Geochemical Analyses of Aliphatic Hydrocarbons and Polycyclic Aromatics in Sediments Using Gas Chromatograph

doi:10.21203/rs.3.rs-4613077/v1

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Geochemical Analyses of Aliphatic Hydrocarbons and Polycyclic Aromatics in Sediments Using Gas Chromatograph

https://doi.org/10.21203/rs.3.rs-4613077/v1

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In a process that begun in the mid-20th century, the city of Volta Redonda has presented a large demographic evolution with the industrialization of the region. Due to the fact that demographic growth and industrialization often carry environmental hazards along, it becomes necessary to monitor such activities with techniques that permit the detection of sediment contamination in order to minimize such environmental impacts. The geochemical analyses of biomarkers allowed the identification of the contributions of biogenic and anthropogenic sources of organic matter. The aim of this study was to carry out geochemical analyses of surface sediments for the detection of aliphatic and aromatic hydrocarbons. These compounds are classified by environmental protection agencies as priorities since they are harmful to health and to the integrity of ecosystems. Sediment samples were extracted using ultrasound and examined by gas chromatography and gas chromatography–mass spectrometry. The results indicated that most of the compounds were derived from anthropogenic sources, but also from plants and other biogenic sources. The data demonstrated that the concentrations of some polycyclic aromatic hydrocarbons (PAHs) were above the limits permitted by law, indicating contamination of the study area.

PAHs

Volta Redonda

sediment

pollution

GC-MS

Industrial activity is one of the main activities responsible for environmental contamination, especially in sediment. Industrial processes result in the production of large volumes of waste containing toxic compounds that are difficult to degrade (e.g., steel industries, automobiles, petrochemicals). These products can damage the health of the population through land use and occupation. Nevertheless, it is important to emphasize that urban soils are important not only for population health but also for city development and sustainable urban ecosystem development (Pavao-Zuckerman & Byrne, 2009; Ambade et al., 2023).

Biomarkers are used to analyze the environment once they provide information about the types of organisms that contribute to the organic matter incorporated into the sediments and are used to characterize, correlate and/or reconstruct the depositional environment (Tissot & Welte, 1984). It is possible to correlate the structure of modern organisms to their biological precursors and indicate characteristics of the biogenic and/or anthropogenic input at the site (Eglinton & Calvin, 1967). Aliphatic hydrocarbons are chemically stable in water and sediments. They are widely used as biomarkers and indicators of oil contamination (Peters & Moldonwan, 1993). Polycyclic aromatic hydrocarbons (PAHs) or polynuclear hydrocarbons are compounds that have two to seven aromatic rings condensed or fused in their structure. They are organic contaminants of great environmental persistence that are potentially carcinogenic and mutagenic. PAHs are generally found in low concentrations in water sources, as these compounds are highly hydrophobic. It usually accumulates in sediments, creating deposits of these compounds (Schwarzenbach et al., 2003). PAHs come from natural or anthropogenic sources; however, the high proportion of PAHs in urban areas is related to anthropogenic emissions (Buczynska et al., 2013. Ambade et al.,2023)

Sediment quality depends on continuous assessments before, during and after occupation in relation to organic pollutants such as polycyclic aromatic hydrocarbons (CONAMA, 2009). In this context, sediment contamination by polycyclic aromatic hydrocarbons (PAHs) has been studied worldwide, as these substances are toxic and, in some cases, even carcinogenic (WHO, 1998; Wang et al., 2006). The United States Environmental Protection Agency (USEPA, 1994) classified sixteen PAHs compounds due to their mutagenic and carcinogenic properties: naphthalene, acenaphthylene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, benzo(a)anthracene, chrysene, benzo(b)fluoranthene, benzo(k)fluoranthene, benzo(a)pyrene, dibenz(a,h)anthracene, indeno(1,2,3-cd)pyrene, and benzo(ghi)perylene.

