The spectral distribution of biologically active solar radiation at Miami, Florida, USA

The spectral distribution of solar radiation was studied under different sky conditions during a 15- month period in Miami, Florida (USA), and over a latitudinal gradient at solar maximum. Spectroradiometric scans were characterized for total irradiance (300- 3000 nm) and the relative energetic and photon contributions of the following wavelength regions: UV-B (300-320nm); UV-A (320-400nm); B (400-500rim); PAR (400-700 nm); R (600-700 nm); and FR (728- 732 rim). Notable results include: (i) significantly higher UV-A energy fluxes than currently in use for laboratory experiments involving the biological effects of this bandwidth (values ranged from 33.6 to 55.4 W/m 2 in Miami over the year); (ii) marked diurnal shifts in B:R and R:FR, with elevated R:FR values in early morning: (iii) a strong correlation between R: FR and atmospheric water content; and (iv) unusually high PAR values under direct sunlight with cloudy skies (2484 ~tmot/2 per s).

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.^

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.

The Spectral Distribution of Radiation in Two Neotropical Rainforests

The spectral quality of radiation in the understory of two neotropical rainforests, Barro Colorado Island in Panama and La Selva in Costa Rica, is profoundly affected by the density of the canopy. Understory light conditions in both forests bear similar spectral characteristics. In both the greatest changes in spectral quality occur at low flux densities, as in the transition from extreme shade to small light flecks. Change in spectral quality, as assessed by the red: far-red (R:FR) ratio, the ratio of radiant energy 400-700: 300-1100 nm, and the ratio of quantum flux density 400-700:300-1100 nm, is strongly correlated with a drop in percentage of solar radiation as measurable by a quantum radiometer. Thus, by knowing the percentage of photosynthetic photon flux density (PPFD) in relation to full sunlight, it is possible to estimate the spectral quality in the forest at a particular time and microsite.

Solar radiation–enhanced dissolution of particulate organic matter from coastal marine sediments

We investigated the influence of solar radiation on the transfer of organic matter from the particulate to dissolved phase during resuspension of coastal sediments collected from seven sites across Florida Bay (organic carbon values ranged from 2% to 9% by weight). Sediments were resuspended in oligotrophic seawater for 48 h in 1-liter quartz flasks in the dark and under simulated solar radiation (SunTest XLS+) at wet weight concentrations of 100 mg L21 and 1 g L21 (dry weights ranged from 27 to 630 mg L21). There were little to no dissolved organic carbon (DOC) increases in dark resuspensions, but substantial DOC increases occurred in irradiated resuspensions. DOC levels increased 4 mg C L21 in an irradiated 1 g L21 suspension (dry weight 400 mg L21) of an organic-rich (7% organic carbon) sediment. At a particle load commonly found in coastal waters (dry weight 40 mg L21), an irradiated suspension of the same organic-rich sediment produced 1 mg C L21. DOC increases in irradiated resuspensions were well-correlated with particulate organic carbon (POC) added. Photodissolution of POC ranged from 6% to 15% at high sediment levels and 10% to 33% at low sediment levels. Parallel factor analysis modeling of excitation-emission matrix fluorescence data (EEM PARAFAC) suggested the dissolved organic matter (DOM) produced during photodissolution included primarily humic-like components and a less important input of protein-like components. Principal component analysis (PCA) of EEM data revealed a marked similarity in the humic character of photodissolved DOM from organic-rich sediments and the humic character of Florida Bay waters.

Variation and Uncertainty in Evaporation from a Subtropical Estuary: Florida Bay

Variation and uncertainty in estimated evaporation was determined over time and between two locations in Florida Bay, a subtropical estuary. Meteorological data were collected from September 2001 to August 2002 at Rabbit Key and Butternut Key within the Bay. Evaporation was estimated using both vapor flux and energy budget methods. The results were placed into a long-term context using 33 years of temperature and rainfall data collected in south Florida. Evaporation also was estimated from this long-term data using an empirical formula relating evaporation to clear sky solar radiation and air temperature. Evaporation estimates for the 12-mo period ranged from 144 to 175 cm yr21, depending on location and method, with an average of 163 cm yr21 (6 9%). Monthly values ranged from 9.2 to 18.5 cm, with the highest value observed in May, corresponding with the maximum in measured net radiation. Uncertainty estimates derived from measurement errors in the data were as much as 10%, and were large enough to obscure differences in evaporation between the two sites. Differences among all estimates for any month indicate the overall uncertainty in monthly evaporation, and ranged from 9% to 26%. Over a 33-yr period (1970–2002), estimated annual evaporation from Florida Bay ranged from 148 to 181 cm yr21, with an average of 166 cm yr21. Rainfall was consistently lower in Florida Bay than evaporation, with a long-term average of 106 cm yr21. Rainfall considered alone was uncorrelated with evaporation at both monthly and annual time scales; when the seasonal variation in clear sky radiation was also taken into account both net radiation and evaporation were significantly suppressed in months with high rainfall.

Early diagenesis of plant-derived dissolved organic matter along a wetland, mangrove, estuary ecotone

We studied the role of photochemical and microbial processes in contributing to the transformation of dissolved organic matter (DOM) derived from various plants that dominate the Florida Everglades. Plant-derived DOM leachate samples were exposed to photochemical and microbial degradation and the optical, chemical, and molecular weight characteristics measured over time. Optical parameters such as the synchronous fluorescence intensity between 270 and 290 nm (Fnpeak I), a strong indicator of protein and/or polyphenol content, decreased exponentially in all plant leachate samples, with microbial decay constants ranging from 21.0 d21 for seagrass to 20.11 d21 for mangrove (half-life [t1/2] 5 0.7–6.3 d). Similar decreases in polyphenol content and dissolved organic carbon (DOC) concentration also occurred but were generally an order of magnitude lower or did not change significantly over time. The initial molecular weight composition was reflected in the rate of Fnpeak I decay and suggests that plantderived DOM with a large proportion of high molecular weight structures, such as seagrass derived DOM, contain high concentrations of easily microbially degradable proteinaceous components. For samples exposed to extended simulated solar radiation, polyphenol and Fnpeak I photochemical decay constants were on average 20.7 d21 (t1/2 1.0 d). Our data suggest that polyphenol structures of plant-derived DOM are particularly sensitive to photolysis, whereas high molecular weight protein-like structures are degraded primarily through physical–chemical and microbial processes. Furthermore, microbial and physical processes initiated the formation of recalcitrant, highly colored high molecular weight polymeric structures in mangrove-derived DOM. Thus, partial, biogeochemical transformation of plant-derived DOM from coastal areas is rapid and is likely to influence carbon and nutrient cycling, especially in areas dominated by seagrass and mangrove forests.