Investigation into the role of carboxylic acid and phenolic hydroxyl groups in the plant biostimulant activity of a humic acid purified from an oxidized sub-bituminous coal.

Introduction: Humic substances (HS) are increasingly being applied as crop plant biostimulants because they have been shown to increase plant productivity, especially under environmentally stressful conditions. There has been intense interest in elucidating the HS molecular structures responsible for eliciting the plant biostimulant response (PBR). The polar and weakly acidic carboxylic (COOH) and phenolic hydroxyl (ArOH) functional groups play major roles in the acid nature, pH dependent solubilities, conformation, and metal- and salt-binding capabilities of HS. Reports on the role played by these groups in the PBR of HS found growth parameters being both positively and negatively correlated with COOH and ArOH functionalities. Materials and methods: To investigate the role of COOH and ArOH in HS biostimulant activity we used a humic acid (HA), purified from an oxidized sub bituminous coal to prepare HAs with COOH groups methylated (AHA), ArOH groups acetylated (OHA), and with both COOH and ArOH groups methylated (FHA). The original HA was designated (NHA). The four HAs were subjected to elemental, 13C-NMR, FTIR, and EPR analyses and their antioxidant properties were assessed using the trolox equivalents antioxidant capacity assay (TEAC). 13C-NMR and FTIR analysis revealed significant alkylation/acetylation. To determine the effects of alkylating/acetylating these functional groups on the HA elicited PBR, the HAs were evaluated in a plant bioassay on corn (Zea mays L.) seedling under nutrient and non-nutrient stressed conditions. Treatments consisted of the four HAs applied to the soil surface at a concentration of 80 mg C L-1, in 50 ml DI H2O with the control plants receiving 50ml DI H2O. Results: The HA-treated plants, at both fertilization rates, were almost always significantly larger than their respective control plants. However, the differences produced under nutrient stress were always much greater than those produced under nutrient sufficiency, supporting previous reports that HA can reduce the effects of stress on plant growth. In addition, for the most part, the HAs with the alkylated/acetylated groups produced plants equal to or larger than plants treated with NHA. Conclusion: These results suggests that COOH and ArOH groups play a limited or no role in the HA elicited PBR. Alternatively, the HA pro-oxidant to antioxidant ratio may play a role in the magnitude of the biostimulant response.

High carbon losses from oxygen-limited soils challenge biogeochemical theory and model assumptions.

Oxygen (O2 ) limitation contributes to persistence of large carbon (C) stocks in saturated soils. However, many soils experience spatiotemporal O2  fluctuations impacted by climate and land-use change, and O2 -mediated climate feedbacks from soil greenhouse gas emissions remain poorly constrained. Current theory and models posit that anoxia uniformly suppresses carbon (C) decomposition. Here we show that periodic anoxia may sustain or even stimulate decomposition over weeks to months in two disparate soils by increasing turnover and/or size of fast-cycling C pools relative to static oxic conditions, and by sustaining decomposition of reduced organic molecules. Cumulative C losses did not decrease consistently as cumulative O2 exposure decreased. After >1 year, soils anoxic for 75% of the time had similar C losses as the oxic control but nearly threefold greater climate impact on a CO2 -equivalent basis (20-year timescale) due to high methane (CH4 ) emission. A mechanistic model incorporating current theory closely reproduced oxic control results but systematically underestimated C losses under O2  fluctuations. Using a model-experiment integration (ModEx) approach, we found that models were improved by varying microbial maintenance respiration and the fraction of CH4 production in total C mineralization as a function of O2 availability. Consistent with thermodynamic expectations, the calibrated models predicted lower microbial C-use efficiency with increasing anoxic duration in one soil; in the other soil, dynamic organo-mineral interactions implied by our empirical data but not represented in the model may have obscured this relationship. In both soils, the updated model was better able to capture transient spikes in C mineralization that occurred following anoxic-oxic transitions, where decomposition from the fluctuating-O2 treatments greatly exceeded the control. Overall, our data-model comparison indicates that incorporating emergent biogeochemical properties of soil O2 variability will be critical for effectively modeling C-climate feedbacks in humid ecosystems.

