Please wait a minute...

Frontiers of Environmental Science & Engineering

Front. Environ. Sci. Eng.    2020, Vol. 14 Issue (5) : 86
Reactivity of Pyrogenic Carbonaceous Matter (PCM) in mediating environmental reactions: Current knowledge and future trends
Wenqing Xu(), Mark L. Segall, Zhao Li
Department of Civil and Environmental Engineering, Villanova University, Villanova, PA 19085, USA
Download: PDF(857 KB)   HTML
Export: BibTeX | EndNote | Reference Manager | ProCite | RefWorks

• Pyrogenic Carbonaceous Matter (PCM) promote both chemical and microbial synergies.

• Discussion of PCM-enhanced abiotic transformation pathways of organic pollutants.

• Conjugated microporous polymers (CMPs) can mimic the performance of PCM.

• CMPs offer a platform that allows for systematic variation of individual properties.

Pyrogenic Carbonaceous matter (PCM; e.g., black carbon, biochar, and activated carbon) are solid residues from incomplete combustion of fossil fuel or biomass. They are traditionally viewed as inert adsorbents for sequestering contaminants from the aqueous phase or providing surfaces for microbes to grow. In this account, we reviewed the recently discovered reactivity of PCM in promoting both chemical and microbial synergies that are important in pollutant transformation, biogeochemical processes of redox-active elements, and climate change mitigation with respect to the interaction between biochar and nitrous oxide (N2O). Moreover, we focused on our group’s work in the PCM-enhanced abiotic transformation of nitrogenous and halogenated pollutants and conducted in-depth analysis of the reaction pathways. To understand what properties of PCM confer its reactivity, our group pioneered the use of PCM-like polymers, namely conjugated microporous polymers (CMPs), to mimic the performance of PCM. This approach allows for the controlled incorporation of specific surface properties (e.g., quinones) into the polymer network during the polymer synthesis. As a result, the relationship between specific characteristics of PCM and its reactivity in facilitating the decay of a model pollutant was systematically studied in our group’s work. The findings summarized in this account help us to better understand an overlooked environmental process where PCM synergistically interacts with various environmental reagents such as hydrogen sulfide and water. Moreover, the knowledge gained in these studies could inform the design of a new generation of reactive carbonaceous materials with tailored properties that are highly efficient in contaminant removal.

Keywords pyrogenic carbonaceous matter      Conjugated microporous polymer      remediation      Biochar      Hydrolysis      Pollutant degradation     
This article is part of themed collection: Accounts of Aquatic Chemistry and Technology Research (Responsible Editors: Jinyong Liu, Haoran Wei & Yin Wang)
Corresponding Author(s): Wenqing Xu   
Issue Date: 13 July 2020
 Cite this article:   
Wenqing Xu,Mark L. Segall,Zhao Li. Reactivity of Pyrogenic Carbonaceous Matter (PCM) in mediating environmental reactions: Current knowledge and future trends[J]. Front. Environ. Sci. Eng., 2020, 14(5): 86.
E-mail this article
E-mail Alert
Articles by authors
Wenqing Xu
Mark L. Segall
Zhao Li
Fig.1  (A) Schematic structure of PCM (Pignatello et al., 2017) (B) A photo of activated carbon under a scanning electron microscope (photo from Pristine Filtration, Inc.) (C) A plot of the minimum average cluster size of chars versus heat treatment temperature. = range of number of carbons in aromatic cluster as a function of temperature (Cao et al., 2012)
Fig.2  (A) (I) Quinone/hydroquinone pairs, (II) polyaromatic ring clusters, (III) persistent free radicals (PFRs) of PCM in facilitating redox reactions. (B) Electrochemical cell set up.
