Direct radiative effects of airborne microplastics.

Microplastics are now recognized as widespread contaminants in the atmosphere, where, due to their small size and low density, they can be transported with winds around the Earth1-25. Atmospheric aerosols, such as mineral dust and other types of airborne particulate matter, influence Earth's climate by absorbing and scattering radiation (direct radiative effects) and their impacts are commonly quantified with the effective radiative forcing (ERF) metric26. However, the radiative effects of airborne microplastics and associated implications for global climate are unknown. Here we present calculations of the optical properties and direct radiative effects of airborne microplastics (excluding aerosol-cloud interactions). The ERF of airborne microplastics is computed to be 0.044 ± 0.399 milliwatts per square metre in the present-day atmosphere assuming a uniform surface concentration of 1 microplastic particle per cubic metre and a vertical distribution up to 10 kilometres altitude. However, there are large uncertainties in the geographical and vertical distribution of microplastics. Assuming that they are confined to the boundary layer, shortwave effects dominate and the microplastic ERF is approximately -0.746 ± 0.553 milliwatts per square metre. Compared with the total ERF due to aerosol-radiation interactions27 (-0.71 to -0.14 watts per square metre), the microplastic ERF is small. However, plastic production has increased rapidly over the past 70 years28; without serious attempts to overhaul plastic production and waste-management practices, the abundance and ERF of airborne microplastics will continue to increase.

Comparison of dynamic corrections to the quasistatic polarizability and optical properties of small spheroidal particles.

The optical properties of small spheroidal metallic nanoparticles can be simply studied within the quasistatic/electrostatic approximation, but this is limited to particles much smaller than the wavelength. A number of approaches have been proposed to extend the range of validity of this simple approximation to a range of sizes more relevant to applications in plasmonics, where resonances play a key role. The most common approach, called the modified long-wavelength approximation, is based on physical considerations of the dynamic depolarization field inside the spheroid, but alternative empirical expressions have also been proposed, presenting better accuracy. Recently, an exact Taylor expansion of the full electromagnetic solution has been derived [Majic et al., Phys. Rev. A 99, 013853 (2019)], which should arguably provide the best approximation for a given order. We here compare the merits of these approximations to predict orientation-averaged extinction/scattering/absorption spectra of metallic spheroidal nanoparticles. The Taylor expansion is shown to provide more accurate predictions over a wider range of parameters (aspect ratio and prolate/oblate shape). It also allows us to consider quadrupole and octupole resonances. This simple approximation can therefore be used for small and intermediate-size nanoparticles in situations where computing the full electromagnetic solution is not practical.

Quantitative theory of integrating sphere throughput: comparison with experiments.

We present a rigorous approach for measuring the throughput of an integrating sphere, from which the so-called sphere multiplier M can be derived. The critical ingredients of this approach are: (i) the transmitted power is measured at the base of an integrating port to avoid non-ideal port effects associated with reflections on the port wall; (ii) to implement this last point, optical fibers are used for light collection, providing a well-defined collection area and numerical aperture; (iii) the angular-dependent fiber throughput and detector sensitivity are determined experimentally and accounted for. We demonstrate in particular that a more realistic theory, accounting for the propagation of skew rays through the fiber, is needed to quantitatively model the fiber effect on the measured sphere throughput. We show experimentally that failure to fulfill these three points produces erroneous results, by as much as 50%. With an accurate experimentally derived sphere multiplier, agreement with theory is then obtained only if realistic ports (with non-zero reflectivity) are assumed. This provides experimental evidence for recent theoretical predictions of the importance of realistic ports [Tang et al., Appl. Opt.57, 1581 (2018)APOPAI0003-693510.1364/AO.57.001581]. Using the same experimental techniques, we also present clear experimental proof of two other predictions from that study: that the angular distribution exiting the port is strongly altered and that the overall port transmittivity is drastically reduced for high aspect ratio ports. This work will provide a solid basis for future quantitative measurements of absolute throughput and for further developments of the theory of integrating spheres.

Anion-regulated binding selectivity of Cr(III) in collagen.

We present a mechanism for the selectivity of covalent/electrostatic binding of the Cr(III) ion to collagen, mediated by the kosmotropicity of the anions. Although a change in the long-range ordered structure of collagen is observed after covalent binding (Cr(III)-OOC) in the presence of SO4 2- at pH 4.5, the νsym (COO- ) band remains intense, suggesting a relatively lower propensity for the Cr(III) to bind covalently instead of electrostatically through Cr(H2 O)6 3+ . Replacing SO4 2- with Cl- reduces the kosmotropic effect which further favors the electrostatic binding of Cr(III) to collagen. Our findings allow a greater understanding of mechanism-specific metal binding in the collagen molecule. We also report for the first time, surface-enhanced Raman spectroscopy to analyze binding mechanisms in collagen, suggesting a novel way to study chemical modifications in collagen-based biomaterials.

