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Article

Polycyclic Aromatic Hydrocarbons in Seafood: Occurrence, Trophic Bioaccumulation, and Human Health Risks

by
Fabíola Helena dos Santos Fogaça
1,2,*,
Pamella Talita da Silva Melo
1,2,3,
Carlos German Massone
3,
Renato da Silva Carreira
3,
Leonardo Rocha Vidal Ramos
2 and
João Paulo Machado Torres
4
1
Embrapa Agroindústria de Alimentos, 23020-470 Rio de Janeiro, RJ, Brazil
2
Animal Production Department, Rural Federal University of Rio de Janeiro, 23897-000 Seropédica, RJ, Brazil
3
Chemistry Department, Pontifical Catholic University of Rio de Janeiro, 22451-900 Rio de Janeiro, RJ, Brazil
4
Institute of Biophysics, Federal University of Rio de Janeiro, 21941-902 Rio de Janeiro, RJ, Brazil
*
Author to whom correspondence should be addressed.
Fishes 2025, 10(11), 591; https://doi.org/10.3390/fishes10110591 (registering DOI)
Submission received: 31 August 2025 / Revised: 13 November 2025 / Accepted: 15 November 2025 / Published: 18 November 2025
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Abstract

Polycyclic aromatic hydrocarbons (PAHs) can enter the human body through the consumption of contaminated food, particularly seafood, which can bioaccumulate these toxic compounds. This study evaluated PAH contamination levels in fish, crabs, and shellfish from the Parnaiba River estuary following the 2019 oil spill that impacted over 3000 km of Brazil’s northeastern coastline with weathered, heavy crude. The results showed that PAH concentrations in 2019 were approximately 50% higher than those detected in 2021, indicating an acute contamination event linked to the spill. Among the sampled organisms, crabs had the lowest PAH levels, followed by shellfish with intermediate contamination levels, and fish with the highest concentrations. PAH profiles varied by species: shellfish were dominated by high-molecular-weight (HMW) compounds typical of pyrogenic sources; fish were primarily contaminated with low-molecular-weight (LMW) PAHs associated with crude oil; and crabs exhibited a balanced mix of both. Toxicity equivalency analysis revealed the presence of benzo[a]pyrene (BaP) only in 2019 shellfish samples, while BaP contamination was found in both fish and shellfish in 2021. Some samples exceeded regulatory limits for indeno[1,2,3-cd]pyrene. Mollusks collected during the 2021 dry season presented BaP and benzo[k]fluoranthene levels above the threshold of concern. These findings demonstrate the acute impact of the oil spill, characterized by a predominance of LMW PAHs, as well as a residual contamination pattern in 2021, likely associated with pyrogenic sources and driven by environmental degradation processes. This study also indicates that although overall carcinogenic PAH levels decreased, some carcinogenic PAHs continue to exceed legal limits in fish and shellfish samples, even 2 years after the oil spill. This work highlights the need for long-term monitoring and reinforces the importance of including food safety in environmental impact assessments, especially in vulnerable fishing communities.
Keywords:
crab; shellfish; mullet; health risks
Key Contribution: Concentration levels of PAHs in Brazilian seafood were updated post-oil spill, revealing that fish and shellfish were more contaminated than crabs. In 2019, PAH levels were approximately 50% higher than in 2021, suggesting acute contamination from the spill. A residual effect persisted in 2021, with an increase in pyrogenic PAH sources. Notably, indeno[1,2,3-cd]pyrene concentrations in fish and shellfish, as well as benzo[a]pyrene in 2021 shellfish, exceeded legal limits for human consumption.