Type of PCM Proposed important feature of PCM Contaminant undergoing decay Type of reaction Reference(s)
SA-4 (steam activated carbon) and SX-4 (acid washed,steam activated carbon Quinones Azo dye (hydrolyzed Reactive Red 2) Reduction Van Der Zee et al., (2003)
Graphene Oxide, graphite,
multi-walled carbon nanotubes
graphitic carbon
Hexachloroethane Reduction Fu et al. (2014)
Graphite (sheet and powder) Graphitic carbon Nitroglycerin, DDE Reduction Xu et al. (2010); Ding and Xu (2016)
Red oak wood chars, activated carbon, graphite Surface bound intermediate as nucleophile (sulfide) RDX, DDT Nucleophilic substitution Xu et al. (2013); Ding and Xu (2016)
Multi-walled carbon nanotubes and various types of PCM Oxidized sulfide, forming reactive sulfur species at surface Azo dye, (di)chloroacetamide safeners, chloroacetamide herbicides Nucleophilic substitution Zhao et al. (2019); Xu et al. (2020)
Graphite powder Surface bound sulfite, thiosulfate DDT Nucleophilic substitution Ding et al. (2019)
Carbon nanotubes -NH2 and-OH groups acting as strong base 1,1,2,2-tetrachloroethane (TeCA) hydrolysis Chen et al. (2014b)
Graphite, biochar -OH groups TNT, DNAN hydrolysis Ding et al. (2018)
Tab.1  PCM-facilitated abiotic reactions for pollutant transformation
Fig.3  Schematic illustration of the nucleophilic substitution and hydrolysis pathways in which PCM could participate to promote contaminant transformation.
Fig.5  The PCM-like polymer platform, CMP, allows for systematic variation of functional groups, conductivity, and porosity.
1 E Anders, A Watzinger, F Rempt, B Kitzler, B Wimmer, F Zehetner, K Stahr, S Zechmeister-Boltenstern, G Soja (2013). Biochar affects the structure rather than the total biomass of microbial communities in temperate soils. Agricultural and Food Science, 22(4): 404–423
2 M Boehler, B Zwickenpflug, J Hollender, T Ternes, A Joss, H Siegrist (2012). Removal of micropollutants in municipal wastewater treatment plants by powder-activated carbon. Water Science and Technology, 66(10): 2115–2121
3 X Cao, J J Pignatello, Y Li, C Lattao, M A Chappell, N Chen, L F Miller, J Mao (2012). Characterization of wood chars produced at different temperatures using advanced solid-state 13C NMR spectroscopic techniques. Energy & Fuels, 26(9): 5983–5991
4 M L Cayuela, L Van Zwieten, B P Singh, S Jeffery, A Roig, M A Sanchez-Monedero (2014). Biochar’s role in mitigating soil nitrous oxide emissions: A review and meta-analysis. Agriculture, Ecosystems & Environment, 191: 5–16
5 S Chen, A E Rotaru, P M Shrestha, N S Malvankar, F Liu, W Fan, K P Nevin, D R Lovley (2015). Promoting interspecies electron transfer with biochar. Scientific Reports, 4(1): 5019–5025
6 W Chen, D Zhu, S Zheng, W Chen (2014b). Catalytic effects of functionalized carbon nanotubes on dehydrochlorination of 1,1,2,2-tetrachloroethane. Environmental Science & Technology, 48(7): 3856–3863
7 Y M Cho, U Ghosh, A J Kennedy, A Grossman, G Ray, J E Tomaszewski, D W Smithenry, T S Bridges, R G Luthy (2009). Field application of activated carbon amendment for in-situ stabilization of polychlorinated biphenyls in marine sediment. Environmental Science & Technology, 43(10): 3815–3823
8 G P Curtis, M Reinhard (1994). Reductive dehalogenation of hexachlorethane, carbon-tetrachloride, and bromoform by anthrahydroquinone disulfonate and humic-acid. Environmental Science & Technology, 28(13): 2393–2401
