Coal-related sources of organic contamination in sediments and water from the Bierawka River (Poland)

International Journal of Coal Geology 152 (2015) 94–109

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International Journal of Coal Geology journal homepage: www.elsevier.com/locate/ijcoalgeo

Coal-related sources of organic contamination in sediments and water from the Bierawka River (Poland) Ádám Nádudvari ⁎, Monika J. Fabiańska Faculty of Earth Sciences, University of Silesia, Sosnowiec 41-200, Poland

a r t i c l e

i n f o

Article history: Received 21 May 2015 Received in revised form 7 October 2015 Accepted 11 November 2015 Available online 12 November 2015 Keywords: River sediments Biomarkers Aromatic hydrocarbons Water-washing Coal particles Fluvial transport

a b s t r a c t River sediments mixed with coaly material occur all along the length of the Bierawka River (Poland). To identify the origin of the coal in the sediment, the coaly material was investigated by reflected light microscopy and Rock Eval Pyrolysis, and solvent extracts by gas chromatography–mass spectrometry (GC–MS). Organic compounds dissolved in water were separated by solid phase extraction (SPE) and analyzed by GC–MS. The results point to a kerogen III source. Petrographic analyses confirm abundant coal-, charred- and coked particles in the sediments. Vitrinite reflectance varied between 0.66–0.80 Rr% without any large spatial variation. The coaly particles have different sources. Generally, the primary origin of coal particles is from coal processing and the dumping the ash with unburned coal particles from a glass factory near the river source. Later, this material was redeposited along the entire river course. In addition, hard coal processing (crushing–washing) features are visible in larger coal pieces. A second source of coaly organic matter is a coal waste dump at Szczygłowice where intensive erosion of steep slopes has delivered copious amounts of organic matter into the river. The mixing of this organic matter with that from the glass factory is clearly identified on a ternary diagram. PAH distributions also show differences between sections. The coal particle input from the waste dump increased the relative content of naphthalene relative content downstream. As in the coal waste, 4–5 ring PAHs predominate in the sediments. The pyrogenic origin of PAHs and aromatic compounds such as methylbiphenyls and dibenzofurane in the sediment is indicated by diagnostic PAH ratios; burned particles were identified petrographically. The river water contains only 2–3 ring PAHs, possibly of industrial origin or leached from coal particles in the river sediments. © 2015 Elsevier B.V. All rights reserved.

1. Introduction The coal mining industry has had a significant impact on the Silesia region in Poland where the original landscape is disturbed by hundreds of coal-waste dumps, subsidence caused by underground mining, mine construction and coal transportation. In Upper Silesia, intensive coal mining dates from the end of the 19th and beginning of the 20th centuries when coal production greatly increased and exploitation from greater depths started (Dulias, 2003). This interval was also a period of local industry growth on the basis of local- and imported iron ores, charcoal production and hard coal exploitation (Klimek et al., 2013). Soils and river sediments can contain coaly material from both natural- and anthropogenic sources (e.g., Stout and Emsbo-Mattingly, 2008; Geršlova and Schwarzbauer, 2014) occurs in (Pies et al., 2007; Pies et al., 2008; Yang et al., 2008; Merrill and Wade, 1985; Johnson and Bustin, 2006; French, 1998). This can be a source of pollutants such as polycyclic aromatic hydrocarbons (PAHs) and their derivatives. Many of these are carcinogenic- and mutagenic substances that are generally stable in the environment (Grimmer et al., 1983; Achten and ⁎ Corresponding author. E-mail address: [email protected] (Á. Nádudvari).

http://dx.doi.org/10.1016/j.coal.2015.11.006 0166-5162/© 2015 Elsevier B.V. All rights reserved.

Hofmann, 2009). The U.S. Environmental Protection Agency has regulated 16 priority pollutant PAH (16 EPA-PAH) spanning 2–6 condensed aromatic rings (Achten and Hofmann, 2009). The average number of aromatic rings per structural unit in most coals is 2–6. Furthermore, they are linked by methylene bridges with aliphatic side chains and phenol functional groups (Stout et al., 2002; Faure et al., 2007; Achten and Hofmann, 2009). In sediment, PAHs can be free, absorbed in a mineral matrix (bioavailable) or can be strongly sorbed and accumulated (trapped) in sedimentary organic macromolecules (Merrill and Wade, 1985; Kim et al., 1999; Ghosh and Hawthorne, 2010; Faure and Landais, 2000). Depending on their status (free or trapped), the impact of these carcinogenic compounds will be very different (Faure and Landais, 2000). The bioavailability of PAHs from different coal types such as lignite, sub-bituminous coal and anthracite is very limited (Meyer et al., 2013; Meyer et al., 2014; Geršlova and Schwarzbauer, 2014; Achten et al., 2011). Rates of biodegradation often decrease with increasing numbers of aromatic rings and alkyl groups (Achten et al., 2011). However, since the content of PAHs in bituminous coal is much higher, PAH bioavailability in these coals is also high (Meyer et al., 2014). The aim of this study was to determine the origin of coal particles occurring as black layers in the Bierawka River sediments, to identify

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the source of the organic contamination in the polluted river and to define any geochemical differences in water and sediment from different parts of the river. 2. The Bierawka River area The Bierawka River (Fig. 1) is a tributary of the upper part of the Odra River in southern Poland. High levels of contamination by sulfate-, sodium- and chloride species arising from the discharge of mining waters upstream have made the river one of the most saline in Upper Silesia. Near the river source, there had also been three glass factories starting from 1846, but only one now operates between m1–m1(6) sampling points (Fig. 1; http://hso.futbolowo.pl/menu,4,historia.html). As a result, the groundwater and water from the river cannot now be used (Sracek et al., 2010). As result of coal mining and processing, there are easily identified fine coal particles in the river sediments. 3. Experimental 3.1. Sampling At each sampling point, ca 1–2 kg material was collected at a depth of 10 cm at the river bank. Sampling was performed in May and November 2013, and in February, April and May 2014. All together 44 sediment and 31 water samples were collected. Along the entire length of the river, visible black layers were evident in the river sediment and, where samples

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m5 and m4 were taken, larger coal particles were visible in the river bed. All sediment samples comprised silty and sandy mixtures, except m16–m18(1) which is eroded coal waste from the river (Fig. 1); there are two coal-waste dumps storing gangue rocks from coal mining on the river bank at Szczygłowice and Trachy settlements. Water samples (ca 1 l) were also taken at the sediment sampling points. In some cases, more sediment samples were collected to achieve reliable results. 3.2. Methods of organic compounds separation The samples of coal waste and sediments were dried at room temperature (ca 22 °C) for ca 5 days and powdered in a rotary mill to b0.2 mm grain size. After powdering, they were extracted in dichloromethane (DCM) in the Dionex 350 apparatus designed for accelerated solvent extraction. Dissolved organic compounds in the water samples were isolated using solid phase extraction (SPE) on 60 ml C18 PolarPlus columns (BAKERBOND), 500 mg of solid phase bonded on silica gel (40 μm APD, 20 Å). About 500 ml of water mixed with isopropanol (analytical) in proportions of 50:3 (vol.) was passed through the conditioned column. Adsorbed organic compounds were eluted with dichloromethane (DCM). 3.3. Gas chromatography–mass spectrometry An Agilent gas chromatograph 7890A with a HP–35 column (60 m × 0.25 mm i.d.), coated by a 0.25 μm stationary phase film

Fig. 1. The location of the study area and sampling points along the Bierawka River.

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coupled with an Agilent Technology mass spectrometer 5975C XL MDS was used. The experimental conditions were as follows: carrier gas — He; temperature — 50 °C (isothermal for 2 min); heating rate — up to 175 °C at 10 °C/min, to 225 °C at 6 °C/min and, finally, to 300 °C at 4 °C/min. The final temperature (300 °C) was held for 20 min. The mass spectrometer was operated in the electron impact ionization mode at 70 eV and scanned from 50–650 Da. Data were acquired in a full scan mode and processed with the Hewlett Packard Chemstation software. The compounds were identified by using their mass spectra, comparison of peak retention times with those of standard compounds (15 PAHs standards, n-alkanes from n-C11–n-C31, 17α(H),21β(H)-29homohopane 22S, and quinoline), interpretation of MS fragmentation patterns and literature data (Philp, 1985). All biomarker parameters

were calculated using peak areas acquired in the manual integration mode. The analyses were carried out in the laboratory of Faculty of Earth Sciences, University of Silesia. 3.4. Petrographical analysis Twenty-six samples with visible organic matter were examined (× 500) using an Axioplan II optical microscope in reflected light. Maceral group determinations, and the various forms of their alteration (color of oxidized vitrinite of paler color, cracks or oxidation rims, massive- and porous coke) and mineral matter was carried out at 1000 points in each sample according to ISO 7404-3 (2009). Depending on the degree of alteration, random reflectance measurements of

Fig. 2. Representative organic matter in sediments along the Bierawka River. A — general view of organic matter mixed with coal particles in m32(2); B — well preserved trimacerite from m32(2); C — well preserved megaspore with pyrite from m10; D — unaltered vitrinite particle (gray) with massive coke particle (white) in m21; E — trimacerite surrounded with vitrinite particles in m29(2); F — fusinite (white) with vitrinite particles (gray) in m29(2); G — fusinite (whitish) with semifusinite (gray) in m11; H — general view of m29(2) sample with abundant amount of inertinite and vitrinite particles; I — thermally altered particle (light gray–whitish color) with large devolatilization pores, surrounded with inertinite and vitrinite particles in m29(2); J — strongly thermally altered organic matter with coke laminae in m15; K — strongly thermally altered particle with plasticized edges and large devolatilization pores in m7, L — large char particle in m7; M — massive coke particle with coke detritus and laminae within transformed clay minerals in m7, N — coke laminaes occurring with transformed minerals in m3, O — porous strongly thermally altered organic matter in m12.

