Estimating wastewater emissions and environmental levels of typical organic contaminants based on regionalized modelling

Organic contaminants (OCs) are released into the environment through effluent discharges from wastewater treatment plants (WWTP), posing risks to environment health. However, emissions from various source, particularly large-scale investigations across different industries, remain poorly understood. Based on both sampling and statistical data, this study estimates the emissions of 10 OCs, including perfluorooctane acid (PFOA), perfluorooctane sulfonate (PFOS), 4-nonylphenol (4-NP), 4-tert-octylphenol (4-t-OP), dibutyl phthalate (DBP), di-iso-butyl phthalate (DIBP), dimethyl phthalate (DMP), butyl benzyl phthalate (BBP), di(2-ethylhexyl) phthalate (DEHP), and bisphenol A (BPA), from the effluents of 160 factories across 8 industries, 541 municipal wastewater treatment plants (MWWTPs), and 8 waste treatment plants (WTPs) in the upper Yangtze River Basin. A level III fugacity multimedia model was used to assess the impacts of these emissions on local watersheds. Among the 8 industries, paper production was the largest contributor, accounting for over 80% of total OC emissions, which amounted to 89.1 kg/yr. The contributions of domestic and industrial sources were 91.5% and 8.5%, respectively, underscoring the predominance of domestic sources in the release of the 10 OCs. PFOA emerged as the most dominant compound, with total emissions amounting to 4464 kg/yr from domestic sources and 170 kg/yr from industrial sources. The predicted concentrations of OCs in the receiving rivers closely aligned with values reported in existing literature, differing by no more than one order of magnitude. To our knowledge, this is the first comprehensive report on emissions from various sources in the upper Yangtze River Basin

Estimating wastewater emissions and environmental levels of typical organic contaminants based on regionalized modelling

Organic contaminants (OCs) are released into the environment through effluent discharges from wastewater treatment plants (WWTP), posing risks to environment health. However, emissions from various source, particularly large-scale investigations across different industries, remain poorly understood. Based on both sampling and statistical data, this study estimates the emissions of 10 OCs, including perfluorooctane acid (PFOA), perfluorooctane sulfonate (PFOS), 4-nonylphenol (4-NP), 4-tert-octylphenol (4-t-OP), dibutyl phthalate (DBP), di-iso-butyl phthalate (DIBP), dimethyl phthalate (DMP), butyl benzyl phthalate (BBP), di(2-ethylhexyl) phthalate (DEHP), and bisphenol A (BPA), from the effluents of 160 factories across 8 industries, 541 municipal wastewater treatment plants (MWWTPs), and 8 waste treatment plants (WTPs) in the upper Yangtze River Basin. A level III fugacity multimedia model was used to assess the impacts of these emissions on local watersheds. Among the 8 industries, paper production was the largest contributor, accounting for over 80% of total OC emissions, which amounted to 89.1 kg/yr. The contributions of domestic and industrial sources were 91.5% and 8.5%, respectively, underscoring the predominance of domestic sources in the release of the 10 OCs. PFOA emerged as the most dominant compound, with total emissions amounting to 4464 kg/yr from domestic sources and 170 kg/yr from industrial sources. The predicted concentrations of OCs in the receiving rivers closely aligned with values reported in existing literature, differing by no more than one order of magnitude. To our knowledge, this is the first comprehensive report on emissions from various sources in the upper Yangtze River Basin

Ultrahigh-pressure to high-pressure eclogite in Cuban ophiolitic melange reveals proto-Caribbean spreading ridge subduction

