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Zhihao Zhang, Hongxuan Guo, Bo Liu, Dali Xian, Xuanxuan Liu, [Bo Da](https://orcid.org/0000-0002-0785-8662), Litao Sun

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[Understanding Complex Electron Radiolysis in Saline Solution by Big Data Analysis](https://mdr.nims.go.jp/datasets/e71fc4ea-293d-4a30-8236-dcdec297ac17)

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Understanding Complex Electron Radiolysis in Saline Solution by Big Data AnalysisUnderstanding Complex Electron Radiolysis in Saline Solution byBig Data AnalysisZhihao Zhang,∥ Hongxuan Guo,*,∥ Bo Liu, Dali Xian, Xuanxuan Liu, Bo Da, and Litao Sun*Cite This: ACS Omega 2022, 7, 15113−15122 Read OnlineACCESS Metrics & More Article Recommendations *sı Supporting InformationABSTRACT: In this article, we developed a new method to analyze the complex chemical reactions induced by electron beamradiolysis based on big data analysis. At first, we built an element transport network to show the chemical reactions. Furthermore, thelinearity between the species was quantified by Pearson correlation coefficient analysis. Based on the analysis, the mechanism of thehigh linearity between the special species pairs was interpreted by the element transport roadmap and chemical equations. The timevariation of the pH of the solution and bubble formation in the solution were analyzed by simulation and data analysis. Thesimulation indicates that O2 and H2 can easily oversaturate and form bubbles. Finally, the radiolysis of high-energy electrons in purewater was analyzed as a reference for the radiolysis of high-energy electrons in saline solution. This work provides a new method forinvestigating a high-energy electron radiolysis process and for simplifying a complex chemical reaction based on quantitative analysisof the species variation in the reaction.■ INTRODUCTIONRadiolysis is a complicated phenomenon induced by ionbeams, electron beams, and other radioactive particles oncondensed materials. It is important to analyze the radiolysis ofan aqueous solution, such as saline, in various applications. Forinstance, the efficiency of radiotherapy is dominated by theradiolysis of the external radioactive beam, radiotherapyimplants, and injections on tumors and living cells.1,2 Livingcells exposed to beta rays and other radioactive sources aredamaged by direct radiation hazards and radiation chemicalreactions.3−11 In addition to health science, radiolysis has beeninvestigated in other fields. In radioactive waste disposal work,the service life of metal containers for high-radioactivity liquidstorage is reduced because the corrosion of the metals isaccelerated by the products of water radiolysis. In somechemical experiments, radiolysis products actuate the experi-ments for nanoparticle formation and evolution.12−15 Nano-structures printed by electron beams are also controlled by freeradicals induced by the radiolysis of high-energy electrons inwater and other solutions.13,16−22 Thus, the exploration ofradiolysis is important and instructive to engineering andtechnologies.Multiple water radiolysis product yield rates by pulsedelectron beams have been measured since 1962.23,24 Le Caer̈defined the water radiolysis process into three stages.25 In thefirst stage, water molecules undergo relaxation processes afterenergy is deposited and provide excited molecules, ionizedmolecules, and subexcitation electrons. In the second stage,molecules undergo complex physical reactions such as ion−molecule reactions and dissociative relaxation. In the last stage,species undergo chemical reactions and diffuse in water.Schneider revealed the relationship between the waterradiolysis product concentration and electron beam settingdata by mathematical models and experiments.26Based on the radiolysis of water, the relationship betweenthe yield rate of the radiolysis products and the concentrationReceived: February 19, 2022Accepted: April 8, 2022Published: April 21, 2022Articlehttp://pubs.acs.org/journal/acsodf© 2022 The Authors. Published byAmerican Chemical Society15113https://doi.org/10.1021/acsomega.2c01010ACS Omega 2022, 7, 15113−15122Downloaded via NATL INST FOR MATLS SCIENCE (NIMS) on June 27, 2022 at 04:25:19 (UTC).See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.https://pubs.acs.org/action/doSearch?field1=Contrib&text1="Zhihao+Zhang"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://pubs.acs.org/action/doSearch?field1=Contrib&text1="Hongxuan+Guo"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://pubs.acs.org/action/doSearch?field1=Contrib&text1="Bo+Liu"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://pubs.acs.org/action/doSearch?field1=Contrib&text1="Dali+Xian"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://pubs.acs.org/action/doSearch?field1=Contrib&text1="Xuanxuan+Liu"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://pubs.acs.org/action/doSearch?field1=Contrib&text1="Bo+Da"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://pubs.acs.org/action/doSearch?field1=Contrib&text1="Litao+Sun"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://pubs.acs.org/action/showCitFormats?doi=10.1021/acsomega.2c01010&ref=pdfhttps://pubs.acs.org/doi/10.1021/acsomega.2c01010?ref=pdfhttps://pubs.acs.org/doi/10.1021/acsomega.2c01010?goto=articleMetrics&ref=pdfhttps://pubs.acs.org/doi/10.1021/acsomega.2c01010?goto=recommendations&?ref=pdfhttps://pubs.acs.org/doi/10.1021/acsomega.2c01010?goto=supporting-info&ref=pdfhttps://pubs.acs.org/doi/10.1021/acsomega.2c01010?fig=abs1&ref=pdfhttps://pubs.acs.org/doi/10.1021/acsomega.2c01010?fig=abs1&ref=pdfhttps://pubs.acs.org/doi/10.1021/acsomega.2c01010?fig=abs1&ref=pdfhttps://pubs.acs.org/doi/10.1021/acsomega.2c01010?fig=abs1&ref=pdfhttps://pubs.acs.org/toc/acsodf/7/17?ref=pdfhttps://pubs.acs.org/toc/acsodf/7/17?ref=pdfhttps://pubs.acs.org/toc/acsodf/7/17?ref=pdfhttps://pubs.acs.org/toc/acsodf/7/17?ref=pdfhttp://pubs.acs.org/journal/acsodf?ref=pdfhttps://pubs.acs.org?ref=pdfhttps://pubs.acs.org?ref=pdfhttps://doi.org/10.1021/acsomega.2c01010?