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The experiments were not described in the abstract. Experimental conditions were not described in the abstract. Experimental procedure not described in the abltr,ct. WE, KR A mechanism for the NaO. No check was made on the validity of the rate equation. An empirical relationship was develop- ed relating 10g[NO. There was a minimum in the' plot log [NO;] vs. SxlO-'" NO,.

The rate for NIIO, depends on its equilibrium concentra- tion in the gas. The hydrolysis mechanism WaS con- sidered N. The reasons are not clearly described in the abstract. Tho article 18 un- available at preaent. The sorbing solution must contain at least. The absorption rate was lowered when the density of the sorb- ing solution w:JS increased by large amounts of NO; and NO;.

The rate of absorption was found to be independent of the liquid velocity. The resistance was caused by the liquid phase. The driving force was determined by [N. If both NO, and N. O, are present. At low concentrot ans the rate is indepen- dent of gas velocity but at some concentration it begins to depend on the velocity.

The rate of absorption of N. O, is 1. Equimolar mixture of NO and NO. NO mixtures in nitrogen Concentra- tion not given in the abstract. N oxides. No further des- cription given 10 abstract NO, NO. Total concen- tration from 0. N:I con- centrsUons given in thL "batract. Total concen- trstion 0.

NO mix ture.. Concentra- tion not g1 van in abstract. Some NO. Some measure,- ments mede with pure NO.. Gas bubbled through liquid. Surface absorp tion with r spid movement of gss end liquid. Surface absorption with quiet state of gas and liquid. A 45 mm diameter column filled with glass rings was used. Gas velo- cities of 0. The experimental proce- dure was not described in the ebstract.

The absorption efficiency is sharply reduced when [Na,CO. The rate for N,O. Packing was ceramic rings. The apparatus is called the Penn apparatus. It is not described further in the abstract. Gas flow rates of. A rapidly revolving mechanical absorber was used. The gas veloci ty corresponded to a contact time of 2. The con- di tions were highly turbulent. HNO, solutions normality. HCl present to determine influ- ence of Cl -. Water The apparatus was not described in the abstrsct. Tempera- ture was 30'C.

The jet diameter was 0. An absorption coefficient is also discussed but not defined in the abstract. The absorp- tion rate was expressed as the rate of forma- tion of IINO.. The exit liquid was analyzed for total acid HNO. The IINO. The products from sorption with NaaCO. It was found that the coefficient of efficiency a increases with increasing liquid flow rate and increasing initial con- centration of N oxides, and b de- creases with increasing gas flow rate and increasing NaaCOs concentration.

In testing the hypothesis, the rates of NO, end N, O. HNOa were found to be equal. PO-Ol5 GA! It was a maximum 'ae cunver- dion of NO to NOa. It decreased with decreasing concentration of N oxides in the entering gas. It decreased with an increase in Ns:,CO, concentration. It was found that Cl- acce!

Cd appeered to accelerate absorption. The original article is in Japsnese. An empirical equation for the dependence of the total acid concen- tration on [eNO, , [eND. Concentration of N oxides. II1xtures of N. O, and IINO, in Mixtures containing NO and NOa. II1x ture of 0. Water N Experiments were ther- mostated at Since the gas contained 00 diluent gas, diffusion resistance was considered negligible and the rate was was considered determined by the two reactions: N. O ;I lINe.

The results are glven in the following figure. Vtt"",ribtil dn Sluhl, ,. An equation derived previously and used by Kremers KR was used to obtain a rate constant for reaction 2. The equation is based on the pene- tration theory. According to the equa- tion, tha rate should be proportional to the concentration of N. There was e deviation from linearity. The authors steted also that another posaible mechanism is the gas phase forma- tion and subsequent diffusion of lINe..

The liquid was analyzed for discs were perforated nitrite and nitrate. The gas had to be the speed of rotation of separated from entrained the discs, the tempera- mist after it left the ture. Gas velocity concentration. The tempera- atm. A bubble-cap column in an autoclave: was used. The temperacure and pressure were varied up to C and 50 atm. A column. The temperature was The measurements were not described in the abstract.

The degree of absorption J a. Inlet and outlet NO end NO; were determined in the gas and the volu- metric absorption coef The degree of ebsorption was also calculated. The rate of absorption was dependent on the concentration of nitrogen oxides at low peripheral disc speeds. At higher speeds, the absorption rates became equal for high and low initial concentrations. The rates of absorp- tion for gases of equal concentra- tions containing 1 NO. The proposed mechanism inVOlved the following steps.

AT When '7. With increasing temper.. Pure NO NO in nitrogen in the range 0. Three series of experiments were conducted in. I t-' VI I cont. The resul ts were independertt of the concentration of FeCI,. The absorption rate 'Was linearly proportional to the concentration of NO in the gss up to 8' At concen- trations hi! The high solubility of NO in the range. A stirred pot reactor was used.

Gas was passed over the surface of a stirred liquid at 0. Liquid sur- face was Temperature was A packed column mm high and Aas used. Gas 'elocity was 0. The absorbing A mechanical absorber medium was a similar to that des- solution of ca! The concentration of NO in the inlet and exi t gas was measured. The entering and exit concentrations of NO in the gas were meas- ured.

NaCl, and NaN Reynold's number. Data were usually plotted in the form It has been pointed out CA and DE that the rate equation for diffusion controlling shows the rate propor- tional to the sum of the concentrations of NOg and Na04' Peters and coworkers PE, 7, 8, and CH, Table I, numbers 4, 5, 6, and 11 on the other hand used a variety of equipment types and showed the absorption rate linearly proportional to the concentration of Na04 or the square of the concentration of NOa.

They also demonstrated that even when no NO is added in the inlet gas, its presence must be taken into account in the rate equation due to the decomposition of HNOa in acid sorbents. Several mechanisms for the reaction have been proposed and the rate of the reaction has been measured. Moll MO gives a good summary and discussion Table I numbers 22, 36, 37, and 38 are concerned with the absorption of pure nitric oxide or nitric oxide diluted with inert carrier gas. Pozin PO, number 22 found that absorp- tion rate for sulfites as the absorbent depended on the con- centration of NO in bulk gas and at the gas-liquid interface.

Sirotkin and coworkers SI, number 36 also used FeS The abstract of the original article reported that the complex [FeNO]-- was formed. Since the article was a translation, it is aq quite possible that an error was made. That the absorption rate liquid contact area was demonstrated in a variety of equipment types with is a function of the gas- by conducting experiments other factors held constant.

In absorption experiments, the concentration of components NO, NO,. Early investigators assumed that the concentration of HNO,. Os is faster than that of N,. Analytical techniques are important in the NOx-H,. O system. For instance, many investigators titrated the liquid absorption products directly with NaOH.

Koval showed that decomposition of HNO,. In addition, the titration curve for titration of nitrous acid with sodium hydroxide is not sharp since HNO,. Varlamov and Drobysheva VA, number 35 tried to determine the relative effects of mass transfer and chemical reaction on the absorption of NO-NO,.

The factor 8 is the coefficient representing the effect of chemical reaction and H is the Henry's Law coefficient. It was concluded that "the boundary of chemical interaction between reacting components moves toward the liquid surface" with increasing liquid flow rate, and that "the rate is influenced by both diffusion of the active component in the gas and diffusion of the active component and the reaction product in the liquid". When NO and NO,.

The equilibrium for the second reaction in the gas phase is well described but in the aqueous phase it has not been studied extensively. The equipment used was a horizontal mechanical absorber containing a revolving axial shaft to which were connected blades or discs causing highly turbulent flow conditions.

Most of the work of Ganz is generally concerned with developing empirical relationships between the absorption coefficient and hydrodynamic or physical factors with little regard for theory and mechanism. However, in the case of the mechanical absorber, discussion of a possible reaction pathway was presented.

The influence of the NOa :NO ratio in the gas and the concentration of nitrate, nitrite and CaO in the absorbing medium were investigated see Table I, numbers 39 and Some of the qualitative results are summarized in points 1 through 4. When there is an excess reaction 7 takes place and NO is given off or thus limiting the percent absorption. It was proposed that in the mechanical absorber, reaction takes place simultaneously via NOa and Na03 and that the rates of the two reactions are equal.

The proposition is based on several observed facts. Depending on the concentrations of calcium oxide, calcium nitrite and calcium nitrate, formation and precipitation of the basic salt Ca 0H; a. Ca N03 a. Gorfunke1 GO also reports the possibility of formation of CaO.

Ca N03 ;. If only N;03 absorption were taking place, the products would be totally nitrite. However, more nitrate than nitrite is formed. When the nitrite-nitrate concentration in the absorbing liquor is small the presence or concentration of calcium oxide has no effect on the percent of nitrogen oxides absorbed.

An increase in the CaO concentration then retards the decrease in absorption. Ganz explained this effect by stating that in the mechanical absorber, calcium oxide is dissolved faster than Ca OH a can react to fOrlli nitrites and nitrates so there is an excess of 4. It was proposed that in the mechanical absorber, nitrogen oxides are almost completely oxidized to NO; and the rate of NOa absorption becomes equal to the rate of Na03 absorption resulting in the formation of equimo1ar amounts of nitrite and nitrate.

The nitrite undergoes inversion accord- ing to reaction 7 and NO is liberated and oxidized in the liquid. The authors stated that the mechanism of absorption is dependent on the relative concentrations of NO and NOa. They described four possible absorption mechanisms and developed rate equations for a laboratory sieve plate for each mechanism. The mechanisms corresponding to the alphabetic designations in Figure 1 are as follows.

