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How to Change the Chemical Composition of Sea Spray Aerosol via Marine Bloom
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How to Change the Chemical Composition of Sea Spray Aerosol via Marine Bloom Fenfen Zhang1 and Jinzhou Du1,* Sea spray aerosol (SSA) is the most important medium for material and energy exchange between the ocean and the atmosphere, which strongly influences global climate change. In this issue of Chem, Grassian and colleagues depict the chemical composition and the hygroscopic variation of individual nascent SSA particles in ocean biological processes. Sea spray aerosol (SSA) is one of the most widely distributed natural aerosols. It accounts for up to 40%–60% of the aerosols in Earth’s atmosphere, representing the largest aerosol source.1 It is primarily formed at the air-sea interface upon the rupturing of bubbles entrained by wave breaking and consists of a mixture of distinct particle populations of inorganic salts, particulate biological components (e.g., whole bacteria and viruses), and organic matter (OM) from individual particles, as well as from seawater.1–3 In general, the granular size of individual SSA particles can be strongly affected by the OM fraction (the organic-to-inorganic ratio). Most of the OM in supermicron SSA contains mostly water-soluble species, i.e., oxygen-rich species such as short-chain fatty acids and free saccharides, with increased particle hygroscopicity. In contrast, in submicron SSA, the OM contains a relatively water-insoluble fraction, i.e., aliphatic-rich species such as long-chain fatty acids and polysaccharides, with decreased particle hygroscopicity.3,4 Moreover, supermicron and submicron SSAs have different effects on climate. Supermicron SSA affects the exchange processes of momentum and heat via the air-sea interface, which enhances the development of tropical cyclones.
610
However, submicron SSA contributes to 5%–90% of the cloud condensation nuclei (CCNs) in the marine boundary layer (MBL), altering cloud reflectivity, lifetime, and precipitation processes.5 Thus, submicron SSA plays a great role in climate change. Previous studies on marine environments have shown changes in atmospheric properties in regions where biological processes occur through changes in the chemical composition of the MBL.1,3 Although submicron SSA particles are enriched with fatty acids and other aliphatic-rich organic species, which is expected to result in reduced particle hygroscopicity,1,4 the concentrations of CCNs throughout induced microbial blooms (which lead to an enrichment of aliphatic-rich species in submicron SSA) have been observed to change by less than 3%.6 However, measurements of ice nucleation exhibited 50-fold more ice-nucleating particles (INPs) during the peaks of multiple microbial blooms than before the blooms, which could be attributed to changes in SSA chemical composition (Figure 1).1,7,8 Moreover, the SSA particles had large heterogeneous sizes with different hygroscopicities. Therefore, the properties of the particle-size spectrum of the SSA and particle-particle interaction (i.e., aggre-
Chem 2, 610–620, May 11, 2017 ª 2017 Elsevier Inc.