Native American fire management at an ancient wildland-urban interface in the Southwest United States.

The intersection of expanding human development and wildland landscapes-the "wildland-urban interface" or WUI-is one of the most vexing contexts for fire management because it involves complex interacting systems of people and nature. Here, we document the dynamism and stability of an ancient WUI that was apparently sustainable for more than 500 y. We combine ethnography, archaeology, paleoecology, and ecological modeling to infer intensive wood and fire use by Native American ancestors of Jemez Pueblo and the consequences on fire size, fire-climate relationships, and fire intensity. Initial settlement of northern New Mexico by Jemez farmers increased fire activity within an already dynamic landscape that experienced frequent fires. Wood harvesting for domestic fuel and architectural uses and abundant, small, patchy fires created a landscape that burned often but only rarely burned extensively. Depopulation of the forested landscape due to Spanish colonial impacts resulted in a rebound of fuels accompanied by the return of widely spreading, frequent surface fires. The sequence of more than 500 y of perennial small fires and wood collecting followed by frequent "free-range" wildland surface fires made the landscape resistant to extreme fire behavior, even when climate was conducive and surface fires were large. The ancient Jemez WUI offers an alternative model for fire management in modern WUI in the western United States, and possibly other settings where local management of woody fuels through use (domestic wood collecting) coupled with small prescribed fires may make these communities both self-reliant and more resilient to wildfire hazards.

Ferrate(VI) pretreatment of water containing natural organic matter, bromide, and iodide: A potential strategy to control soluble lead release from PbO2(s).

Lead dioxide (PbO2(s)) is a corrosion product of lead-containing plumbing materials in water distribution pipelines. The presence of reductants in water could cause the release of soluble lead (mainly Pb(II)) from PbO2(s). Lead in drinking water is detrimental to public health. This paper presents the first application of ferrate (FeVIO42-, Fe(VI)) to decreasing the generation of soluble lead in water containing PbO2(s) and common reducing constituents (e.g., natural organic matter (NOM), iodide (I-), and bromide (Br-)) at different pH conditions (i.e., 6.0, 7.0, and 8.0). The released soluble lead from PbO2(s) was found to be dominantly controlled by NOM in water, via the redox dissolution of PbO2(s) and the reduction of PbO2(s) by reducing moieties of NOM. The feasibility of both processes increased when pH decreased. The I- and Br- in water played minor roles in generating soluble lead. Fe(VI) reacted with reducing functional groups of NOM, as determined by 13C nuclear magnetic resonance spectroscopy. Water pretreatment with Fe(VI) inhibited the reaction of NOM with PbO2(s) and therefore, caused lower soluble lead concentrations compared to water samples without Fe(VI) treatment. This study indicates that Fe(VI) pretreatment is a potential approach to controlling soluble lead in drinking water.

Trade-offs in soil carbon protection mechanisms under aerobic and anaerobic conditions.

Oxygen (O2 ) limitation is generally understood to suppress oil carbon (C) decomposition and is a key mechanism impacting terrestrial C stocks under global change. Yet, O2 limitation may differentially impact kinetic or thermodynamic versus physicochemical C protection mechanisms, challenging our understanding of how soil C may respond to climate-mediated changes in O2 dynamics. Although O2 limitation may suppress decomposition of new litter C inputs, release of physicochemically protected C due to iron (Fe) reduction could potentially sustain soil C losses. To test this trade-off, we incubated two disparate upland soils that experience periodic O2 limitation-a tropical rainforest Oxisol and a temperate cropland Mollisol-with added litter under either aerobic (control) or anaerobic conditions for 1 year. Anoxia suppressed total C loss by 27% in the Oxisol and by 41% in the Mollisol relative to the control, mainly due to the decrease in litter-C decomposition. However, anoxia sustained or even increased decomposition of native soil-C (11.0% vs. 12.4% in the control for the Oxisol and 12.5% vs. 5.3% in the control for the Mollisol, in terms of initial soil C mass), and it stimulated losses of metal- or mineral-associated C. Solid-state 13 C nuclear magnetic resonance spectroscopy demonstrated that anaerobic conditions decreased protein-derived C but increased lignin- and carbohydrate-C relative to the control. Our results indicate a trade-off between physicochemical and kinetic/thermodynamic C protection mechanisms under anaerobic conditions, whereby decreased decomposition of litter C was compensated by more extensive loss of mineral-associated soil C in both soils. This challenges the common assumption that anoxia inherently protects soil C and illustrates the vulnerability of mineral-associated C under anaerobic events characteristic of a warmer and wetter future climate.

