High Molecular Weight Polycyclic Aromatic Hydrocarbons Research Articles

Fine-tuning an aromatic ring-hydroxylating oxygenase to degrade high molecular weight polycyclic aromatic hydrocarbon

Rieske nonheme iron aromatic ring-hydroxylating oxygenases (RHOs) play pivotal roles in determining the substrate preferences of polycyclic aromatic hydrocarbon (PAH) degraders. However, their potential to degrade high molecular weight PAHs (HMW-PAHs) has been relatively unexplored. NarA2B2 is an RHO derived from a thermophilic Hydrogenibacillus sp. strain N12. In this study, we have identified four “hotspot” residues (V236, Y300, W316, and L375) that may hinder the catalytic capacity of NarA2B2 when it comes to HMW-PAHs. By employing structure-guided rational enzyme engineering, we successfully modified NarA2B2, resulting in NarA2B2 variants capable of catalyzing the degradation of six different types of HMW-PAHs, including pyrene, fluoranthene, chrysene, benzo[a]anthracene, benzo[b]fluoranthene, and benzo[a]pyrene. Three representative variants, NarA2B2W316I, NarA2B2Y300F-W316I, and NarA2B2V236A-W316I-L375F, not only maintain their abilities to degrade low molecular weight PAHs (LMW-PAHs), but also exhibited 2-4 times higher degradation efficiency for HMW-PAHs in comparison to another isozyme, NarAaAb. Computational analysis of the NarA2B2 variants predict that these modifications altering the size and hydrophobicity of the active site pocket making it more suitable for HMW-PAHs. These findings provide a comprehensive understanding of the relationship between three-dimensional structure and functionality, thereby opening up possibilities for designing improved RHOs that can be more effectively used in the bioremediation of PAHs.

Evaluation of historical data on persistent organic pollutants and heavy metals in Lake Baikal: Implications for accumulation in marine environments

Lake Baikal, the largest freshwater lake by volume, provides drinking water and aquatic food supplies to over 2.5 million people. However, the lake has been contaminated with recalcitrant pollutants released from surrounding industrial complexes, agriculture, and natural lands, thereby increasing the risk of their bioaccumulation in fish and seals. Yet, a collective analysis of historical concentration data and their bioaccumulation potential as well as what factors drive their accumulation in fish or seals remains largely unknown. We analyzed concentration data from 42 studies collected between 1985 and 2019 in water, sediment, fish, and seals of Lake Baikal. Heavy metals had the highest concentrations in water and biota followed closely by polycyclic aromatic hydrocarbons (PAHs) and organochlorines. Among organochlorines, polychlorinated biphenyls (PCBs) showed the highest levels in water, surpassing hexachlorocyclohexane (HCH) concentrations, particularly after normalizing to solubility. While naphthalene and phenanthrene exhibited the highest average concentrations among polycyclic aromatic hydrocarbons (PAHs), their relative concentrations significantly decreased upon solubility normalization. The analysis confirmed that bioconcentration and biomagnification of organochlorine pesticides, PCBs, PAHs, and heavy metals depend primarily on source strength to drive their concentration in water and secondarily on their chemical characteristics as evidenced by the higher concentrations of low-solubility PCBs and high molecular weight PAHs in water and sediment. The differential biomagnification patterns of Cu, Hg, and Zn compared to Pb are attributed to their distinct sources and bioavailability, with Cu, Hg, and Zn showing more pronounced biomagnification due to prolonged industrial release, in contrast to the declining Pb levels. Dibenzo-p-dioxins were detected in sediment and seals, but not in water or fish compartments. These data highlight the importance of addressing even low concentrations of organic and inorganic pollutants and the need for more consistent and frequent monitoring to ensure the future usability of this and other similar essential natural resources.

