Polycyclic Aromatic Compounds Research Articles

Oil sands process-affected water composition effect on Henry's law constants for polycyclic aromatic compounds: Theory and experiment

Oil sands process-affected water (OSPW) is a source of atmospheric emission for polycyclic aromatic compounds (PACs), compounds known to have toxic effects on humans. Estimating emissions and assessing the chemical fate of PACs requires measured or predicted physical-chemical properties such as Henry's law constants (H), that can be used to predict chemical transfer into the atmosphere. OSPW is a complex water-based mixture that is highly variable in composition and nature and contains both organic and inorganic ions. This study uses COSMO-RS solvation theory to estimate and compare Henry's law constants for a set of PACs in both water and theoretically modelled OSPW, to assess the expected deviation that occurs from pure water H values due to the ionic content within OSPW. Experimental measurements of Henry's law constants for PACs in pure water and OSPW using EVA-coated passive dosing and sampler beads were also made in support of our theoretical predictions. For the theory work, OSPW composition data for the Athabasca oil sands in Alberta were used to model a simulated OSPW environment with realistic sodium, chloride, fluoride, sulfate, potassium, bicarbonate, and naphthenic acid concentrations. Theory results indicate that the combined presence of these ions at OSPW concentrations has a negligible effect on H values, causing on average a 3% or 0.014 log unit deviation. By comparison, temperature has a much larger influence on H values, with estimations showing an average 0.20 log unit increase for a 5 °C increase in temperature. The experimental results demonstrate that Henry's law constants can be accurately and precisely measured with this technique in pure water but with less precision in OSPW. Nevertheless, the experimental results support the conclusion that Henry's law constants for OSPW can be accurately estimated assuming a pure water phase.

Aliphatic and polycyclic aromatic compounds in coal and coal-based solid wastes: Relationship with coal-forming paleoenvironment and implications for environmental pollution

In this study, coal and coal-based solid wastes (coal gangue, fly ash, bottom ash, desulfurized gypsum and tar residue) were collected from major coal mines, power plants and coking plants in Lianghuai mining area (LH), China, and were analyzed for 76 polycyclic aromatic compounds (PACs), 27 n-alkanes and 2 isoprenoids (phytane and pristane). The total n-alkanes concentrations and ∑76 PACs in raw coals (640 ± 600 and 180 ± 87 μg/g) were higher than those in coal-based solid wastes (47 ± 40 and 24 ± 25 μg/g), but were lower than those in tar residue (3700 and 63,000 μg/g). It was discovered that the depositional paleoenvironment in LH was mostly a lacustrine and freshwater environment with oxidizing conditions and mixed organic matter input, but the Huainan coalfield had stronger oxidizing conditions and more input of terrestrial organic matter than that of the Huaibei coalfield. Alkylated PACs made up 56 ± 12 % of the ∑76PACs in raw coals, whereas solid wastes mainly consisted of 16 EPA PAHs (66 ± 16 %). Coal combustion and gangue weathering altered the structural properties of n-alkanes and PACs, resulting in a significant loss of n-alkanes and PACs, a higher proportion of parent PACs, and an increased abundance of short n-alkanes in the products (No apparent change of n-alkanes composition was observed through gangue weathering). The toxicity of PACs in raw coal and its solid wastes in LH from high to low was tar residue, raw coal, coal gangue, and coal-fired products. This investigation further confirmed that traditional diagnostic ratios may distort source information, and that they should not be used to assess PACs sources from raw coal particles or coal gangues, but rather to identify combustion sources near the point source. In addition, Retene/(Retene + Chrysene) < 0.03 may indicate direct contamination of raw coal particles.