Ferrate(VI) pretreatment before disinfection: An effective approach to controlling unsaturated and aromatic halo-disinfection byproducts in chlorinated and chloraminated drinking waters.

Disinfection is an essential process of drinking water treatment to eliminate harmful pathogens, but it generates potentially toxic disinfection byproducts (DBPs). Ferrate (FeO42-, Fe(VI)) was used to pre-oxidize natural organic matter (NOM, the precursor of DBPs) in source water to control DBP formation in subsequent chlorine or chloramine disinfection. Currently, it is unclear how Fe(VI) changes the structure of NOM, and no information details the effect of Fe(VI) pretreatment on the aromatic DBPs or the speciation of overall DBPs generated in subsequent disinfection of drinking water. In the present paper, Fe(VI) was applied to pretreat simulated source water samples at a Fe(VI) to dissolved organic carbon mole ratio of 1:1 at pH 8.0. 13C nuclear magnetic resonance spectroscopy was newly employed to characterize NOM in simulated source waters with and without Fe(VI) treatment, and it was demonstrated that Fe(VI) converted unsaturated aromatic C functional groups in NOM to saturated aliphatic ones. High-resolution mass spectrometry (HRMS) and high performance liquid chromatography/triple quadrupole MS were applied to analyze the DBPs generated in chlorination and chloramination of the source waters with and without Fe(VI) pretreatment. It was confirmed that Fe(VI) pretreatment followed by chlorination (or chloramination), generated DBPs containing less unsaturated, halogenated, and aromatic moieties than chlorination (or chloramination) without pretreatment by Fe(VI). Finally, the cytotoxicity of disinfected drinking water samples were assessed with the human epithelial colorectal adenocarcinoma Caco-2 cell line (a model of the intestinal barrier for ingested toxicants), and the results show that Fe(VI) pretreatment detoxified the chlorinated and chloraminated drinking waters.

Solid-state NMR reveals differential carbohydrate utilization in diapausing Culex pipiens.

Culex pipiens is the mosquito that vectors West Nile Virus and other human-pathogenic flavivruses in North America. In response to shortened day length and lower temperatures, female Cx. pipiense prepares for the diapause by actively feeding on carbohydrates to increase the biosynthesis of glycogen and lipid to store energy for overwintering. The effect of feeding different carbohydrates on glycogen and lipid biosynthesis in diapausing mosquitoes was investigated in vivo using 13C solid-state NMR. Diapause-destined adult females and nondiapausing counterparts after adult eclosion were fed with three different carbohydrate sources for 7 days: 1) 10% sucrose, 2) 10% D-[13C6]glucose, and 3) 1% D-[13C6]glucose co-provisioned with 10% sucrose. NMR measurements show that sucrose and glucose are metabolized differently in diapausing mosquitoes. Mosquitoes fed on sucrose primarily accumulate glycogen with increased branching structures, but less of lipids. In contrast, mosquitoes fed exclusively on glucose show accumulation of both glycogen and lipid with increased aliphatic chain length. Glucose is exclusively metabolized for the biosynthesis of triacylglyceride when mosquitoes were co-fed with sucrose. Our findings provide novel insights into the insect carbohydrate metabolism that governs glycogen and lipid biosynthesis during diapause, which is fundamental for the insect survival during inimical environments.

Chemical and Isotopic Thresholds in Charring: Implications for the Interpretation of Charcoal Mass and Isotopic Data.