Lagging pollution of polycyclic aromatic hydrocarbons in the rebuilt e-waste site: From the perspective of characteristics, sources, and risk assessment

Little information is known regarding how the lagged pollution of polycyclic aromatic hydrocarbon (PAH) influenced the environment and human health after an e-waste dismantling site was rebuilt. This study investigated the characteristics, sources, and risk assessment of PAHs in a rebuilt e-waste site and its surrounding farmland by analyzing the samples of soil, dust, water, and vegetable. Concentrations of PAHs in soil, vegetable and water in the rebuilt site were relatively higher than in its surrounding farmland. The concentrations in surface soils, soil columns, dust, vegetables, and water varied from 55.4 to 3990 ng g−1, 1.65 to 5060 ng g−1, 2190 to 2420 ng g−1, 2670 to 10,300 ng g−1, and 46.8 to 110 μg L−1 in the e-waste site, respectively. On the farmland, PAH concentrations in surface soils, vegetables, and water ranged from 41.5 to 2760 ng g−1, 506 to 7640 ng g−1, and 56.6 to 89.2 μg L−1, respectively. A higher proportion of high-molecular-weight PAHs (HMW-PAHs) appeared in all multimedia compared with low-molecular-weight PAHs (LMW-PAHs). Diagnostic ratio together with positive matrix factorization (PMF) revealed that vehicle emission was the primary source in this area, and the activity of e-waste disposal was another important source in the rebuilt e-waste site. Based on the deterministic health risks, people working in the reconstructed e-waste site were exposed to low risks, whereas the residents living near the surrounding farmland were exposed to low risk. Sensitivity analyses indicated that exposure frequency and PAH concentrations were the main factors that influenced exposure risk. This study provides valuable insight into the comprehension of the lagging pollution effects of PAH on the environment and human health after the e-waste site was rebuilt.

Seasonal variation and concentration of PAHs in Lake Balaton sediment: A study on molecular weight distribution and sources of pollution

The temporal and spatial variations of 16 Polycyclic Aromatic Hydrocarbons (PAHs) were examined at multiple sites around Lake Balaton from February 2023 to January 2024. The results indicated that the concentrations of PAHs in sediment were high during the winter months, 448.35 to 619.77 ng/g dry weight, and low during the summer months, 257.21 to 465.49 ng/g dry weight. The concentration of high molecular weight PAHs (HMWPAHs), consisting of 5–6 rings, was greater than that of low molecular weight PAHs (LMWPAHs), which had 2–3 rings. The total incremental lifetime cancer risk (ILCR) for both dermal and ingestion pathways was high for both adults and children during the four seasons, with the highest records as the following: winter > spring > summer > autumn. The ecological effects of the 16 PAHs were negligible except for acenaphthylene (Acy) and fluorene (Fl), which displayed slightly higher concentrations during the autumn and spring, respectively.

Performance evaluation of four sampling techniques and source apportionment for the atmospheric deposition fluxes of polycyclic aromatic hydrocarbons

Polycyclic aromatic hydrocarbons (PAHs) are primarily emitted into the atmosphere through anthropogenic activities and can be transported to receptor sites at varying distances. In this study, the atmospheric PAH deposition was investigated using a dry deposition plate (DDP) with Mylar, a dry deposition disk (DDD) with Velcro, a resin bulk deposition sampler (Resin-BDS), and a water bulk deposition sampler (Water-BDS) in Ulsan, South Korea, during May–October 2013. Additionally, ambient PAH concentrations were monitored using high-volume air samplers. The mean deposition fluxes of Σ13 PAHs were 8.62 ± 1.44, 36.9 ± 6.81, 56.9 ± 9.74, and 63.8 ± 8.04 μg/m2/d for the DDP, DDD, Resin-BDS, and Water-BDS, respectively. The DDD was more effective than the DDP because it could collect high molecular weight (HMW) PAHs from dry deposition, which are more toxic than low molecular weight PAHs. The Water-BDS had the highest fluxes of Σ13 PAHs; however, the Resin-BDS may be more suitable for collecting HMW PAHs from both dry and wet deposition due to relatively constant values for the deposition velocity of PAHs. Furthermore, the PAH fluxes in the Resin-BDS samples were significantly positively correlated with the gaseous and total (gaseous + particulate) concentrations of ambient PAHs. Hence, the fluxes obtained by the Resin-BDS were further used to apply principal component analysis, multiple linear regression, and backward air trajectory simultaneously to identify the emission sources of the deposited PAHs. The results indicate that the combustion of fossil fuels and biomass was the major source. In particular, the industrial complexes using petroleum and coal on the city's east coast and vehicular exhausts were the main local sources. Meanwhile, long-range sources may be forest fires, harbors, and industrial activities in nearby countries. Our study suggests that BDS, considering both dry and wet deposition, can be selectively used for research on PAH deposition.

