Instead of containing stable and chemically unique ‘humic substances’, as has been widely accepted, soil organic matter is a mixture of progressively decomposing organic compounds; this has broad implications for soil science and its applications. The exchange of nutrients, energy and carbon between soil organic matter, the soil environment, aquatic systems and the atmosphere is important for agricultural productivity, water quality and climate. Long-standing theory suggests that soil organic matter is composed of inherently stable and chemically unique compounds. Here we argue that the available evidence does not support the formation of large-molecular-size and persistent ‘humic substances’ in soils. Instead, soil organic matter is a continuum of progressively decomposing organic compounds. We discuss implications of this view of the nature of soil organic matter for aquatic health, soil carbon–climate interactions and land management. Soil organic matter contains a large portion of the world's carbon and plays an important role in maintaining productive soils and water quality. Nevertheless, a consensus on the nature of soil organic matter is lacking. Johannes Lehmann and Markus Kleber argue that soil organic matter should no longer be seen as large and persistent, chemically unique substances, but as a continuum of progressively decomposing organic compounds.

The contentious nature of soil organic matter

The combined adsorption and partition effects of biochars with varying fractions of noncarbonized organic matter have not been clearly defined. Biochars, produced by pyrolysis of pine needles at different temperatures (100-700 degrees C, referred as P100-P700), were characterized by elemental analysis, BET-N2 surface areas and FTIR. Sorption isotherms of naphthalene, nitrobenzene, and m-dinitrobenzene from water to the biochars were compared. Sorption parameters (N and logKf) are linearly related to sorbent aromaticities, which increase with the pyrolytic temperature. Sorption mechanisms of biochars are evolved from partitioning-dominant at low pyrolytic temperatures to adsorption-dominant at higher pyrolytic temperatures. The quantitative contributions of adsorption and partition are determined by the relative carbonized and noncarbonized fractions and their surface and bulk properties. The partition of P100-P300 biochars originates from an amorphous aliphatic fraction, which is enhanced with a reduction of the substrate polarity; for P400-P600, the partition occurs with a condensed aromatic core that diminishes with a further reduction of the polarity. Simultaneously, the adsorption component exhibits a transition from a polarity-selective (P200-P400) to a porosity-selective (P500-P600) process, and displays no selectivity with P700 and AC in which the adsorptive saturation capacities are comparable to predicted values based on the monolayer surface coverage of molecule.

Transitional Adsorption and Partition of Nonpolar and Polar Aromatic Contaminants by Biochars of Pine Needles with Different Pyrolytic Temperatures

Water quality issues are a major challenge that humanity is facing in the twenty-first century. Here, we review the main groups of aquatic contaminants, their effects on human health, and approaches to mitigate pollution of freshwater resources. Emphasis is placed on chemical pollution, particularly on inorganic and organic micropollutants including toxic metals and metalloids as well as a large variety of synthetic organic chemicals. Some aspects of waterborne diseases and the urgent need for improved sanitation in developing countries are also discussed. The review addresses current scientific advances to cope with the great diversity of pollutants. It is organized along the different temporal and spatial scales of global water pollution. Persistent organic pollutants (POPs) have affected water systems on a global scale for more than five decades; during that time geogenic pollutants, mining operations, and hazardous waste sites have been the most relevant sources of long-term regional and local water pollution. Agricultural chemicals and wastewater sources exert shorter-term effects on regional to local scales.

https://www.annualreviews.org/doi/pdf/10.1146/annurev-environ-100809-125342

Global Water Pollution and Human Health

Carbon nanotubes (CNTs) have drawn special research attention because of their unique properties and potential applications. This review summarizes the research progress of organic chemical adsorption on CNTs, and will provide useful information for CNT application and risk assessment. Adsorption heterogeneity and hysteresis are two widely recognized features of organic chemical−CNT interactions. However, because different mechanisms may act simultaneously, mainly hydrophobic interactions, π−π bonds, electrostatic interactions, and hydrogen bonds, the prediction of organic chemical adsorption on CNTs is not straightforward. The dominant adsorption mechanism is different for different types of organic chemicals (such as polar and nonpolar), thus different models may be needed to predict organic chemical−CNT interaction. Adsorption mechanisms will be better understood by investigating the effects of properties of both CNTs and organic chemicals along with environmental conditions. Another major factor affec...

Adsorption Mechanisms of Organic Chemicals on Carbon Nanotubes

The reactions between peroxymonosulfate (PMS) and quinones were investigated for the first time in this work, where benzoquinone (BQ) was selected as a model quinone. It was demonstrated that BQ could efficiently activate PMS for the degradation of sulfamethoxazole (SMX; a frequently detected antibiotic in the environments), and the degradation rate increased with solution pH from 7 to 10. Interestingly, quenching studies suggested that neither hydroxyl radical (•OH) nor sulfate radical (SO4•–) was produced therein. Instead, the generation of singlet oxygen (1O2) was proved by using two chemical probes (i.e., 2,2,6,6-tetramethyl-4-piperidinol and 9,10-diphenylanthracene) with the appearance of 1O2 indicative products detected by electron paramagnetic resonance spectrometry and liquid chromatography mass spectrometry, respectively. A catalytic mechanism was proposed involving the formation of a dioxirane intermediate between PMS and BQ and the subsequent decomposition of this intermediate into 1O2. Accordi...