Graphical Abstract

1. Introduction

The increasing presence of organic contaminants in marine environments raises serious concerns regarding the health of aquatic organisms [1,2,3,4]. These animals are vulnerable to different exposure pathways for these chemicals [2], which exhibit distinct toxicities, bioavailability, and environmental persistence [5,6,7]. Polycyclic aromatic hydrocarbons (PAHs) are among the contaminants of environmental concern because they are ubiquitous, persistent, and toxic. Some PAHs may act as endocrine disruptors and have mutagenicity and/or carcinogenicity [8,9,10,11,12]. These organic compounds are composed of 2–6 fused aromatic rings with petrogenic, pyrogenic, and biogenic origins [13,14] and represent up to ~5% of the total composition of crude oils [6]. They directly affect marine ecosystems and come from activities related to oil and gas exploration, production, transport, refining, and consumption [15].
PAHs in marine and aquatic food webs involve complex processes, including uptake via multiple exposure pathways, dietary absorption, and organisms’ ability to metabolize and excrete these compounds. Understanding these dynamics is essential for accurately assessing ecological and human health risks. Bioaccumulation refers to the net uptake of a substance by an organism from all exposure routes, including water, air, sediment, and food [16]. Organisms at the base of the food chain, such as filter-feeding bivalves like oysters and mussels, are highly susceptible to bioaccumulation [17]. Biomagnification, on the other hand, is the increase in concentration of a substance in an organism as it consumes prey at a lower trophic level. This phenomenon is typical of compounds that exhibit significant resistance to degradation, are lipophilic, and are not readily excreted [18], exemplified by high-molecular-weight (HMW) PAHs [19].
The concentration of PAHs in higher-trophic-level organisms, such as fish, is more variable and complex due to their more efficient metabolic detoxification systems. Fish possess a highly developed mixed-function oxygenase (MFO) system that metabolizes PAHs into more water-soluble derivatives, thereby reducing PAH concentrations in their muscle tissue [20]. On the other hand, filter feeders, lacking the advanced metabolic capacity of vertebrates, serve as effective bioindicators for monitoring environmental contamination [21]. Therefore, the bioaccumulation of PAHs in marine food webs involves complex interactions influenced by the distinct properties of different PAH compounds, primary exposure pathways, and the diverse metabolic capabilities of organisms across trophic levels [22]. The resulting pattern often reflects a combination of bioaccumulation, biomagnification, and trophic dilution, all of which must be considered when assessing the risks associated with PAH contamination in seafood.
When an oil spill occurs, as in the Deepwater Horizon disaster in 2010 and the Exxon Valdez spill in 1989, it has been clearly demonstrated that marine food chains are vulnerable to widespread hydrocarbon contamination [8,11,23,24,25,26,27]. Fish and shellfish can absorb PAHs—toxic, persistent compounds found in crude oil—through their gills, skin, or diet. These substances accumulate in fatty tissues and can remain for extended periods, compromising the safety of seafood for consumption [28,29,30,31,32]. Post-spill assessments have documented elevated PAH levels in commercially important species, at times exceeding acceptable thresholds for human consumption. The resulting bans on fishing and seafood sales often hit hardest in coastal communities that rely on these resources for both income and subsistence, deepening social and economic inequalities and prolonging recovery for the most vulnerable populations [33,34,35]. A vast and unusual oil spill affected Brazil’s northeastern coast between 2019 and 2020. It polluted more than 3000 km of shoreline in 11 states [36,37,38]. Unlike spills from well-documented accidents, this event involved weathered, heavy oil that appeared suddenly on beaches, reefs, and mangroves, making containment and tracking efforts especially difficult [38]. The spill had immediate ecological consequences, contaminating sensitive coastal ecosystems and threatening marine biodiversity [39,40,41]. It also had a direct impact on artisanal fishing communities, many of whom depend on daily catches for both income and food security [33,41]. However, PAH levels in relevant seafood species from one of the most impacted coastal regions did not pose a risk to human consumption based on international thresholds [28]. The lack of clear attribution and the slow institutional response further exposed systemic weaknesses in Brazil’s environmental monitoring and crisis management, disproportionately affecting already vulnerable coastal populations [36,42,43].
Here, we evaluated the level of contamination by PAHs and determined the risks associated with consuming seafood, including fish, crabs, and shrimp, from the estuary of the Parnaiba River, which already exhibited low to moderate contamination [44] by PAH before the spill but was also affected by the new event. This study demonstrates the importance of comprehensive post-spill monitoring strategies in Brazil that include not only heavily impacted zones but also less visible, ecologically sensitive areas. It also highlights the importance of integrating food safety assessments into emergency response protocols, particularly in regions where fishing is essential to local livelihoods and nutrition.

2. Materials and Methods

2.1. Chemicals and Reagents

The organic reagents, such as n-hexane, dichloromethane (DCM), methanol (MeOH), acetonitrile (ACN), and methyl tert-butyl ether (MTBE), were all chromatographic grade. Additionally, the other chemicals and reagents used were also of high purity (>98%).
A standard PAH solution was obtained from Sigma Aldrich, Supelco (Saint Louis, MO, USA). It contained the following PAHs: naphthalene, acenaphthylene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, benz(a)anthracene, chrysene, benzo(b)fluoranthene, benzo(k)fluoranthene, benzo(a)pyrene, dibenz(a,h)anthracene, benzo(g,h,i)perylene and indeno(1,2,3-cd)pyrene and individual standards of each compound, benzo(j)fluoranthene and dibenz(a,h)pyrene. To prevent volatilization and photodegradation, mixed standard solutions containing all PAHs were prepared by diluting the stock solutions with acetonitrile (Sigma–Aldrich, Saint Louis, MO, USA) and stored in darkness at −20 °C. We obtained ultrapure water from a Milli-Q simplicity 185 system (Millipore, Bedford, MA, USA).

2.2. Sample Collection

Seafood samples were collected from the Parnaiba Delta River during the rainy and dry seasons of 2019 (shortly after the oil spill) and during the dry season in 2021 (post-spill) to evaluate the bioaccumulation of PAHs. The Parnaiba River Delta, in Northeast Brazil, is located within an Environmental Protection Area that extends over the states of Ceará, Maranhão, and Piauí [45]. This complex ecosystem features unique fluvial-marine interactions, leading to brackish waters that sustain substantial plant and animal populations [46]. This extensive coverage area of 2750 km2 includes islands formed by the accumulation of terrigenous materials conveyed by canals that cross expansive marine-fluvial plains [46]. The area’s tropical dry climate is characterized by a rainy summer and a dry winter, with an annual average precipitation of 1200 mm [47]. The shellfish and crabs were collected at Ilha Grande, Piaui State (−2.828559, −41.834833); the fish were collected at Parnaiba River, between Maranhão and Piaui states (−2.875584, −41.866228) [48].
The seafood samples were caught with the help of local fishermen and lasted 4–8 h. Three species were collected, including shellfish (Anomalocardia brasiliana) (F1, n = 40), mangrove crab (Ucides cordatus) (F2, n = 25), and mullet (Mugil curema) (F3, n = 25). Samples were individually wrapped in aluminum foil, stored in polyethylene bags, and kept on ice during transportation. At the laboratory, the specimens were measured (Table 1), processed, and then stored at −20 °C before further analysis. Raw crab and shellfish specimens were carefully cleaned and opened to extract edible tissues. Fishes were filleted for muscle separation.

