The optical properties of secondary brown carbon (BrC) aerosols are poorly understood, hampering quantitative assessments of their impact. We propose a new method for estimating secondary source of BrC using excitation-emission matrix (EEM) fluorescence spectroscopy, combined with parallel factor analysis (PARAFAC) and partial least squares regression (PLSR). Experiments were conducted on a collection of PM2.5 samples from urban areas in five Chinese cities during winter and summer. The humic-like component with long-emission wavelengths (L-HULIS) was identified as a secondary source tracer of BrC. This was confirmed by correlating PARAFAC components with secondary organic aerosol tracers and molecular oxidation indices obtained from Fourier transform ion cyclotron resonance mass spectrometry analysis. Using L-HULIS as a secondary tracer of BrC, it was determined that the contribution of secondary sources to water-soluble BrC (WS-BrC) in source emission samples is significantly smaller than in PM2.5 from five Chinese cities, supporting our method. In the five cities, secondary source derived via L-HULIS contributes a dominant potion (80% +/- 3.5%) of WS-BrC at 365 nm during the summer, which is approximately twice as high as during the winter (45% +/- 4.9%). Radiocarbon isotope (14C) analysis provides additional constraints to the sources of L-HULIS-derived secondary WS-BrC in urban PM2.5, suggesting that aged biomass burning is the dominant contributor to secondary WS-BrC in winter, and biogenic emission is dominant during summer. This study is the first report on identification of secondary sources of BrC using the fluorescence technique. It demonstrates the potential of this method in characterizing non-fossil source secondary BrC in the atmosphere. Brown carbon (BrC) originates from primary combustion emissions and secondary formation, with large source-dependent uncertainties of radiative forcing. Direct measurements to separate the primary and secondary BrC are challenging due to the chemical complexity. Recent online studies have shown that excitation-emission matrix fluorescence spectroscopy coupled with parallel factor (PARAFAC) analysis identified some fluorescent components that may be linked to secondary sources. However, there is a knowledge gap on whether PARAFAC components correlate closely with atmospheric secondary chemical components, particularly biogenic and anthropogenic secondary organic aerosol, as their precursors can also form secondary BrC chromophores. We established the correlations between PARAFAC components and secondary organic aerosol tracers and compound oxidations to identify the long-emission-wavelength humic-like component as a secondary source tracer of BrC. Then, we estimated non-fossil source secondary BrC in urban aerosols during the winter and summer. Our studies provide references for quantifying secondary sources of BrC in the atmosphere. A fluorescence-based method was developed to investigate secondary sources of water-soluble brown carbon in five cities in China The contribution of secondary sources to water-soluble brown carbon in the summer is approximately twice as high as during the winter This secondary water-soluble brown carbon was more associated with aging biomass burning in winter and biogenic emissions in summer

The vegetation and ecosystem in the source region of the Yangtze River and the Yellow River (SRYY) are fragile. Affected by climate change, extreme droughts are frequent and permafrost degradation is serious in this area. It is very important to quantify the drought-vegetation interaction in this area under the influence of climate-permafrost coupling. In this study, based on the saturated vapor pressure deficit (VPD) and soil moisture (SM) that characterize atmospheric and soil drought, as well as the Normalized Differential Vegetation Index (NDVI) and solar-induced fluorescence (SIF) that characterize vegetation greenness and function, the evolution of regional vegetation productivity and drought were systematically identified. On this basis, the technical advantages of the causal discovery algorithm Peter-Clark Momentary Conditional Independence (PCMCI) were applied to distinguish the response of vegetation to VPD and SM. Furthermore, this study delves into the response mechanisms of NDVI and SIF to atmospheric and soil drought, considering different vegetation types and permafrost degradation areas. The findings indicated that low SM and high VPD were the limiting factors for vegetation growth. The positive and negative causal effects of VPD on NDVI accounted for 47.88% and 52.12% of the total area, respectively. Shrubs were the most sensitive to SM, and the response speed of grassland to SM was faster than that of forest land. The impact of SM on vegetation in the SRYY was stronger than that of VPD, and the effect in the frozen soil degradation area was more obvious. The average causal effects of NDVI and SIF on SM in the frozen soil degradation area were 0.21 and 0.41, respectively, which were twice as high as those in the whole area, and SM dominated NDVI (SIF) changes in 62.87% (76.60%) of the frozen soil degradation area. The research results can provide important scientific basis and theoretical support for the scientific assessment and adaptation of permafrost, vegetation, and climate change in the source area and provide reference for ecological protection in permafrost regions.