gation) can have a substantial impact on the atmospheric model as a result of the changes in SSA hygroscopicity. Recent studies have shown that bacteria-driven alterations in the seawater composition lead to changes in both the external and internal mixing state of SSA, as well as particle hygroscopicity.9 However, the chemical composition and associated properties of fresh SSA, especially for individual SSA particles with different granular sizes, are not well characterized to date.3,8 In this issue of Chem,8 integrating single-particle Raman spectroscopy with quantitative analysis of bulk particle aerosols, Grassian and colleagues report the changing major classes of OM in size-dependent SSA across two consecutive oceanic phytoplankton blooms including autotrophic and heterotrophic processes. They specifically describe the interparticle variability of SSA and the influence on hygroscopic growth as a function of ocean biological dynamics. During the first phytoplankton bloom, the submicron SSA decreased its hygroscopicity in relation to increasing long-chain fatty acid (aliphatic-rich) fractions. However, after the second heterotrophic bacterial bloom, the submicron SSA increased its hygroscopicity by decreasing the fraction of long-chain fatty acids and increasing the more hygroscopic polysaccharides. In contrast, the supermicron SSA increased its hygroscopicity by decreasing the polysaccharide fraction and increasing the oxygen-rich (short-chain fatty acid and free saccharide) fractions. The authors provide details of the variations in the major classes of OM and hygroscopicity in individual SSA particles in the same size
1State
Key Laboratory of Estuarine and Coastal Research, East China Normal University, 3663 North Zhongshan Road, 200062 Shanghai, China *Correspondence: [email protected] http://dx.doi.org/10.1016/j.chempr.2017.04.019
Figure 1. Diagram of the Pathways for Individual SSA Particles and Their Linkage with Climate-Relevant Properties via Biological Processes in Seawater The lower section shows the changing major classes of OM in size-dependent SSA across two consecutive oceanic phytoplankton blooms including autotrophic and heterotrophic processes. The upper section shows the fundamental chemical properties that govern a primary individual SSA particle’s ability to interact with solar radiation directly and indirectly (through the formation of CCNs and INPs) and undergo secondary chemical transformations. Adapted from Cochran et al.1,8
range. They highlight that the average hygroscopicity of individual particles changed with the chemical composition of the particle types. Their results link the changing specific major classes of OM within SSA particles to ocean biological processes (Figure 1). Studying individual SSA particles through the analysis of major classes of OM helps us to further reveal particle-to-particle variability within the SSA population, which can critically influence the cloud-forming potential of SSA.10 Such work can provide helpful
information for better understanding the SSA climate properties by using the key parameter of hygroscopicity for both bulk SSA and individual SSA particles. To improve the understanding of ocean-SSA-climate interactions, chemists, oceanographers, meteorologists, and physical scientists need to collaborate to develop and/or use unique ocean-atmosphere facilities, new methodologies, and modeling to elucidate the key parameter of hygroscopicity for both bulk SSA and individual SSA particles for various ocean processes.
1. Cochran, R.E., Ryder, O.S., Grassian, V.H., and Prather, K.A. (2017). Acc. Chem. Res. 50, 599–604. 2. Prather, K.A., Bertram, T.H., Grassian, V.H., Deane, G.B., Stokes, M.D., Demott, P.J., Aluwihare, L.I., Palenik, B.P., Azam, F., Seinfeld, J.H., et al. (2013). Proc. Natl. Acad. Sci. USA 110, 7550–7555. 3. Quinn, P.K., Collins, D.B., Grassian, V.H., Prather, K.A., and Bates, T.S. (2015). Chem. Rev. 115, 4383–4399. 4. Wang, X., Sultana, C.M., Trueblood, J., Hill, T.C.J., Malfatti, F., Lee, C., Laskina, O., Moore, K.A., Beall, C.M., McCluskey, C.S., et al. (2015). ACS Cent. Sci. 1, 124–131. 5. Clarke, A.D., Owens, S.R., and Zhou, J.C. (2006). J. Geophys. Res. Atmos. 111, D06202.
Chem 2, 610–620, May 11, 2017
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6. Collins, D.B., Bertram, T.H., Sultana, C.M., Lee, C., Axson, J.L., and Prather, K.A. (2016). Geophys. Res. Lett. 43, 9975–9983. 7. DeMott, P.J., Hill, T.C.J., McCluskey, C.S., Prather, K.A., Collins, D.B., Sullivan, R.C., Ruppel, M.J., Mason, R.H., Irish, V.E., Lee, T., et al. (2016). Proc. Natl. Acad. Sci. USA 113, 5797–5803.
8. Cochran, R.E., Laskina, O., Trueblood, J.V., Estillore, A.D., Morris, H.S., Jayarathne, T., Sultana, C.M., Lee, C., Lin, P., Laskin, J., et al. (2017). Chem 2, this issue, 655–667. 9. Collins, D.B., Zhao, D.F., Ruppel, M.J., Laskina, O., Grandquist, J.R., Modini, R.L., Stokes, M.D., Russell, L.M., Bertram, T.H.,
Grassian, V.H., et al. (2014). Atmos. Meas. Tech. 7, 3667–3683. 10. Ault, A.P., Moffet, R.C., Baltrusaitis, J., Collins, D.B., Ruppel, M.J., Cuadra-Rodriguez, L.A., Zhao, D., Guasco, T.L., Ebben, C.J., Geiger, F.M., et al. (2013). Environ. Sci. Technol. 47, 5603–5612.