2.3. Extraction and Quantitative Analysis

PAHs were extracted by QuEChERS within six months of sampling. A deuterated PAH mixture (5 ng/mL), including naphthalene-d8, acenaphthene-d10, phenanthrene-d10, chrysene-d12, and perylene-d12, was added to each 2 g wet-weight sample as internal standards. An extraction solution comprising ultrapure water, acetone, ethyl acetate, isooctane (2:2:1), MgSO4, and NaCl was used. To purify the extract, a deactivated alumina/silica column was cleaned. Standard p-terphenyl-d14 (5 ng/mL) was used as an analytical control. Samples for GC/MS injection were filtered using a 0.20 µm PTFE membrane filter (Whatman®, Buckinghamshire, UK).
PAHs were measured by gas chromatography-mass spectrometry (Thermo Trace-ITQ instrument, Bremen, Germany) using the EPA 8270-D [49] procedure. For each extract, 1 μL was injected into a DB-5ms column (30 m × 0.25 mm × 0.25 μm) at a constant flow rate of 1.2 mL/min. The temperature program used was: 50 °C for 5 min, then 50 °C/min to 80 °C, 6 °C/min to 280 °C for 25 min, and 12 °C/min to 305 °C for 10 min. Selected ion monitoring (SIM) mode was used to collect data on typical PAH ions (m/z) [50]. Quantification was carried out using a 9-point calibration curve (1.0, 2.0, 5.0, 10.0, 20.0, 50.0, 100.0, 200.0, and 400.0 ng/mL) with 16 priority PAHs and dibenzotyophene, perylene, and benzo[e]pyrene. The concentration of alkylated homologs not in the mixture was quantified using structurally related homologs’ reaction factors, making the following compounds semi-quantitative: C1 naphthalenes, C2 naphthalenes, C3 naphthalenes, C4 naphthalenes, C1 fluorenes, C2 fluorenes, C3 fluorenes, C1 dibenzothiophenes, C3 dibenzothiophenes, C1(phenanthrenes + anthracenes): C2(phenanthrenes + anthracenes), and C3(phenanthrenes + anthracenes). In total, 37 parental and alkylated PAHs were quantified.
Quality analysis and quality control criteria included laboratory blank analysis (only traces of naphthalene were detected), surrogate standard recoveries (60–120%), precision better than 20%, and spiked tissue samples spiked with a mixture to assess method accuracy. The calibration curve’s limit of detection ranged from 0.033 to 0.068 ng g−1 for PAHs. In contrast, the limit of quantification was 0.500 ng g−1 for all compounds at the first point (the limits of detection (LOD) and quantification (LOQ) for each identified PAH are detailed in the Supplementary Material, Table S1).

2.4. Toxicity Equivalent Concentration (TEP)

Benzo(a)pyrene (BaP) exhibited the highest levels of carcinogenicity and toxicity among the seven carcinogenic PAHs. BaP is commonly used to evaluate the carcinogenic potential of PAHs, with the toxic effect factor (TEF) serving as a measure of each PAH’s carcinogenic capacity relative to BaP. The formula for calculating the equivalent concentration of PAHs using the toxic equivalent factor [51] is as follows:
TEQ = Σ (PAHi × TEFi)
where: PAHi represents the concentration of PAH monomer i, TEFi denotes the toxicity equivalent factor of PAH monomer i, TEQ signifies the toxicity equivalent of the compound’s equivalent concentration, and the TEF value for BaP is 1, the highest among all PAHs (Table 2).

2.5. Carcinogenic Risks Assessment

The National Health Surveillance Agency [52] published the concern levels for evaluating the safety of seafood in Brazil after the 2019 oil disaster. The cancer risk for individual PAHs after seafood ingestion by humans was determined using the toxic equivalency (TEQ) approach in comparison to benzo[a]pyrene, as outlined in the equation:
LOC = (RL × BW × AT × CF)/(CSF × CR × ED)
where: LOC is the concern level, RL is the acceptable risk level (1 × 10−5), BW is the estimated average body weight of the exposed adult (60 kg), AT is the average lifetime of exposition (70 years), CF is the conversion factor (106 µg kg−1), CSF is the cancer slope factor or carcinogenic potency relative to benzo[a]pyrene (BaP) (Table 2), CR is the consumption rate of seafood, and ED is the estimated exposure duration (5 years). The CR for fish was set at 180 g day−1, and for mollusks/crustaceans at 60 g day−1 [52]. The values for individual PAH relative carcinogenic and non-carcinogenic potencies were taken from ICF-EPA [53] and [52], respectively.

2.6. Data Analysis

Means and standard deviations were calculated in Excel. PCA, PLS, normality tests (Shapiro–Wilk), and ANOVA (Kruskal–Wallis) were performed using PAST (Paleontological Statistics Software Package, version 5, Oslo, Norway) [54]. The Shapiro–Wilk test was used to assess data normality, with a 95% confidence interval. To modify non-parametric data, we employed the Box-Cox method, substituting zero values with 1 [55]. The Kruskal–Wallis test was used to compare means. For ΣPAHs, the min-max normalization was used, which is a data scaling method that linearly adjusts data to a specified range, frequently employed in practice. The process involves subtracting the minimum value from each data point and dividing by the overall range (the difference between the highest and lowest values) [56].

