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.

Water for the Wayuu: Procurement and maximization of a limited resource among indigenous pastoralists on the Guajira Peninsula of northern Colombia

For the Wayuu of the Guajira Peninsula of northern Colombia, water procurement has historically been challenging. The ancestral territory of this indigenous pastoral society is windy and arid, with low rainfall, high temperatures and an absence of perennial rivers or streams. In the past, the Wayuu adapted to these environmental conditions by practicing transhumance during the prolonged dry seasons, digging spring wells and artificial ponds and by following guiding principles for water usage. Since the 1930s, the government has made efforts to build additional wind-powered wells and ponds for a growing native population. Notwithstanding, these water solutions have only partly met the necessities; public water sources are limited or unreliable and few attempts are made to generate safe drinking water. Furthermore, the ubiquitous practice of animal husbandry places added pressure on existing sources; livestock consume more water than the human populations in the areas visited. Rapid assessments in four Wayuu areas on the peninsula were conducted by the author and an interdisciplinary team working for the Cerrejón Foundation for Water in La Guajira from 2010 to 2013. The assessments were part of a larger pilot project to design and implement a sustainability plan for reservoir-based water supply systems in the region. This study brings cultural practices and local knowledge to the forefront as key elements for the success of water works and other development projects carried out in Wayuu territory.

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.

Water loss management strategies for developing countries

Diese Arbeit beschäftigt sich mit nicht in Rechnung stellbaren Wasserverlusten in städtischen Versorgungsnetzen in Entwicklungsländern. Es soll das Wissen über diese Verluste erweitert und aufgezeigt werden, ob diese auf ein ökonomisch vertretbares Maß reduziert werden können. Die vorliegende Doktorarbeit untersucht solche unberechneten Wasserverluste und versucht, neben der Quantifizierung von Leckagen auch Entscheidungswerkzeuge für ein verbessertes Management der Versorgungsnetze in Entwicklungsländern zu erarbeiten. Als Fallstudie dient Harare, die Hauptstadt von Simbabwe. Wasserverluste in Verteilungsnetzen sind unvermeidbar, sollten aber auf ein ökonomisch tragbares Niveau reduziert werden, wenn ein nachhaltiger Betrieb erreicht werden soll. Wasserverluste können sowohl durch illegale und ungenehmigte Anschlüsse oder durch Undichtigkeiten im Verteilnetz, als auch durch mangelhafte Mess- und Berechnungssysteme entstehen. Es sind bereits viele Ansätze zur Verringerung von Verlusten in Wasserverteilsystemen bekannt geworden, entsprechend existieren dazu auch zahlreiche Methoden und Werkzeuge. Diese reichen von computergestützten Verfahren über gesetzliche und politische Vorgaben sowie ökonomische Berechnungen bis hin zu Maßnahmen der Modernisierung der Infrastruktur. Der Erfolg dieser Anstrengungen ist abhängig von der Umsetzbarkeit und dem Umfeld, in dem diese Maßnahmen durchgeführt werden. Die Bewertung der