Preview
Low-Cost Synthesis of Hole Transporting Materials for Efficient Perovskite Solar Cells Valentina Mirruzzo1 and Aldo Di Carlo1,* Given their high efficiency and easy fabrication procedures, perovskite solar cells are one of the most promising third-generation photovoltaic technologies. In this issue of Chem, Sun and colleagues identify a smart synthetic strategy for achieving efficient and low-cost hole transporting materials, a step forward for the success of this technology.
Nowadays, with the continuously increasing energy demand and the effects of global warming on climate change, the transition to environmentally sustainable energy is no longer deferrable. Energy can be defined as renewable if it is derived from natural process (e.g., sunlight and wind) that are replenished at a higher rate than that consumed. Solar, wind, geothermal, hydropower, bioenergy, and ocean power are sources of renewable energy.1 Among all of the renewable energy technologies, photovoltaic (PV) technology, which directly converts solar energy into electricity, is considered the most promising. In fact, even though solar power is reduced by atmospheric absorption and scattering, the earth benefits from the sun’s great power supply. For these reasons, it is not surprising that solar PV technology is the fastest-growing energy technology, and the PV market has increased dramatically during recent decades. As discussed by Han and collabo-
612
rators,2 the vast majority of PV plants are dominated by silicon solar modules, and although it has decreased dramatically, the cost of electricity produced by PV technology is still higher than that of electricity supplied by conventional fossil fuels. Efforts to lower the cost have resulted in the development of many emerging solar technologies based on cheap materials and low-cost processes, including thin-film silicon solar cells and organic PV and dye-sensitized solar cells. Recently, perovskite solar cells (PSCs) have attracted wide attention because of their easy solution-processable fabrication and high performance and have reached a certified power conversion efficiency (PCE) of 22.1%. In order to make PSCs appealing for the market, it is of paramount importance to move toward materials that guarantee both high efficiency and stable performance. Among all of the PSC components, hole transporting material (HTM) plays a significant role in that it is responsible for the extrac-
Chem 2, 610–620, May 11, 2017 ª 2017 Elsevier Inc.
tion of photogenerated holes from the perovskite layer and their transport toward the electrode.3 For this purpose, an optimal HTM should have energy levels well matched with those of the absorber material, high thermal and chemical stability, good solubility for solution-processed devices (e.g., by spin-coating deposition), and nonplanar 3D structure.3,4 In fact, the HTM architecture is important for reducing electronic coupling and charge recombination and also forming a compact film over the absorber layer. One of the key methods for achieving such properties is the utilization of a spiro carbon in the central core of the HTM chemical structure, and 0 0 0 0 N2,N2,N2 ,N2 ,N,7N,7N7 ,N7 -octakis(40 methoxyphenyl)-9,9 -spirobi[9H-fluorene]2,20 ,7,70 -tetramine (spiro-OMeTAD), where two fluorene units are orthogonally interconnected, is still the most widely and successful used HTM. However, the large-scale production of spiro-OMeTAD still remains prohibitive because it involves several synthetic steps with consequent purification stages, has low yields (total yield less than 30%), and uses expensive materials such as Pd catalyst and phenylboronic acid.5 For this reason, the use of this HTM negatively affects the entire PSC cost balance, limiting the commercialization of this technology. Moreover, the stability of spiro-OMeTAD to