Figure 1, taken directly from Andrew and Hanson AN-DOl shows the plate efficiencies predicted from the rate equations for each mechanism. Some physical constants had to be estimated to obtain Figure 1. T - 10 SEC. Diffusion as HNOa g - Na03 g equilibrium mixture.

HNOa decomposition in aqueous phase. NO given off. HN03 both dissolves in mist and diffuses into aqueous phase. HNOa g decomposes. The values obtained experimentally are indicated by 0 and X, while the predicted values are indicated by the lines. IO' FIG.

Predicted component and total plate efficiencies. A camparison of measured wilb predicted plate efficiencies. Figure 1 shows that at low gas strengths, mechanisms e and cd diffusion as NO; and HNOa-Na03 are important while at higher strengths, mechanism fh diffusion as N; NOa is most important. The point was also made that as the proportion of NO increases, mechanism cd involving NaHNOa becomes more important than mechanism e involving NOa. The con- tribution of mechanism ik is never important.

The mechanisms operable at different gas concencrations are shown in Table II. ScL, 14, p. Atroshchenko, V. Atroschenko, V. Borok, M. Caudle, P. ScL, 2" , Chambers, F. S USSR , 30, KR Ganz, S. USSR , 30, 91 MI Hofmeister, H. Mixtures by a Laminar Water Jet," Ber. MO Koval, E. Koval, E. Kramers, H. Blind, and E. Eng, Sci. Nauki, Bu1g. Nauk, , 1 1 , ; f.!. Krustev, Iv. Sofia , 4 , ; f. Marrucci, G.

O"," Rend. Mirev, D. Bu1gare Sci. BOX ". Japan, Ind. Velocity of Nitric Oxide Conditions," ;[. Ross, and J. Journal, Vol. VA Peters, M. Absorption USSR , 17, 6 , ;. WE Pozin, M. Vysshikh Uchebn. Zavedenii, Khim. Lensoveta, 36, ;. Sirotkin, G. Nitric Oxide Zhur. Starostin, "Absorption of Solutions of Ferrous Salts," ;.

Varlamov, M. Vysshikh Ucheb. Zavedenii Khim. Wendel J M. Zhavoronkov, N. Parsons Philip S. It includes changes made when an equation involv- ing N;Os was added to the system of equations used to describe gaseous nitrogen oxides equilibria. Note 03a is identical to Note 03 except for addit'ions on pages 2, 3, 6, 7, 9, 10, 11, 15, 16, and 17, and corrections on pages 10 and The system of interest contains nitrogen oxides, water, and their reaction products.

The ability to quantitatively describe the chemical composition at equilibrium is important. With this informa- tion it is possible to predict which species are significant in the mass transfer mechanism. This note, however, describes only the chemical basis and problem formulation. The appli- cations of the computer program and the results will be discussed in a later note.

The oxides NgO and NgOS are not formed in amounts great enough to be of significance for the mass balance. Both NO and NOg are stable with respect to decomposition into their elements. Reaction is slow enough to be considered the rate limiting step in nitric acid manufacture.

Chilton CH, pp. Reactions 2. For the purposes of these calculations, the only components present in the gas phase were assumed to be the various nitrogen oxides and water, their reaction products, and inerts see section 3. The interaction between sulfur dioxide and nitrogen oxides is a kinetics problem and was not considered.

Others reported no mist formation or were able to eliminate it by filtering the carrier gas repeatedly. The equilibria in , , and have been investigated and found to be attained quite rapidly CH, p. Wayne and Yost WA, WA measured the rate of formation of HNOa, but expressed the rate constant and the equilibrium constant for the reaction as written in , 2 Nitric oxide has been found in the exit gas when sodium hydroxide was the sorbent for gases initially containing only NOa. The nitric oxide must then have resulted from decomposition of gaseous HNOa.

Since no nitric oxide was present in the inlet gas, reaction In many cases, it was concluded that no reaction took place. The conclusions were based on the fact that either no pressure change occurred, or no mist was visible.

They reported half times as short as 0. Whether or not nitric acid is formed by reaction in the gas phase such as that given in has long been a matter of some controversy. The question has been discussed by nearly every author that has written about nitrogen oxides absorption.

Carberry CA summarized some of the data published up to and Wendel and Pigford WE also gave a summary and discussion of the findings of many investigators. The pertinent facts are: 1 Many investigators have observed mist or fog formation when gaseous nitrogen oxides are absorbed into aqueous solutions.

They have interpreted the mist formation as proof of a homogeneous gas phase reaction to produce HN03 g Wendel and Pigford WE discussed a possible explanation for mist formation and for the presence of NO in the exit gas. According to their theory, the heat of solution of highly soluble gases causes vaporization of some water.

The vapor diffuses outward into the relatively cooler gas stream and condenses forming a mist or fog. NaNOa mixtures can then be absorbed in the condensed water vapor forming nitric and nitrous acids. The NO is given off when nitrous acid decomposes. As suggested to him in a private communication from S. A nitrogen stream saturated with NOa was mixed with an air stream saturated with water vapor in a mixing chamber.

NOa was determined photometrically in the inlet and outlet gases. Apparently no condensed phase was present in the mixing chamber other than a mist which formed on mixing. At higher relative humidities the mist was collected on a filter and analyzed for HN It was therefore concluded that NOa removal occurred through a gas phase reaction mechanism rather than through absorption into mist droplets. The components 1- are listed below. In some experiments, the gases were heated upon mixing.

In these cases, the amount of mist formed was slight and remained constant. In these experiments, mist formation was quite exten- sive due to the condensation of water vapor. At lower temperatures the NOa removal decreased due to the decrease in reaction rate between NOa g and HaO g ' At temperatures below the dew point, mist formation also decreased since there were few HN03 nuclei due to decreased reaction rate.

A heavy mist "Inerts" is used to describe flue gas components which are not considered chemically reactive in the equilibrium formulation. The other eight components are involved in the j reactions which are also listed. The relation between the mole fraction Yi and the number of moles, ni' for each component is defined by where NT is the total number of moles including inerts. Fugacities may be calculated from partial pressures using where Yi is the mole fraction, P is the total pressure, and vi is the fugacity coefficient.

H0 - t:. The enthalpy term is evaluated from Equation and likewise, the entropy term from Equation The mass balance equations are solved in the log domain as are the equilibrium expressions described in 3. When the three mass balance equations are combined with the five equilibrium constant expressions the number of equations 8 is equal to the number of unknowns and the Yi'S can be calculated.

J a. The following is a J description of how K. Consider the J general gas phase reaction indicated by Equation , with i reactants and Products where a IC' 1. The values in Table were used. The resulting constants for each reaction are given in Table J N:a04 g 2. Ten minutes was allowed for equilibrium to be reached. The pressure at a measured volume and temperature of NO added was reported. The amount of N:a04o added in grams was reported.

The total pressure at equili- brium in the system at a measured volume and tempera- ture was measured. HN03 g was not included in the mass balance or the calculations. Calculated Quantities The total pressure P in the bulb was calculated from the vapor pressure of NaO at the tempera- ture o! CS to equilibrium mixtures were found. Mellor's Comprehensive Treatise on Inorganic and Theoretical Chemistry was also consulted, including a supplement on nitrogen published in ME The supplement contains a twenty-page review on the analytical chemistry of nitrogen compounds.

Nothing was reported there on the determination of gaseous HN02 or HN A comparison of these calculated values with the reported values is shown in Table It is obvious that the concentrations are all of the same order of magnitude.

The data of Vosper VO and Beattie and Bell BE as discussed in Table were also used to calculate equili- brium concentrations using the equilibrium program. Vosper's' data are compared with calculated values in Table and Beattie's in Table Note that Beattie measured only the total pressure at equilibrium.

Using his reported volumes and temperatures, the number of moles present at equilibrium was derived. That number is compared with the sum of the number of moles calculated for each component by the equilibrium pro- gram. The input NO pressure was not reported either, so calculations or comparisons could not be made with their data.

Ashmore and Tyler AS, see Table investigated the equilibrium system and reported the equilibrium concentrations of each of the species of interest. The only one of the re- ported values that was a measured value was the NOp' concentration.

The other values were calculated using reported equilibrium constants and mass balance equations. Again, the only equilibrium concentration measured was N02, and all the other reported equilibrium concentrations were calculated from equilibrium constants and mass balance equations. Waldorf and Babb ignored the formation of HN03 and also apparently neglected to account for the reaction of Ng03 to form HN They reported WA corrected values for the equilibrium constant, but they did not report the corrected equilibrium concentrations, so no calculations or comparisons could be made with their data.

The data were not reported in Waldorf's dissertation WA In summary, an attempt was made to compare measured and calculated values of equilibrium composition in the gas phase system NO,-H BOX 99i BOX ""8. BOX 99J Theoretical Chemistry, Vol. VIII, Supp. Stern, Kurt H. Vosper, Alan J. Waldorf, D. Wayne, L. TEXAS Phillips Terry B. Corrections appear on page the text and page 18 of the Bibliography.

In addition and VI of the Appendix have been replaced by tables in estimated values of nitrate and nitrite heat capacities the heat of formation of CuO have been corrected. These reactions are of interest in describing the thermal decomposition of nitrates and nitrites for regeneration of metal oxide sorbents for NOx' Thermodynamic data were collected for the nitrates, nitrites, nitrides, and hydroxides of 35 metals and for several nitrogen oxides. The data were compiled in a data base using a previously written program PA-9l6 which also retrieves the stored data.