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organic matter were carried out at 100–500 points according to ISO 7404-5 (2009). 3.5. Rock Eval of sediments After crushing to 0.5–2 cm, 200 g of each sediment sample was milled to b 0.2 mm for Rock-Eval analyses. The analysis was performed on a Delsi Model VI Rock-Eval instrument equipped with a total organic carbon module with a computer program to process results. Each sample was heated up to 300 °C for 3 min followed by a programmed pyrolysis at 25 °C/min up to 600 °C under a He flow before being oxidized at 600 °C for 7 min under an oxygen flow. The applied calibration standard was the IFP (Institut Français du Pétrole) 55,000. Total organic carbon (TOC), thermally released bitumen (S1), the pyrolysate (S2), carbon dioxide (S3) and temperature at maximum pyrolysate yield (Tmax — peak temperature of S2 peak) were measured. The Hydrogen Index (HI in mg/g TOC), Oxygen Index (OI in mg/g TOC) and S1/(S1 + S2) — production index (PI) were calculated (Espitalié et al., 1977, 1985). Twenty-six samples were analyzed. 4. Results and discussion For the following, the course of the river can usefully be divided into three sections (Fig. 1). Section I stretches from the source spring to the area of Szczygłowice coal waste dumps. Section II covers the vicinity of the dumps. Section III extends between Szczygłowice and the estuary to the Odra River. 4.1. Results of petrographical analysis The river sediment is compositionally rather heterogeneous. It is possible to identify unaltered-, strongly-altered weathered, and

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thermally-altered organic materials. The identified coal particles are of bituminous coal with macerals and trimacerals such as telinite, fusinite, sporinite and resinite (Fig. 2B–E), and abundant quartz. Charred- and coked particles were also present in all sediments (Fig. 2 J.M.N.O). The sediments from I and III Sections contained on average 10–12% of coaly material. The vitrinite reflectance varies between 0.66–0.80 R r% without large differences (Table 1). These values match the average reflectance of unaltered organic matter in coal wastes in Poland (0.60–0.76%; Misz-Kennan, 2010). In general, Section II samples contain the highest percentage of vitrinite, liptinite, inertinite and pyrite, because of the eroded coal waste there. Sections I (2.65 vol.%) and III (1.47 vol.%) contain the highest amounts of burned out whitish particles (Fig. 2I–O). In the sediments, well-preserved coal particles, both small and large are abundant (Fig. 2B–E). According Yang et al. (2008), larger coal particles in sediments may be associated with coal industry/mining and show weak or no alteration. Complete- and fragmented particles of inertinite (semifusinite and fusinite) and vitrinite particles in the river sediments may be related to hard-coal crushing processes in mines or at the processing site (Fig. 2F–I). By the glass factory, the sediments contain large amounts of burnedand unburned coal particles (Fig. 2D). The ash from the factory was probably dumped on the floodplain of the Bierawka River; burned coal particles are found all along its course. Ash from domestic- or low-temperature (~ 270 °C) furnaces can also contain unburned coal particles (Ligouis et al., 2005; Fabiańska and Smołka-Danielowska, 2012). The whitish burned out material possibly reflect two kinds of sources. The first, stoker boilers and domestic furnaces, tend to provide particles that have larger devolitilization pores and plasticized edges; the burning process was not fast enough to completely oxidize the organic matter. It was possible to identify particles of coke used both for domestic purposes and in smelters. The second source was probably a

Table 1 Vitrinite reflectance and maceral composition together with various forms of organic from the river sediments. Rr %

Vitrinite (vol.%)

Liptinite (vol.%)

Inertinite (vol.%)

Mineral matter (vol.%)

Pyrite (vol.%)

Water washed vitrinite with cracks (vol.%)

Totally burned out whitish material (vol.%)

Sediments from Section I m1 0.70 0.2 m3 0.67 0.4 m4 0.74 2.4 m5 0.73 4 m6 0.70 1.8 m7 0.67 1.2 m9 0.66 3.0 m10 0.66 9.2 m11 0.75 10.2 m12 0.79 2.6 m13 0.75 3.2 m14 0.76 2.6 m15 0.72 2 Aver. 0.72 3.29

– – – 1.6 – 0.2 1.0 2 3 0.2 – 0.4 0.2 0.96

– 1 – 1 0.2 0.2 2.4 3 3.4 1.8 0.4 1.4 0.8 1.42

97.2 98.4 94.6 89 95.2 96.4 89.4 72.6 75.2 94.2 95.0 90.6 91.4 90.71

– – – – – – – 0.6 – – – 0.8 0.4 0.23

0.4 0.2 1.6 1.8 0.2 0.4 0.6 2.8 4.2 0.8 0.4 3 1.2 1.35

2.2 – 1.4 2.6 2.6 1.6 3.6 9.8 4 0.4 1.0 1.2 4 2.65

Coal wastes from Section II m16 0.78 16.6 m17 0.75 21.8 m18(1) 0.74 9.2 m18(2) 0.80 22 Aver. 0.77 17.40

4.6 3 2 1.8 2.85

7.8 13.6 1.4 4.4 6.80

65.2 58.6 86.4 71.1 70.33

0.8 1.2 0.2 0.4 0.65

5 1.6 0.6 – 2.40

– 0.2 0.2 – 0.13

Sediments from Section III m19 0.77 4.0 m21 0.76 12.4 m22(1) 0.76 4.4 m22(2) 0.74 3.4 m27 0.74 0.6 m29(2) 0.78 18.8 m30(2) 0.80 6.0 m31(2) 0.80 13.8 m32(2) 0.79 7.8 Aver. 0.77 7.91

0.2 1.8 1 0.8 – 0.8 0.6 1.2 0.4 0.85

3.2 5.8 1 0.2 0.2 9.4 2.8 3.6 2 3.13

90.2 68.8 92.4 95.2 97.6 66.6 89.4 78.8 83.4 84.71

0.2 0.2 0.8 – – – – – 0.2 0.28

0.8 5.8 – – 0.8 2 1.0 1.4 5 2.10

1.4 5.2 0.4 0.4 0.8 2.4 0.2 1.2 1.2 1.47

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Table 2 The results of Rock Eval Pyrolysis in the different river sections. S1 '3)

S2 4)

S3 5)

S3′ 6)

420 422 418 429 420 429 436 433 436 438 431 434 433 429

0.16 0.18 0.34 0.08 0.17 0.08 0.05 0.29 0.13 0.06 0.25 0.65 0.19 0.20

1.78 2.0 1.87 5.1 1.63 0.76 1.61 15.7 3.1 1.11 3.8 10.3 5.4 4.17

2.9 1.95 1.73 1.41 3.4 1.70 1.26 3.7 1.21 1.08 2.7 3.0 1.71 2.13

4.5 3.7 3.1 4.4 4.3 4.3 4.5 8.4 3.1 3.5 6.9 6.4 5.2 4.8

Coal waste from Section II m16 21.3 m17 23.2 m18(2) 21.0 m18(1) 16.1 Aver. 20.4

436 437 434 430 434

0.22 0.23 0.12 0.10 0.17

29.1 30.3 21.8 17.9 24.8

1.45 2.0 2.4 2.5 2.09

Sediments from Section III m19 3.5 m21 3.9 m22(2) 9.3 m22(1) 7.1 m27 2.2 m29(2) 55.6 m30(2) 1.8 m31(2) 10.0 m32(2) 10.9 Aver. 11.6

432 434 438 434 426 433 439 434 432 434

0.30 0.20 0.05 0.25 0.25 0.60 0.05 1.39 0.77 0.43

4.1 4.4 11.2 8.7 2.3 76.8 1.69 11.3 14.4 15.0

3.7 1.71 3.3 1.88 4.2 3.9 0.99 3.8 6.0 3.28

Sample code

TOC (% wt.) 1)

S3CO 7)

S3′CO 8)

PI 9)

PC (% wt.) 10)

RC (% wt.) 11)

HI 12)

OICO 13)

OI 14)

pyroMINC (% wt.) 15)

oxiMINC (% wt.) 16)

MINC (% wt.) 17)