PAHs present limits established by the Conama Resolution 420/2009 (CONAMA, 2009) in Brazil. Brazilian legislation is increasingly related to the presence of PAHs in sediments and other environments. Thus, it is essential to use more sensitive analytical techniques for the detection of these compounds. Therefore, the aim of this study was to perform geochemical characterization of aliphatic hydrocarbons and polycyclic aromatic hydrocarbons in industrial areas through the identification and quantification of such compounds, as well as the identification of possible sources. Sediment samples collected in Volta Redonda were used to verify the occurrence of concentrations above the limits imposed by legislation for some of the substances using GC-FID and GC-MS techniques.

Volta Redonda is located in the far western portion of the state of Rio de Janeiro, Brazil. It is characterized by the presence of industrial complexes, which have generated strong and accelerated development, transforming it into one of the main industrial zones in Brazil.

Four surface sediment samples (S1, S2, S3, and S4) were collected near residential sites and the Paraíba do Sul River. The samples were collected from industrial waste deposits. These deposits are composed of piles of industrial waste forming elevations throughout the study area (Fig. 1). The first two sampling sites (S1 and S2) show the typical vegetation of the Atlantic Forest Biome. Both samples are characterized by disaggregated sediments ranging from clay to pebbles. At sampling sites S3 and S4, no vegetation cover was observed. The sediment grains obtained were from different sizes (silts, clays, sands and pebbles). Another similar characteristic between points S3 and S4 is the reddish color of the collected sediments.

The surface sediments were sampled in the field and stored in a freezer at -20°C in decontaminated aluminum containers. The S1, S2, S3, and S4 samples were dried at 40°C. After drying, they were macerated to separate the grains and promote their homogenization. The samples were fortified with pyrene-d10 solution. Approximately 30 g of sample was subjected to extraction with 50 mL of dichloromethane:methanol solution (9:1) under ultrasonic bath (40 kHz) for 20 min at room temperature. This procedure was repeated three more times, after which the extracts were concentrated in a rotary evaporator under reduced pressure. The extracts obtained were fractionated (saturated and aromatic hydrocarbons) in an activated silica fractionation column, in which the saturated hydrocarbon fraction was eluted with 10 mL of n-hexane and the aromatic hydrocarbon fraction was eluted with 10 mL of n-hexane:dichloromethane (8:2).

The obtained fractions were analyzed by gas chromatography with a flame ionization detector (CG-DIC - Agilent Technologies model 7890). The analyses were carried out with a fused silica capillary column with stationary phase HP-5MS (Agilent Technologies, USA) (J&W, 30 m × 0.25 mm i.d., df = 0.25 µm). The analytical conditions used were 40°C to 15°C, 150°C to 310°C, 3.0°C/min, and isotherm for 10 min at 310°C. The injector had a temperature of 300°C, and the detector had a temperature of 320°C. Hydrogen was used as carrier gas and it was injected 1 µL of sample in splitless mode.

Gas chromatography coupled mass spectrometry (GC-MS) analysis was performed using an Agilent Technologies model 6890 gas chromatograph and Agilent Technologies 5973 mass spectrometer to identify sample compounds. Analyses were performed with a fused silica capillary column with an HP-5MS stationary phase, Agilent Technologies, USA (J & W, 30 m × 0.25 mm i.d., df = 0.25 µm). The analytical conditions used were 40°C to 150°C, 15°C/min, 150°C to 310°C, 3°C/min, and isotherm for 10 min at 310°C. The injector temperature was 300°C, and the detector temperature was 320°C, with helium used as the carrier gas and injection without dividing the flow and 1 µL of sample injected. The samples were analyzed by total mass scanning (SCAN) and selected ion monitoring (SIM) with electron impact ionization at 70 eV.

The identification of compounds was carried out by comparing the mass spectrum obtained with the reference spectrum (Electronic Library Wiley 275 and Nist 02), literature data and mass spectrum of authentic standards. For the quantification of aliphatic hydrocarbon fractions, n-tetracosane d-50 from Cambridge Isotope Laboratories, Inc., USA, was used, and for the identification of aromatic hydrocarbons, the deuterated pyrene standard from Cambridge Isotope Laboratories, Inc., was used. Quantification was obtained by comparing the peak areas of the internal standards with the areas of the compounds of interest. The internal standard was added to the sample before analyses by GC/DIC and GC/MS.

