RESUMEN
Hg(I) may control Hg redox kinetics; however, its metastable nature hinders analysis. Herein, the stability of Hg(I) during standard preparation and analysis was studied. Gravimetric analysis showed that Hg(I) was stable in its stock solution (1000 mg L-1), yet completely disproportionated when its dilute solution (10 µg L-1) was analyzed using liquid chromatography (LC)-ICPMS. The Hg(I) dimer can form through an energetically favorable comproportionation between Hg(0) and Hg(II), as supported by density functional theory calculation and traced by the rapid isotope exchange between 199Hg(0)aq and 202Hg(II). However, the separation of Hg(0) and Hg(II) (e.g., LC process) triggered its further disproportionation. Polypropylene container, increasing headspace, decreasing pH, and increasing dissolved oxygen significantly enhanced the disproportionation or redox transformations of Hg(I). Thus, using a glass container without headspace and maintaining a slightly alkaline solution are recommended for the dilute Hg(I) stabilization. Notably, we detected elevated concentrations of Hg(I) (4.4-6.1 µg L-1) in creek waters from a heavily Hg-polluted area, accounting for 54-70% of total dissolved Hg. We also verified the reductive formation of Hg(I) in Hg(II)-spiked environmental water samples, where Hg(I) can stably exist in aquatic environments for at least 24 h, especially in seawater. These findings provide mechanistic insights into the transformation of Hg(I), which are indicative of its further environmental identification.
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Mercurio , Contaminantes Químicos del Agua , Mercurio/análisis , Agua de Mar/análisis , Agua de Mar/química , Isótopos/análisis , Contaminantes Químicos del Agua/análisisRESUMEN
The Paris Agreement and the Minamata Convention on Mercury are two of the most important environmental conventions being implemented concurrently, with a focus on reducing carbon and mercury emissions, respectively. The relation between mercury and carbon influences the interactions and outcomes of these two conventions. This perspective investigates the link between mercury and CO2, assessing the consequences and exploring the policy implications of this link. We present scientific evidence showing that mercury and CO2 levels are negatively correlated under natural conditions. As a result of this negative correlation, the CO2 level under the current mercury reduction scenario is predicted to be 2.4-10.1 ppm higher than the no action scenario by 2050, equivalent to 1.0-4.8 years of CO2 increase due to human activity. The underlying causations of this negative correlation are complex and need further research. Economic analysis indicates that there is a trade-off between the benefits and costs of mercury reduction actions. As reducing mercury emission may inadvertently undermine efforts to achieve climate goals, we advocate for devising a coordinated implementation strategy for carbon and mercury conventions to maximize synergies and reduce trade-offs.
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Dióxido de Carbono , Mercurio , Humanos , Mercurio/análisis , Políticas , ClimaRESUMEN
Sorption to activated carbon is a common approach to reducing environmental risks of waterborne perfluorooctanoic acid (PFOA), while effective and flexible approaches to PFOA sorption are needed. Variations in temperature or the use of electrokinetic phenomena (electroosmosis and electromigration) in the presence of external DC electric fields have been shown to alter the contaminant sorption of contaminants. Their role in PFOA sorption, however, remains unclear. Here, we investigated the joint effects of DC electric fields and the temperature on the sorption of PFOA on activated carbon. Temperature-dependent batch and column sorption experiments were performed in the presence and absence of DC fields, and the results were evaluated by using different kinetic sorption models. We found an emerging interplay of DC and temperature on PFOA sorption, which was linked via the liquid viscosity (η) of the electrolyte. For instance, the combined presence of a DC field and low temperature increased the PFOA loading up to 38% in 48 h relative to DC-free controls. We further developed a model that allowed us to predict temperature- and DC field strength-dependent electrokinetic benefits on the drivers of PFOA sorption kinetics (i.e., intraparticle diffusivity and the film mass transfer coefficient). Our insights may give rise to future DC- and temperature-driven applications for PFOA sorption, for instance, in response to fluctuating PFOA concentrations in contaminated water streams.
