Assessment of the occurrence and potential effects of pharmaceuticals and personal care products in South Florida waters and sediments

A LLE-GC-MS method was developed to detect PPCPs in surface water samples from Big Cypress National Park, Everglades National Park and Biscayne National Park in South Florida. The most frequently found PPCPs were caffeine, DEET and triclosan with detected maximum concentration of 169 ng/L, 27.9 ng/L and 10.9 ng/L, respectively. The detection frequencies of hormones were less than PPCPs. Detected maximal concentrations of estrone, 17β-estradiol, coprostan-3-ol, coprostane and coprostan-3-one were 5.98 ng/L, 3.34 ng/L, 16.5 ng/L, 13.5 ng/L and 6.79 ng/L, respectively. An ASE-SPE-GC-MS method was developed and applied to the analysis of the sediment and soil area where reclaimed water was used for irrigation. Most analytes were below detection limits, even though some of analytes were detected in the reclaimed water at relatively high concentrations corroborating the fact that PPCPs do not significantly partition to mineral phases. An online SPE-HPLC-APPI-MS/MS method and an online SPE-HPLC-HESI-MS/MS method were developed to analyze reclaimed water and drinking water samples. In the reclaimed water study, reclaimed water samples were collected from the sprinkler for a year-long period at Florida International University Biscayne Bay Campus, where reclaimed water was reused for irrigation. Analysis results showed that several analytes were continuously detected in all reclaimed water samples. Coprostanol, bisphenol A and DEET's maximum concentration exceeded 10 μg/L (ppb). The four most frequently detected compounds were diphenhydramine (100%), DEET (98%), atenolol (98%) and carbamazepine (96%). In the study of drinking water, 54 tap water samples were collected from the Miami-Dade area. The maximum concentrations of salicylic acid, ibuprofen and DEET were 521 ng/L, 301 ng/L and 290 ng/L, respectively. The three most frequently detected compounds were DEET (93%), carbamazepine (43%) and salicylic acid (37%), respectively. Because the source of drinking water in Miami-Dade County is the relatively pristine Biscayne aquifer, these findings suggest the presence of wastewater intrusions into the delivery system or the onset of direct influence of surface waters into the shallow aquifer.

Online solid phase extraction liquid chromatography tandem mass spectrometry (SPE-LC-MS/MS) method for the determination of sucralose in reclaimed and drinking waters and its photo degradation in natural waters from South Florida

Background Sucralose has gained popularity as a low calorie artificial sweetener worldwide. Due to its high stability and persistence, sucralose has shown widespread occurrence in environmental waters, at concentrations that could reach up to several μg/L. Previous studies have used time consuming sample preparation methods (offline solid phase extraction/derivatization) or methods with rather high detection limits (direct injection) for sucralose analysis. This study described a faster and sensitive analytical method for the determination of sucralose in environmental samples. Results An online SPE-LC–MS/MS method was developed, being capable to quantify sucralose in 12 minutes using only 10 mL of sample, with method detection limits (MDLs) of 4.5 ng/L, 8.5 ng/L and 45 ng/L for deionized water, drinking and reclaimed waters (1:10 diluted with deionized water), respectively. Sucralose was detected in 82% of the reclaimed water samples at concentrations reaching up to 18 μg/L. The monthly average for a period of one year was 9.1 ± 2.9 μg/L. The calculated mass loads per capita of sucralose discharged through WWTP effluents based on the concentrations detected in wastewaters in the U. S. is 5.0 mg/day/person. As expected, the concentrations observed in drinking water were much lower but still relevant reaching as high as 465 ng/L. In order to evaluate the stability of sucralose, photodegradation experiments were performed in natural waters. Significant photodegradation of sucralose was observed only in freshwater at 254 nm. Minimal degradation (<20%) was observed for all matrices under more natural conditions (350 nm or solar simulator). The only photolysis product of sucralose identified by high resolution mass spectrometry was a de-chlorinated molecule at m/z 362.0535, with molecular formula C12H20Cl2O8. Conclusions Online SPE LC-APCI/MS/MS developed in the study was applied to more than 100 environmental samples. Sucralose was frequently detected (>80%) indicating that the conventional treatment process employed in the sewage treatment plants is not efficient for its removal. Detection of sucralose in drinking waters suggests potential contamination of surface and ground waters sources with anthropogenic wastewater streams. Its high resistance to photodegradation, minimal sorption and high solubility indicate that sucralose could be a good tracer of anthropogenic wastewater intrusion into the environment.