Properties for compounds for which no experi- mentally determined values have been reported were estimated. The standard heat heat capacity is lower; and tions. Values 3. Kelley, et al. Kubaschewski, et al. This technical note describes the methods of data collection, the extent to which data were available, the method of storing and retrieving the data, and the methods of estimating data that were unavailable from the literature.

A survey of the open literature from through January was carried out by searching Chemical Abstracts from to January It was felt that all earlier reliable values would have been reported in the compilations. The topics searched included: 2. Two values were considered to be conflicting if there was greater than one kilocalorie per mole difference for the heats of formation or greater than one calorie per mole per degree K difference for the absolute entropies.

In such cases, the original articles were obtained, if possible, in an attempt to resolve the conflict. One of the values was selected to be added to the data base. The selected value was accompanied by the bibliographic entry RA, which references this technical note and indicates that values differing from the one selected have been reported.

Abstracts of all promising articles from the open literature were obtained. Approximately 30 of the original articles were collected for further study. In some cases, it was necessary to extract the data directly from the abstract when the original publication was not available.

If so, care was taken to insure that the bibliographic entry includes the volume and number of the abstract. The following criteria have been used in selecting the values used in the data base for the heat of formation. Calorimetric measurements have generally been preferred. These methods are usually the most straight- forward and the experiments are normally carried out at or near room temperature. Vapor pressure or EMF measurements are usually recorded at elevated temperatures. The accuracy of conversion to standard conditions depends on availability of heat capacity data, for which the authors sometimes rely A previously written computer program was used to store, tabulate, and retrieve the thermodynamic data and references.

The program is also capable of calculating and plotting equilibrium constants, enthalpies, entropies, and heat capacities of specified reactions as a function of temperature. The data for each compound of interest as well as for sulfates, sulfites, carbonates and mixed metal oxides are tabulated and printed in the Appendix in Tables V and VI.

Table V contains standard heats of formation, absolute entropies, and transition data. Table VI contains heat capacity data. Data for which the author has described his estimation of error have been preferred. Values which fit best into our estimation correlation were chosen. Entropy values calculated capacities have been preferred over temperature data.

Values for which an error estimation was made The selected heats of formation are discussed in Table I and the selected entropy values in Table II. Where one reference follows another in parentheses, the second reference was cited by the first author as the basis for his data.

Tables I and II are ineluded in the Appendix. Data were tabulated for approxi- mately compounds, including hydrates. It was found that the nitrites as a group lacked the most data, especially for heat capacity and entropy.

Since thermodynamic properties were not reported for all the compounds of interest, some of the data were estimated. Methods for estimating heats of formation, absolute entropies, and heat capacities were previously developed and had been applied to metal sulfates, sulfites, carbonates, and mixed metal oxides under Contract PH to the National Air Pollution Control Administration.

A detailed discussion of the methods and results has been published PA-9l6. Reported values for heat of formation for the corresponding metal oxides, nitrites, nitrates and carbonate or sulfate were used to estimate the unknown nitrite and nitrate heats. A computer program retrieved the 71 known heats of formation indicated by K in Table III for sulfates, carbonates, nitrates, and nitrites which had previously been stored in the data base.

The program employs a method based on that of Erdos ER to perform the estima- tion. This method is based on the theory that the heat of reaction may be determined by summing the energies of all bonds formed during the course of the reaction. When a metal oxide cation i and an acid anion j react to form a salt, ij, the following equation may be written for estimating the heat of reaction.

J The heat of formation of a salt from a.. J' '" a. The 1J solution for K, A, and n involved solving a set of 30 simultaneous nonlinear equations. Once K. Table IV gives the estimated values and the reported values on which the correla- tion was based.

The RMS error is 2. The known and estimated values are compiled in Table V in the Appendix. In order to estimate the nitrate and nitrite entropies, a computer program retrieved known compound entropies from the data base. This method is based on subtraction of the metal or cation contribution from the compound entropy and making a correction for ionic forces.

The anion contribu- tions were then added to Latimer's cation values LA to obtain the estimated compound entropies. I W' 23 3 1. The results were based on reported data for the nitrates, nitrites, and oxides of shown in Table III. The p increment was calculated by a computer program by subtracting oxide heat capacity coefficients from known nitrate heat capacity coefficients.

Using a least squares method, an average nitrate increment was obtained. The temperature range of validity for the estimated coefficients was taken to be that of the coefficients for the corresponding oxide. The same method was applied to the estimation of nitrite heat capacities. The accuracy of this estimation technique was indicated by the fractional error, which is defined as the RMS error divided by the average known heat capacity for the group of compounds of interest. For the nitrate correlation, the fractional error was 0.

The fractional error for the nitrite correlation could not be estimated on the basis of one compound. The estimated values were added to the data base. Table VI is a compila- tion of kaown and estimated heat capacity coefficients. It is included in the Appendix. Data were collected and evaluated from the compilations and the open literature.

When widely differing values were reported, one value was selected after consulting the original references. Standard heats of formation and absolute entropies were estimated for nitrates and nitrites for which no data were reported.

Co- efficients for heat capacity equations were estimated for 39 nitrates and 45 nitrites for which no data were reported. The accuracy of each correlation was determined by comparing accepted values with those calculated by each method and computing a root mean square RMS error.

The estimated values were also compiled in the data base. A copy of the data base arranged in alphabetical order is contained in the Appendix in Tables V and VI. Table V contains the standard heats of formation, absolute entropies, and transition data; Table VI is a tabulation of the heat capacity data. Tables I and II are also included in the Appendix. They contain a description of values selected for heat of formation and entropy when widely differing reported values were found.

IC 4L A'! KING U. UZ Nrrs. SEt: TI 5F. I GORN. OELO ET AL. SEE TR VOL 5. VOL VOL, M, 1JULL. Comparison with Uranyl Nitrate," Compt. Paris , Dreger, Lloyd H. Dadape, and J. Ewing, Warren W. Glick, and H. Fox, R. Swinehart, and A. Fricke, R. Gwinner, and C. Fricke und Mitarbeitern," Ber. B 11, AND L. LER, J. Gcr,r1, J. Gross, P. Faraday Soc. Guntz, A. Paris , Ser. Ha tton, W. II S'S HUS 1. Justice, Bruce H. Juza, Robert, A. Neuber, and H.

My, Le Van, "E'tude mic! Nitrates de cuivre et de nickel," Bull. Abt A P4RT IT. TN Z 11' VON lJ.. Neubauer, C. Neumann, B. Kroger, auJ rt. Kroger, and H. Kunz, "Die Bildungswarmen der Nitride. Die Verbrennungswarmen einiger Metalle und Metallnitride," Z. Kroger, and R. Kunz, "Uber die Bildungswarmen der Nitride.

SOlt I1SSq. TR-OC, ;. Parsons, Terry, Gary D. D JFA'. Schwei te, H. Schwiete, H. Seybolt, A. TE, "]t,YL! CK,r, u. E'l and G. Slade, R. PB PB ]-Z. KURT H.. PART 3. Taylor, K. AND D. Thomsen, J. I lAR. Chern Soc 53, NOTE ". Wagman, Donald D. MOLE Ewing EW calori- metrically measured the heat solution and the heats of dilution up to 24m for Mn N03 :a' Guntz GU-9l1 also measured the heat of solution.

In a private communication WA Wagman stated the reference used in his compila- tion WA , but did not cite the values used to calculate the heat of formation from Ewing's solution data. Rossini RO gave no further infor- mation concerning the calculation of his value.

The value which agreed closest with the Radian esti- mate RA was accepted. The most recently calcu- lated value was adopted. The revised value was accepted. P1ekhotkin PL stated that the value he gives has been reported in reference books, but he does not give the reference.

Wagman's value was adopted. However, Ca NOa a was not included in Wagman's com- pilation. Assuming that this was the case for Ca NOa a Stern's value was accepted. Guntz GU in his article describes his determination of the heat of formation. The heat of solu- tion of Ba3Na in hydrochloric acid was measured by calorimetry. The data were then employed in a Hess cycle to obtain the heat of formation. Mah MA in , both of which were ob- tained by calorimetric measure- ments.

In a article, Dreger and co- workers DR reviewed the heat of formation data published for AlN, and they stated that Neumann's data are in error, but do not give any reason for this decision. This includes nearly all the reported values. Kelley KE-9ll applied an estimated entropy value to Slade's data to obtain the heat of forma- tion.

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More by Fabio Benfenati. More by Denis Scaini. More by Laura Ballerini. More by Kostas Kostarelos. More by Maurizio Prato. More by Alberto Bianco. Cite this: ACS Nano , 12 , 11 , — ACS AuthorChoice. Article Views Altmetric -. Citations Abstract High Resolution Image. Graphene is first-in-class—the first two-dimensional 2D atomic crystal. Material characterization, in turn, is a key element of hazard assessment. The toxicological evaluation of carbon nanotubes is a case in point.

Thus, while it is evident that important lessons can be learned from previous studies of other engineered nanomaterials, it is equally important to avoid extrapolation from the study of one class of nanomaterials to another—if we acknowledge that new materials have new and useful properties, then we must also accept that such new materials could pose new or unanticipated risks.

Indeed, the final common pathways of cellular or organ damage e. We need to understand the properties of the materials and how these are connected to the biological effects in order to make them both useful and safe. The Graphene Flagship Project www.

The Graphene Flagship was launched in and is expected to run for 10 years; the consortium consists of over academic and industrial research groups in more than 20 countries. Safety assessment is an essential requirement that cannot be dissociated from the development of new technologies.