Sources, gas-particle distribution and health risks of atmospheric PAHs in two typical basin cities in China

The sources of polycyclic aromatic hydrocarbons (PAHs) in the atmosphere of various cities are highly intricate. Conducting research on the pollution characteristics of different types of PAHs in cities will help to focus on solving air pollution problems based on urban characteristics. Polycyclic aromatic hydrocarbons (PAHs) in the PM2.5-bound state and gas-phase were analyzed in the winter atmosphere of Yuncheng and Nanyang, China, to determine their pollution and spatial characteristics. The results revealed that in Yuncheng, the average concentrations of these 16 PAHs were 129.83 ± 96.63 ng m−3 in the PM2.5-bound form and 168.05 ± 88.64 ng m−3 in the gas phase, surpassing those observed in Nanyang, where the averages were 66.53 ± 32.49 ng m−3 and 112.80 ± 65.90 ng m−3 for particulate and gas phases, respectively. Gaseous samples primarily contained low molecular weight PAHs, while medium and high molecular weight PAHs were more prevalent in particulate samples. The linear relationship between the gas-particle partition coefficient (logKP) and the gas partition coefficient (PL0) and KOA value of PAHs in both cities suggested that during winter, PAHs in Yuncheng and Nanyang predominantly adsorb onto particles, failing to achieve gas-particle equilibrium. Source analysis using positive matrix factorization (PMF) identified coal combustion (26.4%–41.9%), biomass combustion (26.3%–29.6%), motor vehicle emissions (16.3%–30.4%), and evaporation sources (15.8%–26.9%) as the primary sources of atmospheric PAHs in both cities. Potential source contribution function (PSCF) and concentration-weighted trajectory (CWT) analyses indicated that pollutants originating from the northwest direction and near-earth air masses exerted a substantial influence on both cities. According to health risk assessments, both Yuncheng City and Nanyang City exhibited a certain risk of cancer due to atmospheric PAH exposure. However, the risk of cancer was higher in Yuncheng City compared to Nanyang City. The research results uncover the pollution characteristics and primary sources of polycyclic aromatic hydrocarbons (PAHs) in different types of urban air. It emphasizes the substantial contribution of local pollution sources to atmospheric PAHs and emphasizes the necessity of prioritizing control measures.

Novel insights into the synergetic degradation of pyrene by microbial communities from mangroves in China

Pyrene is a high molecular weight polycyclic aromatic hydrocarbon (HMW-PAHs). It is a ubiquitous, persistent, and carcinogenic environmental contaminant that has raised concern worldwide. This research explored synergistic bacterial communities for efficient pyrene degradation in seven typical Southern China mangroves. The bacterial communities of seven typical mangroves were enriched by pyrene, and enriched bacterial communities showed an excellent pyrene degradation capacity of > 95% (except for HK mangrove and ZJ mangrove). Devosia, Hyphomicrobium, Flavobacterium, Marinobacter, Algoriphahus, and Youhaiella all have significant positive correlations with pyrene (R>0, p < 0.05) by 16SrRNA gene sequencing and metagenomics analysis, indicated that these genera play a vital role in pyrene metabolism. Meanwhile, the functional genes were involved in pyrene degradation that was enriched in the bacterial communities, including the genes of nagAa, ndoR, pcaG, etc. Furthermore, the analyses of functional genes and binning genomes demonstrated that some bacterial communities as a unique teamwork to cooperatively participate in pyrene degradation. Interestingly, the genes related to biogeochemical cycles were enriched, such as narG , soxA, and cyxJ, suggested that bacterial communities were also helpful in maintaining the stability of the ecological environment. In addition, some novel species with pyrene-degradation potential were identified in the pyrene-degrading bacterial communities, which can enrich the resource pool of pyrene-degrading strains. Overall, this study will help develop further research strategies for pollutant removal.

