Resolving Ultraviolet-Visible Spectra for Complex Dissolved Mixtures of Multitudinous Organic Matters in Aerosols.

Light-absorbing organic aerosols, referred to as brown carbon (BrC), play a vital role in the global climate and air quality. Due to the complexity of BrC chromophores, the identified absorbing substances in the ambient atmosphere are very limited. However, without comprehensive knowledge of the complex absorbing compounds in BrC, our understanding of its sources, formation, and evolution mechanisms remains superficial, leading to great uncertainty in climatic and atmospheric models. To address this gap, we developed a constrained non-negative matrix factorization (NMF) model to resolve the individual ultraviolet-visible spectrum for each substance in dissolved organic aerosols, with the power of ultrahigh-performance liquid chromatography-diode array detector-ultrahigh-resolution mass spectrometry (UHPLC-DAD-UHRMS). The resolved spectra were validated by selected standard substances and validation samples. Approximately 40,000 light-absorbing substances were recognized at the MS1 level. It turns out that BrC is composed of a vast number of substances rather than a few prominent chromophores in the urban atmosphere. Previous understanding of the absorbing feature of BrC based on a few identified compounds could be biased. Weak-absorbing substances missed previously play an important role in BrC absorption when they are integrated due to their overwhelming number. This model brings the property exploration of complex dissolved organic mixtures to a molecular level, laying a foundation for identifying potentially significant compositions and obtaining a comprehensive chemical picture.

Diatom cell-size composition as a novel tool for quantitative estimates of the water table in peatlands.

Diatom cell-size composition is an indicator of aquatic environmental changes but has been rarely investigated, especially in semi-terrestrial peatlands. In this study, both taxonomic composition and cell-size composition of diatoms were analysed in 41 samples from two montane peatlands, northeastern China. Redundancy analyses revealed that diatom taxonomic composition was significantly related to the depth to the water table (DWT) and Ca2+, while cell-size composition was significantly associated with DWT and Si. DWT was the most important factor and its sole effect explained 26.2% and 17.9% of the total variance in taxonomic composition and cell-size composition, respectively. Accordingly, diatom-based water-table transfer functions were developed based on taxonomic composition and cell-size composition, respectively. The maximum-likelihood (ML) model based on diatom taxonomic composition had the best performance, with a correlation coefficient value (R2) of 0.78 and the root mean squared error of prediction (RMSEP) of 6.66 cm. The ML model based on cell-size composition had similar performance, with an R2 of 0.78 and the RMSEP of 6.87 cm, suggesting that diatom cell-size composition can be a new quantitative means to track past water-table changes. This method requires further appraisal with palaeoecological data but offers a new option that deserves exploration.

Global Measurements of Brown Carbon and Estimated Direct Radiative Effects.

Brown carbon (BrC) is an organic aerosol material that preferentially absorbs light of shorter wavelengths. Global-scale radiative impacts of BrC have been difficult to assess due to the lack of BrC observational data. To address this, aerosol filters were continuously collected with near pole-to-pole latitudinal coverage over the Pacific and Atlantic basins in three seasons as part of the Atmospheric Tomography Mission. BrC chromophores in filter extracts were measured. We find that globally, BrC was highly spatially heterogeneous, mostly detected in air masses that had been transported from regions of extensive biomass burning. We calculate the average direct radiative effect due to BrC absorption accounted for approximately 7% to 48% of the top of the atmosphere clear-sky instantaneous forcing by all absorbing carbonaceous aerosols in the remote atmosphere, indicating that BrC from biomass burning is an important component of the global radiative balance.

Review of Acellular Assays of Ambient Particulate Matter Oxidative Potential: Methods and Relationships with Composition, Sources, and Health Effects.

Oxidative stress is a potential mechanism of action for particulate matter (PM) toxicity and can occur when the body's antioxidant capacity cannot counteract or detoxify harmful effects of reactive oxygen species (ROS) due to an excess presence of ROS. ROS are introduced to the body via inhalation of PM with these species present on and/or within the particles (particle-bound ROS) and/or through catalytic generation of ROS in vivo after inhaling redox-active PM species (oxidative potential, OP). The recent development of acellular OP measurement techniques has led to a surge in research across the globe. In this review, particle-bound ROS techniques are discussed briefly while OP measurements are the focus due to an increasing number of epidemiologic studies using OP measurements showing associations with adverse health effects in some studies. The most common OP measurement techniques, including the dithiothreitol assay, glutathione assay, and ascorbic acid assay, are discussed along with evidence for utility of OP measurements in epidemiologic studies and PM characteristics that drive different responses between assay types (such as species composition, emission source, and photochemistry). Overall, most OP assays respond to metals like copper than can be found in emission sources like vehicles. Some OP assays respond to organics, especially photochemically aged organics, from sources like biomass burning. Select OP measurements have significant associations with certain cardiorespiratory end points, such as asthma, congestive heart disease, and lung cancer. In fact, multiple studies have found that exposure to OP measured using the dithiothreitol and glutathione assays drives higher risk ratios for certain cardiorespiratory outcomes than PM mass, suggesting OP measurements may be integrating the health-relevant fraction of PM and will be useful tools for future health analyses. The compositional impacts, including species and emission sources, on OP could have serious implications for health-relevant PM exposure. Though more work is needed, OP assays show promise for health studies as they integrate the impacts of PM species and properties on catalytic redox reactions into one measurement, and current work highlights the importance of metals, organic carbon, vehicles, and biomass burning emissions to PM exposures that could impact health.