• Aliphatic hydrocarbons

The four surface sediment samples showed variations in the concentrations of aliphatic hydrocarbons, which can be seen in the axis that expresses the abundance of compounds (Fig. 2). Sample S1 presented the lowest concentration (386.88 ng/g), and sample S2 presented the highest concentration (1917.62 ng/g) (Table 1). The total n-alkanes of the samples ranged from nC₁₅ to nC₃₅. These hydrocarbons are useful biomarkers that provide information about the sources of organic matter (Apostolopoulou et al. 2015)

The ion chromatograms of the aliphatic hydrocarbon fractions of samples S1, S2, and S3 show bimodality, suggesting two distinct sources (Fig. 2). A clear contribution of waxes from vascularized plants was demonstrated by the C_max at C₂₉ or C₃₁. According to Clarck and Blumer, 1967, Cranwell, 1973, Nishimura and Baker, 1986, Zaghden et al., 2007, Sonibari and Sojinu, 2009), the maximum contributions (C_max) of nC₂₅ to nC₃₁ compounds indicate the contributions of terrestrial plants.

Concentrations of n-alkanes with C_max ≤ 23 demonstrate the influence of petrogenic signatures (Santos et al., 2004). The predominance of even nC₁₂ to nC₂₂ indicates the presence of bacterial and petroleum residues (Heemken et al., 2000; Gao et al., 2007). In samples S1, S2 and S4 (Fig. 2A, 2B, 2D), C_max was observed at C₂₀, C₁₇ and C_18, suggesting the contribution of bacteria or petroleum residues. The ion chromatogram of sample S4 (Fig. 2D) exhibited a predominance of lighter compounds with C_max at C₁₈, indicating that bacteria were the main source (Heemken et al., 2000), probably because this sample (S4) was collected in a landfill.

The terrestrial/aquatic ratio (TAR) indicates the type of organic matter source. It represents the proportion of n-alkanes of terrestrial origin (n-C₂₇, n-C₂₉ and n-C₃₁) in relation to n-alkanes of marine origin (n-C₁₅, n-C₁₇ and n-C₁₉) (Bourbonniere and Meyers, 1996; He et al., 2016; Zhang et al., 2018, Behera et al., 2024). S1, S2 and S3 presented TAR > 1, suggesting that the greatest contribution was from terrestrial sources (Table 1). Otherwise, sample S4 exhibited a TAR < 1, suggesting the predominance of aquatic sources over terrestrial sources (Table 1).

The carbon preference index (CPI) represents the relationship between odd and even carbon alkanes (Bray & Evans, 1961; He et al., 2016; Szymczak-Żyła & Lubecki, 2022). According to Table 1, the CPI values (2.37 and 5.09) at sites S1 and S3, respectively, represent contributions from biomass burning. At sites S2 and S4, the values of 6.81 and 2.66, respectively, indicate contributions from plants (Wang et al., 2006).

Another index that can be used to identify a possible source is the ratio between low molecular weight and high molecular weight hydrocarbons (low molecular weight/high molecular weight – LMW/HMW) (Wang et al., 2006; Gao et al., 2007). A ratio of LMW/HMW < 1 indicates the presence of n-alkanes originating from biogenic sources (higher plants, marine animals and sedimentary bacteria). On the other hand, ratios close to 1 suggest that n-alkanes originate from oil or plankton (Gearing et al., 1976), while values greater than 2 are indicative of recent oil in sediments (Commendatore et al., 2000). For these samples, the LMW/HMW ratio is represented by the concentration ratio of the low-molecular-weight (sum of n-C₁₅ to n-C₂₀) to high-molecular-weight (sum of n-C₂₁ to n-C₃₃) n-alkanes. According to Table 1, the ratio of LMW/HMW < 1 at points S1, S2 and S3 indicates the contribution of higher plants, while site S4 has LMW/HMW = 1,27, suggesting the contribution of oil or plankton.