0.76 0.51 0.27 0.89 0.55 0.79 0.31 1.30 0.48 0.37 0.60 1.08 0.66 0.66

0.70 0.8 0.80 1.6 1.10 0.9 0.60 2.1 0.9 0.4 0.80 1.7 1.4 1.1

0.08 0.08 0.16 0.02 0.10 0.10 0.03 0.02 0.04 0.05 0.06 0.06 0.03 0.06

0.29 0.28 0.26 0.54 0.29 0.17 0.20 1.53 0.34 0.15 0.45 1.07 0.57 0.47

1.68 1.6 0.99 4.3 1.54 0.95 2.0 12.4 2.6 1.1 2.6 6.4 3.6 3.21

90 109 150 106 89 68 73 112 108 89 124 138 129 107

39 27 22 18 30 71 14 9 16 30 19 15 16 25

149 105 138 29 186 152 57 27 41 86 86 40 41 87

0.14 0.12 0.10 0.15 0.14 0.14 0.14 0.27 0.10 0.10 0.21 0.21 0.17 0.15

0.16 0.13 0.06 0.14 0.09 0.03 0.79 1.09 0.53 0.10 0.28 0.51 0.12 0.31

0.30 0.25 0.16 0.3 0.23 0.17 0.92 1.36 0.64 0.20 0.49 0.72 0.29 0.46

12.3 8.7 6.6 5.5 8.3

1.06 1.71 1.86 1.69 1.58

3.0 4.4 3.9 2.9 3.6

0.01 0.01 0.01 0.01 0.01

2.6 2.8 2.1 1.7 2.3

18.7 20.5 18.9 14.4 18.1

137 130 104 111 121

5 7 9 10 8

7 9 11 15 11

0.40 0.33 0.26 0.21 0.30

0.29 0.89 0.05 0.04 0.32

0.69 1.22 0.31 0.25 0.62

7.3 4.2 5.7 5.7 4.3 9.1 2.5 7.2 9.7 6.2

0.99 0.71 1.20 1.09 1.07 4.1 0.38 1.36 2.03 1.44

1.10 1.2 2.5 1.8 0.90 10.4 0.70 2.4 2.9 2.7

0.07 0.04 0.03 0.10 0.01 0.03 0.11 0.05 0.05

0.53 0.49 1.13 0.88 0.40 6.9 0.20 1.26 1.57 1.48

3.0 3.4 8.2 6.3 1.83 48.7 1.56 8.7 9.3 10.11

115 113 120 122 105 138 96 112 132 117

28 18 13 15 48 7 22 14 19 20

105 44 35 26 190 7 56 38 55 62

0.22 0.14 0.21 0.19 0.14 0.47 0.08 0.25 0.33 0.23

0.06 0.04 0.02 0.04 0.02 0.05 0.02 0.09 0.04 0.04

0.28 0.18 0.23 0.24 0.15 0.52 0.10 0.34 0.37 0.27

1) TOC (% wt.): Total organic carbon [wt.%]. 2) Tmax (°C): temperature of maximal expulsion of pyrolytic hydrocarbons from kerogen [°C]. 3) S1: free hydrocarbons [mg HC/g rock]. 4) S2: hydrocarbons generated by pyrolytic degradation of kerogen [mg HC/g rock]. 5) S3: CO2 generated by pyrolytic degradation of kerogen [mg CO2/g rock]. 6) S3′: CO2 by pyrolytic degradation of mineral substances (carbonates) [mg CO2/g rock]. 7) S3CO: The amount of CO resulting from destruction of organic matter [mg CO/g rock]. 8) S3′CO: The amount of CO formed in the reaction of Boudouard [mg CO/g rock]. 9) PI: Production Index; PI = S1 / (S1 + S2). 10) PC (% wt.): pyrolyzable carbon. It corresponds to carbon content of hydrocarbons volatilized and pyrolyzed during the analysis. 11) RC (% wt.): Residual carbon content. 12) HI: Hydrogen Index [mg HC/g TOC]; HI = S2/TOC·100. 13) OICO: The ratio of CO [mg CO/g TOC]. 14) OI: Oxygen Index [mg CO2/g TOC]; OI = S3/TOC·100. 15) pyroMINC (% wt.): Pyrolytic carbon content of the mineral. 16) oxiMINC (% wt.): The indicated oxidative carbon content of the mineral in the oven. 17) MINC(% wt.): The total carbon content of the mineral.

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Tmax (°C) 2)

Sediments from Section I m1 2.0 m3 1.9 m4 1.3 m5 4.8 m6 1.8 m7 1.1 m9 2.2 m10 14.0 m11 2.9 m12 1.3 m13 3.1 m14 7.4 m15 4.2 Aver. 3.7

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pulverized fluid boiler where the burned-out particles were between 50 and 100 μm. As the heat was intensive and the combustion fast, the devolatilization pores are smaller. This technology is well developed and widespread (Misz, 2002; Lester et al., 2010). Among the coal-, burned coal-, coke- and charred particles, vitrinite is present in the highest percentage (3.3–7.9%) in river Sections I and III. A very similar picture has been described in sediment from the Mosel River in Germany where identified coal particles counted as vitrinite are of highly fragmented bituminous coal (coal dust) containing mainly vitrinite. The dust and particles are clearly related to the former intensive Saar coal production. The Mosel floodplain sediments also contain coke, charcoal, char and other carbonaceous materials. The coke particles are emitted by, e.g., coking plants, steel smelters, or manufacturing gas plants (Pies et al., 2007; Pies et al., 2008; Yang et al., 2008). 4.2. Results of Rock Eval Pyrolysis Calculated parameters show differences between the river sections (Table 2). In Section II (coal-waste material), TOC and S2 values are fairly increased and OI (Oxygen Index) considerably decreased compared to in the other sections. Total organic carbon (TOC) contents range from 1.1–55.6 wt.% where the lowest average value in Section I (3.69) compared to values of (20.4) in Section II and 11.58 in Section III (Table 2). Hydrogen Index (HI) values decrease near the glass factory to 68–90, related to the analyzed organic material itself or to trapped oil pollutants causing reduction of the value (Udo et al., 1986; Dahl et al., 2004). Tmax

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values range from 418–439 °C. For some unknown reason, they are slightly decreased between the m1–m7 sampling points in Section I. By reference to the proposed boundary of Tmax = 434 °C (Espitalié et al., 1985), both immature- and mature kerogen types are present. In Fig. 3, S2–TOC, HI–OI and HI–Tmax values indicating kerogen III type point to the same organic matter origin. The S1–TOC values indicate a syngenetic hydrocarbon source (coal, coal-waste material) which excludes other sources, e.g. oil, petroleum derivatives (Fig. 3). The S2–TOC ratio shows Section II to have generally higher TOC values because coalwaste material was analyzed. The exception, sample m29(2), is sediment from the river bank full of coaly particles, mostly fusinite and vitrinite. Lighter fusinite is easier to transport over large distance. HIOI values show input of recent organic matter (e.g., plants, algae) in those sediments where the oxygen contents increased, but OI values are lowered by coal waste in Section II. The values of HI–Tmax ratio correlate well with the measured vitrinite reflectance values (Fig. 3), except for the m1, m4, and m6 samples which fall below the 0.5% R0 line. The vitrinite reflectance Ro%, and the pyrolysis parameter Tmax of type-III kerogen, show a very strong linear correlation (Teichmüller and Durand, 1983). 4.3. Composition of sediment extracts 4.3.1. Distribution of n-alkanes In the extracts, it was possible to distinguish bimodal- and monomodal n-alkane distributions. Representative samples were chosen from the different river sections to show the typical n-alkane

Fig. 3. The S1–TOC, HI–OI, HI–Tmax and S2–TOC results of Rock Eval Pyrolysis.

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Fig. 4. The representative n-alkane chromatograms from the river sections.

distributions. The bimodal distribution appeared mostly in river Sections I and III the monomodal distribution in Section II (Fig. 4). In the bimodal distribution, the maximum of long-chain n-alkanes varied from n-C23 to n-C31, most commonly in the range n-C27 to n-C29. Calculated averages for various ratios indicate remarkable differences between the river sections (Table 3). The Σ2/Σ1 (long- and short-chain n-alkanes ratio) and the CPI (Carbon Preference Index) are higher for Sections I and III, reflecting the input of recent organic matter from vegetation. In Section II, the input of coal-waste dominates and the averages decrease. An n-alkane distribution with a strong odd over even predominance in the range n-C25 to n-C34 and a high CPI (N5.0) is characteristic for epicuticular waxes of higher plant (Eglinton and Hamilton, 1967; Faure et al., 2007; Jeanneau et al., 2006). In coal tars, the short-chain n-alkanes dominate and in coals n-alkanes ranging from n-C21 to n-C33 with CPI between 1.1–1.3 occur (Faure et al., 2007). The n-C23/n-C31, Pr/Ph (pristane/phytane), and Pr/n-C17 averages are highest in Section II, again reflecting coal-waste input but the Ph/n-C18 had not evaluable differences. On the ternary diagram (Fig. 5A), the notable shift from n-alkanes in the range n-C11–n-C28 to n-alkanes in the range n-C25–n-C38 reflects increasing removal of the former in Sections I and III. The Section III sediments contain mixed organic material from upstream, perhaps from

coal waste and/or recent vegetation. The Hunt diagram (Fig. 5B) shows that the coal wastes and most of the sediment samples correspond to kerogen III, as was indicated by the Rock Eval Pyrolysis data. However, in samples such as m1, m1(4), m1(5), m5, m6, m14, and m13 from the upper part of the river, a mixture of kerogen II-III and kerogen II is indicated. The occurrence of such an unusual kerogen type is probably related to operations in the glass factory. In addition, sample m1(6) showed a significant input of biodegraded lubricant containing steranes; these are essentially absent in the bituminous coals/coal wastes of this region (Fabiańska et al., 2013). In water-sample extracts, n-alkanes with monomodal distribution are common. The n-alkane maximum is variable, in some samples ranging from n-C24 to n-C26, in others from n-C16 to n-C20. Pristane and phytane were not identified, nor were any major differences in CPI, n-C23/n-C31 or Σ2/Σ1 values (Table 3). 4.3.2. Pentacyclic triterpanes All of the sediments contain pentacyclic triterpanes. Calculated hopane ratios show no major variations between the river sections and indicate kerogen III type (Table 3). The sediments and coal-waste samples (Section II) contain to the same type of organic matter, despite

n-C23/n-C31 2)