Source apportionment of particle-bound polycyclic aromatic hydrocarbons (PAHs), oxygenated PAHs (OPAHs), and their associated long-term health risks in a major European city

Many studies have drawn attention to the associations of oxygenated polycyclic aromatic hydrocarbons (OPAHs) with harmful health effects, advocating for their systematic monitoring alongside simple PAHs to better understand the aerosol carcinogenic potential in urban areas. To address this need, this study conducted an extensive PM2.5 sampling campaign in Athens, Greece, at the Thissio Supersite of the National Observatory of Athens, from December 2018 to July 2021, aiming to characterize the levels and variability of polycyclic aromatic compounds (PACs), perform source apportionment, and assess health risk. Cumulative OPAH concentrations (Σ-OPAHs) were in the same range as Σ-PAHs (annual average 4.2 and 5.6 ng m−3, respectively). They exhibited a common seasonal profile with enhanced levels during the heating seasons, primarily attributed to residential wood burning (RWB). The episodic impact of biomass burning was also observed during a peri-urban wildfire event in May 2021, when PAH and OPAH concentrations increased by a factor of three compared to the monthly average. The study period also included the winter 2020–2021 COVID-19 lockdown, during which PAH and OPAH levels decreased by >50 % compared to past winters. Positive matrix factorization (PMF) source apportionment, based on a carbonaceous aerosol speciation dataset, identified PAC sources related to RWB, local traffic (gasoline vehicles) and urban traffic (including diesel emissions), as well as an impact of regional organic aerosol. Despite its seasonal character, RWB accounted for nearly half of Σ-PAH and over two-thirds of Σ-OPAH concentrations. Using the estimated source profiles and contributions, the source-specific carcinogenic potency of the studied PACs was calculated, revealing that almost 50 % was related to RWB. These findings underscore the urgent need to regulate domestic biomass burning at a European level, which can provide concrete benefits for improving urban air quality, towards the new stricter EU standards, and reducing long-term health effects.

19]Starphene: Combined In‐Solution and On‐Surface Synthesis Towards the Largest Starphene

Starphenes are structurally appealing three‐fold symmetric polycyclic aromatic compounds with potential interesting applications in molecular electronics and nanotechnology. This family of star‐shaped polyarenes can be regarded as three acenes that are connected through a single benzene ring. In fact, just like acenes, unsubstituted large starphenes are poorly soluble and highly reactive molecules under ambient conditions making their synthesis difficult to achieve. Herein, we report two different synthetic strategies to obtain a starphene formed by 19 cata‐fused benzene rings distributed within three hexacene branches. This molecule, which is the largest starphene that has been obtained to date, was prepared by combining solution‐phase and on‐surface synthesis. [19]Starphene was characterized by high‐resolution scanning tunneling microscopy (STM) and spectroscopy (STS) showing a remarkable small HOMO‐LUMO transport gap (0.9 eV).

19]Starphene: Combined In-Solution and On-Surface Synthesis Towards the Largest Starphene.

Starphenes are structurally appealing three-fold symmetric polycyclic aromatic compounds with potential interesting applications in molecular electronics and nanotechnology. This family of star-shaped polyarenes can be regarded as three acenes that are connected through a single benzene ring. In fact, just like acenes, unsubstituted large starphenes are poorly soluble and highly reactive molecules under ambient conditions making their synthesis difficult to achieve. Herein, we report two different synthetic strategies to obtain a starphene formed by 19 cata-fused benzene rings distributed within three hexacene branches. This molecule, which is the largest starphene that has been obtained to date, was prepared by combining solution-phase and on-surface synthesis. [19]Starphene was characterized by high-resolution scanning tunneling microscopy (STM) and spectroscopy (STS) showing a remarkable small HOMO-LUMO transport gap (0.9 eV).

Clearing the Smoke: The Evidence behind Risk of Electrocautery Smoke and Mitigation Strategies.

Electrocautery has been a useful, fundamental instrument utilized for surgical procedures since its implementation in the 1920s. However, concerns exist regarding the health hazards of the by-product smoke associated with the use of electrocautery. A comprehensive review of articles on the composition, mitigation, and effects of smoke was conducted using the PubMed search engine and excluding articles that did not meet the predetermined inclusion criteria. From January 1963 to December 2021, a total of 264 articles resulted, and a total of 69 articles were included in this narrative review. Surgical smoke contains volatile organic compounds, polycyclic aromatic compounds, viral particles, and ultrafine particles. There has been some evidence of mutagenicity to bacterial cells during animal in vivo studies, and one human survey study has shown similar mutagenic effects. We also discuss additional hemostatic techniques that can be used, including the use of hemostatic and antithrombolytic agents, epinephrine infiltration, and the use of tourniquet when appropriate. Further studies should be conducted regarding human effects, but until the data are available, we recommend precautionary measures and actions to protect operating room staff from cautery smoke exposure.

