Pyrogenic carbon accelerates iron cycling and hydroxyl radical production during redox fluctuations of paddy soils

Carbon materials(e.g.,pyrogenic carbon(PyC))are widely used in agricultural soils and can participate in various biogeochemical processes,including iron(Fe)cycling.In soils,Fe (Ⅱ)species have been proposed as the main active contributor to produce reactive oxygen species(ROS),which are involved in various biogeochemical processes.However,the effects of PyC on the transformation of different Fe species in soils and the associated production of ROS are rarely investigated.This study examined the influence of PyC(pyrolyzed at 300-700°C)on Fe (Ⅱ)/Fe(Ⅲ)cycling and hydroxyl radical(·OH)production during redox fluctuations of paddy soils.Results showed that the reduction of Fe(Ⅲ)in soils was facilitated by PyC during anoxic incubation,which was ascribed to the increased abundance of dissimilatory Fe(Ⅲ)-reducing microorganisms(biotic reduction)and the electron exchange capacity of PyC(abiotic reduction).During oxygenation,PyC and higher soil pH promoted the oxidation of active Fe (Ⅱ)species(e.g.,exchangeable and low-crystalline Fe (Ⅱ)),which consequently induced higher yield of·OH and further led to degradation of imidacloprid and inactivation of soil microorganisms.Our results demonstrated that PyC accelerated Fe (Ⅱ)/Fe(Ⅲ)cycling and·OH production during redox fluctuations of paddy soils(especially those with low content of soil organic carbon),providing a new insight for remediation strategies in agricultural fields contaminated with organic pollutants.

Nutrients Available and Stable Carbon from Archaeological Black Earth

The present study aims affinity between available concentrations of phosphorus, micronutrients (Cu, Zn and Mn) and stable carbon (SC) in archaeological black earth (ABE) from area “Ilha de Terra”/Caxiuanã—Pará. The relevance of this study refers especially to the determination of carbon concentrations (total, oxidable and semi-labile carbon) directly associated with those of pyrogenic carbon, common in ABE, which should add their contributions to the understanding of soil organic matter recalcitrance. Chemical properties such as CEC and base saturation were determined for ABE and subjacent Latossoil. The available concentrations of nutrients were performed from sequential extraction F1 to F5 phases. Phosphorus was obtained by spectrophotometric method and micronutrients by MP-AES. TOC was determined by the combustion method;stable carbon was obtained from thermoxidation method CTO-375. The following results were obtained from ABE: CEC effective = 21 to 28 (cmolc·L-1);base saturation = 58% to 69%;Carbon concentrations (%): TOC = 2.95 to 3.94;SC = 0.25 to 0.88;semi-labile carbon = 1.75 to 3.63;oxidable = 2.11 to 3.65;inorganic carbon 0.01 to 0.38;P2O5 concentrations (mg·kg-1) in the ABE phases F3 (Fe-Mn oxides, F4 (organic ) and F5 (residual)) in the following order: 35 to 65;200 to 400;140 to 230. It was concluded that the chemical properties in ABE from Ilha de Terra site fall within the range of fertile and the high concentrations of phosphorus are biogenic origin. Phases F3 and F4 are those considered nutrient stocks from ABE studied area.

Once upon a time biomass burning in the western Alps: Nesting effects of climate and local drivers on long-term subalpine fires

