Other articles by Piero Gardinali on PubMed

• Trace Determination of Caffeine in Surface Water Samples by Liquid Chromatography--atmospheric Pressure Chemical Ionization--mass Spectrometry (LC-APCI-MS) Environment International. Dec, 2002  |   Pubmed ID: 12503918 A new method based on liquid-liquid extraction (LLE) coupled to reverse phase liquid chromatography and atmospheric pressure chemical ionization mass spectrometry (LC-APCI-MS) has been applied to determine trace amounts of caffeine (1,3,7-trimethylxanthine) in surface water samples from a near coastal ecosystem such as Biscayne Bay, Florida. The rational behind the development of such method will be to evaluate the use of unmetabolized caffeine as a potential dissolved phase tracer of human waste contamination. The method allows for the determination of caffeine at levels as low as 4.0 ng/l (ppt) in both salt and freshwater by extracting and concentrating a 1-1 water sample to a final volume of 500 microl and using HPLC separation coupled to an atmospheric pressure chemical ionization mass spectrometry (APCI-MS) system operated in selected ion monitoring (SIM) for the protonated molecular ions (M + H(+)). Samples from different portions of Biscayne Bay and the Miami River, one of its major tributaries, were analyzed and caffeine was detected in those areas previously identified for consistently exceeding the water quality criteria for fecal coliform bacteria contamination. The caffeine concentration in the samples with positive detection was generally low at levels equal or lower than 41 ng/l. However, there is a marked difference between samples collected in open bay areas and those collected from the Miami River.
• Occurrence of IRGAROL 1051 in Coastal Waters from Biscayne Bay, Florida, USA Marine Pollution Bulletin. Aug, 2002  |   Pubmed ID: 12269481 Surface water samples from marinas, commercial ports and open bay areas collected from Biscayne Bay and the Miami River, Florida, USA, were analyzed for the occurrence of IRGAROL 1051 by GC/MS. The anifouling boosting herbicide was found in 80% (46/57) of the samples collected between March 1999 and September 2000. Concentrations within the bay range between non-detected (
• Organic Compounds and Trace Metals of Anthropogenic Origin in Sediments from Montego Bay, Jamaica: Assessment of Sources and Distribution Pathways Environmental Pollution (Barking, Essex : 1987). 2003  |   Pubmed ID: 12628208 Surface sediments throughout Montego Bay, Jamaica were collected in 1995 and analyzed for their trace metal and trace organic contaminant content. A variety of trace metals, petroleum hydrocarbons, polycyclic aromatic hydrocarbons, coprostanol as well as chlorinated hydrocarbons such as pesticides and polychlorinated biphenyls were detected and provide evidence for several anthropogenic inputs to the bay. Two main sources of these chemicals are the Montego River and the North Gully, the latter being more significant. Particle-associated pollutants were found to be distributed along the Montego River plume, as well as being transported by the prevailing water currents to the South-Western sections of the bay, probably through re-suspension of enriched fine sediments from the North Gully outfall area.
• Occurrence and Transport of Irgarol 1051 and Its Major Metabolite in Coastal Waters from South Florida Marine Pollution Bulletin. Dec, 2004  |   Pubmed ID: 15556195 Irgarol 1051, a boosting antifouling agent often used to supplement copper based paints was found in surface waters from South Florida at stations collected from the Miami River, Biscayne Bay and selected areas of the Florida Keys. Concentrations of the herbicide ranged from below the method detection limit (1 ng/L) to as high as 182 ng/L in a canal system in Key Largo. The herbicide was present at 93% of the stations and often found in conjunction with its descyclopropyl metabolite (M1) previously reported to be the major degradation product of Irgarol under natural environmental conditions. The 90th percentile concentration calculated for all South Florida samples was 57.6 ng/L. Based on available data on the toxicity of Irgarol to algae and coral, only two stations (approximately 3%) ranked above the LC50 of 136 ng/L reported for the marine algae Naviculla pelliculosa and above the 100 ng/L level reported to reversibly inhibit photosynthesis of intact corals. However, a basic dissipation model for Irgarol using the Key Largo Harbor station as a point source indicated that concentrations of the herbicide decreased rapidly and concentrations below the MDL are observed within 2000 m of the source. No major coral based benthic habitats are documented for all the stations surveyed at distances that Irgarol may pose a substantial risk. However, other types of submerged vegetation like seagrasses are common around the marinas and the effects of Irgarol to such endpoints should be investigated further.
• South Florida Ecosystems Ecotoxicology (London, England). Apr, 2004  |   Pubmed ID: 15217242
• Occurrence of Irgarol 1051 and Its Major Metabolite in Maryland Waters of Chesapeake Bay Marine Pollution Bulletin. Mar, 2004  |   Pubmed ID: 14980471 Irgarol and its major metabolite (GS26575) were measured in Maryland waters of Chesapeake Bay: (1) in and near 10 marinas, a mainstem Bay site and two Severn River locations during a general survey in July and December of 2002; (2) at various sites in the Port Annapolis Marina and the Severn River area during March of 2002 before the boating season began; and (3) during July (peak boating season) in the same Port Annapolis Marina and Severn River sites area during both an ebb and flood tide. Irgarol concentrations ranged from 1.82 ng/l at the mid-Bay site to 585 ng/l in Port Annapolis marina during the July and December general survey. An Irgarol 90th centile of 239 ng/l was reported for the 10 marina sites, two Severn River sites and one mainstem site sampled during the general survey conducted in July and December. Temporal analysis of all pooled data showed that 90th centiles were over seven times higher in July when compared to December. A comparison of Irgarol concentrations at 12 sites in the Port Annapolis marina and Severn River area during both an ebb and flood tide in July showed no consistent trend with tidal cycle by site although significant reductions in concentrations were reported with distance from the three Port Annapolis marina sites. Ecological risk from Irgarol exposure was judged to be low for most Chesapeake Bay sites sampled. Possible exceptions were Port Annapolis marina, Severn River sites in close proximity to this marina and Chesapeake Harbor marina where Irgarol concentrations exceeded a conservative effects threshold during the peak boating season in July. Ecological risk from GS26575 exposure was low for all sites.
• Brevetoxin Degradation and By-Product Formation Via Natural Sunlight Harmful Algae 2002 : Proceedings of the Xth International Conference on Harmful Algae, St. Pete Beach, Florida, USA, October 21-25, 2002. International Conference on Harmful Algae (10th : 2002 : St. Pete Beach, Florida). 2004  |   Pubmed ID: 26436141 We investigated the effects of solar radiation on brevetoxin (PbTx2). Our findings suggest that natural sunlight mediates brevetoxin (PbTx2) degradation and results in brevetoxin by-product formation via photochemical processes.
• Uptake and Depuration of Toxic Halogenated Aromatic Hydrocarbons by the American Oyster (Crassostrea Virginica): a Field Study Chemosphere. Jan, 2004  |   Pubmed ID: 14559258 Uptake and depuration of toxic chlorinated compounds such as planar polychlorinated biphenyls (PCBs 77, 126, 169), 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) and 2,3,7,8-tetrachlorodibenzofuran (TCDF) were monitored during a 50-day field study where American oysters (Crassostrea virginica) were transplanted back and forth between a heavily polluted area (Houston Ship Channel, SC) and a relatively unimpacted area (Hanna's Reef, HR) within Galveston Bay, TX. In general, low molecular weight, less lipophilic compounds accumulated in the oysters to a larger extent than high molecular weight ones. Estimated half-lives for planar PCB congeners 77 and 126 were 28 and 51 days, respectively for depuration of newly contaminated oysters (HR-SC-HR) while longer half-lives (42 and 60 days, respectively) were observed for the same compounds as they were eliminated from chronically contaminated individuals (SC-HR). Estimated half-lives for 2,3,7,8-TCDD and 2,3,7,8-TCDF were 35 and 36 days, respectively and were similar to the tetrachlorinated biphenyls (PCBs 77 and 81). Compared with ortho-substituted PCB congeners of the same chlorination level, the more toxic PCBs take longer to depurate from the oysters. With few exceptions, elimination of all toxic compounds investigated proceeded at a slower rate from the chronically exposed population that from the newly contaminated one.
• Monitoring of Irgarol 1051 Concentrations with Concurrent Phytoplankton Evaluations in East Coast Areas of the United States Marine Pollution Bulletin. Jun, 2005  |   Pubmed ID: 15935182 The objectives of this study were to measure: (1) Irgarol and GS26575 (major metabolite) during the peak 2004 boating season at selected marinas and reference areas in the Carolinian Zoogeographic Province of the Eastern United States; (2) Irgarol and GS26575 at selected stations during the summer months in the Back Creek/Severn River area in Maryland in 2003 and 2004; and (3) structural and functional characteristics of resident phytoplankton communities concurrently with Irgarol and GS26575 monitoring in Back Creek/Severn River area. Irgarol concentrations from 14 marinas in the Carolinian Province ranged from non-detectable (
• Assessing the Effects of Irgarol 1051 on Marine Phytoplankton Populations in Key Largo Harbor, Florida Marine Pollution Bulletin. Aug, 2006  |   Pubmed ID: 16472825 The antifouling boosting agent Irgarol 1051 is a strong inhibitor of the photosystem II (PSII) with high efficiency/toxicity towards algae. However, because some phytoplankton species are more sensitive to Irgarol than others, its persistent release into the environment could result in adverse changes in the phytoplankton community structure at heavily impacted sites such as marinas. Continuous monitoring in the Florida Keys showed Irgarol concentrations of up to 635 ngL(-1) in the canal system leading to Key Largo Harbor Marina (KLH) with a sharp decrease in concentration at stations offshore from the mouth of the canal. Preliminary phytoplankton community assessments from surface water samples collected in KLH between February and August 2004 showed changes in several phytoplankton species in concordance with the increase of the herbicide concentrations. Typical responses include an increase in the abundance of eukaryotes and Cryptomonas sp. as Irgarol concentrations increase.