CPI 3)

Pr/Ph 4)

Pr/n-C17 5)

Ph/n-C18 6)

C31S/(S + R) 7)

Ts/(Tm + Ts) 8)

C29βα/ (αβ + βα) 9)

C30βα/(αβ + βα) 10)

C31βα/ (αβ + βα) 11)

C29Ts/ (C29 + C29Ts) 12)

Sediments from Section I m1 0.05 1.30 m1(2) 0.03 13.70 m1(3) 0.23 34.11 m1(4) 0.15 4.55 m1(5) 0.06 5.79 m1(6) 1.77 – m2 0.09 – m3 0.12 48.97 m4 0.15 – m5 0.04 2.93 m6 0.03 10.06 m7 0.08 7.06 m8 0.10 6.72 m9 0.06 1.28 m10 0.12 1.51 m11 0.06 3.08 m12 0.02 7.40 m13 0.10 4.08 m14 0.19 2.38 m15 0.05 3.55 Aver. 0.18 8.80

– – 0.20 0.09 0.16 – – 0.26 0.23 0.35 0.13 0.23 0.24 0.98 0.40 0.38 0.18 0.22 0.29 0.32 0.29

1.04 4.82 11.81 5.15 6.34 – – 12.77 7.76 29.36 31.25 3.97 3.90 1.40 3.69 2.69 2.66 4.69 3.78 2.78 7.77

1.37 2.15 – 1.64 2.21 – – – – 3.93 1.77 3.59 3.61 7.60 5.34 2.91 2.73 2.17 1.89 3.52 3.10

0.31 1.04 – 1.33 0.90 – – – – 1.54 0.60 1.68 1.77 4.05 1.80 1.78 1.66 1.15 1.27 1.93 1.52

0.94 0.48 – 2.08 0.47 – – – – 0.85 0.79 0.76 0.68 0.56 0.44 0.64 0.71 0.89 0.90 0.62 0.79

– 0.48 0.76 0.51 0.49 – 0.57 0.63 0.71 0.62 0.60 0.62 0.59 0.57 0.58 0.58 0.54 0.58 0.58 0.56 0.59

– 0.82 0.73 0.89 0.71 – 0.48 0.42 0.38 0.31 0.33 0.88 0.89 0.92 0.95 0.90 0.93 0.86 0.92 0.84 0.73

– 0.30 0.15 0.20 0.10 – 0.09 0.11 0.23 0.16 0.08 0.08 0.06 0.11 0.10 0.10 0.17 0.25 0.13 0.14 0.14

– 0.35 0.23 0.24 0.11 – 0.09 0.07 0.09 0.09 0.10 0.20 0.12 0.07 0.05 0.10 0.11 0.12 0.11 0.16 0.13

– 0.27 0.29 0.13 0.06 – 0.04 0.04 0.06 0.05 0.07 0.08 0.06 0.10 0.07 0.10 0.12 0.08 0.04 0.09

– 0.07 0.07 0.10 0.05 – 0.18 0.17 0.19 0.14 0.15 0.20 0.17 0.10 0.15 0.16 0.19 0.11 0.13 0.18 0.14

Water samples from Section I w1 0.00002 1.37 1.17 – – – – w1(3) 0.00006 – – – – – – w1(5) 0.00004 13.61 – w1(6) 0.00004 – – w2 0.00006 3.14 0.91 w3 0.00006 14.23 – w4 0.00006 1.07 – w5 0.00008 10.64 0.29 w6 0.00008 2.90 0.80 w7 0.00004 2.68 1.11 w8 0.00008 2.27 1.17 w9 0.00004 2.66 0.94 w10 0.00038 2.29 1.23 w11 0.00004 2.31 1.37 w12 0.00006 2.57 1.07 w13 0.00006 1.91 1.34 w14 0.00012 2.71 1.07 w15 0.00008 4.69 0.67 Aver. 0.00008 3.83 1.01

Coal wastes from Section II m16 0.24 0.67 m17 0.19 0.86 m18(2) 0.17 0.77 m18(1) 0.79 0.48

4.32 3.03 3.58 –

1.13 1.21 1.48 1.26

9.44 8.55 6.31 8.87

2.47 3.67 4.13 4.67

0.27 0.39 0.51 0.60

0.61 0.58 0.58 0.58

0.97 0.95 0.95 0.95

0.02 0.03 0.03 0.14

0.16 0.19 0.23 0.22

0.02 0.03 0.03 0.12

0.03 0.02 0.03 0.01

Water samples from Section II – – – – – – – – w16 0.00018 7.27 0.96 w17 0.00002 0.48 –

Sample codes

Extracted yields [% wt.]

Σ2/Σ1 1)

Sample codes

Extracted yields [% wt.]

Σ2/Σ1 1)

n-C23/n-C31 2)

CPI 3)

1.25 – – – – 1.27 0.77 0.93 0.90 0.82 0.91 0.91 0.96 1.06 0.94 1.06 0.96 1.02 1.01 0.98

Á. Nádudvari, M.J. Fabiańska / International Journal of Coal Geology 152 (2015) 94–109

Table 3 Ranges of extracted yields together with calculated biomarker ratios from the sediment and water samples.

– – 0.78 1.18 101

(continued on next page)

Extracted yields [% wt.]

Σ2/Σ1 1)

n-C23/n-C31 2)

CPI 3)

Pr/Ph 4)

Pr/n-C17 5)

Ph/n-C18 6)

C31S/(S + R) 7)

Ts/(Tm + Ts) 8)

C29βα/ (αβ + βα) 9)

C30βα/(αβ + βα) 10)

C31βα/ (αβ + βα) 11)

C29Ts/ (C29 + C29Ts) 12)

Sample codes

Extracted yields [% wt.]

Σ2/Σ1 1)

n-C23/n-C31 2)

CPI 3)

Aver.

0.35

0.70

3.64

1.27

8.29

3.74

0.44

0.59

0.96

0.06

0.20

0.05

0.02

Aver.

0.00010

3.88

0.96

0.98

Sediments from Section III m19 0.21 1.08 m20 0.06 0.96 m21 0.03 0.94 m22(2) 0.02 1.34 m22(1) 0.13 0.83 m23 0.07 0.84 m24 0.01 1.56 m25 0.11 1.26 m26 0.05 1.89 m27 0.08 3.12 m28(2) 0.25 2.86 m28(1) 0.15 3.34 m29(2) 0.26 0.84 m29(1) 0.10 1.53 m30(2) 0.02 0.82 m30(1) 0.01 1.28 m31(2) 0.10 1.02 m31(1) 0.09 0.94 m32(2) 0.12 0.96 m32(1) 0.22 1.50 Aver. 0.10 1.45

– – – 0.50 0.49 – 0.45 0.70 0.28 0.30 0.44 0.27 2.66 0.44 – – – – – 0.62 0.65

2.67 1.80 1.82 2.69 3.93 2.25 3.70 3.74 3.45 4.60 4.35 4.97 1.28 3.27 1.96 3.54 2.32 3.77 2.98 2.63 3.09

4.42 3.79 4.22 6.88 7.07 4.70 5.85 4.80 6.34 7.94 6.09 6.31 8.28 8.22 6.01 5.81 4.45 4.64 4.90 6.48 5.86

2.21 2.17 2.50 2.58 3.08 2.96 2.44 2.28 2.84 2.76 3.04 3.00 3.56 2.88 3.05 2.32 3.13 2.09 2.30 2.39 2.68

0.61 0.70 0.67 0.53 0.58 0.70 0.56 0.66 0.56 0.36 0.51 0.48 0.53 0.42 0.60 0.51 0.87 0.52 0.64 0.38 0.57

0.58 0.58 0.58 0.59 0.60 0.55 0.56 0.57 0.57 0.56 0.56 0.56 0.58 0.56 0.55 0.55 0.57 0.57 0.58 0.57 0.57

0.90 0.91 0.90 0.90 0.93 0.92 0.86 0.89 0.85 0.87 0.87 0.87 0.93 0.89 0.87 0.88 0.90 0.90 0.89 0.89 0.89

0.13 0.17 0.16 0.14 0.15 0.14 0.18 0.21 0.18 0.11 0.08 0.07 0.04 0.16 0.21 0.17 0.18 0.16 0.05 0.13

0.14 0.16 0.19 0.17 0.13 0.19 0.24 0.16 0.19 0.22 0.16 0.17 0.22 0.17 0.20 0.19 0.18 0.16 0.15 0.18 0.18

0.08 0.11 0.11 0.10 0.09 0.10 0.15 0.12 0.10 0.05 0.18 0.19 0.14 0.10 0.12 0.11 0.11 0.09 0.11 0.11

0.12 0.10 0.08 0.10 0.12 0.07 0.11 0.09 0.10 0.05 0.06 0.06 0.03 0.07 0.06 0.09 0.10 0.12 0.12 0.08 0.09

Water samples from Section III w18 0.00004 0.80 – w19 0.00008 1.02 – w20 0.00004 1.58 2.85 w21 0.00008 1.03 3.24 – – – – – – – – w22 0.00008 2.84 1.57 w23 0.00004 2.77 0.75 w24 0.00006 2.45 1.69 – – – – – – – – – – – – w25 0.00012 1.70 2.96 – – – – – – – – w26 0.00008 2.57 1.80 – – – – w27 0.00008 3.82 2.95 – – – – w28 0.00004 2.28 0.96 Aver. 0.00007 2.08 2.09