9 R Dawson, A Laybourn, R Clowes, Y Z Khimyak, D J Adams, A I Cooper (2009). Functionalized conjugated microporous polymers. Macromolecules, 42(22): 8809–8816
10 K Ding, C Byrnes, J Bridge, A Grannas, W Xu (2018). Surface-promoted hydrolysis of 2,4,6-trinitrotoluene and 2,4-dinitroanisole on pyrogenic carbonaceous matter. Chemosphere, 197: 603–610
11 K Ding, M Duran, W Xu (2019). The synergistic interaction between sulfate-reducing bacteria and pyrogenic carbonaceous matter in DDT decay. Chemosphere, 233: 252–260
12 K Ding, W Xu (2016). Black carbon facilitated dechlorination of DDT and its metabolites by sulfide. Environmental Science & Technology, 50(23): 12976–12983
13 D Fan, E J Gilbert, T Fox (2017). Current state of in situ subsurface remediation by activated carbon-based amendments. Journal of Environmental Management, 204: 793–803
14 G Fang, J Gao, D D Dionysiou, C Liu, D Zhou (2013). Activation of persulfate by quinones: free radical reactions and implication for the degradation of PCBs. Environmental Science & Technology, 47(9): 4605–4611
15 G Fang, J Gao, C Liu, D D Dionysiou, Y Wang, D Zhou (2014). Key role of persistent free radicals in hydrogen peroxide activation by biochar: Implications to organic contaminant degradation. Environmental Science & Technology, 48(3): 1902–1910
16 H Fu, Y Guo, W Chen, C Gu, D Zhu (2014). Reductive dechlorination of hexachloroethane by sulfide in aqueous solutions mediated by graphene oxide and carbon nanotubes. Carbon, 72: 74–81
17 U Ghosh, R G Luthy, G Cornelissen, D Werner, C A Menzie (2011). In-situ sorbent amendments: a new direction in contaminated sediment management. Environmental Science & Technology, 45(4): 1163–1168
18 S E Hale, J E Tomaszewski, R G Luthy, D Werner (2009). Sorption of dichlorodiphenyltrichloroethane (DDT) and its metabolites by activated carbon in clean water and sediment slurries. Water Research, 43(17): 4336–4346
19 M I Inyang, B Gao, Y Yao, Y Xue, A Zimmerman, A Mosa, P Pullammanappallil, Y S Ok, X Cao (2016). A review of biochar as a low-cost adsorbent for aqueous heavy metal removal. Critical Reviews in Environmental Science and Technology, 46(4): 406–433
20 J X Jiang, F Su, A Trewin, C D Wood, H Niu, J T Jones, Y Z Khimyak, A I Cooper (2008). Synthetic control of the pore dimension and surface area in conjugated microporous polymer and copolymer networks. Journal of the American Chemical Society, 130(24): 7710–7720
21 M T Jonker, A A Koelmans (2002). Sorption of polycyclic aromatic hydrocarbons and polychlorinated biphenyls to soot and soot-like materials in the aqueous environment: Mechanistic considerations. Environmental Science & Technology, 36(17): 3725–3734
22 M Kah, G Sigmund, F Xiao, T Hofmann (2017). Sorption of ionizable and ionic organic compounds to biochar, activated carbon and other carbonaceous materials. Water Research, 124: 673–692
23 A Kappler, M L Wuestner, A Ruecker, J Harter, M Halama, S Behrens (2014). Biochar as an electron shuttle between bacteria and Fe(III) minerals. Environmental Science & Technology Letters, 1(8): 339–344
24 T Karanfil (2006). Interface Science and Technology. Amsterdam: Elsevier,345–373
25 B Kjellerup, C Naff, S Edwards, U Ghosh, J Baker, K Sowers (2014). Effects of activated carbon on reductive dechlorination of PCBs by organohalide respiring bacteria indigenous to sediments. Water Research, 52: 1–10
26 A A Koelmans, M T Jonker, G Cornelissen, T D Bucheli, P C Van Noort, Ö Gustafsson (2006). Black carbon: The reverse of its dark side. Chemosphere, 63(3): 365–377
