Influence of carbonization methods on the aromaticity of pyrogenic dissolved organic carbon

Minori Uchimiya, Syuntaro Hiradate, Michael Jerry Antal

Research output: Contribution to journalArticle

12 Citations (Scopus)

Abstract

Dissolved organic carbon (DOC) components of soil amendments, such as biochar, will influence the fundamental soil chemistry, including the metal speciation, nutrient availability, and microbial activity. Quantitative correlation is necessary between (i) pyrogenic DOC components of varying aromaticity and ionizable (carboxyl and hydroxyl) substituents and (ii) bulk and solution properties of biochars. This study employed fluorescence excitation-emission (EEM) spectrophotometry with parallel factor analysis (PARAFAC) to understand the influence of the pyrolysis platform (flash and high-yield carbonization, slow pyrolysis, and fast pyrolysis) and solution pH on the DOC structure of carbonaceous materials. The PARAFAC fingerprint representative of conjugated, polyaromatic DOC correlated (Pearson's r ≥ 0.6; p < 0.005) with (i) volatile matter content and (ii) total organic carbon and nitrogen concentrations in water and base (50-100 mM NaOH) extracts. Electric conductivity of the extracts correlated with S (indicative of labile sulfate species) and Na + K concentrations (r > 0.9; p < 0.0005). The pH-dependent changes in fluorescence peak position and intensity suggested (i) protonation of carboxylate/phenolic functionalities and (ii) acid-induced aggregation of colloidal particles for ≤350°C slow-pyrolysis biochars; DOC of high-yield/flash carbonization charcoals and ≥500°C slow-pyrolysis biochars were less sensitive to pH. Solid-state 13C cross-polarization and magic angle spinning nuclear magnetic resonance analysis of bulk aromaticity (-C=C- peak at 110-160 ppm) suggested that both recalcitrant and labile fluorescence DOC fingerprints are composed of polyaromatic structures that begin to form near 350°C. These biochar-borne DOC components of varying aromaticity and carboxyl substituents will participate in hydrophobic and hydrogen-bonding interactions with soil components that will ultimately impact the biogeochemical cycles.

Original languageEnglish
Pages (from-to)2503-2513
Number of pages11
JournalEnergy and Fuels
Volume29
Issue number4
DOIs
Publication statusPublished - Apr 16 2015
Externally publishedYes

Fingerprint

Carbonization
Organic carbon
Pyrolysis
Fluorescence
Factor analysis
Soils
Magic angle spinning
Charcoal
Protonation
Spectrophotometry
Hydroxyl Radical
Nutrients
Hydrogen bonds
Agglomeration
Metals
Nuclear magnetic resonance
biochar
Availability
Polarization
Acids

All Science Journal Classification (ASJC) codes

  • Chemical Engineering(all)
  • Fuel Technology
  • Energy Engineering and Power Technology

Cite this

Influence of carbonization methods on the aromaticity of pyrogenic dissolved organic carbon. / Uchimiya, Minori; Hiradate, Syuntaro; Antal, Michael Jerry.

In: Energy and Fuels, Vol. 29, No. 4, 16.04.2015, p. 2503-2513.

Research output: Contribution to journalArticle

Uchimiya, Minori ; Hiradate, Syuntaro ; Antal, Michael Jerry. / Influence of carbonization methods on the aromaticity of pyrogenic dissolved organic carbon. In: Energy and Fuels. 2015 ; Vol. 29, No. 4. pp. 2503-2513.
@article{44cd2395a84342d889ff8449f12ee6d4,
title = "Influence of carbonization methods on the aromaticity of pyrogenic dissolved organic carbon",
abstract = "Dissolved organic carbon (DOC) components of soil amendments, such as biochar, will influence the fundamental soil chemistry, including the metal speciation, nutrient availability, and microbial activity. Quantitative correlation is necessary between (i) pyrogenic DOC components of varying aromaticity and ionizable (carboxyl and hydroxyl) substituents and (ii) bulk and solution properties of biochars. This study employed fluorescence excitation-emission (EEM) spectrophotometry with parallel factor analysis (PARAFAC) to understand the influence of the pyrolysis platform (flash and high-yield carbonization, slow pyrolysis, and fast pyrolysis) and solution pH on the DOC structure of carbonaceous materials. The PARAFAC fingerprint representative of conjugated, polyaromatic DOC correlated (Pearson's r ≥ 0.6; p < 0.005) with (i) volatile matter content and (ii) total organic carbon and nitrogen concentrations in water and base (50-100 mM NaOH) extracts. Electric conductivity of the extracts correlated with S (indicative of labile sulfate species) and Na + K concentrations (r > 0.9; p < 0.0005). The pH-dependent changes in fluorescence peak position and intensity suggested (i) protonation of carboxylate/phenolic functionalities and (ii) acid-induced aggregation of colloidal particles for ≤350°C slow-pyrolysis biochars; DOC of high-yield/flash carbonization charcoals and ≥500°C slow-pyrolysis biochars were less sensitive to pH. Solid-state 13C cross-polarization and magic angle spinning nuclear magnetic resonance analysis of bulk aromaticity (-C=C- peak at 110-160 ppm) suggested that both recalcitrant and labile fluorescence DOC fingerprints are composed of polyaromatic structures that begin to form near 350°C. These biochar-borne DOC components of varying aromaticity and carboxyl substituents will participate in hydrophobic and hydrogen-bonding interactions with soil components that will ultimately impact the biogeochemical cycles.",
author = "Minori Uchimiya and Syuntaro Hiradate and Antal, {Michael Jerry}",
year = "2015",
month = "4",
day = "16",
doi = "10.1021/acs.energyfuels.5b00146",
language = "English",
volume = "29",
pages = "2503--2513",
journal = "Energy & Fuels",
issn = "0887-0624",
publisher = "American Chemical Society",
number = "4",