A novel mycelial pellet applied to remove polycyclic aromatic hydrocarbons: High adsorption performance & its mechanisms

Mycelial pellets formed by Penicillium thomii ZJJ were applied as efficient biosorbents for the removal of polycyclic aromatic hydrocarbons (PAHs), which are a type of ubiquitous harmful hydrophobic pollutants. The live mycelial pellets were able to remove 93.48 % of pyrene at a concentration of 100 mg/L within 48 h, demonstrating a maximum adsorption capacity of 285.63 mg/g. Meanwhile, the heat-killed one also achieved a removal rate of 65.01 %. Among the six typical PAHs (pyrene, phenanthrene, fluorene, anthracene, fluoranthene, benzo[a]pyrene), the mycelial pellets preferentially adsorbed the high molecular weight PAHs, which also have higher toxicity, resulting in higher removal efficiency. The experimental results showed that the biosorption of mycelial pellets was mainly a spontaneous physical adsorption process that occurred as a monolayer on a homogeneous surface, with mass transfer being the key rate-limiting step. The main adsorption sites on the surface of mycelia were carboxyl and N-containing groups. Extracellular polymeric substances (EPS) produced by mycelial pellets could enhance adsorption, and its coupling with dead mycelia could achieve basically the same removal effect to that of living one. It can be concluded that biosorption by mycelial pellets occurred due to the influence of electrostatic and hydrophobic interactions, consisting of five steps. Furthermore, the potential applicability of mycelial pellets has been investigated considering diverse factors. The mycelia showed high environmental tolerance, which could effectively remove pyrene across a wide range of pH and salt concentration. And pellets diameters and humic acid concentration had a significant effect on microbial adsorption effect. Based on a cost-effectiveness analysis, mycelium pellets were found to be a low-cost adsorbent. The research outcomes facilitate a thorough comprehension of the adsorption process of pyrene by mycelial pellets and their relevant applications, proposing a cost-effective method without potential environmental issues (heat-killed mycelial pellets plus EPS) to removal PAHs.

Dermal absorption of high molecular weight parent and alkylated polycyclic aromatic hydrocarbons from manufactured gas plant soils using in vitro assessment

An enhanced in vitro human dermal bioavailability method was developed to measure the release of twenty parent and seven alkylated high molecular weight (HMW) polycyclic aromatic hydrocarbons (PAHs) from contaminated soils collected from five former manufactured Gas Plants (MGP) in England. GC-MS/MS was used to quantify HMW PAHs in soil, Strat-M artificial membrane representing skin, and synthetic receptor solution (RS) representing systemic circulation at 1-h, 10-h, and 24-h timesteps. Fluoranthene and pyrene exhibited the highest fluxes from soils to membrane (ranging from 9.5 - 281 ng/cm2/h) and soil to RS (<LOQ to 16.9 ng/cm2/h). Chrysene, benzo[a]anthracene, benzo[b]fluoranthene and the alkylated C1-fluoranthene/pyrene homologue series demonstrated fluxes higher than other HMW PAHs. The dermal fluxes were generally lower than those reported in previous investigations and suggests that dermal absorption varies between both HMW parent and alkylated PAHs and individual PAHs. The utilisation of real-world contaminated soils allowed for a more realistic representation; this is important because current risk assessment guidance is baseed on results from experiments that used artificially spiked soils. This research shows that the the ranges of dermal fluxes are PAH dependent and impact the mass of absorbed from soil after dermal exposure and therefore the potential risk contaminated soil poses to human health.

Formation and biotoxicity of environmentally persistent free radicals in steelworks soil under thermal treatment

Thermal treatment are commonly used to address organic contaminated soils. In particular, the pyrolysis of organic substances can result in the creation of environmentally persistent free radicals (EPFRs). We investigated a steelworks site in Chongqing (China) to observe changes in EPFRs before and after thermal treatment. Our findings revealed that the EPFRs were carbon-centered radicals with a g-factor < 2.0030 and a spin density ranging from n.d.–5.23 × 1015 spins/mg. The formation of EPFRs was driving by polycyclic aromatic hydrocarbons (PAHs), Mn, Cu, and total organic carbon (TOC). Following the thermal treatment, the spin densities of EPFRs increased by a factor of 0.25 to 1.81, with maximum levels reached at 300 °C. High molecular weight PAHs exhibited high heat capacity, enabling the generation of more EPFRs. The thermal decay of EPFRs occurred in two stages, with the shortest 1/e lifetime lasting up to 16.8 h. Raising the temperature or prolonging time can significantly reduce EPFRs levels. Thermal treatment increased the generation of EPFRs, hydroxyl radicals (•OH) and superoxide radical (•O2–), leading to a decrease in bacterial luminescence. Specifically, •OH contributed to approximately 73% of the B. brilliantus inhibition. Our results highlight that the thermal treatment significantly enhance EPFRs concentrations, and the treated soil remained ecologically risky. The knowledge of the formation of EPFRs and their biotoxicity is shedding new light on the thermal treatment risk management.

