The changing nature of groundwater in the global water cycle.

In recent decades, climate change and other anthropogenic activities have substantially affected groundwater systems worldwide. These impacts include changes in groundwater recharge, discharge, flow, storage, and distribution. Climate-induced shifts are evident in altered recharge rates, greater groundwater contribution to streamflow in glacierized catchments, and enhanced groundwater flow in permafrost areas. Direct anthropogenic changes include groundwater withdrawal and injection, regional flow regime modification, water table and storage alterations, and redistribution of embedded groundwater in foods globally. Notably, groundwater extraction contributes to sea level rise, increasing the risk of groundwater inundation in coastal areas. The role of groundwater in the global water cycle is becoming more dynamic and complex. Quantifying these changes is essential to ensure sustainable supply of fresh groundwater resources for people and ecosystems.

Maternal or Paternal Antibiotics? Intergenerational Transmission and Reproductive Toxicity in Zebrafish.

Despite the known direct toxicity of various antibiotics to aquatic organisms, the potential chronic impact through intergenerational transmission on reproduction remains elusive. Here, we exposed zebrafish to a mixture of 15 commonly consumed antibiotics at environmentally relevant concentrations (1 and 100 µg L-1) with a cross-mating design. A high accumulation of antibiotics was detected in the ovary (up to 904.58 ng g-1) and testis (up to 1704.49 ng g-1) of F0 fish. The transmission of antibiotics from the F0 generation to the subsequent generation (F1 offspring) was confirmed with a transmission rate (ki) ranging from 0.11 to 2.32. The maternal transfer of antibiotics was significantly higher, relative to paternal transfer, due to a greater role of transmission through ovarian enrichment and oviposition compared to testis enrichment. There were similar impairments in reproductive and developmental indexes on F1 eggs found following both female and male parental exposure. Almost all antibiotics were eliminated in F2 eggs in comparison to F1 eggs. However, there were still reproductive and developmental toxic responses observed in F2 fish, suggesting that antibiotic concentration levels were not the only criterion for evaluating the toxic effects for each generation. These findings unveil the intergenerational transmission mechanism of antibiotics in fish models and underscore their potential and lasting impact in aquatic environments.

Uncovering the processes of microbial community assembly in the near-surface sediments of a climate-sensitive glacier-fed lake.

Glacier-fed lakes are characterized by cold temperatures, high altitudes, and nutrient-poor conditions. Despite these challenging conditions, near-surface sediments of glacier-fed lakes harbor rich microbial communities that are critical for ecosystem functioning and serve as a bridge between aquatic ecology and the deep subsurface biosphere. However, there is limited knowledge regarding the microbial communities and their assembly processes in these sediments, which are highly vulnerable to climate change. To fill this knowledge gap, this study systematically analyzed environmental variables, microbial communities, diversity, co-occurrence relationships, and community assembly processes in the near-surface sediments of a glacier-fed lake in the Tibetan Plateau. The results revealed distinct vertical gradients in microbial diversity and subcommunities, highlighting the significant influence of selection processes and adaptive abilities on microbial communities. Specifically, specialists played a crucial role within the overall microbial communities. Microbial assembly was primarily driven by homogeneous selection, but its influence declined with increasing depth. In contrast, homogenizing dispersal showed an opposite pattern, and the bottom layer exhibited heterogeneous selection and undominated processes. These patterns of microbial assembly were primarily driven by environmental gradients, with significant contributions from processes associated to ammonium and organic matter deposition, as well as chemical precipitation in response to a warming climate. This study enhances our understanding of the microbial communities and assembly processes in the near-surface sediments of glacier-fed lakes and sheds light on geo-microbiological processes in climate-sensitive lacustrine sediments.

A Fractional-order dual-continuum model to capture non-Fickian solute transport in a regional-scale fractured aquifer.

