Quantitative Analysis and Determination of Microcystin in water by Capillary Electrophoresis Mass Spectrometry

The presence of harmful algal blooms (HAB) is a growing concern in aquatic environments. Among HAB organisms, cyanobacteria are of special concern because they have been reported worldwide to cause environmental and human health problem through contamination of drinking water. Although several analytical approaches have been applied to monitoring cyanobacteria toxins, conventional methods are costly and time-consuming so that analyses take weeks for field sampling and subsequent lab analysis. Capillary electrophoresis (CE) becomes a particularly suitable analytical separation method that can couple very small samples and rapid separations to a wide range of selective and sensitive detection techniques. This paper demonstrates a method for rapid separation and identification of four microcystin variants commonly found in aquatic environments. CE coupled to UV and electrospray ionization time-of-flight mass spectrometry (ESI-TOF) procedures were developed. All four analytes were separated within 6 minutes. The ESI-TOF experiment provides accurate molecular information, which further identifies analytes.

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

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

Arctic ecosystem responses to changes in water availability and warming: Short and long-term responses

Arctic soils store close to 14% of the global soil carbon. Most of arctic carbon is stored below ground in the permafrost. With climate warming the decomposition of the soil carbon could represent a significant positive feedback to global greenhouse warming. Recent evidence has shown that the temperature of the Arctic is already increasing, and this change is associated mostly with anthropogenic activities. Warmer soils will contribute to permafrost degradation and accelerate organic matter decay and thus increase the flux of carbon dioxide and methane into the atmosphere. Temperature and water availability are also important drivers of ecosystem performance, but effects can be complex and in opposition. Temperature and moisture changes can affect ecosystem respiration (ER) and gross primary productivity (GPP) independently; an increase in the net ecosystem exchange can be a result of either a decrease in ER or an increase in GPP. Therefore, understanding the effects of changes in ecosystem water and temperature on the carbon flux components becomes key to predicting the responses of the Arctic to climate change. The overall goal of this work was to determine the response of arctic systems to simulated climate change scenarios with simultaneous changes in temperature and moisture. A temperature and hydrological manipulation in a naturally-drained lakebed was used to assess the short-term effect of changes in water and temperature on the carbon cycle. Also, as part of International Tundra Experiment Network (ITEX), I determined the long-term effect of warming on the carbon cycle in a natural hydrological gradient established in the mid 90's. I found that the carbon balance is highly sensitive to short-term changes in water table and warming. However, over longer time periods, hydrological and temperature changed soil biophysical properties, nutrient cycles, and other ecosystem structural and functional components that down regulated GPP and ER, especially in wet areas.

Analysis of organomercurials in environmental and biological samples by capillary column gas chromatography with atomic fluorescence detection

The general method for determining organomercurials in environmental and biological samples is gas chromatography with electron capture detection (GC-ECD). However, tedious sample work up protocols and poor chromatographic response show the need for the development of new methods. Here, Atomic Fluorescence-based methods are described, free from these deficiencies. The organomercurials in soil, sediment and tissue samples are first released from the matrices with acidic KBr and cupric ions and extracted into dichloromethane. The initial extracts are subjected to thiosulfate clean up and the organomercury species are isolated as their chloride derivatives by cupric chloride and subsequent extraction into a small volume of dichloromethane. In water samples the organomercurials are pre-concentrated using a sulfhydryl cotton fiber adsorbent, followed by elution with acidic KBr and CuSO 4 and extraction into dichloromethane. Analysis of the organomercurials is accomplished by capillary column chromatography with atomic fluorescence detection.

Determination of Arsenic Species in Water and Grape-Based Beverages

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

Experimental determination of effects of water depth on Nymphaea odorata growth, morphology and biomass allocation

Growth, morphology and biomass allocation in response to water depth was studied in white water lily,Nymphaea odorata Aiton. Plants were grown for 13 months in 30, 60 and 90 cm water in outdoor mesocosms in southern Florida. Water lily plant growth was distinctly seasonal with plants at all water levels producing more and larger leaves and more flowers in the warmer months. Plants in 30 cm water produced more but smaller and shorter-lived leaves than plants at 60 cm and 90 cm water levels. Although plants did not differ significantly in total biomass at harvest, plants in deeper water had significantly greater biomass allocated to leaves and roots, while plants in 30 cm water had significantly greater biomass allocated to rhizomes. Although lamina area and petiole length increased significantly with water level, lamina specific weight did not differ among water levels. Petiole specific weight increased significantly with increasing water level, implying a greater cost to tethering the larger laminae in deeper water. Lamina length and width scaled similarly at different water levels and modeled lamina area (LA) accurately (LAmodeled = 0.98LAmeasured + 3.96, R2 = 0.99). Lamina area was highly correlated with lamina weight (LW = 8.43LA − 66.78, R2 = 0.93), so simple linear measurements can predict water lily lamina area and lamina weight. These relationships were used to calculate monthly lamina surface area in the mesocosms. Plants in 30 cm water had lower total photosynthetic surface area than plants in 60 cm and 90 cm water levels throughout, and in the summer plants in 90 cm water showed a great increase in photosynthetic surface area as compared to plants in shallower water. These results support setting Everglades restoration water depth targets for sloughs at depths ≥45 cm and suggest that in the summer optimal growth for white water lilies occurs at depths ≥75 cm.