Char black carbon (BC), the solid residue of incomplete combustion, is continuously being added to soils and sediments due to natural vegetation fires, anthropogenic pollution, and new strategies for carbon sequestration (“biochar”). Here we present a molecular-level assessment of the physical organization and chemical complexity of biomass-derived chars and, specifically, that of aromatic carbon in char structures. Brunauer−Emmett−Teller (BET)−N2 surface area (SA), X-ray diffraction (XRD), synchrotron-based near-edge X-ray absorption fine structure (NEXAFS), and Fourier transform infrared (FT-IR) spectroscopy are used to show how two plant materials (wood and grass) undergo analogous but quantitatively different physical−chemical transitions as charring temperature increases from 100 to 700 °C. These changes suggest the existence of four distinct categories of char consisting of a unique mixture of chemical phases and physical states: (i) in transition chars, the crystalline character of the precursor ma...

/pdf/dynamic-molecular-structure-of-plant-biomass-derived-black-7gpeuzb3di.pdf

Dynamic molecular structure of plant biomass-derived black carbon (biochar)

Black Carbon (BC) may significantly affect nutrient retention and play a key role in a wide range of biogeochemical processes in soils, especially for nutrient cycling. Anthrosols from the Brazilian Amazon (ages between 600 and 8700 yr BP) with high contents of biomassderived BC had greater potential cation exchange capacity (CEC measured at pH 7) per unit organic C than adjacent soils with low BC contents.Synchrotron-based near edge X-ray absorption fine structure (NEXAFS) spectroscopy coupled with scanning transmission X-ray microscopy (STXM) techniques explained the source of the higher surface charge of BC compared with non-BC by mapping crosssectional areas of BC particles with diameters of 10 to 50 mm for C forms. The largest cross-sectional areas consisted of highly aromatic or only slightly oxidized organic C most likely originating from the BC itself with a characteristic peak at 286.1 eV, which could not be found in humic substance extracts, bacteria or fungi. Oxidation significantly increased from the core of BC particles to their surfaces as shown by the ratio of carboxyl-C/aromatic-C. Spotted and non-continuous distribution patterns of highly oxidized C functional groups with distinctly different chemical signatures on BC particle surfaces (peak shift at 286.1 eV to a higher energy of 286.7 eV) indicated that non-BC may be adsorbed on the surfaces of BC particles creating highly oxidized surface. As a consequence of both oxidation of the BC particles themselves and adsorption of organic matter to BC surfaces, the charge density (potential CEC per unit surface area) was greater in BC-rich Anthrosols than adjacent soils. Additionally, a high specific surface area was attributable to the presence of BC, which may contribute to the high CEC found in soils that are rich in BC.

/pdf/black-carbon-increases-cation-exchange-capacity-in-soils-3fak9ns4e1.pdf

Black Carbon Increases Cation Exchange Capacity in Soils

Chemical characterization of particulate emissions from diesel engines: A review

Biochar is the carbon-rich product of the pyrolysis of biomass under oxygen-limited conditions, and it has received increasing attention due to its multiple functions in the fields of climate change mitigation, sustainable agriculture, environmental control, and novel materials. To design a “smart” biochar for environmentally sustainable applications, one must understand recent advances in biochar molecular structures and explore potential applications to generalize upon structure–application relationships. In this review, multiple and multilevel structures of biochars are interpreted based on their elemental compositions, phase components, surface properties, and molecular structures. Applications such as carbon fixators, fertilizers, sorbents, and carbon-based materials are highlighted based on the biochar multilevel structures as well as their structure-application relationships. Further studies are suggested for more detailed biochar structural analysis and separation and for the combination of macros...

/pdf/insight-into-multiple-and-multilevel-structures-of-biochars-26ak0hya85.pdf

Insight into Multiple and Multilevel Structures of Biochars and Their Potential Environmental Applications: A Critical Review

Two new soft X-ray scanning transmission microscopes located at the Advanced Light Source (ALS) have been designed, built and commissioned. Interferometer control implemented in both microscopes allows the precise measurement of the transverse position of the zone plate relative to the sample. Long-term positional stability and compensation for transverse displacement during translations of the zone plate have been achieved. The interferometer also provides low-distortion orthogonal x, y imaging. Two different control systems have been developed: a digital control system using standard VXI components at beamline 7.0, and a custom feedback system based on PC AT boards at beamline 5.3.2. Both microscopes are diffraction limited with the resolution set by the quality of the zone plates. Periodic features with 30 nm half period can be resolved with a zone plate that has a 40 nm outermost zone width. One microscope is operating at an undulator beamline (7.0), while the other is operating at a novel dedicated bending-magnet beamline (5.3.2), which is designed specifically to illuminate the microscope. The undulator beamline provides count rates of the order of tens of MHz at high-energy resolution with photon energies of up to about 1000 eV. Although the brightness of a bending-magnet source is about four orders of magnitude smaller than that of an undulator source, photon statistics limited operation with intensities in excess of 3 MHz has been achieved at high energy resolution and high spatial resolution. The design and performance of these microscopes are described.

/pdf/interferometer-controlled-scanning-transmission-x-ray-x9zjh2sv28.pdf

Interferometer‐controlled scanning transmission X‐ray microscopes at the Advanced Light Source

Determination of chemical-structural changes in vitrinite accompanying luminescence alteration using C-NEXAFS analysis

STXM and C-NEXAFS (carbon near edge absorption micro-spectroscopy) microanalysis were used to analysis the microchemistry of cokes and highly carbonaceous materials. The issue of molecular orientation is addressed by using the intrinsic polarization of the x-ray beam at X1A beamline at NSLS.

/pdf/soft-x-ray-microanalysis-and-microscopy-a-unique-probe-of-4zg9bn8ike.pdf

Soft x-ray microanalysis and microscopy: A unique probe of the organic chemistry of heterogeneous solids

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Determination of chemical-structural changes in vitrinite accompanying luminescence alteration using C-NEXAFS analysis

Soft x-ray microanalysis and microscopy: A unique probe of the organic chemistry of heterogeneous solids