As an important component of carbonaceous matters, dissolved organic carbon (DOC) can absorb and scatter the solar radiation at ultraviolet and blue wavelengths. The wet deposition process has great impact on the concentration and light absorption ability of precipitation DOC, affecting the climatic effect caused by DOC in the atmosphere. In this study, light absorption and fluorescence characteristics of precipitation DOC was investigated in the central Tibetan Plateau (TP). The results showed that the mean DOC concentration and mass absorption cross- measured at 365 nm (MAC365) in Tanggula (TGL) station were 0.59 +/- 0.42 mg/L and 0.37 +/- 0.19 m2/g, respectively, while both values showed much higher volatilities than those of aerosols. DOC concentrations had significant negative correlation with the precipitation amount, while MAC365 values increase with the precipitation amount in TGL station. Therefore, DOC with high light-absorbing ability was preferred to be retained in the atmosphere during wet deposition. In this study, precipitation DOC contained three fluorescent components (one humic-like component and two tyrosine-like components) mainly from local biomass burning sources. DOC concentration showed a negative relationship with MAC365 value in TGL station. The wet deposition of DOC with low light-absorbing ability can reduce the strong negative radiative forcing caused by secondary organic aerosol due to high proportion of DOC in secondary organic carbon. Similar phenomenon was also found in Nam Co, Lulang and Everest stations of previous study, which may have a potential impact on radiative forcing in the atmosphere of TP.

Brown carbon (BrC) is a light-absorbing aerosol component that has a significant impact on atmospheric photochemistry and climate effects. Many studies on light absorbing characteristics of BrC (such as a fraction of water-soluble and/or water-insoluble) have been carried out in cities over the Guanzhong Basin, including radiative forcing, optical properties and sources. However, research on the Qinling Mountains is still lacking. Therefore, PM2.5 samples were collected at the northern piedmont of Qinling Mountains (QL) and Xi'an (XN) in the winter of 2020, and the optical properties and radiation effects of water extracts were analyzed and eval-uated. The mass absorption efficiency (MAE) of water-soluble organic carbon (WSOC) at 365 nm (MAE365) obtained in QL and XN were 0.18 +/- 0.03 m2 g-1 and 0.78 +/- 0.96 m2 g-1, respectively. In the ultraviolet range, the relative light absorption of WSOC relative to elemental carbon (EC) was 6.76% and 33.41% in QL and XN, respectively, and the simple forcing efficiency (SFE280-400) were 0.71 +/- 0.43 and 2.82 +/- 1.71 W g-1 in QL and XN. It may have important effects on the radiation balance of regional climate systems. The chromophores in WSOC of XN and QL are mainly composed of humic-like and protein-like substances, and humus-like substances play a dominant role in two sites (52.61% and 71.13%). Biomass combustion has a limited contribution to chromophore abundance in WSOC of QL, which is more affected by urban transmission. The fluorescence index revealed that the chromophores in WSOC had autogenous characteristics and that the organic matter was mostly newly generated. Furthermore, the molecular weight and aromatic degree in XN samples were higher than that in QL, indicating a greater capacity for light absorption. This work will be instrumental in assessing the inter-action and influence between the city and the northern piedmont of the Qinling Mountains and improve the capability of air pollution prevention and control of Guanzhong Basin.

Dissolved organic carbon (DOC) makes an important contribution to glacier melting in the Himalayas and the Tibetan Plateau (HTP). Photobleaching can effectively reduce the light absorption ability of DOC, further changing its impact on glacier melting, which is not yet well researched in the HiP. Therefore, snowpit samples from the Bayi, Ganglongjiama (GLJM), Jiemayangong (JMYZ) and Demula (DML) glaciers were collected to study the influence of photobleaching on the light absorption ability of DOC and its impact on glacier melting. The results showed that the DOC concentration of snowpit samples, which was affected by the melting state and photobleaching, decreased from the northern HTP to the southern HIP. At an early stage of melting, the mass absorption cross- value at 365 nm (MAC 365 ) values showed a negative correlation with DOC concentrations in the snowpit at the JMYZ and DML glaciers, indicating that colored DOC tended to be concentrated in the snowpit during the melting process. With the aggravation of ablation, some snowpit samples in the GLJM and Bayi glaciers had both low concentrations and MAC 365 values of DOC due to the reduced influence of photobleaching on the light absorption ability of DOC. Similarly, two fluorescence components (one protein-like component and one hurnic-like component) were identified in the extracted DOC at the JMYZ and DML glaciers, while those components were not detected in the GLJM glacier. Based on the sources of fluorescent DOC and five-day backward air mass trajectories, long-distance transport of pollutants from South Asia was an important source of snowpit DOC in the southern HIP. In this study, photobleaching can effectively remove colored and fluorescent DOC from snowpit samples in the HIP, further reducing the radiation forcing and glacier melting caused by DOC. (C) 2021 Elsevier B.V. All rights reserved.