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Fluorocarburos , Contaminantes Químicos del Agua , Temperatura , Carbón Orgánico , Adsorción , Fluorocarburos/análisis , Caprilatos , Cinética , Contaminantes Químicos del Agua/análisisRESUMEN
Complexes with low-molecular-weight thiols are crucial species of methylmercury (MeHg) excreted by anaerobic Hg-methylating microbes, notably, MeHg-cysteine (MeHg-Cys). As MeHg-Cys diffuses into surface water, it would undergo a ligand exchange process with dissolved organic matter (DOM) under nonsulfidic conditions, inevitably altering MeHg speciation and bioavailability to phytoplankton. In this study, we investigated the competitive binding kinetics between MeHg-Cys and Suwannee River natural organic matter, and their influence on the adsorption and uptake of MeHg by the cyanobacterium, Synechocystis sp. PCC6803. Liquid chromatography-inductively coupled plasma mass spectrometry was employed to monitor the kinetics processes involving competition of DOM with Cys for MeHg binding, which revealed that competitive binding kinetics were dictated by the abundance of thiol moieties in DOM. Thiol concentrations of 0.97 and 49.34 µmol of thiol (g C)-1 resulted in competitive binding rate constant (k values) of 0.30 and 3.47 h-1, respectively. Furthermore, the time-dependent competitive binding of DOM toward MeHg-Cys significantly inhibited MeHg adsorption and uptake by cyanobacteria, an effect that was amplified by an increased thiol abundance in DOM. These findings offer valuable insights into the kinetic characteristics of MeHg's fate and transport, as well as their impact on bioconcentration in aquatic organisms within natural aquatic ecosystems.
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Compuestos de Metilmercurio , Compuestos de Sulfhidrilo , Compuestos de Metilmercurio/metabolismo , Compuestos de Metilmercurio/química , Adsorción , Cinética , Compuestos de Sulfhidrilo/metabolismo , Compuestos de Sulfhidrilo/química , Cisteína/metabolismo , Cisteína/química , Contaminantes Químicos del Agua/metabolismo , Contaminantes Químicos del Agua/químicaRESUMEN
Algae are an entry point for mercury (Hg) into the food web. Bioconcentration of Hg by algae is crucial for its biogeochemical cycling and environmental risk. Herein, considering the cell heterogeneity, we investigated the bioconcentration of coexisting isotope-labeled inorganic (199IHg) and methyl Hg (201MeHg) by six typical freshwater and marine algae using dual-mass single-cell inductively coupled plasma mass spectrometry (scICP-MS). First, a universal pretreatment procedure for the scICP-MS analysis of algae was developed. Using the proposed method, the intra- and interspecies heterogeneities and the kinetics of Hg bioconcentration by algae were revealed at the single-cell level. The heterogeneity in the cellular Hg contents is largely related to cell size. The bioconcentration process reached a dynamic equilibrium involving influx/adsorption and efflux/desorption within hours. Algal density is a key factor affecting the distribution of Hg between algae and ambient water. Cellular Hg contents were negatively correlated with algal density, whereas the volume concentration factors almost remained constant. Accordingly, we developed a model based on single-cell analysis that well describes the density-driven effects of Hg bioconcentration by algae. From a novel single-cell perspective, the findings improve our understanding of algal bioconcentration governed by various biological and environmental factors.
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Mercurio , Mercurio/metabolismo , Espectrometría de Masas , Compuestos de Metilmercurio/metabolismo , Contaminantes Químicos del Agua/metabolismo , Cadena Alimentaria , Análisis de la Célula IndividualRESUMEN
Biodegradation of soil organic matter (SOM), which involves greenhouse gas (GHG) emissions, plays an essential role in the global carbon cycle. Over the past few decades, this has become an important research focus, particularly in natural ecosystems. SOM biodegradation significantly affects contaminants in the environment, such as mercury (Hg) methylation, producing highly toxic methylmercury (MeHg). However, the potential link between GHG production from SOM turnover in contaminated soils and biogeochemical processes involving contaminants remains unclear. In this study, we investigated the dynamics of GHG, MeHg production, and the relationship between biogeochemical processes in soils from two typical Hg mining sites. The two contaminated soils have different pathways, explaining the significant variations in GHG and MeHg production. The divergence of the microbial communities in these two biogeochemical processes is essential. In addition to the microbial role, abiotic factors such as Hg species can significantly affect MeHg production. On the other hand, we found an inverse relationship between CH4 and MeHg, suggesting that carbon emission reduction policies and management could inadvertently increase the MeHg levels. This highlights the need for an eclectic approach to organic carbon sequestration and contaminant containment. These findings suggest that it is difficult to establish a general pattern to describe and explain the SOM degradation and MeHg production in contaminated soils within the specific scenarios. However, this study provides a case study and helpful insights for further understanding the links between environmental risks and carbon turnover in Hg mining areas.
