Pelagic Sargassum in the Gulf of Mexico driven by ocean currents and eddies.

Pelagic Sargassum in the Gulf of Mexico (GoM) plays an important role in ocean biology and ecology, yet our knowledge of its origins and transport pathways is limited. Here, using satellite observations of Sargassum areal density and ocean surface currents between 2000 and 2023, we show that large amounts of Sargassum in the GoM can either originate from the northwestern GoM or be a result of physical transport from the northwestern Caribbean Sea, both with specific transport pathways. Sargassum of the northwestern GoM can be transported to the eastern GoM by ocean currents and eddies, eventually entering the Sargasso Sea. Sargassum entering the GoM from the northwestern Caribbean Sea can be transported in three different directions, with the northward and eastward transports governed by the Loop Current System (LCS) and westward transport driven by the westward extension of the LCS, the propagation or relaying of ocean eddies, the wind-driven westward currents on the Campeche Bank with or without eddies, and the westward currents with/without currents associated with eddies in the northern/central GoM. Overall, the spatial distribution patterns of pelagic Sargassum in the GoM are strongly influenced by the LCS and relevant eddies.

Naturally acquired antibodies against Plasmodium vivax pre-erythrocytic stage vaccine antigens inhibit sporozoite invasion of human hepatocytes in vitro.

In Plasmodium vivax, the most studied vaccine antigens are aimed at blocking merozoite invasion of erythrocytes and disease development. Very few studies have evaluated pre-erythrocytic (PE) stage antigens. The P. vivax circumsporozoite protein (CSP), is considered the leading PE vaccine candidate, but immunity to CSP is short-lived and variant specific. Thus, there is a need to identify other potential candidates to partner with CSP in a multivalent vaccine to protect against infection and disease. We hypothesize that sporozoite antigens important for host cell infection are considered potential targets. In this study, we evaluated the magnitude and quality of naturally acquired antibody responses to four P. vivax PE antigens: sporozoite surface protein 3 (SSP3), sporozoite protein essential for traversal 1 (SPECT1), cell traversal protein of ookinetes and sporozoites (CelTOS) and CSP in plasma of P. vivax infected patients from Thailand. Naturally acquired antibodies to these antigens were prevalent in the study subjects, but with significant differences in magnitude of IgG antibody responses. About 80% of study participants had antibodies to all four antigens and only 2% did not have antibodies to any of the antigens. Most importantly, these antibodies inhibited sporozoite infection of hepatocytes in vitro. Significant variations in magnitude of antigen-specific inhibitory antibody responses were observed with individual samples. The highest inhibitory responses were observed with anti-CelTOS antibodies, followed by anti-SPECT1, SSP3 and CSP antibodies respectively. These data highlight the vaccine potential of these antigens in protecting against hepatocyte infection and the need for a multi-valent pre-erythrocytic vaccine to prevent liver stage development of P. vivax sporozoites.

Scale dependence of coral reef oases and their environmental correlates.

Identifying relatively intact areas within ecosystems and determining the conditions favoring their existence is necessary for effective management in the context of widespread environmental degradation. In this study, we used 3766 surveys of randomly selected sites in the United States and U.S. Territories to identify the correlates of sites categorized as "oases" (defined as sites with relatively high total coral cover). We used occupancy models to evaluate the influence of 10 environmental predictors on the probability that an area (21.2-km2 cell) would harbor coral oases defined at four spatial extents: cross-basin, basin, region, and subregion. Across all four spatial extents, oases were more likely to occur in habitats with high light attenuation. The influence of the other environmental predictors on the probability of oasis occurrence were less consistent and varied with the scale of observation. Oases were most likely in areas of low human population density, but this effect was evident only at the cross-basin and subregional extents. At the regional and subregional extents oases were more likely where sea-surface temperature was more variable, whereas at the larger spatial extents the opposite was true. By identifying the correlates of oasis occurrence, the model can inform the prioritization of reef areas for management. Areas with biophysical conditions that confer corals with physiological resilience, as well as limited human impacts, likely support coral reef oases across spatial extents. Our approach is widely applicable to the development of conservation strategies to protect biodiversity and ecosystems in an era of magnified human disturbance.

Extensive coral mortality and critical habitat loss following dredging and their association with remotely-sensed sediment plumes.