Contaminant transport in fractured media exhibits complex dynamics, including multiple peaks in breakthrough curves (BTCs) and non-Fickian diffusion, thereby posing significant challenges to the application of traditional transport models. Here we undertook a detailed study of a natural-gradient tracer test conducted in a regional-scale fractured carbonate aquifer situated in southwestern Germany, where the observed BTCs contained both dual peaks and positive skewness. These BTCs were used to optimize parameters and interpret their physical meanings for several transport models, including the dual-continuum model (DCM) and the fractional derivative equation (FDE) model. Tracer concentration distributions were simulated in both single- and dual-continuum media employing the DCM and FDE models. Our results demonstrated that while the DCM model could reasonably replicate the bimodal BTC, the FDE (which accounts for solute retention) outperformed in capturing the heavy-tailed BTC. This was attributed to the limitations of grid-based numerical models that assume Fickian diffusion and fail to map small-scale medium heterogeneity exhaustively. In contrast, a parsimonious model like the FDE, with upscaled parameters, was found to be more effective in capturing regional-scale non-Fickian transport. To further characterize the multiple BTC peaks the standard FDE missed, we proposed a fractional derivative dual-continuum model (fDCM). This model was found to be adept at capturing both the multi-peak and late-time heavy tail in the BTC. Our study thus opens an alternate pathway for modeling solute transport in regional-scale fractured to partially karstified aquifers.

Poly- and Perfluoroalkyl Substances Induce Immunotoxicity via the TLR Pathway in Zebrafish: Links to Carbon Chain Length.

Previous studies have reported the immunotoxicity of per- and polyfluoroalkyl substances (PFASs), but it remains a significant challenge to assess over 10,000 distinct PFASs registered in the distributed structure-searchable toxicity (DSSTox) database. We aim to reveal the mechanisms of immunotoxicity of different PFASs and hypothesize that PFAS immunotoxicity is dependent on the carbon chain length. Perfluorobutanesulfonic acid (PFBA), perfluorooctanoic acid (PFOA), and perfluorononanoic acid (PFNA) representing different carbon chain lengths (4-9) at environmentally relevant levels strongly reduced the host's antibacterial ability during the zebrafish's early-life stage. Innate and adaptive immunities were both suppressed after PFAS exposures, exhibiting a significant induction of macrophages and neutrophils and expression of immune-related genes and indicators. Interestingly, the PFAS-induced immunotoxic responses were positively correlated to the carbon chain length. Moreover, PFASs activated downstream genes of the toll-like receptor (TLR), uncovering a seminal role of TLR in PFAS immunomodulatory effects. Myeloid differentiation factor 88 (MyD88) morpholino knock-down experiments and MyD88 inhibitors alleviated the immunotoxicity of PFASs. Overall, the comparative results demonstrate differences in the immunotoxic responses of PFASs due to carbon chain length in zebrafish, providing new insights into the prediction and classification of PFASs mode of toxic action based on carbon chain length.

Evaluating the spatial and temporal distribution of emerging contaminants in the Pearl River Basin for regulating purposes.

Little information is available on how the types, concentrations, and distribution of chemicals have evolved over the years. The objective of the present study is therefore to review the spatial and temporal distribution profile of emerging contaminants with limited toxicology data in the pearl river basin over the years to build up the emerging contaminants database in this region for risk assessment and regulatory purposes. The result revealed that seven groups of emerging contaminants were abundant in this region, and many emerging contaminants had been detected at much higher concentrations before 2011. Specifically, antibiotics, phenolic compounds, and acidic pharmaceuticals were the most abundant emerging contaminants detected in the aquatic compartment, while phenolic compounds were of the most profound concern in soil. Flame retardants and plastics were the most frequently studied chemicals in organisms. The abundance of the field concentrations and frequencies varied considerably over the years, and currently available data can hardly be used for regulation purposes. It is suggested that watershed management should establish a regular monitoring scheme and comprehensive database to monitor the distribution of emerging contaminants considering the highly condensed population in this region. The priority monitoring list should be formed in consideration of historical abundance, potential toxic effects of emerging contaminants as well as the distribution of heavily polluting industries in the region.

Groundwater Quality and Health: Making the Invisible Visible.

