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Dissolved organic matter (DOM) in soils drives biogeochemical cycling and soil functions in different directions depending on its molecular signature. Notably, there is a distinct paucity of information concerning how the molecular signatures of soil DOM vary with different degrees of weathering across wide geographic scales. Herein, we resolved the DOM molecular signatures from 22 diverse Chinese reference soils and linked them with soil organic matter and weathering-related mineralogical properties. The mixed-effects models revealed that the yields of DOM were determined by soil organic carbon content, whereas the molecular signature of DOM was primarily constrained by the weathering-related dimension. The soil weathering index showed a positive effect on the lability and a negative effect on the aromaticity of DOM. Specifically, DOM in highly weathered acidic soils featured more amino sugars, carbohydrates, and aliphatics, as well as less O-rich polyphenols and condensed aromatics, thereby conferring a higher DOM biolability and lower DOM aromaticity. This study highlights the dominance of the weathering-related dimension in constraining the molecular signatures and potential functions of DOM in soils across a wide geographic scale.

High-intensity wildfires alter the chemical composition of organic matter, which is expected to be distinctly different from low-intensity prescribed fires. Herein, we used pyrolysis gas chromatography/mass spectrometry (Py-GC/MS), in conjunction with solid-state 13C nuclear magnetic resonance (NMR) and Fourier transform infrared (FT-IR) spectroscopy, to assess chemical alterations from three wildfires and a long-term frequent prescribed fire site. Our results showed that black ash formed under moderate intensity burns contained less aromatic (ArH), polyaromatic hydrocarbon (PAH), and nitrogen-containing compounds (Ntg) but more lignin (LgC) and phenol compounds (PhC), compared to white ash formed under high intensity burns. Both 13C NMR and FT-IR confirmed a higher relative percentage of carboxyl carbon in white ash, indicating the potential for higher water solubility and more mobile carbon, relative to black ash. Compared to wildfires, ash from low-intensity prescribed fire contained less ArH, PAH, and Ntg and more LgC and PhC. Controlled laboratory burning trials indicated that organic matter alteration was sensitive to the burn temperature, but not related to the fuel type (pine vs fir) nor oxygen absence/presence at high burn temperatures. This study concludes that higher burn temperatures resulted in higher (poly)aromatic carbon/nitrogen and lower lignin/phenol compounds.

Triple-negative breast cancer (TNBC) is a heterogeneous disease with a poor prognosis due to the lack of an effective targeted therapy. Histone lysine methyltransferases (KMTs) have emerged as attractive drug targets for cancer therapy. However, the function of the majority of KMTs in TNBC has remained largely unknown. In the current study, we found that KMT nuclear receptor binding SET domain protein 2 (NSD2) is overexpressed in TNBC tumors and that its overexpression is associated with poor survival of TNBC patients. NSD2 regulates TNBC cell survival and invasion and is required for tumorigenesis and tumor growth. Mechanistically, NSD2 directly controls the expression of EGFR and ADAM9, a member of the ADAM (a disintegrin and metalloproteinase) family that mediates the release of growth factors, such as HB-EGF. Through its methylase activity, NSD2 overexpression stimulates EGFR-AKT signaling and promotes TNBC cell resistance to the EGFR inhibitor gefitinib. Together, our results identify NSD2 as a major epigenetic regulator in TNBC and provide a rationale for targeting NSD2 alone or in combination with EGFR inhibitors as a targeted therapy for TNBC.

Wildfire-altered soil may be an important source of polycyclic aromatic hydrocarbons (PAHs) in the environment. With projected increase of wildfire frequency and intensity due to changing global climate, understanding the quantity and speciation of PAHs, including halogenated PAHs (XPAHs), resulting from different burn intensities has important ramifications for environmental quality concerns and global soil carbon dynamics. Here, we quantified levels of 16 U.S. Environmental Protection Agency regulated PAHs, 3 chlorinated PAHs, and 6 brominated PAHs in nonburned forest soils and burned ash/soil samples covered with black ash (B-Ash; moderate burn intensity) or white ash (W-Ash; severe burn intensity) from the 2013 Rim Fire (1,041 km 2 ) in California. The - 16 PAH concentrations follow (mean ± standard deviation; μg/kg) B-Ash (893 ± 285) > W-Ash (515 ± 333) ≈ nonburned soils (247 ± 58). Moreover, the - 16 PAH profiles were altered by both moderate and severe burn conditions with the size of aromatic structures following B-Ash > W-Ash > nonburned soils. Neither chlorinated nor brominated PAH concentration was significantly elevated by moderate or severe wildfire. Overall, fire intensity is critical in regulating soil PAH concentrations and profiles. Given the high erodibility of wildfire ash, these PAHs can be easily transported to rivers and reservoirs where they could impact the aquatic food web and drinking source water.