27 L A Langley, D H Fairbrother (2007). Effect of wet chemical treatments on the distribution of surface oxides on carbonaceous materials. Carbon, 45(1): 47–54
28 E Lefèvre, N Bossa, C M Gardner, G E Gehrke, E M Cooper, H M Stapleton, H Hsu-Kim, C K Gunsch (2018). Biochar and activated carbon act as promising amendments for promoting the microbial debromination of tetrabromobisphenol A. Water Research, 128: 102–110
29 J Lehmann, M C Rillig, J Thies, C A Masiello, W C Hockaday, D Crowley (2011). Biochar effects on soil biota: A review. Soil Biology & Biochemistry, 43(9): 1812–1836
30 X Li, B Gámiz, Y Wang, J J Pignatello, B Xing (2015). Competitive sorption used to probe strong hydrogen bonding sites for weak organic acids on carbon nanotubes. Environmental Science & Technology, 49(3): 1409–1417
31 Z Li, J Mao, W Chu, W Xu (2019). Probing the surface reactivity of pyrogenic carbonaceous material (PCM) through synthesis of PCM-like conjugated microporous polymers. Environmental Science & Technology, 53(13): 7673–7682
32 K A Lippa, A L Roberts (2002). Nucleophilic aromatic substitution reactions of chloroazines with bisulfide (HS−) and polysulfides (Sn2−). Environmental Science & Technology, 36(9): 2008–2018
33 F Liu, A E Rotaru, P M Shrestha, N S Malvankar, K P Nevin, D R Lovley (2012). Promoting direct interspecies electron transfer with activated carbon. Energy & Environmental Science, 5(10): 8982–8989
34 A R Loch, K A Lippa, D L Carlson, Y P Chin, S J Traina, A L Roberts (2002). Nucleophilic aliphatic substitution reactions of propachlor, alachlor, and metolachlor with bisulfide (HS−) and polysulfides (Sn2−). Environmental Science & Technology, 36(19): 4065–4073
35 R G Luthy, G R Aiken, M L Brusseau, S D Cunningham, P M Gschwend, J J Pignatello, M Reinhard, S J Traina, W J Weber, J C Westall (1997). Sequestration of hydrophobic organic contaminants by geosorbents. Environmental Science & Technology, 31(12): 3341–3347
36 C A Masiello (2004). New directions in black carbon organic geochemistry. Marine Chemistry, 92(1–4): 201–213
37 P McCleaf, S Englund, A Östlund, K Lindegren, K Wiberg, L Ahrens (2017). Removal efficiency of multiple poly-and perfluoroalkyl substances (PFASs) in drinking water using granular activated carbon (GAC) and anion exchange (AE) column tests. Water Research, 120: 77–87
38 L P Sumaraj, Padhye (2017). Influence of surface chemistry of carbon materials on their interactions with inorganic nitrogen contaminants in soil and water. Chemosphere, 184: 532–547
39 R B Payne, U Ghosh, H D May, C W Marshall, K R Sowers (2019). A pilot-scale field study: in situ treatment of PCB-impacted sediments with bioamended activated carbon. Environmental Science & Technology, 53(5): 2626–2634
40 J J Pignatello, W A Mitch, W Xu (2017). Activity and reactivity of pyrogenic carbonaceous matter toward organic compounds. Environmental Science & Technology, 51(16): 8893–8908
41 Y Qin, G Li, Y Gao, L Zhang, Y S Ok, T An (2018). Persistent free radicals in carbon-based materials on transformation of refractory organic contaminants (ROCs) in water: A critical review. Water Research, 137: 130–143
42 J F III Quensen, S A Mueller, M K Jain, J M Tiedje (1998). Reductive dechlorination of DDE to DDMU in marine sediment microcosms. Science, 280(5364): 722–724
43 P M Shrestha, A E Rotaru (2014). Plugging in or going wireless: strategies for interspecies electron transfer. Frontiers in Microbiology, 5: 237–244