Insights into the variations of polycyclic aromatic hydrocarbons and their nitrated and oxygenated derivatives in urban airborne PM2.5

Polycyclic aromatic hydrocarbons (PAHs) can be transformed into more toxic species in the atmosphere, but field evidence for their transformation remains rare. Here, polycyclic aromatic compounds (PACs), including PAHs and their nitrated and oxygenated derivatives (NPAHs and OPAHs), in fine particulate matter (PM2.5) were measured in the seasons at multiple locations in a megacity (Guangzhou, China). Molecular diagnostic ratios (MDRs), meteorological factors, and atmospheric oxidant measurements were employed to understand the atmospheric behaviors of PM2.5-bound PACs. The results indicated that similarities/differences in the short-term variations of PAC concentrations between the locations depended on their sources and seasons. The temporal trends in MDRs were more distinct than those in concentrations among the locations. Meteorological factors affected PAC concentrations through a similar pathway (demodulating loadings on PM). Their influence on the ratios can be explained by compounds’ atmospheric half-life, vapor pressure, or particle-size distribution. Temperature was the most powerful factor for both the concentrations and MDRs. Relative humidity was minor, but its positive influence on the reaction to OH radicals was appreciable. The dependence on PM2.5 concentrations suggests that PM plays a more significant role in the sorption or formation of N/OPAHs than in their parent compounds. The OH radical-initiated reaction is the major formation mechanism of N/OPAHs throughout the year, but substantial reactions to NO3 radical in autumn were observed due to high ozone levels. Multiple linear regression revealed that parent PAHs, NO2, and/or O3 are significant contributing factors to the secondary formation of N/OPAHs. Partial least squares-discriminant analysis showed the distinguishing characteristics of summer and autumn PM2.5-bound PACs. This study provides field evidence for the gaseous and heterogeneous reactions of PAHs.

Synthesis and Properties of Fused Polycyclic Donor–Acceptor Compounds Containing Carbazole and Diazapyrene Skeletons

Fused polycyclic aromatic compounds containing carbazole and diazapyrene skeletons as electron donors and acceptors, respectively, were synthesized in a few steps from readily accessible starting materials. The incorporation of diazapyrene units into the polycyclic compounds resulted in significant bathochromic shifts in their absorption and emission bands compared to those of the corresponding carbazole derivatives. Electrochemical measurements and density functional theory calculations were performed to gain further insight into their electronic properties. Our findings demonstrate that the incorporation of nitrogen atoms and substituents, as well as the different topologies of the fused‐ring system, exert a profound effect on the electronic properties of the polycyclic compounds.

Online SPE-LC-MS-MS method for eight hydroxylated metabolites of polycyclic aromatic hydrocarbons in urine and determination of optimal sampling time after firefighter training

Polycyclic aromatic compounds (PAHs) are formed during incomplete combustion and firefighters are inadvertently at risk of being exposed to these and other hazardous compounds. Exposure to PAHs is often estimated by measuring their hydroxylated metabolites (OH-PAH) in urine. Here, an online-SPE LC-MS-MS method was set up for eight OH-PAHs thus increasing sample throughput and minimizing manual handling. The method was validated over a 5-month period and showed good reproducibility with intra- and inter-day variation of 2.4–8.1 % and 1.6–6.5 %, respectively, of low-level samples and accuracy (91.6–104.8 %) for a standard reference material. The method was applied to urine samples from conscripts training to become firefighters to determine the optimal sampling time for this training activity before a large intervention study. In total, six conscripts sampled urine 6–8 times over a 40-hr period during a 3-day training course. All eight metabolites were detected in ≥ 97 % of the samples and showed peak excretion 4–6 hrs after the training corresponding to 8–10 hrs after first exposure. Samples taken the morning after the exercise contained low levels of most metabolites. Consequently, 4–6 hrs post exposure is recommended as the optimal sampling time for quantification of PAH exposure and monitoring of potential differences in exposure.