As an important type of light-absorbing aerosol, brown carbon (BrC) has the potential to affect the atmospheric photochemistry and Earth's energy budget. A comprehensive field campaign was carried out along the transport pathway of Asian dust during the spring of 2016, including a desert site (Erenhot), a rural site (Zhangbei), and an urban site (Jinan), in northern China. Optical properties, bulk chemical compositions, and potential sources of water-soluble brown carbon (WS-BrC) were investigated in atmospheric total suspended particulate (TSP) samples. Samples from Zhangbei had higher mass absorption efficiency at 365 nm (MAE(365), 132 +/- 0.34 m(2) g(-1)) than those from Jinan (1.00 +/- 023 m(2) g(-1)) and Erenhot (0.84 +/- 0.30 m(2) g(-1)). Compere to the non-dust samples, elevated water-soluble organic carbon (WSOC) concentrations and MAE 365 values of dust samples from Erenhot are related to the input of high molecular weight organic compounds and biogenic matter from the Gobi Desert, while lower values from Zhangbei and Jinan are attributed to the dilution effect caused by strong northwesterly winds. Based on fluorescence excitation-emission matrix spectra and parallel factor analysis, two humic-like (C1 and C2) and two protein-like (C3 and C4) substances were identified. Together, C1 and C2 accounted for similar to 64% of total fluorescence intensity at the highly polluted urban Jinan site; C3 represented similar to 45% at the rural Zhangbei site where local biomass burning affects; and C4 contributed similar to 24% in the desert region (Erenhot) due to dust-sourced biogenic substances. The relative absorptive forcing of WS-BrC compared to black carbon at 300-400 nm was about 31.3%, 13.9%, and 9.2% during non-dust periods at Erenhot, Zhangbei, and Jinan, respectively, highlighting that WS-BrC may significantly affect the radiative balance of Earth's climate system and should be included in radiative forcing models. (C) 2021 Elsevier B.V. All rights reserved.

Recent warming in the Andes is affecting the region's water resources including glaciers and lakes, which supply water to tens of millions of people downstream. High-elevation wetlands, known locally as bofedales, are an understudied Andean ecosystem despite their key role in carbon sequestration, maintenance of biodiversity, and regulation of water flow. Here, we analyze subfossil diatom assemblages and other siliceous bioindicators preserved in a peat core collected from a bofedal in Peru's Cordillera Vilcanota. Basal radiocarbon ages show the bofedal likely formed during a wet period of the Little Ice Age (1520-1680 CE), as inferred from nearby ice core data. The subfossil diatom record is marked by several dynamic assemblage shifts documenting a hydrosere succession from an open-water system to mature peatland. The diatoms appear to be responding largely to changes in hydrology that occur within the natural development of the bofedal, but also to pH and possibly nutrient enrichment from grazing animals. The rapid peat accretion recorded post-1950 at this site is consistent with recent peat growth rates elsewhere in the Andes. Given the many threats to Peruvian bofedales including climate change, overgrazing, peat extraction, and mining, these baseline data will be critical to assessing future change in these important ecosystems.