Linking groundwater quality to health will make the invisible groundwater visible, but there are knowledge gaps to understand the linkage which requires cross-disciplinary convergent research. The substances in groundwater that are critical to health can be classified into five types according to the sources and characteristics: geogenic substances, biogenic elements, anthropogenic contaminants, emerging contaminants, and pathogens. The most intriguing questions are related to quantitative assessment of human health and ecological risks of exposure to the critical substances via natural or induced artificial groundwater discharge: What is the list of critical substances released from discharging groundwater, and what are the pathways of the receptors' exposure to the critical substances? How to quantify the flux of critical substances during groundwater discharge? What procedures can we follow to assess human health and ecological risks of groundwater discharge? Answering these questions is fundamental for humans to deal with the challenges of water security and health risks related to groundwater quality. This perspective provides recent progresses, knowledge gaps, and future trends in understanding the linkage between groundwater quality and health.

Coastal phytoplankton blooms expand and intensify in the 21st century.

Phytoplankton blooms in coastal oceans can be beneficial to coastal fisheries production and ecosystem function, but can also cause major environmental problems1,2-yet detailed characterizations of bloom incidence and distribution are not available worldwide. Here we map daily marine coastal algal blooms between 2003 and 2020 using global satellite observations at 1-km spatial resolution. We found that algal blooms occurred in 126 out of the 153 coastal countries examined. Globally, the spatial extent (+13.2%) and frequency (+59.2%) of blooms increased significantly (P < 0.05) over the study period, whereas blooms weakened in tropical and subtropical areas of the Northern Hemisphere. We documented the relationship between the bloom trends and ocean circulation, and identified the stimulatory effects of recent increases in sea surface temperature. Our compilation of daily mapped coastal phytoplankton blooms provides the basis for global assessments of bloom risks and benefits, and for the formulation or evaluation of management or policy actions.

Integrated effects of bioturbation, warming and sea-level rise on mobility of sulfide and metalloids in sediment porewater of mangrove wetlands.

Global warming and sea-level rise exert profound impacts on coastal mangrove ecosystems, where widespread benthic crabs change sediment properties and regulate material cycles. How crab bioturbation perturbs the mobilities of bioavailable arsenic (As), antimony (Sb) and sulfide in sediment-water systems and their variability in response to temperature and sea-level rise is still unknown. By combining field monitoring and laboratory experiments, we found that As was mobilized under sulfidic conditions while Sb was mobilized under oxic conditions in mangrove sediments. Crab burrowing greatly enhanced oxidizing conditions, resulting in enhanced Sb mobilization and release but As sequestration by iron/manganese oxides. In control experiments with non-bioturbation, the more sulfidic conditions triggered the contrasting situation of As remobilization and release but Sb precipitation and burial. Moreover, the bioturbated sediments were highly heterogeneous for spatial distributions of labile sulfide, As and Sb as presented by 2-D high-resolution imaging and Moran's Index (patchy at the <1 cm scale). Warming stimulated stronger burrowing activities, which led to more oxic conditions and further Sb mobilization and As sequestration, whilst sea-level rise did the opposite via suppressing crab burrowing activity. This work highlights that global climate changes have the potential to significantly alter element cycles in coastal mangrove wetlands by regulating benthic bioturbation and redox chemistry.

Coastal aquaculture regulates phosphorus cycling in estuarine wetlands: Mobilization, kinetic resupply, and source-sink process.

Estuarine mangrove wetlands have gradually declined owing to the growing construction of aquaculture ponds. How the speciation, transition, and migration of phosphorus (P) adaptively change in the sediments of this pond-wetland ecosystem remains unclear. In this study, we used high-resolution devices to explore the contrasting P behaviors associated with the redox cycles of Fe-Mn-S-As in estuarine and pond sediments. The results showed that the construction of aquaculture ponds increased the content or percentage of the silt, organic carbon, and P fractions in sediments. Dissolved organic P (DOP) concentrations in pore water were fluctuant with depths, accounting for only 18±15% and 20±11% of total dissolved P (TDP) in estuarine and pond sediment, respectively. Furthermore, DOP was less strongly correlated with other P species, including Fe, Mn, and sulfide. The coupling of dissolved reactive P (DRP) and TDP with Fe and sulfide confirmed that P mobility is regulated by Fe redox cycling in estuarine sediments, whereas Fe(III) reduction and sulfate reduction co-regulate P remobilization in pond sediments. The apparent diffusion flux revealed all sediments acting as sources for TDP (0.04-0.1 mg m-2 d-1) to the overlying water, while mangrove sediments were sources of DOP, and pond sediments were major sources of DRP. The DIFS model overestimated the P kinetic resupply ability, which was evaluated using DRP rather than TDP. This study improves our understanding of P cycling and budget in aquaculture pond-mangrove ecosystems and has important implications for understanding water eutrophication more effectively.