Benzo[a]pyrene exposure disrupts the organelle distribution and function of mouse oocytes

Benzo[a]pyrene (BaP) is a polycyclic aromatic hydrocarbon compound that is generated during combustion processes, and is present in various substances such as foods, tobacco smoke, and burning emissions. BaP is extensively acknowledged as a highly carcinogenic substance to induce multiple forms of cancer, such as lung cancer, skin cancer, and stomach cancer. Recently it is shown to adversely affect the reproductive system. Nevertheless, the potential toxicity of BaP on oocyte quality remains unclear. In this study, we established a BaP exposure model via mouse oral gavage and found that BaP exposure resulted in a notable decrease in the ovarian weight, number of GV oocytes in ovarian, and oocyte maturation competence. BaP exposure caused ribosomal dysfunction, characterized by a decrease in the expression of RPS3 and HPG in oocytes. BaP exposure also caused abnormal distribution of the endoplasmic reticulum (ER) and induced ER stress, as indicated by increased expression of GRP78. Besides, the Golgi apparatus exhibited an abnormal localization pattern, which was confirmed by the GM130 localization. Disruption of vesicle transport processes was observed by the abnormal expression and localization of Rab10. Additionally, an enhanced lysosome and LC3 fluorescence intensity indicated the occurrence of protein degradation in oocytes. In summary, our results suggested that BaP exposure disrupted the distribution and functioning of organelles, consequently affecting the developmental competence of mouse oocytes.

Field study on the uptake pathways and their contributions to the accumulation of organophosphate esters, phthalates, and polycyclic aromatic hydrocarbons in upland rice

Plant uptake of organic contaminants generally occurs through either root, gas-phase foliar, or particle-phase foliar uptake. Understanding these pathways is essential for food-system practitioners to reduce human exposures, and to clean contaminated-sites with phytoremediation. Herein, we conducted a field-based experiment using an improved specific exposure chamber to elucidate the uptake pathways of organophosphate esters, phthalates, and polycyclic aromatic compounds, and quantitatively assessed their contributions to organic contaminant accumulations in field-grown rice. For most target compounds, all three uptake pathways (root, foliar gas, and foliar particle uptakes) contributed substantially to the overall contaminant burden in rice. Compounds with lower octanol–water partition coefficients (Kow) were more readily translocated from roots to leaves, and compounds with higher octanol−air partition coefficients (Koa) tended to enter rice leaves mostly through particle deposition. Most compounds were mostly stored in the inner leaves (55.3–98.2 %), whereas the relatively volatile compounds were more readily absorbed by the waxy layer and then transferred to the inner leaves. Air particle desorption was a key process regulating foliar uptake of low-volatility compounds. The results can help us to better understand and predict the environmental fate of those contaminants, and develop more effective management strategies for reducing their human exposure through food ingestion.

Scalable and Selective Electrochemical Hydrogenation of Polycyclic Arenes.

The reduction of aromatic compounds constitutes a fundamental and ongoing area of investigation. The selective reduction of polycyclic aromatic compounds to give either fully or partially reduced products remains a challenge, especially in applications to complex molecules at scale. Herein, we present a selective electrochemical hydrogenation of polycyclic arenes conducted under mild conditions. A noteworthy achievement of this approach is the ability to finely control both the complete and partial reduction of specific aromatic rings within polycyclic arenes by judiciously varying the reaction solvents. Mechanistic investigations elucidate the pivotal role played by in situ proton generation and interface regulation in governing reaction selectivity. The reductive electrochemical conditions show a very high level of functional-group tolerance. Furthermore, this methodology represents an easily scalable reduction (demonstrated by the reduction of 1 kg scale starting material) using electrochemical flow chemistry to give key intermediates for the synthesis of specific drugs.

Mountaintop Removal Coal Mining Contaminates Snowpack across a Broad Region.