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-ashttps://http://pubs.acs.org/journal/acsodf?ref=pdfhttps://http://pubs.acs.org/journal/acsodf?ref=pdfhttps://creativecommons.org/licenses/by-nc-nd/4.0/https://creativecommons.org/licenses/by-nc-nd/4.0/https://creativecommons.org/licenses/by-nc-nd/4.0/https://creativecommons.org/licenses/by-nc-nd/4.0/https://acsopenscience.org/open-access/licensing-options/of the aqueous saline solution was investigated.27−32 Moleculardecomposition and chemical reactions are used to explain thecomplex species generated during radiolysis. Energy absorp-tion-induced molecular decomposition in solution yields freeradicals and other species. Chemical reactions rebuild specieschemical bonds and produce other species. These complexspecies irreversibly change solutions. This complex process isdifficult to understand through the related more than onehundred chemical equations. Normal saline is a basiccomponent of human cells, and normal saline radiolysisprocess research is important to understand radioactivedamage to cells. Thus, we analyzed the radiolysis of high-energy electrons in normal saline solution by a big datamethod. The chemical reaction induced by radiolysis wasclarified based on big data analysis.■ MODEL DEVELOPMENTKinetic Model. A kinetic model of the radiolysis processwas established based on the chemical reactions in normalsaline solution. In this model, we analyzed the formation ofspecies and the chemical reaction among them. According toLe Caer̈’s three-stage theory, the radiolysis process can bedivided into three stages. However, the theory of how theelectron beams affect water during the radiolysis process hasgreat development.33 In Taylor’s words, the radiolysis effect isthe reactions by free radicals produced by water and electron.Thus, the radiolysis process can be grouped into two stages byvaried features in the species transformation. In the first stage,the electron beam transmits energy to the water molecules andyields free radicals. This process stops with the removal of theelectron beam. In the first stage, new species yielded by theelectron beam are listed in eqs 1 and 2. In eq 1, the speciesyield hydrogen and oxygen atoms with new bonds. Moreover,in eq 2, chloride ions become chloride atoms with electronslost, and sodium ions are always stable. In radiation dosimetry,the G value is used to define the rate of the new species’ yieldor disappearance in the radiolysis process. In the second stage,all species react with others based on the chemical equationsshown in the SI (Supporting Information).H O e , H , OH , H , H O , H O , HO2 h 2 2 2 3 2· − · · + ·(1)Cl e , Clh·− −(2)The temporal evolution of the species induced by electronbeam irradiation was analyzed in this paper; thus, we assumedthat the cross area of the solution was exposed homogeneously.A simplified kinetic model was established to describe thetemporal evolution of the species concentrations.26 In addition,the mass of the analyzed solution is a constant in the model. Itis suggested that the heat effect induced by laser pulseirradiation increases the temperature of the sample by morethan 10 °C.34 We find that the dose rate in Liu’s work34 isabout 2.5 × 107(Gy/S), this dose rate is the same as theelectron beam with 300 keV voltage and 350 pA current.However, living cell research will not use such huge dose rates;on the one hand, the high current will kill the living cell quicklywhile, on the other hand, the high voltage cannot provideimage information clearly. The settings of dose rate in livingcell research35,36 usually are under 2.5 × 106(Gy/s); thus, theheat effect is limited and it can be ignored in this model. Thediffusion calculation was neglected because space influence wasexcluded from consideration in this paper.The concentration variation rate of all species in the salinesolution was calculated by eq 3 with an improved Eulermethod, where Ri was calculated by eq 4, the dose rate ofradiolysis was 7.5 × 107 (Gy/s), and the G values of theradiolysis are listed in Table 1. The detailed symbol descriptionis listed in Table 3. In this work, we calculated the speciesconcentration with time from 0 to 0.1 s with a step of 10−10 s;thus, we had 109 data points for each species.Ctr C C r C C Riii j i jl k il k l k i,,,∑ ∑∂∂= ‐ + +≠ (3)RGFM s( / )iiρψ=(4)Pearson Correlation Coefficient (PCC) Calculation.PCC analysis is an effective method for displaying twodatabase relationships in machine learning technique studies.37In