Therefore, the Graphene Flagship has invested considerable efforts in evaluating the potential impact of graphene-based materials GBMs on human health and the environment. We address the main exposure routes for GBMs and the key target organs including the immune system, the skin, the lungs, the cardiovascular system, the gastrointestinal system, the central nervous system, and the reproductive system, as well as a wide range of organisms including bacteria, algae, plants, invertebrates, and vertebrates in a variety of ecosystems.

We also address the synthesis and characterization of GBMs as a thorough understanding of the material itself is crucial in any nano toxicological evaluation. Furthermore, close attention both to human health and the environment 19,20 is needed in order to maximize the societal benefits of these novel materials. Synthesis and Characterization of Graphene-Based Materials.

High Resolution Image. In addition to chemical contaminants arising from the synthesis, biological contaminants, i. Graphene dispersions can be produced via exfoliation of graphite using ultrasonication. For instance, insertion of chlorin-e 6 Ce6 showed a successful exfoliation of graphite in biocompatible media water or phosphate buffer. Stable water dispersions of graphene can also be prepared by ball-milling treatments. In particular, the exfoliation of graphite through interactions with melamine allows the production of the material with low amount of defects.

Moreover, after lyophilization of these aqueous graphene suspensions, a soft powder of few-layer FLG graphene is obtained, which can be easily dispersed in aqueous media. The process, developed in the Graphene Flagship, thus comprises four steps: i the mechanochemical intercalation of organic molecules melamine into graphite, followed by suspension in water; ii the washing of suspended graphene to eliminate most of the melamine; iii the isolation of stable graphene sheets; and iv freeze-drying to obtain graphene powder.

However, this method yields GO with different degrees of oxidation and impurities. Additional purification steps are necessary to enhance the purity of the material. Chemical reduction prevails over nonchemical reduction approaches because of the improved quality, efficiency, and the fact that stable dispersions of rGO can be obtained. The most effective chemical reductant is hydrazine; however, this reagent is not very popular because of its toxicity to humans and the environment.

Although most of the synthetic methodologies discussed above yield high-quality graphene, the impossibility of scaling these methods limits their industrial applications. Therefore, obtaining a large amount of biocompatible graphene in a simple and low-cost manner remains a considerable challenge. Recently, some companies have developed the electrochemical exfoliation of graphite. For proper hazard assessment, the materials need to be well-characterized using standardized and validated characterization techniques.

The limulus amoebocyte lysate LAL assay is commonly used to check for endotoxin content of nano- and biomaterials, but recent studies have shown that GBMs cause interferences with the assay, and an alternative macrophage-based assay was proposed. Table 1. Characterization of Graphene-Based Materials. It is important to note that even when using a synthetic methodology that selectively leads to a certain graphene material e. Hence, whereas apparently contradictory results have appeared in the literature, for example, in terms of bioaccumulation in different organs discussed below , it is important to point out that these disparities may be due to the existence of different graphene morphologies as well as the use of different biological model systems.

In general, the toxicity or safety of GBMs depends on physicochemical properties such as size, number of layers, and surface chemistry 22 supporting text and Figure S1. Moreover, the presence of impurities and the graphene synthetic methodology used may also influence the toxicological responses. The number of graphene layers is also important as this will determine specific surface area, absorptive capacity, and bending stiffness.

As the surface area is inversely proportional to the number of layers, it is expected that the adsorptive capacity for biological molecules biocorona formation 10 increases as this number decreases. GBMs may possess a wide variety of chemical surfaces.

Hence, the surface of pristine graphene is hydrophobic, and the surface of GO with extensive oxygenated functions like carboxyl, epoxy, and hydroxyl groups is highly hydrophilic, whereas rGO presents intermediate characteristics. In conclusion, the way in which GBMs are prepared is of key importance for the potential impact on biological systems.

Furthermore, for specific applications, quality and adherence to regulatory standards will be critical. For such applications, heterogeneity in the produced materials batch-to-batch variability for a single producer or variability between different producers and lack of international and regulatory standards are important issues, perhaps not for their initial translation to the market but for a wider acceptance and penetration of the market. Moreover, in the context of clinical translation of GBMs, one of the issues that one will have to overcome is the current medium-to-high variability observed between different synthesis batches.

Production methods will have to progress toward better GMP good manufacturing practices compliance e. To dissect the role of nano material properties on the biological impact, access to appropriate reference material libraries should be considered. In , Nel and co-workers proposed the creation of a standard nanomaterial library including the principal classes of nanomaterials and nanoparticles. Since then, some examples of such material libraries have emerged.

Hence, a custom-designed material library for testing the toxicity of metal oxides was developed taking into account well-established methods available to produce and characterize such nanoparticles. Zhou et al. A systematic methodology relying on the combination of computational methods and the properties of nanomaterials to generate libraries that permit rapid screening of cells and biologically relevant organisms has been recently proposed.

Graphene was included in the family of nanocarbons along with carbon nanotubes and fullerenes. However, we believe that the chemical composition is not the only parameter that one should consider as the chemical structure of graphene differs remarkably from that of nanotubes and fullerenes. Furthermore, graphene constitutes a whole class of materials with different characteristics and, therefore, likely also different biological effects. The inclusion of graphene as a representative industrial nanomaterial in the aforementioned repository and the creation of a specific reference library of well-characterized GBMs will be fundamental for benchmarking purposes in basic and regulatory research.

However, in this moment, we need to rely mainly on the physicochemical characteristics of individual GBMs that are reported in the literature. Biodistribution and Fate of Graphene-Based Materials. The intrinsic characteristics of GBMs are expected to influence their biodistribution, translocation to secondary organs, accumulation, degradation, and clearance. However, these characteristics may be altered by the adsorption of proteins and other biomolecules present in the biological milieu.

However, the intrinsic material properties are also subject to change, as a result of degradation by immune cells discussed below or other forms of biotransformation, 78 thus underscoring the importance of characterizing the material not only in its pristine form but also in situ in the test system during or after exposure to the extent that this is possible. With this in mind, we discuss studies on the biodistribution and fate of GBMs upon various routes of administration relevant either for occupational or environmental exposures or routes that are relevant for biomedical applications of GBMs.

To investigate the impact of oral administration, Zhang et al. These results suggest that both materials were quickly absorbed in the gastrointestinal tract and reached secondary organs via the systemic circulation. Radioactivity was detected in the stomach and intestine but not in any other major organs at 4 h.

In line with these findings, it was demonstrated that GO small and large lateral dimensions does not penetrate across a fully differentiated enterocyte-like Caco-2 cell monolayer. The inhalation route is of key relevance for human exposure.

Li et al. Minor amounts were also detected in the blood, liver, and kidneys. These results could be ascribed to translocation to the blood either directly from the lungs or via intestinal adsorption as large amounts of the material were also detected in the stomach and intestines, potentially due to mucocilliary clearance, swallowing, and redistribution to the gastrointestinal tract. Macroscopic observation of the blackness of the lungs revealed that materials were long-lasting black regions found for up to 3 months.

However, there was a clear decrease of the blackness from day 1 to 90, suggesting clearance from the lungs. The authors noted a time-dependent decrease in all investigated organs and a negligible amount of material in the liver and spleen, suggesting a very limited translocation to the bloodstream. The observed biodistribution of the graphene platelets is reminiscent of the biodistribution of 14 C-labeled multiwalled carbon nanotubes following pharyngeal aspiration, with accumulation in the spleen of mice.

Unlike GO, there was evidence of early monocyte recruitment at the interface between GO-R and the subcutaneous tissue and also infiltration of monocytes within the GO-R macrostructure at day 3. At days 7 and 14, some infiltration of the GO macrostructure by macrophages and fibroblasts was noted, whereas these cells had completely infiltrated GO-R, with material-laden macrophages evidenced in both conditions.

By day 30, the GO macrostructure was fully infiltrated by macrophages, fibroblasts, and giant cells as expected for a typical foreign body reaction, whereas the GO-R macrostructure showed more advanced signs of healing, tissue repair processes, and extracellular matrix remodeling but without fibrosis.

The authors suggested that the absence of fibrosis could be explained by the combination of macrophage uptake of the materials, a mild inflammatory response at the edges of the macrostructure, and indications of clearance from the site of injection. Following repeated intraperitoneal i. Furthermore, in order to assess the influence of GO oxidation degree i.

Cells retrieved from the peritoneal cavity of treated animals and cultured for 12 h in vitro were more prone to secrete pro-inflammatory cytokines and chemokines in GO compared to cells retrieved from animals exposed to GO-R. To study the biodistribution after i. Interestingly, upon i. However, this result was only based on macroscopic observation, as the authors did not perform radioactivity-based biodistribution analyses for the non-PEGylated materials.

Black materials thought to be the injected materials were found in the histological sections up to 30 days postinjection. Following i. However, whereas material content decreased over time in the spleen, it increased in the brain at 7 and 14 days, decreasing by day 21, and increased dramatically in the liver by day The authors suggested that the materials crossed the blood—brain barrier, but direct evidence to support this notion was not presented.

One of the most common routes of administration for biomedical applications of nanomaterials is the intravenous i. Considerable research and development efforts in nanomedicine have established that shape, size, and surface charge are the most important physicochemical parameters determining biodistribution and fate of a nanomaterial after i. Qu et al. GO sheets functionalized with poly sodium 4-styrenesulfonate lateral dimension: — nm, thickness: 1—4 nm and labeled with the fluorescent Cy7 dye were used to assess biodistribution using whole-body live imaging.