Proto-Caribbean oceanic crust produced during ocean-floor spreading between diverging North and South American plates was subsequently subducted beneath the Caribbean plate. However, the timing and spatial configuration of proto-Caribbean spreading ridge subduction remain subjects of debate. High-pressure (HP) basaltic metamorphic rocks, representing relics of the sub ducted proto-Caribbean oceanic crust, commonly occur in Cuban ophiolitic m & eacute;langes. In this study, an integrated set of petrological, geochemical, and geochronological data is presented for eclogite from the Las Villas m & eacute;lange, central Cuba. The typical geochemical signature of mid-ocean-ridge basalt (MORB) indicates that the protolith of eclogite formed at the proto-Caribbean spreading ridge. Based on pressure-temperature (P-T) estimates obtained by pseudosection analysis as well as Zr-in-rutile and Ti-in-zircon thermometry, the following P-T paths for representative samples can be derived: a prograde path from 24-25 kbar and 510-520 degrees C to peak conditions of 29-31 kbar and 525-575 degrees and a complex retrograde path initially following almost isothermal exhumation to 25-27 kbar, followed by near-isobaric heating to 610-640 degrees C before final exhumation. This is the first documentation of prograde oceanic ultrahigh-pressure (UHP) metamorphism in the northern Caribbean area. U-Pb dating of magmatic zircon with steep heavy rare earth element (HREE) patterns and negative Eu anomalies yielded a protolith age of 126.3 +/- 0.7 Ma. In contrast, metamorphic zircon with flat HREE patterns and without an Eu anomaly yielded a weighted mean age of 118.6 +/- 1.6 Ma. The short time interval of >8 m.y. between MORB magmatism and UHP metamorphism suggests that the oceanic crust was subducted to great depth (similar to 100 km) shortly after generation in an oceanic ridge, which provides robust evidence for subduction of the proto-Caribbean spreading ridge. Furthermore, this work demonstrates high potential to trace ancient spreading ridge subduction by joint petrological, geochemical, and geochronological study of oceanic eclogite

Ultrahigh-pressure to high-pressure eclogite in Cuban ophiolitic melange reveals proto-Caribbean spreading ridge subduction

Proto-Caribbean oceanic crust produced during ocean-floor spreading between diverging North and South American plates was subsequently subducted beneath the Caribbean plate. However, the timing and spatial configuration of proto-Caribbean spreading ridge subduction remain subjects of debate. High-pressure (HP) basaltic metamorphic rocks, representing relics of the sub ducted proto-Caribbean oceanic crust, commonly occur in Cuban ophiolitic m & eacute;langes. In this study, an integrated set of petrological, geochemical, and geochronological data is presented for eclogite from the Las Villas m & eacute;lange, central Cuba. The typical geochemical signature of mid-ocean-ridge basalt (MORB) indicates that the protolith of eclogite formed at the proto-Caribbean spreading ridge. Based on pressure-temperature (P-T) estimates obtained by pseudosection analysis as well as Zr-in-rutile and Ti-in-zircon thermometry, the following P-T paths for representative samples can be derived: a prograde path from 24-25 kbar and 510-520 degrees C to peak conditions of 29-31 kbar and 525-575 degrees and a complex retrograde path initially following almost isothermal exhumation to 25-27 kbar, followed by near-isobaric heating to 610-640 degrees C before final exhumation. This is the first documentation of prograde oceanic ultrahigh-pressure (UHP) metamorphism in the northern Caribbean area. U-Pb dating of magmatic zircon with steep heavy rare earth element (HREE) patterns and negative Eu anomalies yielded a protolith age of 126.3 +/- 0.7 Ma. In contrast, metamorphic zircon with flat HREE patterns and without an Eu anomaly yielded a weighted mean age of 118.6 +/- 1.6 Ma. The short time interval of >8 m.y. between MORB magmatism and UHP metamorphism suggests that the oceanic crust was subducted to great depth (similar to 100 km) shortly after generation in an oceanic ridge, which provides robust evidence for subduction of the proto-Caribbean spreading ridge. Furthermore, this work demonstrates high potential to trace ancient spreading ridge subduction by joint petrological, geochemical, and geochronological study of oceanic eclogite

Molybdenum isotopes demonstrate that multistage upgrading is required to generate heavy rare earth element-enriched carbonatites