Assessing the sources, quantities, and trends on human waste contamination along protected south Florida ecosystem: A chemical tracer based study

The common occurrence of human derived contaminants like pharmaceuticals, steroids and hormones in surface waters has raised the awareness of the role played by the release of treated or untreated sewage in the water quality along sensitive coastal ecosystems. South Florida is home to many important protected environments ranging from wetlands to coral reefs which are in close proximity to large metropolitan cities. Since large portions of South Florida and most of the Florida Keys population are not served by modern sewage treatment plants and rely heavily on the use of inefficient septic systems; a comprehensive survey of selected human waste contamination markers is needed in these areas to assess water quality with respect to non-traditional micro-constituents. ^ This study reports the development and application of new sensitive and selective analytical methods for the fast screening of multiple wastewater tracers, classified as Emergent Pollutants of Concern (EPOC). Novel methods for the trace analysis of non-traditional markers of human-specific contamination such as aminopropanone were developed and used to assess the potential of non-traditional markers as wastewater tracers. ^ During our investigation, surface water samples collected from near shore environments along the South Florida were analyzed for fifteen hormones and steroids, and five commonly detected pharmaceuticals. The compounds most frequently detected were: coprostanol, cholesterol, estrone, β-estradiol, caffeine, triclosan and DEET. Concentrations of caffeine, bisphenol A and DEET were usually higher and more prevalent than the hormonal steroids. In general, it was found that common pharmaceuticals and steroids are widely present in major coastal environments in South Florida. It is also evident that aquatic bodies in heavily urbanized sectors such as the Miami River and Key Largo Harbor contain higher concentrations of several compounds while relatively open bay waters and agricultural areas show reduced chemical signatures. Concentrations of hormones in the Little Venice area of Marathon Key were above the Lowest Observable Effect Levels (LOELs) for several species, indicating that biological resources in this area are at risk. Water quality issues in some of these coastal water environments go beyond eutrophication, thus EPOC should be the target goal for future mitigation projects. ^

Mangrove production and carbon sinks: A revision of global budget estimates

Mangrove forests are highly productive but globally threatened coastal ecosystems, whose role in the carbon budget of the coastal zone has long been debated. Here we provide a comprehensive synthesis of the available data on carbon fluxes in mangrove ecosystems. A reassessment of global mangrove primary production from the literature results in a conservative estimate of ∼218 ± 72 Tg C a−1. When using the best available estimates of various carbon sinks (organic carbon export, sediment burial, and mineralization), it appears that >50% of the carbon fixed by mangrove vegetation is unaccounted for. This unaccounted carbon sink is conservatively estimated at ∼112 ± 85 Tg C a−1, equivalent in magnitude to ∼30–40% of the global riverine organic carbon input to the coastal zone. Our analysis suggests that mineralization is severely underestimated, and that the majority of carbon export from mangroves to adjacent waters occurs as dissolved inorganic carbon (DIC). CO2 efflux from sediments and creek waters and tidal export of DIC appear to be the major sinks. These processes are quantitatively comparable in magnitude to the unaccounted carbon sink in current budgets, but are not yet adequately constrained with the limited published data available so far.

Occurrence and distribution of novel botryococcene hydrocarbons in freshwater wetlands of the Florida Everglades

A high abundance of isoprenoid hydrocarbons, the botryococcenes, with carbon numbers from 32 to 34 were detected in the Florida Everglades freshwater wetlands. These compounds were present in varying amounts up to 106 μg/gdw in periphyton, 278 μg/gdw in floc, and 46 μg/gdw in soils. Their structures were determined based on comparison to standards, interpretation of their mass spectra and those of their hydrogenation products, and comparison of Kovats indexes to those reported in the literature. A total of 26 cyclic and acyclic botryococcenes with 8 skeletons were identified, including those with fewer degrees of unsaturation, which are proposed as early diagenetic derivatives from the natural products. This is the first report that botryococcenes occur in the Everglades freshwater wetlands. Their potential biogenetic sources from green algae and cyanobacteria were examined, but neither contained botryococcenes. Thus, the source implication of botryococcenes in this ecosystem needs further study.