The Rim Fire ignited on August 17, 2013 and became the third largest wildfire in California history. The fire consumed 104,131 ha of forested watersheds that were the drinking water source for 2.6 million residents in the San Francisco Bay area. To understand temporal variations in dissolved organic matter (DOM) after the wildfire and its potential impacts on disinfection byproduct (DBP) formation in source water supply, we collected the 0-5 cm ash/soil layer with surface deposits of white ash (high burn severity) and black ash (moderate burn severity) within the Rim Fire perimeter in Oct 2013 (pre-rainfall) for five sequential extractions, and in Dec 2013 (∼87 mm cumulative precipitation) and Aug 2014 (∼617 mm cumulative precipitation) for a single water extraction. Water-extractable DOM was characterized by absorption and fluorescence spectroscopy and DBP formation tests. Both increasing cumulative precipitation in the field or number of extractions in the lab resulted in a significant decrease in specific conductivity, dissolved organic carbon, and DBP formation potential, but an increase in DOM aromaticity (reflected by specific UV absorbance). However, the lab sequential leaching failed to capture the increase of the NOx(-)-N/NH4(+)-N ratio and the decrease in pH and dissolved organic carbon/nitrogen ratio of ash/soil extracts from Oct 2013 to Aug 2014. Increasing cumulative precipitation, inferring an increase in leaching after fire, led to an increase in DOM reactivity to form trihalomethanes, haloacetic acids, and chloral hydrate, but not for haloketones, haloacetonitrile, or N-nitrosodimethylamine, which were more related to the original burn severity. This study highlights that fire-affected DBP precursors for different DBP species have distinct temporal variation possibly due to their various sensitivity to biogeochemical alterations.

Forest fires occur with increasing frequency and severity in the western United States, potentially altering the chemistry and quantity of dissolved organic matter (DOM) and disinfection byproduct (DBP) precursors exported from forested watersheds. However, little is known concerning effects of the fire triangle (heat, oxygen, and fuel) on DOM alteration. Using detritus from Pinus ponderosa and Abies concolor (dominant species in forests in the western United States), we prepared DOM from unburned and burned detritus under hypoxic (pyrolysis) and oxic conditions (thermal oxidation) at 250 and 400 °C. DOM characteristics and chlorine reactivity were evaluated by absorption and fluorescence spectroscopy and chlorination-based DBP formation potential tests. Spectroscopic results suggest that burned-detritus extracts had lower molecular weight (reflected by increased E2:E3 and fluorescence index) and divergent aromaticity (reflected by SUVA254) depending on oxygen availability. Temperature and oxygen availability interacted to alter the chlorine reactivity of fire-affected DOM. Increasing temperature from 50 to 400 °C resulted in decreased reactivities for trihalomethane and chloral hydrate formation and divergent reactivities for haloacetonitrile formation (unchanged for pyrolysis and increased for oxidation) and haloketone formation (increased for pyrolysis and decreased for oxidation). We demonstrate that DBP precursors in fire-affected forest detritus are highly dependent on temperature and oxygen availability.

Wildfire occurrence and intensity are increasing worldwide causing severe disturbances to forest watersheds used for potable water supply. The effects of wildfire on drinking water quality are not well understood, especially in terms of terrestrial dissolved organic matter (DOM) and DOM-associated formation of disinfection byproducts (DBP). As the forest floor layer is a major source of terrestrial DOM, we investigated characteristics and DBP formation of water extractable organic matter (WEOM) from the 0-5 cm depth of nonburned detritus (control) and burned detritus with black ash (moderate severity) and white ash (high severity) associated with the 2013 Rim Fire in California. Spectroscopic results suggested that the aromaticity of WEOM followed white ash > control > black ash and fluorescence region II (excitation 220-250 nm; emission 330-380 nm) of the emission-excitation-matrix was identified as a potential burn severity indicator. Compared to the control, WEOM from white and black ashes had lower reactivity in forming trihalomethanes (55%-of-control) and haloacetic acids (67%-of-control), but higher reactivity in forming the more carcinogenic haloacetonitrile after chlorination (244%-of-control) and N-nitrosodimethylamine after chloramination (229%-of-control). There was no change in reactivity for chloral hydrate formation, while WEOM from black ash showed a higher reactivity for haloketone formation (150%-of-control). Because wildfire consumed a large portion of organic matter from the detritus layer, there was lower water extractable organic carbon (27%-of-control) and organic nitrogen (19%-of-control) yields in ashes. Consequently, the wildfire caused an overall reduction in water extractable terrestrial DBP precursor yield from detritus materials.