44 J A Simon (2015). Editor’s perspective—An in situ revelation: First retard migration, then treat. Remediation Journal, 25(2): 1–7
45 B P Singh, B J Hatton, B Singh, A L Cowie, A Kathuria (2010). Influence of biochars on nitrous oxide emission and nitrogen leaching from two contrasting soils. Journal of Environmental Quality, 39(4): 1224–1235
46 H Valdés, M Sánchez-Polo, J Rivera-Utrilla, C Zaror (2002). Effect of ozone treatment on surface properties of activated carbon. Langmuir, 18(6): 2111–2116
47 F P van der Zee, I A Bisschops, G Lettinga, J A Field (2003). Activated carbon as an electron acceptor and redox mediator during the anaerobic biotransformation of azo dyes. Environmental Science & Technology, 37(2): 402–408
48 F Xiao, J J Pignatello (2015). Interactions of triazine herbicides with biochar: Steric and electronic effects. Water Research, 80: 179–188
49 S Xu, D Adhikari, R Huang, H Zhang, Y Tang, E Roden, Y Yang (2016). Biochar-facilitated microbial reduction of hematite. Environmental Science & Technology, 50(5): 2389–2395
50 W Xu, K E Dana, W A Mitch (2010). Black carbon-mediated destruction of nitroglycerin and RDX by hydrogen sulfide. Environmental Science & Technology, 44(16): 6409–6415
51 W Xu, J J Pignatello, W A Mitch (2013). Role of black carbon electrical conductivity in mediating hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) transformation on carbon surfaces by sulfides. Environmental Science & Technology, 47(13): 7129–7136
52 W Xu, J J Pignatello, W A Mitch (2015). Reduction of nitroaromatics sorbed to black carbon by direct reaction with sorbed sulfides. Environmental Science & Technology, 49(6): 3419–3426
53 X Xu, J D Sivey, W Xu (2020). Black carbon-enhanced transformation of dichloroacetamide safeners: Role of reduced sulfur species. Science of the Total Environment: 139908
54 L Yu, Y Yuan, J Tang, Y Wang, S Zhou (2015). Biochar as an electron shuttle for reductive dechlorination of pentachlorophenol by Geobacter sulfurreducens. Scientific Reports, 5(1): 16221–16230
55 H Q Zhao, S Q Huang, W Q Xu, Y R Wang, Y X Wang, C S He, Y Mu (2019). Undiscovered mechanism for pyrogenic carbonaceous matter-mediated abiotic transformation of azo dyes by sulfide. Environmental Science & Technology, 53(8): 4397–4405
56 W Zhao, L Lian, X Jin, R Zhang, G Luo, H Hou, S Chen, R Zhang (2020). In situ electron-induced reduction of NOx via CNTs activated by DBD at low temperature. Frontiers of Environmental Science & Engineering, 14(2): 20
57 H Zhou, Y F Xie (2002). Using BAC for HAA removal. Part 1: Batch study. Journal- American Water Works Association, 94(4): 194–200
58 D Zhu, J J Pignatello (2005). Characterization of aromatic compound sorptive interactions with black carbon (charcoal) assisted by graphite as a model. Environmental Science & Technology, 39(7): 2033–2041
Related articles from Frontiers Journals
[1] Weichuan Qiao, Rong Li, Tianhao Tang, Achuo Anitta Zuh. Removal, distribution and plant uptake of perfluorooctane sulfonate (PFOS) in a simulated constructed wetland system[J]. Front. Environ. Sci. Eng., 2021, 15(2): 20-.
[2] Karla Ilić Đurđić, Raluca Ostafe, Olivera Prodanović, Aleksandra Đurđević Đelmaš, Nikolina Popović, Rainer Fischer, Stefan Schillberg, Radivoje Prodanović. Improved degradation of azo dyes by lignin peroxidase following mutagenesis at two sites near the catalytic pocket and the application of peroxidase-coated yeast cell walls[J]. Front. Environ. Sci. Eng., 2021, 15(2): 19-.