Effects of hydrologic and water quality drivers on periphyton dynamics in the southern Everglades

Everglades periphyton mats are tightly-coupled autotrophic (algae and cyanobacteria) and heterotrophic (eubacteria, fungi and microinvertebrates) microbial assemblages. We investigated the effect of water column total phosphorus and nitrogen concentrations, water depth and hydroperiod on periphyton of net production, respiration, nutrient content, and biomass. Our study sites were located along four transects that extended southward with freshwater sheetflow through sawgrass-dominated marsh. The water source for two of the transects were canal-driven and anchored at canal inputs. The two other transects were rain-driven (ombrotrophic) and began in sawgrass-dominated marsh. Periphyton dynamics were examined for upstream and downstream effects within and across the four transects. Although all study sites were characterized as short hydroperiod and phosphorus-limited oligotrophic, they represent gradients of hydrologic regime, water source and water quality of the southern Everglades. Average periphyton net production of 1.08 mg C AFDW−1 h−1 and periphyton whole system respiration of 0.38 mg C AFDW−1 h−1 rates were net autotrophic. Biomass was generally highest at ombrotrophic sites and sites downstream of canal inputs. Mean biomass over all our study sites was high, 1517.30 g AFDW m−2. Periphyton was phosphorus-limited. Average periphyton total phosphorus content was 137.15 μg P g−1 and average periphyton total N:P ratio was 192:1. Periphyton N:P was a sensitive indicator of water source. Even at extremely low mean water total phosphorus concentrations ( ≤ 0.21 μmol l−1), we found canal source effects on periphyton dynamics at sites adjacent to canal inputs, but not downstream of inflows. These canal source effects were most pronounced at the onset of wet season with initial rewetting. Spatial and temporal variability in periphyton dynamics could not solely be ascribed to water quality, but was often associated with both hydrology and water source.

Determination of Arsenic Species in Water and Grape-Based Beverages

Arsenic is a human carcinogen that has been found in various waters and wines throughout the world. Therefore, close examination of these liquids is necessary to prevent the intoxication of animals and humans. Wines and waters often contain significant amounts of toxic arsenic species. The source of arsenic in wines and waters is generally believed to be the result of arsenic-based pesticides and herbicides. Recent studies have also shown that toxic arsenic may be used in the cultivation and acceleration of the ripening process of fruit, ultimately contaminating fruit-based beverages. The determination of total arsenic can be found by using several methods, including AFS or ICP/MS. No pretreatment of water is necessary, except for filtering by means of a Fisherbrand PTFE 0.45 connected to a Becton-Dickinson 10 mL syringe to filter particles from water. The pretreatment of the wine includes ethanol evaporation and an addition of 0.1% nitric acid. A number of commercial drinking waters and regional lake water were analyzed. Since we have confirmed the presence of arsenic in a variety of waters and wines from different countries, we decided to test a number of commercially available beverages for the presence of arsenic. The focus ofthis project is to establish the presence of arsenic in various commercially available beverages. ICP-MS was used to determine total arsenic using certified standards. Internal standards Indium and Yttrium were also used to verify the concentration readings, which varied from 0- 20 ppb.