this paper, the linearity of the concentration of the specieswas indicated by the Pearson correlation coefficient (PCC).After that, highly correlated species pairs were set according tolinearity. In this work, the PCC of species was calculated witheqs 5−7. We chose 1.1 × 105 data points from 109 data points.The data picking rule was as follows: the complete data from10−10 to 10−5 s were chosen; one data point for each 10−5 sfrom 10−5 to 10−1 s was chosen. We performed logarithmiccalculations for previously selected data in the PCCcalculation.PccABl i, =(5)A n C C n C Cvnl v i vvnl vtni v1, ,1,1,∑ ∑ ∑= −= = = (6)ikjjjjjjy{zzzzzzikjjjjjjy{zzzzzzB n C C n C Cvnl vvnl vvni vvni v1,21,21,21,2∑ ∑ ∑ ∑= ‐ · ‐= = = = (7)Normalized Conventional Rate Calculation. In eq 8,variable Vie(t) is the conventional rate, which stands for thetransform rate from original species i to product e. ri,j is the rateconstant in the chemical reaction about species i and j to yieldspecies e. Ci and Cj is the concentration of species i and j,respectively. In eq 9, variable Pie(t) is the normalizedconventional rate, which stands for the form percent forspecies e, x in variable Vix(t) is the species that can be yieldedby species i, for instance, species O3 can yield O2, HO2, and O3−; thus, x stands for O2, HO2, and O3−. Species transform patheffect can be qualified by Pie(t): high Pie(t) means species iTable 1. G Value for Nine Speciesname G value (100 eV)eh− 3.58H3O+ 4.09OH− 0.95H2O2 2.83H· 1OH· 3.32HO2· 0.08H2 0.27Cl 0.6175ACS Omega http://pubs.acs.org/journal/acsodf Articlehttps://doi.org/10.1021/acsomega.2c01010ACS Omega 2022, 7, 15113−1512215114https://pubs.acs.org/doi/suppl/10.1021/acsomega.2c01010/suppl_file/ao2c01010_si_001.pdfhttp://pubs.acs.org/journal/acsodf?ref=pdfhttps://doi.org/10.1021/acsomega.2c01010?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-astransformation to e with high percent while low Pie(t) meansspecies i transformation to e with low percent.t r C CV ( )ie i j i j,∑= (8)tV tV tP ( )( )( )ieieix=Σ (9)Ci and Cj are functions of time; thus, Pie(t) is dependent ontime. According to Pie(t) development, transform paths can beclassified into three groups as Table 2 shows. The first group isthe void path, which has Pie(t) < 0.03 at all times. In this group,the conversion of species from i to e is negligible even with atheoretical equation to interpret the reaction. In the secondgroup, the path with Pie(t) > 0.03 and the disturbance of Pie(t)< 0.01 were defined as stable paths. This definition means thatspecies e was convened from species i without timedependence. In the third group, paths with time-dependentPie(t) were considered time-variant paths, and most transformpaths belong to group 3. Group 2 and group 3 are shown inFigure 2 with different colors.■ RESULTSElement Transport Roadmap (ETR). The elementtransport roadmap (ETR) denotes the efficient elementtransport paths in the chemical reactions. The ETR wasdrawn from the analysis of 32 species based on big data ontime-scale species concentrations and the correspondingchemical equations. The possible transport paths wereprovided based on the chemical equations. Then, those pathswere classified into three groups according to different Piefeatures, the stable and time-variant paths were retained, andthe void paths were removed. Table 4 and Figure 1 areinstances of the calculation of the ClOH− transport pathefficiency by Vie and Pie.First, all chemical equations that use ClOH− as a reactantwere listed.Second, Vij for each product was calculated. In Table 4,V C C CC C8 10 106.1 10ClOH ,Cl9H ClOH10eqClOH9ClOH= × × × + ×× + × ×− − − −− −V C C9 10ClOH ,Cl4Cl ClOH= × × ×− − − −V C C2.1 10ClOH ,Cl10H ClOH= × × ×− − + −Third, Pij was calculated. In Table 4, the denominator forPij.isV t V V V( )ix ClOH ,Cl ClOH ,Cl ClOH ,Cl2∑ = + +− − − ‐ − −Last, Pie for the complete simulation time was plotted andthose paths were classified into different groups. The pathsfrom ClOH− to Cl− or Cl are time-varying paths, and the pathfrom ClOH− to Cl2− is a void path because of the lowPClOH−,Cl2−.Hydrogen, oxygen, and chlorine reactions were analyzedwith the corresponding ETRs. In the H ETR, time-variantpaths are the overwhelming majority, and these complex time-variant paths display the fixability of the H elementtransformation network. In the O ETR, species havedirectional close relationships by effective paths that havehigh Pie. In the Cl ETR, species have a clear feature withtransformation paths, and special species ClOH− and other Clformed only species are linked by time-variant paths and theremaining species are linked by stable paths. Oxychloridespecies use stable paths to contract themselves in the O and ClETRs.Pearson Correlation Coefficient (PCC) Calculation.Figure 3a shows the PCC for all possible special pairs in thechemical reaction induced by electron radiolysis. The speciescan be classified into different groups according to the PCCvalue. More details about the classification can be seen in theDiscussion section. Species pairs with high correlation werearranged in the same group. Figure 3b1 shows that the highPCC species pair has a similar shape. Meanwhile, the low PCCspecies pairs have significantly different shapes, as shown inFigure 3b2.