Carbonatites with heavy rare earth element (HREE) enrichment are a rare and intriguing prospect for economic geology research, due to the growing global demand for HREEs in various industries. However, debate persists over the mechanism responsible for HREE enrichment in carbonatites, with the mantle source, magmatic-hydrothermal evolution, or a combination of these factors proposed to be responsible. This study examines three adjacent Late Triassic carbonatites (from the Huanglongpu, Huayangchuan, and Jialu carbonatite dike systems) in the Lesser Qinling of Central China and uses Mo isotope systematics to provide unique insights into the HREE enrichment process of these magmas. All three carbonatites exhibit elevated total REE (Sigma REE) concentrations (up to 4600 ppm), along with significant HREE enrichment (Sigma HREE/Sigma REE = 0.1-0.4). Notably, Jialu carbonatite stands out for having the highest total HREE concentrations (>= 360 ppm) and Sigma HREE/Sigma REE ratios (0.2-0.4). Regardless of their variable degrees of HREE enrichment, the three carbonatites display similar Sr-Nd-Pb isotope signatures, which indicates a shared enriched mantle source. The Huanglongpu and Huayangchuan carbonatites mostly display significantly lighter delta Mo-98/95 (-1.71 parts per thousand to -0.15 parts per thousand) values than the depleted mantle, which indicates an origin from an enriched mantle influenced by recycled pelagic clays and Fe-Mn nodules. Both types of marine sediments are enriched in REEs and would have undergone initial HREE enrichment during slab dehydration and metamorphism, resulting in an HREE-enriched mantle source region. In contrast, Jialu carbonatite possesses significantly heavier delta Mo-98/95 (0.13 parts per thousand-1.89 parts per thousand), which is indicative of the subsequent influence of hydrothermal processes. Additional evidence of this hydrothermal influence at Jialu is preserved in calcite crystal fluid inclusions, elevated delta O-18 (8.71 parts per thousand-10.72 parts per thousand), non-charge-and-radius-controlled (CHARAC) Y/Ho ratios (36-41), and low Sr concentrations (<4800 ppm). Secondary upgrading of HREEs at Jialu occurred due to preferential complexation and transportation during hydrothermal exsolution. This study demonstrates that maximum HREE enrichment in carbonatites is achieved through a two-stage process that involves both a refertilized mantle source and late-stage hydrothermal exsolution

Presence and sources of per- and polyfluoroalkyl substances (PFASs) in the three major rivers on Hainan Island

Per- and polyfluoroalkyl substances (PFASs) have attracted considerable attention because of their toxicity, persistence and bioaccumulation potential. With the construction of the Hainan Free Trade Port and the rapid development of economy, environmental pollution on Hainan Island is becoming increasingly prominent. PFASs have been detected in the seawater and sediments of mangrove ecosystems on Hainan Island. As the receiving water of wastewater treatment plants (WWTPs) and industrial wastewater, rivers are inevitably contaminated by PFASs. However, few studies have focused on PFAS pollution in three large rivers (the Nandu, Changhua, and Wanquan rivers) on Hainan Island. In the present study, the pollution status, potential sources, and ecological risks of PFASs in these three major rivers were explored. Perfluorobutanonic acid (PFBA) (48.7%) was found to be the major PFASs in the surface waters, and perfluoroundecanoic acid (PFUnDA) (19.7%) was the major PFASs in the sediments of the three major rivers. The concentrations of & sum;PFASs in the upper-midstream region were low due to minimal human influence and increased in the middle-lower reaches with increasing industrial activity and urbanization, whereas decreased at downstream sites near estuaries where river water was diluted with seawater. WWTP effluent, industrial wastewater discharge, the application and discharge of aqueous firefighting foam, storm runoff and landfill leachate were the major sources of PFASs in the three major rivers. In surface water, perfluorooctanoic acid (PFOA), perfluorooctane sulfonamide (PFOSA) and perfluorooctadecanoic acid (PFODA) posed low-moderate risks at 5.71-85.6% of the sampling sites. PFASs in the sediment posed no ecological risk. This study provides key data regarding the pollution status and potential sources of PFASs in large rivers on subtropical islands

Bimetal-organic framework derived single-atom-like Co/Fe catalysts for peroxydisulfate activation: The dual amplification of radical and nonradical pathways