Photo-Reactivity of Natural Dissolved Organic Matter from Fresh to Marine Waters in the Florida Everglades, USA

Natural dissolved organic matter (DOM) is the major absorber of sunlight in most natural waters and a critical component of carbon cycling in aquatic systems. The combined effect of light absorbance properties and related photo-production of reactive species are essential in determining the reactivity of DOM. Optical properties and in particular excitation–emission matrix fluorescence spectroscopy combined with parallel factor analysis (EEM-PARAFAC) have been used increasingly to track sources and fate of DOM. Here we describe studies conducted in water from two estuarine systems in the Florida Everglades, with a salinity gradient of 2 to 37 and dissolved organic carbon concentrations from 19.3 to 5.74 mg C L−1, aimed at assessing how the quantity and quality of DOM is coupled to the formation rates and steady-state concentrations of reactive species including singlet oxygen, hydroxyl radical, and the triplet excited state of DOM. These species were related to optical properties and PARAFAC components of the DOM. The formation rate and steady-state concentration of the carbonate radical was calculated in all samples. The data suggests that formation rates, particularly for singlet oxygen and hydroxyl radicals, are strongly coupled to the abundance of terrestrial humic-like substances. A decrease in singlet oxygen, hydroxyl radical, and carbonate radical formation rates and steady-state concentration along the estuarine salinity gradient was observed as the relative concentration of terrestrial humic-like DOM decreased due to mixing with microbial humic-like and protein-like DOM components, while the formation rate of triplet excited-state DOM did not change. Fluorescent DOM was also found to be more tightly coupled to reactive species generation than chromophoric DOM.

Bilirubin Present in Diverse Angiosperms

Background and aims: Bilirubin is an orange-yellow tetrapyrrole produced from the breakdown of heme by mammals and some other vertebrates. Plants, algae, and cyanobacteria synthesize molecules similar to bilirubin, including the protein-bound bilins and phytochromobilin which harvest or sense light. Recently, we discovered bilirubin in the arils of Strelitzia nicolai, the White Bird of Paradise Tree, which was the first example of this molecule in a higher plant. Subsequently, we identified bilirubin in both the arils and flowers of Strelitzia reginae, the Bird of Paradise Flower. In the arils of both species, bilirubin is present as the primary pigment, and thus functions to produce color. Previously, no tetrapyrroles were known to generate display color in plants. We were therefore interested in determining whether bilirubin is broadly distributed in the plant kingdom, and whether it contributes to color in other species.

Pink shrimp as an indicator for restoration of everglades ecosystems

The pink shrimp, Farfantepenaeus duorarum, familiar to most Floridians as either food or bait shrimp, is ubiquitous in South Florida coastal and offshore waters and is proposed as an indicator for assessing restoration of South Florida's southern estuaries: Florida Bay, Biscayne Bay, and the mangrove estuaries of the lower southwest coast. Relationships between pink shrimp and salinity have been determined in both field and laboratory studies. Salinity is directly relevant to restoration because the salinity regimes of South Florida estuaries, critical nursery habitat for the pink shrimp, will be altered by changes in the quantity, timing, and distribution of freshwater inflow planned as part of the Comprehensive Everglades Restoration Project (CERP). Here we suggest performance measures based on pink shrimp density (number per square meter) in the estuaries and propose a restoration assessment and scoring scheme using these performance measures that can readily be communicated to managers, policy makers, and the interested public. The pink shrimp is an appropriate restoration indicator because of its ecological as well as its economic importance and also because scientific interest in pink shrimp in South Florida has produced a wealth of information about the species and relatively long time series of data on both juveniles in estuarine nursery habitats and adults on the fishing grounds. We suggest research needs for improving the pink shrimp performance measure.

Potential role of sponge communities in controlling phytoplankton blooms in Florida Bay

