Epilepsy is one of the most common chronic neurological diseases. High-frequency oscillations (HFOs) have emerged as promising biomarkers for the epileptogenic zone. However, visual marking of HFOs is a time-consuming and laborious process. Several automated techniques have been proposed to detect HFOs, yet these are still far from being suitable for application in a clinical setting. Here, ripples and fast ripples from intracranial electroencephalograms were detected in six patients with intractable epilepsy using a convolutional neural network (CNN) method. This approach proved more accurate than using four other HFO detectors integrated in RIPPLELAB, providing a higher sensitivity (77.04% for ripples and 83.23% for fast ripples) and specificity (72.27% for ripples and 79.36% for fast ripples) for HFO detection. Furthermore, for one patient, the Cohen's kappa coefficients comparing automated detection and visual analysis results were 0.541 for ripples and 0.777 for fast ripples. Hence, our automated detector was capable of reliable estimates of ripples and fast ripples with higher sensitivity and specificity than four other HFO detectors. Our detector may be used to assist clinicians in locating epileptogenic zone in the future.
We investigate the chemical composition of organic light-absorbing components, also known as brown carbon (BrC) chromophores, formed in a proxy of anthropogenic secondary organic aerosol generated from the photooxidation of naphthalene (naph-SOA) in the absence and presence of NO x . Highperformance liquid chromatography equipped with a photodiode array detector and electrospray ionization high-resolution mass spectrometer is employed to characterize naph-SOA and its BrC components. We provide molecular-level insights into the chemical composition and optical properties of individual naph-SOA components and investigate their BrC relevance. This work reveals the formation of strongly absorbing nitro-aromatic chromophores under high-NO x conditions and describes their degradation during atmospheric aging. NO x addition enhanced the light absorption of naph-SOA while reducing wavelength-dependence, as seen by the mass absorption coefficient (MAC) and absorption Ångstrom exponent (AAE). Optical parameters of naph-SOA generated under low-and high-NO x conditions showed a range of values from MAC OM 405nm ∼ 0.12 m 2 g −1 and AAE 300−450nm ∼ 8.87 (low-NO x ) to MAC OM 405nm ∼ 0.19 m 2 g −1 and AAE 300−450nm ∼ 7.59 (high-NO x ), consistent with "very weak" and "weak" BrC optical classes, respectively. The weak-BrC class is commonly attributed to biomass smoldering emissions, which appear to have optical properties comparable with the naph-SOA. Molecular chromophores contributing to naphthalene BrC absorption were identified with substantial nitro-aromatics, indicating that these species may be used as source-specific markers of BrC related to the anthropogenic emissions.
Polycyclic aromatic hydrocarbons (PAHs) are toxic organic trace components in atmospheric aerosols that have impacts on climate and human health. They are bound to airborne particles and transported over long distances. Observations of their distribution, transport pathways, and degradation are crucial for risk assessment and mitigation. Such estimates would benefit from online detection of PAHs along with analysis of the carrying particles to identify the source. Typically, laser desorption/ ionization (LDI) in a bipolar mass spectrometer reveals the inorganic constituents and provides limited molecular information. In contrast, twostep ionization approaches produce detailed PAH mass spectra from individual particles but without the source-specific inorganic composition. Here we report a new technique that yields the single-particle PAH composition along with both positive and negative inorganic ions via LDI. Thus, the complete particle characterization and source apportionment from conventional bipolar LDI-analysis becomes possible, combined with a detailed PAH spectrum for the same particle. The key idea of the method is spatiotemporal matching of the ionization laser pulse to the transient component distribution in the particle plume after laser desorption. The technique is robust and field-deployable with only slightly higher costs and complexity compared to two-step approaches. We demonstrate its capability to reveal the PAH-distribution on different particle types in combustion aerosols and ambient air.
Secondary organic aerosols (SOAs) affect incoming solar radiation by interacting with light at ultraviolet and visible wavelength ranges. However, the relationship between the chemical composition and optical properties of SOA is still not well understood. In this study, the complex refractive index (RI) of SOA produced from OH oxidation of naphthalene in the presence of nitrogen oxides (NOx) was retrieved online in the wavelength range of 315–650 nm and the bulk chemical composition of the SOA was characterized by an online high-resolution time-of-flight mass spectrometer. In addition, the molecular-level composition of brown carbon chromophores was determined using high-performance liquid chromatography coupled to a photodiode array detector and a high-resolution mass spectrometer. The real part of the RI of the SOA increases with both the NOx/naphthalene ratio and aging time, likely due to the increased mean polarizability and decreased molecular weight due to fragmentation. Highly absorbing nitroaromatics (e.g., C 6 H 5 NO 4 , C 7 H 7 NO 4 , C 7 H 5 NO 5 , C 8 H 5 NO 5 ) produced under higher NOx conditions contribute significantly to the light absorption of the SOA. The imaginary part of the RI linearly increases with the NOx/VOCs ratio due to the formation of nitroaromatic compounds. As a function of aging, the imaginary RI increases with the O/C ratio (slope = 0.024), mainly attributed to the achieved higher NOx/VOCs ratio, which favors the formation of light-absorbing nitroaromatics. The light-absorbing enhancement is not as significant with extensive aging as it is under a lower aging time due to the opening of aromatic rings by reactions.
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