A novel single-atom-like Co/Fe catalyst (i.e., Co/Fe-N-C) was synthesized by pyrolysis of a Zn/Co/Fe zeolitic imidazolate framework, and applied in peroxydisulfate (PDS) activation for removal of organic contaminants from wastewater. The isolated diatomic metal-nitrogen sites were detected by X-ray adsorption fine-structure. The degradation of four contaminants (i.e., phenol, bisphenol A, 2,4-dichlorophenol, and N-methyl-2-pyrrolidone) with a concentration of 100 mg/L could be degraded separately within 20 min by the Co/Fe-N-C system with 10 mmol/L of PDS, 0.5 g/L of catalyst dosage, and initial pH of 3. Besides, 79.2 % of phenol could be mineralized in 120 min, and the turn-over frequency value of the catalyst was calculated to be 27.17 min(-1), which was higher than the commonly reported homogeneous PS-AOPs. Moreover, the Co/Fe-N-C exhibited high stability (mineralization rate over 70 % after 5 cycles), a wide initial pH range (3-9), and high catalytic performance at 5-20 mmol/L of PDS concentrations. Based on the analysis of radical scavenging experiments and electron spin resonance spectra, the radical and non-radical pathways for PDS activation were proved in the system, and the contribution of phenol degradation by each pathway was clarified

Molecular and carbon isotopic geochemistry of oils with different fluorescence color from the Upper Jurassic Qigu formation and oil accumulation process in Yongjin area, Junggar Basin in China

The Yongjin area, located in the middle of the Junggar Basin, is an important oil-producing region. Its major oilproducing formation is the Upper Jurassic Qigu Formation, which has experienced multiple oil-charging events that have resulted in oils with various fluorescent colors. However, the source of oils from the Qigu Formation is currently debated. As exploration and development progressed, the productivity of the Qigu Formation was observed to vary owing to oil viscosity differences. Conventional extraction methods can only be used to obtain a mixture of fluorescing oils of different colors, making it difficult to analyze the properties of oils that charge during different periods. Using microscopy to observe fluorescence the characteristics of oil in various samples were analyzed. Then, accelerated sequential extraction was used to separate the oils with different fluorescent colors (Groups I-IV). Through GC-MS (gas chromatography), GC-IRMS (gas chromatography-mass spectrometry), FT-IR (fourier transform infrared spectroscopy), and fluid inclusion observations and measurements, in conjunction with the geological context, the sources of oils from different charge periods and genesis of heavy oil were determined and the process of oil accumulation was reconstructed. Three stages of oil charging were identified: (1) During the Middle to Late Jurassic, low-mature and mature oil from the Lower Permian Fengcheng Formation and a low quantity of low-mature oil from the Middle Permian Lower Wuerhe Formation charged the Qigu Formation. These oils underwent notable biodegradation and oxidation, with some captured by inclusions (Group III) for preservation. (2) During the Late Cretaceous to Early Paleogene, mature oil from the Wuerhe Formation charged the Qigu Formation. This oil mixed with early oil that was not captured by the inclusions, resulting in the formation of black-brown fluorescing oil (Group IV) and yellow fluorescing inclusion oil (Group II). (3) From the Late Paleogene to the present, highly mature condensates from the Lower Wuerhe Formation charged the Qigu Formation. The oil mixed with early oil to generate yellow-brown (Group II) and blue-white (Group I) fluorescing oils. Low-mature and mature oil from the Fengcheng Formation charged the Jurassic reservoirs and underwent secondary alteration, whereas high-mature oil and gas did not. These oils likely predominantly accumulated in reservoirs between the Fengcheng and Lower Wuerhe formations. Although the Jurassic source rocks began to generate oil, this oil did not migrate upward to the Qigu Formation, indicating that the conventional and unconventional reservoirs under the Jurassic Qigu Formation have exploration potential

A systematic review of the source, formation mechanism, and environmental effects of HONO in the indoor air