0.89 1.07 0.97 1.01 – – 1.03 1.03 0.93 – – – 1.13 – – 1.03 – 0.98 – 0.91 1.00

1) Σ2/Σ1 = [Σ (from n-C23 to n-C37)]/[Σ (from n-C11 to n-C22)]; m/z = 71, source indicator (Tissot and Welte, 1984). 2) n-C23/n-C31; m/z = 71 (Pancost et al., 2002); source indicator. 3) CPI = 0.5{[(n-C25 + n-C27 + n-C29 + n-C31 + n-C33) / (n-C24 + n-C26 + n-C28 + n-C30 + n-C32)] + [(n-C25 + n-C27 + n-C29 + n-C31 + n-C33) / (n-C26 + n-C28 + n-C30 + n-C32 + n-C34)]; Carbon Preference Index; m/z = 71; thermal maturity parameter (Bray and Evans, 1961). 4) Pr/n-C17 = pristane/n-heptadecane; m/z = 71 (Leythauser and Schwartzkopf, 1985). 5) Ph/n-C18 = phytane/n-octadecane; m/z = 71 (Leythauser and Schwartzkopf, 1985). 6) Pr/Ph = pristane/phytane; parameter of environment oxicity (with exception of coals); m/z = 71 (Didyk et al., 1978). 7) C31S/(S + R) = 17α(H),21β(H)-29-homohopane 22S / (17α(H),21β(H)-29-homohopane 22S + 17α(H),21β(H)-29-homohopane 22R); m/z = 191; thermal maturity parameter (Peters et al., 2005). 8) Ts/Ts + Tm = 18α(H)-22,29,30-trisnorneohopane / (18α(H)-22,29,30-trisnorneohopane + 17α(H)-22,29,30-trisnorhopane); m/z = 191; thermal maturity parameter (Peters et al., 2005). 9) C29βα/(αβ + βα) = 17β(H),21α(H)-29-hopane C29 / (17α(H),21β(H)-29-hopane C29 + 17β(H),21α(H)-29-hopane C29) (Seifert and Moldowan, 1978; Peters et al., 2005). 10) C30βα/(αβ + βα) = 17β(H),21α(H)-29-hopane C30 / (17α(H),21β(H)-29-hopane C30 + 17β(H),21α(H)-29-hopane C30); m/z = 191 (Seifert and Moldowan, 1980). 11) C31βα/(αβ + βα) = 17β(H),21α(H)-29-hopane C31 / (17α(H),21β(H)-29-hopane C31 + 17β(H),21α(H)-29-hopane C31); m/z = 191 (Seifert and Moldowan, 1978; Peters et al., 2005). 12) C29Ts/(C29 + C29Ts) = 18α-30-norneohopane / (17α-hopane + 18α-30-norneohopane); m/z = 191 (Seifert and Moldowan, 1978; Peters et al., 2005). “–” concentrations were too low to calculate a parameter value.

Á. Nádudvari, M.J. Fabiańska / International Journal of Coal Geology 152 (2015) 94–109

Sample codes

102

Table 3 (continued)

Á. Nádudvari, M.J. Fabiańska / International Journal of Coal Geology 152 (2015) 94–109

Fig. 5. The distribution samples from the river sections on ternary (A) and Hunt (B) diagrams.

the different mining sources, exploitation histories encompassing, e.g., combustion, water-washing, and later biodegradation.

4.3.3. Distribution of phenols In contrast to the sediment samples m1(3)–m1(6) which contain some phenols, and those between m2–m6 which contain none, in those from m7–m32(1) downstream to the mouth of river, phenols appear in relatively large amounts, including phenol, 2-methylphenol, 4-methylphenol, 2,4- dimethylphenol, and 2,5-dimethylphenol. Phenols in river sediments may originate from factories, coke producers or from fungal and/or bacterial degradation of the coaly sediments and other organic matter such as pine needles, leaves, grass or wood (Saiz-Jimenez and De Leeuw, 1986; Faure et al., 1999; Orem et al., 2010; Haider et al., 2013). In coals, the major chemical structural elements of vitrinites are simple phenols with a high contribution of para alkyl-substituted derivatives (Iglesias et al., 2000). Phenols in soils can exist in a dissolved form moving freely in the soil solution, in a sorbed form which reversibly binds to soil particles or proteins, and in a polymerized form consisting of humic substances (Hättenschwiler and Vitousek, 2001; Freeman et al., 2001; Rovira and Vallejo, 2002). The phenols 2-dimethylphenol, 3-(1,1-dimethylethyl)phenol, and 4-(1,1-dimethylethyl)phenol present in water samples from m4– m30(1) can have an industrial or domestic origin. They are used in cosmetics, petroleum products, pharmaceutical preparations, and in insecticides, fungicides and pesticides, etc. They are carcinogenic. Though they may be degraded in water and sediment, they are persistent pollutants (SAC (Screening Assessment for the Challenge), 2010).

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4.3.4. Distribution of aromatic hydrocarbons in the sediments along the river Along the river, the MNR (methylnaphthalene ratio) average is 2.14 in Section III, somewhat lower (1.46) in I, and lowest (1.27) in II Sections (Table 4). The DNR (dimethylnaphthalene ratio) average varies in a similar pattern between in Section III (6.57), in I (5.73), and in II (3.51) Sections (Table 4). As the MNR and DNR values are easily influenced by leaching due to their relatively high solubility in water, these ratios can be applied to assess the stage of water-washing (MiszKennan and Fabiańska, 2011). Average values of TNR-1, TNR-2, and TNR-5 (trimethylnaphthalene ratio) do not show large variations (Table 4). In contrast, the P/A (phenanthrene/anthracene) ratio varies significantly; values are very high (14.01) in Section II, lower (3.55) in Section I and lowest of all (2.41) in Section II. Average values of MPI-1 and MPI-3 (methylphenanthrene index) decrease in Section II whereas MB/DBF (methylbiphenyl/dibenzofurane) values increase as DBF, present in coal tar, is more soluble in water than MB (Adams and Richardson, 1953; U.S. Department of Health and Human Services, 1993). Alkyl aromatic compounds appear in water samples all along the river (Table 4). From these, due to low concentrations of methylnaphthalenes and methylphenanthrenes, only MNR-1, MPI-1 and MPI-3 values proved possible to calculate. In the samples, 15 unsubstituted polycyclic aromatic hydrocarbons (PAHs) were detected: naphthalene, phenanthrene, anthracene, fluoranthene, pyrene, benzo[a]anthracene, chrysene, benzo[a]fluoranthene, benzo[k]fluoranthene, benzo[e]fluoranthene, benzo[e]pyrene, benzo[a]pyrene, perylene, indeno[1,2,3-cd]pyrene, and benzo[ghi]perylene. Values of common ratios were calculated to reveal any variation in their distribution along the river. Generally, phenanthrene, fluoranthene and pyrene have dominant relative % contents in Sections I and III where the 4–5 ring PAHs dominated over those with 2–3 ring-PAHs (Table 5). In Section II, naphthalene and phenanthrene have higher relative contents due to coal-waste input. In Section III, higher naphthalene contents probably reflect leaching from coal waste (Section II). Phenanthrene shows the highest concentrations among PAHs in Section II, a common occurrence in sedimentary organic matter as there are many biochemical precursors of this compound; transformations paths of most diterpenoids end with phenanthrene (Ellis, 1995). Vliex (1994) demonstrated a high concentration of naphthalenes and phenanthrenes in Saar coals. The highest contents of naphthalene and phenanthrene in the Bierawka River (Section II) are related to coal-waste material. Naphthalene, phenanthrene, chrysene, and their alkylated derivatives, are characteristic petrogenic PAHs (Achten and Hofmann, 2009). In addition, on the floodplain of Mosel River, light sediment fractions have elevated PAH concentrations which are associated with coal and coal-derived particles. Most of the PAHs, e.g., naphthalenes and fluorenes, are linked to coal mining in Saarland. Furthermore, the PAH distribution patterns indicate an upstream of pyrogenic PAH input, and a mixed petrogenic- and pyrogenic input (Pies et al., 2007; Pies et al., 2008; Yang et al., 2008). Perylene, present in almost all sediment samples (Table 5) except in Section II, can have various anthropogenic origins, e.g., street runoff, steel smelting, coke production, combustion of municipal waste, oil refining and fossil-fuel combustion (Hites et al., 1980; Venkatesan, 1988; Baumard et al., 1998; Jiang et al., 2000). Perylene may also form during in situ anaerobic diagenesis in anoxic subaqueous sediments of organic matter from biogenic precursors. The conversion of perylenequinone pigments and their derivatives to perylene is a reduction reaction (Baumard et al., 1998; Silliman et al., 2001; Boonyatumanond et al., 2006; Marynowski et al., 2013). In addition, anthracene, fluoranthene, chrysene, pyrene, indeno[1,2,3-cd]pyrene, and benzo[ghi]perylene compounds are occurring in samples which may be related to the ash deposit upstream. These are typical pyrogenic PAHs (Fernandes et al., 1997; Ahrens and Depree, 2004). This probably explains the high

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Á. Nádudvari, M.J. Fabiańska / International Journal of Coal Geology 152 (2015) 94–109

Table 4 The calculated alkylnaphthalene and alkylphenanthrene ratios in the group of samples. Sample code