[3] Yanqing Duan, Aijuan Zhou, Xiuping Yue, Zhichun Zhang, Yanjuan Gao, Yanhong Luo, Xiao Zhang. Acceleration of the particulate organic matter hydrolysis by start-up stage recovery and its original microbial mechanism[J]. Front. Environ. Sci. Eng., 2021, 15(1): 12-.
[4] Milan Malhotra, Anurag Garg. Characterization of value-added chemicals derived from the thermal hydrolysis and wet oxidation of sewage sludge[J]. Front. Environ. Sci. Eng., 2021, 15(1): 13-.
[5] Xiling Li, Tianwei Hao, Yuxin Tang, Guanghao Chen. A “Seawater-in-Sludge” approach for capacitive biochar production via the alkaline and alkaline earth metals activation[J]. Front. Environ. Sci. Eng., 2021, 15(1): 3-.
[6] Zhengqing Cai, Xiao Zhao, Jun Duan, Dongye Zhao, Zhi Dang, Zhang Lin. Remediation of soil and groundwater contaminated with organic chemicals using stabilized nanoparticles: Lessons from the past two decades[J]. Front. Environ. Sci. Eng., 2020, 14(5): 84-.
[7] Nima Kamali, Abdollah Rashidi Mehrabadi, Maryam Mirabi, Mohammad Ali Zahed. Synthesis of vinasse-dolomite nanocomposite biochar via a novel developed functionalization method to recover phosphate as a potential fertilizer substitute[J]. Front. Environ. Sci. Eng., 2020, 14(4): 70-.
[8] Alisa Salimova, Jian’e Zuo, Fenglin Liu, Yajiao Wang, Sike Wang, Konstantin Verichev. Ammonia and phosphorus removal from agricultural runoff using cash crop waste-derived biochars[J]. Front. Environ. Sci. Eng., 2020, 14(3): 48-.
[9] Ziwen Du, Chuyi Huang, Jiaqi Meng, Yaru Yuan, Ze Yin, Li Feng, Yongze Liu, Liqiu Zhang. Sorption of aromatic organophosphate flame retardants on thermally and hydrothermally produced biochars[J]. Front. Environ. Sci. Eng., 2020, 14(3): 43-.
[10] Zhenyu Yang, Rong Xing, Wenjun Zhou, Lizhong Zhu. Adsorption characteristics of ciprofloxacin onto g-MoS2 coated biochar nanocomposites[J]. Front. Environ. Sci. Eng., 2020, 14(3): 41-.
[11] Kanha Gupta, Nitin Khandelwal, Gopala Krishna Darbha. Removal and recovery of toxic nanosized Cerium Oxide using eco-friendly Iron Oxide Nanoparticles[J]. Front. Environ. Sci. Eng., 2020, 14(1): 15-.
[12] Ling Huang, Syed Bilal Shah, Haiyang Hu, Ping Xu, Hongzhi Tang. Pollution and biodegradation of hexabromocyclododecanes: A review[J]. Front. Environ. Sci. Eng., 2020, 14(1): 11-.
[13] Yu Jiang, Beidou Xi, Rui Li, Mingxiao Li, Zheng Xu, Yuning Yang, Shaobo Gao. Advances in Fe(III) bioreduction and its application prospect for groundwater remediation: A review[J]. Front. Environ. Sci. Eng., 2019, 13(6): 89-.
[14] Gaoling Wei, Jinhua Zhang, Jinqiu Luo, Huajian Xue, Deyin Huang, Zhiyang Cheng, Xinbai Jiang. Nanoscale zero-valent iron supported on biochar for the highly efficient removal of nitrobenzene[J]. Front. Environ. Sci. Eng., 2019, 13(4): 61-.
[15] Kaikai Zhang, Peng Sun, Yanrong Zhang. Decontamination of Cr(VI) facilitated formation of persistent free radicals on rice husk derived biochar[J]. Front. Environ. Sci. Eng., 2019, 13(2): 22-.
Full text