The vast majority of human life is spent in indoor environments, and indoor air quality is closely related to human health and well-being. Nitrous acid (HONO), as the main pollutant in indoor environment, has become an emerging indoor contaminant which is widely concerned at home and abroad. HONO is prone to produce hydroxyl free radicals (center dot OH) upon exposure to ultraviolet radiation, which leads to a series of photochemical reactions and ultimately indoor pollution, causing adverse effects on human health. HONO is ubiquitous in indoor environment, and its production process is dynamic and complex. In this work, the primary sources and mechanisms of indoor HONO were reviewed, including the homogeneous reactions, heterogeneous reactions, photolysis of surface nitrates, and other major reaction processes as well as detailed mechanisms leading to the formation of HONO were analyzed. The research progress related to NO2 heterogeneous light-induced reaction on indoor surfaces were summarized. Furthermore, the environmental implications of HONO on indoor air quality and health risk were emphasized, and some important research directions such as indoor multiphase chemical processes, emerging contaminants transformation, modeling and health risk assessment under complex environment were discussed. Indoor HONO serves as a bridge connecting indoor chemistry with the assessment of indoor air quality. Consequently, the comprehensive understanding of the primary sources and formation mechanisms of HONO will help to further improve the current major air quality models, ultimately optimizing the research of indoor chemistry and its impact on human health

The partitioning of chalcophile and siderophile elements (CSEs) between sulfide liquid and carbonated melt

Carbonated melts play a significant role in mobilizing lithophile and volatile elements in the Earth's mantle and mantle metasomatism. However, there has been limited investigation into their potential for mobilizing chalcophile and siderophile elements (CSEs). In this study, we experimentally determine the sulfide liquid- -carbonated melt partition coefficients of CSEs ( D Sul / C melt CSE) for a range of elements, including Co, Ni, Cu, Zn, Se, Mo, Ag, Cd, In, Sn, Re, and Pb, at 1300-1600 degrees C, 1.0-3.0 GPa, and oxygen fugacity (fO2) close to the graphiteCO2 fluid buffer. Furthermore, the D Sul / C melt values for lithophile elements Cr, Mn, Rb, Sr, Y, Zr, Nb, Cs, Ba, Hf, and Ta ( D Sul / C melt LithoE ) are also determined. The obtained D Sul / C melt values are 34-1230 for Co, 380-75200 for Ni,CSE 200-14900 for Cu and Ag, 0.5-28 for Zn and Mo, 42-98 for Se, 24-640 for Cd, 5-52 for In and Sn, 650-15200 for Re, and 22-2470 for Pb. The obtained D Sul / C melt LithoE values are below 1-10. The variations of D Sul / C melt and D Sul / C melt CSE LithoE are primarily influenced by the FeOtot content in the carbonated melts. A partitioning model was developed to parameterize D Sul / C melt and D Sul / C melt LithoE as a multi-function of pressure, temperature, composition of the carbonCSE ated melt (mainly the FeOtot content), and composition of the sulfide liquid. Our parameterization can explain the observed large variations of D Sul / C melt and D Sul / C melt CSE LithoE for most of the trace elements studied. Using our D Sul / C melt parameterization, we model the CSE and U-Th contents of low-degree partial melts of carbonated CSE mantle peridotite and slab eclogite with sulfur concentrations ranging from 50 to 500 mu g/g. The modeling results can generally explain the trace element patterns observed in natural kimberlites and carbonatites; however, the peridotite- or slab-derived carbonated melts have a low capability in mobilizing CSEs, which can extract less than 3 % of Cu, Ni, Co, Re, and Os, 3-30 % of Mo, Pb, and Se, but up to 30-50 % U and Th from the source lithology. Consequently, the influence of carbonatite metasomatism on the Cu, Ni, Co, Re, and Os systematics of the Earth's mantle is minimal, although local enrichments of CSEs may occur when sulfides precipitate from carbonated melts. Because of the elevated concentrations of U and Th and the corresponding U/Pb and Th/Pb ratios in the carbonated melts, the mantle lithology that has undergone metasomatism by these melts can become a geochemical reservoir with high 208 Pb/ 206 Pb ratios. However, the effect of carbonatite metasomatism on Re-Os isotopic systems of the mantle is minimal due to the low Re concentrations in the carbonated melts. Accordingly, the radiogenic Pb-Os isotopic signatures of HIMU ocean island basalts cannot be explained solely by carbonatite metasomatism in the mantle