3. Results

3.1. PAHs Profile

PAH concentrations were measured in 90 organisms (40 shellfish, 25 crustaceans, and 25 fish) during (2019) and after (2021) the oil spill. The combined concentrations of 37 PAH and alkylated compounds ranged from 22.39 ng g−1 ww in crab samples to 445.69 ng g−1 ww in shellfish samples, with a global average of 199.90 ± 175.71 ng g−1 ww during the dry season of 2019. For crabs and fish, the lowest PAH levels were observed during the 2019 oil spill, while for shellfish, the lowest values occurred 2 years after the spill in 2021. The PAH profiles varied among species. For crab, 12 PAHs were detected and quantified; for fish, 25 PAHs; and for shellfish, 35 PAHs (Figure 1). Low-molecular-weight (LMW) compounds classified as having 2–3 rings—especially naphthalene and its alkylated homologs—were common in fish samples. For shellfish and crab collected during the rainy season, there was an equal distribution of LMW and high molecular weight (HMW; 5–6 rings) PAHs in the samples. Medium molecular weight (4 rings, MMW) PAHs were only significant (13.20%) in crab samples from the dry season (Figure 2).
PCA analysis separated two groups (Figure 3). A clear group composed of crabs showed a predominance of LMW PAHs (88%). The shellfish group displayed a wide diversity of PAHs (35 out of 37 monitored compounds), with a slight overlap indicating some similarity in PAHs found in crab samples. The fish group was dispersed and showed no clustering. PAHs that contributed most to sample differentiation in the PLS (Partial Least Squares) model were fluoranthene and benzo[p]fluoranthene, which were the strongest in the applied model (Figure 3).

3.2. PAHs Source Analysis

The feature ratio method is frequently employed to determine the source of PAHs in the environment: LMW/HMW  >  1 indicates a crude oil source, and LMW/HMW  <  1 indicates a high-temperature pyrolysis and combustion source [21]. The LMW/HMW ratio for crab and fish was greater than 1, indicating oil spill contamination in 2019 and 2021. The contrary was observed for shellfish. In 2019, this ratio was less than 1 (0.6); however, in 2021, it exceeded 1, indicating an increased concentration of low-molecular-weight PAHs (Figure 2).

3.3. Bioaccumulation of PAHs

Bioaccumulation was assessed by the ΣPAHs (16 priority compounds and 21 additional ones) in each species. The impact of contamination varied among the studied species. The species influenced the measured PAH concentration, irrespective of the season (dry or rainy) and the year of collection (2019, during the oil spill, and 2021, post-incident) (Figure 4). Crabs, which feed on organic matter in mangrove areas, had the lowest contamination rate compared to the other species studied (p = 0.03). Fish showed intermediate contamination levels, despite having different feeding habits (omnivorous), followed by shellfish, which demonstrated the highest PAH bioaccumulation (filter-feeding) (Figure 4).
The seasonal effects (dry and rainy) were exclusively examined for the crab samples. The findings indicated no substantial difference in PAH bioaccumulation across the samples (p = 0.74). Regarding contamination over time (before and after the oil spill), there was no difference between the years 2019 and 2021 (p = 0.19). Fish showed higher contamination with 16 PAHs, considered to have the most significant carcinogenic potential, in 2019, followed by a reduction in contamination levels in 2021 (p > 0.05). For 37 PAHs, there was no change in species during the monitoring period (p > 0.05). In summary, crabs were less affected by the oil spill, while fish and shellfish remained contaminated, with PAH levels persisting even 2 years after the accident (Figure 4).
A correlation in the data was investigated to enhance comprehension. No association between contamination and the time or year of collection was observed; instead, contamination was associated with the species examined. This suggests that the species’ trophic level and habitat affected PAH bioaccumulation (Figure 5).

3.4. Risk Assessment

The toxicity equivalent concentration (TEF; Table 3) was used to calculate levels of concern for non-carcinogenic and carcinogenic PAHs in the samples (Table 4). The concentrations of non-carcinogenic PAHs were significantly lower than the concern thresholds established for oil spill incidents in Brazil [52] (Table 4).
The levels of concern (LOC) identified in the samples for all non-carcinogenic PAHs were below the suggested thresholds, indicating no hazards associated with fish consumption for these compounds (Table 4). Nonetheless, regarding the hazardous substances, indene[1,2,3-cd]pyrene concentrations exceeded the concern threshold (>5 ng g−1 ww) established by Brazilian authorities in all samples except for the analyzed crab. Fish samples from 2019 and 2021 contained 13 ± 10.45 ng g−1 ww and 38 ± 14.43 ng g−1 ww of indeno[1,2,3-cd]pyrene, respectively. Shellfish samples collected in 2019 and 2021 contained 14 ± 17.69 ng g−1 ww and 47 ± 17.29 ng g−1 ww, respectively. Shellfish also exceeded the acceptable limit for benzo[a]pyrene (BaP) (8 + 14.10 ng g−1 ww) and benzo[k]fluoranthene (BkF) (97 ± 25.17 ng g−1 ww) (Table 4).
Supplementary Materials presented other scenarios, including the estimated average body weight of the exposed adult (70 kg) and the average duration of exposure (30–50 years). Similar results were observed for 30–50 years of exposition for indeno in fish and shellfish (Table S2, Supplementary Material).