Biochars assisted phytoremediation of polycyclic aromatic hydrocarbons contaminated agricultural soil: Dynamic responses of functional genes and microbial community

A biochar-intensified phytoremediation experiment was designed to investigate the dynamic effects of different biochars on polycyclic aromatic hydrocarbon (PAH) removal in ryegrass rhizosphere contaminated soil. Maize and wheat straw biochar pyrolyzed at 300 °C and 500 °C were amended into PAH-contaminated soil, and then ryegrass (Lolium multiflorum L.) was planted for 90 days. Spearman's correlations among PAH removal, enzyme activity, abundance of PAH-ring hydroxylating dioxygenase (PAH-RHDα), and fungal and bacterial community structure were analyzed to elucidate the microbial degradation mechanisms during the combined remediation process. The results showed that 500 °C wheat straw biochar had higher surface area and more nutrients, and significantly accelerated the phytoremediation of PAHs (62.5 %), especially for high molecular weight PAH in contaminated soil. The activities of urease and dehydrogenase and the abundance of total and PAH-degrading bacteria, which improved with time by biochar and ryegrass, had a positive correlation with the removal rate of PAHs. Biochar enhanced the abundance of gram-negative (GN) PAH-RHDα genes. The GN PAH-degraders, Sphingomonas, bacteriap25, Haliangium, and Dongia may play vital roles in PAH degradation in biochar-amended rhizosphere soils. Principal coordinate analysis indicated that biochar led to significant differences in fungal community structures before 30 days, while the diversity of the bacterial community composition depended on planting ryegrass after 60 days. These findings imply that the structural reshaping of microbial communities results from incubation time and the selection of biochar and ryegrass in PAH-contaminated soils. Applying 500 °C wheat straw biochar could enhance the rhizoremediation of PAH-contaminated soil and benefit the soil microbial ecology.

Variations of the atmospheric polycyclic aromatic hydrocarbon concentrations, sources, and health risk and the direct medical costs of lung cancer around the Bohai Sea against a background of pollution prevention and control in China

Abstract. The Bohai Sea (BS) region, an area of China that is severely polluted with atmospheric polycyclic aromatic hydrocarbons (PAHs), has received wide attention in recent decades. To characterize the variations of the concentrations and sources of PAHs from June 2014 to May 2019, 15 PAH congeners (Σ15PAHs) were measured in atmospheric samples (N = 228) collected at 12 sites around the BS, and the health risk and direct medical costs associated with lung cancer caused by exposure to PAHs were also estimated. The annual daily average concentration of Σ15PAHs was 56.78 ± 4.75 ng m−3, which was dominated by low molecular weight PAHs (LMW-PAHs) containing three rings (58.7 ± 7.8 %). During the 5-year sampling period, the atmospheric Σ15PAHs concentration reduced by 17.5 % for the whole BS region, with an especially large drop of 51.7 % observed in the tightly controlled area of Tianjin (TJ), which was mainly due to a decrease in the concentration of high molecular weight PAHs (HMW-PAHs) containing five or six rings. Generally, the concentration of Σ15PAHs was highest in winter and lowest in summer, which can mainly be attributed to the change in LMW-PAH concentration. Based on the positive matrix factorization (PMF) model, PAHs in the BS region were mainly ascribed to coal combustion and biomass burning. The PAH contributions of coal combustion and motor vehicles showed different trends for the BS region (PAHs from coal combustion rose by 7.2 % and PAHs from motor vehicles fell by 22.4 %) and for TJ (PAHs from coal combustion fell by 12.6 % and PAHs from motor vehicles rose by 6.9 %). The incidence of lung cancer (ILCR) caused by exposure to atmospheric PAHs decreased by 74.1 % and 91.6 % from 2014 to 2018 in the BS region and in TJ, respectively. This was mainly due to the decrease in the concentration of highly toxic HMW-PAHs and was reflected in USD 10.7 million of savings in direct medical costs of lung cancer caused by exposure to PAHs, which represent a decrease of 46.1 % compared to the corresponding costs before air pollution prevention and control was implemented around the BS. There was an even higher reduction in medical costs of 54.5 % in TJ. Hence, this study proves that implementing pollution prevention and control not only effectively reduced the concentration of pollutants and the risks caused by them, but it also significantly reduced the medical costs of diseases caused by the corresponding exposure.