• Free Radical Chemistry of Disinfection-byproducts. 1. Kinetics of Hydrated Electron and Hydroxyl Radical Reactions with Halonitromethanes in Water The Journal of Physical Chemistry. A. Feb, 2006  |   Pubmed ID: 16466253 Halonitromethanes are disinfection-byproducts formed during ozonation and chlorine/chloramine treatment of waters that contain bromide ion and natural organic matter. In this study, the chemical kinetics of the free-radical-induced degradations of a series of halonitromethanes were determined. Absolute rate constants for hydroxyl radical, *OH, and hydrated electron, e(aq)-, reaction with both chlorinated and brominated halonitromethanes were measured using the techniques of electron pulse radiolysis and transient absorption spectroscopy. The bimolecular rate constants obtained, k (M(-1) s(-1)), for e(aq)-/*OH, respectively, were the following: chloronitromethane (3.01 +/- 0.40) x 10(10)/(1.94 +/- 0.32) x 10(8); dichloronitromethane (3.21 +/- 0.17) x 10(10)/(5.12 +/- 0.77) x 10(8); bromonitromethane (3.13 +/- 0.06) x 10(10)/(8.36 +/- 0.57) x 10(7); dibromonitromethane (3.07 +/- 0.40) x 10(10)/(4.75 +/- 0.98) x 10(8); tribromonitromethane (2.29 +/- 0.39) x 10(10)/(3.25 +/- 0.67) x 10(8); bromochloronitromethane (2.93 +/- 0.47) x 10(10)/(4.2 +/- 1.1) x 10(8); bromodichloronitromethane (2.68 +/- 0.13) x 10(10)/(1.02 +/- 0.15) x 10(8); and dibromochloronitromethane (2.95 +/- 0.43) x 10(10) / (1.80 +/- 0.31) x 10(8) at room temperature and pH approximately 7. Comparison data were also obtained for hydroxyl radical reaction with bromoform (1.50 +/- 0.05) x 10(8), bromodichloromethane (7.11 +/- 0.26) x 10(7), and chlorodibromomethane (8.31 +/- 0.25) x 10(7) M(-1) s(-1), respectively. These rate constants are compared to recently obtained data for trichloronitromethane and bromonitromethane, as well as to other established literature data for analogous compounds.
• Trace Determination of 1-aminopropanone, a Potential Marker for Wastewater Contamination by Liquid Chromatography and Atmospheric Pressure Chemical Ionization-mass Spectrometry Water Research. Feb, 2006  |   Pubmed ID: 16443254 1-Aminopropanone (APR) is a volatile aminoketone of human origin that has been identified in raw sewage and surface waters. However, the traditional methodology for the determination of APR is extremely complicated and requires a skilled chemist to achieve consistent results. This investigation presents a novel and simple method for the analysis of APR by direct derivatization in aqueous media. APR is synthesized as its hydrochloride and derivatized using mercaptoethanol and o-phthalaldehyde. The product of reaction is separated on a 15 cm x 4.6 mm Luna C-18 column (1 mL/min, 45:55 acetonitrile: Water) and detected using a single quadrupole mass spectrometer detector operated in atmospheric pressure chemical ionization (APCI) mode. Method detection limits as low as 100 nM were routinely obtained with a precision of 1.7%. Recoveries of APR were always found to be greater then 88% in surface and wastewater samples fortified at three different levels. However, despite the robustness of the method and the fact that APR was consistently detected in urine it was not present in a variety surface or wastewaters analyzed during the course of the study. These results pose a critical question on the use of APR as a tracer for human derived wastewaters.
• Free Radical Chemistry of Disinfection Byproducts. 2. Rate Constants and Degradation Mechanisms of Trichloronitromethane (chloropicrin) Environmental Science & Technology. Feb, 2007  |   Pubmed ID: 17328195 Absolute rate constants for the free-radical-induced degradation of trichloronitromethane (TCNM, chloropicrin) were determined using electron pulse radiolysis and transient absorption spectroscopy. Rate constants for hydroxyl radical, *OH, and hydrated electron, e(aq)-, reactions were (4.97 +/- 0.28) x 10(7) M(-1) s(-1) and (2.13 +/- 0.03) x 10(10) M(-1) s(-1), respectively. It appears that the *OH adds to the nitro-group, while the e(aq)- reacts via dissociative electron attachment to give two carbon centered radicals. The mechanisms of these free radical reactions with TCNM were investigated, using 60Co gamma irradiation at various absorbed doses, measuring the disappearance of TCNM and the appearance of the product nitrate and chloride ions. The rate constants and mechanistic data were combined in a kinetic computer model that was used to describe the major free radical pathways for the destruction of TCNM in solution. These data are applicable to other advanced oxidation/reduction processes.
• Copper Desorption in Flooded Agricultural Soils and Toxicity to the Florida Apple Snail (Pomacea Paludosa): Implications in Everglades Restoration Environmental Pollution (Barking, Essex : 1987). Jul, 2008  |   Pubmed ID: 18068282 Copper (Cu) desorption and toxicity to the Florida apple snail were investigated from soils obtained from agricultural sites acquired under the Comprehensive Everglades Restoration Plan. Copper concentrations in 11 flooded soils ranged from 5 to 234 mg/kg on day 0 and from 6.2 to 204 mg/kg on day 28 (steady-state). The steady-state Cu concentration in overlying water ranged from 9.1 to 308.2 microg/L. In a 28-d growth study, high mortality in snails occurred within 9 to 16 d in two of three soil treatments tested. Growth of apple snails over 28 d was affected by Cu in these two treatments. Tissue Cu concentrations by day 14 were 12-23-fold higher in snails exposed to the three soil treatments compared to controls. The endangered Florida snail kite and its main food source, the Florida apple snail, may be at risk from Cu exposure in these managed agricultural soil-water ecosystems.
• The Relationship of Irgarol and Its Major Metabolite to Resident Phytoplankton Communities in a Maryland Marina, River and Reference Area Marine Pollution Bulletin. Jun, 2009  |   Pubmed ID: 19296991 The objectives of this study were to: (1) measure water column concentrations of Irgarol 1051 and its major metabolite GS26575 annually (2004-2006) during mid-June and mid-August at 14 sites in a study area comprised of three sub-regions chosen to reflect a gradient in Irgarol exposure (Port Annapolis marina, Severn River and Severn River reference area); (2) use a probabilistic approach to determine ecological risk of Irgarol and its major metabolite in the study area by comparing the distribution of exposure data with toxicity-effects endpoints; and (3) measure both functional and structural resident phytoplankton parameters concurrently with Irgarol and metabolite concentrations to assess relationships and determine ecological risk at six selected sites in the three study areas described above. The three-year summer mean Irgarol concentrations by site clearly showed a gradient in concentrations with greater values in Back Creek (400-500ng/L range), lower values in the Severn River sites near the confluence with Back Creek (generally values less than 100ng/L) and still lower values (
• Ecological Risk of Irgarol 1051 and Its Major Metabolite in Coastal California Marinas and Reference Areas Marine Pollution Bulletin. May, 2009  |   Pubmed ID: 19178917 The objective of this study was to use a probabilistic approach to determine the ecological risk of Irgarol and its major metabolite (GS26575) in coastal California marinas and reference areas by using monitoring data collected during the summer of 2006. Distributions of environmental exposure data were compared with the distribution of plant species response data from laboratory toxicity studies and the no observed effect concentration (NOEC) from a microcosm study to quantify the likelihood and significance of ecological risk. Toxicity testing indicates plants are much more sensitive to Irgarol than animals; therefore, the conservative effects benchmark used to characterize risk was the plant 10th centile for both Irgarol (193 ng/L) and GS26575 (5622 ng/L). In addition, the microcosm NOEC of 323 ng/L was also used to characterize risk. Irgarol concentrations from 15 California marinas ranged from 1.45 to 339 ng/L while GS26575 concentrations ranged from non-detected to 74 ng/L. The probability of exceeding the Irgarol plant 10th centile of 193 ng/L for 15 marinas sampled in coastal California in 2006 was 7.3% while the probability of exceeding the microcosm NOEC of 323 ng/L was even lower (5.5%). In general, this probability of exceedence for either effects benchmark and subsequent ecological risk is considered to be low for these marinas as only one marina (Kings Harbor marina in Redondo Beach) had measured concentrations of Irgarol exceeding 193 ng/L. Irgarol exposure is concentrated within marinas and ecological risk from Irgarol exposure in adjoining reference areas was judged to be very low. Ecological risk from GS26575 exposure was also low in both marina and reference areas in California.
• Assessment of Silicone Polymer Composites for Environmental Forensic Applications: a Proof of Concept Study Journal of Forensic Sciences. Sep, 2010  |   Pubmed ID: 20487157 This study evaluates the use of polydimethylsiloxane polymer composites (PDMS, Fe-PDMS) as a passive sampling media to preconcentrate analytes found in environmental settings. Samplers were made using commercially available silicone products. The composite samplers were assessed for their sorption properties using Atrazine and Irgarol 1051 as model compounds. The initial study assessed the utility of PDMS sheets as adsorption material by following analyte depletion from spiked water samples by solid-phase microextraction gas chromatography/mass spectrometry (GC/MS). Follow-up studies conducted at high and low concentrations using lab manufactured iron- PDMS rods (Fe-PDMS) showed effective uptake at differential rates from concentrations ranging between 1 μg/L and 10 μg/L. Adsorption mechanism was reversible, and compounds were recovered from the exposed materials and analyzed by liquid-liquid extraction-GC/MS. Both composites showed better affinity for Irgarol 1051, 100% removal, than for Atrazine, 30% removal, likely representing their K(OW) differences, 3.6 and 2.6, respectively. This "proof of concept" study demonstrates the positive implications for the use of silicon polymer composites as a monitoring tool for environmental forensic purposes.