Activation of Peroxymonosulfate by Benzoquinone: A Novel Nonradical Oxidation Process

Soils and sediments worldwide contain appreciable amounts of thermally altered organic matter (chars). Chars contain electroactive quinoid functional groups and polycondensed aromatic sheets that were recently shown to be of biogeochemical and envirotechnical relevance. However, so far no systematic investigation of the redox properties of chars formed under different pyrolysis conditions has been performed. Here, using mediated electrochemical analysis, we show that chars made from different feedstock and over a range of pyrolysis conditions are redox-active and reversibly accept and donate up to 2 mmol electrons per gram of char. The analysis of two thermosequences revealed that chars produced at intermediate to high heat treatment temperatures (HTTs) (400–700 °C) show the highest capacities to accept and donate electrons. Combined electrochemical, elemental, and spectroscopic analyses of the thermosequence chars provide evidence that the pool of redox-active moieties is dominated by electron-donating, ...

/pdf/redox-properties-of-plant-biomass-derived-black-carbon-1lpd8690wq.pdf

Redox Properties of Plant Biomass-Derived Black Carbon (Biochar)

Two electrochemical methods to assess the redox properties of humic substances (HS) are presented: direct electrochemical reduction (DER) on glassy carbon working electrodes (WE) and mediated electrochemical reduction (MER) and oxidation (MEO) using organic radicals to facilitate electron transfer between HS and the WE. DER allows for continuous monitoring of electron and proton transfer to HS by chronocoulometry and automated acid titration, respectively, and of changes in bulk HS redox potential Eh. Leonardite Humic Acid (LHA) showed an H+/e− ratio of unity and a decrease in potential from Eh = +0.18 to −0.23 V upon transfer of 822 μmole- gLHA−1 at pH 7, consistent with quinones as major redox-active functional moieties in LHA. MER and MEO quantitatively detected electrons in LHA samples that were prereduced by DER to different extents. MER and MEO therefore accurately quantify the redox state of HS. Cyclic DER and O2-reoxidation revealed that electron transfer to LHA was largely reversible. However, LH...

Novel electrochemical approach to assess the redox properties of humic substances.

Humic substances (HS) are heterogeneous, redox-active organic macromolecules. While electron transfer to and from HS under reducing conditions is well investigated, comparatively little is known on the electron donating (i.e., antioxidant) properties of HS under oxic conditions. In this work, the electron donating capacities (EDCs) of terrestrial and aquatic HS were quantified by mediated electrochemical oxidation over a wide range of pH values and applied redox potentials (Eh) using 2,2′-azino-bis(3-ethylbenzthiazoline-6-sulfonic acid) as an electron transfer mediator. Electrochemical oxidation of three model humic acids (HAs) was largely irreversible, and the EDCs of these HAs increased with increasing Eh and pH. These results suggest that HS contain a wide variety of moieties that are oxidized at different potentials and that, upon oxidation, release protons and undergo irreversible follow-up reactions. At a given pH and Eh, the EDCs of the HS correlated well with their titrated phenol contents suggest...

Antioxidant Properties of Humic Substances

Humic substances make up a significant fraction of the natural organic matter in terrestrial and aquatic environments. Laboratory experiments suggest that humic substances serve as fully regenerable electron acceptors in recurrently anoxic environments such as peatlands.

Humic substances as fully regenerable electron acceptors in recurrently anoxic environments

Plastic materials are widely used in agricultural applications to achieve food security for the growing world population The use of biodegradable instead of nonbiodegradable polymers in single-use agricultural applications, including plastic mulching, promises to reduce plastic accumulation in the environment We present a novel approach that allows tracking of carbon from biodegradable polymers into CO2 and microbial biomass The approach is based on 13C-labeled polymers and on isotope-specific analytical methods, including nanoscale secondary ion mass spectrometry (NanoSIMS) Our results unequivocally demonstrate the biodegradability of poly(butylene adipate-co-terephthalate) (PBAT), an important polyester used in agriculture, in soil Carbon from each monomer unit of PBAT was used by soil microorganisms, including filamentous fungi, to gain energy and to form biomass This work advances both our conceptual understanding of polymer biodegradation and the methodological capabilities to assess this process in natural and engineered environments

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Michael Sander

Papers

Redox Properties of Plant Biomass-Derived Black Carbon (Biochar)

Novel electrochemical approach to assess the redox properties of humic substances.

Antioxidant Properties of Humic Substances

Humic substances as fully regenerable electron acceptors in recurrently anoxic environments

Biodegradation of synthetic polymers in soils: Tracking carbon into CO2 and microbial biomass.