Highly Acidic Ambient Particles, Soluble Metals, and Oxidative Potential: A Link between Sulfate and Aerosol Toxicity.

Soluble transition metals in particulate matter (PM) can generate reactive oxygen species in vivo by redox cycling, leading to oxidative stress and adverse health effects. Most metals, such as those from roadway traffic, are emitted in an insoluble form, but must be soluble for redox cycling. Here we present the mechanism of metals dissolution by highly acidic sulfate aerosol and the effect on particle oxidative potential (OP) through analysis of size distributions. Size-segregated ambient PM were collected from a road-side and representative urban site in Atlanta, GA. Elemental and organic carbon, ions, total and water-soluble metals, and water-soluble OP were measured. Particle pH was determined with a thermodynamic model using measured ionic species. Sulfate was spatially uniform and found mainly in the fine mode, whereas total metals and mineral dust cations were highest at the road-side site and in the coarse mode, resulting in a fine mode pH < 2 and near neutral coarse mode. Soluble metals and OP peaked at the intersection of these modes demonstrating that sulfate plays a key role in producing highly acidic fine aerosols capable of dissolving primary transition metals that contribute to aerosol OP. Sulfate-driven metals dissolution may account for sulfate-health associations reported in past studies.

Ambient Size Distributions and Lung Deposition of Aerosol Dithiothreitol-Measured Oxidative Potential: Contrast between Soluble and Insoluble Particles.

Ambient particulate matter may upset redox homeostasis, leading to oxidative stress and adverse health effects. Size distributions of water-insoluble and water-soluble OPDTT (dithiothreitol assay, measure of oxidative potential per air volume) are reported for a roadside site and an urban site. The average water-insoluble fractions were 23% and 51%, and 37% and 39%, for fine and coarse modes at the roadside and urban sites, respectively, measured during different periods. Water-soluble OPDTT was unimodal, peaked near 1-2.5 µm due to contributions from fine-mode organic components plus coarse-mode transition metal ions. In contrast, water-insoluble OPDTT was bimodal, with both fine and coarse modes. The main chemical components that drive both fractions appear to be the same, except that for water-insoluble OPDTT the compounds were absorbed on surfaces of soot and non-tailpipe traffic dust. They were largely externally mixed and deposited in different regions in the respiratory system, transition metal ions predominately in the upper regions and organic species, such as quinones, deeper in the lung. Although OPDTT per mass (toxicity) was highest for ultrafine particles, estimated lung deposition was mainly from accumulation and coarse particles. Contrasts in the phases of these forms of OPDTT deposited in the respiratory system may have differing health impacts.

Sedimentary Evidence of Environmental Degradation in Sanliqi Lake, Daye City (A Typical Mining City, Central China).

To reconstruct the history of environmental degradation in Sanliqi Lake (Daye City, central China), multiple proxies were analyzed in a sedimentary core which was dated using (137)Cs and spheroidal carbonaceous particles (SCPs). The results show that Sanliqi Lake has experienced serious degradation during the past 60 years, resulting from a large influx of metals and nutrients. Expansion of agricultural and industrial activities between 1945 and 1993 enhanced nutrient and metal enrichment, indicated by increases in metals, SCPs, magnetic susceptibility, total phosphorus, total nitrogen and total organic carbon. Further enrichment of Zn, Cd, Ni and Cr after 1993 was linked to a recent intensification of mining activities. Decreases in Cu and Pb after 2006 probably resulted from recent environmental remediation. This study verified the coupling between lake sediment pollution and human activities in Daye City during the past 60 years. The reconstructed history of lake pollution can provide reference information for continued restoration of Sanliqi Lake and other similar heavily polluted lakes in the developing regions.

Seasonal and interannual changes (2005-2021) of lake water quality and the implications for sustainable management in a rapidly growing metropolitan region, central China.