• Endosulfan and Its Metabolite, Endosulfan Sulfate, in Freshwater Ecosystems of South Florida: a Probabilistic Aquatic Ecological Risk Assessment Ecotoxicology (London, England). Jun, 2010  |   Pubmed ID: 20204505 Endosulfan is an insecticide-acaricide used in South Florida and is one of the remaining organochlorine insecticides registered under the Federal Insecticide Fungicide and Rodenticide Act by the U.S.EPA. The technical grade material consists of two isomers (alpha-, beta-) and the main environmental metabolite in water, sediment and tissue is endosulfan sulfate through oxidation. A comprehensive probabilistic aquatic ecological risk assessment was conducted to determine the potential risks of existing exposures to endosulfan and endosulfan sulfate in freshwaters of South Florida based on historical data (1992-2007). The assessment included hazard assessment (Tier 1) followed by probabilistic risk assessment (Tier 2). Tier 1 compared actual measured concentrations in surface freshwaters of 47 sites in South Florida from historical data to U.S.EPA numerical water quality criteria. Based on results of Tier 1, Tier 2 focused on the acute and chronic risks of endosulfan at nine sites by comparing distributions of surface water exposure concentrations of endosulfan [i.e., for total endosulfan (summation of concentrations of alpha- and beta-isomers plus the sulfate), alpha- plus beta-endosulfan, and endosulfan sulfate (alone)] with distributions of species effects from laboratory toxicity data. In Tier 2 the distribution of total endosulfan in fish tissue (whole body) from South Florida freshwaters was also used to determine the probability of exceeding a distribution of whole body residues of endosulfan producing mortality (critical lethal residues). Tier 1 showed the majority of endosulfan water quality violations in South Florida were at locations S-178 followed by S-177 in the C-111 system (southeastern boundary of Everglades National Park (ENP)). Nine surface water sampling sites were chosen for Tier 2. Tier 2 showed the highest potentially affected fraction of toxicity values (>10%) by the estimated 90th centile exposure concentration (total endosulfan) was at S-178. At all other freshwater sites there were
• Free-radical Chemistry of Disinfection Byproducts. 3. Degradation Mechanisms of Chloronitromethane, Bromonitromethane, and Dichloronitromethane The Journal of Physical Chemistry. A. Jan, 2010  |   Pubmed ID: 20055512 Halonitromethanes (HNMs) are byproducts formed through ozonation and chlorine/ chloramine disinfection processes in drinking waters that contain dissolved organic matter and bromide ions. These species occur at low concentration but have been determined to have high cytotoxicity and mutagenicity and therefore may represent a human health hazard. In this study, we have investigated the chemistry involved in the mineralization of HNMs to nonhazardous inorganic products through the application of advanced oxidation and reduction processes. We have combined measured absolute reaction rate constants for the reactions of chloronitromethane, bromonitromethane, and dichloronitromethane with the hydroxyl radical and the hydrated electron with a kinetic computer model in an attempt to elucidate the reaction pathways of these HNMs. The results are compared to measurements of stable products resulting from steady-state (60)Co gamma-irradiations of the same compounds. The model predicted the decomposition of the parent compounds and ingrowth of chloride and bromide ions with excellent accuracy, but the prediction of the total nitrate ion concentration was slightly in error, reflecting the complexity of nitrogen oxide species reactions in irradiated solution.
• UV and Solar TiO(2) Photocatalysis of Brevetoxins (PbTxs) Toxicon : Official Journal of the International Society on Toxinology. May, 2010  |   Pubmed ID: 19931554 Karenia brevis, the harmful alga associated with red tide, produces brevetoxins (PbTxs). Exposure to these toxins can have a negative impact on marine wildlife and serious human health consequences. The elimination of PbTxs is critical to protect the marine environment and human health. TiO(2) photocatalysis under 350 nm and solar irradiation leads to significant degradation of PbTxs via first order kinetics. ELISA results demonstrate TiO(2) photocatalysis leads to a significant decrease in the bioactivity of PbTxs as a function of treatment time. Experiments conducted in the presence of synthetic seawater, humic material and a hydroxyl scavenger showed decreased degradation. PbTxs are highly hydrophobic and partition to organic microlayer on the ocean surface. Acetonitrile was employed to probe the influence of an organic media on the TiO(2) photocatalysis of PbTxs. Our results indicate TiO(2) photocatalysis may be applicable for the degradation of PbTxs.
• Occurrence and Distribution of Steroids, Hormones and Selected Pharmaceuticals in South Florida Coastal Environments Ecotoxicology (London, England). Feb, 2010  |   Pubmed ID: 19779818 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 of many important protected environments ranging from wetlands to coral reefs which are in close proximity to large metropolitan cities. Because, 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 septic systems, a comprehensive survey of selected human waste contamination markers was conducted in three areas to assess water quality with respect to non-traditional micro-constituents. This study documents the occurrence and distribution of fifteen hormones and steroids and five commonly detected pharmaceuticals in surface water samples collected from different near shore environments along South Florida between 2004 and 2006. The compounds most frequently detected were: cholesterol, caffeine, estrone, DEET, coprostanol, biphenol-A, beta-estradiol, and triclosan. The concentration detected for estrone and beta-estradiol were up to 5.2 and 1.8 ng/L, respectively. Concentrations of caffeine (5.5-68 ng/L) and DEET (4.8-49 ng/L) were generally higher and more prevalent than were the steroids. Distribution of microconstituents was site specific likely reflecting a diversity of sources. In addition to chemical analysis, the yeast estrogen screen assay was used to screen the samples for estrogen equivalency. Overall, the results show that water collected from inland canals and restricted circulation water bodies adjacent to heavily populated areas had high concentrations of multiple steroids, pharmaceuticals, and personal care products while open bay waters were largely devoid of the target analytes.
• Oxidation of Trimethoprim by Ferrate(VI): Kinetics, Products, and Antibacterial Activity Environmental Science & Technology. Dec, 2011  |   Pubmed ID: 22032699 Kinetics, stoichiometry, and products of the oxidation of trimethoprim (TMP), one of the most commonly detected antibacterial agents in surface waters and municipal wastewaters, by ferrate(VI) (Fe(VI)) were determined. The pH dependent second-order rate constants of the reactions of Fe(VI) with TMP were examined using acid-base properties of Fe(VI) and TMP. The kinetics of reactions of diaminopyrimidine (DAP) and trimethoxytoluene (TMT) with Fe(VI) were also determined to understand the reactivity of Fe(VI) with TMP. Oxidation products of the reactions of Fe(VI) with TMP and DAP were identified by liquid chromatography-tandem mass spectrometry (LC-MS/MS). Reaction pathways of oxidation of TMP by Fe(VI) are proposed to demonstrate the cleavage of the TMP molecule to ultimately result in 3,4,5,-trimethoxybenzaldehyde and 2,4-dinitropyrimidine as among the final identified products. The oxidized products mixture exhibited no antibacterial activity against E. coli after complete consumption of TMP. Removal of TMP in the secondary effluent by Fe(VI) was achieved.
• Bioconcentration and Depuration of Endosulfan Sulfate in Mosquito Fish (Gambusia Affinis) Chemosphere. Jul, 2011  |   Pubmed ID: 21550631 Endosulfan is an insecticide which has been widely used in agriculture. The technical grade material consists of two isomers (alpha and beta). Under natural environmental conditions, endosulfan is metabolized through oxidation and the main metabolite in the environment is endosulfan sulfate. Most ecotoxicology research has been conducted with technical grade endosulfan to determine effects on non-target aquatic organisms. Little data on the effects of endosulfan sulfate on aquatic organisms are available in the literature. This study characterizes endosulfan sulfate bioconcentration and depuration in mosquito fish (Gambusia affinis). During the study, G. affinis was exposed to an environmentally relevant endosulfan sulfate concentration of 0.25 μg L(-1) for 5 weeks (uptake phase) followed by a 3-week period (depuration phase) in clean water. This study found that G. affinis bioconcentrated endosulfan sulfate. During the exposure phase, fish tissue concentrations of endosulfan sulfate increased with time up to 730 μg kg(-1) dw or 215 μg kg(-1) ww. The bioconcentration data followed Michaelis-Menten kinetics better than the one-compartment first order kinetics (1-CFOK). Using these models, the bioconcentration factors for endosulfan sulfate-exposed G. affinis were from 687 to 888 L kg(-1) in wet weight or 2263 to 2936 L kg(-1) in dry weight. During the depuration phase, endosulfan sulfate concentrations in tissue significantly decreased and the data followed first order kinetics. The half-life of endosulfan sulfate in G. affinis was about 9 d. There was no significant difference in standard length or weight between control and exposed fish. The growth data followed the von Bertalanffy growth model. However, the condition factor of exposed fish increased with time during the exposure phase.