Charcoal plays a significant role in the long-term carbon cycle, and its use as a soil amendment is promoted as a C sequestration strategy (biochar). One challenge in this research area is understanding the heterogeneity of charcoal properties. Although the maximum reaction temperature is often used as a gauge of pyrolysis conditions, pyrolysis duration also changes charcoal physicochemical qualities. Here, we introduce a formal definition of charring intensity (CI) to more accurately characterize pyrolysis, and we document variation in charcoal chemical properties with variation in CI. We find two types of responses to CI: either linear or threshold relationships. Mass yield decreases linearly with CI, while a threshold exists across which % C, % N, and δ(15)N exhibit large changes. This CI threshold co-occurs with an increase in charcoal aromaticity. C isotopes do not change from original biomass values, supporting the use of charcoal δ(13)C signatures to infer paleoecological conditions. Fractionation of N isotopes indicates that fire may be enriching soils in (15)N through pyrolytic N isotope fractionation. This influx of "black N" could have a significant impact on soil N isotopes, which we show theoretically using a simple mass-balance model.

Toward a "molecular thermometer" to estimate the charring temperature of wildland charcoals derived from different biomass sources.

The maximum temperature experienced by biomass during combustion has a strong effect on chemical properties of the resulting charcoal, such as sorption capacity (water and nonpolar materials) and microbial degradability. However, information about the formation temperature of natural charcoal can be difficult to obtain in ecosystems that are not instrumented prior to fires. Benzene polycarboxylic acids (BPCA) are molecular markers specific for pyrogenic carbon (PyC) which can provide information on the degree of aromatic condensation in charcoals. Here we apply the BPCA molecular marker method to a set of 10 charcoals produced during an experimental fire in a Pitch pine-scrub oak forest from litter and bark of pitch pine and inkberry plants in the Pinelands National Reserve in New Jersey, USA. We deployed temperature-sensitive crayons throughout the burn site, which recorded the maximum air temperature and made comparisons to the degree of thermal alteration recorded by BPCA molecular markers. Our results show an increase of the degree of aromatic condensation with monitored temperatures for bark biomass, while for needles no clear trend could be observed. For leaf-derived charcoals at increasing monitored fire temperatures, decreasing degree of aromatic condensation was obtained. This suggests that molecular markers can be used to roughly estimate the maximum fire temperatures experienced by bark and wood materials, but not based on leaf- and needle-derived materials. Possible applications include verifying declared pyrolysis temperatures of biochars and evaluating ecosystem fire temperature postburn.

Biochemical suitability of crop residues for cellulosic ethanol: disincentives to nitrogen fertilization in corn agriculture.

Concerns about energy security and climate change have increased biofuel demand, particularly ethanol produced from cellulosic feedstocks (e.g., food crop residues). A central challenge to cropping for cellulosic ethanol is the potential environmental damage from increased fertilizer use. Previous analyses have assumed that cropping for carbohydrate in residue will require the same amount of fertilizer as cropping for grain. Using (13)C nuclear magnetic resonance, we show that increases in biomass in response to fertilization are not uniform across biochemical classes (carbohydrate, protein, lipid, lignin) or tissues (leaf and stem, grain, reproductive support). Although corn grain responds vigorously and nonlinearly, corn residue shows only modest increases in carbohydrate yields in response to high levels of fertilization (25% increase with 202 kg N ha(-1)). Lignin yields in the residue increased almost twice as much as carbohydrate yields in response to nitrogen, implying that residue feedstock quality declines as more fertilizer is applied. Fertilization also increases the decomposability of corn residue, implying that soil carbon sequestration becomes less efficient with increased fertilizer. Our results suggest that even when corn is grown for grain, benefits of fertilization decline rapidly after the ecosystem's N demands are met. Heavy application of fertilizer yields minimal grain benefits and almost no benefits in residue carbohydrates, while degrading the cellulosic ethanol feedstock quality and soil carbon sequestration capacity.

Temperature sensitivity of black carbon decomposition and oxidation.