A series of restoration measures such as municipal wastewater treatment and aquaculture closures have been implemented in Wuhan City during recent years. In order to explore the impact of restoration measures and climate change on lake water quality, long-term (2005-2021) water quality data of 47 lakes were explored to reveal spatiotemporal changes in lake water quality. Percentages of polluted lakes were calculated according to six water-quality parameters, including total phosphorus (TP), ammonia nitrogen (NH3-N), chemical oxygen demand (COD), biological oxygen demand (BOD), chemical oxygen demand using potassium permanganate as oxidant (CODMn) and petroleum contamination (PET), at interannual and monthly timescales. At the interannual timescale, percentages of COD, BOD, CODMn and PET pollution decreased significantly, suggestive of water quality improvement during recent years. At the monthly timescale, low percentages of NH3-N and BOD pollution in March 2020 probably resulted from the sharp reduction in human activities during the COVID-19 lockdown. At the monthly timescale, temperature was positively correlated with percentage of CODMn pollution, but negatively correlated with percentage of NH3-N pollution; precipitation was negatively correlated with percentage of BOD pollution. The similarity of water-quality parameters generally decreased with an increase in geographical distance between each pair of lakes. However, the regression coefficients between the similarity of lake water quality and the geographical distance decreased with time, probably resulting from enhanced similarity of water quality parameters among all lakes with rapid urbanization. Our results highlight the importance of active restoration measures for sustainable management of lakes in Wuhan City, as well as in similar developing regions.

Centurial changes in sedimentary phosphorus forms and trace elements in response to damming and anthropogenic pollution in a floodplain lake, central China.

A massive increase in dam construction has decreased fluvial sediment discharge at a global scale. In order to explore potential effects of the Three Gorges Dam (TGD) on floodplain lakes in the middle Yangtze reaches (central China), this study investigated phosphorus forms (i.e., Ca-bound phosphorus, Fe/Al-bound phosphorus, and organic phosphorus) and trace elements (i.e., Sc, Ba, Be, Pb, and Zn) in a 210Pb-dated sediment core collected from East Dongting Lake, a hydrologically open lake proximal to the TGD. Sedimentary records revealed that the fluxes of phosphorus in different forms and trace elements were high before 2005. Thereafter, the fluxes of Ca-bound phosphorus, Sc, Ba, and Be declined sharply, probably due to declining supply of riverine detritus from the upstream after the TGD operation. In contrast, the fluxes of Fe/Al-bound phosphorus and heavy metals remained high after 2005, indicating the impacts of industrial sewage inputs. Our results underscore that river damming and anthropogenic pollution have altered sedimentary geochemical composition in East Dongting Lake. This phenomenon might be widespread in similar floodplain lakes due to increasing human disturbance during recent decades.

Regime shifts in shallow lake ecosystems along an urban-rural gradient in central China.

Due to differential exploitation pressure, ecosystems along the urban to rural gradients often exhibit different status in ecological structure and function. This can be challenging for lake restoration, given the relative strengths, magnitudes and speed of the exploitation. In this paper, we reconstructed the ecological changes over the past century and identified the regime shifts based on subfossil aquatic biota (chironomid records) in three shallow lakes (Shahu, Yanxi and Futou Lake) along an urban-rural gradient in the Yangtze floodplain, China. Our results illustrated the differences among lakes in trajectories, timing of critical transition and current ecological status. Eutrophic chironomid taxa increased markedly and replaced macrophyte-related taxa in urban Shahu Lake and suburban Yanxi Lake, indicated by the shift from a stable, vegetation-dominated state to an alternative, algal-dominated state in 1963 CE and 1975 CE respectively. The ecological regime in rural Futou Lake transited around 1980 CE but it is still in a relatively clear water state with abundant macrophytes due to anthropogenic hydrological controls. The greatest variance of chironomid compositional changes in both Shahu and Yanxi Lake was captured by anthropogenic pollutants, and analyses show that when these pressures are high they may be further amplified by climate warming. Responses along the urban-rural gradient are exemplified by urban Shahu Lake having shifted to a fragile regime with weak resistance and resilience, while rural Futou Lake has stabilized in a new regime with improved ecological resilience. Suburban Yanxi Lake is still moving toward a new state, and as such is unstable, because the types and magnitudes of external stressors are changing with urbanization in the city. It is suggested that active and precise management strategies for lakes should be established along the urban-rural gradient given their distinct development trajectories, drivers and current status.

Diatom-based water-table reconstruction in Sphagnum peatlands of northeastern China.