• Acute Toxicity and Effects Analysis of Endosulfan Sulfate to Freshwater Fish Species Archives of Environmental Contamination and Toxicology. Feb, 2011  |   Pubmed ID: 21127850 Endosulfan sulfate is a persistent environmental metabolite of endosulfan, an organochlorine insecticide-acaricide presently registered by the United States Environmental Protection Agency. There is, however, limited acute fish toxicity data for endosulfan sulfate. This study determines the acute toxicity (LC₅₀s and LC₁₀s) of endosulfan sulfate to three inland Florida native fish species (mosquitofish [Gambusia affinis]; least killifish [Heterandria formosa]; and sailfin mollies [Poecilia latipinna]) as well as fathead minnows (Pimephales promelas). Ninety-six-h acute toxicity tests were conducted with each fish species under flow-through conditions. For all of the above-mentioned fish species, 96-h LC₅₀ estimates ranged from 2.1 to 3.5 μg/L endosulfan sulfate. The 96-h LC₁₀ estimates ranged from 0.8 to 2.1 μg/L endosulfan sulfate. Of all of the fish tested, the least killifish appeared to be the most sensitive to endosulfan sulfate exposure. The above-mentioned data were combined with previous acute toxicity data for endosulfan sulfate and freshwater fish for an effects analysis. The effects analysis estimated hazardous concentrations expected to exceed 5, 10, and 50% of the fish species' acute LC₅₀ or LC₁₀ values (HC₅, HC₁₀, and HC₅₀). The endosulfan sulfate freshwater-fish acute tests were also compared with the available freshwater-fish acute toxicity data for technical endosulfan. Technical endosulfan is a mixture of α- and β-endosulfan. The LC₅₀s had a wider range for technical endosulfan, and their distribution produced a lower HC₁₀ than for endosulfan sulfate. The number of freshwater-fish LC₅₀s for endosulfan sulfate is much smaller than the number available for technical endosulfan, reflecting priorities in examining the toxicity of the parent compounds of pesticides. The toxicity test results and effects analyses provided acute effect values for endosulfan sulfate and freshwater fish that might be applied in future screening level ecologic risk assessments. The effects analyses also discussed several deficiencies in conventional methods for setting water-quality criteria and determining ecologic effects from acute toxicity tests.
• Comparison of Multiple API Techniques for the Simultaneous Detection of Microconstituents in Water by On-line SPE-LC-MS/MS Journal of Mass Spectrometry : JMS. Oct, 2012  |   Pubmed ID: 23019157 This study described a fully automated method using on-line solid phase extraction of large volume injections coupled with high performance liquid chromatography (HPLC) and tandem mass spectrometry (MS/MS) to simultaneously detect a group of recalcitrant microconstituents (pharmaceuticals and personal care products, steroid hormones and sterols) in aqueous matrices. Samples (1 mL to 20 mL) were loaded to the preconcentration column at 1 mL/min, and the column was washed with 1000 μL of 25% methanol in LC/MS water to remove polar and ionic interferences before LC-MS/MS analysis. Three different atmospheric pressure ionization (API) techniques, including photoionization (APPI) with four different dopants (acetone, anisole, chlorobenzene and toluene), heated electrospray ionization (HESI) and atmospheric pressure chemical ionization (APCI), were evaluated on the basis of method detection limits (MDLs) and recoveries from different aqueous matrixes. Results indicated that APPI with toluene as dopant was the most sensitive ionization method for the majority of the analytes. When using 5 mL of sample, MDLs for pharmaceuticals and personal care products, including carbamazepine, DEET, caffeine, naproxen, acetaminophen and primidone, were between 0.3 ng/L and 15 ng/L. MDLs of hormones, including testosterone, equilenin, progesterone, equilin, 17β-estradiol, 17α-ethynylestradiol, estrone, androsterone, mestranol and estriol, were between 1.2 ng/L and 37 ng/L. The combination of APPI with dopant allowed the detection of two difficult to ionize fecal related sterols, such as coprostan-3-ol and coprostan-3-one with MDLs of 5.4 ng/L and 11 ng/L, respectively. Calculated MDLs are more than adequate for analysis of wastewater using 1 to 5 mL sample size and for surface waters using up to 20 mL sample size.
• Identification of Phototransformation Products of Sildenafil (Viagra) and Its N-demethylated Human Metabolite Under Simulated Sunlight Journal of Mass Spectrometry : JMS. Jun, 2012  |   Pubmed ID: 22707162 Recent publications on pharmaceutical monitoring are increasingly covering the field of illicit drugs and lately the forensic evaluation of designing illegal analogs of lifestyle drugs like the phosphodiesterase type 5 (PDE-5) inhibitors Viagra (sildenafil), Levitra (vardenafil) and Cialis (tadalafil). Recently, the presence of all three erectile dysfunction treatment drugs has been reported in wastewaters at very low concentrations. In the environment, contaminants undergo various physical or chemical processes classified into abiotic (photolysis, hydrolysis) and biotic (biodegradation) reactions. Thus, changes in the chemical structure lead to the formation of new transformation products, which may persist in the environment or be further degraded. This study describes the photolysis of sildenafil (SDF) and its human metabolite N-demethylsildenafil (DM-SDF) under simulated solar radiation (Xenon lamp). Following chromatographic separation of the irradiated samples, eight photoproducts in the SDF samples and six photoproducts for DM-SDF were detected and characterized. The combination of ultra performance liquid chromatography-electrospray ionization-quadrupole time-of-flight-mass spectrometry (UPLC-ESI-QToF-MS), liquid chromatography-atmospheric pressure chemical ionization-triple quadrupole mass spectrometry (LC-APCI-QqQ-MS) and hydrogen/deuterium-exchange experiments allowed to propose plausible chemical structures for the photoproducts, taking into account the characteristic fragmentation patterns and the accurate mass measurements. These mass spectral data provided sound evidence for the susceptibility of the piperazine ring toward photodegradation. A gradual breakdown of this heterocyclic structure gave rise to a series of products, which in part were identical for SDF and DM-SDF. The sulfonic acid, as the formal product of sulfonamide hydrolysis, was identified as key intermediate in the photolysis pathway. In both drug/metabolite molecules, phototransformation processes taking place beyond the sulfonamide group were deemed to be of minor relevance.
• Analysis of Selected Pharmaceuticals in Fish and the Fresh Water Bodies Directly Affected by Reclaimed Water Using Liquid Chromatography-tandem Mass Spectrometry Analytical and Bioanalytical Chemistry. Nov, 2012  |   Pubmed ID: 22678759 A comprehensive method for the analysis of 11 target pharmaceuticals representing multiple commonly used therapeutic classes was developed for biological tissues (fish), reclaimed water, and the surface water directly affected by irrigation with reclaimed water. One gram of fish tissue homogenate was extracted by accelerated solvent extraction with methylene chloride followed by mixed-mode cation exchange solid phase extraction (SPE) cleanup and analyzed by liquid chromatography-tandem mass spectrometry. Compared to previously reported methods, the protocol produces cleaner extracts resulting in lower method detection limits. Similarly, an SPE method based on Oasis HLB cartridges was used to concentrate and cleanup reclaimed and surface water samples. Among the 11 target compounds analyzed, trimethoprim, caffeine, sulfamethoxazole, diphenhydramine, diltiazem, carbamazepine, erythromycin, and fluoxetine were consistently detected in reclaimed water. Caffeine, diphenhydramine, and carbamazepine were consistently detected in fish and surface water samples. Bioaccumulation factors for caffeine, diphenhydramine, and carbamazepine in mosquito fish (Gambusia holbrooki) were calculated at 29 ± 26, 821 ± 422, and 108 ± 144, respectively. This is the first report of potential accumulation of caffeine in fish from a water body directly influenced by reclaimed water. Figure The pharmaceuticals detected in reclaimed water and the fresh water directly affected by reclaimed water.
• Occurrence and Distribution of Endosulfan in Water, Sediment, and Fish Tissue: an Ecological Assessment of Protected Lands in South Florida Journal of Agricultural and Food Chemistry. Dec, 2013  |   Pubmed ID: 24111802 Over the past 30 years, endosulfan, one of the last polychlorinated pesticides still in use, has received considerable attention and has been the subject of a number of international regulations and restriction action plans worldwide. This study aimed to monitor the presence and to assess the potential transport of endosulfan within the protected areas of Everglades National Park, Biscayne National Park, and Big Cypress National Preserve, South Florida, USA. Endosulfan sulfate was the major metabolite detected in all matrices in areas along the C-111 and C-111E canals, which drain the Homestead agricultural area and discharge to either Florida or Biscayne Bays, both of which are critical wildlife habitats. Endosulfan concentrations of up to 158 ng L(-1) and 57 ng g(-1) were observed in surface water and sediments, respectively, which exceeded the U.S. EPA's chronic water quality criteria (56 ng L(-1)). Elevated levels of up to 371 ng g(-1) of endosulfan sulfate were detected in whole fish tissue.
• 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 Chemistry Central Journal. Aug, 2013  |   Pubmed ID: 23965251 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.