1Center
for Hybrid and Organic Solar Energy, University of Rome Tor Vergata, via del Politecnico 1, 00133 Rome, Italy *Correspondence: [email protected] http://dx.doi.org/10.1016/j.chempr.2017.04.005
How to Change the Chemical Composition of Sea Spray Aerosol via Marine Bloom Fenfen Zhang1 and Jinzhou Du1,* Sea spray aerosol (SSA) is the most important medium for material and energy exchange between the ocean and the atmosphere, which strongly influences global climate change. In this issue of Chem, Grassian and colleagues depict the chemical composition and the hygroscopic variation of individual nascent SSA particles in ocean biological processes. Sea spray aerosol (SSA) is one of the most widely distributed natural aerosols. It accounts for up to 40%–60% of the aerosols in Earth’s atmosphere, representing the largest aerosol source.1 It is primarily formed at the air-sea interface upon the rupturing of bubbles entrained by wave breaking and consists of a mixture of distinct particle populations of inorganic salts, particulate biological components (e.g., whole bacteria and viruses), and organic matter (OM) from individual particles, as well as from seawater.1–3 In general, the granular size of individual SSA particles can be strongly affected by the OM fraction (the organic-to-inorganic ratio). Most of the OM in supermicron SSA contains mostly water-soluble species, i.e., oxygen-rich species such as short-chain fatty acids and free saccharides, with increased particle hygroscopicity. In contrast, in submicron SSA, the OM contains a relatively water-insoluble fraction, i.e., aliphatic-rich species such as long-chain fatty acids and polysaccharides, with decreased particle hygroscopicity.3,4 Moreover, supermicron and submicron SSAs have different effects on climate. Supermicron SSA affects the exchange processes of momentum and heat via the air-sea interface, which enhances the development of tropical cyclones.
610
However, submicron SSA contributes to 5%–90% of the cloud condensation nuclei (CCNs) in the marine boundary layer (MBL), altering cloud reflectivity, lifetime, and precipitation processes.5 Thus, submicron SSA plays a great role in climate change. Previous studies on marine environments have shown changes in atmospheric properties in regions where biological processes occur through changes in the chemical composition of the MBL.1,3 Although submicron SSA particles are enriched with fatty acids and other aliphatic-rich organic species, which is expected to result in reduced particle hygroscopicity,1,4 the concentrations of CCNs throughout induced microbial blooms (which lead to an enrichment of aliphatic-rich species in submicron SSA) have been observed to change by less than 3%.6 However, measurements of ice nucleation exhibited 50-fold more ice-nucleating particles (INPs) during the peaks of multiple microbial blooms than before the blooms, which could be attributed to changes in SSA chemical composition (Figure 1).1,7,8 Moreover, the SSA particles had large heterogeneous sizes with different hygroscopicities. Therefore, the properties of the particle-size spectrum of the SSA and particle-particle interaction (i.e., aggre-
Chem 2, 610–620, May 11, 2017 ª 2017 Elsevier Inc.