Dredging poses a potential threat to coral reefs, yet quantifying impacts is often difficult due to the large spatial footprint of potential effects and co-occurrence of other disturbances. Here we analyzed in situ monitoring data and remotely-sensed sediment plumes to assess impacts of the 2013-2015 Port of Miami dredging on corals and reef habitat. To control for contemporaneous bleaching and disease, we analyzed the spatial distribution of impacts in relation to the dredged channel. Areas closer to dredging experienced higher sediment trap accumulation, benthic sediment cover, coral burial, and coral mortality, and our spatial analyses indicate that >560,000 corals were killed within 0.5 km, with impacts likely extending over 5-10 km. The occurrence of sediment plumes explained ~60% of spatial variability in measured impacts, suggesting that remotely-sensed plumes, when properly calibrated against in situ monitoring data, can reliably estimate the magnitude and extent of dredging impacts.

The great Atlantic Sargassum belt.

Pelagic Sargassum is abundant in the Sargasso Sea, but a recurrent great Atlantic Sargassum belt (GASB) has been observed in satellite imagery since 2011, often extending from West Africa to the Gulf of Mexico. In June 2018, the 8850-kilometer GASB contained >20 million metric tons of Sargassum biomass. The spatial distribution of the GASB is mostly driven by ocean circulation. The bloom of 2011 might be a result of Amazon River discharge in previous years, but recent increases and interannual variability after 2011 appear to be driven by upwelling off West Africa during boreal winter and by Amazon River discharge during spring and summer, indicating a possible regime shift and raising the possibility that recurrent blooms in the tropical Atlantic and Caribbean Sea may become the new norm.

VIIRS captures phytoplankton vertical migration in the NE Gulf of Mexico.

In summer 2014, a toxic Karenia brevis bloom (red tide) occurred in the NE Gulf of Mexico, during which vertical migration of K. brevis has been observed from glider measurements. The current study shows that satellite observations from the Visible Infrared Imaging Radiometer Suite (VIIRS) can capture changes in surface reflectance and chlorophyll concentration occurring within 2h, which may be attributed this K. brevis vertical migration. The argument is supported by earlier glider measurements in the same bloom, by the dramatic changes in the VIIRS-derived surface chlorophyll, and by the consistency between the short-term reflectance changes and those reported earlier from field-measured K. brevis vertical migration. Estimates using the quasi-analytical algorithm also indicate significant increases in both total absorption coefficient and backscattering coefficient in two hours. The two observations in a day from a single polar-orbiting satellite sensor are thus shown to be able to infer phytoplankton vertical movement within a short timeframe, a phenomenon difficult to capture with other sensors as each sensor can provide at most one observation per day, and cross-sensor inconsistency may make interpretation of merged-sensor data difficult. These findings strongly support geostationary satellite missions to study short-term bloom dynamics.

Island building in the South China Sea: detection of turbidity plumes and artificial islands using Landsat and MODIS data.

The South China Sea is currently in a state of intense geopolitical conflict, with six countries claiming sovereignty over some or all of the area. Recently, several countries have carried out island building projects in the Spratly Islands, converting portions of coral reefs into artificial islands. Aerial photography and high resolution satellites can capture snapshots of this construction, but such data are lacking in temporal resolution and spatial scope. In contrast, lower resolution satellite sensors with regular repeat sampling allow for more rigorous assessment and monitoring of changes to the reefs and surrounding areas. Using Landsat-8 data at ≥15-m resolution, we estimated that over 15 km(2) of submerged coral reef area was converted to artificial islands between June 2013 and December 2015, mostly by China. MODIS data at ≥250-m resolution were used to locate previously underreported island building activities, as well as to assess resulting in-water turbidity plumes. The combined spatial extent of observed turbidity plumes for island building activities at Mischief, Subi, and Fiery Cross Reefs was over 4,300 km(2), although nearly 40% of this area was only affected once. Together, these activities represent widespread damage to coral ecosystems through physical burial as well as indirect turbidity effects.

Vertical migration of Karenia brevis in the northeastern Gulf of Mexico observed from glider measurements.

The toxic marine dinoflagellate, Karenia brevis (the species responsible for most of red tides or harmful algal blooms in the Gulf of Mexico), is known to be able to swim vertically to adapt to the light and nutrient environments, nearly all such observations have been made through controlled experiments using cultures. Here, using continuous 3-dimensional measurements by an ocean glider across a K. brevis bloom in the northeastern Gulf of Mexico between 1 and 8 August 2014, we show the vertical migration behavior of K. brevis. Within the bloom where K. brevis concentration is between 100,000 and 1,000,000cellsL-1, the stratified water shows a two-layer system with the depth of pycnocline ranging between 14-20m and salinity and temperature in the surface layer being <34.8 and >28°C, respectively. The bottom layer shows the salinity of >36 and temperature of <26°C. The low salinity is apparently due to coastal runoff, as the top layer also shows high amount of colored dissolved organic matter (CDOM). Within the top layer, chlorophyll-a fluorescence shows clear diel changes in the vertical structure, an indication of K. brevis vertical migration at a mean speed of 0.5-1mh-1. The upward migration appears to start at sunrise at a depth of 8-10m, while the downward migration appears to start at sunset (or when surface light approaches 0) at a depth of ∼2m. These vertical migrations are believed to be a result of the need of K. brevis cells for light and nutrients in a stable, stratified, and CDOM-rich environment.