Assessment of particulate PAHs toxicity from alcohol-diesel blends fuelled high compression ratio CI engine

Transport and power generation applications will play an important role in current and next-generation compression ignition (CI) engines. Methanol, ethanol, and butanol have emerged as potential alternative fuels for internal combustion engines capable of reducing overall greenhouse gases (GHG) and pollutant emissions. This study deals with the morphological characterization of particulate matter (PM) and toxicity assessment of polycyclic aromatic hydrocarbons (PAHs) for methanol, ethanol and butanol blending with diesel, and provides new findings and results in the specific literature. It defines new limits of alcohol fractions in diesel blends for their applications in CI engines. For the experimental assessment, a single-cylinder CI engine was used with an increased compression ratio (CR) from 17.5 to 26. Alcohol fraction of 20% (v/v) in diesel reduced the PM emissions in the range of 29–38% than diesel. PM was further reduced, up to ∼50%, for higher ethanol and butanol fractions (∼50%), and the soot morphological characteristics exhibit smaller particle sizes (400–600 nm) than diesel (up to 2 μm). Moreover, 20% of alcohol fraction led to a 34–60% reduction in PAHs. The toxicity evaluation of the tested alcohol-diesel blend indicates that high molecular weight PAHs and nitro-PAHs are the main contributors to the overall toxicity. Benzo[a]pyrene and dibenzo-anthracene were the prominent PAHs. Increasing the alcohol blend ratio significantly reduced the toxicity potential, ranging from 20 to 67%.

Polycyclic aromatic hydrocarbons in coastal rivers in Jiangsu Province, China: Spatial distribution, source apportionment and human impacts

The ocean is the ultimate sink for all pollutants, rivers are important channels for land-based pollutants to enter the oceans. Riverine transport of polycyclic aromatic hydrocarbons (PAHs) to coastal seas in China poses environmental threats. This study examined the spatial and temporal distribution of PAHs in coastal rivers in Yancheng City in Jiangsu Province of China, with the aim of identifying their likely sources, concentrations, and influencing factors. Surface sediments were taken from the Xinyanggang River (XYR) and the Sheyang River (SYR). The concentrations of Ʃ16PAHs in river sediments were measured on average 477.05 ng/g dry weight (dw), with values varying from 2.18 to 6351.42 ng/g, indicating a moderate pollution level, with a dominance of high molecular weight (HMW) PAHs. The XYR exhibited significantly higher PAHs concentrations compared to the SYR. The key sources of PAHs were vehicle emissions (47.87%), coal and natural gas combustion (35.07%). Geographically weighted regression and redundancy analysis linked PAHs pollution to distinct land use patterns and socioeconomic indicators, highlighting urban land as the major contributor, driven by high urbanization and industrialization (70.91%). In XYR, industrial activities and transport emissions were major contributors, while in SYR, agricultural activities predominantly influenced PAHs pollution. Urgent mitigation strategies are needed to reduce PAHs pollution in river sediments, mitigating ecological and human risks associated with these contaminants.

Hydrocarbon-based parameters for the identification of oil contamination in an area with brown coal mining: Emphasis on pyrogenic index and alkylated PAHs

The aim of the study was to propose hydrocarbon-based parameters that can ben used to identify oil derived contamination in an area with a long-term load of coal mining industry. Aliphatic hydrocarbons and PAHs have been quantified for bottom sediments in the Bílina River, Czechia. Presented data demonstrate that all river sediments are highly contaminated with PAHs. The results showed that the distribution of PAHs was not possible to interpret by using the standard evaluation due to multisource long-term sedimentation of petroleum by-products, coal tars, and accidents of processing industry in the river system. The presence of petroleum derived hydrocarbons has been initially screened by the bulk parameter TEH and confirmed by the occurrence of steranes, hopanes and the unresolved complex mixture (UCM) in the chromatograms. The identification of the biomarkers 25-Norhopane and Gammacerane point out onsite microbial degradation of parent hydrocarbon compounds. The interpretation of the ratios Fl/Py, An/P, BaAn/Ch were not decisive to prove petrogenic origin of PAHs in the river sediments. However, using the combined evaluation of TEH together with the ratio of low molecular over high molecular weight PAHs, pyrogenic index and the presence of specific oil derived biomarkers allowed to prove the presence of petroleum contamination. Environmental implicationDue to oil spill accidents and intensive coal mining over the years, polycyclic aromatic hydrocarbons (PAHs) have been present in extreme amounts in bottom sediments of a tributary of the Elbe River, so called the Bílina River. Due to its hydrophobic and carcinogenic character, mutual understanding of the fate of alkylated PAHs homologues are usually overlooked within EPA PAHs 16 monitoring programme. This study pays attention to alkylated PAHs homologues and conventional diagnostic ratios when identifying oil derived contamination.