■ DISCUSSIONComplexity Analysis for Element Transport Roadmap(ETR). The complexity of the ETR is qualified by the numberof paths connecting special species in the ETR. The indegree isthe number of species that can transform into destined species.The outdegree is the number of destined species transformedfrom a special species. The degree is the sum of the indegreeand outdegree in an ETR. The species degree for the H ETRwas calculated from Figure 2a2. It can be seen from the speciesdegrees of H2O (15) and H2O2 (10) that these two species areTable 2. Path Classificationpath type Pie featurevoid path Pie < 0.03stable path Pie > 0.01 and ΔPie < 0.01time-variant path Pie depends on timeTable 3. Symbol Description for eqs 3 to 9symbol explanationCi concentration of species iT exposed timeI target speciesJ species that can react with i and yield other speciesL species that can yield i in the chemical equationsK species that can react with l and yield i in the chemical equationsri,j rate constant for the equation that uses i and j as reactantsRi yield rate of species i due to irradiationρ solution densityΨ absorbed dose rateGi G value for species iF Faraday constantPccl,i PCC value for species l and iN length of the data listV data serial number in the data listVie(t) convention rate from species i to e at time tE product species in chemical equations that use i as a reactantX possible product species in chemical reactions by species iPie(t) convention possibility from species i to edegi+ species i indegreeadegi− species i outdegreebdegi sum of indegree and outdegree for species iaIndegree: the number of product types from the target species bychemical reactions. bOutdegree: the number of reactant types that canyield the target species by chemical reactions.ACS Omega http://pubs.acs.org/journal/acsodf Articlehttps://doi.org/10.1021/acsomega.2c01010ACS Omega 2022, 7, 15113−1512215115http://pubs.acs.org/journal/acsodf?ref=pdfhttps://doi.org/10.1021/acsomega.2c01010?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-asthe dominating transformation stations in the H elementtransport system. This is because H2O is the original species insolution. Moreover, H2O2 has high activity, can be the reactantin bountiful reactions, and is the product of multiple species.The indegree of HO3 (0) and outdegree of HO3 (1) meansthat no species produces HO3 in the H ETR. However, thePie(t) of the reaction to produce HO3 is small, inducing aninsignificant transformation path. Therefore, the HO3production paths are not shown in Figure 2a2.The H element transport network is maneuverable, andmost species have multiple removal paths. Figure 2a2 showsthat H2O is the core transport station, is the largest source, andsaves the most H atoms.Figure 2b2 is the O ETR. The species degree of OH− (10)suggests that OH− is a dominant transport station for the Otransport network. The species indegree of O2 (7) indicatesthat complex reactions produce O2. Moreover, speciesoutdegrees of O2 (2) suggest that O2 only has two removalpaths in the reaction. Thus, bubbles easily form in the solutionbecause the species O2 generation rate is higher than thedestruction rate. The indegree for species O3 and Cl2O is zero,meaning that the forming paths for these two species areremoved in the O ETR because of low Pie(t).Species in Figure 2b2 were classified into two groups. Thefirst group includes O4, Cl2O4, ClO2, ClO3−, ClO, ClO2−, andCl2O2, and the second group includes the remaining species.Group 1 is mainly formed by oxychloride and O4. Trans-formation paths for group 1 species except for ClO2− arealmost stable. These paths are stable because reactionsbetween group 1 species are sampled, and there are absolutedisparities in the concentration of group 1 species. Thus, theeffective transformation paths between species of group 1 arefew. Group 2 species build a complex and flexible transportnetwork with time-variant transformation paths based onchemical reactions.Figure 2c2 shows the Cl ETR with all possible trans-formation paths. Cl2− has the largest degree, which suggeststhat Cl2− is an important species. The species indegree of Cl2O(0) means that the Cl2O yield paths are too small to beconsidered. Similar to the previous discussion, we classified thespecies into two groups: the first group included Cl2O4, ClO2,ClO3−, ClO, ClO2−, and Cl2O2, and the second group includedthe remaining species. Species transformation paths in group 2are time-varying. HClO and HCl are the bridge that links thetwo groups. The first group species can transform to thesecond group species, but not vice versa.ETR uses species transformation paths to exhibit the contactfor species based on chemical reaction and speciesconcentration data. The dominant species and importantspecies were discovered by ETR. Species were classified intoseveral groups for the Cl ETR and O ETR according to thetransformation path features between them, which will simplifythe complex species relationship.PCC Result Analysis Based on the ETR. According toFigure 3a, species were classified into three groups based onthe PCC analysis. The PCC of the species pair in the identicalgroup was high. Moreover, the PCC of the species pair indifferent groups was low. The classification is shown in Table5.The PCCs between the species pairs in group I, such