Table 1

Total n-alkane concentration results and index calculations for the aliphatic hydrocarbon fraction.
Sample	Total n-alkanes (ng/g)	CPI	TAR	C_max	LMW/HMW
S1	386.88	2.37 (Biomass Burning)	4.37 (Terrestrial sources)	18, 20 (bacteria) 29, 31 (plants)	0.20 (Higher plants)
S2	1,917.62	6.81 (Plants)	5.98 (Terrestrial sources)	17 (bacteria) 29,31 (plants)	0.14 (Higher plants)
S3	907.20	5.09 (Biomass Burning)	7.54 (Terrestrial sources)	29,31,33 (plants)	0.15 (Higher plants)
S4	1,043.67	2.66 (Plants)	0.29 (Aquatic sources over terrestrial)	17,18 (bacteria)	1.27 (oil or plankton)

CPI = carbon preference index; TAR = terrestrial/aquatic ratio; C_max = maximum carbon number; LMW/HMW = low molecular weight/high molecular weight.

• Aromatic hydrocarbons

Among the 16 individual PAHs cited as priorities by the United States Environmental Protection Agency (USEPA) for evaluation in environmental studies, 13 PAHs were identified (Table 2). The total PAHs concentrations ranged from 1,471.7 ng/g in dry sediment (sample S3) to 29,335.1 ng/g in dry sediment (sample S1). The values obtained for the 13 individual PAHs in the sediment samples are described in Table 2.

Table 2

PAHs concentrations (ng/g) at the Volta Redonda sites (S1, S2, S3 and S4).
Aromatics compounds	Molecular formula	S1 (ng/g)	S2 (ng/g)	S3 (ng/g)	S4 (ng/g)
Fluorene (Flu)	C₁₃H₁₀	173.9	*	*	39.5
Phenanthrene (Phe)	C₁₄H₁₀	3,322.9	83.4	126.4	418.9
Anthracene (Ant)	C₁₄H₁₀	1,406.9	25.9	19.3	99.2
Fluoranthene (Flth)	C₁₆H₁₀	5,897.9	385.1	294.9	897.9
Pyrene (Py)	C₁₆H₁₀	4,604.4	270.9	210.2	756.2
Benz(a)anthracene (B(a)A)	C₁₈H₁₂	2,464.8	201.6	136.3	441.0
Chrysene (Chr)	C₁₈H₁₂	2,450.3	248.3	152.2	480.4
Benz(b)fluoranthene (B(b)A)	C₂₀H₁₂	2,749.9	229.6	147.3	425.7
Benz(k)fluoranthene (B(k)A)	C₂₀H₁₂	13.9	26.7	18.1	50.7
Benz(a)pyrene	C₂₀H₁₂	2,378.7	186.2	114.8	339.9
Indene(1,2,3-cd)pyrene	C₂₂H₁₂	1,833.6	227.9	116.3	319.6
Dibenz(a,h)anthracene	C₂₂H₁₄	426.6	214.2	18.8	37.8
Benz(ghi)perylene	C₂₂H₁₄	1,611.3	281.9	117.1	337.8
Total PAHs		29,335.1	2,381.7	1,471.7	4,644.6
* Unidentified

The distribution of aromatic compound fractions from the sediments of Volta Redonda showed different chromatographic profiles at all the sites collected (S1, S2, S3 and S4) (Fig. 3). At site S1, the PAHs concentrations varied from 13.9 to 5,897,9 ng/g (Table 2). The presence of fluoranthene, anthracene, and pyrene may be associated with the source of emissions from coke ovens and incineration (Khalili et al., 1995; Martens et al., 1997). The PAHs with the highest concentrations at this site were fluoranthene, phenanthrene, pyrene, benzo(a)anthracene, chrysene, benzo(j)fluoranthene, benzo(e)pyrene, indene(1,2,3-cd)pyrene and debenzo(ghi)perylene (Fig. 3A). Samples S2, S3 and S4 (Fig. 3B, 3C, 3D) also presented the highest concentrations of fluoranthene, followed by pyrene (Table 2). The occurrence of chrysene, benzo(a)anthracene, benzo(j)fluoranthene, benzo(e)pyrene, indene(1,2,3-cd)pyrene and debenzo(ghi)perylene was also observed.