Fourteen days after injection, there was obvious macroscopic presence of materials in the lungs, liver, and spleen, which all appeared black in comparison to corresponding organs from PBS-treated animals. Materials were still present in these organs after days, as evidenced by black matter in histological sections. The biodistribution and degradation of oxidized FLG platelets lateral dimension: — nm were studied over 90 days using Raman confocal imaging.

The aggregates were still present after 90 days despite some signs of degradation at the material edges. Yang et al. The decrease could be explained by a continuous clearance as radioactivity was detected in both urine and feces over the 60 day period, with a higher amount in urine compared to feces, suggesting glomerular filtration of the material. Both materials accumulated in the lungs without evidence of clearance during the tested period from 10 min to 6 h.

Although a very small amount of the two materials could be found in the spleen, there was an extensive accumulation of both materials in the liver that decreased with time. Three months after injection, black matter was still found in both lungs and liver, with signs of tissue injury and remodeling, evidenced by collagen deposition fibrosis. Hence, whereas PEGylation reduced the accumulation in reticuloendothelial system organs by extending the blood circulation, this only marginally alleviated the adverse outcomes upon accumulation of GO in these organs.

Sasidharan et al. Conversely, small GO sheets accumulated mainly in the liver peaking at 5 min then progressively decreasing by min with only a limited amount found in the lungs and spleen rapidly disappearing from these organs. In contrast, large GO sheets were mostly detected in the lungs, with only a marginal decrease over the min period. A small amount of large GO was also found in the liver. Finally, when increasing the dose of injected small GO by a factor of 10, the authors reported that organ accumulation of GO clearly shifted from the liver to the lungs, suggesting congestion in the capillary bed of the lungs possibly due to the formation of agglomerates of GO sheets.

Finally, a series of investigations using radiolabeled GO sheets functionalized with dioctyltin diacetate DOTA to chelate the radiolabel were executed in the Graphene Flagship Figure 2. Single- to few-layer GO sheets lateral dimension: — nm with DOTA, thickness: 2—10 nm were found to accumulate in both liver and spleen, with a decrease of radioactivity from 1 to 24 h in the liver and an increase in the spleen.

Importantly, in both studies, a large amount of radioactivity was observed in the bladder at early time points. These results suggested that a large amount of i. One may assume that the plate-like GO sheets would need to transiently adopt a different shape e. Collectively, these studies have shed light on the biodistribution and fate of some GBMs following various administration routes.

Overall, there is evidence that various GBMs are able to cross physiological barriers, reaching secondary organs distant from the point of entry. However, due to the scarcity of the published data and lack of systematic investigations, it is still too early to reach definitive conclusions with respect to relationships between physicochemical features and the biodistribution patterns of GBMs.

Moreover, the long-term fate of GBMs at the site of accumulation is also important. It is acknowledged that the generation of such data is, however, far from trivial and requires labeled materials that can be tracked and quantitatively measured over long periods of time, even as GBMs undergo transformation or biodegradation in the body.

Hazard Assessment of Graphene-Based Materials. Nanomaterials can enter into the body through different routes, and inhalation, dermal adsorption, and ingestion are the most likely routes of unintended exposure in occupational or environmental settings. Nanomaterials may subsequently travel through the body and reach sites beyond their initial portal of entry, as discussed above.

However, at some point, the materials manifest their biological or toxicological effects at the level of specific target organs. These studies have informed us on specific material features that contribute to toxicity, for instance, particle dissolution and the release of toxic metal ions in the case of certain metal nanoparticles, or the high aspect ratio and fiber-like dimensions in the case of long and rigid carbon nanotubes.

The following sections provide an overview of the toxicological impact of GBMs on the immune system, our primary defense against foreign intrusion, as well as the pulmonary, dermal, cardiovascular, gastrointestinal, reproductive, and central nervous systems, following which we will discuss the environmental impact of GBMs. The immune system consists of complex molecular and cellular networks that protect our body from infections and other exogenous materials while maintaining tolerance to self-components.

In the development of new materials, it is fundamental to assess their impact on the immune system in order to understand if the presence of such materials can be tackled, eventually leading to their elimination, or to clarify if the persistence of the materials provokes chronic diseases.

These size-dependent responses to GO were also evidenced in vivo. Hence, large GO was able to generate inflammatory responses significantly higher than those of small GO in mice after intraperitoneal injection. In particular, endotoxin content must be controlled in any studies using immune-competent cells.

In contrast to the above-mentioned study, the effects were independent of the lateral dimensions of GO. These differences could be ascribed to differences between the cell models, i. In a recent study, Li et al. The authors also demonstrated that hGO was more prone than the other materials to trigger lung inflammation, accompanied by lipid peroxidation in alveolar macrophages.

In addition to primary macrophages, the effects of GO were studied on macrophage-like cell lines. Chen et al. Hu et al. In addition, GO possesses many surface defects that could serve as binding sites for proteins, and this could contribute to the observed differences in protein adsorption ability of GO and carbon nanotubes. In another study, protein adsorption was confirmed using experimental and theoretical approaches, and the authors proposed that protein-coated GO sheets lack the capacity for destructive membrane interactions due to the increase in the thickness of the GO sheets and reduction of the available surface area of GO, instead exposing largely hydrophilic surfaces that may lead to more benign interactions with membrane phospholipids.

The differences in biocompatibility were suggested to be due to the differential compositions of the protein corona, formed on their surfaces that determine their cell interactions and pro-inflammatory effects. PEGylation was shown in several studies to reduce the cytotoxic effects of GO on macrophages. PEGylated GO appeared to preferentially adsorb onto and partially insert into cell membranes, thereby amplifying the interactions with stimulatory surface receptors.

Clearly, not only the characteristics of the parent material GO but also the surface modification i. Macrophages belong to the front line of the innate immune defense against pathogens or foreign materials. However, alveolar macrophages are likely one of the first cell types, along with epithelial cells, to interact with GBMs, reaching the lungs after pulmonary exposure.

Studies on alveolar macrophages are scarce, but Weimann et al. Neutrophils are among the first cells to be recruited in the airways upon pulmonary exposure to GBMs and also play a key role in inflammation in many other tissues. Interestingly, a recent study has shown that when GO sheets interact with isolated human neutrophils, this triggers a dose-dependent loss of cell viability and size-dependent formation of neutrophil extracellular traps NETs.

In the latter study, the effects of GO were attributed to cholesterol oxidation in the plasma membrane, as evidenced by time-of-flight secondary ion mass spectrometry ToF-SIMS of exposed cells. In contrast to GO, there are relatively fewer studies on graphene and its effects on the immune system.

As graphene is too hydrophobic to obtain homogeneous dispersions in aqueous solutions, it is necessary to use appropriate biocompatible surfactants or coating molecules. In a recent study, Graphene Flaghsip scientists discovered that FLG obtained by solvent-free ball-milling treatment of graphite in the presence of melamine, subsequently dispersed in cell culture medium, is able to specifically kill monocytes while preserving the viability of macrophages.

One of the most biocompatible surfactants used to disperse nanomaterials is pluronic F Further treatment with strong acid generates oxidized micro graphite. Both types of micro graphite were shown to trigger a weak cytotoxicity with dose-dependent pro-inflammatory cytokine release. High-throughput technologies have revolutionized the analysis of immune cells and their complex interactions.

These findings were confirmed by genomics approaches using Jurkat T cells as representative for the adaptive immune system and THP-1 cells, a monocytic cell line representative of the innate immune system. Moreover, by using single-cell mass cytometry, multidimensional cytometry experiments in which simultaneous investigations of 15 immune cell populations with interrogation of 30 markers at the single-cell level was possible.

Following surface functionalization of the two GO with amino groups GO-NH 2 , these materials resulted more specific, affecting the production of only a few cytokines in selected cell subpopulations. Taken together, these studies confirmed that the functionalization of GO significantly affected the number of transcripts altered by graphene. The study lays the foundation for an innovative approach for multidimensional, high-throughput analysis of the effects of GBMs on immune cells Figure 4.

Overall, when comparing the results of different studies on GBMs above, and refer to Supporting Information , the toxicity of this class of materials toward macrophages, in particular, appears to be less pronounced as compared to the effects of carbon nanotubes.

For other immune-competent cells, there are only a few studies available. Furthermore, as we shall discuss in the following section, GBMs are susceptible to biodegradation, meaning that these materials are not biopersistant. Biodegradation of nanomaterials is a topic of considerable relevance both in toxicology and in nanomedicine. The very fact that some carbon-based nanomaterials such as single-walled carbon nanotubes are susceptible to degradation by immune cells sets them aside from asbestos, which is nondegradable in biological systems.

Here, we focus our discussion on the degradation of GBMs, emphasizing the role of the three fundamental material properties, i. Kotchey et al. Zhang et al. Interestingly, whereas both graphene and GO were found to reduce enzyme stability, rGO was able to preserve the catalytic activity of the enzyme, presumably by scavenging superoxide radicals, thereby protecting the enzyme from oxidation. In a recent study from the Graphene Flagship, Kurapati et al.

In this case, aqueous dispersibility of the material was found to play a crucial role in the biodegradation process. Based on these in vitro results, it is possible to suggest that inhalation of GO with the recruitment of neutrophils and macrophages may potentially lead to intra- or extracellular digestion of GO, which could mitigate the overall pulmonary impact, as previously shown for certain carbon nanotubes.

Girish et al. Confocal Raman imaging was conducted to identify the gradual development of structural disorder occurring over a period of 3 months in lung, liver, kidney, and spleen of mice exposed by i. The authors argued that graphene degradation was mainly orchestrated by macrophages in the different organs. The degradation potential of GO has been also studied using acellular oxidative systems such as the photo-Fenton reaction or sodium hypochlorite NaClO , colloquially known as bleach.