gation) can have a substantial impact on the atmospheric model as a result of the changes in SSA hygroscopicity. Recent studies have shown that bacteria-driven alterations in the seawater composition lead to changes in both the external and internal mixing state of SSA, as well as particle hygroscopicity.9 However, the chemical composition and associated properties of fresh SSA, especially for individual SSA particles with different granular sizes, are not well characterized to date.3,8 In this issue of Chem,8 integrating single-particle Raman spectroscopy with quantitative analysis of bulk particle aerosols, Grassian and colleagues report the changing major classes of OM in size-dependent SSA across two consecutive oceanic phytoplankton blooms including autotrophic and heterotrophic processes. They specifically describe the interparticle variability of SSA and the influence on hygroscopic growth as a function of ocean biological dynamics. During the first phytoplankton bloom, the submicron SSA decreased its hygroscopicity in relation to increasing long-chain fatty acid (aliphatic-rich) fractions. However, after the second heterotrophic bacterial bloom, the submicron SSA increased its hygroscopicity by decreasing the fraction of long-chain fatty acids and increasing the more hygroscopic polysaccharides. In contrast, the supermicron SSA increased its hygroscopicity by decreasing the polysaccharide fraction and increasing the oxygen-rich (short-chain fatty acid and free saccharide) fractions. The authors provide details of the variations in the major classes of OM and hygroscopicity in individual SSA particles in the same size
1State
Key Laboratory of Estuarine and Coastal Research, East China Normal University, 3663 North Zhongshan Road, 200062 Shanghai, China *Correspondence: [email protected] http://dx.doi.org/10.1016/j.chempr.2017.04.019
Figure 1. Diagram of the Pathways for Individual SSA Particles and Their Linkage with Climate-Relevant Properties via Biological Processes in Seawater The lower section shows the changing major classes of OM in size-dependent SSA across two consecutive oceanic phytoplankton blooms including autotrophic and heterotrophic processes. The upper section shows the fundamental chemical properties that govern a primary individual SSA particle’s ability to interact with solar radiation directly and indirectly (through the formation of CCNs and INPs) and undergo secondary chemical transformations. Adapted from Cochran et al.1,8
range. They highlight that the average hygroscopicity of individual particles changed with the chemical composition of the particle types. Their results link the changing specific major classes of OM within SSA particles to ocean biological processes (Figure 1). Studying individual SSA particles through the analysis of major classes of OM helps us to further reveal particle-to-particle variability within the SSA population, which can critically influence the cloud-forming potential of SSA.10 Such work can provide helpful
information for better understanding the SSA climate properties by using the key parameter of hygroscopicity for both bulk SSA and individual SSA particles. To improve the understanding of ocean-SSA-climate interactions, chemists, oceanographers, meteorologists, and physical scientists need to collaborate to develop and/or use unique ocean-atmosphere facilities, new methodologies, and modeling to elucidate the key parameter of hygroscopicity for both bulk SSA and individual SSA particles for various ocean processes.
1. Cochran, R.E., Ryder, O.S., Grassian, V.H., and Prather, K.A. (2017). Acc. Chem. Res. 50, 599–604. 2. Prather, K.A., Bertram, T.H., Grassian, V.H., Deane, G.B., Stokes, M.D., Demott, P.J., Aluwihare, L.I., Palenik, B.P., Azam, F., Seinfeld, J.H., et al. (2013). Proc. Natl. Acad. Sci. USA 110, 7550–7555. 3. Quinn, P.K., Collins, D.B., Grassian, V.H., Prather, K.A., and Bates, T.S. (2015). Chem. Rev. 115, 4383–4399. 4. Wang, X., Sultana, C.M., Trueblood, J., Hill, T.C.J., Malfatti, F., Lee, C., Laskina, O., Moore, K.A., Beall, C.M., McCluskey, C.S., et al. (2015). ACS Cent. Sci. 1, 124–131. 5. Clarke, A.D., Owens, S.R., and Zhou, J.C. (2006). J. Geophys. Res. Atmos. 111, D06202.
Chem 2, 610–620, May 11, 2017
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6. Collins, D.B., Bertram, T.H., Sultana, C.M., Lee, C., Axson, J.L., and Prather, K.A. (2016). Geophys. Res. Lett. 43, 9975–9983. 7. DeMott, P.J., Hill, T.C.J., McCluskey, C.S., Prather, K.A., Collins, D.B., Sullivan, R.C., Ruppel, M.J., Mason, R.H., Irish, V.E., Lee, T., et al. (2016). Proc. Natl. Acad. Sci. USA 113, 5797–5803.
8. Cochran, R.E., Laskina, O., Trueblood, J.V., Estillore, A.D., Morris, H.S., Jayarathne, T., Sultana, C.M., Lee, C., Lin, P., Laskin, J., et al. (2017). Chem 2, this issue, 655–667. 9. Collins, D.B., Zhao, D.F., Ruppel, M.J., Laskina, O., Grandquist, J.R., Modini, R.L., Stokes, M.D., Russell, L.M., Bertram, T.H.,
Grassian, V.H., et al. (2014). Atmos. Meas. Tech. 7, 3667–3683. 10. Ault, A.P., Moffet, R.C., Baltrusaitis, J., Collins, D.B., Ruppel, M.J., Cuadra-Rodriguez, L.A., Zhao, D., Guasco, T.L., Ebben, C.J., Geiger, F.M., et al. (2013). Environ. Sci. Technol. 47, 5603–5612.