A data-driven approach to exploring the causal relationships between distributed pumping activities and aquifer drawdown.

Groundwater depletion, typically caused by the distributed pumping activities of multiple stakeholders (i.e., water users) that share a hydrologically connected aquifer, has led to severe environmental and ecological problems in many river basins worldwide. Conventionally, the effects of pumping on aquifer depletion are quantified using well hydraulics or physically based hydrological models in groundwater management. However, the derivation of well hydraulics-based analytical solutions requires numerous simplifying assumptions, while the construction and calibration of a physically based groundwater flow model require detailed information about the subsurface properties, which are subject to large uncertainties. In this study, we develop a novel modeling framework that does not rely on well hydraulics or groundwater flow models. The proposed framework integrates (1) a deep learning model that captures the spatiotemporal variations in the aquifer in response to distributed pumping activities in multiple well fields and (2) a statistical causal inference model that identifies the causal networks among stakeholders to quantify the causal effects of individual pumping activities on aquifer depletion. The proposed framework is tested on a synthetic case study site with well fields that have various spatial distributions and pumping rates. The modeling results show that the deep learning method can effectively capture the water table dynamics influenced by distributed pumping activities with R2 >90 % for all observation data. More importantly, our model is capable of assessing the causal networks between the drawdown of water table and the pumping activities of multiple well fields and quantifying their causal strengths. These results suggest that our modeling framework can be used to explicitly assess the extent to which each individual stakeholder's pumping activities contribute to aquifer depletion at the system level. The concepts and techniques developed in this study can be used to resolve classic externality problems in the context of common-pool groundwater management.

Perfluorononanoic Acid Induces Neurotoxicity via Synaptogenesis Signaling in Zebrafish.

Perfluorononanoic acid (PFNA), commonly used as an alternative polyfluorinated compound (PFC) of perfluorooctanoic acid (PFOA), has been widely detected in the aquatic environment. Previous ecotoxicological and epidemiological results suggested that some neurobehavioral effects were associated with PFC exposure; however, the ecological impacts and underlying neurotoxicity mechanisms remain unclear, particularly in aquatic organisms during sensitive, early developmental stages. In this study, zebrafish embryos were exposed to environmentally relevant concentrations of PFNA for 120 h, and the neurological effects of PFNA were comprehensively assessed using transcriptional, biochemical, morphological, and behavioral assays. RNA sequencing and advanced bioinformatics analyses predicted and characterized the key biological processes and pathways affected by PFNA exposure, which included the synaptogenesis signaling pathway, neurotransmitter synapse, and CREB signaling in neurons. Neurotransmitter levels (acetylcholine, glutamate, 5-hydroxytryptamine, γ-aminobutyric acid, dopamine, and noradrenaline) were significantly decreased in zebrafish larvae, and the Tg(gad67:GFP) transgenic line revealed a decreased number of GABAergic neurons in PFNA-treated larvae. Moreover, the swimming distance, rotation frequency, and activity degree were also significantly affected by PFNA, linking molecular-level changes to behavioral consequences.

Sunlight-mediated CaO2 inactivation of pathogen indicator organisms in surface water system: Roles of reactive species, characterization of pathogen inactivation.