Arbeitsgüte einer jeden Wasserversorgungseinheit basiert auf der Effektivität des jeweiligen Verteilungssystems. Leistungs- und Bewertungszahlen sind die meist genutzten Ansätze, um Wasserverteilsysteme und ihre Effizienz einzustufen. Weltweit haben sich zur Bewertung als Indikatoren die finanzielle und die technische Leistungsfähigkeit durchgesetzt. Die eigene Untersuchung zeigt, dass diese Indikatoren in vielen Wasserversorgungssystemen der Entwicklungsländer nicht zur Einführung von Verlust reduzierenden Managementstrategien geführt haben. Viele durchgeführte Studien über die Einführung von Maßnahmen zur Verlustreduzierung beachten nur das gesamte nicht in Rechnung stellbare Wasser, ohne aber den Anteil der Leckagen an der Gesamthöhe zu bestimmen. Damit ist keine Aussage über die tatsächliche Zuordnung der Verluste möglich. Aus diesem Grund ist ein Bewertungsinstrument notwendig, mit dem die Verluste den verschiedenen Ursachen zugeordnet werden können. Ein solches Rechenwerkzeug ist das South African Night Flow Analysis Model (SANFLOW) der südafrikanischen Wasser-Forschungskommission, das Untersuchungen von Wasserdurchfluss und Anlagendruck in einzelnen Verteilbezirken ermöglicht. In der vorliegenden Arbeit konnte nachgewiesen werden, dass das SANFLOW-Modell gut zur Bestimmung des Leckageanteiles verwendet werden kann. Daraus kann gefolgert werden, dass dieses Modell ein geeignetes und gut anpassbares Analysewerkzeug für Entwicklungsländer ist. Solche computergestützte Berechnungsansätze können zur Bestimmung von Leckagen in Wasserverteilungsnetzen eingesetzt werden. Eine weitere Möglichkeit ist der Einsatz von Künstlichen Neuronalen Netzen (Artificial Neural Network – ANN), die trainiert und dann zur Vorhersage der dynamischen Verhältnisse in Wasserversorgungssystemen genutzt werden können. Diese Werte können mit der Wassernachfrage eines definierten Bezirks verglichen werden. Zur Untersuchung wurde ein Mehrschichtiges Künstliches Neuronales Netz mit Fehlerrückführung zur Modellierung des Wasserflusses in einem überwachten Abschnitt eingesetzt. Zur Bestimmung des Wasserbedarfes wurde ein MATLAB Algorithmus entwickelt. Aus der Differenz der aktuellen und des simulierten Wassernachfrage konnte die Leckagerate des Wasserversorgungssystems ermittelt werden. Es konnte gezeigt werden, dass mit dem angelernten Neuronalen Netzwerk eine Vorhersage des Wasserflusses mit einer Genauigkeit von 99% möglich ist. Daraus lässt sich die Eignung von ANNs als flexibler und wirkungsvoller Ansatz zur Leckagedetektion in der Wasserversorgung ableiten. Die Untersuchung zeigte weiterhin, dass im Versorgungsnetz von Harare 36 % des eingespeisten Wassers verloren geht. Davon wiederum sind 33 % auf Leckagen zurückzuführen. Umgerechnet bedeutet dies einen finanziellen Verlust von monatlich 1 Millionen Dollar, was 20 % der Gesamteinnahmen der Stadt entspricht. Der Stadtverwaltung von Harare wird daher empfohlen, aktiv an der Beseitigung der Leckagen zu arbeiten, da diese hohen Verluste den Versorgungsbetrieb negativ beeinflussen. Abschließend wird in der Arbeit ein integriertes Leckage-Managementsystem vorgeschlagen, das den Wasserversorgern eine Entscheidungshilfe bei zu ergreifenden Maßnahmen zur Instandhaltung des Verteilnetzes geben soll.