• Baseline Occurrence of Organochlorine Pesticides and Other Xenobiotics in the Marine Environment: Caribbean and Pacific Collections Marine Pollution Bulletin. May, 2013  |   Pubmed ID: 23597795 This ongoing survey reports the levels of persistent organic pollutants (POPs) in sea surface slicks collected on a global circumnavigation. Hydrophobic xenobiotic compounds such as POPs are known to accumulate on the sea surface in slicks at concentrations many fold greater than the underlying water column, raising concerns about the ecological impacts due to the high biological activity associated with this zone. Six different categories of POPs were reported: chlorobenzenes, hexachlorocyclohexanes, chlordane related compounds, organochlorine pesticides and other cyclodiene pesticides, DDTs and metabolites, and polychlorinated biphenyls. Concentrations ranged from
• Uptake and Depuration of Pharmaceuticals in Reclaimed Water by Mosquito Fish (Gambusia Holbrooki): a Worst-case, Multiple-exposure Scenario Environmental Toxicology and Chemistry. Aug, 2013  |   Pubmed ID: 23595768 Previous studies showed that caffeine, diphenhydramine, and carbamazepine were bioconcentrated by mosquito fish (Gambusia holbrooki) from freshwater bodies directly affected by reclaimed water. To understand the uptake, depuration, and bioconcentration factors (BCFs) under the worst-case conditions, the authors exposed 84 mosquito fish to reclaimed water under static renewal for 7 d, followed by a 14-d depuration phase in clean water. Characterization of the exposure media revealed the presence of 26 pharmaceuticals, whereas only 5 pharmaceuticals-caffeine, diphenhydramine, diltiazem, carbamazepine, and ibuprofen-were present in the organisms after only 5 h of exposure. Caffeine, diltiazem, and carbamazepine were quickly taken up by mosquito fish following a similar uptake curve. Diphenhydramine and ibuprofen, on the other hand, were more gradually taken up by mosquito fish but were also eliminated fairly quickly, resulting in the 2 shortest depuration half-lives at 34 h and 32 h, respectively. For comparison, BCFs based on rate constants (BCFb ), steady-state concentrations (BCFa ), and saturation-state concentrations (BCFc ) were calculated. Values of BCFb ranged from 0.23 to 29 and increased in the order of caffeine 
• Online Solid-phase Extraction-liquid Chromatography-electrospray-tandem Mass Spectrometry Determination of Multiple Classes of Antibiotics in Environmental and Treated Waters Analytical and Bioanalytical Chemistry. Jul, 2013  |   Pubmed ID: 23494277 An online solid-phase extraction and liquid chromatography in combination with tandem mass spectrometry method was developed for the simultaneous determination of 31 antibiotics in drinking water, surface water and reclaimed waters. The developed methodology requires small sample volume (10 mL), very little sample preparation and total sample run time was 20 min. An Ion Max API heated electrospray ionization source operated in the positive mode with two selected reaction monitoring transitions was used per antibiotic for positive identity and quantification performed by the internal standard approach, to correct for matrix effects and any losses in the online extraction step. Method detection limits were in the range of 1.2-9.7, 2.2-15, 5.5-63 ng/L in drinking water, surface water and reclaimed waters, respectively. The method accuracy in matrix spiked samples ranged from 50-150% for the studied antibiotics. The applicability of the method was demonstrated using various environmental and reclaimed water matrices. Erythromycin was detected in more than 85% of the samples in all matrices (28-414, n.d.-199, n.d.-66 ng/L in reclaimed, river and drinking waters respectively). The other frequently detected antibiotics in reclaimed waters were nalidixic acid, clarithromycin, azithromycin, trimethoprim, and sulfamethoxazole.
• High Sensitivity Liquid Chromatography Tandem Mass Spectrometric Methods for the Analysis of Dioctyl Sulfosuccinate in Different Stages of an Oil Spill Response Monitoring Effort Analytical and Bioanalytical Chemistry. May, 2013  |   Pubmed ID: 23471369 After the incident on the Deepwater Horizon platform, around 1.8 million gallons of dispersants were used in the field as part of the response cleanup efforts. This study describes an online solid phase extraction-liquid chromatography (LC)-tandem mass spectrometry (MS/MS) method and a direct-injection LC-MS/MS method for the analysis of dioctyl sulfosuccinate (DOSS; a component in Corexit® EC9500A) in seawater at trace levels, with method detection limits (MDLs) of 7.0 and 440 ng/L and run times of 7 and 17 min, respectively. Stability and preservation studies demonstrated that samples at 4.7 μg/L could be preserved for up to 150 days without loss of analyte when stored with 33 % acetonitrile in glass containers. Data acquisition was performed by heated electrospray ionization (ESI) MS/MS operating in negative mode. Methods were validated in terms of percent recovery in fortified blank and matrix samples and to evaluate carryover. A simple modification of the direct-injection method allowed quantitation of 2-butoxyethanol, a dispersant component specific to the Corexit® EC9527A formulation. This method was used to simultaneously quantify DOSS and 2-butoxyethanol in two Corexit® formulations and extracts from an MC-252 source oil standard. MDLs in crude oil were 0.723 and 4.46 mg/kg, respectively, with recoveries of (92 ± 9)% for DOSS and (104 ± 8)% for 2-butoxyethanol. Detection of both indicators was achieved in a single chromatographic run by ESI-MS/MS operating sequentially in positive and negative mode. Corexit® EC9500A and Corexit® EC9527A were found to contain (21 ± 2)% and (22 ± 5)% w/w DOSS and 0 and (37 ± 2)% w/w 2-butoxyethanol, respectively.
• Detection and Occurrence of Microconstituents in Reclaimed Water Used for Irrigation--a Potentially Overlooked Source Analytical and Bioanalytical Chemistry. Jul, 2013  |   Pubmed ID: 23436167 An online SPE-HPLC-HESI-MS/MS method and an online SPE-HPLC-APPI-MS/MS method were developed to analyze 72 microconstituents in reclaimed water. In this study, 55 reclaimed water samples were collected from the sprinkler system for a year-long period at Florida International University Biscayne Bay Campus, where reclaimed water was reused for daily irrigation. Analysis results showed that several analytes were continuously detected in all reclaimed water samples and others will show rather transient signal increases. Coprostanol, bisphenol A, and DEET's maximum concentration exceeded 10,000 ng/L. The four most frequently detected compounds were diphenhydramine (100%), DEET (98%), atenolol (98%) and carbamazepine (96%).
• Outcompeting GC for the Detection of Legacy Chlorinated Pesticides: Online-SPE UPLC APCI/MSMS Detection of Endosulfans at Part Per Trillion Levels Analytical and Bioanalytical Chemistry. Jul, 2013  |   Pubmed ID: 23386002 Endosulfan, the last remaining organochlorine pesticide, has been the subject of a number of international regulations and restriction/banning action plans worldwide. Occurrence of endosulfan residues in South Florida environments has been widely described in the literature for more than two decades. This work describes a selective, sensitive, and fast online solid-phase extraction (SPE) method coupled with liquid chromatography separation and tandem mass spectrometry (LC-MS/MS) for the determination of endosulfan isomers and endosulfan sulfate in water samples at low part per trillion levels with very little sample preparation. A negative atmospheric pressure chemical ionization source was carefully optimized to produce reproducible spectra of the target compounds with no adduct ion formation. Selected reaction monitoring transitions were monitored and quantitation was performed against a per-deuterated internal standard β-endosulfan (d4). The automated online SPE clean-up was performed using only 20 mL of untreated water sample prior to LC-MS/MS analysis. The method was capable of separating and quantifying endosulfan within a 24-min run using acetonitrile and water as mobile phases and presenting statistically calculated method detection limits of 3, 10, and 7 ng/L for endosulfan sulfate, α-endosulfan, and β-endosulfan, respectively. In addition, a QuEChERS method was successfully developed and applied for endosulfan determination in sediments/soils, floating and submerged algal mats, and small fish. Minimal matrix effects were observed in all matrices analyzed and recoveries for all analytes ranged from 50-144 %. The developed methodology was applied to monitor the occurrence and to assess the potential transport of endosulfan in the Loveland Slough watershed, an area adjacent to Everglades National Park showing long-term contamination with endosulfans.
• Ferrate(VI) Oxidation of Propranolol: Kinetics and Products Chemosphere. Mar, 2013  |   Pubmed ID: 23305748 The oxidation of propranolol (PPL), a β-blocker by ferrate(VI) (Fe(VI)) was studied by performing kinetics, stoichiometry, and analysis of the reaction products. The rate law for the oxidation of PPL by Fe(VI) was first-order with respect to each reactant. The dependence of second-order rate constants of the reaction of Fe(VI) and PPL on pH was explained using acid-base equilibrium of Fe(VI) and PPL. The required molar stoichiometry for the complete removal of PPL was determined to be 6:1 ([Fe(VI)]:[PPL]). The identified products using liquid chromatography-tandem mass spectrometry were oxidized product (OP)-292, OP-308, and OP-282. The formed OPs could possibly compete with the parent molecule to react with Fe(VI) and thus resulted in a non-linear relationship between degradation of PPL and the added amount of Fe(VI). Rate and removal studies indicate the Fe(VI) is able to oxidize PPL and hence can also oxidize other β-blockers, e.g., atenolol and metoprolol.
• Concentration of Trace Metals in Sediments and Soils from Protected Lands in South Florida: Background Levels and Risk Evaluation Environmental Monitoring and Assessment. Aug, 2013  |   Pubmed ID: 23288595 A comprehensive environmental evaluation was completed on 20 metals: two reference metals (Fe, Al) and several minor trace metals (As, Ba, Co, Cr, Cu, Mn, Ni, Pb, V, and Zn) for surface soils and sediments collected from 50 sites in Everglades National Park (ENP), the coastal fringes of Biscayne National Park (BNP), and Big Cypress National Preserve. Samples were prepared by acid digestion (EPA3050) and analyzed by ICP/MS detection (EPA6020). Although no widespread contamination was detected across the two parks and one preserve, there were some specific areas where metal concentrations exceeded Florida's ecological thresholds, suggesting that some metals were of concern. A screening-level evaluation based on a proposed effect index grouped trace metals by their potential for causing negligible, possible, and probable effects on the biota. For example, Cu in BNP and Cr and Pb in ENP were considered of concern because their adverse effect likelihood to biota was assessed as probable; consequently, these trace metals were selected for further risk characterization. Also, stations were ranked based on a proposed overall contamination index that showed that: site BB10 in BNP and sites E3 and E5 in ENP had the highest scores. The first site was located in a marina in BNP, and the other two sites were along the eastern boundary of ENP adjacent to current or former agricultural lands. An assessment tool for south Florida protected lands was developed for evaluating impacts from on-going Everglades restoration projects and to assist State and Federal agencies with resource management. The tool consists of enrichment plots and statistically derived background concentrations based on soil/sediment data collected from the two national parks and one preserve. Finally, an equally accurate but much simplified approach is offered for developing enrichment plots for other environmental settings.