Peatlands are important ecosystems for biodiversity conservation, global carbon cycling and water storage. Hydrological changes due to climate variability have accelerated the degradation of global and regional ecosystem services of peatlands. Diatoms are important producers and bioindicators in wetlands, but comprehensive diatom-based inference models for palaeoenvironmental reconstruction in peatlands are scarce. To explore the use of diatoms for investigating peatland hydrological change, this study established a training set consisting of diatom composition and twelve environmental factors from 105 surface samples collected from five Sphagnum peatlands in northeastern China. Diatom communities were dominated by Eunotia species. Ordination analyses showed that depth to the water table (DWT) was the most important factor influencing diatom distribution, independently accounting for 4.99% of total variance in diatom data. Accordingly, a diatom-based DWT transfer function was developed and thoroughly tested. The results revealed that the best-performing model was based on weighted averaging with inverse deshrinking (R2 = 0.66, RMSEP = 8.8 cm with leave-one-out cross validation). Quantitative reconstruction of DWT on a short peat core collected from the Aershan Peatland (Inner Mongolia) recorded climate-mediated hydrological changes over the last two centuries. This study presents the first diatom-water table transfer function in Sphagnum peatlands, and highlights the potential of diatoms as a powerful tool to assess the magnitude of past hydrological changes in peatlands of northeastern China, as well as similar peaty environments worldwide.

Effects of dam construction and increasing pollutants on the ecohydrological evolution of a shallow freshwater lake in the Yangtze floodplain.

Large river-floodplain systems which provide a variety of societal, economic and biological benefits are undergoing extensive and intensive human disturbance. However, floodplain lakes responses to multiple stressors are poorly understood. The Yangtze River and its floodplain which provide water and food resources for more than 300 million people are an important region in China. Hydrological regulation as well as socio-economic development have brought profound negative influence on this ecologically important area. To improve understanding of decadal-scale responses of floodplain lakes to multiple stressors, lake sediment proxies including particle size, geochemical elements, diatoms and chironomids were analysed in a lead-210 dated core from Futou Lake. The analyses show that dams constructed in 1935 and the early 1970s stabilized hydrological conditions in Futou Lake and impeded the interaction with the Yangtze River, resulting in a decrease in major elements (e.g., Mg, Al, Fe) transported into the lake and an increase of macrophyte-related chironomids (C. sylvestris-type, P. penicillatus-type and Paratanytarsus sp.). After the late 1990s, further decreases in major elements and increases in median grain size are attributed to the erosion of the Yangtze riverbed and declining supply of major elements-enriched sediments from the upper Yangtze caused by the impoundment of the Three Gorges Dam. Chironomid and diatom assemblages indicate that hydrological stabilization caused by dam constructions stimulated the growth of macrophytes, which may be important in buffering against an ecosystem state change towards a phytoplankton-dominated and turbid state with ongoing eutrophication. However, a recent increase in Zn, TP and the emergence of eutrophic diatom and chironomid species indicate initial signs of water quality deterioration which may be related to the combined effects of hydrological stabilization and aquaculture. Over all, the sediment record from Futou Lake emphasizes the importance of interactions between hydrological change and pollutant loads in determining floodplain lake ecosystem state.

Variations in diatom communities at genus and species levels in peatlands (central China) linked to microhabitats and environmental factors.

Peatlands are a specialized type of organic wetlands, fulfilling essential roles as global carbon sinks, headwaters of rivers and biodiversity hotspots. Despite their importance, peatlands are being lost at an alarming rate due to human disturbance and climatic variability. Both the scientific and regulatory communities have focused considerable attention on developing tools for assessing environmental changes in peatlands. Diatoms are widely used in biomonitoring studies of lakes, rivers and streams as they have high abundance, specific ecological preferences and can respond rapidly to environmental change. However, diatom-based assessment studies in peatlands remain limited. The aims of this study were to identify indicator species and genus for three types of habitats (hummocks, hollows and ditch edges) in peatlands (central China), to examine the effects of physiochemical factors on diatom composition at genus and species levels, and to compare the efficiency of species- and genus-level identification in environmental assessment. Our results revealed that hummocks were characterized by drought-tolerant diatoms, while hollows were dominated by species and genus preferring wet conditions. Ditch edges were characterized by diatoms with different life strategies. Depth to water table, redox potential, conductivity and calcium were significant predictors of both genus- and species-level composition. According to ordination analyses, pH was not correlated with species composition while it was a significant factor associated with genus-level composition. Genus-level composition outperformed species composition in describing the response of diatoms to environmental variables. Our results indicate that diatoms can be useful environmental indicators of peatlands, and show that genus-level taxonomic analysis can be a potential tool for assessing environmental change in peatlands.