Differential influences of forest floor-pyrolyzed biochar-derived and leached dissolved organic matter interaction with natural iron-bearing minerals in forest subsoil on the formation of mineral-associated soil organic matter.

The vertical sequestration of dissolved organic matter (DOM) by iron minerals along the soil profile is assumed to be central to the long-term storage of the soil organic matter (SOM) pool. However, there is limited information available about how the interaction between DOM and natural iron-bearing minerals shape mineral SOM associations quantitatively and qualitatively in forest subsoils. Here, we systematically investigated the influences of forest organic layer-pyrolyzed biochar-derived DOM (BDOM) and leached DOM (LDOM) on quantity, molecular composition, and diversity of deposition layer-derived iron minerals-associated OM by using Fourier transform ion cyclotron resonance mass spectrometry and other complementary spectroscopy. Results indicated natural iron minerals (FeOx1 and FeOx2) had a greater capacity for sorbing LDOM with higher aromaticity and molecular weight than those of BDOM, and the higher proportion of goethite and short-order-range phase in natural iron minerals was closely related to the increased OM adsorption capacity. We also observed the preferential sorption of oxygen/nitrogen-rich polycyclic aromatic compounds and carboxylic-containing compounds in LDOM and concurrent the potential release of lignin-like/aromatics compounds and carboxyl/nitrogen-less aliphatic compounds from native OM coprecipitates into the solution. However, unsaturated and oxidized phenolic compounds in BDOM had a stronger affinity for FeOx through hydrophobic partitioning and specific polar interactions, and concomitantly the partial release of nitrogen-free aliphatic and other carboxyl-rich compounds. More nitrogen structures in aromatic-containing compounds can improve the saturation level and polarity of BDOM. Compared with BDOM, LDOM exerted a stronger control over the exchange of native OM from subsoil natural iron-bearing minerals and substantially enhanced the molecular diversity of the reconstituted mineral-associated OM during the adsorptive fractionation. Overall, these findings suggest the compositional evolution of DOM profoundly shapes SOM formation and persistence in forest subsoils, which is the key to understanding DOM cycling and contaminant fate during its passage through the soil.

Regulation of SiO2 Nanoparticles on the Adsorptive Fractionation of Dissolved Organic Matter by Goethite.

SiO2 nanoparticles (SiO2NPs) are most widely available and coexisting with DOM at the mineral-water interface; however, the role of SiO2NPs in DOM fractionation and the underlying mechanisms have not been fully understood. Using Fourier transform ion cyclotron resonance mass spectrometry, combined with Fourier transform infrared spectroscopy and X-ray adsorption fine structure spectroscopy, was employed to investigate the adsorptive fractionation of litter layer-derived DOM on goethite coexisting with SiO2NPs under different pH conditions. Results indicated that the inhibitory effect of the coexisting SiO2NPs on OM sorbed by goethite was waning as environmental pH increased due to the reduced steric interactions and the concurrent elevated hydrogen bonding/hydrophobic partitioning interactions on the goethite surface. We observed the coexisting SiO2NPs inhibited the adsorption of high carboxylic-containing condensed aromatic/aromatics compounds on goethite under different pH conditions while improving the adsorption of highly unsaturated aliphatic/phenolic and carbohydrate-like compounds in an alkaline and/or circumneutral environment. More nitrogen-containing structures may favor the adsorption of phenolic and nonaromatic compounds to goethite by counteracting the negative effect of SiO2NPs. These findings suggest that DOM sequestration may be significantly regulated by the coexisting SiO2NPs at the mineral-water interface, which may further influence the carbon-nitrogen cycling and contaminant fate in natural environments.

[Effect of Coconut Fiber Biochar and Its Nitrate Modification on Pb Passivation in Paddy Soils].