Background:The present article questions the relative importance of local-and large-scale processes on the long-term dynamics of fire in the subalpine belt in the western Alps.The study is based on soil charcoal dating and identification,several study sites in contrasting environmental conditions,and sampling of soil charcoal along the elevation gradient of each site.Based on local differences in biomass combustion,we hypothesize that local-scale or landscape-scale processes have driven the fire history,while combustion homogeneity supports the hypothesis of the importance of large-scale or macro-ecological processes,especially climate.Results:Biomass burning during the Holocene resulted from the nesting effects of climate,land use,and altitude,but was little influenced by slope exposure(north versus south),soil(dryness,pH,depth),and vegetation.The mid-Holocene(6500–2700 cal BP)was an important period for climate-driven biomass burning in the subalpine ecosystems of the western Alps,while fires over the last 2500 years appear much more episodic,prompting us to speculate that human activity has played a vital role in their occurrence.Conclusion:Our working hypothesis that the strength of local drivers should offset the effects of regional climate is not validated.The homogeneity of the fire regime between sites thus underscores that climate was the main driver during the Holocene of the western Alps.Long-term subalpine fires are controlled by climate at the millennial scale.Local conditions matter for little in determining variability at the century scale.The mid-Holocene was a chief period for climatic biomass burning in the subalpine zone,while fires during the late Holocene appear much more episodic,suggesting that social drivers has exercised key function on their control.

Biochar Increases Diuron Sorption and Reduces the Potential Contamination of Subsurface Water with Diuron in a Sandy Soil

The herbicide diuron is widely used in agricultural areas in Brazil, whereas it has high potential for subsurface water contamination due to its physicochemical characteristics. Recent studies have demonstrated the potential of biochar as a sorbent and possible pesticide leaching mitigation. The objective of this study was to investigate the long-term effect of biochar application on the kinetics of sorption and desorption of diuron in a Cerrado Haplic Plinthosol. Samples were collected in an experiment conducted in the field in a randomized block design consisting of the combination of two levels of fertilizer application (0 and 300 kg ha −1 of 5-25-15 formula of NPK fertilizers) and three doses of biochar (0, 16, and 32 Mg ha −1 ). The Freundlich isotherm accurately described the sorption of diuron in all treatments. Biochar application increased the sorption and reduced the desorption of diuron. This effect was attributed to the contribution of biochar to total organic carbon (C) and C in the humin fraction and to the increase in the reactivity of the humic acid and humin fractions, which was significantly highly correlated with the sorption coefficient ( K f ). A positive correlation between the partition coefficient of organic C and K f confirmed the importance of the soil organic compartment for the sorption of diuron. The higher diuron sorption and lower diuron desorption capacities of sandy soils after biochar application could reduce the potential risk of diuron leaching and contamination of subsurface water.

Microwave-assisted combustion to produce benzene polycarboxylic acids as molecular markers for biochar identification and quantification

Biochar is a promising carbon dioxide removal(CDR)technology for climate change mitigation.Current procedures for its determination are lengthy,labor-intensive,and difficult to conduct.Benzene polycarboxylic acids(BPCA)are the most promising molecular markers for identification and quantification of biochar and its quality as they specifically represent the stable polyaromatic backbone of biochar.Therefore,using the BPCA method,its stability and,thus,its C sequestration potential could be used for CDR accounting.The current BPCA method relies on a specific high-pressure digestion apparatus,which is not available around the world.Therefore,the aims of the present work were(i)to compare the conventional high-pressure nitric acid oxidation with a microwave-assisted digestion technique and optimize the oxidation conditions in such a way that previous results are comparable with future ones,and(ii)to significantly reduce the digestion time of soil samples of 8 h and to develop a suitable routine method that produces comparable and reproducible results.For this purpose,soil and control sample series were prepared for different temperature-time-program.Obtained results were compared with the values of the conventional method both for individual samples and for the whole dataset separately.To ensure the representative-ness of the results,in addition to various soil samples with different properties,we included two reference materials into our data set,one without biochar(wheat flour)and a biochar sample.Our results showed that conventional nitric acid oxidation in the BPCA determination at 170°C and 8 h can be substituted by digestion in a microwave reaction system(CEM Mars6)at 190°C and 1 h.Our results further showed that this condition needs to be strictly matched,because,otherwise,over-or underestimation of biochar quantity and/or quality will be the consequence.The goal of a less time-consuming BPCA extrac-tion from soil samples was achieved by reducing the extraction time from 8 to 1 h using the microwave-assisted method.However,one disadvantage of the new method is that five times more sample material and chemicals are needed for further BPCA analysis,compared to the original method.