asH2O-Cl−, H-eh−, OH−-O−, and ClOH−-OH are high. Thisresult indicates that correlation bandings are only formedbetween the special species pairs. In group II and group III, thePCCs between every species in the identical group are high, asshown in Figure 3a. Here, species pairs with PCCs > 0.99 arelisted in Table 6.The relationship between the high PCC species pairs wasinterpreted by ETR, as shown in Figures 2 and 4. As shown inFigure 2, the transformation paths between species pairs withdirect paths are single steps. For instance, the PCC valuebetween O4 and O2 is more than 0.99, which can beinterpreted as the transformation path between O4 and O2being a single-step reaction, as shown in equation K108 (SI).Moreover, the PCC value between ClO2 and Cl2O is alsohigher than 0.99. However, the single-step reaction betweenClO2 and Cl2O is absent from the reaction equation list in theTable 4. ClOH− Transformation Path Efficiency Calculationequation number equation rate constant product Vie Pie87 H + ClOH− = Cl− + H2O 8 × 109 Cl− VClOH−,Cl− PClOH−,Cl−79 eaq− + ClOH− = Cl− + OH− 1 × 1010113 ClOH− = OH + Cl− 6.1 × 109110 Cl− + ClOH− = Cl2− + OH− 9 × 104 Cl2− VClOH−,Cl2− PClOH−,Cl2−102 H+ + ClOH− = Cl + H2O 2.1 × 1010 Cl VClOH−,Cl PClOH−,ClFigure 1. ClOH− transformation path efficiency calculation in the Cl ETR.ACS Omega http://pubs.acs.org/journal/acsodf Articlehttps://doi.org/10.1021/acsomega.2c01010ACS Omega 2022, 7, 15113−1512215116https://pubs.acs.org/doi/suppl/10.1021/acsomega.2c01010/suppl_file/ao2c01010_si_001.pdfhttps://pubs.acs.org/doi/10.1021/acsomega.2c01010?fig=fig1&ref=pdfhttps://pubs.acs.org/doi/10.1021/acsomega.2c01010?fig=fig1&ref=pdfhttps://pubs.acs.org/doi/10.1021/acsomega.2c01010?fig=fig1&ref=pdfhttps://pubs.acs.org/doi/10.1021/acsomega.2c01010?fig=fig1&ref=pdfhttp://pubs.acs.org/journal/acsodf?ref=pdfhttps://doi.org/10.1021/acsomega.2c01010?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-asSI. Only a multiple-step reaction (Cl2O - HClO - Cl2O2 - ClO- ClO2− - Cl2O4 - ClO2), as shown in Figure 4a, links the ClO2-Cl2O pairs with a high PCC value. In contrast to the speciespairs with time-variant paths, as shown in Figure 4b, thetransformation paths between the species list in Figure 4a arestable.The indirect transformation path group species pairs in theETR lack the direct transformation path. However, species inone pair in the indirect path group both have the same stronglinear correlation species. This intermediate species could bethe bridge to contact the species pairs and induce highlinearity. Figure 4a shows that the species pair of Cl2O4 and O4is an important bridge that links the Cl ETR to the O ETR.Moreover, these species pairs have a high correlation andstable transformation path. Similar to Cl2O4 and O4, theoxychloride species (ClO, ClO2−, ClO3−, Cl2O2, Cl2O, ClO2,Cl2O4) are in contact with each other by stable transformationpaths. Another species, HCl and oxychloride, showed a strongrelationship because of the stable transformation paths fromHCl to Cl2O4.No direct stable transformation path or effective inter-mediate species contacts O2 and H2. Thus, instead of the ETR,chemical reactions were analyzed to determine the relationshipbetween O2 and H2. The most important reactions of the O2-H2 pair were selected according to the reaction rate. Clearly,H2 is mainly formed by H2O, which reacts with eh− or Hatoms, and H2 mainly reacts with OH to consume itself. O2 isyielded from OH, HO2, and O2−, and O2 mainly reacts witheh− or H atoms. Thus, OH, H, and eh− could be theintermediate species to provide a unique relationship for theO2-H2 pair.Figure 2. (a1) Initial H ETR (element transport roadmap). (a2) Complete H ETR. (b1) Initial O ETR. (b2) Complete O ETR. (c1) Initial ClETR. (c2) Complete Cl ETR. Arrows are transport paths, arrow colors from blue to red represent path transformation percentages from 99 to 3%for time-varying paths, and gray arrows are stable transformation percentage paths.ACS Omega http://pubs.acs.org/journal/acsodf Articlehttps://doi.org/10.1021/acsomega.2c01010ACS Omega 2022, 7, 15113−1512215117https://pubs.acs.org/doi/suppl/10.1021/acsomega.2c01010/suppl_file/ao2c01010_si_001.pdfhttps://pubs.acs.org/doi/10.1021/acsomega.2c01010?fig=fig2&ref=pdfhttps://pubs.acs.org/doi/10.1021/acsomega.2c01010?fig=fig2&ref=pdfhttps://pubs.acs.org/doi/10.1021/acsomega.2c01010?fig=fig2&ref=pdfhttps://pubs.acs.org/doi/10.1021/acsomega.2c01010?fig=fig2&ref=pdfhttp://pubs.acs.org/journal/acsodf?ref=pdfhttps://doi.org/10.1021/acsomega.2c01010?