Mountaintop removal coal mining is a source of downstream pollution. Here, we show that mountaintop removal coal mining also pollutes ecosystems downwind. We sampled regional snowpack near the end of winter along a transect of sites located 3-60 km downwind of coal mining in the Elk River valley of British Columbia, Canada. Vast quantities of polycyclic aromatic compounds (PACs), a toxic class of organic contaminants, are emitted and transported atmospherically far from emission sources. Summed PAC (ΣPAC) snowpack concentrations ranged from 29-94,866 ng/L. Snowpack ΣPAC loads, which account for variable snowpack depth, ranged from <10 μg/m2 at sites >50 km southeast of the mines to >1000 μg/m2 at sites in the Elk River valley near mining operations, with one site >15,000 μg/m2. Outside of the Elk River valley, snowpack ΣPAC loads exhibited a clear spatial pattern decreasing away from the mines. The compositional fingerprint of this PAC pollution matches closely with Elk River valley coal. Beyond our study region, modeling results suggest a depositional footprint extending across western Canada and the northwestern United States. These findings carry important implications for receiving ecosystems and for communities located close to mountaintop removal coal mines exposed to air pollution elevated in PACs.

It's time to reevaluate the list of priority polycyclic aromatic compounds: Evidence from a large urban shallow lake

Monitoring only 16 priority PAHs (Pri-PAHs) may greatly underestimate the pollutant load and toxicity of polycyclic aromatic compounds (PACs) in aquatic environments. There is an urgent need to reevaluate the list of priority PACs. To determine which PACs deserve priority monitoring, the occurrence, sources, and toxicity of 78 PACs, including 24 parent PAHs (Par-PAHs), 49 alkylated PAHs (Alk-PAHs), 3 oxygenated PAHs (OPAHs), carbazole, and dibenzothiophene were investigated for the first time in Lake Chaohu sediments, China. Concentrations of ∑Par-PAHs, ∑Alk-PAHs, and ∑OPAHs ranged from 35 to 165, 3.4–26, and 7.7–26 ng g−1, respectively. Concentrations of 16 Pri-PAHs have decreased by 1–2 orders of magnitude compared to a decade ago, owing to the effective implementation of PAHs emission control measures. Comparisons with the sediment quality guidelines indicated that 16 Pri-PAHs have negligible adverse effects on benthic organisms. Positive matrix factorization (PMF) model results showed that coal combustion was the major source of PACs (accounting for 23.5 %), followed by traffic emissions (23.4 %), petroleum volatilization (21.9 %), wood/biomass combustion (18.2 %), and biological/microbial transformation (13.1 %). The toxicity of PACs was assessed by calculating the BaP toxic equivalent concentrations (TEQBaP) and toxic units. It was found that Par-PAHs were the predominant toxic substances. In addition, monomethyl-BaPs, OPAHs, BeP, and 7,12-DMBaA should be prioritized for monitoring due to their noticeable contributions to overall toxicity. The contributions of different sources to the toxicity of PACs were determined based on PMF model results and TEQBaP values, which revealed that combustion sources mainly contributed to the comprehensive toxicity of PACs in Lake Chaohu sediments.

The Versatile and Strategic O-Carbamate Directed Metalation Group in the Synthesis of Aromatic Molecules: An Update.

The aryl O-carbamate (ArOAm) group is among the strongest of the directed metalation groups (DMGs) in directed ortho metalation (DoM) chemistry, especially in the form Ar-OCONEt2. Since the last comprehensive review of metalation chemistry involving ArOAms (published more than 30 years ago), the field has expanded significantly. For example, it now encompasses new substrates, solvent systems, and metalating agents, while conditions have been developed enabling metalation of ArOAm to be conducted in a green and sustainable manner. The ArOAm group has also proven to be effective in the anionic ortho-Fries (AoF) rearrangement, Directed remote metalation (DreM), iterative DoM sequences, and DoM-halogen dance (HalD) synthetic strategies and has been transformed into a diverse range of functionalities and coupled with various groups through a range of cross-coupling (CC) strategies. Of ultimate value, the ArOAm group has demonstrated utility in the synthesis of a diverse range of bioactive and polycyclic aromatic compounds for various applications.