Microbial degradation is another promising way to degrade GBMs as this does not require controlled conditions such as controlled temperature and pH. Lalwani et al. Furthermore, Liu et al. Taken together, these studies suggest the potentiality of degrading GBMs released in the environment.

In conclusion, studies conducted in the past several years have clearly shown that intra- and extracellular degradation of GO can be executed by immune cells. However, more research is required on the degradation of other GBMs with defined properties using relevant in vitro and in vivo models to better understand the possible risks of long-term biopersistence of such materials and in order to make them safer-by-design.

The skin is the major barrier between the human body and the environment, and it can be considered as one of the most important exposure sites for GBMs, not least in the occupational setting. However, skin sensitization cannot be excluded in light of the propensity of GBMs to interact with proteins.

Limited toxicological data are currently available for GBMs at the skin level. Liao et al. In addition, using various in vitro assays, the results demonstrated that FLG and GOs were able to induce a significant mitochondrial dysfunction after a sustained plasma membrane damage.

Only one in vivo study has been published thus far on dermal effects of GBMs. The results showed an increased infiltration of lymphocytes and macrophages at the injected site up to 2 days postinjection decreasing gradually between days 4 and 7. Qualitative and quantitative aspects of the leukocyte infiltration suggested a cell-mediated immune response, probably initiated by GO interactions with host proteins. Overall, the currently available literature, limited to one in vivo and a few in vitro studies, is not sufficient to draw any conclusions on the hazard related to dermal exposure to GBMs.

Among the different routes of unintended exposure to nanomaterials in occupational settings, inhalation is the route of highest concern. A long history of studies on the impact of air pollution and ultrafine particles on human pulmonary health has supported the notion that nano- and micron-sized particles may cause harm to the lungs reviewed in ref This section will focus on studies investigating GBM pulmonary effects after exposure of the pulmonary system via the common routes i.

Pulmonary effects of GBMs injected intravenously will not be discussed here, as this topic has been reviewed previously by others. Roberts et al. The adverse pulmonary and systemic effects observed at early time points at the highest dose showed signs of resolution for all materials.

Despite the persistence of all three materials, neither fibrosis nor granulomatous lesions were observed. The authors highlighted that not only size but also surface reactivity and agglomeration are important to consider when studying GBMs.

Indeed, examination of pleural macrophages of exposed mice showed signs of frustrated phagocytosis after exposure to graphene platelets, whereas nanoparticulate carbon black was fully taken up by cells. Similarly, there was no fibrosis despite the obvious persistence of large amounts of graphene platelets in the airways. Importantly, there was no sign of the materials in the pleural cavity neither after 1 day nor after 6 weeks. This result thus indicated that graphene platelets were not able to translocate into the pleural space, thus preventing them from inducing granuloma on the pleural mesothelium, a hallmark of asbestos pathogenicity.

Mao et al. Histopathological analysis of the lung sections after 1 day confirmed the absence of damage after exposure to low doses, despite the material burden. In contrast, lungs exposed to the high dose of FLG showed interstitial and parenchymal damages, with a large amount of macrophages in alveoli at day 1.

The lungs exposed to a high dose of FLG recovered slowly, with damage still present after 7 days but disappearing by day 28, despite a persistent burden estimated at almost half of the initial dose. In a follow-up study, animals were exposed to similar FLG and assessed at day 90 after a single bolus exposure. Elevated levels of cytokines and chemokines were also found 90 days after exposure in the high-dose-treated animals. The authors concluded that the pulmonary persistence of materials, in part within macrophages, was the reason for the pulmonary and systemic immune responses observed at the highest dose tested.

The pulmonary effects of GNPs were also evaluated in animals exposed via inhalation, which is the gold standard method for assessing pulmonary toxicity. Inhaled materials were found in macrophages, but no signs of inflammation were noticed at any time points, regardless of the doses applied. Interestingly, inhaled materials were also found in the mediastinal lymph nodes, suggesting translocation of materials from the airways to the lymphatic system.

Oxidized graphene derivatives have also been investigated for their potential impact on the lungs. Nanoscale GO sheets lateral dimension: 10— nm, 1—2 layers were intratracheally instilled in mice, and their impact on lungs was assessed at various time points from 1 day and up to 3 months. The peak of the response was observed at 2 days, returning to levels close to, but still above, control levels by day 7.

Material-laden macrophages started to appear in lung sections by day 7 and were still present in the lungs at3 months, though a decrease in the blackness of the lungs from day 1 to day 90 suggested an ongoing clearance process. The pulmonary effects of GO sheets dispersed in water 0. In contrast, GNPs were less inflammogenic, and this was further minimized when the GNPs were well-dispersed using the block copolymer pluronic. The authors suggested that oxidation of graphene is a major contributor to its pulmonary toxicity.

This was paralleled by a pulmonary acute phase response. However, all three dose levels induced statistically significantly increased neutrophil influx at 90 days postexposure. The inflammatory response to rGO sheets was lower than or similar to the response to carbon black, whereas on day 1 and 3, the inflammatory response to GO sheets was stronger than the inflammatory response to carbon black.

However, similar genotoxic effects have been reported for some multiwalled carbon nanotubes. GBMs are produced with a range of different lateral dimensions, and it is important to investigate the role of size on pulmonary effects, not least because other carbon-based materials including carbon nanotubes clearly display a size-dependent toxicity. In contrast, Wang et al. However, in contrast to the previous study, no fibrosis was observed after 28 days despite the presence of granulomas in the lungs of animals treated with large GO.

The hydrated materials produced the highest amount of carbon radicals and induced the highest production of ROS, whereas the reduced materials induced the lowest amount of free radicals and ROS. The GBMs with the highest pro-oxidative potential hydrated GO caused more lung damage in this acute model. Finally, whereas in vivo studies are typically performed in healthy laboratory animals, susceptible models of disease should also be investigated.

Shurin et al. Interestingly, without coexposure to allergens, GO sheets did not induce any significant adverse effects. In conclusion, it appears that the extent of pulmonary impact is directly correlated to the specific physicochemical properties of the tested materials. Dimensions seem once again to be an essential driver of the biological response to GBMs. Of note, only few studies so far have reported the induction of fibrosis, a hallmark of lung damage, after pulmonary exposure to GBMs.

The lack of pulmonary fibrosis is an important difference when comparing GBMs with pathogenic multiwalled carbon nanotubes i. Over the past 20 years, there has been compelling evidence of a relationship between air pollution, inhalation of fine and ultrafine particles, their impact on the lungs, and cardiovascular diseases. Despite the established connection between pulmonary exposure and cardiovascular disease, information regarding the possible cardiovascular impact of inhalable nanomaterials remains limited.

In another study, increased expression of the acute phase gene encoding SAA1 in the liver was found after pharyngeal aspiration of graphite platelets. In addition to these studies, there are only a few studies on the interactions of GBMs with cells of the cardiovascular system. Singh et al. For comparison, reduced GO was significantly less effective in aggregating platelets in the lung vasculature.

The authors argued that variations in surface properties may be responsible for the observed differences between the two materials. On the other hand, in biodistribution studies conducted in the Graphene Flagship, no obvious acute cardiovascular or hematological adverse effects were noted upon i. Overall, the lack of consistency between published studies underlines the need to correlate biological effects with physicochemical properties and suggests that further studies on the potential impact of GBMs on the blood and cardiovascular system are needed.

The gastrointestinal GI system enables organisms to take in food, digest it to extract and absorb nutrients and essential elements, as well as expel the remaining waste as feces. There are two major sources of potential oral exposure to nanomaterials: i direct ingestion materials present in food or released from food packaging and ii indirect ingestion of inhaled materials.

Nanomaterials that enter the GI tract are immediately exposed to saliva. Thereafter, they will be transported into the stomach where they are exposed to its harsh conditions the pH of gastric acid whose main constituent is hydrochloric acid is between 1. Several factors such as digestive enzymes, pH, ionic strength, surface-active compounds, and type and amount of food intake have the potential to change the physicochemical properties of nanomaterials, which has to be taken into account in the hazard assessment of nanomaterials following the oral exposure route.

The intestinal epithelium is composed mainly of enterocytes, mucus-producing goblet cells, and so-called microfold cells M cells important for the induction of an efficient immune response. In addition to the cellular barrier, the mucus lining of the GI tract forms an important and effective biological barrier against nanoparticle uptake and translocation into the systemic circulation.

One of the most commonly accepted in vitro intestinal models in pharmaceutical and toxicological research consists of the human colon adenocarcinoma cell line, Caco This cell line can be maintained as subconfluent cultures representing pre-enterocytes. However, after 3 weeks of cultivation, the cells fully differentiate to enterocytes, undergoing intense morphological and physiological changes such as polarization, formation of microvilli structures, and changes in gene and protein expression compared to nondifferentiated cells.

Nevertheless, some recent studies have addressed the potential toxicity of GBMs using the Caco-2 cell model supporting Figure S5. Nguyen et al. In a recent study conducted in the Graphene Flagship, the uptake of GBMs was shown to be strongly dependent on the differentiation state of the cells. This suggests that the choice of in vitro models is crucial for the outcome of the study.

Ruiz et al. The results showed that GO film coated on glass slides enhanced cell attachment, growth, and proliferation of these cells. In order to further elucidate the influence of the physicochemical properties of GBMs on Caco-2 responses, Kucki et al. The main outcome of this study was that all four GOs were noncytotoxic toward nonconfluent Caco-2 cells, which are considered to be more sensitive than the differentiated cells.