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Mercurio , Compuestos de Metilmercurio , Oryza , Contaminantes del Suelo , Suelo , Ecosistema , Contaminantes del Suelo/análisis , Mercurio/análisis , Carbono , Biodegradación Ambiental , Monitoreo del AmbienteRESUMEN
Slow release of emerging contaminants limits their accessibility from soil to pore water, constraining the treatment efficiency of physio-chemical treatment sites. DC fields mobilize organic contaminants and influence their interactions with geo-matrices such as zeolites. Poor knowledge, however, exists on the joint application of heating and electrokinetic approaches on perfluorooctanoic acid (PFOA) transport in porous media. Here, we investigated electrokinetic PFOA transport in zeolite-filled percolation columns at varying temperatures. Variations of pseudo-second-order kinetic constants (kPSO) were correlated to the liquid viscosity variations (η) and elctroosmotic flow velocities (vEOF). Applying DC fields and elevated temperature significantly (>37%) decreased PFOA sorption to zeolite. A good correlation between η, vEOF, and kPSO was found and used to develop an approach interlinking the three parameters to predict the joint effects of DC fields and temperature on PFOA sorption kinetics. These findings may give rise to future applications for better tailoring PFOA transport in environmental biotechnology.
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Caprilatos , Fluorocarburos , Zeolitas , Caprilatos/química , Fluorocarburos/química , Adsorción , Zeolitas/química , Cinética , Modelos QuímicosRESUMEN
Riverine mercury (Hg) is mainly transported to coastal areas in suspended particulate matter (SPM)-bound form, posing a potential threat to human health. Water discharge and SPM characteristics in rivers vary naturally with seasonality and can also be arbitrarily disrupted by anthropogenic regulation events, but their effects on Hg transport remain unresolved. Aiming to understand the confounding effects of seasonality and anthropogenic river regulation on Hg and SPM transport, this study selected the highly sediment-laden Yellow River as a representative conduit. Significant variations in SPM concentrations (108 - 7097 mg/L) resulted in fluctuations in total mercury (THg, 3.79 - 111 ng/L) in river water corresponding to seasonality and anthropogenic water/sediment regulation. Principal component analysis and structural equation model revealed that SPM was the essential factor controlling THg and particulate Hg (PHg) in river water. While SPM exhibited equilibrium state in the dry season, a net resuspension during the anthropogenic regulation and net deposition in the wet season demonstrated the impact of SPM dynamics on Hg distribution and transport to coastal regions. Combining water discharge, SPM, and Hg concentrations, a modified model was developed to quantify Hg flux (2256 kg), over 98% of which was in particulate phase.
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Mercurio , Contaminantes Químicos del Agua , Humanos , Ríos/química , Material Particulado/análisis , Monitoreo del Ambiente , Contaminantes Químicos del Agua/análisis , Mercurio/análisis , Agua/análisis , Polvo/análisis , Océanos y Mares , Sedimentos Geológicos/análisisRESUMEN
In the past few decades, mercury (Hg) discharged into the coastal bays of China has significantly increased; however, long-term trends regarding the pollution status and sources of Hg in these bays have yet to be clear. Focusing on this issue, surface sediments and core sediments were collected in the Jiaozhou Bay (JZB), a typical bay highly affected by human activities in China, to analyze the concentrations and stable isotopic composition of Hg. Total mercury (THg) concentrations in surface sediment varied from 7 to 163 ng/g, with higher levels located in the eastern JZB, possibly attributed to intensive industrial and population density. THg in sediment cores 14 and 20 displayed fluctuating increasing trends from 1936 to 2019, reflecting the deterioration of Hg pollution. In contrast, THg in sediment core 28 near the river mouth exhibited a declining trend, possibly due to the river dam construction. Using a stable isotope mixing model, contributions of various sources (atmospheric, riverine, and industrial emissions) to Hg in the JZB were estimated. The results showed that industrial emissions were the main source (over 50%) of mercury in the JZB in 2019. Sediment cores recorded an increase in industrial Hg due to early industrialization and Reform and Opening-up before 2000. In addition, sediment core 20 demonstrated a rise in the percentage of riverine Hg due to land reclamation at the bay's mouth during 2000-2007.
