Occurrence and environmental fate of Irgarol 1051, a new antifouling agent

The purpose of this study is to characterize the degradation products of Irgarol 1051(2-methylthio-4-tertbutylamino-6-cyclopropylamino- s-triazine), a compound recently developed for use as an antifouling agent on boat hulls. The photolytic fate of this compound in different natural waters will be used in the development of a monitoring program designed to survey the occurrence of this compound and its degradation products in South Florida marinas, the Miami River and surrounding coastal areas. ^ The transformation of Irgarol 1051 and degradation rate constants were characterized in a photo-reactor under simulated natural conditions. The degradation pathway in the UVB-UVA region (300nm to 350nm) closely resembled the transformations under natural conditions in the pond, showing that both direct photolysis and the presence of natural sensitizers play an important role in the abiotic transformation of this compound. Irgarol 1051 has an average environmental half-life of 10 days in surface waters. Average concentrations from samples around Biscayne Bay and the Miami River increased from 1–5 ng/L during 1999 and increased to between 28 and 38 ng/L in 2001, respectively. Irgarol concentrations showed a strong correlation with concentrations of its major transformation product, M1, from samples collected as part of the study ([M1]/[Irgarol] = 0.247, R2 = 0.9165, n = 125). ^

An Investigation on Biocompatibility of Bio-Absorbable Polymer Coated Magnesium Alloys

Advances in biomaterials have enabled medical practitioners to replace diseased body parts or to assist in the healing process. In situations where a permanent biomaterial implant is used for a temporary application, additional surgeries are required to remove these implants once the healing process is complete, which increases medical costs and patient morbidity. Bio-absorbable materials dissolve and are metabolized by the body after the healing process is complete thereby negating additional surgeries for removal of implants. Magnesium alloys as novel bio-absorbable biomaterials, have attracted great attention recently because of their good mechanical properties, biocompatibility and corrosion rate in physiological environments. However, usage of Mg as biodegradable implant has been limited by its poor corrosion resistance in the physiological solutions. An optimal biodegradable implant must initially have slow degradation to ensure total mechanical integrity then degrade over time as the tissue heals. The current research focuses on surface modification of Mg alloy (MZC) by surface treatment and polymer coating in an effort to enhance the corrosion rate and biocompatibility. It is envisaged that the results obtained from this investigation would provide the academic community with insights for the utilization of bio-absorbable implants particularly for patients suffering from atherosclerosis. The alloying elements used in this study are zinc and calcium both of which are essential minerals in the human metabolic and healing processes. A hydrophobic biodegradable co-polymer, polyglycolic-co-caprolactone (PGCL), was used to coat the surface treated MZC to retard the initial degradation rate. Two surface treatments were selected: (a) acid etching and (b) anodization to produce different surface morphologies, roughness, surface energy, chemistry and hydrophobicity that are pivotal for PGCL adhesion onto the MZC. Additionally, analyses of biodegradation, biocompatibility, and mechanical integrity were performed in order to investigate the optimum surface modification process, suitable for biomaterial implants. The study concluded that anodization created better adhesion between the MZC and PGCL coating. Furthermore, PGCL coated anodized MZC exhibited lower corrosion rate, good mechanical integrity, and better biocompatibility as compared with acid etched.

Synthesis and Characterization of Photochromic Copolymers Containing 3-Indolylfulgides/Indolylfulgimides

Fulgides and fulgimides are important organic photochromic compounds and can switch between the open forms and the closed forms with light. The 3-indolylfulgides and 3-indolylfulgimides exhibit promising photochromic properties and have great potential in optical memory devices, optical switches and biosensors. Copolymers containing 3-indolylfulgides/indolylfulgimides synthesized via free radical polymerizations increase conformation changes and allow the photochromic compounds to be uniformly distributed in the polymer matrix. A trifluoromethyl 3-indolylfulgide and two trifluoromethyl 3-indolylfulgimides with one or two polymerizable N-stryryl group(s) were prepared. Copolymerization with methyl methacrylate provided two linear copolymers or a cross-linked copolymer. The properties of the monomeric fulgide/fulgimides and copolymers in toluene or as thin films were characterized. In general, the photochromic monomers and copolymers revealed similar photochromic properties and exhibited good thermal and photochemical stability. All compounds absorb visible light in both open forms and closed forms. The closed form copolymers were more stable than the open form copolymers and showed little or no degradation after 400 h. The photochemical degradation rate was less than 0.03% per cycle. In films, conformational restrictions were observed for the open forms suggesting that the preparation of films from the closed forms is advantageous. Two novel methyl 3-indolylfulgimides with one or two polymerizable N-stryryl group(s) were prepared. Copolymerization of acrylamide with the methyl indolylfulgimides or the trifluoromethyl indolylfulgimides yielded two aqueous soluble linear copolymers and two photochromic hydrogels. The closed form copolymers containing trifluoromethyl indolylfulgimides were hydrolyzed in aqueous solution by replacing the trifluoromethyl group with a carboxylic acid group. The resulting carboxylic copolymers were also photochromic. The copolymers containing methyl fulgimides were stable in aqueous solutions and did not hydrolyze. Both methyl and carboxylic copolymers exhibited good stability in aqueous solutions. In general, the open form copolymers were more stable than the closed form copolymers, and the copolymers revealed better stability in acidic solution than neutral solution. The linear copolymers displayed better photochemical stability in neutral solution and degraded up to 22% after 105 cycles. In contrast, the hydrogels showed enhanced fatigue resistance in acidic condition and underwent up to 60 cycles before degrading 24%.

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.^

Improving performance of a permeable reactive barrier in the degradation of trichloroethylene using ultrasound

The impact of ultrasound on improving the performance of a granular iron Permeable Reactive Barrier (PRB) in the degradation of Trichloroethylene (TCE) was evaluated. Two treatment columns made of clear Plexiglas with a height of 1ft and a diameter of 2 inches and filled with granular iron were used. One was fitted with 25Khz ultrasound probes. A solution of TCE was run through at constant flow rate. Samples obtained from the column at different residence times before and after sonication were analyzed for concentrations of TCE and used to generate concentration profiles to obtain rate constants, which were compared. An improvement of 23.4% in the reaction rate of TCE degradation was observed after sonication of the iron media suggesting that ultrasound may contribute to improving the performance of PRBs in the degradation of TCE in contaminated groundwater.

Photo Degradation of Cotnaminants 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.