Common carp sperm chromatin as an economical and effective remover for benzo(a)pyrene from pollutants

Benzo (a) pyrene is a highly carcinogenic polycyclic aromatic compound, difficult to be degraded, widely present in the environment. However, there is currently no cost-effective and efficient method for removing benzo (a) pyrene. In this study, a feasible method was introduced to cheaply and efficiently adsorb benzo(a)pyrene using chromatin. Scanning electron microscopy analysis showed that the chromatin had a filamentary fiber structure. Fourier transform infrared (FTIR) spectroscopy showed that benzo(a)pyrene formed a bond with the chromatin. Effective binding was confirmed using fluorescence microscopy. Influence factors exploration experiments indicated that the amount of benzo(a)pyrene adsorbed by chromatin was 0.16 mg g−1. The adsorption process of BaP by chromatin is consistent with a pseudo-second-order kinetics model of adsorption. The adsorption isotherm model is consistent with the langmuir isotherm model.This study suggests that chromatin can be utilized as a ordinary and high efficiency adsorbent for removing benzo(a)pyrene and can be utilized in further studies.

The missing information of aliphatic-like & aromatic-like Unresolved Complex Mixtures (UCMs) in background oceanic atmosphere: occurrence, identification and deposition

Oceanic air samples (gas + particle phases) were collected over the Shanghai-Arctic background oceanic region during the Chinese Arctic Research expedition 2021. Full scan mode (semi-quantitative) and selective ion monitoring mode (quantitative) were used to analyze separately 72 polycyclic aromatic compounds (PACs) & C11–C35 n-Alkanes (n-Alks) and unresolved complex mixtures (UCMs, including aromatic-like and aliphatic-like compounds) in these samples. The concentration of ΣPACs in the gas-phase and particle-phase were 0.40–8.5 ng m−3 (2.4 ± 1.7 ng m−3) and 0.059–1.1 ng m−3 (0.21 ± 0.23 ng m−3), respectively. While Σn-Alks in the gas-phase and particle-phase were 2.2–80 ng m−3 (mean = 18 ± 24 ng m−3) and 2.2–20 ng m−3 (mean = 8.6 ± 5.0 ng m−3), respectively. The semi-quantitative result indicated that aromatic-like UCMs were 14–1400 times higher than those of ΣPACs in these two phases, while aliphatic-like UCMs were 1.2–25 times higher than those of Σn-Alks. Through three-dimensional identification of the one-dimensional GC-MS chromatogram (with the x-axis representing GC retention time, the y-axis representing m/z, and the z-axis representing peak intensity), we found that aromatic-like UCMs were primarily composed of phenanthrene & anthracene similar PACs, while aliphatic-like UCMs were predominated by long-chain alkanes. The source identification shows that oil-gas leakage was the dominant source of PACs, followed by petroleum & coal combustion and biomass combustion; n-Alks might be mainly originated from anthropogenic sources, while nature sources at high latitudes cannot be ignored as well. Aromatic-like UCMs had a decreasing latitude trend and the presence of 5–6 ring aromatic-like UCMs enclosed within organic aerosols could pose a significant ecological risk, particularly in high latitude regions. Net uptake of atmospheric carbon caused by dry deposition of aromatic-like & aliphatic-like UCMs varied significantly geographically with mid- and low-latitude seas. The non-polar and weakly polar substances were not the major components of organic carbon in oceanic air of high latitude areas.

Predicting the Occurrence of Substituted and Unsubstituted, Polycyclic Aromatic Compounds in Coking Wastewater Treatment Plant Effluent using Machine Learning Regression

Organic contaminants such as polycyclic aromatic compounds (PACs) occurring in industrial effluents can not only persist in wastewater but transform into more toxic and mobile, substituted heterocyclic products during treatment. Thus, predicting the occurrence of PACs and their heterocyclic derivatives (HPACs) in coking wastewater is of utmost importance to reduce the environmental risks in water bodies that receive industrial effluents. Although HPACs can be monitored through sampling and analysis, the characterisation techniques used in their analyses are costly and time-consuming. In this study, we propose 3 distinct kernel-based machine learning (ML) models for predicting PACs including substituted HPACs and alkylated PACs occurring in coking wastewater. By using routinely measured wastewater quality data as input for our models, we predicted the occurrence of 14 HPACs in the final effluent of a coking wastewater treatment plant. Support Vector Machine based regression model (SVR) used for HPAC prediction showed the highest R2 of 0.83. Performance assessment of SVR model showed a mean absolute logarithmic error (MALE) of 0.46 and root mean square error (RMSE) of 0.073 ng/L. Comparatively, K-Nearest Neighbor and Random Forest models showed lower R2 of 0.75 and 0.76 respectively for HPAC prediction. Feature analysis attributed the superior predictability of SVR model likely to its higher weightage (81%) towards dissolved organic carbon and total ammonia as input variables. Both these variables could capture the underlying secondary PAC transformations likely occurring in the treatment plant. Partial dependence plots predicted that ammonia levels higher than 120 mg/L and DOC levels of 50–60 mg/L were likely linked to higher HPACs occurring in the final effluent. This work highlights the capability of kernel-based ML models in capturing nonlinear wastewater chemistry and offers a tool for monitoring trace organic contaminants released in coking effluents.