Preview
Low-Cost Synthesis of Hole Transporting Materials for Efficient Perovskite Solar Cells Valentina Mirruzzo1 and Aldo Di Carlo1,* Given their high efficiency and easy fabrication procedures, perovskite solar cells are one of the most promising third-generation photovoltaic technologies. In this issue of Chem, Sun and colleagues identify a smart synthetic strategy for achieving efficient and low-cost hole transporting materials, a step forward for the success of this technology.
Nowadays, with the continuously increasing energy demand and the effects of global warming on climate change, the transition to environmentally sustainable energy is no longer deferrable. Energy can be defined as renewable if it is derived from natural process (e.g., sunlight and wind) that are replenished at a higher rate than that consumed. Solar, wind, geothermal, hydropower, bioenergy, and ocean power are sources of renewable energy.1 Among all of the renewable energy technologies, photovoltaic (PV) technology, which directly converts solar energy into electricity, is considered the most promising. In fact, even though solar power is reduced by atmospheric absorption and scattering, the earth benefits from the sun’s great power supply. For these reasons, it is not surprising that solar PV technology is the fastest-growing energy technology, and the PV market has increased dramatically during recent decades. As discussed by Han and collabo-
612
rators,2 the vast majority of PV plants are dominated by silicon solar modules, and although it has decreased dramatically, the cost of electricity produced by PV technology is still higher than that of electricity supplied by conventional fossil fuels. Efforts to lower the cost have resulted in the development of many emerging solar technologies based on cheap materials and low-cost processes, including thin-film silicon solar cells and organic PV and dye-sensitized solar cells. Recently, perovskite solar cells (PSCs) have attracted wide attention because of their easy solution-processable fabrication and high performance and have reached a certified power conversion efficiency (PCE) of 22.1%. In order to make PSCs appealing for the market, it is of paramount importance to move toward materials that guarantee both high efficiency and stable performance. Among all of the PSC components, hole transporting material (HTM) plays a significant role in that it is responsible for the extrac-
Chem 2, 610–620, May 11, 2017 ª 2017 Elsevier Inc.
tion of photogenerated holes from the perovskite layer and their transport toward the electrode.3 For this purpose, an optimal HTM should have energy levels well matched with those of the absorber material, high thermal and chemical stability, good solubility for solution-processed devices (e.g., by spin-coating deposition), and nonplanar 3D structure.3,4 In fact, the HTM architecture is important for reducing electronic coupling and charge recombination and also forming a compact film over the absorber layer. One of the key methods for achieving such properties is the utilization of a spiro carbon in the central core of the HTM chemical structure, and 0 0 0 0 N2,N2,N2 ,N2 ,N,7N,7N7 ,N7 -octakis(40 methoxyphenyl)-9,9 -spirobi[9H-fluorene]2,20 ,7,70 -tetramine (spiro-OMeTAD), where two fluorene units are orthogonally interconnected, is still the most widely and successful used HTM. However, the large-scale production of spiro-OMeTAD still remains prohibitive because it involves several synthetic steps with consequent purification stages, has low yields (total yield less than 30%), and uses expensive materials such as Pd catalyst and phenylboronic acid.5 For this reason, the use of this HTM negatively affects the entire PSC cost balance, limiting the commercialization of this technology. Moreover, the stability of spiro-OMeTAD to
1Center
for Hybrid and Organic Solar Energy, University of Rome Tor Vergata, via del Politecnico 1, 00133 Rome, Italy *Correspondence: [email protected] http://dx.doi.org/10.1016/j.chempr.2017.04.005