MNR 1)

DNR 2)

Sediments from Section I m1 – – m1(2) 1.19 6.01 m1(3) 1.08 2.28 m1(4) 1.21 3.11 m1(5) 1.07 2.80 m1(6) – – m2 – – m3 1.16 4.71 m4 0.91 3.57 m5 2.61 5.10 m6 2.12 4.36 m7 1.65 5.14 m8 1.29 3.54 m9 1.05 4.89 m10 1.42 5.08 m11 1.59 9.26 m12 1.37 8.42 m13 1.79 11.99 m14 1.79 9.65 m15 1.46 7.48 Aver. 1.46 5.73

TNR-1 3)

TNR-2 4)

TNR-5 5)

MPI-1 6)

MPI-3 7)

P/A 8)

MB/DBF 9)

– 0.64 0.75 0.75 0.78 – – 0.49 0.47 0.54 0.43 0.71 0.76 0.62 0.48 0.78 0.93 0.79 0.74 0.77 0.67

0.32 0.70 0.67 0.70 – – 0.48 0.49 0.62 0.53 0.51 0.48 0.64 0.54 0.70 0.76 0.73 0.73 0.71 0.61

– 0.52 0.47 0.38 0.49 – – 0.59 0.48 0.71 0.69 0.63 0.57 0.54 0.42 0.39 0.43 0.36 0.40 0.44 0.50

0.13 0.27 0.13 0.53 0.23 – 0.28 0.30 0.14 0.22 0.19 – 0.24 0.23 0.28 0.18 0.23 0.22 0.19 0.19 0.27

1.92 1.19 1.13 1.09 0.86 – 1.51 1.54 2.12 1.65 1.71 – 1.20 1.45 1.26 1.83 1.55 1.67 2.04 1.81 1.45

4.38 4.62 6.51 4.48 1.67 – 4.39 2.56 5.23 4.11 3.83 3.94 3.61 3.16 1.53 2.83 3.43 2.39 2.12 2.69 3.55

– 0.35 0.16 0.17 0.09 – – 0.24 0.12 0.14 0.12 0.16 0.17 0.10 0.10 0.12 0.15 0.15 0.12 0.13 0.14

Coal waste samples from Section II m16 1.36 3.48 0.36 m17 1.31 4.14 0.32 m18(2) 1.23 3.55 0.38 m18(1) 1.20 2.88 0.44 Aver. 1.27 3.51 0.38

0.62 0.56 0.58 0.65 0.60

0.50 0.51 0.52 0.53 0.51

0.77 0.77 0.83 0.70 0.77

1.05 1.03 0.99 0.87 0.98

15.75 17.52 11.76 11.03 14.01

0.60 0.56 0.68 0.64 0.62

Sediments from Section III m19 2.04 7.27 m20 1.95 9.16 m21 1.86 6.43 m22(2) 2.01 5.94 m22(1) 2.08 6.57 m23 2.20 7.77 m24 1.83 5.13 m25 2.26 7.59 m26 2.30 7.07 m27 2.84 4.64 m28(2) 2.29 6.14 m28(1) 2.51 6.01 m29(2) 1.88 8.74 m29(1) 2.25 5.53 m30(2) 1.88 6.13 m30(1) 1.93 5.55 m31(2) 2.29 8.05 m31(1) 2.04 6.24 m32(2) 1.99 6.45 2.35 5.02 m32(1) Aver. 2.14 6.57

0.57 0.62 0.59 0.54 0.68 0.58 0.52 0.62 0.57 0.67 0.53 0.51 0.61 0.59 0.59 0.55 0.63 0.55 0.58 0.54 0.58

0.54 0.49 0.51 0.51 0.49 0.50 0.57 0.50 0.67 0.48 0.50 0.52 0.48 0.53 0.50 0.49 0.49 0.51 0.50 0.51 0.51

0.35 0.19 0.17 0.20 0.26 0.18 0.21 0.21 0.20 0.30 0.34 0.33 0.15 0.34 0.19 0.22 0.28 0.24 0.32 0.38 0.25

1.40 1.51 1.58 1.38 1.41 1.50 1.23 1.48 1.58 1.04 1.30 1.29 1.82 1.25 1.49 1.48 1.31 1.34 1.34 1.27 1.40

3.48 2.80 2.98 3.09 2.82 2.82 1.79 2.25 2.51 0.94 1.53 1.58 3.04 1.81 2.41 2.74 1.98 3.17 2.52 1.88 2.41

0.15 0.10 0.10 0.12 0.12 0.09 0.11 0.09 0.09 0.10 0.09 0.09 0.06 0.10 0.10 0.10 0.09 0.10 0.12 0.10 0.10

0.27 0.31 0.30 0.37 0.35 0.29 0.43 0.28 0.31 0.55 0.35 0.32 0.37 0.35 0.35 0.36 0.28 0.30 0.28 0.28 0.34

Sample code

MNR 1)

MPI-1 6)

MPI-3 7)

P/A 8)

– –

– –

– –– – 1.29 1.15 1.44 1.07 1.10 1.08 1.09 – 1.04 – – – – 1.16

– – – 23.17 85.80 23.03 63.64 35.37 38.74 7.62 4.02 8.64 10.48 8.19 6.45 4.81 24.61

0.39 – 0.39

1.17 – 1.17

16.71 – 16.71

Water samples of Section w18 4.07 w19 4.96 w20 1.45 w21 –

III – – – –

– – – –

– – 1.97 6.96

w22 w23 w24

1.31 – –

– – –

– – –

3.74 12.11 2.81

w25

–

–

–

1.19

w26

–

–

–

9.12

w27

2.03

–

–

2.11

w28 Aver

– 1.60

– –

– –

4.44 4.94

Water samples from Section I w1 – – w1(3) – –

w1(5) w1(6) w2 w3 w4 w5 w6 w7 w8 w9 w10 w11 w12 w13 w14 w15 Aver.

– – – 0.55 – 1.38 0.81 – – – – – – – – – 0.92

– – – 0.45 0.53 0.33 0.40 0.33 0.37 0.27 – 0.37 – – – – 0.34

Water samples from Section II

w16 w17 Aver.

0.94 – 0.94

1) MNR = 2-methylnaphthalene/1-methylnaphthalene, m/z = 142 (Radke et al., 1986). 2) DNR = (2,6-dimethylnaphthalene + 2,7-dimethylnaphthalene) / 1,5-dimethylnaphthalene, m/z = 156 (Radke et al., 1982). 3) TNR-1 = 2,3,6-trimethylnaphthalene / (1,3,6-trimethylnaphthalene + 1,4,6-trimethylnaphthalene), m/z = 170 (Radke et al., 1986). 4) TNR-2 = (1,3,7-trimethylnaphthalene + 2,3,6-trimethylnaphthalene) / (1,3,5-trimethylnaphthalene + 1,4,6-trimethylnaphthalene + 1,3,6-trimethylnaphthalene), m/z = 170 (Radke et al., 1986). 5) TNR-5 = 1,2,5-trimethylnaphthalene / (1,2,5-trimethylnaphthalene + 1,6,7-trimethylnaphthalene + 1,2,7-trimethylnaphthalene), m/z = 170 (Radke, 1987). 6) MPI-1 = 1.5(2 methylphenanthrene + 3 methylphenanthrene) / (phenanthrene + 1 methylphenanthrene + 9 methylphenanthrene) (Radke and Welte, 1983). 7) MPI-3 = (2-methylphenanthrene + 3-methylphenanthrene) / (1-methylphenathrene + 9-methylphenanthrene), m/z = 192 (Radke and Welte, 1983). 8) P/A = phenanthrene/anthracene. 9) MB/DBF = (3-methylbiphenyl + 4 methylbiphenyl) / dibenzofurane, m/z = 168 (Radke, 1987). “–” concentrations were too low to calculate a parameter value.

concentrations of fluoranthene and pyrene in the Bierawka sediments. Moreover, sediments contain sand-, clay-, coal and soot particles on which these compounds could be absorbed (Merrill and Wade, 1985; Fang et al., 2004; Yang et al., 2008; Meyer et al., 2013). 4.3.5. The distribution of aromatic hydrocarbons in water samples Naphthalene occurs in higher concentration between the m19–m21 sampling points near the Szczygłowice coal-waste dump. In general, phenanthrene, anthracene, fluoranthene, and pyrene appear all along

the river, with phenanthrene having the highest concentration from m1 to m8 and a decreased concentration from m9 up to the Szczygłowice dump (Table 5). The most common PAHs present have 2-, 3-, and 4 rings. These PAHs may be leached from the coaly sediment and coal wastes, but may also derive from industrial or domestic sources. Compounds with 5–6 rings do not occur, due to their low solubility in water. Similar PAH distributions, also with high concentrations of 2–3 ringPAHs, have been reported from the Gao Ping River (Doong and Lin, 2004) and the Xijiang River in China (Deng et al., 2006),

Table 5 The identified PAHs and their distribution in the sample groups. N — naphthalene; P — phenanthrene; A — anthracene; Fl — fluoranthene; Py — pyrene; B(a)A — benzo[a]anthracene; Ch — chrysene; B(a)F — benzo[a]fluoranthene; B(k)F — benzo[k]fluoranthene; B(e)F — benzo[e]fluoranthene; B(e)P — benzo[e]pyrene; B(a)P — benzo[a]pyrene; Per — perylene; IndP — indeno[1,2,3-cd]pyrene; B(ghi)per — benzo[ghi]perylene. Sample codes