In the era of the current epidemic, it is urgent to control pathogens in sewage, eliminate the source of infection, and optimize the technology for killing pathogens. Combining calcium peroxide (CaO2) with sunlight is considered a potentially efficient, economical, and eco-friendly method for pathogen-contaminated water remediation. This paper evaluated the solar activating properties of CaO2 for inactivating pathogenic indicators and explored the roles of reactive species contributing to pathogen inactivation. Moreover, these reactive species' average steady-state concentrations and second-order reaction rate were tentatively explored, and mechanistic model for photoinactivation were establishment. Pathogen's inactivation was mainly attributed to direct photoinactivation (13∼50%) and exogenous indirect mechanisms with corresponding contributions of reactive species, i.e., OH- (14∼23%), 1O2 (12∼28%), •OH (20∼32%), O2•- (12∼16%), and H2O2 (6∼11%). Furthermore, cell membrane rupture and DNA damage were observed by transmission electron microscopy (TEM) and agarose gel electrophoresis (AGE) experiments. Among experiments on common aqueous constituents influencing photoinactivation, copper and iron ions were found to promote a pathogen-inactivating ability of the system, while fulvic acids (FA) and humic acid (HA) had the opposite effect. This study revealed the potential of CaO2/sunlight to inactivate pathogens and laid a foundation for its application in inactivating pathogens in surface water.

Vertical Hydrologic Exchange Flows Control Methane Emissions from Riverbed Sediments.

CH4 emissions from inland waters are highly uncertain in the current global CH4 budget, especially for streams, rivers, and other lotic systems. Previous studies have attributed the strong spatiotemporal heterogeneity of riverine CH4 to environmental factors such as sediment type, water level, temperature, or particulate organic carbon abundance through correlation analysis. However, a mechanistic understanding of the basis for such heterogeneity is lacking. Here, we combine sediment CH4 data from the Hanford reach of the Columbia River with a biogeochemical-transport model to show that vertical hydrologic exchange flows (VHEFs), driven by the difference between river stage and groundwater level, determine CH4 flux at the sediment-water interface. CH4 fluxes show a nonlinear relationship with the magnitude of VHEFs, where high VHEFs introduce O2 into riverbed sediments, which inhibit CH4 production and induce CH4 oxidation, and low VHEFs cause transient reduction in CH4 flux (relative to production) due to reduced advective CH4 transport. In addition, VHEFs lead to the hysteresis of temperature rise and CH4 emissions because high river discharge caused by snowmelt in spring leads to strong downwelling flow that offsets increasing CH4 production with temperature rise. Our findings reveal how the interplay between in-stream hydrologic flux besides fluvial-wetland connectivity and microbial metabolic pathways that compete with methanogenic pathways can produce complex patterns in CH4 production and emission in riverbed alluvial sediments.

Deficiency and excess of groundwater iodine and their health associations.

More than two billion people worldwide have suffered thyroid disorders from either iodine deficiency or excess. By creating the national map of groundwater iodine throughout China, we reveal the spatial responses of diverse health risks to iodine in continental groundwater. Greater non-carcinogenic risks relevant to lower iodine more likely occur in the areas of higher altitude, while those associated with high groundwater iodine are concentrated in the areas suffered from transgressions enhanced by land over-use and intensive anthropogenic overexploitation. The potential roles of groundwater iodine species are also explored: iodide might be associated with subclinical hypothyroidism particularly in higher iodine regions, whereas iodate impacts on thyroid risks in presence of universal salt iodization exhibit high uncertainties in lower iodine regions. This implies that accurate iodine supply depending on spatial heterogeneity and dietary iodine structure optimization are highly needed to mitigate thyroid risks in iodine-deficient and -excess areas globally.

Mapping global lake dynamics reveals the emerging roles of small lakes.

Lakes are important natural resources and carbon gas emitters and are undergoing rapid changes worldwide in response to climate change and human activities. A detailed global characterization of lakes and their long-term dynamics does not exist, which is however crucial for evaluating the associated impacts on water availability and carbon emissions. Here, we map 3.4 million lakes on a global scale, including their explicit maximum extents and probability-weighted area changes over the past four decades. From the beginning period (1984-1999) to the end (2010-2019), the lake area increased across all six continents analyzed, with a net change of +46,278 km2, and 56% of the expansion was attributed to reservoirs. Interestingly, although small lakes (<1 km2) accounted for just 15% of the global lake area, they dominated the variability in total lake size in half of the global inland lake regions. The identified lake area increase over time led to higher lacustrine carbon emissions, mostly attributed to small lakes. Our findings illustrate the emerging roles of small lakes in regulating not only local inland water variability, but also the global trends of surface water extent and carbon emissions.