• Ambient Iron-mediated Aeration (IMA) for Water Reuse Water Research. Feb, 2013  |   Pubmed ID: 23232032 Global water shortages caused by rapidly expanding population, escalating water consumption, and dwindling water reserves have rendered water reuse a strategically significant approach to meet current and future water demand. This study is the first to our knowledge to evaluate the technical feasibility of iron-mediated aeration (IMA), an innovative, potentially economical, holistic, oxidizing co-precipitation process operating at room temperature, atmospheric pressure, and neutral pH, for water reuse. In the IMA process, dissolved oxygen (O₂) was continuously activated by zero-valent iron (Fe⁰) to produce reactive oxygen species (ROS) at ambient pH, temperature, and pressure. Concurrently, iron sludge was generated as a result of iron corrosion. Bench-scale tests were conducted to study the performance of IMA for treatment of secondary effluent, natural surface water, and simulated contaminated water. The following removal efficiencies were achieved: 82.2% glyoxylic acid, ~100% formaldehyde as an oxidation product of glyoxylic acid, 94% of Ca²⁺ and associated alkalinity, 44% of chemical oxygen demand (COD), 26% of electrical conductivity (EC), 98% of di-n-butyl phthalate (DBP), 80% of 17β-estradiol (E2), 45% of total nitrogen (TN), 96% of total phosphorus (TP), 99.8% of total Cr, >90% of total Ni, 99% of color, 3.2 log removal of total coliform, and 2.4 log removal of E. Coli. Removal was attributed principally to chemical oxidation, precipitation, co-precipitation, coagulation, adsorption, and air stripping concurrently occurring during the IMA treatment. Results suggest that IMA is a promising treatment technology for water reuse.
• Structure Elucidation of Phototransformation Products of Unapproved Analogs of the Erectile Dysfunction Drug Sildenafil in Artificial Freshwater with UPLC-Q Exactive-MS Journal of Mass Spectrometry : JMS. Dec, 2014  |   Pubmed ID: 25476946 In this study, four unapproved analogues of Sildenafil (SDF) were photodegraded under synthetic sunlight in artificial freshwater. Homosildenafil (H-SDF), hydroxyhomo-sildenafil (HH-SDF), norneosildenafil (NR-SDF) and thiosildenafil (T-SDF) were selected because they are frequently detected as adulterants in natural herbal products. Using UPLC-Orbitrap (Q Exactive)-MS, six photoproducts common to H-SDF, HH-SDF and T-SDF and nine unique transformation products of different molecular weights were identified based on their high-resolution (+)ESI product ion spectra. Mass spectral analysis of deuterated H-SDF, labeled on the N-ethyl group, allowed to gain mechanistic insight into the fragmentation pathway of the substituted piperazine ring and to support the postulated photoproduct structures. The mass spectral fragmentation confirmed the stepwise destruction of the piperazine ring eventually producing a sulfonic acid derivative (C17 H20 N4 O5 S: 392.1151 Da). In contrast, the photodegradation of NR-SDF, which lacks a piperazine ring in its structure, formed only two prominent photoproducts originating from N,N-dealkylation of the sulfonamide followed by hydrolysis. The current work constitutes the first study on the photodegradation of analogs of erectile dysfunction drugs and the first detection of two transformation products (m/z 449 and 489) in environmental samples.
• Oxidation of Microcystin-LR by Ferrate(VI): Kinetics, Degradation Pathways, and Toxicity Assessments Environmental Science & Technology. Oct, 2014  |   Pubmed ID: 25215438 The presence of the potent cyanotoxin, microcystin-LR (MC-LR), in drinking water sources poses a serious risk to public health. The kinetics of the reactivity of ferrate(VI) (Fe(VI)O4(2-), Fe(VI)) with MC-LR and model compounds (sorbic acid, sorbic alcohol, and glycine anhydride) are reported over a range of solution pH. The degradation of MC-LR followed second-order kinetics with the bimolecular rate constant (kMCLR+Fe(VI)) decreasing from 1.3 ± 0.1 × 10(2) M(-1) s(-1) at pH 7.5 to 8.1 ± 0.08 M(-1) s(-1) at pH 10.0. The specific rate constants for the individual ferrate species were determined and compared with a number of common chemical oxidants employed for water treatment. Detailed product studies using liquid chromatography-mass spectrometry/mass spectrometry (LC-MS/MS) indicated the oxidized products (OPs) were primarily the result of hydroxylation of the aromatic ring, double bond of the methyldehydroalanine (Mdha) amino acid residue, and diene functionality. Products studies also indicate fragmentation of the cyclic MC-LR structure occurs under the reaction conditions. The analysis of protein phosphatase (PP1) activity suggested that the degradation byproducts of MC-LR did not possess significant biological toxicity. Fe(VI) was effective for the degradation MC-LR in water containing carbonate ions and fulvic acid (FA) and in lake water samples, but higher Fe(VI) dosages would be needed to completely remove MC-LR in lake water compared to deionized water.
• A Simple Method for Routine Monitoring of Glyphosate and Its Main Metabolite in Surface Waters Using Lyophilization and LC-FLD+MS/MS. Case Study: Canals with Influence on Biscayne National Park The Science of the Total Environment. Oct, 2014  |   Pubmed ID: 25089697 A novel method was developed for the analysis of the herbicide glyphosate and its main metabolite aminomethylphosphonic acid (AMPA) based on lyophilization. Sample preparation steps are limited to fortification with aspartic acid as internal standard and water removal by lyophilization (3-4 days for 72 samples), followed by suspension of dry residues in borate buffer (pH=9.0) and addition of ethylenediaminetetraacetic acid (EDTA) and 9-fluorenylmethylchloroformate (FMOC-Cl) for pre-column derivatization. The obtained derivatization mixture was injected on a highly endcapped C18 column where a basic pH gradient separation of the anionic analytes from neutral derivatization byproducts was achieved, with simultaneous quantitation by fluorescence and compound confirmation by tandem mass spectrometry. Method detection limits (for 20 mL samples) were 0.058 μg/L and 0.108 μg/L for glyphosate and AMPA, respectively. The method had a high dynamic range (0.1-50.0 μg/L) which allowed quantitation at both background and high levels of the herbicide. As a case study, the methodology was successfully applied to detect the occurrence of these compounds in water canals managed by the South Florida Water Management District. These canals will be used as freshwater source to hydrate estuarine wetlands of Biscayne National Park under the Comprehensive Everglades Restoration Project, in order to decrease ecosystem stress from hypersaline conditions caused by anthropogenic reduction of historical freshwater flow towards the Biscayne Bay. Method development, validation, advantages, limitations and measured environmental concentrations are discussed. This methodology has minimal requirements in terms of materials, instruments and analyst training, which could represent a desirable tool for laboratories interested in the monitoring of glyphosate in surface waters.
• Identification of Phase II Pharmaceutical Metabolites in Reclaimed Water Using High Resolution Benchtop Orbitrap Mass Spectrometry Chemosphere. Jul, 2014  |   Pubmed ID: 24875872 This study described an analytical method for the identification of common phase II pharmaceutical metabolites in reclaimed water using liquid chromatography high resolution Orbitrap mass spectrometry after solid phase extraction (SPE). Orbitrap mass spectrometer was operated at resolution of 70000 in MS mode and 35000 in data-dependent MS/MS mode, without using lock mass. Firstly, parent drugs and their metabolites were tentatively identified based on accurate mass using a mass tolerance of 5 ppm. A detailed examination of the extracted ion chromatograms (XICs) for all potential metabolites revealed the presence of two phase II metabolites of sulfamethoxazole, acetylsulfamethoxazole and sulfamethoxazole glucuronide in reclaimed water. Secondly, the high resolution data-dependent MS/MS spectra of each compound were further investigated using metabolic profiling software. After comparing characteristic ions obtained in MS/MS mode with those predicted by the software and reported in previous studies, the two phase II metabolites were positively identified in reclaimed water. Lastly, the two metabolites were detected and quantified in the reclaimed water samples collected during a period of one month. As a result, averaged concentrations of sulfamethoxazole, acetylsulfamethoxazole and sulfamethoxazole glucuronide were calculated at 2848 ± 1367 ng L(-)(1), 1980 ± 1410 ng L(-)(1), and 2859 ± 1526 ng L(-)(1), respectively. The two metabolites represented 54% of the source of sulfamethoxazole in reclaimed water suggesting the importance of measuring pharmaceutical metabolites in the environment. To our knowledge, this is the first known report of sulfamethoxazole glucuronide surviving intact through wastewater treatment plants and occurring in environmental water samples.
• Stability of Dioctyl Sulfosuccinate (DOSS) Towards Hydrolysis and Photodegradation Under Simulated Solar Conditions The Science of the Total Environment. May, 2014  |   Pubmed ID: 24602910 Dioctyl sulfosuccinate (DOSS) is one of the main components of Corexit® EC9500A, a chemical dispersant formulation used at the surface and at depth during the response to the Deepwater Horizon incident. Despite being a high volume use chemical, data on its environmental stability are scarce. Hydrolysis and photodegradation of DOSS in both pure water and seawater were reported in the present study. DOSS photodegraded much faster under ultraviolet light source (254 nm, with half-life in hours) compared to relevant environmental light sources i.e., 350 nm and solar simulator (with half-lives in days). LC/MS-MS analysis of hydrolysis and photo-irradiated samples showed the presence of a common degradation product. MS/MS fragmentation of that product indicated a substitution of an octyl group by a hydroxyl group with a corresponding formula of C12H21O7S, which was confirmed by HRMS detection (Q-TOF, m/z 309.1017, +1.29 ppm).
• Photodegradation of Sulfonamide Antibiotics in Simulated and Natural Sunlight: Implications for Their Environmental Fate Journal of Environmental Science and Health. Part. B, Pesticides, Food Contaminants, and Agricultural Wastes. 2014  |   Pubmed ID: 24380620 The photochemical fate of seven sulfonamides was investigated in matrices representative of natural water bodies under various light sources. Fundamental photolysis parameters such as molar absorption coefficient, quantum yield (QY) and first-order rate constants were determined. The photolysis decay rate was dependent on the protonation state of the molecule, pH of the water sample and dissolved organic matter. Natural organic matter was the most significant factor in the indirect photolysis of sulfonamides. Half-lives were in the range of minutes at 254 nm to days under natural sunlight. Under natural sunlight, all sulfonamides showed higher removal rates in natural waters implying that indirect photolysis is the predominant mechanism.