The effects of coconut fiber biochar (CFB) and nitrate-modified coconut fiber biochar (NCFB) on the passivation of exogenous lead (Pb) in paddy soils and their underlying mechanisms were investigated using soil incubation experiments combined with spectroscopic techniques such as scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), synchrotron radiation X-ray fluorescence (SRXRF), and Fourier transform infrared absorption spectroscopy (FTIR). The effects of NCFB and CFB on the passivation of exogenous lead (Pb) in paddy soils and its underlying mechanisms were investigated. Compared with that of CFB, the inner wall of NCFB honeycomb pores was rougher, and the amount of alcohol-phenol-ether functional groups containing the C-O structure and the amount of carboxyl groups containing the C[FY=,1]O/O[FY=,1]C-O structure on the surface of CFB was significantly decreased after nitric acid modification. Compared with that in the control (without biochar) paddy soil after 150 d of incubation, the EDTA-extracted Pb content in the paddy soil with CFB and NCFB was reduced by 39.7% and 105.4%, respectively. The carbonate-bound and Fe-Mn oxide-bound Pb contents were significantly lower, and the organic-bound and residue Pb contents were significantly higher in the NCFB-added soil. The SRXRF scans showed that the exogenous Pb was enriched in the microregions of CFB particles rich in Ca and Cu elements and relatively less so in the microregions of soil aggregates rich in the Fe, Mn, and Ti elements. In addition, the characteristic peaks of carboxylates (1384 cm-1) in A-CFBPb and A-NCFBPb were significantly enhanced in the incubation experiment in the presence of exogenous Pb compared to A-CFB and A-NCFB in the absence of exogenous Pb. The addition of CFB or NCFB was more effective in passivating exogenous Pb in paddy soils and promoted the gradual transformation of Pb from unstable to more stable forms in paddy soils to achieve the effect of passivating Pb. The greater amount of carboxyl functional groups in NCFB participated in the passivation of exogenous Pb, which made NCFB more effective than CFB in passivating Pb. NCFB was more effective than CFB in passivating exogenous Pb in paddy soils due to its rougher inner walls of honeycomb pores and abundant carboxyl functional groups. In tropical areas such as Hainan, coconut fiber biochar and its modification can be considered as an environmentally friendly candidate method for the remediation of soil Pb contamination.

Molecular size-dependent compositions and lead (II) binding behaviors of two origins of organic fertilizers-derived dissolved organic matter.

The application of organic fertilizers caused large amounts of dissolved organic matter (DOM) entering the soil environment and influencing the behaviors and fates of heavy metals. Here, we investigated the molecular weight-dependent (high molecular weight [HMW], 1 kDa-0.7 µm; low molecular weight [LMW], <1 kDa) compositions and lead (Pb) binding behaviors of DOM derived from sheep manure-based (SMOF) and shrimp peptide-based organic fertilizers (SPOF) using chromophoric and fluorescent spectroscopy, Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) and two-dimensional correlation spectroscopy (2D-COS). Results showed that SMOF released more DOM with higher aromaticity and hydrophobicity, containing more fluvic-like components, carboxylic-rich alicyclic molecules (CRAMs) and lignin phenolic compounds compared to SPOF-DOM with more microbially-transformed heteroatom-containing compounds (CHON, CHONS and CHOS). Furthermore, there was more aromatic compounds with ample carboxyl and hydroxyl groups in HMW-DOM but abundant protein-like components and heteroatom-containing compounds (CHONS and CHOS) in LMW-DOM. SMOF-DOM exhibited more obvious MW-dependent heterogeneity in molecular components compared to SPOF-DOM with higher molecular diversity. Moreover, 2D-COS indicated phenol and carboxyl groups in SMOF-DOM and polysaccharides in SPOF-DOM exhibited superior binding affinities for Pb. Pb binding to HMW-DOM derived from SMOF first occurred in the phenolic groups in fulvic-like substances, while polysaccharides in LMW-DOM first participated in the binding of Pb. In contrast, irrespective of MWs, polysaccharides and humic-like substances with aromatic (CC) groups in SPOF-DOM displayed a faster response to Pb. Furthermore, the polysaccharides which preferentially participated in the binding of Pb to SPOF-DOM and SMOF-derived LMW-DOM may pose a higher risk of Pb in the environment. These results were helpful to understand the effects of sources and size-dependent compositions of DOM on the associated risks of heavy metals in the environments.

Impacts of Cold-Stress Stimulation On Mice Pregnancy.

BACKGROUND: Animals exposed to cold stress develop hypertension; however, the effects of cold-induced hypertension on pregnancy remain unclear. We therefore, aimed to investigate the impacts of cold-stress stimulation on mice pregnancy. METHODS: Four groups of mice were used in the study: non-pregnant control group (NN), non-pregnant cold-stress group (NC), pregnant control group (PN) and pregnant cold-stress group (PC). control groups were kept at 25℃, and the cold-stress groups were kept in a room for cold-stress stimulation (4 ± 2℃) for 4 hours (then back to 25℃) every day from the 1st to the 18th day. RESULTS: The blood pressure of the PC was the highest among the four groups, and the hypertensive percentage of the PC was significantly increased. However, plasma angiotensinⅡ levels of the PC were the lowest. The weights of the foetus and placenta in the PC were significantly decreased compared to the PN. More apparent changes in kidneys and placenta were observed in the PC compared to the PN. The blood pressure of pregnant mice showed no difference between the PN and PC groups 50 days after delivery. CONCLUSIONS: Intermittent cold-stress stimulation had significantly adverse effects on the pregnant mice, leading to maternal hypertension, renal and placental lesions, body weight and placenta reduction in offspring. The study results may offer a non-invasive method to establish an animal model of hypertensive disorders in pregnancy. Cold-stress stimulation may be one of the inducible factors of pregnancy-induced hypertension.Cold-stress stimulation may be one of the inducible factors of pregnancy-induced hypertension.