Pretreatment of the materials with acid to mimic the conditions in the GI tract did not influence the outcome. In conclusion, the first explorative studies in this relatively new field have shown no or only mild acute cytotoxicity of several different GBMs on intestinal epithelial cells. However, the field is in its infancy, and aspects of long-term effects of GBMs including the influence on the microbiota remain unanswered today.

Therefore, further studies are needed to understand the potential impact of different GBMs following oral exposure. Pregnant women, fetuses, and neonates are among the most vulnerable populations and therefore warrant particular attention in regard to GBM hazard assessment.

In pregnancy, major physiological changes occur that are expected to affect particokinetics and subsequent biological effects. Likewise, developing fetuses and neonates are more susceptible to toxic effects of xenobiotics than adults due to ongoing organogenesis, physiological changes, or immaturity of the immune system. To date, it is unknown whether GBMs can reach the placental barrier or reproductive organs.

The low transfer of nanoparticles at the air—lung, skin, and intestinal barrier and the rapid clearance of GBMs from the bloodstream discussed above would argue for a low acute exposure under currently prevailing inhalation and oral exposure scenarios. However, emerging biomedical applications of GBMs and the possibility of tissue accumulation upon chronic exposure of these materials clearly suggests that close attention is needed to the potential reproductive and developmental risks of GBMs. As a consequence, research on the placental transfer of nanoparticles and the impact on reproductive and developmental systems was intensified.

Male fertility and reproduction was not affected after intravenous and intraperitoneal injection of small or large GO in mice nor by pulmonary exposure to GO. Thus, based on these observations, the toxicity of rGO should be seriously considered in progestational drawing near pregnancy females, although the rGO-exposed mice could still produce healthy offspring depending on the administered dose. The placenta forms the interface between mother and fetus and enables successful pregnancy by mediating essential functions including exchange of gases, nutrients, and waste products, hormone secretion, feto-maternal immune tolerance, and fetal protection against pathogens and xenobiotics.

Therefore, it is critical to understand placental translocation and effects of GBMs in order to estimate their embryo fetotoxic risks. However, it is currently unclear if and by which pathway s GBMs may pass the placental barrier at different stages of pregnancy.

A single study investigating transplacental transfer of I-rGO after intravenous injection in pregnant mice in late gestation measured only trace amounts of radioactivity in the placental or fetal tissues approximately 0. Another example of a maternally mediated effect was a reduced growth of the offspring when maternal mice were given GO-containing drinking water 0. It is pertinent to note that rGO has been suggested to induce a transitory decrease in the tightness of the blood—brain barrier in rats; rGO was systemically injected in the latter study, and the relatively large size average size: nm of the material was apparently not an obstacle for its entry into the brain.

Finally, in addition to direct effects of GBMs on reproductive and developmental systems, the indirect consequences of GBMs on maternal and placental tissues and the release of mediators deserves attention as the creation of a hostile environment in the womb may increase the risk for pregnancy complications and the development of diseases later in life.

Graphene holds exciting prospects in neuroscience; the unique physicochemical properties, such as the high conductivity, transparency, or flexibility, make this material an attractive candidate to engineer functional brain implants with excellent performance for neuromodulation therapies or to design scaffolds able to support the reconstruction of functional neurons and glial cells networks, also an imperative requirement for neural regeneration of central nervous system CNS injuries.

Naturally, the implementation of multifunctional neurodevices based on graphene will expose brain cells and neuronal circuits directly to this material by injection or implantation, and safety assessment of graphene and its derivatives is therefore of paramount importance. Studies conducted in the Graphene Flagship have disclosed that GBMs are able to interact with and perturb cells of the CNS in different ways, as a function of their intrinsic characteristics. Interestingly, when cells were treated with the same concentration of FLG, no reduction in cell density or viability was observed in both neuronal and glial populations, thus demonstrating that CNS cells survival in vitro seems crucially dependent on the graphene sheet dimensions as well as its chemical composition.

Passive cell properties, neuronal network organization, and overall network activity of neurons interfaced with FLG at both concentrations did not differ from control hippocampal cells. Instead, small GO flakes interfered specifically with neuronal synapses, albeit without affecting cell viability. Thus, GO nanoflakes at higher concentrations seem able to specifically downregulate synaptic activity.

Studies were also conducted to test the ability of nanosized FLG and GO to reduce exocytosis and recycling of synaptic-like microvesicles from cultured primary glial cells. FLG and GO did not affect astrocyte density, excluding a cytotoxic effect. Intriguingly, similar experiments with FLG at the same concentration and duration did not induce shedding of microvesicles in glial cell cultures.

Summarizing the results obtained thus far, one can conclude that while the lateral size of graphene flakes is critical in defining material cytotoxicity, the oxidative state also plays a role and may explain the difference between a neutral effect of FLG versus the ability of GO to perturb innate vesicular regulation mechanisms presumably via plasma membrane interactions.

The physical interaction of GBMs with the plasma membrane is strongly affected by the physicochemical properties of the material. Furthermore, and in contrast to the aforementioned studies in which cells were exposed to nano- or micron-sized flakes, studies on surface-immobilized GBMs have also been reported. Tu et al. Recent studies from the Graphene Flagship focused on surface-immobilized graphene produced by liquid phase exfoliation or ball-milling of graphite and showed that such substrates are inert neuron-interfacing materials, able to preserve the basal physiological level of neuronal activity.

In a related study, changes in membrane cholesterol were noted in hippocampal neurons grown on graphene-coated surfaces, resulting in a presynaptic potentiation of neurotransmission. In this context, the uncommon ability of surfaces decorated by immobilized graphene to support neuronal development in terms of neuronal passive properties, spontaneous synaptic activity, synaptogenesis, and short-term synaptic plasticity without precoating with adhesion-promoting peptides e.

Previous work demonstrated the biocompatibility of peptide-coated chemical vapor deposited graphene interfaces with hippocampal neurons polylysine-coated graphene or neural stem cells laminin-coated graphene. However, more studies are needed to evaluate the long-term integrity of such substrates. Furthermore, although studies on explanted neurons are informative, detailed in vivo studies on the influence of graphene on neuronal microcircuits are lacking. For a comprehensive view of the impact of GBMs on the brain, it is important to address not only effects on neurons but also effects on non-neuronal cells, i.

To better understand the molecular and cellular processes affected by the exposure to GBMs, proteomic and lipidomic analyses were conducted on primary neuron and astrocyte cultures exposed to GO and, in the case of astrocytes, to GO or FLG.

PE is one of the major components of the plasma membrane and synaptic vesicle membrane and plays important roles in vesicle fusion and fission. Interestingly, these effects were elicited only by chronic GO exposure, whereas acute exposure to FLG and GO did not cause any functional alterations in both culture systems.

Interestingly, a significant increase in astrocyte-released microvesicles was also observed in cell cultures treated with GO. To conclude, in vitro studies on primary neurons and glial cells show that, while chronic exposure to FLG or GO does not cause cell death, it has a strong impact on a number of fundamental physiological processes, thus potentially leading to toxicity when administered for prolonged amounts of time. In fact, studies performed in the Graphene Flagship have revealed a size-dependent toxicity of graphene toward neurons and glial cells.

Thus, future studies should address the possibility of functionalizing GBMs to exploit selected features while tuning properties that could potentially lead to unwanted effects. The tremendous advancement in the field of nanotechnology has been accompanied by a slower progress in the understanding of its impact on the environment.

Large-scale production, leaching out of from enriched products, accidental spills during industrial production, and poor disposal of the derived wastes might result in significant release and accumulation of GBMs in the environment. However, although the promises were fulfilled, the benefits were unfortunately counterbalanced by unexpected environmental problems, which emerged in dramatic fashion only half a century later.

Studying the effects of carbon-based nanomaterials on bacteria is essential as they are at the basis of the trophic chains in the environment, involved in many stages of the nutrient cycles, and have complex associations with other organisms. Effects of GBMs on bacteria are rather well-studied, compared to other living systems. The most commonly used laboratory model is Escherichia coli. Several studies have shown that direct contact between GBM and bacteria is responsible for the observed toxicity toward E.

GO dispersions exhibited the highest antibacterial activity, followed by rGO, graphite, and graphite oxide. On the other hand, Ruiz et al. The authors proposed that the antibacterial mechanism requires penetration of the cell membrane, suggesting that the enhanced antibacterial activity of the film with vertically aligned GO is due to an increased density of edges with an orientation that is more compatible with membrane disruption.

Thus, the properties of GBMs as well as their orientation and the degree of membrane interactions control their antibacterial effects. Recently, the ecotoxicity of GBMs was evaluated on various model and nonmodel photoautotrophs, from cyanobacteria to seed plants. These organisms are all characterized by the presence of a cell wall of different composition and ultrastructure peptidoglycans in cyanobacteria, cellulose in algae, and embryophytes , often completed by further external structures in cyanobacteria, an outer lipopolysaccharidic membrane, a capsule, and a gelatinous sheath; in many algae, a layer of exopolymeric substances.

The cell wall is a physical barrier that retards the entrance of GBMs larger than the pore size of the cell wall. In the cells of seed plants, for instance, thickness and complexity of cell wall change drastically from the pectic-rich primary wall, generally a thin, flexible, and extensible layer formed when the cell is growing, to the thick secondary wall, formed after the cell is fully grown, made of cellulose, xylan, and lignin, which strengthens and waterproofs the wall. Observations on GBM internalization carried out on cell cultures in active division can thus produce divergent results in comparison to studies based on adult tissues or organs.