A harmful algal bloom of Karenia brevis in the northeastern Gulf of Mexico as revealed by MODIS and VIIRS: a comparison.

The most recent Visible Infrared Imager Radiometer Suite (VIIRS) is not equipped with a spectral band to detect solar-stimulated phytoplankton fluorescence. The lack of such a band may affect the ability of VIIRS to detect and quantify harmful algal blooms (HABs) in coastal waters rich in colored dissolved organic matter (CDOM) because of the overlap of CDOM and chlorophyll absorption within the blue-green spectrum. A recent HAB dominated by the toxin-producing dinoflagellate Karenia brevis in the northeastern Gulf of Mexico, offshore of Florida's Big Bend region, allowed for comparison of the capacities of VIIRS and Moderate Resolution Imaging Spectroradiometer (MODIS) to detect blooms in CDOM-rich waters. Both VIIRS and MODIS showed general consistency in mapping the CDOM-rich dark water, which measured a maximum area of 8900 km2 by mid-July 2014. However, within the dark water, only MODIS allowed detection of bloom patches-as indicated by high normalized fluorescence line height (nFLH). Field surveys between late July and mid-September confirmed Karenia brevis at bloom abundances up to 20 million cells·L(-1) within these patches. The bloom patches were well captured by the MODIS nFLH images, but not by the default chlorophyll a concentration (Chla) images from either MODIS or VIIRS. Spectral analysis showed that VIIRS could not discriminate these high-phytoplankton water patches within the dark water due to its lack of fluorescence band. Such a deficiency may be overcome with new algorithms or future satellite missions such as the U.S. NASA's Pre-Aerosol-Clouds-Ecology mission and the European Space Agency's Sentinel-3 mission.

"Measure Your Gradient": a new way to measure gradients in high performance liquid chromatography by mass spectrometric or absorbance detection.

The gradient produced by an HPLC is never the same as the one it is programmed to produce, but non-idealities in the gradient can be taken into account if they are measured. Such measurements are routine, yet only one general approach has been described to make them: both HPLC solvents are replaced with water, solvent B is spiked with 0.1% acetone, and the gradient is measured by UV absorbance. Despite the widespread use of this procedure, we found a number of problems and complications with it, mostly stemming from the fact that it measures the gradient under abnormal conditions (e.g. both solvents are water). It is also generally not amenable to MS detection, leaving those with only an MS detector no way to accurately measure their gradients. We describe a new approach called "Measure Your Gradient" that potentially solves these problems. One runs a test mixture containing 20 standards on a standard stationary phase and enters their gradient retention times into open-source software available at www.measureyourgradient.org. The software uses the retention times to back-calculate the gradient that was truly produced by the HPLC. Here we present a preliminary investigation of the new approach. We found that gradients measured this way are comparable to those measured by a more accurate, albeit impractical, version of the conventional approach. The new procedure worked with different gradients, flow rates, column lengths, inner diameters, on two different HPLCs, and with six different batches of the standard stationary phase.

What experimental factors influence the accuracy of retention projections in gas chromatography-mass spectrometry?

Programmed-temperature gas chromatographic (GC) retention information is difficult to share because it depends on so many experimental factors that vary among laboratories. Though linear retention indexing cannot properly account for experimental differences, retention times can be accurately calculated, or "projected", from shared isothermal retention vs. temperature (T) relationships, but only if the temperature program and hold-up time vs. T profile produced by a GC is known with great precision. The effort required to measure these profiles were previously impractical, but we recently showed that they can be easily back-calculated from the programmed-temperature retention times of a set of 25 n-alkanes using open-source software at www.retentionprediction.org/gc. In a multi-lab study, the approach was shown to account for both intentional and unintentional differences in the temperature programs, flow rates, and inlet pressures produced by the GCs. Here, we tested 16 other experimental factors and found that only 5 could reduce accuracy in retention projections: injection history, exposure to very high levels of oxygen at high temperature, a very low transfer line temperature, an overloaded column, and a very short column (≤15m). We find that the retention projection methodology acts as a hybrid of conventional retention projection and retention indexing, drawing on the advantages of both; it properly accounts for a wide range of experimental conditions while accommodating the effects of experimental factors not properly taken into account in the calculations. Finally, we developed a four-step protocol to efficiently troubleshoot a GC system after it is found to be yielding inaccurate retention projections.