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Mercurio , Contaminantes Químicos del Agua , Humanos , Mercurio/análisis , Bahías , Contaminantes Químicos del Agua/análisis , Monitoreo del Ambiente/métodos , Sedimentos Geológicos , Isótopos , ChinaRESUMEN
Photo-induced degradation of dimethylmercury (DMHg) is considered to be an important source for the generation of methylmercury (MMHg). However, studies on DMHg photodegradation are scarce, and it is even debatable about whether DMHg can be degraded in natural waters. Herein, we found that both DMHg and MMHg could be photodegraded in three natural waters collected from the Yellow River Delta, while in pure water only DMHg photodegradation occurred under visible light irradiation. The effects of different environmental factors on DMHg photodegradation were investigated, and the underlying mechanisms were elucidated by density functional theory calculations and a series of control experiments. Our findings revealed that the DMHg degradation rate was higher in the tidal creek water compared to Yellow River, Yan Lake, and purified water. NO3-, NO2-, and DOM could promote the photodegradation with DOM and NO3- showing particularly strong positive effects. Different light sources were employed, and UV light was found to be more effective in DMHg photodegradation. Moreover, MMHg was detected during the photodegradation of DMHg, confirming that the photochemical demethylation of DMHg is a source of MMHg in sunlit water. This work may provide a novel mechanistic insight into the DMHg photodegradation in natural waters and enrich the study of the global biogeochemical cycle of Hg.
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Compuestos de Metilmercurio , Fotólisis , Contaminantes Químicos del Agua , Compuestos de Metilmercurio/química , Compuestos de Metilmercurio/análisis , Compuestos de Metilmercurio/efectos de la radiación , Contaminantes Químicos del Agua/química , Contaminantes Químicos del Agua/efectos de la radiación , Contaminantes Químicos del Agua/análisis , Luz , Rayos Ultravioleta , Nitratos/química , Nitratos/análisis , Ríos/químicaRESUMEN
Mercury (Hg), particularly organic mercury, poses a global concern due to its pronounced toxicity and bioaccumulation. Bioremediation of organic mercury in high-salt wastewater faces challenges due to the growth limitations imposed by elevated Cl- and Na+ concentrations on microorganisms. In this study, an isolated marine bacterium Alteromonas macleodii KD01 was demonstrated to degrade methylmercury (MeHg) efficiently in seawater and then was applied to degrade organic mercury (MeHg, ethylmercury, and thimerosal) in simulated high-salt wastewater. Results showed that A. macleodii KD01 can rapidly degrade organic mercury (within 20 min) even at high concentrations (>10 ng/mL), volatilizing a portion of Hg from the wastewater. Further analysis revealed an increased transcription of organomercury lyase (merB) with rising organic mercury concentrations during the exposure process, suggesting the involvement of mer operon (merA and merB). These findings highlight A. macleodii KD01 as a promising candidate for addressing organic mercury pollution in high-salt wastewater.
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Alteromonas , Biodegradación Ambiental , Mercurio , Mercurio/metabolismo , Alteromonas/metabolismo , Aguas Residuales/química , Contaminantes Químicos del Agua/metabolismo , Agua de Mar/microbiología , Aerobiosis , Compuestos de Metilmercurio/metabolismoRESUMEN
Sulfate-reducing bacteria (SRB) play pivotal roles in the biotransformation of mercury (Hg). However, unrevealed global responses of SRB to Hg have restricted our understanding of details of Hg biotransformation processes. The absence of protein-protein interaction (PPI) network under Hg stimuli has been a bottleneck of proteomic analysis for molecular mechanisms of Hg transformation. This study constructed the first comprehensive PPI network of SRB in response to Hg, encompassing 67 connected nodes, 26 independent nodes, and 121 edges, covering 93% of differentially expressed proteins from both previous studies and this study. The network suggested that proteomic changes of SRB in response to Hg occurred globally, including microbial metabolism in diverse environments, carbon metabolism, nucleic acid metabolism and translation, nucleic acid repair, transport systems, nitrogen metabolism, and methyltransferase activity, partial of which could cover the known knowledge. Antibiotic resistance was the original response revealed by this network, providing insights into of Hg biotransformation mechanisms. This study firstly provided the foundational network for a comprehensive understanding of SRB's responses to Hg, convenient for exploration of potential targets for Hg biotransformation. Furthermore, the network indicated that Hg enhances the metabolic activities and modification pathways of SRB to maintain cellular activities, shedding light on the influences of Hg on the carbon, nitrogen, and sulfur cycles at the cellular level.