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-asThe relationship between each species was analyzed by PCCcalculation, which provided an efficient approach to analyzethe radiolysis and reaction by a big data method. However,PCC data are defective in indicating the complete connectionfor all species because PCC results are not based on thecomplete transformation paths, as shown in the ETR, but areonly calculated by the concentration data of two species. Thetransformation paths were ignored in the PCC calculation,inducing the low linearity of core species with other species.On the other hand, PCC is based on calculated concentrationdata that include complete chemical reaction information,although the ETR only analyzes the important reactants andoverlooks other reactant influences on the species. Thus, theETR analysis method can help to identify the dominantspecies, which is a protagonist in chemical reactions, and PCCis an effective tool for providing highly correlated species pairinformation that we cannot find in the ETR.pH, Oversaturated Gas, and the Difference betweenSaline and Pure Water. Solution pH is well known as a time-varying property during the radiolysis process becausechemical reactions change the H+ concentration. Moreover,when the radiolysis process is sufficiently long, the solutioncannot dissolve all the O2 and H2 yielded by chemicalreactions, and these gases quickly form bubbles and keep theconcentrations of O2 and H2 constant in the solution.In Figure 5a1, the pH decreases at a high rate before 10−6 s,and then the pH increases. Finally, the pH in a low stagesuggests that the solution became acidic. The unusual increasein pH during 10−6−10−4 s can be explained in terms ofchemical reactions. Several reaction equations that include H+Figure 3. (a) PCC (Pearson correlation coefficient) for each species pair. The x axis represents the first species, the y axis represents the secondspecies, and the color and height represent the PCC value. (b1). Time-varying Cl2− concentration (solid line, left label) and HO2− concentration(dotted line, right label). (b2). Time-varying HO2 concentration (solid line, left label) and ClOH− concentration (dotted line, right label). (b3).Time-varying H+ concentration (solid line, left label) and OH− concentration (dotted line, right label). It is easy to see the relationship betweendifferent shapes and PCCs.Table 5. Species Classificationgroup speciesI H2O↔ Cl−, H↔ eh−, OH−↔ O−, ClOH−↔ OHII H+, Cl, HO2III HClO, H2O2, HO2−, O3, O3−, HO3, O2−, ClO, ClO2−, ClO3−, O2, H2,Cl2, Cl2−, Cl3−, Cl2O2, Cl2O, HCl, ClO2, Cl2O4, O4Table 6. PCC > 0.99 Species Pairsindirect pathbdirect patha stable path time-variant pathO3− ↔ O3 ClO2 ↔ O4 Cl2− ↔ ClO O3 ↔ ClOO3 ↔ HO3 O2 ↔ HCl Cl3− ↔ HClO HO3 ↔ Cl2−O2 ↔ O4 HCl ↔ O4 Cl3− ↔ ClO HO3 ↔ Cl2−ClO2 ↔ Cl2O4 Cl2O ↔ O4 Cl3− ↔ ClO2- HO3 ↔ HClOClO2− ↔ Cl2O2 HClO ↔ ClO Cl3− ↔ ClO3- HO3 ↔ ClOClO2 ↔ ClO3− ClO2 ↔ ClO2− Cl3− ↔ Cl2O2 O3− ↔ HO3HCl ↔ Cl2O4 ClO2 ↔ HCl ClO2 ↔ Cl2 O3− ↔ ClOCl2O4 ↔ O4 ClO2 ↔ Cl2O2 Cl2 ↔ HCl O3 ↔ Cl3−Cl2O2 ↔ Cl2O Cl2 ↔ Cl2O2 O3 ↔ HClOClO2− ↔ Cl2O Cl2 ↔ Cl2O4 HO2− ↔ HO3ClO3− ↔ Cl2O2 Cl2 ↔ Cl2O H2 ↔ ClO2ClO3− ↔ Cl2O Cl2 ↔ O4 H2 ↔ HClClO2 ↔ Cl2O HO2− ↔ O3− H2 ↔ Cl2O4Cl2O4 ↔ Cl2O HO2− ↔ O3 H2 ↔ O4ClO2− ↔ ClO3−aA direct path between species pairs, as shown above, means that thetransformation between the species pairs can be completed in onereaction. bSpecies pairs in the indirect path group need multiplereactions to complete the species transformation in ETRs.Figure 4. Species transformation network for indirect paths. Thisfigure shows the intermediates for species pairs in the Table 6 indirectpath group, which includes stable path parts (a) and time-variant pathparts (b).ACS Omega http://pubs.acs.org/journal/acsodf Articlehttps://doi.org/10.1021/acsomega.2c01010ACS Omega 2022, 7, 15113−1512215118https://pubs.acs.org/doi/10.1021/acsomega.2c01010?fig=fig3&ref=pdfhttps://pubs.acs.org/doi/10.1021/acsomega.2c01010?fig=fig3&ref=pdfhttps://pubs.acs.org/doi/10.1021/acsomega.2c01010?fig=fig3&ref=pdfhttps://pubs.acs.org/doi/10.1021/acsomega.2c01010?fig=fig3&ref=pdfhttps://pubs.acs.org/doi/10.1021/acsomega.2c01010?fig=fig4&ref=pdfhttps://pubs.acs.org/doi/10.1021/acsomega.2c01010?fig=fig4&ref=pdfhttps://pubs.acs.org/doi/10.1021/acsomega.2c01010?fig=fig4&ref=pdfhttps://pubs.acs.org/doi/10.1021/acsomega.2c01010?fig=fig4&ref=pdfhttp://pubs.acs.org/journal/acsodf?ref=pdfhttps://doi.org/10.1021/acsomega.2c01010?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-asas a reactant or product and with a high reaction rate wereanalyzed as key equations. The rate of the chemical reactionthat yields H+ always increases, while the H+ consumptionchemical reaction rate increases and decreases. Thus, a possiblereason is that the H+ decrease rate grew faster than the H+increase rate and induced an increase in pH. Theconcentrations of HO2− and O2− increased, and the twospecies can react with H+. Thus, the increase in HO2− and O2−concentrations accelerated the H+ consumption rate and finallyinduced an increase in pH during 10−6−10−4 s.Figure 5c shows that the shape of the escaped O2concentration is similar to that of H2, and the O2 dissolutionsaturation time is shorter than that of H2. However, O2 is moresoluble than H2 in solution, suggesting that O2-relatedreactions are stronger than H2-related reactions.To find the differences in radiolysis inference between purewater and saline solution, species concentration databases ofpure water and saline solution were plotted against time, asshown in Figure 6.Here, we only consider those species that appeared in purewater under electron beam exposure.The Schneider pure water model26 was used to calculate thespecies concentration variation in pure water. The G value isidentical for the same species in pure water and saline solution,and the saline solution has a G value for Cl− in addition. Othersettings, including the calculation step, the initial value, and thesimulation completion time, were identical for the two types ofsolutions. In Figure 6, the salt−water