Impact of reversed phase column pairs in comprehensive two-dimensional liquid chromatography.

A major issue in optimizing the resolving power of two-dimensional chromatographic separations is the choice of the two phases so as to maximize the distribution of the analytes over the separation space. In this work, we studied the choice of appropriate reversed phases to use in on-line comprehensive two-dimensional liquid chromatography (LC×LC). A set of four chemically different conventional bonded reversed phases was used in the first dimension. The second dimension column was either a conventional bonded C18 phase or a carbon-clad phase (CCP). The LC×LC chromatograms and contour plots were all rather similar indicating that the selectivities of the two phases were also similar regardless of the reverse phase column used in the first dimension. Further, the spatial coverage seen with all four first dimension stationary phases when paired with a second dimension C18 phase were low and the retention times were strongly correlated. However, when the C18 column was replaced with the CCP column much improved separations were observed with higher spatial coverages, greater orthogonalities and significant increases in the number of observed peaks.

"Retention projection" enables reliable use of shared gas chromatographic retention data across laboratories, instruments, and methods.

Gas chromatography/mass spectrometry (GC/MS) is a primary tool used to identify compounds in complex samples. Both mass spectra and GC retention times are matched to those of standards; however, it is often impractical to have standards on hand for every compound of interest, so we must rely on shared databases of MS data and GC retention information. Unfortunately, retention databases (e.g., linear retention index libraries) are experimentally restrictive, notoriously unreliable, and strongly instrument dependent, relegating GC retention information to a minor, often negligible role in compound identification despite its potential power. A new methodology called "retention projection" has great potential to overcome the limitations of shared chromatographic databases. In this work, we tested the reliability of the methodology in five independent laboratories. We found that, even when each lab ran nominally the same method, the methodology was 3-fold more accurate than retention indexing because it properly accounted for unintentional differences between the GC/MS systems. When the laboratories used different methods of their own choosing, retention projections were 4- to 165-fold more accurate. More importantly, the distribution of error in the retention projections was predictable across different methods and laboratories, thus enabling automatic calculation of retention time tolerance windows. Tolerance windows at 99% confidence were generally narrower than those widely used even when physical standards are on hand to measure their retention. With its high accuracy and reliability, the new retention projection methodology makes GC retention a reliable, precise tool for compound identification, even when standards are not available to the user.

Determination of steroids, caffeine and methylparaben in water using solid phase microextraction-comprehensive two dimensional gas chromatography-time of flight mass spectrometry.

Analysis of several emerging contaminants (steroids, caffeine and methylparaben) in water using automated solid-phase microextraction with comprehensive two dimensional gas chromatography coupled to time of flight mass spectrometry (SPME-GCxGC-ToF/MS) is presented. Experimental design was used to determine the best SPME extraction conditions and the steroids were not derivatized prior to injection. SPME-GCxGC-ToF/MS provided linear ranges from 0.6 to 1200µgL(-1) and limits of detection and quantitation from 0.02 to 100µgL(-1). A series of river water samples obtained locally were subjected to analysis. SPME-GCxGC-ToF/MS is readily automated, straightforward and competitive with other methods for low level analysis of emerging contaminants.

Analysis of Salvinorin A in plants, water, and urine using solid-phase microextraction-comprehensive two-dimensional gas chromatography-time of flight mass spectrometry.

Salvinorin A, a psychoactive hallucinogen, and related compounds, were analyzed in plants, water, and urine using liquid-liquid extraction (LLE), solid-phase microextraction (SPME) and comprehensive two-dimensional gas chromatography-time of flight mass spectrometry (GC×GC-ToFMS). A semi-qualitative study of the extraction of Salvinorin A and analogs from Salvia divinorum plants by LLE showed ppb levels of Salvinorin A and several analogs in the leaves and stems of S. divinorum plants, much lower than expected. Quantitative analysis of Salvinorin A spiked into water and urine showed much better figures of merit for SPME than LLE, with limit of detection of about 5 ng/mL, linear range from 8 to 500 ng/mL and precision about ±10% for the SPME-based analyses using external standard quantitation. GC×GC-ToFMS was especially effective in separating the peaks of interest from matrix and chromatographic interferences.