The distribution of PAHs listed as a priority showed that the site with the highest concentration was S1, followed by S4 (Fig. 4). S1 and S4 are the sites closest to residential areas, but they indicate that currently inhabited areas may be old industrial waste dumps. S2 and S3 showed lower concentrations of total PAHs, and differences in concentration results may be directly related to the proximity of these points to the source area (waste deposits). Points S2 and S3 are further from the source area (industrial deposits), while points S1 and S4 are closer. Most PAHs remain relatively close to their source of origin, and their concentration decreases as they move away from this location because the affinity of PAHs for the organic phase is greater than that for water, thus making transportation difficult (Woodhead et al., 1999). The S1 and S4 sites were the samples that presented higher concentrations of high-molecular-mass PAHs and higher concentrations of low-molecular-mass PAHs targeted by environmental legislation.

The Brazilian Resolution (CONAMA n°28/18/2009) establishes guiding values for some PAHs in sediments and groundwater as a reference for prevention and intervention (Table 3). The concentration of benzo(k)fluoranthene ranged from 13.9 ng/g to 50.7 ng/g, while that of chrysene ranged from 152.2 ng/g to 2450.3 ng/g (Table 2), values lower than those established by legislation (Table 3). On the other hand, phenanthrene ranged from 83.4 ng/g to 3322.9 ng/g; anthracene ranged from 19.3 ng/g to 1,406.9 ng/g; benzo(a)anthracene ranged from 136.3 ng/g to 2,464.8 ng/g; benzo(a)pyrene ranged from 114.8 ng/g to 2,378.7 ng/g; benzo(g,h,i)perylene ranged from 117.1 ng/g to 1,611.3 ng/g; dibenzo(a,h)anthracene ranged from 18.8 ng/g to 426.6 ng/g; and indene(1,2,3-cd)pyrene ranged from 116.3 ng/g to 1,833.6 ng/g. All these values are higher than what is established by legislation (Table 3), indicating a polluted environment.

Table 3

Values (ng/g) for PAH concentrations in sediment from CONAMA 420/2009.
Substance	Sediment (ng/g dry weight)
	Prevention value	Intervention value
Anthracene	39	N/R
Benz(a)anthracene	25	9,000
Benz(k)fluoranthene	380	N/R
Benz(g,h,i)perylene	570	N/R
Benz(a)pyrene	52	400
Chrysene	8,100	N/R
Dibenz(a,h)anthracene	80	150
Phenanthrene	3,300	15,000
Indene(1,2,3-c,d)pyrene	31	2,000
Naphthalene	120	30,000
N/R = Not referenced

• PAHs Sources

Isomeric ratios between some PAHs were used to comprehend source emissions. It is necessary to consider that they are determined by the differences in thermodynamic stabilities between the different isomers. Combustion processes are generally associated with an increase in the proportion between the most stable and least stable isomers due to the energy involved. The emissions of petrogenic origin are not subject to the same energetic conditions as those of combustion processes, resulting in low relative values of this proportion (Yunker et al., 2002). The number of rings is also indicative. The predominance of PAHs with 2 or 3 aromatic rings is mainly due to petrogenic sources (Wang et al., 1999). However, they may also be associated with incomplete combustion processes of fossil hydrocarbons (Yunker & Macdonald, 2003). PAHs with 4 or 6 aromatic rings are mainly associated with the burning of fossil fuels and combustion processes at high temperatures (Yunker et al., 2002).

Different diagnostic ratios were used with the aim of determining the potential origin of PAHs: LMW PAHs/HMW PAHs, Ant/(Ant + Phe), Flth/(Flth + Py), BaA/(BaA + Chr) and Phe/Ant.