model speciesconcentrations approach pure water before 10−6 s, and thenthe two models’ concentrations become different for mostspecies.After 10−5 s, the concentration ratios differ. Species OH−,HO2−, O−, O2−, and O3− are always in the decreasing stage(Figure 6a), which indicates that these species are lessabundant in saltwater than in pure water. Moreover, speciesFigure 5. (a1) pH and pOH of solution versus time. pH undergoes a drastic change in 0.1 s. (a2) Time variation of pH + pOH. (b) Time variationof O2 concentration (solid line) and H2 concentration (dotted line); the straight line is the gas saturation moment. (c) Escaped concentration forH2 (solid line) and O2 (dotted line). O2 escaped before H2, but both species have the same curve track.Figure 6. Species concentration ratio between the salt solution and pure water. x axis is time, and y axis is Csalt/Cpurewater. (a) Species whoseconcentrations are lower in salt solution rather than pure water. (b) Species whose concentrations are higher in salt solution rather than pure water.(c) Species whose concentrations are first lower and then higher in salt solution rather than pure water. (d) O2 and H2 concentration ratio in saltsolution and pure water.ACS Omega http://pubs.acs.org/journal/acsodf Articlehttps://doi.org/10.1021/acsomega.2c01010ACS Omega 2022, 7, 15113−1512215119https://pubs.acs.org/doi/10.1021/acsomega.2c01010?fig=fig5&ref=pdfhttps://pubs.acs.org/doi/10.1021/acsomega.2c01010?fig=fig5&ref=pdfhttps://pubs.acs.org/doi/10.1021/acsomega.2c01010?fig=fig5&ref=pdfhttps://pubs.acs.org/doi/10.1021/acsomega.2c01010?fig=fig5&ref=pdfhttps://pubs.acs.org/doi/10.1021/acsomega.2c01010?fig=fig6&ref=pdfhttps://pubs.acs.org/doi/10.1021/acsomega.2c01010?fig=fig6&ref=pdfhttps://pubs.acs.org/doi/10.1021/acsomega.2c01010?fig=fig6&ref=pdfhttps://pubs.acs.org/doi/10.1021/acsomega.2c01010?fig=fig6&ref=pdfhttp://pubs.acs.org/journal/acsodf?ref=pdfhttps://doi.org/10.1021/acsomega.2c01010?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-asH+, H2O2, OH, HO2, and H2O are in the opposite state(Figure 6b). The concentration ratios of species eh−, O3, HO3,and H initially decrease and then increase (Figure 6c). O2 andH2 have multiple trend changes and finally obtain ratios of 1(Figure 6d) because both species remain at saturationconcentrations.From Table 7, the yields of OH−, H2O2, HO2, O−, O3−, O3,HO3, and H2O and the applied rate in pure water are higherthan those in salt solution. The yield and applied rate ofspecies H, OH, HO2, O2−, H2, and H+ are lower in pure waterthan in salt solution. O2 has approximate data for yield andapplied rate in the two solutions. The yield rate for eh− ismuch better in pure water than in saline solution, and theapplied rate is similar in the two solutions.For species OH−, HO2, O−, O3−, O3, HO3, and H2O, theirreaction rates are higher in pure water than in saline solution,and the concentrations in pure water are higher than those insalt solution, suggesting that the addition of Cl decreases theirreaction rate and provides a negative environment toaccumulate these species. In contrast, the saline solutionprovides a positive environment for the accumulation ofspecies H, OH, HO2, O2−, and H+ with a high reaction rate. Incontrast to other species, the accumulation rate of H2O2species is high in saline solution, but the reaction rate is highin a pure water environment. This is because the differencebetween the provision rate and depletion rate of H2O2 in salinesolution is lower than that in pure water. O2 and H2 are alreadyoversaturated in both solutions; thus, their concentrations insolution are constant. H2O has a larger basic concentration,and the yield and consumed concentration can hardly infer theH2O data. Thus, the H2O data in the two types ofenvironments are similar.■ CONCLUSIONSIn this article, we built the ETR of the chemical reactioninduced by high-energy electron radiolysis (HEER) based onthe chemical reaction equation and big data analysis. Based onthe simulation and PCC analysis, the highly linear species pairswere selected and interpreted by the ETR. The ETR providesessential information on the chemical reaction, such as theelement transport, reaction rate, and reaction direction.Combining ETR and PCC analysis, we developed an effectiveand reliable method for analyzing the complex chemicalreaction induced by high-energy electron radiolysis in salinesolution. The time variation of pH and bubble formationinduced by high-energy electron radiolysis were analyzed basedon this method.