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Mercurio , Mercurio/metabolismo , Mapas de Interacción de Proteínas , Proteínas Bacterianas/metabolismo , Biotransformación , Sulfatos/metabolismo , Bacterias/metabolismo , Proteómica , Bacterias Reductoras del Azufre/metabolismoRESUMEN
Coastal seas contribute the majority of human methylmercury (MeHg) exposure via marine fisheries. The terrestrial area surrounding the Bohai Sea and Yellow Sea (BS and YS) is one of the mercury (Hg) emission "hot spots" in the world, resulting in high concentrations of Hg in BS and YS seawater in comparison to other marine systems. However, comparable or even lower Hg levels were detected in seafood from the BS and YS than other coastal regions around the word, suggesting a low system bioaccumulation of Hg. Reasoning a low system efficiency of MeHg production (represented by MeHg/THg (total Hg) in seawater) may be present in these two systems, seven cruises were conducted in the BS and YS to test this hypothesis. MeHg/THg ratios in BS and YS seawater were found to be lower than that in most coastal systems, indicating that the system efficiency of MeHg production is relatively lower in the BS and YS. The low system efficiency of MeHg production reduces the risk of Hg in the BS and YS with high Hg discharge intensity. By measuring in situ production and degradation of MeHg using double stable isotope addition method, and MeHg discharge flux from various sources and its exchange at various interfaces, the budgets of MeHg in the BS and YS were estimated. The results indicate that in situ methylation and demethylation are the major source and sink of MeHg in the BS and YS. By comparing the potential controlling processes and environmental parameters for MeHg/THg in the BS and YS with the other coastal seas, estuaries and bays, lower transport efficiency of inorganic Hg from water column to the sediment, slower methylation of Hg, and rapid demethylation of MeHg were identified to be major reasons for the low system efficiency of MeHg production in the BS and YS. This study highlights the necessity of monitoring the system efficiency of MeHg production, associated processes, and controlling parameters to evaluate the efficiency of reducing Hg emissions in China as well as the other countries.
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Monitoreo del Ambiente , Compuestos de Metilmercurio , Agua de Mar , Contaminantes Químicos del Agua , Agua de Mar/química , Océanos y Mares , China , MercurioRESUMEN
Coastal wetland soils play a critical role in the global mercury (Hg) cycle, serving as both an important repository for total mercury (THg) and a hotspot for methylmercury (MeHg) production. This study investigated Hg pollution in soils dominated by Phragmites australis (PA) and Spartina alterniflora (SA) across five representative China's coastal wetlands (Yellow River (YR), Linhong River (LHR), Yangtze River (CJR), Min River (MR), and Nanliu River (NLR)). The THg concentrations ranged from 16.7 to 446.0 (96.3 ± 59.3 ng g-1, dw), while MeHg concentrations varied from 0.01 to 0.81 (0.12 ± 0.12 ng g-1, dw). We further evaluated Hg risk in these wetlands using potential ecological risk index (Er) and geographical enrichment factor (Igeo). Most wetlands exhibited low to moderate ecological risk, except the PA habitat in the YR wetland, showing moderate to high risk. Soil organic matter significantly influenced THg and MeHg distribution, while MeHg% correlated well with soil salinity and pH. These findings highlight the importance of organic-rich coastal wetland soils in THg and MeHg accumulation, with the soil properties influencing net MeHg production. Furthermore, SA habitat generally exhibited higher MeHg%, suggesting its invasion elevates the ecological risk of MeHg in coastal wetlands. ENVIRONMENTAL IMPLICATION: Mercury (Hg), a global pollutant, poses great risks to wildlife and humans. Since industrialization, anthropogenic Hg release surpassed natural sources. Long-term exposure leads to biomagnification of Hg. This study assessed Hg and methylmercury pollution and risks in soils of five China's coastal wetlands dominated by Phragmites australis and Spartina alterniflora. Environmental factors (total carbon, total organic carbon, total nitrogen, salinity, pH) were analyzed to reveal key variables influencing Hg pollution and methylation. Essential for quantifying Hg pollution in coastal wetlands, the findings provide a scientific basis for effective wetland conservation policies and addressing environmental health in these regions.