PAHs can be divided into two large groups: low molecular weight compounds contain two or three fused aromatic rings (naphthalene, cenaphthylene, fluorene, phenanthrene, and anthracene), and higher molecular weight PAHs contain four or more fused rings (fluoranthene, benzo(a)anthracene, benzo(b)fluoranthene, benzo(k)fluoranthene, chrysene, pyrene, benzo(g,h,i)perylene, benzo(a)pyrene, dibenzo(a,h)anthracene, and indene(1,2,3-cd)pyrene) (Moore & Ramamoothy, 1984). The possible sources of PAH emissions in industrial waste deposits are determined by summing the concentrations of low-molecular-weight PAHs and high-molecular-weight PAHs at the collection points (LMW/HMW), where ratios greater than 1 indicate a predominance of low-molecular-weight PAHs and petrogenic sources, while ratios of LMW/HMW < 1 indicate combustion sources (Yunker et al., 2002).

Figure 5 shows the distribution of the LMW/HMW ratio for the analyzed aromatic compounds. LMW/HMW > 1 at only point S1, which suggests that the PAHs are emitted from a petrogenic source, while at the other sampling points, the ratio of LMW/HMW < 1 suggests combustion emission.

Table 4

Total PAHs concentrations and isomeric ratios.
Sample	Total PAHs (ng/g)	LMW/ HMW	Ant/ (Ant + Phe)	Flth/ (Flth + Py)	B(a)A/ B(a)A + Chr	Phe/ Ant
S1	29,335.10	1.11 (petrogenic)	0.3 (combustion)	0.56 (combustion)	0.5 (combustion)	2.36 (petrogenic)
S2	2,381.70	0.47 (combustion)	0.24 (combustion)	0.59 (combustion)	0.45 (combustion)	3.22 (petrogenic)
S3	1,471.70	0.79 (combustion)	0.13 (combustion)	0.58 (combustion)	0.47 (combustion)	6.56 (petrogenic)
S4	4,644.60	0.91 (combustion)	0.19 (combustion)	0.54 (combustion)	0.48 (combustion)	4.22 (petrogenic)

Table 4 shows the distribution of the LMW/HMW ratio for the samples analyzed. LMW PAH/HMW PAH > 1 is observed only at point S1, which suggests that at this site, PAHs are emitted from a petrogenic source, while at the other sampling sites, LMW PAH/HMW PAH < 1 suggests combustion emission.

Phenanthrene is more thermodynamically stable than anthracene. Low values of the Ant/(Ant + Phe) ratio indicate petrogenic sources, while high values indicate combustion processes. In general, it can be concluded that when the ratio Ant/(Ant + Phe) < 0.10, the origin of PAHs is petrogenic (crude oil, diesel, fuels and kerosene), while Ant/(Ant + Phe) > 0.10 indicates the predominance of combustion processes (burning of different types of coal, biomass and raw oil) (Brum, 2007; Yunker et al., 2002; Zheng et al., 2002). According to this distribution, the origins of all samples analyzed suggest sources with combustion processes since the ratio of the isomers present values greater than 0.10 (Fig. 5 and Table 4).

The ratio between the fluoranthene concentration divided by the sum of the concentrations of the fluoranthene and pyrene isomers (Flth/(Flth + Py)) with values lower than 0.5 suggests petrogenic sources, while higher values indicate combustion processes. Flth/(Flth + Py) < 0.5 are found in samples of petroleum and derivatives, as well as in the combustion of gasoline, diesel, crude oil and vehicle emissions. Values greater than 0.5 are associated with the combustion processes of kerosene, vegetable biomass and most types of coal (vegetable, coke and bituminous) (Yunker et al., 2002). Figure 5 shows that for all the sampling sites, Flth/(Flth + Py) > 0.5, suggesting that the emission of PAHs occurs through combustion.