Midwest Technology Assistance Center for Small Public Water Systems Final Report

U.S. Environmental Protection Agency

Analysis of N-nitrosames in water using micellar electrokinetic chromatography (MEKC) and development of online and offline methods of extraction and enrichment of neutral polar analytes

Evaluation of the quality of the environment is essential for human wellness as pollutants in trace amounts can cause serious health problem. Nitrosamines are a group of compounds that are considered potential carcinogens and can be found in drinking water (as disinfection byproducts), foods, beverages and cosmetics. To monitor the level of these compounds to minimize daily intakes, fast and reliable analytical techniques are required. As these compounds are relatively highly polar, extraction and enrichment from environmental samples (aqueous) are challenging. Also, the trend of analytical techniques toward the reduction of sample size and minimization of organic solvent use demands new methods of analysis. In light of fulfilling these requirements, a new method of online preconcentration tailored to an electrokinetic chromatography is introduced. In this method, electroosmotic flow (EOF) was suppressed to increase the interaction time between analyte and micellar phase, therefore the only force to mobilize the neutral analytes is the interaction of analyte with moving micelles. In absence of EOF, polarity of applied potential was switched (negative or positive) to force (anionic or cationic) micelles to move toward the detector. To avoid the excessive band broadening due to longer analysis time caused by slow moving micelles, auxiliary pressure was introduced to boost the micelle movement toward the detector using an in house designed and built apparatus. Applying the external auxiliary pressure significantly reduced the analysis times without compromising separation efficiency. Parameters, such as type of surfactants, composition of background electrolyte (BGE), type of capillary, matrix effect, organic modifiers, etc., were evaluated in optimization of the method. The enrichment factors for targeted analytes were impressive, particularly; cationic surfactants were shown to be suitable for analysis of nitrosamines due to their ability to act as hydrogen bond donors. Ammonium perfluorooctanoate (APFO) also showed remarkable results in term of peak shapes and number of theoretical plates. It was shown that the separation results were best when a high conductivity sample was paired with a BGE of lower conductivity. Using higher surfactant concentrations (up to 200 mM SDS) than usual (50 mM SDS) for micellar electrokinetic chromatography (MEKC) improved the sweeping. A new method for micro-extraction and enrichment of highly polar neutral analytes (N-Nitrosamines in particular) based on three-phase drop micro-extraction was introduced and its performance studied. In this method, a new device using some easy-to-find components was fabricated and its operation and application demonstrated. Compared to conventional extraction methods (liquid-liquid extraction), consumption of organic solvents and operation times were significantly lower.

Optimization of flocculation process and continuous filtration for sea water primary treatment filtration to reduce SDI for entree to reverse osmosis system

Today , Providing drinking water and process water is one of the major problems in most countries ; the surface water often need to be treated to achieve necessary quality, and in this way, technological and also financial difficulties cause great restrictions in operating the treatment units. Although water supply by simple and cheap systems has been one of the important objectives in most scientific and research centers in the world, still a great percent of population in developing countries, especially in rural areas, don't benefit well quality water. One of the big and available sources for providing acceptable water is sea water. There are two ways to treat sea water first evaporation and second reverse osmosis system. Nowadays R.O system has been used for desalination because of low budget price and easily to operate and maintenance. The sea water should be pretreated before R.O plants, because there is some difficulties in raw sea water that can decrease yield point of membranes in R.O system. The subject of this research may be useful in this way, and we hope to be able to achieve complete success in design and construction of useful pretreatment systems for R.O plant. One of the most important units in the sea water pretreatment plant is filtration, the conventional method for filtration is pressurized sand filters, and the subject of this research is about new filtration which is called continuous back wash sand filtration (CBWSF). The CBWSF designed and tested in this research may be used more economically with less difficulty. It consists two main parts first shell body and second central part comprising of airlift pump, raw water feeding pipe, air supply hose, backwash chamber and sand washer as well as inlet and outlet connections. The CBWSF is a continuously operating filter, i.e. the filter does not have to be taken out of operation for backwashing or cleaning. Inlet water is fed through the sand bed while the sand bed is moving downwards. The water gets filtered while the sand becomes dirty. Simultaneously, the dirty sand is cleaned in the sand washer and the suspended solids are discharged in backwash water. We analyze the behavior of CBWSF in pretreatment of sea water instead of pressurized sand filter. There is one important factor which is not suitable for R.O membranes, it is bio-fouling. This factor is defined by Silt Density Index (SDI).measured by SDI. In this research has been focused on decreasing of SDI and NTU. Based on this goal, the prototype of pretreatment had been designed and manufactured to test. The system design was done mainly by using the design fundamentals of CBWSF. The automatic backwash sand filter can be used in small and also big water supply schemes. In big water treatment plants, the units of filters perform the filtration and backwash stages separately, and in small treatment plants, the unit is usually compacted to achieve less energy consumption. The analysis of the system showed that it may be used feasibly for water treating, especially for limited population. The construction is rapid, simple and economic, and its performance is high enough because no mobile mechanical part is used in it, so it may be proposed as an effective method to improve the water quality and consequently the hygiene level in the remote places of the country.