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Monitoreo del Ambiente , Mercurio , Compuestos de Metilmercurio , Contaminantes del Suelo , Humedales , Compuestos de Metilmercurio/análisis , China , Mercurio/análisis , Contaminantes del Suelo/análisis , Suelo/químicaRESUMEN
Dominant microorganisms and functional genes, including hgcA, hgcB, merA, and merB, have been identified to be responsible for mercury (Hg) methylation or methylmercury (MeHg) demethylation. However, their in situ correlation with MeHg levels and the processes of Hg methylation and MeHg demethylation in coastal areas remains poorly understood. In this study, four functional genes related to Hg methylation and MeHg demethylation (hgcA, hgcB, merA, and merB) were all detected in the sediments of the Eastern China Coastal Seas (ECCSs) (representative coastal seas highly affected by human activities) using metagenomic approaches. HgcA was identified to be the key gene controlling the in situ net production of MeHg in the ECCSs. Based on metagenomic analysis and incubation experiments, sulfate-reducing bacteria were identified as the dominant microorganisms controlling Hg methylation in the ECCSs. In addition, hgcA gene was positively correlated with the MeHg content and Hg methylation rates, highlighting the potential roles of Hg methylation genes and microorganisms influenced by sediment physicochemical properties in MeHg cycling in the ECCSs. These findings highlighted the necessity of conducting similar studies in other natural systems for elucidating the molecular mechanisms underlying MeHg production in aquatic environments.
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Sedimentos Geológicos , Compuestos de Metilmercurio , Océanos y Mares , Contaminantes Químicos del Agua , Sedimentos Geológicos/microbiología , Compuestos de Metilmercurio/metabolismo , China , Contaminantes Químicos del Agua/metabolismo , Bacterias/metabolismo , Bacterias/genética , Biodegradación Ambiental , Metilación , Mercurio/metabolismo , Genes BacterianosRESUMEN
Rice consumption is a major pathway for human cadmium (Cd) exposure. Understanding Cd behavior in the soil-rice system, especially under field conditions, is pivotal for controlling Cd accumulation. This study analyzed Cd concentrations and isotope compositions (δ114/110Cd) in rice plants and surface soil sampled at different times, along with urinary Cd of residents from typical Cd-contaminated paddy fields in Youxian, Hunan, China. Soil water-soluble Cd concentrations varied across sampling times, with δ114/110Cdwater lighter under drained than flooded conditions, suggesting supplementation of water-soluble Cd by isotopically lighter Cd pools, increasing Cd phytoavailability. Both water-soluble Cd and atmospheric deposition contributed to rice Cd accumulation. Water-soluble Cd's contribution increased from 28-52% under flooded to 58-87% under drained conditions due to increased soil Cd phytoavailability. Atmospheric deposition's contribution (12-72%) increased with potential atmospheric deposition flux among sampling areas. The enrichment of heavy Cd isotopes occurred from root-stem-grain to prevent rice Cd accumulation. The different extent of enrichment of heavy isotopes in urine indicated different Cd exposure sources. These findings provide valuable insights into the speciation and phytoavailability changes of Cd in the soil-rice system and highlight the potential application of Cd isotopic fingerprinting in understanding the environmental fate of Cd.
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Cadmio , Oryza , Contaminantes del Suelo , Oryza/metabolismo , Oryza/química , Cadmio/análisis , Cadmio/metabolismo , Contaminantes del Suelo/metabolismo , Contaminantes del Suelo/análisis , China , Suelo/química , Humanos , Isótopos , Raíces de Plantas/metabolismo , Raíces de Plantas/química , Monitoreo del Ambiente , Fraccionamiento QuímicoRESUMEN
Pyrolysis is considered a highly practical, cost-effective, and environment-friendly technology for waste tires disposal. In this study, pyrolysis processes of waste tires were conducted in a pilot scale furnace feeding at 30 kg/h. The properties of pyrolytic products and the distribution patterns of pollutants generated in different operating stages (start-up, steady, and shut-down) were investigated. The pyrolytic gas in the steady state had a high caloric value of 10799 kJ/Nm3, valuable as heating source for pyrolysis. The elements of sulfur and zinc were effectively fixed as ZnS in the pyrolytic carbon. The basic properties of pyrolytic oil were in line with commercial diesel oil except for the lower flash point. Heavy metals were mainly concentrated in the pyrolytic carbon, with slightly higher concentrations in the steady state. Moreover, polycyclic aromatic hydrocarbons (PAHs) and polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) were mainly concentrated in the pyrolytic oil, with predominated low-ring PAHs and high chlorinated PCDD/Fs. The concentrations of PAHs and PCDD/Fs in the gas phase were higher during the start-up stage due to the memory effect, whereas were effectively reduced during the steady stage. The concentration of PAHs in the solid phase was highest during the furnace start-up and lowest in the shut-down stage. In contrast to PAHs, the PCDD/Fs in the solid phase reached their highest concentration during the shut-down stage, which was mainly affected by temperature. The results provide guidance for the reducing of pollutant emissions and the recycling of pyrolytic products.