Diagnostic ratios using benzo(a)anthracene and chrysene (B(a)A/B(a)A + Chr) were also evaluated for the identification of a possible source of contamination. B(a)A is thermodynamically more stable than chrysene. B(a)A/B(a)A + Chr ratio < 0.20 is associated with petrogenic sources, while values greater than 0.35 are associated with the combustion processes of petroleum and its derivatives and plant biomass. For values between 0.20 and 0.35, it is not possible to determine the origin of the sources of PAHs (Yunker et al., 2002). Figure 5 shows that all samples exhibit B(a)A/B(a)A + Chr > 0.35, suggesting a combustion process.

The ratio between the concentration of phenanthrene and that of anthracene (Phe/Ant) was also evaluated to identify a possible source of contamination. Phe/Ant ratios < 10 are associated with thermogenic sources, while values greater than 15 are associated with pyrolytic sources. Values from 10 to 15 do not allow the determination of the origin of the PAHs. The values of these isomers are less than 10 (Table 2), which suggests that they are sources of contamination from petrogenic sources.

Thus, PAHs from industrial waste deposits in the Volta Redonda region are predominantly derived from pyrolytic (combustion) sources (Fig. 5 and Table 4). According to Zhang et al. (2005), however, it must be considered that these reasons are indicative and not definitive, as there are variations in the distribution of isomers from different origins. In addition, many of the samples represent complex matrices that can be provided by different sources, in which PAHs are exposed to all types of weathering capable of modifying the existing distribution profile.

The evaluation of the biomarkers in four sediments samples enabled inferences about the origin of the organic matter. The aliphatic hydrocarbon chromatogram indicated contributions from bacteria and vascularized plant waxes. The n-alkane indices TAR, LMW/HMW and CPI suggest the contribution of terrestrial sources, and the latter also indicates the contribution of biomass-burning compounds. In samples S1, S2 and S4, C_max was observed at C₂₀, C₁₇ or C_18, suggesting the contribution of bacteria or petroleum residues.

There are 16 individual PAHs cited as priorities by the United States Environmental Protection Agency (USEPA) for evaluation in environmental studies, of which 13 PAHs were identified among the 16 individual PAHs cited as priorities by the United States Environmental Protection Agency (USEPA) for evaluation in environmental studies. Analyses of the sediments revealed highly toxic compounds such as anthracene, dibenzo(a,h)anthracene, benzo(g,i,h)perylene and phenanthrene, which presented concentrations below the maximum permitted levels at some sites, while at other sites, the values were well above the maximum permitted. The Ant/(Ant + Phe), Flth/(Flth + Py), BaA/BaA + Chr), and Phe/Ant ratios, which are used to differentiate petrogenic from pyrolytic material, showed that PAHs are the result of biomass and coal burning. This is probably the result of industrial waste in the Volta Redonda region.

Benzo(a)pyrene and indene presented values above the maximum limit at all the sites sampled. On the other hand, the concentrations of benzo(k)fluoranthene and chrysene were below the maximum limits established at all the points. It can be concluded that all the points of the industrial tailings deposit sampled are contaminated with PAHs, which are targets of the legislation of the National Environmental Council (CONAMA 420/2009). Therefore, the presence of these toxic compounds can be harmful to the population of the region.

Author Contribution

D.F.M.I - Writing - Original Draft. Preparation, creation and/or presentation of the published work, specifically writing the initial draft (including substantive translation) and conceptualization.J.M.G- Writing - Reviewed and edited the work, revised it critically for important intellectual content prepared figures and tables;D.E.S.R - Writing - Reviewed and edited the work, revised it critically for important intellectual content prepared figures and tables;T.L.S - Visualization and helped with the organization of the text, corrections and suggestions;M.N.O.P.- Visualization and helped with the organization of the text, corrections and suggestions;Siqueira, C.Y.S - Planned and supervised the work. Contributed to conceptualization and validation. Agree to be accountable for all aspects of the work in ensuring that questions related to the accuracy or integrity of any part of the work are appropriately investigated and resolved

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Geochemical Analyses of Aliphatic Hydrocarbons and Polycyclic Aromatics in Sediments Using Gas Chromatograph

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• Aliphatic hydrocarbons

• Aromatic hydrocarbons

• PAHs Sources

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