An unprecedented series of ecological disturbances have been recurring within Florida Bay since the summer of 1987. Persistent and widespread phytoplankton and cyanobacteria blooms have coincided with the large scale decimation of sponge communities. One hypothesis is that the large scale loss of suspension-feeding sponges has rendered the Florida Bay ecosystem susceptible to these recurring blooms. The primary objective of this study was to experimentally evaluate the potential for suspension-feeding sponges to control nuisance phytoplankton blooms within Florida Bay prior to a large sponge die-off event. To achieve this objective, we determined the extent and biomass of the surviving sponge community in the different basins of Florida Bay. Many areas within Florida Bay possessed sponge densities and biomasses of 1 to 3 ind. m–2 or 100 to 300 g m–2 respectively. The dominant species includedSpheciospongia vesparia, Chondrilla nucula, Cinachyra alloclada, Tedania ignis and Ircinia sp., which accounted for 68% of individual sponges observed and 88% of sponge biomass. Laboratory grazing rates of these dominant sponges were experimentally determined on 4 different algal food treatments: a monoculture of cyanobacteria Synechococcus elongatus, a monoculture of the diatom Cyclotella choctawhatcheeana, a monoculture of the dinoflagellate Prorocentrum hoffmanianum, and an equal volume of the 3 monocultures combined. To estimate the impact of a mass sponge mortality event on the system-wide filtration rate of Florida Bay, we combined estimates of the current sponge biomass and laboratory sponge filtration rates with estimates of mean volumes of the sub-basins of Florida Bay. This study implies that the current blooms occurring within the central region of Florida Bay can be explained by the loss of the dominant suspension feeder in this system, and there is no need to invoke a new addition of nutrients within this region for the blooms to occur.

Photo degradation of contaminants of emerging concern (CECs) under simulated solar radiation: Implications for their environmental fate

Contaminants of emerging concern (CECs) are continuously being released into the environment mainly because of their incomplete removal in the sewage treatment plants (STPs). The CECs selected for the study include antibiotics (macrolides, sulfonamides and ciprofloxacin), sucralose (an artificial sweetener) and dioctyl sulfosuccinate (DOSS, chemical dispersant used in the Deepwater Horizon oil spill). After being discharged into waterways from STPs, photo degradation is a key factor in dictating the environmental fate of antibiotics and sucralose. Photodegradation efficiency depends on many factors such as pH of the matrix, matrix composition, light source and structure of the molecule. These factors exert either synergistic or antagonistic effects in the environment and thus experiments with isolated factors may not yield the same results as the natural environmental processes. Hence in the current study photodegradation of 13 CECs (antibiotics, sucralose and dicotyl sulfosuccinate) were evaluated using natural water matrices with varying composition (deionized water, fresh water and salt water) as well as radiation of different wavelengths (254 nm, 350 nm and simulated solar radiation) in order to mimic natural processes. As expected the contribution of each factor on the overall rate of photodegradation is contaminant specific, for example under similar conditions, the rate in natural waters compared to pure water was enhanced for antibiotics (2-11 fold), significantly reduced for sucralose (no degradation seen in natural waters) and similar in both media for DOSS. In general, it was observed that the studied compounds degraded faster at 254 nm, while when using a simulated sunlight radiation the rate of photolysis of DOSS increased and the rates for antibiotics decreased in comparison to the 350 nm radiation. The photo stability of the studied CECs followed the order sucralose > DOSS > macrolides > sulfonamides > ciprofloxacin and a positive relationship was observed between photo stability and their ubiquitous presence in natural aquatic matrices. An online LC-MS/MS method was developed and validated for sucralose and further applied to reclaimed waters (n =56) and drinking waters (n = 43) from South Florida. Sucralose was detected in reclaimed waters with concentrations reaching up to 18 μg/L. High frequency of detection (> 80%) in drinking waters indicate contamination of ground waters in South Florida by anthropogenic activity.^

Assessment of silicone polymer composites for the trace extraction of herbicides : a tool for environmental forensics

Passive samplers are not only a versatile tool to integrate environmental concentrations of pollutants, but also to avoid the use of live sentinel organisms for environmental monitoring. This study introduced the use of magnetic silicone polymer composites (Fe-PDMS) as passive sampling media to pre-concentrate a wide range of analytes from environmental settings. The composite samplers were assessed for their accumulation properties by performing lab experiments with two model herbicides (Atrazine and Irgarol 1051) and evaluated for their uptake properties from environmental settings (waters and sediments). The Fe-PDMS composites showed good accumulation of herbicides and pesticides from both freshwater and saltwater settings and the accumulation mechanism was positively correlated with the log Kow value of individual analytes. Results from the studies show that these composites could be easily used for a wide number of applications such as monitoring, cleanup, and/or bioaccumulation modeling, and as a non-intrusive and nondestructive monitoring tool for environmental forensic purposes.