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.

Novel online data cleaning protocols for data streams in trajectory, Wireless Sensor Networks

The promise of Wireless Sensor Networks (WSNs) is the autonomous collaboration of a collection of sensors to accomplish some specific goals which a single sensor cannot offer. Basically, sensor networking serves a range of applications by providing the raw data as fundamentals for further analyses and actions. The imprecision of the collected data could tremendously mislead the decision-making process of sensor-based applications, resulting in an ineffectiveness or failure of the application objectives. Due to inherent WSN characteristics normally spoiling the raw sensor readings, many research efforts attempt to improve the accuracy of the corrupted or "dirty" sensor data. The dirty data need to be cleaned or corrected. However, the developed data cleaning solutions restrict themselves to the scope of static WSNs where deployed sensors would rarely move during the operation. Nowadays, many emerging applications relying on WSNs need the sensor mobility to enhance the application efficiency and usage flexibility. The location of deployed sensors needs to be dynamic. Also, each sensor would independently function and contribute its resources. Sensors equipped with vehicles for monitoring the traffic condition could be depicted as one of the prospective examples. The sensor mobility causes a transient in network topology and correlation among sensor streams. Based on static relationships among sensors, the existing methods for cleaning sensor data in static WSNs are invalid in such mobile scenarios. Therefore, a solution of data cleaning that considers the sensor movements is actively needed. This dissertation aims to improve the quality of sensor data by considering the consequences of various trajectory relationships of autonomous mobile sensors in the system. First of all, we address the dynamic network topology due to sensor mobility. The concept of virtual sensor is presented and used for spatio-temporal selection of neighboring sensors to help in cleaning sensor data streams. This method is one of the first methods to clean data in mobile sensor environments. We also study the mobility pattern of moving sensors relative to boundaries of sub-areas of interest. We developed a belief-based analysis to determine the reliable sets of neighboring sensors to improve the cleaning performance, especially when node density is relatively low. Finally, we design a novel sketch-based technique to clean data from internal sensors where spatio-temporal relationships among sensors cannot lead to the data correlations among sensor streams.