• Fully Automated Trace Level Determination of Parent and Alkylated PAHs in Environmental Waters by Online SPE-LC-APPI-MS/MS Analytical and Bioanalytical Chemistry. Jan, 2014  |   Pubmed ID: 24217946 Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous compounds that enter the environment from natural and anthropogenic sources, often used as markers to determine the extent, fate, and potential effects on natural resources after a crude oil accidental release. Gas chromatography-mass spectrometry (GC-MS) after liquid-liquid extraction (LLE+GC-MS) has been extensively used to isolate and quantify both parent and alkylated PAHs. However, it requires labor-intensive extraction and cleanup steps and generates large amounts of toxic solvent waste. Therefore, there is a clear need for greener, faster techniques with enough reproducibility and sensitivity to quantify many PAHs in large numbers of water samples in a short period of time. This study combines online solid-phase extraction followed by liquid chromatography (LC) separation with dopant-assisted atmospheric pressure photoionization (APPI) and tandem MS detection, to provide a one-step protocol that detects PAHs at low nanograms per liter with almost no sample preparation and with a significantly lower consumption of toxic halogenated solvents. Water samples were amended with methanol, fortified with isotopically labeled PAHs, and loaded onto an online SPE column, using a large-volume sample loop with an auxiliary LC pump for sample preconcentration and salt removal. The loaded SPE column was connected to an UPLC pump and analytes were backflushed to a Thermo Hypersil Green PAH analytical column where a 20-min gradient separation was performed at a variable flow rate. Detection was performed by a triple-quadrupole MS equipped with a gas-phase dopant delivery system, using 1.50 mL of chlorobenzene dopant per run. In contrast, LLE+GC-MS typically use 150 mL of organic solvents per sample, and methylene chloride is preferred because of its low boiling point. However, this solvent has a higher environmental persistence than chlorobenzene and is considered a carcinogen. The automated system is capable of performing injection, online SPE, inorganic species removal, LC separation, and MS/MS detection in 28 min. Selective reaction monitoring was used to detect 28 parent PAHs and 15 families of alkylated PAHs. The methodology is comparable to traditional GC-MS and was tested with surface seawater, rainwater runoff, and a wastewater treatment plant effluent. Positive detections above reporting limits are described. The virtual absence of sample preparation could be particularly advantageous for real-time monitoring of discharge events that introduce PAHs into environmental compartments, such as accidental releases of petroleum derivates and other human-related events. This work covers optimization of APPI detection and SPE extraction efficiency, a comparison with LLE+GC-MS in terms of sensitivity and chromatographic resolution, and examples of environmental applications.
• Photodegradation of Antibiotics Under Simulated Solar Radiation: Implications for Their Environmental Fate The Science of the Total Environment. Feb, 2014  |   Pubmed ID: 24144935 Roxithromycin, erythromycin, ciprofloxacin and sulfamethoxazole are frequently detected antibiotics in environmental waters. Direct and indirect photolysis of these problematic antibiotics were investigated in pure and natural waters (fresh and salt water) under irradiation of different light sources. Fundamental photolysis parameters such as molar absorption coefficient, quantum yield and first order rate constants are reported and discussed. The antibiotics are degraded fastest under ultraviolet 254 nm, followed by 350 nm and simulated solar radiation. The composition of the matrix (pH, dissolved organic content, chloride ion concentration) played a significant role in the observed photodegradation. Under simulated solar radiation, ciprofloxacin and sulfamethoxazole degrade relatively quickly with half-lives of 0.5 and 1.5h, respectively. However, roxithromycin and erythromycin, macrolides are persistent (half-life: 2.4-10 days) under solar simulation. The transformation products (15) of the targeted antibiotics produced under irradiation experiments were identified using high resolution mass spectrometry and degradation pathways were proposed.
• Rapid Ultra-trace Analysis of Sucralose in Multiple-origin Aqueous Samples by Online Solid-phase Extraction Coupled to High-resolution Mass Spectrometry Analytical and Bioanalytical Chemistry. May, 2015  |   Pubmed ID: 25772563 Because of its widespread consumption and its persistence during wastewater treatment, the artificial sweetener sucralose has gained considerable interest as a proxy to detect wastewater intrusion into usable water resources. The molecular resilience of this compound dictates that coastal and oceanic waters are the final recipient of this compound with unknown effects on ecosystems. Furthermore, no suitable methodologies have been reported for routine, ultra-trace detection of sucralose in seawater as the sensitivity of traditional liquid chromatography-tandem mass spectrometry (LC-MS/MS) analysis is limited by a low yield of product ions upon collision-induced dissociation (CID). In this work, we report the development and field test of an alternative analysis tool for sucralose in environmental waters, with enough sensitivity for the proper quantitation and confirmation of this analyte in seawater. The methodology is based on automated online solid-phase extraction (SPE) and high-resolving-power orbitrap MS detection. Operating in full scan (no CID), detection of the unique isotopic pattern (100:96:31 for [M-H](-), [M-H+2](-), and [M-H+4](-), respectively) was used for ultra-trace quantitation and analyte identification. The method offers fast analysis (14 min per run) and low sample consumption (10 mL per sample) with method detection and confirmation limits (MDLs and MCLs) of 1.4 and 5.7 ng/L in seawater, respectively. The methodology involves low operating costs due to virtually no sample preparation steps or consumables. As an application example, samples were collected from 17 oceanic and estuarine sites in Broward County, FL, with varying salinity (6-40 PSU). Samples included the ocean outfall of the Southern Regional Wastewater Treatment Plant (WWTP) that serves Hollywood, FL. Sucralose was detected above MCL in 78% of the samples at concentrations ranging from 8 to 148 ng/L, with the exception of the WWTP ocean outfall (at pipe end, 28 m below the surface) where the measured concentration was 8418 ± 3813 ng/L. These results demonstrate the applicability of this monitoring tool for the trace-level detection of this wastewater marker in very dilute environmental waters.
• Analysis of Drugs of Abuse by Online SPE-LC High Resolution Mass Spectrometry: Communal Assessment of Consumption The Science of the Total Environment. Apr, 2015  |   Pubmed ID: 25553546 An online SPE-LC-HRMS method was developed to monitor the consumption of 18 drugs of abuse (DOAs) including amphetamines, opioids, cocainics, cannabinoids, lysergics, and their corresponding metabolites in a well characterized college campus setting via wastewater analysis. Filtered and diluted (10×) sewage water samples (5 mL inj.) were automatically pre-concentrated and analyzed in 15 min using a Thermo EQuan MAX online SPE system equipped with a HyperSep™ Retain PEP (20×2.1 mm×12 μm) SPE column and a Hypersil Gold™ aQ (150×2.1 mm×3 μm) analytical column. A Q Exactive™ Hybrid Quadrupole-Orbitrap HRMS was used in full scan mode (R=140,000) for positive identification, and quantitation of target compounds. Method detection limits for all analytes ranged between 0.6 and 1.7 ng/L in sewage. A total of 14 DOAs were detected from two different locations (dorms and main college campus) within a one-year period. Most frequently detected drugs throughout the entire study were amphetamine (>96%) and THC's metabolite 11-nor-9-carboxy-Δ-9-THC (>100%) with maximum concentrations of 5956 and 2413 ng/L respectively. Daily doses per 1000 people were determined in order to assess consumption of THC, amphetamine, heroin and cocaine, in both dorms and main campus.
• Understanding the Magnitude of Emergent Contaminant Releases Through Target Screening and Metabolite Identification Using High Resolution Mass Spectrometry: Illicit Drugs in Raw Sewage Influents Journal of Hazardous Materials. Jan, 2015  |   Pubmed ID: 25174793 A QExactive Orbitrap was used for the identification of phase I and II transformation products (TPs) of illicit drugs in raw sewage influents. Two operating modes (targeted MS(2) and Data-dependent screening) were used for data acquisition. Even though, data-dependent scan is a faster route towards the potential identification of metabolites, it suffered from its limitation to provide enough data points across the chromatographic peak during the MS(2) cycle in contrast to targeted MS(2). Therefore, the later technique was implemented as the method of choice in this study for the positive confirmation and quantitation of TPs (n=54). The vast majority of the identified TPs were products of phase I transformation reactions, with the latter being more prevalent in the nature. Estimated mole fractions showed that for a large number of the analytes, TPs must also be monitored in order to fully understand their environmental fate and calculate potential consumption.
• Mineralizing Urban Net-zero Water Treatment: Phase II Field Results and Design Recommendations Water Research. Nov, 2016  |   Pubmed ID: 27668994 Net-zero water (NZW) systems, or water management systems achieving high recycling rates and low residuals generation so as to avoid water import and export, can also conserve energy used to heat and convey water, while economically restoring local eco-hydrology. However, design and operating experience are extremely limited. The objective of this paper is to present the results of the second phase of operation of an advanced oxidation-based NZW pilot system designed, constructed, and operated for a period of two years, serving an occupied four-person apartment. System water was monitored, either continuously or thrice daily, for routine water quality parameters, minerals, and MicroTox(®) in-vitro toxicity, and intermittently for somatic and male-specific coliphage, adenovirus, Cryptosporidium, Giardia, emerging organic constituents (non-quantitative), and the Florida drinking water standards. All 115 drinking water standards with the exception of bromate were met in this phase. Neither virus nor protozoa were detected in the treated water, with the exception of measurement of adenovirus genome copies attributed to accumulation of inactive genetic material in hydraulic dead zones. Chemical oxygen demand was mineralized to 90% in treatment. Total dissolved solids were maintained at ∼500 mg/L at steady state, partially through aerated aluminum electrocoagulation. Bromate accumulation is projected to be controlled by aluminum electrocoagulation with separate disposal of backwash water. Further development of such systems and their automated/remote process control systems is recommended.