4. Discussion

This study examines contamination of polycyclic aromatic hydrocarbons (PAHs) in seafood from the Parnaiba Delta River following the 2019 oil spill in Brazil. This research provides significant insights into the variability in bioaccumulation across species and outlines the long-term residual effects of the spill. It is important to note that the Parnaiba River and its estuary cannot be classified as entirely pristine. Before the oil spill, PAH levels in sediment samples collected in 2018 ranged from 5.92 to 1521.2 ng·g−1 (dry weight), with several sites surpassing established international sediment quality guidelines, including Effects Range Low (ERL), Threshold Effects Level (TEL), and Probable Effects Level (PEL) thresholds [44]. The findings presented in this study constitute the first comprehensive assessment of PAH contamination in seafood in this region. The results indicate a significant immediate contamination effect during the 2019 oil spill, which persisted for 2 years, into 2021. Furthermore, this study reveals distinct variations in PAH profiles across different seafood species.
The variability in PAH levels and bioaccumulation among crabs, fish, and shellfish highlights their different physiological and ecological traits. In 2019, shellfish, as filter feeders, exhibited the highest PAH concentrations, which significantly decreased by 2021. This aligns with other research showing that bivalve mollusks, being sessile filter feeders, are especially prone to PAH bioaccumulation and have limited capacity to metabolize these compounds [57]. Conversely, fish—occupying higher trophic levels—had contamination levels similar to shellfish. Higher-trophic organisms typically show greater contaminant buildup due to biomagnification. This study confirms that fish possess enzyme systems, such as cytochrome P450, that effectively metabolize and excrete PAHs, leading to lower bioconcentration factors (BCF) [58].
The high contamination levels in fish during 2019 reflect the spill’s initial severity, which overwhelmed their detoxification systems. The lower contamination in crabs, which feed on organic matter in mangroves, suggests different exposure routes, possibly influenced by their habitat or diet compared to open-water fish and sediment-dwelling shellfish [59]. Research shows that crustaceans can remove PAHs from their bodies by metabolizing them into water-soluble forms such as 1-OH pyrene for urinary excretion. However, this process is not always highly efficient [60]. The lower PAH concentration in crab samples could also be associated with their habitat. Estuarine fish or bivalves were collected from the riverbed, which is the area most affected by the advance of the oil slick during flood tide, a time when the sea moves over the estuary due to tidal variations in the Delta [61,62,63]. Previous studies on oil spill dispersion in estuarine settings have examined various oil-release sites, indicating that the release point along the estuary’s length affects the area impacted by the oil slick. However, no research has examined the impact of altering the oil release point over the estuary’s cross-sectional width on oil slick transport. This research gap is crucial given the unpredictability of oil spills and their associated threats to estuaries and ecosystems (such as mangroves), underscoring the need for further research [64].
Analysis of PAH profiles provides crucial insights into contamination sources over time. The LMW/HMW ratio is a widely used method to distinguish sources, with LMW PAHs typically originating from crude oil (petrogenic sources) and HMW PAHs from high-temperature pyrolysis or combustion (pyrogenic sources) [65]. The predominance of LMW PAHs in fish samples from 2019 and 2021 clearly indicates a persistent petrogenic source, consistent with the oil spill. This reflects an acute impact of the contamination event. Conversely, shellfish showed a different profile, with a greater diversity of PAHs and a more balanced distribution between LMW and HMW compounds in 2019, shifting toward HMW PAHs in 2021. This finding is significant, as it suggests a residual effect of contamination linked to pyrogenic sources, such as combustion and human activities, which became more prominent after the initial crude oil spill subsided. The mixed PAH profile in crabs, with similar proportions of LMW and HMW compounds, further emphasizes the complexity of PAH sources in this coastal environment, influenced by both acute spill events and ongoing pollution from other human activities. The persistence of PAHs is also related to their low solubility and high stability, which allows them to persist in the environment and pose long-term chronic risks [66]. Global studies reveal varying PAH concentrations in edible seafood tissues, with HMW-PAHs dominating over LMW-PAHs in commonly consumed species like Littorina littorea, Crassostrea virginica, and Periophthalmus koeleuteri. This indicates a primarily anthropogenic and pyrolytic origin for these PAHs [67]. In South Korea, katsuobushi, a skipjack tuna product, contains high levels of benzo[a]pyrene, exceeding the EU limit of 5.0 µg/kg. Shellfish, fish, and crustaceans exhibit the highest PAH detection rates, with chrysene as the most prominent congener [68]. In Nigeria, PAH levels range from 0.059 to 0.126 mg/kg in fish, prawns, and crabs. This study also highlights a significant dominance of 3- and 4-ring PAHs, with benzo[a]anthracene being particularly prevalent across all three species [69].
In marine trophic chains, PAH concentrations may vary substantially, influenced by opposing processes: biomagnification, in which pollutant levels increase with each trophic level, and biodilution, in which concentrations decrease due to dilution [70]. Certain studies indicate that biomagnification is prevalent, especially in high-trophic-level species with elevated lipid content [71,72]. Recent research highlights biodilution as a significant mechanism in marine trophic networks, since LMW PAHs have reduced hydrophobicity and trophic magnification factors (TMFs) less than one, hence diminishing their accumulation at higher trophic levels [73,74].
The most important finding of this study concerns the human health risks linked to consuming contaminated seafood. The analysis, in response to ANVISA’s concerns, shows that although overall PAH levels have decreased, some carcinogenic PAHs still exceed legal limits (benzo[a]pyrene at 1.61 ng g−1 ww for shellfish). All fish and shellfish samples had indeno[1,2,3-cd]pyrene levels above the threshold of concern. Additionally, fish samples also surpassed acceptable limits for benzo[b]fluoranthene and benzo[k]fluoranthene. Most notably, shellfish collected in 2021, two years after the oil spill, were the only samples to show contamination above the safe limit for benzo[a]pyrene (BaP). This indicates that even after visible signs of the oil spill disappeared, a residual public health threat remains, primarily due to the buildup of these highly carcinogenic compounds. These results support and expand on global research on PAH contamination in seafood. For example, a study in South Korea also reported elevated levels of benzo[a]pyrene in marine products, highlighting the widespread nature of this health concern [75]. The presence of carcinogenic PAHs from pyrogenic sources underscores the need for ongoing monitoring, as these compounds are known to be particularly persistent and toxic. Risk assessment studies are systematic processes for identifying and evaluating potential hazards, and their scope can range from small-scale, project-specific assessments to extensive, enterprise-wide evaluations, depending on the complexity and context. Our project conducted a targeted diagnosis, using a limited sample size, due to the urgency of the results needed to assist the affected population and to facilitate public measures for immediate environmental and economic reparations, as fishing communities suspended their activities and faced income losses.
PAHs have both carcinogenic and non-carcinogenic hazards linked to their utilization. In addition to these effects, research indicates that PAHs can disrupt estrogenic pathways, resulting in sublethal yet ecologically significant effects. PAHs in marine fish can impair embryonic development and larval survival, resulting in heart defects, skeletal deformities, and structural vulnerability [75,76,77,78,79,80]. In adult marine fish, PAHs disrupt cellular homeostasis and compromise organ integrity. HMW PAHs, such as benzo[a]pyrene, interact with the aryl hydrocarbon receptor, thereby activating xenobiotic metabolic pathways and generating reactive intermediates that may result in cancer [80,81,82]. These implications include metabolic alterations in lipid and glucose pathways, retinal degeneration, neurotoxicity, oxidative damage, and immunological suppression [80,83,84]. These abnormalities can threaten individual and community viability, as cardiac and swim bladder dysfunctions reduce swimming efficiency, hindering predator evasion, feeding, and migration [81]. Visual impairment and metabolic irregularities may also manifest as lethargy and anxiety-like behaviors [84]. Delayed juvenile development can reduce competitive advantage and survival, impede sexual maturation, and affect population replenishment [82,83]. These perturbations may provoke intergenerational consequences, resulting in trophic alterations, upsetting food webs, and potentially causing population collapses [80,81].