■ ASSOCIATED CONTENT*sı Supporting InformationThe Supporting Information is available free of charge athttps://pubs.acs.org/doi/10.1021/acsomega.2c01010.Complete chemical reactions; electron beam dose ratecalculation method; G value calculation method;calculation method contrast; complete PCC data;species concentration in the temporal evolution (PDF)■ AUTHOR INFORMATIONCorresponding AuthorsHongxuan Guo − SEU-FEI Nano-Pico Center, KeyLaboratory of MEMS of Ministry of Education, School ofElectronic Science and Engineering, Southeast University,Nanjing 210096, People’s Republic of China; Center forAdvanced Materials and Manufacture, Joint ResearchInstitute of Southeast University and Monash University,Suzhou 215123, People’s Republic of China; orcid.org/0000-0002-8092-8057; Email: ghx@seu.edu.cnLitao Sun − SEU-FEI Nano-Pico Center, Key Laboratory ofMEMS of Ministry of Education, School of Electronic Scienceand Engineering, Southeast University, Nanjing 210096,People’s Republic of China; Center for Advanced Materialsand Manufacture, Joint Research Institute of SoutheastUniversity and Monash University, Suzhou 215123, People’sRepublic of China; orcid.org/0000-0002-2750-5004;Email: slt@seu.edu.cnAuthorsZhihao Zhang − SEU-FEI Nano-Pico Center, Key Laboratoryof MEMS of Ministry of Education, School of ElectronicScience and Engineering, Southeast University, Nanjing210096, People’s Republic of ChinaBo Liu − SEU-FEI Nano-Pico Center, Key Laboratory ofMEMS of Ministry of Education, School of Electronic Scienceand Engineering, Southeast University, Nanjing 210096,People’s Republic of ChinaDali Xian − SEU-FEI Nano-Pico Center, Key Laboratory ofMEMS of Ministry of Education, School of Electronic Scienceand Engineering, Southeast University, Nanjing 210096,People’s Republic of ChinaXuanxuan Liu − SEU-FEI Nano-Pico Center, Key Laboratoryof MEMS of Ministry of Education, School of ElectronicScience and Engineering, Southeast University, Nanjing210096, People’s Republic of ChinaTable 7. Variation Rate of 16 Species in 10−3 s by TwoModelsa,breaction rate (μmol L−1 s−1)speciesyield bywateryield bysaltapplied inwaterapplied insaltCsalt/Cwaterratioeh− 4.8 × 103 15 2.7 × 107 2.7 × 107 7.8 × 10−1H+ 1.1 × 106 5.7 × 107 3.2 × 107 8.9 × 107 6.2 × 102OH− 5.2 × 1010 1.7 × 108 5.2 × 1010 1.8 × 108 1.5 × 10−3H2O2 5.2 × 1010 1.6 × 108 5.2 × 1010 1.8 × 108 2.0HO2− 5.2 × 1010 1.5 × 108 5.2 × 1010 1.5 × 108 2.8 × 10−3H 9.6 × 104 1.8 × 106 7.8 × 106 9.6 × 106 2.0OH 5.0 × 107 2.8 ×10107.6 × 107 2.8 × 1010 1.9 × 101O− 4.0 × 107 1.0 × 106 4.0 × 107 1.1 × 106 2.5 × 10−2HO2 2.5 × 107 7.0 × 107 2.6 × 107 7.1 × 107 1.0 × 102O2− 3.7 × 107 6.3 × 107 3.6 × 107 6.3 × 107 1.4 × 10−2O2 2.2 × 107 2.3 × 107 1.5 × 107 1.5 × 107 1H2 2.5 × 103 3.8 × 103 9.4 × 104 1.3 × 106 1O3− 1.9 × 106 4.1 × 104 1.9 × 106 4.2 × 104 1.4 × 10−4O3 2.6 × 105 664 2.6 × 105 666 6.2 × 10−2HO3 963 302 975 302 3.1 × 10−1H2O 5.2 × 1010 2.0 × 108 5.2 × 1010 1.5 × 108 1aThis table uses the pure water model and salt solution model resultsto calculate the rate for listed species. Only species that appeared inthe two models were considered. This table uses speciesconcentration data at 10−3 s. b“Yield by water” is the yield speed ofspecies concentrations in the pure water model, and “applied in salt”is the consumption speed of species concentrations in the salt solutionmodel.ACS Omega http://pubs.acs.org/journal/acsodf Articlehttps://doi.org/10.1021/acsomega.2c01010ACS Omega 2022, 7, 15113−1512215120https://pubs.acs.org/doi/10.1021/acsomega.2c01010?goto=supporting-infohttps://pubs.acs.org/doi/suppl/10.1021/acsomega.2c01010/suppl_file/ao2c01010_si_001.pdfhttps://pubs.acs.org/action/doSearch?field1=Contrib&text1="Hongxuan+Guo"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://orcid.org/0000-0002-8092-8057https://orcid.org/0000-0002-8092-8057mailto:ghx@seu.edu.cnhttps://pubs.acs.org/action/doSearch?field1=Contrib&text1="Litao+Sun"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://orcid.org/0000-0002-2750-5004mailto:slt@seu.edu.cnhttps://pubs.acs.org/action/doSearch?field1=Contrib&text1="Zhihao+Zhang"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://pubs.acs.org/action/doSearch?field1=Contrib&text1="Bo+Liu"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://pubs.acs.org/action/doSearch?field1=Contrib&text1="Dali+Xian"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://pubs.acs.org/action/doSearch?field1=Contrib&text1="Xuanxuan+Liu"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://pubs.acs.org/action/doSearch?field1=Contrib&text1="Bo+Da"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttp://pubs.acs.org/journal/acsodf?ref=pdfhttps://doi.org/10.1021/acsomega.2c01010?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-asBo Da − Research and Services Division of Materials Data andIntegrated System, National Institute for Materials Science,Ibaraki 305-0044, JapanComplete contact information is available at:https://pubs.acs.org/10.1021/acsomega.2c01010Author Contributions∥Z.Z. and H.G. contributed equally.Author ContributionsZ. Z. and H. G. conceived the study, analyzed the data, andwrote the original draft. B. L., D. X., and X. L. took part in theresult discussion. B. D. provided the calculation method. Allauthors gave suggestive feedback. L. S. supervised the entirework.NotesThe authors declare no competing financial interest.■ ACKNOWLEDGMENTSThis work was financially supported by the National NaturalScience Foundation of China (Grant no. 11874105).■ REFERENCES(1) Ren, J.-G.; Xia, H.-L.; Just, T.; Dai, Y.-R. Hydroxyl radical-induced apoptosis in human tumor cells is associated with telomereshortening but not telomerase inhibition and caspase activation. FEBSLett. 2001, 488, 123−132.(2) Valko, M.; Izakovic, M.; Mazur, M.; Rhodes, C. J.; Telser, J. Roleof oxygen radicals in DNA damage and cancer incidence. Mol. Cell.Biochem. 2004, 266, 37−56.(3) Peckys, D. B.; Mazur, P.; Gould, K. L.; de Jonge, N. FullyHydrated Yeast Cells Imaged with Electron Microscopy. Biophys. 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