Deciphering dissolved organic matter characteristics and its fate in a glacier-fed desert river—the Tarim river, China

The bioavailable diverse dissolved organic matter (DOM) present in glacial meltwater significantly contributes to downstream carbon cycling in mountainous regions. However, the comprehension of molecular-level characteristics of riverine DOM, from tributary to downstream and their fate in glacier-fed desert rivers remains limited. Herein, we employed spectroscopic and high-resolution mass spectrometry techniques to study both optical and molecular-level characteristics of DOM in the Tarim River catchment, northwest China. The results revealed that the DOC values in the downstream were higher than those in the tributaries, yet they remained comparable to those found in other glacier-fed streams worldwide. Five distinct components were identified using EEM-PARAFAC analysis in both tributary and downstream samples. The dominance of three protein-like components in tributary samples, contrasting with a higher presence of humic-like components in downstream samples, which implied that the dilution and alterations of the glacier DOM signature and overprinting with terrestrial-derived DOM. Molecular composition revealed that thousands of compounds with higher molecular weight and increased aromaticity were transformed, generated and introduced from terrestrial inputs during downstream transportation. The twofold rise in polycyclic aromatic and polyphenolic compounds observed downstream compared to tributaries indicated a greater influx of terrestrial organic matter introduced into the downstream during water transportation. The study suggests that the glacier-sourced DOM experienced minimal photodegradations, with limited influence from human activities, while also being shaped by terrestrial inputs during its transit in the alpine-arid region. This unique scenario offers valuable insights into comprehending the fate of DOM originating from glacial meltwater in arid mountainous regions.

Geochemical implications of uranium-bearing thucholite aggregates in the Upper Permian Kupferschiefer shale, Lubin district, Poland

New inorganic and organic geochemical data from thucholite in the Upper Permian (Wuchiapingian) Kupferschiefer (T1) shale collected at the Polkowice-Sieroszowice Cu-Ag mine in Poland are presented. Thucholite, which forms spherical or granular clusters, appears scattered in the T1 dolomitic shale at the oxic-anoxic boundary occurring within the same shale member. The composition of thucholite concretions and the T1 shale differs by a higher content of U- and REE-enriched mineral phases within the thucholite concretions compared to the T1 shale, suggesting a different mineralising history. The differences also comprise higher Ntot, Ctot, Htot, Stot contents and higher C/N, C/S ratios in thucholite than in the T1 shale. The hydrocarbon composition of the thucholite and the surrounding T1 shale also varies. Both are dominated by polycyclic aromatic compounds and their phenyl derivatives. However, higher abundances of unsubstituted polycyclic aromatic hydrocarbons in the thucholite are indicative of its pyrogenic origin. Pyrolytic compounds such as benz[a]anthracene or benzo[a]pyrene are more typical of the thucholite than the T1 shale. Microscopic observations of the thucholite and its molecular composition suggest that it represents well-rounded small charcoal fragments. These charcoals were formed during low-temperature combustion, as confirmed by semifusinite reflectance values, indicating surface fire temperatures of about 400 °C, and the absence of the high-temperature pyrogenic polycyclic aromatic hydrocarbons. Charred detrital particles, likely the main source of insoluble organic matter in the thucholite, migrated to the sedimentary basin in the form of spherical carbonaceous particulates, which adsorbed uranium and REE in particular, which would further explain their different contents and sorption properties in the depositional environment. Finally, the difference in mineral content between thucholite and the T1 shale could also have been caused by microbes, which might have formed biofilms on mineral particles, and caused a change in the original mineral composition.