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Contaminantes Atmosféricos , Carbono , Contaminantes Ambientales , Dibenzodioxinas Policloradas , Hidrocarburos Policíclicos Aromáticos , Contaminantes Ambientales/análisis , Contaminantes Atmosféricos/análisis , Dibenzodioxinas Policloradas/análisis , Dibenzofuranos , Pirólisis , Dibenzofuranos Policlorados , Hidrocarburos Policíclicos Aromáticos/análisisRESUMEN
To elucidate the potential risks of the toxic pollutant mercury (Hg) in polar waters, the study of accumulated Hg in fish is compelling for understanding the cycling and fate of Hg on a regional scale in Antarctica. Herein, the Hg isotopic compositions of Antarctic cod Notothenia coriiceps were assessed in skeletal muscle, liver, and heart tissues to distinguish the differences in Hg accumulation in isolated coastal environments of the eastern (Chinese Zhongshan Station, ZSS) and the antipode western Antarctica (Chinese Great Wall Station, GWS), which are separated by over 4000 km. Differences in odd mass-independent isotope fractionation (odd-MIF) and mass-dependent fractionation (MDF) across fish tissues were reflection of the specific accumulation of methylmercury (MeHg) and inorganic Hg (iHg) with different isotopic fingerprints. Internal metabolism including hepatic detoxification and processes related to heart may also contribute to MDF. Regional heterogeneity in iHg end-members further provided evidence that bioaccumulated Hg origins can be largely influenced by polar water circumstances and foraging behavior. Sea ice was hypothesized to play critical roles in both the release of Hg with negative odd-MIF derived from photoreduction of Hg2+ on its surface and the impediment of photochemical transformation of Hg in water layers. Overall, the multitissue isotopic compositions in local fish species and prime drivers of the heterogeneous Hg cycling and bioaccumulation patterns presented here enable a comprehensive understanding of Hg biogeochemical cycling in polar coastal waters.
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Mercurio , Compuestos de Metilmercurio , Contaminantes Químicos del Agua , Animales , Mercurio/análisis , Regiones Antárticas , Isótopos de Mercurio/análisis , Bioacumulación , Cubierta de Hielo , Monitoreo del Ambiente , Compuestos de Metilmercurio/metabolismo , Peces/metabolismo , Isótopos , Agua/metabolismo , Contaminantes Químicos del Agua/análisisRESUMEN
Ethylmercury (EtHg), similar to methylmercury (MeHg), is highly neurotoxic and bioaccumulative. Although recent studies suggested its occurrence in natural soils and sediments, the common propylation derivatization for EtHg analysis might generate EtHg artifacts, potentially leading to its overestimation in environmental samples. Furthermore, the extensive environmental prevalence of EtHg remains unverified, keeping its importance largely uncertain. This study investigated the formation of EtHg artifacts during propylation derivatization, evaluating artifacts formation and recoveries under different extraction methods with real samples, and confirmed the widespread occurrence of EtHg in Chinese wetlands. EtHg artifacts were obviously present during the propylation derivatization and strongly dependent on the levels of Hg2+ (0.1-10 ng) in the derivatization solution (R² = 0.99), accounting for 1.38-2.14% of Hg2+. CuSO4-HNO3CH2Cl2 extraction (effectively removing Hg2+) combined with propylation derivatization offers excellent recovery (81-86%) and low artifacts (< LOD: 1.98 × 10-4 ng/g) for EtHg measurement in soils/sediments, with results aligning with those from online solid phase extraction-high performance liquid chromatography-inductively coupled plasma mass spectrometry (R2 = 0.99). Additionally, we observed the occurrence of EtHg in soil and sediment samples across 14 Chinese wetlands, with concentrations varying from 6.08 to 171 pg/g, similar to MeHg concentrations at some sites. EtHg positively correlates with MeHg, total Hg, and total organic carbon across all samples, indicating a possible biological formation. These findings help better understand and predict the prevalence of EtHg in wetlands and its key role in environmental Hg cycle.