Removal of PAHs in paddy fields: How natural periphytic biofilm enhances the removal process and the mechanisms involved

Previous studies on the removal of polycyclic aromatic hydrocarbons (PAHs) from farmland have mostly relied on anthropogenic biotic or abiotic amendments. Here, an indigenous paddy periphytic biofilm (PB) composed of complex symbolic communities was enriched, and its essential role, as well as the potential mechanisms of PAHs dissipation, was investigated. A pot experiment revealed that PB achieved 92.87% and 92.76% removal of the USEPA priority PAHs from the overlying water and soil of a heavily PAHs-contaminated paddy field, respectively. This subsequently decreased ΣPAHs accumulation in rice shoots to 4.12 ± 1.08 ng g-1, under the thresholds based on food safety standards. The physiology of PB in an aquatic culture with PAHs was assessed to understand the toxicity and removal mechanism. Extracellular polymeric substances (EPS) adsorption occurred in the early stage, followed by late biodegradation, which was considered the primary mechanism for removing PAHs. In this process, the PB contributed more to the high molecular weight PAHs compared to the low molecular weight. Furthermore, 16S-rRNA sequencing demonstrated specific functional phyla (Proteobacteria, Ascomycota, and Chloroplastida) with significantly higher relative abundances in periphytic communities with PAHs, which facilitated PAHs degradation. The predicted synergetic metabolic pathway involved 33 PAHs-degrading genes as inferred by PICRUSt. These findings suggest that PB could provide a promising strategy for target PAHs remediation in situ and food safety in contaminated paddy fields.

A 150 years record of polycyclic aromatic compounds in the Sihailongwan Maar Lake, Northeast China: impacts of socio-economic developments and pollution control.

The geochemical composition of sediment cores can serve as a proxy for reconstructing past human and nature-driven environmental and climatic changes. We investigated the temporal variation in the concentrations and fluxes of polycyclic aromatic compounds (PACs) which include polycyclic aromatic hydrocarbons (PAHs), oxygenated PAHs, and azaarenes in the Sihailongwan Maar Lake and found that they remained low before 1950. The PAC concentrations and fluxes increased substantially since 1950, which was in good agreement with the fast socio-economic development, industrialization, and associated growth in fossil fuel consumption in China, particularly since the 1980s. After 2010, the PAC fluxes decreased, which was consistent with the implementation of air pollution control policies in China at that time. The concentration ratios of the sums of low to high molecular weight PAHs (LMW-PAHs/HMW-PAHs), benzo[e]pyrene/benzo[a]pyrene, and benzo[a]anthracene-7,12-dione/benzo[a]anthracene all decreased from bottom to top of the sediment core, reflecting the rapidly increasing contribution of emissions derived from high-temperature fossil fuel combustion (energy, transport and industry) to the PAC emissions in recent times at the expense of biomass burning. In addition, these data reflect the increasing local sources of PACs in more recent times because of the enhanced human activities in the area surrounding the Maar lake. Our results demonstrate that PAC fluxes and concentrations in sediment cores reflect the regional and national economic development and the efficiency of pollution control measures.

The occurrence characteristics, removal efficiency, and risk assessment of polycyclic aromatic hydrocarbons in sewage sludges from across China