N

P

Fl

Py

B(a)A

Ch

B(a)F

B(k)F

B(e)F

B(e)P

B(a)P

Per

IndP

B(ghi) per

2–3 rings

4–5 rings

6 rings

Sediments from Section I m1 0.05 10.87 m1(2) 0.24 4.54 m1(3) 0.22 7.61 m1(4) 0.13 8.39 m1(5) 0.49 9.14 m1(6) – – m2 – 7.11 m3 0.19 4.57 m4 0.23 18.12 m5 0.09 7.57 m6 – 5.70 m7 – 8.71 m8 0.29 10.19 m9 2.21 16.09 m10 1.04 7.18 m11 0.83 17.23 m12 6.18 15.40 m13 1.04 15.24 m14 2.13 14.47 m15 0.21 16.51 Aver. 0.82 10.77

2.48 2.73 1.17 1.82 2.05 – 1.62 1.78 3.46 1.84 1.49 2.21 2.83 5.09 4.70 6.09 4.49 6.36 6.82 6.14 3.43

23.24 10.07 17.05 17.05 21.09 – 19.63 17.62 20.35 18.89 15.72 22.14 20.41 23.11 20.76 21.62 21.43 21.31 23.11 22.63 19.85

17.52 9.89 13.83 15.04 16.62 – 16.08 15.55 15.85 15.97 13.75 17.38 16.00 16.57 16.59 14.61 15.60 14.80 15.63 15.29 15.40

6.90 13.28 6.55 7.74 6.86 6.88 7.21 4.80 5.69 5.02 7.23 7.91 6.94 8.46 7.44 6.73 7.73 7.21 7.47 7.27

7.03 12.14 9.65 9.25 8.89 –– 7.88 9.76 5.58 6.35 6.15 8.28 8.46 6.34 7.46 6.55 6.47 6.89 6.55 6.67 7.70

6.02 5.83 4.01 7.22 6.66 – 7.62 9.14 6.24 8.59 9.15 6.75 6.49 4.46 7.84 5.60 4.95 5.09 5.76 5.13 6.45

3.73 8.26 5.50 5.63 7.40 – 4.35 4.89 3.18 4.36 4.93 2.90 4.37 2.89 3.75 2.47 2.48 3.52 2.60 2.74 4.21

3.30 5.97 7.97 3.72 1.18 – 3.54 4.58 3.26 4.41 4.76 4.65 2.02 1.85 1.81 1.98 2.55 1.92 1.81 1.85 3.32

4.45 7.35 6.92 7.06 4.42 – 6.43 6.75 5.29 7.02 7.46 4.96 5.04 3.39 4.45 3.51 3.36 3.64 3.57 3.54 5.19

5.38 9.46 7.20 6.48 6.72 – 7.72 7.45 5.98 7.17 7.74 5.74 6.45 4.96 7.42 5.47 4.12 5.75 5.06 5.04 6.39

1.56 1.08 1.93 1.55 1.17 – 1.87 2.28 1.55 2.28 6.74 1.99 2.09 1.34 1.80 1.45 1.58 1.54 1.35 1.69 1.94

3.56 4.90 5.18 4.27 3.87 – 4.34 3.85 2.86 4.40 5.16 3.67 3.78 2.44 3.78 2.75 2.37 2.81 2.08 2.62 3.62

3.92 4.25 5.23 4.66 3.44 – 4.95 4.38 3.22 5.36 6.24 3.39 3.66 2.31 2.98 2.42 2.29 2.35 1.85 2.46 3.65

13.40 7.52 8.99 10.34 11.67 – 8.73 6.54 21.82 9.51 7.19 10.92 13.31 23.39 12.91 24.14 26.07 22.65 23.42 22.85 15.02

79.12 83.33 80.60 80.73 81.01 – 81.98 85.22 72.10 80.73 81.42 82.01 79.25 71.87 80.33 70.69 69.27 72.19 72.65 72.06 77.71

7.48 9.15 10.41 8.93 7.31 – 9.29 8.24 6.09 9.76 11.40 7.07 7.44 4.75 6.76 5.17 4.66 5.16 3.93 5.08 7.27

Coal wastes samples from Section m16 22.02 36.14 m17 13.59 32.22 m18(2) 9.60 23.42 m18(1) 4.96 18.19 Aver. 12.54 27.49

II 2.30 1.84 1.99 1.65 1.94

4.09 5.36 7.20 8.60 6.31

6.67 7.46 10.97 13.31 9.60

5.12 6.38 7.05 9.38 6.98

6.39 8.52 8.28 10.5 8.42

3.10 4.23 5.36 5.54 4.56

0.75 1.17 1.28 1.72 1.23

1.12 1.61 2.33 3.09 2.04

5.55 7.60 8.78 8.40 7.58

2.80 3.84 5.19 5.72 4.39

– – – 0.45 0.11

0.61 0.96 1.63 1.83 1.26

3.33 5.21 6.92 6.65 5.53

60.46 47.65 35.01 24.80 41.98

35.60 46.17 56.44 66.72 51.23

3.95 6.18 8.55 8.48 6.79

Sediments from Section III m19 10.40 16.49 m20 5.43 14.53 m21 1.77 17.80 m22(2) 0.46 15.94 m22(1) 7.27 13.34 m23 6.64 12.76 m24 0.11 11.61 m25 8.98 10.90 m26 1.84 12.28 m27 14.31 11.94 m28(2) 10.28 9.09 m28(1) 10.18 8.67 m29(2) 15.04 18.88 m29(1) 13.17 10.91 m30(2) 0.57 13.41 m30(1) 0.58 10.98 m31(2) 9.46 8.90 m31(1) 8.67 13.60 m32(2) 9.31 11.19 m32(1) 8.07 8.19 Aver. 7.13 12.57

4.74 5.18 5.98 5.16 4.73 4.52 6.50 4.85 4.89 12.77 5.93 5.50 7.30 6.02 5.60 4.04 4.97 4.70 4.90 4.75 5.65

15.00 17.33 17.51 17.96 14.45 16.92 17.35 16.51 15.83 12.37 15.07 15.43 18.25 15.94 18.19 19.04 16.18 15.36 14.84 13.28 16.14

11.25 13.53 13.62 14.06 11.77 13.46 14.51 13.11 12.64 10.16 12.01 12.17 13.59 12.70 14.68 15.33 12.98 12.40 11.95 11.04 12.85

5.70 6.20 6.11 6.07 6.20 6.54 6.82 6.44 6.98 5.25 7.00 6.71 5.69 6.24 6.75 7.00 6.85 6.12 6.16 7.29 6.41

6.04 6.09 6.10 6.18 6.34 6.19 7.92 6.33 7.10 6.43 6.95 6.48 5.08 6.03 6.79 6.60 6.65 6.37 6.50 7.28 6.47

5.21 5.45 5.46 5.86 6.17 5.52 6.41 5.62 6.68 6.04 6.20 5.73 3.45 4.38 5.77 6.18 5.87 5.64 6.25 6.83 5.74

2.75 3.07 3.04 3.20 3.43 3.14 3.38 3.17 3.79 3.13 3.49 3.67 1.83 2.93 3.34 3.57 3.34 3.15 3.37 3.92 3.24

2.62 2.85 2.93 3.00 3.10 2.92 3.34 2.90 3.52 2.59 3.27 3.23 1.66 2.49 3.16 3.34 3.07 2.96 3.14 3.50 2.98

4.28 4.13 4.15 4.80 4.92 4.18 5.00 4.21 5.10 4.82 4.49 4.59 2.41 3.82 4.41 4.67 4.42 4.37 4.91 5.36 4.45

5.15 5.79 5.53 5.86 6.01 6.23 6.02 6.05 6.42 3.49 5.93 6.43 3.30 5.05 6.37 6.89 6.42 6.02 5.97 7.45 5.82

2.31 1.91 1.85 1.91 1.76 1.87 2.01 1.87 2.14 – 1.91 2.00 0.80 1.64 1.85 2.08 1.93 1.82 2.07 2.12 1.79

3.87 4.17 3.99 4.54 5.15 4.50 4.17 4.55 5.23 3.17 4.10 4.45 1.90 4.14 4.46 4.63 4.70 4.49 4.88 5.58 4.33

4.20 4.33 4.15 5.02 5.36 4.62 4.87 4.49 5.55 3.52 4.28 4.76 1.90 4.55 4.68 5.10 4.74 4.74 5.02 5.72 4.58

31.63 25.14 25.55 21.56 25.35 23.93 18.21 24.74 19.00 39.02 25.30 24.34 40.78 30.11 19.58 15.59 23.22 26.86 25.29 20.93 25.30

60.30 66.36 66.32 68.87 64.14 66.96 72.75 66.22 70.21 54.29 66.32 66.46 55.46 61.21 71.29 74.68 67.40 63.95 64.86 67.81 65.79

8.07 8.50 8.13 9.57 10.51 9.11 9.04 9.04 10.78 6.69 8.38 9.20 3.76 8.69 9.14 9.73 9.39 9.19 9.85 11.26 8.90

Sample code

N

P

A

Fl

Py

– –

41.13 –

2.66 –

– – 100.00 44.53 39.83 54.24 37.75 53.34 54.35 37.15 13.95 39.92 20.90 23.31 12.15 10.33 33.98

– – – 1.92 0.46 2.36 0.59 1.51 1.40 4.88 3.47 4.62 1.99 2.85 1.88 2.15 2.31

– – – 33.35 37.47 27.98 27.92 29.05 28.27 33.21 46.74 34.46 44.99 42.71 49.37 49.34 37.30

– – 20.20 22.24 15.43 33.73 16.10 15.98 24.77 35.84 20.99 32.12 31.14 36.60 38.18 26.41

Water samples from Section II w16 – 46.09 w17 – –

2.76 –

29.86 –

21.29 –

Aver.