Metabolomics Reveal Nanoplastic-Induced Mitochondrial Damage in Human Liver and Lung Cells.

Plastic debris in the global biosphere is an increasing concern, and nanoplastic (NPs) toxicity in humans is far from being understood. Studies have indicated that NPs can affect mitochondria, but the underlying mechanisms remain unclear. The liver and lungs have important metabolic functions and are vulnerable to NP exposure. In this study, we investigated the effects of 80 nm NPs on mitochondrial functions and metabolic pathways in normal human hepatic (L02) cells and lung (BEAS-2B) cells. NP exposure did not induce mass cell death; however, transmission electron microscopy analysis showed that the NPs could enter the cells and cause mitochondrial damage, as evidenced by overproduction of mitochondrial reactive oxygen species, alterations in the mitochondrial membrane potential, and suppression of mitochondrial respiration. These alterations were observed at NP concentrations as low as 0.0125 mg/mL, which might be comparable to the environmental levels. Nontarget metabolomics confirmed that the most significantly impacted processes were mitochondrial-related. The metabolic function of L02 cells was more vulnerable to NP exposure than that of BEAS-2B cells, especially at low NP concentrations. This study identifies NP-induced mitochondrial dysfunction and metabolic toxicity pathways in target human cells, providing insight into the possibility of adverse outcomes in human health.

Self-supported trimetallic NiZnLa nanosheets on hierarchical porous graphene oxide-polymer composite fibers for enhanced phosphate removal from water.

Phosphate-induced water eutrophication has attracted global attention. Fabricating adsorbents with both high phosphate adsorption affinity and accessible separation property is challenging. Herein, PG@NZL, a hierarchical nanocomposite fibrous membrane, was fabricated via in-situ growth of La-doped NiZn-LDH (NiZnLa0.1) over electrospun graphene oxide-polymer composite fibers (PG). The porous surface of the PG fibers provided abundant anchor sites for the vertical self-supported growth of NiZnLa0.1 nanosheets, contributing to a high surface area. The La-doped NiZnLa0.1 trimetallic LDH achieved a much higher adsorption capacity than NiZn-LDH. The negative adsorption energy (-1.45 eV), calculated with DFT, confirmed its spontaneous adsorption potential for phosphate. Interestingly, the PG fibers contributed to oxygen vacancies and the metal center electronic structure evolution of NiZnLa0.1, thus strengthening the coordination with phosphate. Mechanistic analysis revealed that the high adsorption capacity of PG@NZL is attributed to its superior anion exchange property, oxygen vacancies, and inner-sphere complexation. Therefore, the flexible and easily separated PG@NZL nanocomposite fibrous membrane is a promising adsorbent for effectively treating phosphate-bearing wastewater.

Parental transfer of an antibiotic mixture induces cardiotoxicity in early life-stage zebrafish: A cross-generational study.

Antibiotic residues in the aquatic environment have been shown to induce significant adverse effects on the early-life stage development of aquatic organisms, though the underlying molecular mechanisms of these effects have not been well characterized. In this study, we performed global mRNA-miRNA sequencing, canonical pathway analyses, morphological, physiological, immunohistochemical, and behavioral analyses to comprehensively assess the cross-generational cardiotoxicity and mechanisms of antibiotic mixtures in zebrafish. Following parental treatment to 1 and 100 µg/L antibiotic mixtures (15 of the most commonly detected antibiotics) for 150 days, all 15 assessed antibiotics were detected in the F1 eggs, indicating the cross-generational transfer of antibiotics. Global mRNA-miRNA sequencing functional analysis predicted cardiotoxicity in the F1 generation by using the F1 whole fish. Consistent with canonical pathway analyses, significant cardiotoxicity was observed in F1 larvae, as well as the apoptosis of cardiac cells. Furthermore, let-7a-5p regulated the cardiac hypertrophy signaling pathway, suggesting mechanisms of miRNA of let-7 family mediating cross-generational cardiotoxicity of antibiotics in zebrafish. This study lays some groundwork for developing interventions to prevent parental exposure to environmental pollutants such as antibiotics from adversely affecting offspring development.