5. Conclusions

In conclusion, this research successfully demonstrates the acute impact of the 2019 oil spill on the marine ecosystem of the Parnaiba River Delta, highlighting the differential bioaccumulation of PAHs in fish, crabs, and shellfish.
This study also reveals a potential public health risk from lingering contamination with carcinogenic PAHs, even 2 years after the event, under the projected scenario (adults weighing 60 kg, with 70 years of exposure, and a consumption range of 60 to 180 g/kg of body weight). The persistence of these compounds, even after the acute phase of the spill, underscores the critical need for long-term environmental monitoring and robust regulatory frameworks to protect seafood safety and public health in coastal areas vulnerable to both acute and chronic pollution events.
Future research should focus on continuous monitoring to track the long-term fate and effects of these PAHs. Investigating the specific metabolic pathways and bioavailability of different PAH compounds in a broader range of marine species would be crucial to better understand and model the risks to both aquatic life and human consumers. Moreover, there is a notable lack of specific health policies in Brazil addressing the risks of seafood consumption following oil spills. Establishing clear health guidelines, risk communication strategies, and rapid-response food safety protocols is essential to reduce exposure and support affected communities.

Supplementary Materials

The following supporting information can be downloaded at: https://www.mdpi.com/article/10.3390/fishes10110591/s1, Figure S1: Map delineating the regions impacted by the oil spill in 2019; Table S1: LOD and LOQ of all PAHs compounds analysed; Table S2: Polycyclic aromatic hydrocarbons (PAHs) concentration in crab, fish and shellfish from Parnaiba Delta River, Piaui, during and after the 2019 oil spill; Table S3: Table of PAHs.

Author Contributions

Conceptualization, F.H.d.S.F.; Formal analysis, P.T.d.S.M., C.G.M., R.d.S.C. and F.H.d.S.F.; Funding acquisition, J.P.M.T.; Investigation, F.H.d.S.F. and P.T.d.S.M.; Project administration, J.P.M.T.; Supervision, L.R.V.R. and J.P.M.T.; Writing—original draft, F.H.d.S.F.; Writing—review and editing, F.H.d.S.F., P.T.d.S.M., R.d.S.C. and J.P.M.T. All authors have read and agreed to the published version of the manuscript.

Funding

This work was supported by Capes (Process 009/2020).

Institutional Review Board Statement

In Brazil, our legislation allows us to analyze fish and other vertebrates by purchasing samples from fishermen, without the need for approval from an animal research ethics committee, as these are commercial products. For other species, such as mollusks and crustaceans, there is no legal requirement.