Water samples from Section I w1 – 56.21 w1(3) – –

w1(5) w1(6) w2 w3 w4 w5 w6 w7 w8 w9 w10 w11 w12 w13 w14 w15 Aver.

– – – – – – – – – – – – – – – – –

46.09

2.76

29.86

21.29

Water samples of Section III w18 64.62 6.38 w19 69.34 9.10 w20 35.10 12.93 w21 – 22.82

– – 6.55 3.28

13.32 8.98 22.46 35.59

15.69 12.58 25.26 38.31

w22 w23 w24

12.50 – –

15.16 22.72 19.43

4.05 1.88 6.92

34.31 38.36 29.95

34.49 37.04 43.70

w25

–

21.20

17.78

31.86

29.16

w26

–

27.11

2.97

36.87

33.05

w27

56.39

13.57

6.44

13.37

13.86

w28 Aver.

– 11.55

25.85 20.09

5.82 6.19

34.98 30.86

33.35 32.03

Á. Nádudvari, M.J. Fabiańska / International Journal of Coal Geology 152 (2015) 94–109

A

“–” concentrations were too low to calculate a parameter value. 105

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Fig. 6. Different PAH diagnostic ratios for identification of their sources. Table 6 The results of calculated PAH diagnostic ratios. Calculated ratios

P/A (1), (2) A/P (3) A/(A + P) (1), (4) Fl/(Fl + Py) (4) Fl/Py (4) Fl/(Fl + P) (4) IndP/B[ghi]P (5) IndP/(IndP + B[ghi]P) (4) Per/PAI (6)

Possible source

Average values of this research

Petrogenic

Pyrogenic

Section I

Section II

Section III

N25 b0.1 b0.1 b0.5 b1 b0.1 N1 b0.2 N10

b10 N0.1 N0.1 N0.5 N1 N0.1 b1 N0.5 b10

3.5 0.3 0.2 0.6 1.3 0.7 1.0 0.5 0.12

14.0 0.1 0.1 0.4 0.7 0.2 0.2 0.2 –

2.3 0.5 0.3 0.6 1.3 0.6 0.9 0.5 0.13

(1,2) Phenanthrene/anthracene (Budziski et al., 1997; Benlachen et al., 1997). (3) Anthracene/phenanthrene (Yunker et al., 1999). (4) Anthracene/(Anthracene + Phenanthrene) (Yunker et al., 2002; Budziski et al., 1997). (4) Fluoranthene/(Fluoranthene + Pyrene); Fluoranthene/Pyrene; Fluoranthene/(Fluoranthene + Phenanthrene); indeno[1,2.3-cd]pyrene/(indeno[1,2.3-cd]pyrene + benzo[ghi]perylene) (Yunker et al., 2002; Budziski et al., 1997). (5) Indeno[1,2.3-cd]pyrene/benzo[ghi]perylene (Wasserman et al., 2001). (6) Perylene/pentacyclic aromatic isomers − benzo[k]fluoranthene, benzo[e]pyrene, benzo[a]pyrene (Baumard et al., 1998; Readman et al., 2002). “–” concentrations were too low to calculate a parameter value.

Á. Nádudvari, M.J. Fabiańska / International Journal of Coal Geology 152 (2015) 94–109

107

Fig. 7. Proposed methylphenanthrene index MPI-1, MPI-3, methylbiphenyl/dibenzofurane (MB/DBF), phenanthrene/anthracene (P/A) diagnostic ratios for identification of their origin.

4.3.6. PAH diagnostic ratios In the river sediments, calculated PAH parameters point to pyrogenic- and petrogenic sources (Fig. 6). Samples from Section II by the Szczygłowice coal-waste dumps match well with a petrogenic origin. Samples from Sections I and III match with a pyrolytic origin, not surprising with the abundance of burned coal particles that are present in them. The diagnostic parameters work well, despite of the intensity of various secondary processes, e.g., water-washing and biodegradation. Moreover, the perylene/PAI (pentacyclic aromatic isomers) parameter also indicates its pyrogenic origin in Bierawka sediments (Table 6). The occurrence of other contaminants such as methylphenanthrene, methylbiphenyl, dibenzofurane, phenanthrene and anthracene in the Bierawka River allows the application of additional source-indicating parameters such

as MPI-1, MPI-3, MB/DBF and P/A. These contaminants occur in coal and may derive from other sources such as car exhausts, motor oil, fuel, coal- and wood combustion or from incomplete combustion (U.S. Department of Health and Human Services, 1993; Adams and Richardson, 1953; Karcher, 1988). These parameters corroborate the conclusions drawn from the PAH parameters and also serve to discriminate between pyrolytic and petrogenic sources along the river (Fig. 7). 5. Conclusions The main problem of the research was to find the source of the coaly particles in sediments along the Bierawka River. Upstream of any coal-

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waste dumps, other contamination sources were had to be considered. The conclusions are: 1. Values of S2–TOC, HI–OI and HI–Tmax ratios, Pr/n-C17 versus Ph/n-C18, and pentacyclic triterpane distributions indicate coal/kerogen III as the source of the coaly particles in the river sediments. This is clear despite different mining sources, different periods of exploitation and different secondary environmental/industrial influences (combustion, water-washing, and biodegradation). 2. Coaly particles may have different sources. Generally, the primary origin is from coal usage and the dumping the ash with unburned coal particles by the old glass factory. It produced thousands of tons of slag which were dumped near the river source and washed into the river. This material was redeposited along the entire river course. In addition, hard coal processing (crushing–washing) features were evident in larger coal fragments. A further source of coaly material was the Szczygłowice coal-waste dump where intensive erosion of the steep slopes transferred significant amounts of organic matter into the river. This organic matter is mixed with coal particles from the glass factory downstream. 3. A bimodal n-alkane distribution and elevated Σ2/Σ1 and CPI values identify the input of recent organic material (plants, algae, leaves etc.) upstream and downstream. 4. PAH distributions also show differences along the river. Coal material input from the Szczygłowice dump increased the naphthalene content downstream. In sediments 4–5 ring PAHs are dominating. PAH diagnostic parameters indicate a pyrogenic origin for PAHs, and aromatic compounds such as methylbiphenyls and dibenzofurane, in the sediments — as suggested by burnt particles identified petrographically. 5. The river water samples were polluted by 2–4 ring PAHs, where these compounds can be leached from sediment or related to industrial, domestic origin. The absence of heavier PAHs (5–6 ring) reflects their low water solubility. Acknowledgments The Grant for Young Scientists from University of Silesia funded the research. The authors are grateful to Dr. hab. Magdalena Misz-Kennan for her help with the petrographic analysis and to Dr. Padhraig Kennan (University College Dublin) for the help with language. References Achten, C., Hofmann, T., 2009. Native polycyclic aromatic hydrocarbons (PAH) in coals — a hardly recognized source of environmental contamination. Sci. Total Environ. 407, 2461–2473. Achten, C., Cheng, S., Straub, K.L., Hofmann, T., 2011. The lack of microbial degradation of polycyclic aromatic hydrocarbons from coal-rich soils. Environ. Pollut. 159, 623–629. Adams, N.G., Richardson, D.M., 1953. Isolation and identification of biphenyls from West Edmond crude oil. Anal. Chem. 25 (7), 1073–1074. Ahrens, M.J., Depree, C.V., 2004. Inhomogeneous distribution of polycyclic aromatic hydrocarbons in different size and density fractions of contaminated sediment from Auckland Harbour, New Zealand: an opportunity for mitigation. Mar. Pollut. Bull. 48, 341–350. Baumard, P., Budzinski, H., Mchin, Q., Garrigues, P., Burgeot, T., Bellocq, J., 1998. Origin and bioavailability of PAHs in the Mediterranean Sea from mussel and sediment records. Estuar. Coast. Shelf Sci. 47, 77–90. Benlachen, K.T., Chaoui, H.A., Budzinski, H., Garrigues, P.H., 1997. Distribution and sources of polycyclic aromatic hydrocarbon in some Mediterranean, coastal sediment. Mar. Pollut. Bull. 34, 298–305. Boonyatumanond, R., Wattayakorn, G., Togo, A., Takada, H., 2006. Distribution and origins of polycyclic aromatic hydrocarbons (PAHs) in riverine, estuarine, and marine sediments in Thailand. Mar. Pollut. Bull. 52, 942–956. Bray, E.E., Evans, E.D., 1961. Distribution of n-parafins as a clue to recognition of source beds. Geochim. Cosmochim. Acta 22 (1), 2–15. Budziski, H., Jones, I., Bellocq, J., Piérard, C., Garrigues, P., 1997. Evaluation of sediment contamination by polycyclic aromatic hydrocarbons in the Gironde estuary. Mar. Chem. 58, 85–97. Dahl, B., Bojesen-Koefoed, J., Holm, A., Justwan, H., Rasmussen, E., Thomsen, E., 2004. A new approach to interpreting Rock-Eval S2 and TOC data for kerogen quality assessment. Org. Geochem. 35, 1461–1477.

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