Predicting bilgewater emulsion stability by oil separation using image processing and machine learning.

Bilgewater is a shipboard multi-component oily wastewater, combining numerous wastewater sources. A better understanding of bilgewater emulsions is required for proper wastewater management to meet discharge regulations. In this study, we developed 360 emulsion samples based on commonly used Navy cleaner data and previous bilgewater composition studies. Oil value (OV) was obtained from image analysis of oil/creaming layer and validated by oil separation (OS) which was experimentally determined using a gravimetric method. OV (%) showed good agreement with OS (%), indicating that a simple image-based parameter can be used for emulsion stability prediction model development. An ANOVA analysis was conducted of the five variables (Cleaner, Salinity, Suspended Solids [SS], pH, and Temperature) that significantly impacted estimates of OV, finding that the Cleaner, Salinity, and SS variables were statistically significant (p < 0.05), while pH and Temperature were not. In general, most cleaners showed improved oil separation with salt additions. Novel machine learning (ML)-based predictive models of both classification and regression for bilgewater emulsion stability were then developed using OV. For classification, the random forest (RF) classifiers achieved the most accurate prediction with F1-score of 0.8224, while in regression-based models the decision tree (DT) regressor showed the highest prediction of emulsion stability with the average mean absolute error (MAE) of 0.1611. Turbidity also showed a good emulsion prediction with RF regressor (MAE of 0.0559) and RF classifier (F1-score of 0.9338). One predictor variable removal test showed that Salinity, SS, and Temperature are the most impactful variables in the developed models. This is the first study to use image processing and machine learning for the prediction of oil separation for the application of bilgewater assessment within the marine sector.

Bromide ion-functionalized nanoprobes for sensitive and reliable pH measurement by surface-enhanced Raman spectroscopy.

4-Mercaptopyridine (4-Mpy) is a pH reporter molecule commonly used to functionalize nanoprobes for surface-enhanced Raman spectroscopy (SERS) based pH measurements. However, nanoprobes functionalized by 4-Mpy alone have low pH sensitivity and are subject to interference by halide ions in sample media. To improve nanoprobe pH sensitivity and reliability, we functionalized gold nanoparticles (AuNPs) with both 4-Mpy and bromide ion (Br-). Br- electrostatically stabilizes protonated 4-Mpy, thus enabling sensitive SERS detection of the protonation state of 4-Mpy as a function of pH while also reducing variability caused by external halide ions. Through optimization of the functionalization parameters, including suspension pH, [4-Mpy], and [Br-], the developed nanoprobes enable monitoring of pH from 2.1 to 10 with high SERS activity and minimal interference from halide ions within the sample matrix. As a proof of concept, we were able to track nanoprobe location and image the pH distribution inside individual cancer cells. This study provides a novel way to engineer reliable 4-Mpy-functionalized SERS nanoprobes for the sensitive analysis of spatially localized pH features in halide ion-containing microenvironments.

Identification and characterization of bilgewater emulsions.

Literature on bilgewater focuses on empirically determined treatment methods and lacks specific information on emulsion characteristics. Therefore, this review discusses potential emulsion stabilization mechanisms that occur in bilgewater and evaluates common approaches to study their behavior. Current knowledge on emulsion formation, stabilization, and destabilization is outlined to provide researchers and bilgewater treatment operators with the knowledge needed to determine emulsion prevention and treatment strategies. Furthermore, a broad assessment of bilgewater emulsion characterization techniques, from general water quality analysis to advanced droplet stability characterization methods are discussed in detail. Lastly, a survey of typical bilgewater characteristics and information on standard synthetic bilgewater mixtures used in the testing of oil pollution abatement equipment are presented. Overall, the goal of this article is to provide a better understanding of physical and thermodynamic properties of emulsions to help improve bilgewater treatment and management.

Real-Time Monitoring of Ligand Exchange Kinetics on Gold Nanoparticle Surfaces Enabled by Hot Spot-Normalized Surface-Enhanced Raman Scattering.

Nanoparticle surface coatings dictate their fate, transport, and bioavailability. We used a gold nanoparticle-bacterial cellulose substrate and "hot spot"-normalized surface-enhanced Raman scattering (HSNSERS) to achieve in situ and real-time monitoring of ligand exchange reactions on the gold surface. This approach enables semiquantitative determination of citrate surface coverage. Following exposure of the citrate-coated nanoparticles to a suite of guest ligands (thiolates, amines, carboxylates, inorganic ions, and proteins), the guest ligand signal exhibited first-order growth kinetics, while the desorption mediated decay of the citrate signal followed a first-order model. Guest ligand functional group chemistry dictated the kinetics of citrate desorption, while the guest ligand concentration played only a minor role. Thiolates and BSA were more efficient at ligand exchange than amine-containing chemicals, carboxylate-containing chemicals, and inorganic salts due to their higher binding energies with the AuNP surface. Amine-containing molecules overcoated rather than displaced the citrate layer via electrostatic interaction. Citrate exhibited low resistance to replacement at high surface coverages, but higher resistance at lower coverage, thus suggesting a transformation of the citrate-binding mode during desorption. High resistance to replacement in streamwater suggests that the role of surface-adsorbed citrate in nanomaterial fate and transport must be better understood.

Nanomaterial enabled sensors for environmental contaminants.

The need and desire to understand the environment, especially the quality of one's local water and air, has continued to expand with the emergence of the digital age. The bottleneck in understanding the environment has switched from being able to store all of the data collected to collecting enough data on a broad range of contaminants of environmental concern. Nanomaterial enabled sensors represent a suite of technologies developed over the last 15 years for the highly specific and sensitive detection of environmental contaminants. With the promise of facile, low cost, field-deployable technology, the ability to quantitatively understand nature in a systematic way will soon be a reality. In this review, we first introduce nanosensor design before exploring the application of nanosensors for the detection of three classes of environmental contaminants: pesticides, heavy metals, and pathogens.