Data Availability Statement

The raw data supporting the conclusions of this article will be made available by the authors on request. Correspondence and requests for materials should be addressed to A.D.

Conflicts of Interest

Author Fabíola Helena dos Santos Fogaça and Pamella Talita da Silva Melo were employed by the company Embrapa Agroindústria de Alimentos. The remaining authors declare that this research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest.

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Fishes 10 00591 g001
Figure 1. Mean PAH profiles and alkylated compounds in crab, fish, and shellfish from the Parnaiba Delta River, Piaui, during and after the 2019 oil spill. Error bars depict the 95% confidence level around the means. Legend: naphthalene (Nap), acenaphthylene (Acy), acenaphthene (Ace), fluorine (Flu), dibenzothiophene (DBz), phenanthrene (Phe), anthracene (Ant), fluoranthene (Fla), pyrene (Pyr), benzo[a]anthracene (BaA), chrysene (Chy), benzo[b]fluoranthene (BbF), benzo[k]fluoranthene (BkF), benzo[e]pyrene (BeP), benzo[a]pyrene (BaP), perylene (Per), indeno[1,2,3-cd]pyrene (Ind), dibenz[a,h]anthracene (DahA), and benzo[ghi]perylene (BghiP).
Figure 1. Mean PAH profiles and alkylated compounds in crab, fish, and shellfish from the Parnaiba Delta River, Piaui, during and after the 2019 oil spill. Error bars depict the 95% confidence level around the means. Legend: naphthalene (Nap), acenaphthylene (Acy), acenaphthene (Ace), fluorine (Flu), dibenzothiophene (DBz), phenanthrene (Phe), anthracene (Ant), fluoranthene (Fla), pyrene (Pyr), benzo[a]anthracene (BaA), chrysene (Chy), benzo[b]fluoranthene (BbF), benzo[k]fluoranthene (BkF), benzo[e]pyrene (BeP), benzo[a]pyrene (BaP), perylene (Per), indeno[1,2,3-cd]pyrene (Ind), dibenz[a,h]anthracene (DahA), and benzo[ghi]perylene (BghiP).
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Figure 2. Percentages of PAH compounds in crab, fish, and shellfish from the Parnaiba Delta River, Piaui, during and after the 2019 oil spill.
Figure 2. Percentages of PAH compounds in crab, fish, and shellfish from the Parnaiba Delta River, Piaui, during and after the 2019 oil spill.
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Figure 3. Principal component analysis (PCA) based on PAH concentrations in crab, fish, and shellfish from the Parnaiba Delta River, Piaui, during and after the 2019 oil spill. Black: shellfish from the dry season of 2019; Gray: shellfish from the dry season of 2021; Green: crab from the rainy season of 2019; Lime: crab from the dry season of 2019; Blue: fish from the dry season of 2019; Soft blue: fish from the dry season of 2021. The red circle shows the clusters described by the PCA.
Figure 3. Principal component analysis (PCA) based on PAH concentrations in crab, fish, and shellfish from the Parnaiba Delta River, Piaui, during and after the 2019 oil spill. Black: shellfish from the dry season of 2019; Gray: shellfish from the dry season of 2021; Green: crab from the rainy season of 2019; Lime: crab from the dry season of 2019; Blue: fish from the dry season of 2019; Soft blue: fish from the dry season of 2021. The red circle shows the clusters described by the PCA.
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Figure 4. ΣPAH concentrations in crab, fish, and shellfish from the Parnaiba Delta River, Piaui, during and after the 2019 oil spill. Common lowercase letters indicate differences between the collection seasons (p < 0.05). Capital letters show differences between species (p < 0.05). Bars mean error values (95%).
Figure 4. ΣPAH concentrations in crab, fish, and shellfish from the Parnaiba Delta River, Piaui, during and after the 2019 oil spill. Common lowercase letters indicate differences between the collection seasons (p < 0.05). Capital letters show differences between species (p < 0.05). Bars mean error values (95%).
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Figure 5. Correlation of ΣPAH concentrations in crab, fish, and shellfish from the Parnaiba Delta River, Piaui, during and after the 2019 oil spill.
Figure 5. Correlation of ΣPAH concentrations in crab, fish, and shellfish from the Parnaiba Delta River, Piaui, during and after the 2019 oil spill.
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Table 1. Physiological parameters for the collected seafood samples on the Parnaiba Delta River and their effective concentrations of PAHs predicted using the optimized PBPK model.
Table 1. Physiological parameters for the collected seafood samples on the Parnaiba Delta River and their effective concentrations of PAHs predicted using the optimized PBPK model.