Global warming accelerates decomposition of soil organic carbon (SOC) pools with varying rates and temperature sensitivities. Black carbon (BC) materials are among the slowest decomposing components of the SOC pool. Although BC is a large component of SOC in many systems, the influence of temperature on decomposition of BC bearing different chemical and physical structures remains poorly understood. Four BC materials, produced by carbonizing corn residue and oak wood at 350 and 600 degrees C (corn-350-BC, corn-600-BC, oak-350-BC, and oak-600-BC), were mixed with pure sand and incubated at 4, 10, 20, 30, 45, and 60 degrees C for 1 year. Corn-BC was more porous than oak-BC as determined by scanning electron microscopy (SEM). Increasing the charring temperature from 350 to 600 degrees C led to greater aromaticity with 5-15% more C in aromatic rings and a 39-57% increase in both nonprotonated aromatic C and aromatic bridgehead C quantified by nuclear magnetic resonance (NMR) spectroscopy and a greater degree of order and development of C layers as observed by transmission electron microscopy (TEM). With a temperature increase from 4 to 60 degrees C, C loss of corn-350-BC increased from 10 to 20%, corn-600-BC, from 4 to 20%, oak-350-BC, from 2.3 to 15%, and oak-600-BC from 1.5 to 14% of initial C content, respectively. Temperature sensitivity (Q(10)) decreased with increasing incubation temperature and was highest in oak-600-BC, followed by oak-350-BC, corn-600-BC, and corn-350-BC, indicating that decomposition of more stable BC was more sensitive to increased temperature than less stable materials. Carbon loss and potential cation exchange capacity (CECp) significantly (p < 0.05) correlated with O/C ratios and change in O/C ratios, suggesting that oxidative processes were the most important mechanism controlling BC decomposition in this study.

White-rot basidiomycete-mediated decomposition of C60 fullerol.

Industrially produced carbon-based nanomaterials (CNM), including fullerenes and nanotubes, will be introduced into the environment in increasing amounts in the next decades. One likely environmental chemical transformation of C60 is oxidation to C60 fullerol through both abiotic- and biotic-mediated means. Unfortunately, knowledge of the environmental fate of oxidized CNM is lacking. This study used bulk and compound-specific 13C stable isotope ratio mass spectrometry techniques and spectroradiometry analysis to examine the ability of two white rot basidiomycete fungi (Phlebia tremellosa and Trametes versicolor) to metabolize and degrade an oxygenated CNM, C60 fullerol. After 32 weeks of decay, both fungi were able to bleach and oxidize fullerol to CO2. Additionally, the fungi incorporated minor amounts of the fullerol carbon into lipid biomass. These findings are significant in that they represent the first report of direct biodegradation and utilization of any fullerene derivative and provide valuable information about the possible environmental fates of other CNM.

Effects of long-term soil amendment with sewage sludges on soil humic acid thermal and molecular properties.

Sewage sludges are frequently used as soil amendments due to their high contents of organic matter and nutrients, particularly N and P. However, their effects upon the chemistry of soil humic acids, one of the main components of the soil organic matter, need to be more deeply studied in order to understand the relation between organic matter structure and beneficial soil properties. Two sewage sludges subjected to different types of pre-treatment (composted and thermally dried) with very different chemical compositions were applied for three consecutive years to an agricultural soil under long-term field study. Thermal analysis (TG-DTG-DTA) and solid-state (13)C NMR spectroscopy were used to compare molecular and structural properties of humic acids isolated from sewage sludges, and to determine changes in amended soils. Thermally dried sewage sludge humic acids showed an important presence of alkyl and O/N-alkyl compounds (70%) while composted sludge humic acids comprised 50% aromatic and carbonyl carbon. In spite of important differences in the initial chemical and thermal properties of the two types of sewage sludges, the chemical and thermal properties of the soil humic acids were quite similar to one another after 3 years of amendment. Long-term application of both sewage sludges resulted in 80-90% enrichment in alkyl carbon and organic nitrogen contents of the soil humic acid fraction.