Surface-Enhanced Raman Scattering Based Microfluidics for Single-Cell Analysis.

The integration of surface-enhanced Raman scattering (SERS) with droplet microfluidics has the potential to improve our understanding of cellular systems. Herein, we present the first application of SERS droplet microfluidics for single-cell analysis. A microfluidic device was used to encapsulate single prostate cancer cells and wheat germ agglutin (WGA)-functionalized SERS nanoprobes in water-in-oil droplets that were subsequently locked into a storage droplet array for spectroscopic investigation. The stationary droplets enabled the rapid identification of SERS regions of interest in live cancer cells by allowing collection of "fast" coarse maps over an area of several square millimeters followed by "slower" detailed interrogation of the identified hotspots. We demonstrate SERS at cellular resolution via a proof-of-concept assay that detects glycan expression on the surface of prostate cancer cells using WGA-modified metallic nanoparticles. The data illustrates the potential of SERS optofluidic systems for high-throughput cell screening and illustrates a previously unobserved high degree of cell-to-cell variability in the size and number of glycan islands.

Aerosol microdroplets exhibit a stable pH gradient.

Suspended aqueous aerosol droplets (<50 µm) are microreactors for many important atmospheric reactions. In droplets and other aquatic environments, pH is arguably the key parameter dictating chemical and biological processes. The nature of the droplet air/water interface has the potential to significantly alter droplet pH relative to bulk water. Historically, it has been challenging to measure the pH of individual droplets because of their inaccessibility to conventional pH probes. In this study, we scanned droplets containing 4-mercaptobenzoic acid-functionalized gold nanoparticle pH nanoprobes by 2D and 3D laser confocal Raman microscopy. Using surface-enhanced Raman scattering, we acquired the pH distribution inside approximately 20-µm-diameter phosphate-buffered aerosol droplets and found that the pH in the core of a droplet is higher than that of bulk solution by up to 3.6 pH units. This finding suggests the accumulation of protons at the air/water interface and is consistent with recent thermodynamic model results. The existence of this pH shift was corroborated by the observation that a catalytic reaction that occurs only under basic conditions (i.e., dimerization of 4-aminothiophenol to produce dimercaptoazobenzene) occurs within the high pH core of a droplet, but not in bulk solution. Our nanoparticle probe enables pH quantification through the cross-section of an aerosol droplet, revealing a spatial gradient that has implications for acid-base-catalyzed atmospheric chemistry.

Improved Quantitative SERS Enabled by Surface Plasmon Enhanced Elastic Light Scattering.

The application of surface-enhanced Raman spectroscopy (SERS) for everyday quantitative analysis is hindered by the point-to-point variability of SERS substrates that arises due to the heterogeneous distribution of localized electromagnetic fields across a suite of plasmonic nanostructures. Herein, we adopt surface-enhanced elastic scattering as a SERS internal standard. Both elastic and inelastic (i.e., Raman) scattering are simultaneously enhanced by a given "hot spot", and thus, the surface-enhanced elastic scattering signal provides a localized intrinsic internal standard that scales across all of the plasmon-enhanced electromagnetic fields within a substrate. Elastically scattered light originates from the amplified spontaneous emission (ASE) of the commercial laser, leading to the formation of a low-wavenumber pseudo band that arises from the interaction of the ASE and the edge filter. A theoretical model was developed to illustrate the underlying mechanism supporting this normalization approach. The normalized Raman signals are independent of the incident laser intensity and the density of "hot spots" for numerous SERS substrates. Following "hot-spot" (HS) normalization, the coefficient of variation for the tested SERS substrates decreases from 10 to 60% to 2%-7%. This approach significantly improves SERS quantitation of four chloroanilines and enables collection of highly reproducible analyte adsorption results under both static and dynamic imaging conditions. Overall, this approach provides a simple means to improve SERS reproducibility without the need to use additional chemicals as internal standards.

Highly stable SERS pH nanoprobes produced by co-solvent controlled AuNP aggregation.

Production of gold nanoparticle (AuNP) surface-enhanced Raman spectroscopy (SERS) nanoprobes requires replicable aggregation to produce multimers with high signal intensity. Herein, we illustrate a novel, yet simple, approach to produce SERS nanoprobes through control of co-solvent composition. AuNP multimers were produced by mixing AuNP monomers in water : ethanol co-solvent for variable periods of time. By varying the water : ethanol ratio and the amount of 4-mercaptobenzoic acid (4-MBA) present, the aggregation rate can be systematically controlled. Thiolated poly(ethylene glycol) was then added to halt the aggregation process and provide steric stability. This approach was used to produce pH nanoprobes with excellent colloidal stability in high ionic strength environments and in complex samples. The pH probe exhibits broad pH sensitivity over the range 6-11 and we calculate that a single AuNP dimer in a 35 fL volume is sufficient to generate a detectable SERS signal. As a proof-of-concept, the probes were used to detect the intracellular pH of human prostate cancer cells (PC-3). The internalized probes exhibit a strong 4-MBA signal without any interfering bands from either the cells or the culture media and produce exceptionally detailed pH maps. pH maps obtained from 19 xy surface scans and 14 yz depth scans exhibit highly consistent intracellular pH in the range of 5 to 7, thus indicating the greater reliability and reproducibility of our pH probes compared with other probes previously reported in the literature. Our water : ethanol co-solvent production process is fast, simple, and efficient. Adjustment of solvent composition may become a powerful way to produce SERS tags or nanoprobes in the future.