IDSpeciesHabitat/
Trophic Level		SeasonLength (cm)Weight (g)
ShellfishAnomalocardia brasilianaSediment
Filter		Rainy/20191.28 ± 0.264.19 ± 0.81
Dry/20192.47 ± 0.263.41 ± 1.12
Dry/20212.62 ± 2.225.91 ± 1.44
CrabUcides cordatusMangrove
Detritivore		Rainy/20196.94 + 3.74139.34 + 19.49
Dry/20197.16 + 0.31158.30 + 21.37
Dry/20216.50 + 2.64114.42 + 17.20
FishMugil curemaEstuary
Omnivore		Dry/201924.98 ± 1.77150.63 ± 29.37
Dry/202127.62 + 3.29231.80 + 79.44
Table 2. Relative potency of eight PAHs of high molecular weight.
Table 2. Relative potency of eight PAHs of high molecular weight.
PAHRP
Benzo(a)anthracene0.145
Chrysene0.0044
Benzo(b)fluoranthene0.140
Benzo(k)fluoranthene0.066
Benzo(a)pyrene1.00
Dibenz(a,h)anthracene1.11
Indeno(1,2,3-cd)pyrene0.232
Benzo(g,h,i)perylene0.022
Adapted from [52].
Table 3. Toxicity equivalent concentration of PAHs in crab, fish, and shellfish from the Parnaiba Delta River, Piaui, during and after the 2019 oil spill.
Table 3. Toxicity equivalent concentration of PAHs in crab, fish, and shellfish from the Parnaiba Delta River, Piaui, during and after the 2019 oil spill.
PAHsTEFBapTEQ Average (mg/kg)
20192021
CrabFishShellfishFishShellfish
Nap0.00114.8379.6472.36308.6644.01
Ace0.001008.731.301.80
Acy0.001001.610.860
Flu0.001004.467.109.67
Phe0.00100105.985.4541.00
Ant0.0100034.524.7339.14
Fla0.00100160.721.071.74
Pyr0.0012.962.960017.50
BaA0.100000021.20
Chy0.010008.25074.99
BbF0.100003.781.390
BkF0.1000000.961.44
BaP1.000001.343.651.61
Ind0.10003.3710.191.342.98
DahA1.0003.3705.210.913.64
BghiP0.1000013.6300
Legend: naphthalene (Nap), acenaphthene (Ace), acenaphthylene (Acy), fluorine (Flu), phenanthrene (Phe), anthracene (Ant), fluoranthene (Fla), pyrene (Pyr), benzo[a]anthracene (BaA), chrysene (Chy), benzo[b]fluoranthene (BbF), benzo[k]fluoranthene (BkF), benzo[e]pyrene (BeP), benzo[a]pyrene (BaP), indeno[1,2,3-cd]pyrene (Ind), dibenz[a,h]anthracene (DahA), and benzo[ghi]perylene (BghiP).
Table 4. Polycyclic aromatic hydrocarbons (PAHs) concentration in crab, fish, and shellfish from the Parnaiba Delta River, Piaui, during and after the 2019 oil spill.
Table 4. Polycyclic aromatic hydrocarbons (PAHs) concentration in crab, fish, and shellfish from the Parnaiba Delta River, Piaui, during and after the 2019 oil spill.
PAHsLOC *LOC (ng/g ww)
20192021
CrabFishShellfishFishShellfish
Non-carcinogenic
Nap66709445819315318
Ace20,00000160335887762
Acy-00869754080
Flu13,3300031416571448
Phe-00132856341
Ant100,00000409836
Fla13,330008743528055
Pyr10,0004735157800800
Carcinogenic
BaA4100006
Chy136400169018
BbF430037330
BkF910004897
BaP6001018
Ind5013143847
DahA2600354
BghiP273001000
* Levels of concern (LOC) set for oil-impacted areas in Brazil [52]. The values expressed are average. Legend: naphthalene (Nap), acenaphthene (Ace), acenaphthylene (Acy), fluorine (Flu), phenanthrene (Phe), anthracene (Ant), fluoranthene (Fla), pyrene (Pyr), benzo[a]anthracene (BaA), chrysene (Chy), benzo[b]fluoranthene (BbF), benzo[k]fluoranthene (BkF), benzo[e]pyrene (BeP), benzo[a]pyrene (BaP), indene[1,2,3-cd]pyrene (Ind), dibenz[a,h]anthracene (DahA), and benzo[ghi]perylene (BghiP). Bold letters show values above the established safe limit.
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Fogaça, F.H.d.S.; Melo, P.T.d.S.; Massone, C.G.; Carreira, R.d.S.; Ramos, L.R.V.; Torres, J.P.M. Polycyclic Aromatic Hydrocarbons in Seafood: Occurrence, Trophic Bioaccumulation, and Human Health Risks. Fishes 2025, 10, 591. https://doi.org/10.3390/fishes10110591

AMA Style

Fogaça FHdS, Melo PTdS, Massone CG, Carreira RdS, Ramos LRV, Torres JPM. Polycyclic Aromatic Hydrocarbons in Seafood: Occurrence, Trophic Bioaccumulation, and Human Health Risks. Fishes. 2025; 10(11):591. https://doi.org/10.3390/fishes10110591

Chicago/Turabian Style

Fogaça, Fabíola Helena dos Santos, Pamella Talita da Silva Melo, Carlos German Massone, Renato da Silva Carreira, Leonardo Rocha Vidal Ramos, and João Paulo Machado Torres. 2025. "Polycyclic Aromatic Hydrocarbons in Seafood: Occurrence, Trophic Bioaccumulation, and Human Health Risks" Fishes 10, no. 11: 591. https://doi.org/10.3390/fishes10110591

APA Style

Fogaça, F. H. d. S., Melo, P. T. d. S., Massone, C. G., Carreira, R. d. S., Ramos, L. R. V., & Torres, J. P. M. (2025). Polycyclic Aromatic Hydrocarbons in Seafood: Occurrence, Trophic Bioaccumulation, and Human Health Risks. Fishes, 10(11), 591. https://doi.org/10.3390/fishes10110591

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