Reduced organic sulfur: Analysis and interaction with mercury in the aquatic environment

Reduced organic sulfur (ROS) compounds are environmentally ubiquitous and play an important role in sulfur cycling as well as in biogeochemical cycles of toxic metals, in particular mercury. Development of effective methods for analysis of ROS in environmental samples and investigations on the interactions of ROS with mercury are critical for understanding the role of ROS in mercury cycling, yet both of which are poorly studied. Covalent affinity chromatography-based methods were attempted for analysis of ROS in environmental water samples. A method was developed for analysis of environmental thiols, by preconcentration using affinity covalent chromatographic column or solid phase extraction, followed by releasing of thiols from the thiopropyl sepharose gel using TCEP and analysis using HPLC-UV or HPLC-FL. Under the optimized conditions, the detection limits of the method using HPLC-FL detection were 0.45 and 0.36 nM for Cys and GSH, respectively. Our results suggest that covalent affinity methods are efficient for thiol enrichment and interference elimination, demonstrating their promising applications in developing a sensitive, reliable, and useful technique for thiol analysis in environmental water samples. The dissolution of mercury sulfide (HgS) in the presence of ROS and dissolved organic matter (DOM) was investigated, by quantifying the effects of ROS on HgS dissolution and determining the speciation of the mercury released from ROS-induced HgS dissolution. It was observed that the presence of small ROS (e.g., Cys and GSH) and large molecule DOM, in particular at high concentrations, could significantly enhance the dissolution of HgS. The dissolved Hg during HgS dissolution determined using the conventional 0.22 μm cutoff method could include colloidal Hg (e.g., HgS colloids) and truly dissolved Hg (e.g., Hg-ROS complexes). A centrifugal filtration method (with 3 kDa MWCO) was employed to characterize the speciation and reactivity of the Hg released during ROS-enhanced HgS dissolution. The presence of small ROS could produce a considerable fraction (about 40% of total mercury in the solution) of truly dissolved mercury (< 3 kDa), probably due to the formation of Hg-Cys or Hg-GSH complexes. The truly dissolved Hg formed during GSH- or Cys-enhanced HgS dissolution was directly reducible (100% for GSH and 40% for Cys) by stannous chloride, demonstrating its potential role in Hg transformation and bioaccumulation.

Planning a Medical School to Serve an Educationally and Medically Underserved Area: Florida International University in Miami, FL

This paper provides the historic background of the Florida International University College of Medicine planning process.

Effects of shading on calcareous benthic periphyton in a short-hydroperiod oligotrophic wetland (Everglades, FL, USA)

The effects of shade on benthic calcareous periphyton were tested in a short-hydroperiod oligotrophic subtropical wetland (freshwater Everglades). The experiment was a split-plot design set in three sites with similar environmental characteristics. At each site, eight randomly selected 1-m2 areas were isolated individually in a shade house, which did not spectrally change the incident irradiance but reduced it quantitatively by 0, 30, 50, 60, 70, 80, 90 and 98%. Periphyton mat was sampled monthly under each shade house for a 5 month period while the wetland was flooded. Periphyton was analyzed for thickness, DW, AFDW, chlorophyll a (chl a) and incubated in light and dark BOD bottles at five different irradiances to assess its photosynthesis–irradiance (PI) curve and respiration. The PI curves parameters P max, I k and eventually the photoinhibition slope (β) were determined following non-linear regression analyses. Taxonomic composition and total algal biovolume were determined at the end of the experiment. The periphyton composition did not change with shade but the PI curves were significantly affected by it. I k increased linearly with increasing percent irradiance transmittance (%IT = 1−%shade). P max could be fitted with a PI curve equation as it increased with %IT and leveled off after 10%IT. For each shade level, the PI curve was used to integrate daily photosynthesis for a day of average irradiance. The daily photosynthesis followed a PI curve equation with the same characteristics as P max vs. %IT. Thus, periphyton exhibited a high irradiance plasticity under 0–80% shade but could not keep up the same photosynthetic level at higher shade, causing a decrease in daily GPP at 98% shade levels. The plasticity was linked to an increase in the chl a content per cell in the 60–80% shade, while this increase was not observed at lower shade likely because it was too demanding energetically. Thus, chl a is not a good metric for periphyton biomass assessment across variously shaded habitats. It is also hypothesized that irradiance plasticity is linked to photosynthetic coupling between differently comprised algal layers arranged vertically within periphyton mats that have different PI curves.

The Influence of Hydrologic Restoration on Groundwater-Surface Water Interactions in a Karst Wetland, the Everglades (FL, USA)

Efforts to rehydrate and restore surface water flow in karst wetlands can have unintended consequences, as these highly conductive and heterogeneous aquifers create a close connection between groundwater and surface water. Recently, hydrologic restoration efforts in the karstic Taylor Slough portion of the Everglades has changed from point source delivery of canal water (direct restoration), to the use of a series of surface water recharge retention basins (diffuse restoration). To determine the influence of restoration on groundwater-surface water interactions in the Taylor Slough headwaters, a water budget was constructed for 1997–2011 using 70 hydro-meteorological stations. With diffuse restoration, groundwater seepage from the Everglades toward the urban boundary increased, while the downstream delivery of surface water to the main portion of the slough declined. The combined influence of diffuse restoration and climate led to increased intra-annual variability in the volume of groundwater and surface water in storage but supported a more seasonally hydrated wetland compared to the earlier direct tactics. The data further indicated that hydrologic engineering in karst wetland landscapes enhances groundwater-surface water interactions, even those designed for restoration purposes.