}

TY - JOUR

T1 - Influence of carbonization methods on the aromaticity of pyrogenic dissolved organic carbon

AU - Uchimiya, Minori

AU - Hiradate, Syuntaro

AU - Antal, Michael Jerry

PY - 2015/4/16

Y1 - 2015/4/16

N2 - Dissolved organic carbon (DOC) components of soil amendments, such as biochar, will influence the fundamental soil chemistry, including the metal speciation, nutrient availability, and microbial activity. Quantitative correlation is necessary between (i) pyrogenic DOC components of varying aromaticity and ionizable (carboxyl and hydroxyl) substituents and (ii) bulk and solution properties of biochars. This study employed fluorescence excitation-emission (EEM) spectrophotometry with parallel factor analysis (PARAFAC) to understand the influence of the pyrolysis platform (flash and high-yield carbonization, slow pyrolysis, and fast pyrolysis) and solution pH on the DOC structure of carbonaceous materials. The PARAFAC fingerprint representative of conjugated, polyaromatic DOC correlated (Pearson's r ≥ 0.6; p < 0.005) with (i) volatile matter content and (ii) total organic carbon and nitrogen concentrations in water and base (50-100 mM NaOH) extracts. Electric conductivity of the extracts correlated with S (indicative of labile sulfate species) and Na + K concentrations (r > 0.9; p < 0.0005). The pH-dependent changes in fluorescence peak position and intensity suggested (i) protonation of carboxylate/phenolic functionalities and (ii) acid-induced aggregation of colloidal particles for ≤350°C slow-pyrolysis biochars; DOC of high-yield/flash carbonization charcoals and ≥500°C slow-pyrolysis biochars were less sensitive to pH. Solid-state 13C cross-polarization and magic angle spinning nuclear magnetic resonance analysis of bulk aromaticity (-C=C- peak at 110-160 ppm) suggested that both recalcitrant and labile fluorescence DOC fingerprints are composed of polyaromatic structures that begin to form near 350°C. These biochar-borne DOC components of varying aromaticity and carboxyl substituents will participate in hydrophobic and hydrogen-bonding interactions with soil components that will ultimately impact the biogeochemical cycles.

AB - Dissolved organic carbon (DOC) components of soil amendments, such as biochar, will influence the fundamental soil chemistry, including the metal speciation, nutrient availability, and microbial activity. Quantitative correlation is necessary between (i) pyrogenic DOC components of varying aromaticity and ionizable (carboxyl and hydroxyl) substituents and (ii) bulk and solution properties of biochars. This study employed fluorescence excitation-emission (EEM) spectrophotometry with parallel factor analysis (PARAFAC) to understand the influence of the pyrolysis platform (flash and high-yield carbonization, slow pyrolysis, and fast pyrolysis) and solution pH on the DOC structure of carbonaceous materials. The PARAFAC fingerprint representative of conjugated, polyaromatic DOC correlated (Pearson's r ≥ 0.6; p < 0.005) with (i) volatile matter content and (ii) total organic carbon and nitrogen concentrations in water and base (50-100 mM NaOH) extracts. Electric conductivity of the extracts correlated with S (indicative of labile sulfate species) and Na + K concentrations (r > 0.9; p < 0.0005). The pH-dependent changes in fluorescence peak position and intensity suggested (i) protonation of carboxylate/phenolic functionalities and (ii) acid-induced aggregation of colloidal particles for ≤350°C slow-pyrolysis biochars; DOC of high-yield/flash carbonization charcoals and ≥500°C slow-pyrolysis biochars were less sensitive to pH. Solid-state 13C cross-polarization and magic angle spinning nuclear magnetic resonance analysis of bulk aromaticity (-C=C- peak at 110-160 ppm) suggested that both recalcitrant and labile fluorescence DOC fingerprints are composed of polyaromatic structures that begin to form near 350°C. These biochar-borne DOC components of varying aromaticity and carboxyl substituents will participate in hydrophobic and hydrogen-bonding interactions with soil components that will ultimately impact the biogeochemical cycles.

UR - http://www.scopus.com/inward/record.url?scp=84928138480&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84928138480&partnerID=8YFLogxK

U2 - 10.1021/acs.energyfuels.5b00146

DO - 10.1021/acs.energyfuels.5b00146

M3 - Article

VL - 29

SP - 2503

EP - 2513

JO - Energy & Fuels

JF - Energy & Fuels

SN - 0887-0624

IS - 4

ER -