Numerically stable formulation of Mie theory for an emitter close to a sphere.

Numerical implementations of Mie theory make extensive use of spherical Bessel functions. These functions are, however, known to overflow/underflow (grow too large/small for floating point precision) for orders much larger than the argument. This is not a problem in applications such as plane wave excitation, as the Mie series converge before these numerical problems arise. However, for an emitter close to the surface of a sphere, the scattered field in the vicinity of the sphere is expressed as slowly converging series, with multipoles up to order 1000 required in some cases. These series may be used to calculate experimentally relevant quantities such as the decay rate of an emitter near a sphere. In these cases, overflow/underflow prevents any calculation in double precision using Mie theory, and alternatives are either computationally intensive (e.g., arbitrary precision calculations) or not accurate enough (e.g., the electrostatics approximation). We present here a formulation of Mie theory that overcomes these limitations. Using normalized Bessel functions where the large growth/decay is extracted as a prefactor, we re-express the Mie coefficients for scattering by spheres in a normalized form. These normalized expressions are used to accurately compute the series for the electric field and decay rate of a dipole emitter near a spherical surface, in cases where the Mie coefficients would normally overflow before any degree of accuracy can be obtained.

Combined Extinction and Absorption UV-Visible Spectroscopy as a Method for Revealing Shape Imperfections of Metallic Nanoparticles.

Metallic nanoparticle solutions are routinely characterized by measuring their extinction spectrum (with UV-vis spectroscopy). Theoretical predictions such as Mie theory for spheres can then be used to infer important properties, such as particle size and concentration. Here we highlight the benefits of measuring not only the extinction (the sum of absorption and scattering) but also the absorption spectrum (which excludes scattering) for routine characterization of metallic nanoparticles. We use an integrating sphere-based method to measure the combined extinction-absorption spectra of silver nanospheres and nanocubes. Using a suite of electromagnetic modeling tools (Mie theory, T-matrix, surface integral equation methods), we show that the absorption spectrum, in contrast to extinction, is particularly sensitive to shape imperfections such as roughness, faceting, or edge rounding. We study in detail the canonical case of silver nanospheres, where small discrepancies between experimental and calculated extinction spectra are still common and often overlooked. We show that this mismatch between theory and experiment becomes much more important when considering the absorption spectrum and can no longer be dismissed as experimental imperfections. We focus in particular on the quadrupolar localized plasmon resonance of silver nanospheres, which is predicted to be very prominent in the absorption spectrum but is not observed in our experiments. We consider and discuss a number of possible explanations to account for this discrepancy, including changes in the dielectric function of Ag, size polydispersity, and shape imperfections such as elongation, faceting, and roughness. We are able to pinpoint faceting and roughness as the likely causes for the observed discrepancy. A similar analysis is carried out on silver nanocubes to demonstrate the generality of this conclusion. We conclude that the absorption spectrum is in general much more sensitive to the fine details of a nanoparticle geometry, compared to the extinction spectrum. The ratio of extinction to absorption also provides a sensitive indicator of size for many types of nanoparticles, much more reliably than any observed plasmon resonance shifts. Overall, this work demonstrates that combined absorption-extinction measurements provide a much richer characterization tool for metallic nanoparticles.

Realistic ports in integrating spheres: reflectance, transmittance, and angular redirection.

We use Monte Carlo ray-tracing modeling to follow the stochastic trajectories of rays entering a cylindrical port from inside an integrating sphere. This allows us to study and quantify properties of realistic ports of non-negligible length, as opposed to the common thin-port assumption used in most theoretical treatments, where the port is simply considered as a hole in the spherical wall. We show that most practical ports encountered in integrating sphere applications cannot be modeled as thin ports. Indeed, a substantial proportion of rays entering the port can be reflected back into the sphere, with port reflectances as high as 80% demonstrated on realistic examples. This can have significant consequences on estimates of the sphere multiplier and therefore pathlength inside the sphere, a critical parameter in many applications. Moreover, a nonzero port reflectance is inevitably associated with reduced transmittance through the port, with implications in terms of overall throughput. We also discuss angular redistribution effects in a realistic port and the consequences in terms of detected throughput within a fixed numerical aperture. Those results highlight the importance of real port effects for any quantitative predictions of optical systems using integrating spheres. We believe that those effects can be exploited to engineer ports for specific applications and improve the overall sphere performance in terms of pathlength or throughput. This work carries important implications in our theoretical understanding of integrating spheres and on the practical design of optical systems using them.