• Understanding the Atmospheric Pressure Ionization of Petroleum Components: The Effects of Size, Structure, and Presence of Heteroatoms The Science of the Total Environment. Oct, 2016  |   Pubmed ID: 27363346 Understanding the composition of crude oil and its changes with weathering is essential when assessing its provenience, fate, and toxicity. High-resolution mass spectrometry (HRMS) has provided the opportunity to address the complexity of crude oil by assigning molecular formulae, and sorting compounds into "classes" based on heteroatom content. However, factors such as suppression effects and discrimination towards certain components severely limit a truly comprehensive mass spectrometric characterization, and, despite the availability of increasingly better mass spectrometers, a complete characterization of oil still represents a major challenge. In order to fully comprehend the significance of class abundances, as well as the nature and identity of compounds detected, a good understanding of the ionization efficiency of the various compound classes is indispensable. The current study, therefore, analyzed model compounds typically found in crude oils by high-resolution mass spectrometry with atmospheric pressure photoionization (APPI), atmospheric pressure chemical ionization (APCI), and electrospray ionization (ESI), in order to provide a better understanding of benefits and drawbacks of each source. The findings indicate that, overall, APPI provides the best results, being able to ionize the broadest range of compounds, providing the best results with respect to ionization efficiencies, and exhibiting the least suppression effects. However, just like in the other two sources, in APPI several factors have shown to affect the ionization efficiency of petroleum model compounds. The main such factor is the presence or absence of functional groups that can be easily protonated/deprotonated, in addition to other factors such as size, methylation level, presence of heteroatoms, and ring structure. Overall, this study evidences the intrinsic limitations and benefits of each of the three sources, and should provide the fundamental knowledge required to expand the power of crude oil analysis by high-resolution mass spectrometry.
• Increasing Polyaromatic Hydrocarbon (PAH) Molecular Coverage During Fossil Oil Analysis by Combining Gas Chromatography and Atmospheric-Pressure Laser Ionization Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (FT-ICR MS) Energy & Fuels : an American Chemical Society Journal. Jan, 2016  |   Pubmed ID: 27212790 Thousands of chemically distinct compounds are encountered in fossil oil samples that require rapid screening and accurate identification. In the present paper, we show for the first time, the advantages of gas chromatography (GC) separation in combination with atmospheric-pressure laser ionization (APLI) and ultrahigh-resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) for the screening of polyaromatic hydrocarbons (PAHs) in fossil oils. In particular, reference standards of organics in shale oil, petroleum crude oil, and heavy sweet crude oil were characterized by GC-APLI-FT-ICR MS and APLI-FT-ICR MS. Results showed that, while APLI increases the ionization efficiency of PAHs, when compared to other ionization sources, the complexity of the fossil oils reduces the probability of ionizing lower-concentration compounds during direct infusion. When gas chromatography precedes APLI-FT-ICR MS, an increase (more than 2-fold) in the ionization efficiency and an increase in the signal-to-noise ratio of lower-concentration fractions are observed, giving better molecular coverage in the m/z 100-450 range. That is, the use of GC prior to APLI-FT-ICR MS resulted in higher molecular coverage, higher sensitivity, and the ability to separate and characterize molecular isomers, while maintaining the ultrahigh resolution and mass accuracy of the FT-ICR MS separation.
• Characterization of a Crude Oil Weathering Series by Ultrahigh-resolution Mass Spectrometry Using Multiple Ionization Modes The Science of the Total Environment. Sep, 2016  |   Pubmed ID: 27203365 Accidental crude oil releases, such as the Deepwater Horizon (DWH) accident, are always a potential threat to pristine marine ecosystems. Since the toxicity of crude oil heavily depends on its variable composition, the comprehensive characterization of crude oil compounds as a function of weathering is an important area of research. Traditional gas chromatography-based characterization presents significant limitations, and the use of ultrahigh-resolution mass spectrometric (UHRMS) techniques (that allow for the assignment of molecular formulae) has been shown to be better equipped to address the complex nature of crude oils. This study used an Orbitrap Q Exactive mass spectrometer operated at a resolving power of 140,000FWHM with both electrospray ionization (ESI) and atmospheric pressure photoionization (APPI) sources, in order to characterize a crude oil weathering series of the Macondo oil released during the DWH incident (the source oil, two differently weathered surface slicks, and a beached residue). Preliminary gas chromatography mass spectrometry (GC-MS) and gas chromatography flame ionization detection (GC-FID) results suggested that the four oils comprised a true weathering series (including biodegradation and photodegradation in addition to other well-known processes such as dissolution and evaporation). UHRMS results showed a clear increase in oxygenated compounds with weathering, and further suggested a significant gain of acidic compounds, as well as the transformation of phenols to ketonic and quinonic compounds with weathering. A complementary study on a weathered oil sample amended with selected model compounds contributed additional insight into the functional group types that are accessible in each ionization technique.
• Biodegradation of Dispersed Macondo Crude Oil by Indigenous Gulf of Mexico Microbial Communities The Science of the Total Environment. Jul, 2016  |   Pubmed ID: 27017076 Because of the extreme conditions of the Deepwater Horizon (DWH) release (turbulent flow at 1500m depth and 5°C water temperature) and the sub-surface application of dispersant, small but neutrally buoyant oil droplets
• Risk Assessment of Triazine Herbicides in Surface Waters and Bioaccumulation of Irgarol and M1 by Submerged Aquatic Vegetation in Southeast Florida The Science of the Total Environment. Jan, 2016  |   Pubmed ID: 26490533 Irgarol is a common antifoulant present in coastal environments experiencing high boating activities. Irgarol, its degradation product M1, and the similarly structured herbicide Atrazine, are highly toxic to non-target marine organisms and thus pose a continual risk to the environment. Nearshore areas with intensive boating activity were assessed for environmental exposure to Irgarol, M1, and Atrazine. Irgarol levels up to 241 ng/L were measured in surface water collected at Key Largo Harbor. Irgarol's metabolite, M1, was detected at levels up to 50 ng/L. Atrazine levels reached 21 ng/L throughout Miami River, and were also detected in waters within Biscayne Bay Aquatic Preserve at 7 ± 4 ng/L. The Irgarol 90th percentile exposure concentration (176 ng/L) in Southeast Florida--including Biscayne Bay--surface waters were found to exceed most toxicity benchmarks, suggesting Irgarol concentrations may be high enough to cause undesired effects on aquatic plants. Indigenous species of SAVs were also collected throughout Southeast Florida and assessed for their Irgarol and M1 bioaccumulation capabilities. All SAV species collected revealed Irgarol bioaccumulation capabilities and a 90th centile bioconcentration factor (BCF) of 9830. Several of those species were also capable of bioaccumulating M1, with a 90th centile BCF of 391. A 43-day in situ transplant between an impacted area and a pristine area within Biscayne Bay waters showed SAVs were able to uptake Irgarol from the environment with quick kinetics: tissue concentrations were 66 times greater than the water concentration within 6 weeks. Halodule and Syringodium had the highest capacity to bioaccumulate from marina surface waters, as indicated by the Irgarol BCF (Halodule=6809, Syringodium=6681) and M1 BCF (Halodule=277, Syringodium=558). Halodule and Syringodium are therefore the best candidate species to serve as bioindicators indicators of acute Irgarol contamination.
• Characterization and Environmental Relevance of Oil Water Preparations of Fresh and Weathered MC-252 Macondo Oils Used in Toxicology Testing The Science of the Total Environment. Jan, 2017  |   Pubmed ID: 27783930 Comprehensive characterization of exposure media used in toxicology studies is still an area of significant divergence when evaluating potential oil spill impacts. When preparing exposure media used for toxicology testing, small variations in simple parameters such as mixing energy, oil type and loading can significantly affect the concentration of the oil components to which test organisms are exposed. The key goal of this study was compare and contrast the physical and chemical compositions of oil water mixtures prepared using fresh and weathered Macondo-related oils under different conditions of mixing and in the presence/absence of chemical dispersants. All samples were assessed for the presence of droplets, droplet size distribution, and detailed chemical composition including polycyclic aromatic hydrocarbons (PAHs) and total petroleum hydrocarbon by fluorescence (TPHF). Preparations were also tested for stability over a 96h period relevant to acute toxicity tests. The results indicate that water accommodated fractions (WAFs) produced consistent, droplet free solutions with concentration that represented the soluble components of the oil used. As expected, chemically-enhanced WAFs (CEWAFs) and high-energy WAFs (HEWAFs) generated large amounts of micron-size droplets and their chemical composition corresponded closely with that of the whole oil. However, the HEWAFs were highly dynamic, and unlike CEWAFs, much of the oil resurfaced within few hours of the initial preparation. Viscosity and lack of dispersability are the limiting factors for preparation of CEWAFs with weathered oils, in contrast HEWAFs did effectively introduce large amounts of weathered oil droplets in the test media. Despite this benefit, droplet sizes significantly decreased in HEWAFs with increase in weathering of the oil creating an additional variable to consider. Because the contribution of small droplets to toxicity is a topic that needs further investigation, the interpretation of results from high-energy preparations needs to be further evaluated. When the TPAHs concentrations of all preparations at all loadings were compared with the publicly available water-column data for samples analyzed during and after the DWH incident response they all ranked above the vast majority of the 10,828 samples reported. Until a better characterization of all the available DWH water column individual-component chemistry data is produced the question of environmental relevance and the pursuit of toxicological studies under more realistic conditions continues to be a significant challenge that should be further explored.