Sewage sludge is considered to be an important sink for polycyclic aromatic hydrocarbons (PAHs) in wastewater treatment plants and the potential risks from sludge contaminated with PAHs during land application has attracted attention. To identify the priority PAHs for control and enhance their removal from sludge, the occurrence characteristics, removal efficiency, and risk assessment of PAHs in sewage sludges from across China were analyzed. Data collection was from 2001 to 2023. Results showed that 16 PAHs were widely detected in Chinese sewage sludge with total amounts (∑16PAHs) between 0.06 and 34.93 mg kg dw−1. Fossil fuel, coal, and biomass combustion are main anthropogenic sources of PAHs in China. In general, phenanthrene (PHE), anthracene (ANT), fluorescein (FL), chrysene (CHR), pyrene (PYR), and benzo[b]fluoranthene (BbF) are regarded as the main components and PAHs with 3–5 rings dominate (84.01%–91.53%) sewage sludge in China. Although aerobic composting and anaerobic treatment significantly improve ∑16PAHs removal, sludge stabilization treatment only reduced the risk by a small amount, especially for high-molecular-weight (HMW) PAHs. The benzo[a]anthracene (BaA), benzo[a]pyrene (BaP), and dibenzo[a,h]anthracene (DahA) are proposed as the priority control contaminants for sewage sludge in China because they have consistently high-risk quotient (RQ) values of 2.42–7.47, 1.28–3.16, 1.06–1.83 before and after sludge stabilization, respectively. More attention should be paid to BaA, BbF, benzo[k]fluoranthene (BkF), BaP, DahA, and indeno[1,2,3-cd]pyrene (IcdP) in Beijing; ANT, BaA, and BaP in Shanghai; and BaA and BaP in Guanghzou. Although the toxic equivalent quotient (TEQ) for PAHs met the limit concentration requirements of the national standard, the potential health risks due to long-term exposure to HMW PAHs cannot be ignored because the incremental lifetime cancer risk (ILCR) was consistently in the risk threshold range (>1 × 10−6). Some suggestions on enhanced treatment approaches and land use standards are proposed to further alleviate the risk from HMW PAHs.

Assessing the ecological impacts of polycyclic aromatic hydrocarbons petroleum pollutants using a network toxicity model

Polycyclic aromatic hydrocarbons (PAHs) are significant petroleum pollutants that have long-term impacts on human health and ecosystems. However, assessing their toxicity presents challenges due to factors such as cost, time, and the need for comprehensive multi-component analysis methods. In this study, we utilized network toxicity models, enrichment analysis, and molecular docking to analyze the toxicity mechanisms of PAHs at different levels: compounds, target genes, pathways, and species. Additionally, we used the maximum acceptable concentration (MAC) value and risk quotient (RQ) as an indicator for the potential ecological risk assessment of PAHs. The results showed that higher molecular weight PAHs had increased lipophilicity and higher toxicity. Benzo[a]pyrene and Fluoranthene were identified as core compounds, which increased the risk of cancer by affecting core target genes such as CCND1 in the human body, thereby influencing signal transduction and the immune system. In terms of biological species, PAHs had a greater toxic impact on aquatic organisms compared to terrestrial organisms. High molecular weight PAHs had lower effective concentrations on biological species, and the ecological risk was higher in the Yellow River Delta region. This research highlights the potential application of network toxicity models in understanding the toxicity mechanisms and species toxicity of PAHs and provides valuable insights for monitoring, prevention, and ecological risk assessment of these pollutants.

Air‐Sea Gas Exchange and Its Potential Influence on the Regional Fate of Polycyclic Aromatic Hydrocarbons in the East China Marginal Sea

AbstractTo investigate the air‐sea gas exchange and its potential influence on the regional fate of polycyclic aromatic hydrocarbons (PAHs) in the East China Marginal Seas (ECMS), which consist of the East China Sea (ECS) and Yellow Sea (YS), we collected air and surface seawater samples of this area in the summer 2018 and winter 2019, respectively. Generally, PAHs underwent a strong volatilization process in the ECMS in both summer and winter. Good correlations between wind speed and the magnitude of air‐sea gas exchange were found for low molecular weight PAHs, suggesting the rate of their air‐sea gas exchange was influenced by the static stability of overlying atmosphere. However, such an influence for high molecular weight PAHs was constrained by their low Henry's law constant. Dissolved concentration of PAHs in surface seawater was another key factor regulating their air‐sea gas exchange, which not only influenced the rate of air‐sea gas exchange but also was involved in the exchange direction. Higher air‐sea gas exchange fluxes of PAHs in winter were attributed to their increasing dissolved concentrations in seawater during this season. A mass conservation analysis revealed a huge volatilization loss of PAHs from seawater to atmosphere, suggesting air‐sea gas exchange might be a key process to modulate the distribution and occurrence of PAHs in the ECS and YS. Such a loss of PAHs in seawater might be compensated by the sediment resuspension, which implied that the sedimentary deposit could serve as a secondary source of PAHs in seawater and overlying atmosphere.