Competition between molecular adsorption and diffusion: dramatic consequences for SERS in colloidal solutions.

This study highlights a crucial but often overlooked consideration during sample preparation involving surface-adsorbing species: the competition between analyte adsorption and analyte diffusion/mixing strongly affects the distribution of analytes throughout the sample. In cases of fast analyte adsorption, we argue that the use of large-dilution factors, a common approach for sample preparation in surface-enhanced Raman spectroscopy (SERS), may result in an extreme nonuniformity of the surface coverage. This has a direct effect on the aggregation state of the colloidal solution and therefore on the overall SERS signal. Explicitly, we show that the average SERS signal obtained from typical dyes in colloidal solutions can be drastically different for two seemingly equivalent samples, differing only in the method by which the dye molecules were diluted. We, in addition, discuss the implications of such nonuniformity on the statistics of SERS intensities in the context of single-molecule detection. These results vividly highlight the importance of the dilution step in any experiments involving surface-adsorbing species and position SERS as an ideal tool to evidence such effects. In such cases, a simple half-half dilution procedure should be adopted as the standard method to mitigate these effects.

Single-molecule surface-enhanced Raman spectroscopy with nanowatt excitation.

We demonstrate the possibility of single molecule (SM) detection via surface-enhanced Raman spectroscopy (SERS) in two seemingly challenging and unexpected cases: first with ultra-low excitation powers of the order of nanowatts and second in as-synthesized and not deliberately-aggregated silver colloid solution. The experiments are carried out using the bi-analyte method on a methylated form of Rhodamine 6G and one of its isotopologues excited at 514 nm close to the electronic resonance. This study spectacularly highlights the fact that SM-SERS detection is much more common and easier to achieve than typically thought, in particular in the case of resonance Raman excitation. As a result, SM-SERS detection in such cases should not be viewed as an indication of good SERS substrate performance as sometimes implicitly assumed.

Convergence of Mie theory series: criteria for far-field and near-field properties.

We investigate the convergence of the series arising in Mie theory for the solution of electromagnetic scattering by a sphere. In contrast with previous studies that focused only on the scattering cross section, we here consider a wide spectrum of relevant properties, including scattering, extinction, and absorption cross sections, complex scattering amplitudes (i.e., radiation profile), and near-field properties such as surface electric field and average surface field intensity. The scattering cross section is shown to exhibit the fastest convergence, indicating that existing convergence criteria based on this property are not suitable for the majority of other relevant characteristics computed from Mie theory. Criteria are therefore proposed for those properties.

Enhancement Factors: A Central Concept during 50 Years of Surface-Enhanced Raman Spectroscopy.

In this Perspective, we provide an overview of the core concepts around surface-enhanced Raman spectroscopy (SERS) enhancement factors (EFs), including both theoretical and experimental considerations: EF definitions, the distinction between maximum and average EFs, EF distribution and hot-spot localization, EF measurement and its order of magnitude. We then highlight some of the current challenges in this field, focusing on a selection of topics that we feel are both topical and important: analyte-capture onto a SERS substrate, surface-enhanced resonant Raman scattering, orientation/tensorial effects, and nonradiative effects. We hope this Perspective can provide a platform to reflect on the past 50 years of SERS and its future.

Strong correlation between molecular configurations and charge-transfer processes probed at the single-molecule level by surface-enhanced Raman scattering.

Single-molecule (SM) electrochemistry studied by surface-enhanced Raman scattering (SERS) with high spectral resolution reveals a picture in which the frequency of Raman modes is correlated with the electrochemical process through the interaction with the surface. Previously unexplored phenomena can be revealed by the synergy of electrochemistry and SM-SERS, which explores in this case subtler spectroscopic aspects (like the frequency of a vibration within the inhomogeneous broadening of a many-molecules Raman peak) to gain the information. We demonstrate, among other things, that the interaction with the surface is correlated both with the molecule vibrational frequencies and with the ability of single molecules to be reduced/oxidized at different potentials along the electrochemical cycle. Qualitative models of the interaction of molecules with surfaces are also touched upon.

Single-molecule surface-enhanced Raman spectroscopy.

A general overview of the field of single-molecule (SM) surface-enhanced Raman spectroscopy (SERS) as it stands today is provided. After years of debates on the basic aspects of SM-SERS, the technique is emerging as a well-established subfield of spectroscopy and SERS. SM-SERS is allowing the observation of subtle spectroscopic phenomena that were not hitherto accessible. Examples of the latter are natural isotopic substitutions in single molecules, observation of the true homogeneous broadening of Raman peaks, Raman excitation profiles of individual molecules, and SM electrochemistry. With background examples of the contributions produced by our group, properly interleaved with results by other practitioners in the field, we present some of the latest developments and promising new leads in this new field of spectroscopy.

