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1 9 pages, 2 tables, 6 figures. -Supporting Information- Swift Acid Rain Sensing by Synergistic Rhizospheric Bioelectrochemical Responses Tian Li 1, Xin Wang 1 *, Qixing Zhou 1, Chengmei Liao 1, Lean Zhou 1, Lili Wan 1, Jingkun An 2, Qing Du 1, Nan Li 2, and Zhiyong Jason Ren 3 * 1 MOE Key Laboratory of Pollution Processes and Environmental Criteria / Tianjin Key Laboratory of Environmental Remediation and Pollution Control / College of Environmental Science and Engineering, Nankai University, No. 38 Tongyan Road, Jinnan District, Tianjin , China 2 School of Environmental Science and Engineering, Tianjin University, No. 92 Weijin Road, Nankai District, Tianjin , China 3 Department of Civil, Environmental, and Architectural Engineering, University of Colorado Boulder, Boulder, CO 80309, United States Content Table S1 The metabolites differentiation of root with different peak area Table S2 The metabolites differentiation of leaves with different peak area Figure S1 Baseline current changes of RBS in 10 hours Figure S2 Current density before and after acid rain in rhizospheric bioelectrochemical sensor. It is repeated date of Figure 1 Figure S3 CVs (A), Bond phase (B), Nyquist plots (C) and DPV (D) of RBS before and after acid rain. It is repeated date of Figure 3 Figure S4 The equivalent circuit used for the fitting of Nyquist plots. Figure S5 The KGGE enrichment analysis of differential metabolites induced by acid rain. A: the upregulation of root metabolites; B: the upregulation of leaves metabolites. Page S2 S4 S7 S7 S8 S8 S9 S1

2 Table S1 The metabolites differentiation of root with different peak area Control After acid Arachidonic acid Lactic Acid carbamic acid Glycolic acid Butanoic acid Oxalic acid (R)-3-Hydroxybutyric acid Propanedioic acid Ketoisocaproic acid Benzoic Acid Glyceric acid Butenedioic acid cyclohexanecarboxylic acid L-Aspartic acid Malic acid Aminobutanoic acid Pentanedioic acid Pimelic acid Hydroxybenzoic acid ,3,4,5-Tetrahydroxypentanoic acid 2-Aminoadipic acid Phosphoric acid Ribonic acid Azelaic acid (R*,S*)-2,3-Dihydroxybutanoic acid Shikimic acid Citric acid D-Gluconic acid Palmitic Acid Stearic acid Propanoic acid D-Glucuronic acid Hydroxynicotinic acid Hydracrylic acid Benzeneacetic acid L-Glutamic acid Malonic acid Gallic acid S2

3 Ethanamine Pyridine Ethanolamine L-Valine L-Alanine L-Leucine L-Serine Isoleucine L-Proline Glycine Benzenamine n-butylamine Arabino-Hexos-2-ulose DL-Phenylalanine Asparagine Putrescine L-Tyrosine L-Glutamine Adenine Melamine L-Lysine L-Tryptophan Uridine L-Threonine Pyrimidine L-Methionine Uracil Amphetamine Urea DL-Ornithine Tyramine Tryptamine Arabinofuranose DL-Arabinose D-(+)-Galactose D-Fructose d-mannose D-Allose Sucrose D-Xylose Maltose D-Glucose D-(+)-Cellobiose ,3-Butanediol S3

4 Mannitol Myo-Inositol D-Sorbitol Mannitol ,2,3-Benzenetriol meso-erythritol Scyllo-Inositol Glyceryl-glycoside Naphthalene beta.-D-Galactofuranoside Table S2 The metabolites differentiation of leaves with different peak area Control After acid Disiloxane ,3-Dimethyl-5-pentamethyldisilyloxycyclohexane Propanoic acid Lactic Acid Glycolic acid Glyoxylic acid Oxalic acid Fumaric acid L-2-Aminobutyric acid Phosphoric acid Aminocyclopropanecarboxylic acid Butanedioic acid Glyceric acid Butenedioic acid Butanoic acid L-Aspartic acid Malic acid Pyroglutamic acid Hydroxymandelic acid L-Threonic acid Pentanedioic acid L-Glutamic acid Aminoadipic acid Aconitic acid propanoate Azelaic acid Citric acid Quininic acid Anthranilic acid Phloroglucinic acid S4

5 Galactaric acid Palmitic Acid Butanedioic acid Stearic acid Methyladipic acid D-Glucuronic acid Gluconic acid Gallic acid Ethanimidic acid Aminobutanoic acid Shikimic acid Pyrrolidinethione L-Threonine L-Methionine L-5-Oxoproline Ethanolamine L-Asparagine Glycine L-Glutamine L-5-Oxoproline L-Lysine DL-Phenylalanine Uridine Pyridine L-Valine L-Alanine Putrescine L-Serine DL-Ornithine Tyrosine Glycine Arbutin Tryptamine Methyladenosine Dopamine Glucopyranose E+08 Arabino-Hexos-2-ulose D-Arabinose D-(+)-Xylose DL-Arabinose d-galactose E+08 D-(-)-Fructofuranose D-(-)-Ribofuranose L-(+)-Threose S5

6 D-(+)-Mannose d-galactose beta.-Gentiobiose Sucrose E+08 D-(+)-Turanose Maltose D-(+)-Cellobiose Melibiose Ethylene glycol Propylene glycol ,3-Butanediol Pyridinol Propylene glycol ,2,3-Butanetriol Cyclopentanol meso-erythritol Xylitol D-(+)-Arabitol D-Mannitol Myo-Inositol Galactinol Ethanedione benzoyl-glycine Glyceryl-glycoside Aucubin Glyceryl-glycoside S6

7 Figure S1 Baseline current changes of RBS in 10 hours Figure S2 Current density before and after acid rain in rhizospheric bioelectrochemical sensor. It is repeated date of Figure 1 S7

8 Figure S3 CVs (A), Bond phase (B), Nyquist plots (C) and DPV (D) of RBS before and after acid rain. It is repeated date of Figure 3 Figure S4 The equivalent circuit used for the fitting of Nyquist plots. S8

9 Figure S5 The KGGE enrichment analysis of differential metabolites induced by acid rain. A: the upregulation of root metabolites; B: the upregulation of leaves metabolites. S9

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