Maps of Sea Level Rise - Nautilus Island, Miami Beach, FL

A series of 7 maps illustrating the impact of sea level rise on Nautilus Island in Miami Beach.

The 2008 Terrestrial Vegetation of Biscayne National Parko FL, USA Derived From Aerial Photography, NDVI, and LiDAR

Established as a National Park in 1980, Biscayne National Park (BISC) comprises an area of nearly 700 km2 , of which most is under water. The terrestrial portions of BISC include a coastal strip on the south Florida mainland and a set of Key Largo limestone barrier islands which parallel the mainland several kilometers offshore and define the eastern rim of Biscayne Bay. The upland vegetation component of BISC is embedded within an extensive coastal wetland network, including an archipelago of 42 mangrove-dominated islands with extensive areas of tropical hardwood forests or hammocks. Several databases and vegetation maps describe these terrestrial communities. However, these sources are, for the most part, outdated, incomplete, incompatible, or/and inaccurate. For example, the current, Welch et al. (1999), vegetation map of BISC is nearly 10 years old and represents the conditions of Biscayne National Park shortly after Hurricane Andrew (August 24, 1992). As a result, a new terrestrial vegetation map was commissioned by The National Park Service Inventory and Monitoring Program South Florida / Caribbean Network.

Environmental analysis of polar herbicides in complex organic-rich matrices by high performance liquid chromatography atmospheric pressure ionization mass spectrometry (HPLC-API-MS)

A comprehensive forensic investigation of sensitive ecosystems in the Everglades Area is presented. Assessing the background levels of contamination in these ecosystems represents a vital resource to build up forensic evidence required to enforce future environmental crimes within the studied areas. This investigation presents the development and validation of a fractionation and isolation method for two families of herbicides commonly applied in the vicinity of the study area, including phenoxy acids like 2,4-D, MCPA, and silvex; as well as the most common triazine-based herbicides like atrazine, prometyne, simazine and related metabolites like DIA and DEA. Accelerated solvent extraction (ASE) and solid phase extraction (SPE) were used to isolate the analytes from abiotic matrices containing large amounts of organic material. Atmospheric-pressure ionization (API) with electrospray ionization in negative mode (ESP-), and Chemical Ionization in the positive mode (APCI+) were used to perform the characterization of the herbicides of interest.

Ten Year Study on Water Flushing Times and Water Quality in Southern Taylor Slough, Everglades National Park, FL

The purpose of this research was to investigate the effects of wetland restoration on the water balance, flushing time, and water chemistry of southern Taylor Slough, a major water way in Everglades National Park. Water balance and flushing time equations were calculated on a monthly time step from 2001 – 2011. Water chemistry of major ions and nutrients were analyzed and correlated with water flushing times. Results showed that evapotranspiration followed by water volume had the greatest influence on flushing time. The flushing times varied between 3 and 78 days, with longer times observed between October and December, and the shorter times between March and May. Ion concentrations at the coastal areas decreased with increased flushing times. Increased surface water inflow that resulted from restoration projects and water management changes were productive in the rainy season and should result in increased flushing times and decreased ion concentrations in Taylor Slough.

High-performance liquid chromatography (HPLC) and high-performance liquid chromatography mass spectrometry (HPLC/MS) for the analysis of date rape drugs

The drugs studied in this work have been reportedly used to commit drug-facilitated sexual assault (DFSA), commonly known as "date rape". Detection of the drugs was performed using high-performance liquid chromatography with ultraviolet detection (HPLC/UV) and identified with high performance-liquid chromatography mass spectrometry (HPLC/MS) using selected ion monitoring (SIM). The objective of this study was to develop a single HPLC method for the simultaneous detection, identification and quantitation of these drugs. The following drugs were simultaneously analyzed: Gamma-hydroxybutyrate (GHB), scopolamine, lysergic acid diethylamide, ketamine, flunitrazepam, and diphenhydramine. The results showed increased sensitivity with electrospray (ES) ionization versus atmospheric pressure chemical ionization (APCI) using HPLC/MS. HPLC/ES/MS was approximately six times more sensitive than HPLC/APCI/MS and about fifty times more sensitive than HPLC/UV. A limit of detection (LOD) of 100 ppb was achieved for drug analysis using this method. The average linear regression coefficient of correlation squared (r2) was 0.933 for HPLC/UV and 0.998 for HPLC/ES/MS. The detection limits achieved by this method allowed for the detection of drug dosages used in beverage tampering. This method can be used to screen beverages suspected of drug tampering. The results of this study demonstrated that solid phase microextraction (SPME) did not improve sensitivity as an extraction technique when compared to direct injections of the drug standards.