Simple accurate approximations for the optical properties of metallic nanospheres and nanoshells.

This work aims to provide simple and accurate closed-form approximations to predict the scattering and absorption spectra of metallic nanospheres and nanoshells supporting localised surface plasmon resonances. Particular attention is given to the validity and accuracy of these expressions in the range of nanoparticle sizes relevant to plasmonics, typically limited to around 100 nm in diameter. Using recent results on the rigorous radiative correction of electrostatic solutions, we propose a new set of long-wavelength polarizability approximations for both nanospheres and nanoshells. The improvement offered by these expressions is demonstrated with direct comparisons to other approximations previously obtained in the literature, and their absolute accuracy is tested against the exact Mie theory.

Generalised coupled-dipole model for core-satellite nanostructures.

Plasmonic core-satellite nanostructures have recently attracted interest in photocatalytic applications. The core plasmonic nanoparticle acts like an antenna, funnelling incident light into the near-field region, where it excites the smaller satellite nanoparticles with resonantly enhanced absorption. Computer simulations of the optical absorption by such structures can prove challenging, even with state-of-the-art numerical methods, due to the large difference in size between core and satellite particles. We present a generalised coupled-dipole model that enables efficient computations of light absorption in such nanostructures, including those with many satellites. The method accurately predicts the local absorption in each satellite despite being two orders of magnitude weaker than the absorption in the core particle. We assess the range of applicability of this model by comparing the results against the superposition T-matrix method, a rigorous solution of Maxwell's equations that is much more resource-intensive and becomes impractical as the number of satellite particles increases.

Interface-Dependent Selectivity in Plasmon-Driven Chemical Reactions.

Plasmonic nanoparticles can drive chemical reactions powered by sunlight. These processes involve the excitation of surface plasmon resonances (SPR) and the subsequent charge transfer to adsorbed molecular orbitals. Nonetheless, controlling the flow of energy and charge from SPR to adsorbed molecules is still difficult to predict or tune. Here, we show the crucial role of halide ions in modifying the energy landscape of a plasmon-driven chemical reaction by carefully engineering the nanoparticle-molecule interface. By doing so, the selectivity of plasmon-driven chemical reactions can be controlled, either enhancing or inhibiting the metal-molecule charge and energy transfer or by regulating the vibrational pumping rate. These results provide an elegant method for controlling the energy flow from plasmonic nanoparticles to adsorbed molecules, in situ, and selectively targeting chemical bonds by changing the chemical nature of the metal-molecule interface.

Long-range atmospheric transport of microplastics across the southern hemisphere.

Airborne microplastics (MPs) can undergo long range transport to remote regions. Yet there is a large knowledge gap regarding the occurrence and burden of MPs in the marine boundary layer, which hampers comprehensive modelling of their global atmospheric transport. In particular, the transport efficiency of MPs with different sizes and morphologies remains uncertain. Here we show a hemispheric-scale analysis of airborne MPs along a cruise path from the mid-Northern Hemisphere to Antarctica. We present the inaugural measurements of MPs concentrations over the Southern Ocean and interior Antarctica and find that MPs fibers are transported more efficiently than MPs fragments along the transect, with the transport dynamics of MPs generally similar to those of non-plastic particles. Morphology is found to be the dominant factor influencing the hemispheric transport of MPs to remote Antarctic regions. This study underlines the importance of long-range atmospheric transport in MPs cycling dynamics in the environment.

Tiny peaks vs mega backgrounds: a general spectroscopic method with applications in resonant Raman scattering and atmospheric absorptions.

A simple method using standard spectrometers with charge-coupled device (CCD) detectors is described to routinely measure background-corrected spectra in situations where the signal is composed of weak spectral features (such as Raman peaks or absorption lines) engulfed in a much stronger (by as much as ∼10(5)) broad background. The principle of the method is to subtract the dominant fixed-structure noise and obtain a shot-noise limited spectrum. The final noise level can therefore be reduced as desired by sufficient integration time. The method requires multiple shifts of the diffraction gratings to extract the pixel-dependent noise structure, which is then used as a flat-field correction. An original peak-retrieval procedure is proposed, demonstrating accurate determination of peak lineshapes and linewidths and robustness on practical examples where conventional methods would not be applicable. Examples are discussed to illustrate the potential of the technique to perform routine resonant Raman measurements of fluorescent dyes with high quantum yield, using conventional Raman systems. The method can equally be applied to other situations where small features are masked by a broad overwhelming background. An explicit example is given with the measurement of weak absorption lines in atmospheric gases.