Not surprisingly, internalization has been repeatedly reported in tobacco cell cultures and in a few thin-walled green algae, such as Chlorella pyrenoidosa and C. Despite their considerable ecological importance, cyanobacteria have rarely been studied in relation to ecotoxicology of GBMs.

The freshwater Microcystis aeruginosa was investigated by Tang et al. Microalgae are highly ecologically relevant as primary producers as they are also at the base of the trophic food chain in aquatic ecosystems. The toxicity of carbon-based nanomaterials in algae is mainly due to interactions with the cell surface but is also due to other factors, including shading reducing their photosynthetic activity , oxidative stress, or sequestration of nutrients.

In a recent publication from the Graphene Flagship using the aquatic benthic diatom Nitzschia palea , it has been shown that MLG is able to induce growth inhibition only in the first hours of contamination. However, the extracellular polymeric substances EPS —mainly composed of polysaccharides and proteins naturally secreted by diatoms—showed a strong interaction with graphene, leading to growth recovery after trapping of the EPS.

AGMs are a small group of polyphyletic origin, with a relatively low substrate specificity and with a strong tendency to be cosmopolitan. These species were not negatively affected by short 30 and 60 min and long 4 weeks exposures to FLG and GO. Potential oxidative effects of the same GBMs were also studied through the analysis of quantum yield of primary photochemistry in the dark-adapted state and changes of gene expression of eight genes encoding antioxidant enzymes and stress-related proteins in the lichen photobiont Trebouxia gelatinosa.

These studies suggest a negligible effect of GBMs on AGMs which likely can withstand the interaction with these materials thanks to their constitutive adaptation to extreme environments and the avoidance of internalization of GBMs as a result in Trebouxia of a thick cell wall.

As primary producers, seed plants are essential base components of all terrestrial ecosystems. Under the assumption that aero-dispersed GBMs will eventually settle over the vegetation as wet or dry depositions and thus will reach the soil, seed plants are considered as potent media for the transfer of absorbed nanomaterials to the biota through the food chain. For this reason, the effects of GBMs on seed plants have been studied at different growth stages, from seed to seedling, more rarely in the adult plant, but often starting from cell cultures.

So far, widely variable effects have been reported, possibly owing to different experimental conditions i. In 2 week old seedlings of A. Hence, although methodological problems cannot be ruled out due to the low number of samples, germination inhibition has been reported for wheat Triticum aestivum and broad bean Vicia faba when exposed to graphene and GO.

In wheat, GO inhibited the germination of seeds at high concentrations and was observed to accumulate in the root, with a limited translocation to stem and leaves, inducing oxidative stress. Indeed, carbon-based nanomaterials may have beneficial effects in plants, although the mechanisms remain poorly understood. For example, the absorption of GO by the roots in Vicia faba was found to have both beneficial and toxic effects depending on the concentration.

In spite of their protective cell walls, harmful effects of carbon-based nanomaterials have also been reported in adult seed plants reviewed in ref For instance, the leaves of cabbage, spinach, and tomato exhibited a decrease in size after in vivo exposure to GO and a decrease in number due to oxidative-stress-mediated cell death by necrosis. Aero-dispersed GBMs could interfere with a particularly delicate phase of seed plant life, i. This process is fundamental for the reproduction of almost all seed plants, but it is also important for humankind as the yield of crop species, largely consisting in seed and fruits, relies on this very important process.

The interaction between GBMs and pollen grains might occur directly in the air anemophilous pollen or over the stigmatic surfaces of the flowers all pollen types. Ratiometric pH indicator studies revealed that GO affects intracellular pH homeostasis. Further experiments on C. For terrestrial effects, most studies are carried out with worms, especially the nematode Caenorhabditis elegans , a model system that is amenable to mechanistic studies. The same authors suggested that mir may provide a protective mechanism against toxicity of GO by suppressing the function of the SMKDAF signaling in nematodes.

There are few studies on the response of invertebrates to GBMs, especially with benthic habitat. Artemia salina exposed to GO exhibited no acute toxicity even when GO aggregated in the intestine. Interestingly, the presence of humic acid in the medium increased its colloidal stability in some cases and caused an increase in the toxicity of GO to microcrustaceans growth rate and to C.

The most studied vertebrates in ecotoxicology are aquatic juvenile fishes and amphibian larvae. Among fishes, the zebrafish Danio rerio model is well-represented. As pelagic vertebrates, they may show resistance to carbon-based nanomaterials from the embryonic stage despite the widespread biodistribution observed within the body.

In adult zebrafish, GO exposure caused an increase in the number of apoptotic and necrotic gill cells, but genotoxicity was not observed. Studies conducted on amphibian larvae Ambystoma mexicanum have shown that no mortality or growth inhibition nor any genotoxicity could be observed, despite a high intake of carbon-based nanomaterials in the digestive tract.

Notably, whatever the amphibian organisms, intestinal absorption of carbon-based nanomaterials seems to be limited after oral administration and the materials are then rapidly excreted. Conventional ecotoxicological approaches using single species are very informative and are needed to evaluate toxicity at the organism level to understand the potential toxicity of GBMs.

However, more sophisticated systems are required to get closer to their actual environmental risk assessment. In particular, the notions of biotransformation, bioaccumulation, and biomagnification are generally ignored though they are extremely relevant. Therefore, complex exposure systems with which to evaluate the impact of nanomaterials, particularly through the reconstitution of experimental trophic chains using micro- or mesocosms as experimental tools, are gaining traction.

These complex systems involving interspecies interactions e. It is fundamental to understand how nanomaterials in general, and GBMs, in particular, interact with other pollutants co-occurring in the environment in terms of adsorption, transport, bioavailability, and the subsequent effects upon pollutant toxicity and biodegradability. For instance, GO can apparently amplify phytotoxicity of arsenic in wheat, Triticum aestivum , and of cadmium in the freshwater cyanobacterium, Microcystis aeruginosa.

The main limitation of this research field is the enormous number and possible combinations of substances that might deserve to be tested. One additional aspect concerns the assessment of degradation of GBMs released into the environment. There are only a few studies on the capacity of primary decomposers i. Their metabolic versatility allows them to use organic materials dispersed in the environment as sources of reduced carbon thanks to extracellular degradation processes.

In addition, we believe that further studies are needed to understand whether GBMs may elicit toxicity amplification of other environmental pollutants. However, the data on GBMs provided by using numerous vertebrate and nonvertebrate organisms could be used to inform in silico toxicity models and the development of adverse outcome pathways AOPs. The AOP concept, first presented as a conceptual framework to support ecotoxicology research and risk assessment, has attracted a great deal of attention in recent years.

The overall objective is to support regulatory decision making, such as hazard identification and risk assessment, by delineating the key events leading to adverse outcomes. Nonethelesss, the rich source of hazard data emerging for GBMs could be profitably exploited in the framework of environmental risk assessment and help in the understanding of the contribution of GBMs in the adverse effects observed in humans and wildlife at larger organizational scale.

The main human exposure of concern at present is pulmonary exposure in workers during the production and handling of GBMs, even though dermal or oral exposure may also occur. Five studies related to occupational exposure of GBMs are available. Thus, some results can be applied for GBMs at laboratory scale production volumes less than grams , and some at industrial scale production. Thus, the variation in exposure levels is not well-known. However, all the studies in this sample showed that exposure levels were very low if emission controls were properly applied and good working practices were followed.

They reported the concentrations measured during product harvesting and process tank cleaning. Product harvesting was made without using exposure controls at P1 or by using a blower located downstream and butterfly valves incorporated on the upstream of the collection vessels at P2. GBM release was detected during product harvesting where a collection container was removed from discharger and during process tank cleaning.

Bengtson et al. Only reactor opening and dry wiping the reactor increased the concentration up to around 15 cm —3 for a few seconds. Samples contained no particles according to TEM analysis. The authors also could not exclude that the concentration increases during opening of the reactor and dry wiping were due to disturbance of tubing and flows to the condensation particle counter.

In the industrial site, they could not detect an increase in concentrations measured next to the hatch due to high background particle concentration. The highest release potential was expected to be during sonication, but the process was enclosed and GBMs were not detected in the air. The transfer of the GBMs to the PET sheets and the cutting of the sheets did not result in any detectable increase in concentrations. GBM-like structures were found from particle samples collected from air of both production areas.

However, the authors did not analyze the composition of the airborne particles. Nonetheless, the study suggested, overall, that significant exposure of workers to GBMs is unlikely. However, the results also indicated that workers who are directly involved in specific tasks e. Information on toxicity, biodistribution, fate, and exposure are essential to understand the hazard of introducing GBMs in the environment, but they can also be useful to assess the environmental sustainability of producing and using GBMs.

The life cycle assessment LCA methodology provides a framework for such an assessment by combining models of fabrication processes and their associated supply chains with models of GBM interactions in the environment. Thus far, LCA studies have focused on identifying the main sources of environmental impacts for graphene, , graphite nanoplatelets, and reduced GO.

For instance, studies performed in the frame of the MISTRA Environmental Nanosafety project have highlighted differences for graphene produced by ultrasonication or chemical reduction in terms of energy and water use as well as human and ecotoxicity Figure 9. The results of these studies vary significantly because of the range of considered GBMs, fabrication methods, and scales of production. However, they all show that energy consumption and chemicals used e.

Although these recent LCA studies offer some insights into the environmental sustainability of GBMs, key issues remain to be addressed. The main concern originates from the sources of data for these studies as they are based on scientific papers, patents, and prospective models which instigate model uncertainties that are still difficult to evaluate.

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