The boreal forest is a major contributor to the global climate system, therefore, reducing uncertainties in how the forest will respond to a changing climate is critical. One source of uncertainty is the timing and drivers of the spring transition. Remote sensing can provide important information on this transition, but persistent foliage greenness, seasonal snow cover, and a high prevalence of mixed forest stands (both deciduous and evergreen species) complicate interpretation of these signals. We collected tower-based remotely sensed data (reflectance-based vegetation indices and Solar-Induced Chlorophyll Fluorescence [SIF]), stem radius measurements, gross primary productivity, and environmental conditions in a boreal mixed forest stand. Evaluation of this data set shows a two-phased spring transition. The first phase is the reactivation of photosynthesis and transpiration in evergreens, marked by an increase in relative SIF, and is triggered by thawed stems, warm air temperatures, and increased available soil moisture. The second phase is a reduction in bulk photoprotective pigments in evergreens, marked by an increase in the Chlorophyll-Carotenoid Index. Deciduous leaf-out occurs during this phase, marked by an increase in all remotely sensed metrics. The second phase is controlled by soil thaw. Our results demonstrate that remote sensing metrics can be used to detect specific physiological changes in boreal tree species during the spring transition. The two-phased transition explains inconsistencies in remote sensing estimates of the timing and drivers of spring recovery. Our results imply that satellite-based observations will improve by using a combination of vegetation indices and SIF, along with species distribution information. Plain Language Summary The boreal forest is one of the most sensitive regions on the planet to climate change, yet its sensitivity remains poorly understood. In particular, the timing and drivers of the spring transition, as the forest changes from a winter adapted state to a summer adapted state, carry significant uncertainties. Remote sensing metrics can be used to characterize the spring transition, but their interpretation is complicated by persistent greenness, frequent snow cover, and a high prevalence of forests containing both deciduous and evergreen species. We collected tower-based remotely sensed metrics, stem radius, and carbon uptake measurements and show that the spring transition occurs in two distinct phases. The first phase is a reactivation of photosynthesis in evergreens and is triggered by thawed stems, warm air temperature, and moist soil. The second phase is a change in evergreen photoprotective pigment levels and the leaf-out of deciduous species. It is triggered by soil thaw. Both phases were detected with different remote sensing metrics that depended on species type. Our results illustrate how satellite measurements could be improved to capture the spring transition over diverse landscapes and what environmental factors control the spring transition.

As an important component of carbonaceous matters, dissolved organic carbon (DOC) can absorb and scatter the solar radiation at ultraviolet and blue wavelengths. The wet deposition process has great impact on the concentration and light absorption ability of precipitation DOC, affecting the climatic effect caused by DOC in the atmosphere. In this study, light absorption and fluorescence characteristics of precipitation DOC was investigated in the central Tibetan Plateau (TP). The results showed that the mean DOC concentration and mass absorption cross- measured at 365 nm (MAC365) in Tanggula (TGL) station were 0.59 +/- 0.42 mg/L and 0.37 +/- 0.19 m2/g, respectively, while both values showed much higher volatilities than those of aerosols. DOC concentrations had significant negative correlation with the precipitation amount, while MAC365 values increase with the precipitation amount in TGL station. Therefore, DOC with high light-absorbing ability was preferred to be retained in the atmosphere during wet deposition. In this study, precipitation DOC contained three fluorescent components (one humic-like component and two tyrosine-like components) mainly from local biomass burning sources. DOC concentration showed a negative relationship with MAC365 value in TGL station. The wet deposition of DOC with low light-absorbing ability can reduce the strong negative radiative forcing caused by secondary organic aerosol due to high proportion of DOC in secondary organic carbon. Similar phenomenon was also found in Nam Co, Lulang and Everest stations of previous study, which may have a potential impact on radiative forcing in the atmosphere of TP.

Carbonaceous particles play an important role in climate change, and an increase in their emission and deposition causes glacier melting in the Himalayas and the Tibetan Plateau (HTP). This implies that studying their basic characteristics is crucial for a better understanding of the climate forcing observed in this area. Thus, we investigated characteristics of carbonaceous particles at a typical remote site of southeastern HTP. Organic carbon and elemental carbon concentrations at this study site were 1.86 +/- 0.84 and 0.18 +/- 0.09 mu g m(-3), respectively, which are much lower than those reported for other frequently monitored stations in the same region. Thus, these values reflect the background characteristics of the study site. Additionally, the absorption coefficient per mass (alpha/rho) of water-soluble organic carbon (WSOC) at 365 nm was 0.60 +/- 0.19 m(2) g(-1), with the highest and lowest values corresponding to the winter and monsoon seasons, respectively. Multi-dimensional fluorescence analysis showed that the WSOC consisted of approximately 37% and 63% protein and humic-like components, respectively, and the latter was identified as the component that primarily determined the light absorption ability of the WSOC, which also showed a significant relationship with some major ions, including SO42-, K+, and Ca2+, indicating that combustion activities as well as mineral dust were two important contributors to WSOC at the study site. (C) 2020 Elsevier Ltd. All rights reserved.