereas volatilization leads to the elimination of about 50 % of Aroclor 1254 (Petrasek et al. 1983). According to Pham and Prolux (1997), the removal rates range from 33 %, for PCB-101, to 100 %, for PCBP 194, with an average 13PCB value of 67 %. Most recently, Bolzonella et al. (2010) showed that WWTPs processes can remove PCBs to a high extent, up to 95 % and more for some congeners, while Vogeslang et al. (2006) demonstrated that combined chemical and biological wastewater treatment was the most effective process in PCBs reduction. However, such high purification effectiveness is still unsatisfactory to preserve the environment from decay due to toxic properties of PCBs which even in low concentrations are hazardous to aquatic ecosystems (Pham and Prolux 1997). In the 14 WWTPs examined in the present study, although lower concentrations of the 12 dl-PCBs were P identified compared to those of the 7PCBs and P 13PCBs used by other authors, a significant problem still exists with maintaining proper purification effectiveness. This inefficiency results in lower effluent quality. Other worldwide studies have demonstrated that such uncontrolled PCB discharge within insufficiently treated wastewater may result in significant deteriorations in the quality of river water (Pham and Prolux 1997; Bolzonella
Bull Environ Contam Toxicol (2015) 95:530–535
et al. 2010; Urbaniak et al. 2014), while relatively large volume of PCB-containing effluents discharged on a daily basis into the river recipients additionally affect their quality (Balasubramani et al. 2014). Acknowledgments The research was supported by the Polish Ministry of Science and Higher Education, Project: N N305 365738 ‘‘Analysis of point sources pollution of nutrients, dioxins and dioxinlike compounds in the Pilica River catchment and draw up of reclamation methods’’. The authors want also to thank Maciej Skłodowski MSc for his help during sample collection, and Prof Adam Grochowalski from the Krakow University of Technology for the sample analysis.
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