Magnetic carbon xerogels for the catalytic wet peroxide oxidation of sulfamethoxazole in environmentally relevant water matrices

Novel magnetic carbon xerogels consisting of interconnected carbon microspheres with iron and/or cobalt microparticles embedded in their structure were developed by a simple route. As inferred from the characterization data, materials with distinctive properties may be directly obtained upon inclusion of iron and/or cobalt precursors during the sol-gel polymerization of resorcinol and formaldehyde, followed by thermal annealing. The unique properties of these magnetic carbon xerogels were explored in the catalytic wet peroxide oxidation (CWPO) of an antimicrobial agent typically found throughout the urban water cycle – sulfamethoxazole (SMX). A clear synergistic effect arises from the inclusion of cobalt and iron in carbon xerogels (CX/CoFe),the resulting magnetic material revealing a better performance in the CWPO of SMX at the ppb level(500 microg L−1) when compared to that of monometallic carbon xerogels containing only iron or cobalt.This effect was ascribed to the increased accessibility of highly active iron species promoted by the simultaneous incorporation of cobalt.The performance of the CWPO process in the presence of CX/CoFe was also evaluated in environmentally relevant water matrices, namely in drinking water and secondary treated wastewater, considered in addition to ultrapure water. It was found that the performance decreases when applied to more complex water and wastewater samples. Nevertheless, the ability of the CWPO technology for the elimination of SMX in secondary treated wastewater was unequivocally shown, with 96.8% of its initial content being removed after 6 h of reaction in the presence of CX/CoFe, at atmospheric pressure, room temperature(T = 25◦C), pH = 3, [H2O2]0= 500 mg L−1and catalyst load = 80 mg L−1. A similar performance (97.8% SMX removal) is obtained in 30 min when the reaction temperature is slightly increased up to 60◦C in an ultra-pure water matrix. Synthetic water containing humic acid, bicarbonate, sulphate or chloride, was also tested. The results suggest the scavenging effect of the different anions considered, as well as the negative impact of dissolved organic matter typically found in secondary treated wastewater, as simulated by the presence of humic acid.An in-situ magnetic separation procedure was applied for catalyst recovery and re-use during reusability cycles performed to mimic real-scale applications. CWPO runs performed with increased SMX concentration (10 mg L−1), under a water treatment process intensification approach, allowed to evalu-ate the mineralization levels obtained, the antimicrobial activity of the treated water, and to propose adegradation mechanism for the CWPO of SMX.

Physico-chemical characterization of metal-doped bone chars and their adsorption behavior for water defluoridation

New bone chars for fluoride adsorption from drinking water have been synthetized via metallic doping using aluminum and iron salts. A detailed statistical analysis of the metal doping process using the signal-to-noise ratios from Taguchi's experimental designs and its impact on the fluoride adsorption properties of modified bone chars have been performed. The best conditions, including the proper metallic salt, for metal doping were identified to improve the fluoride uptakes of modified bone chars. Results showed that the fluoride adsorption properties of bone chars can be enhanced up to 600% using aluminum sulfate for the surface modification. This aluminum-based adsorbent showed an adsorption capacity of 31 mg/g, which outperformed the fluoride uptakes reported for several adsorbents. Surface interactions involved in the defluoridation process were established using FTIR, DRX and XPS analysis. Defluoridation using the metal-doped bone chars occurred via an ion exchange process between fluoride ions and the hydroxyl groups on the adsorbent surface, whereas the Al(OH)xFy, FexFy, and CaF2 interactions could play also an important role in the removal process. These metal-doped adsorbents anticipate a promising behavior in water treatment, especially in developing countries where the efficiency – cost tradeoff is crucial for implementing new defluoridation technologies.

Trends in Water Quality within the Broward County Portion of the Biscayne Aquifer

Continuous and reliable monitoring of contaminants in drinking water, which adversely affect human health, is the main goal of the Broward County Well Field Protection Program. In this study the individual monitoring station locations were used in a yearly and quarterly spatiotemporal Ordinary Kriging interpolation to create a raster network of contaminant detections. In the final analysis, the raster spatiotemporal nitrate concentration trends were overlaid with a pollution vulnerability index to determine if the concentrations are influenced by a set of independent variables. The pollution vulnerability factors are depth to water, recharge, aquifer media, soil, impact to vadose zone, and conductivity. The creation of the nitrate raster dataset had an average RMS Standardized error close to 1 at 0.98. The greatest frequency of detections and the highest concentrations are found in the months of April, May, June, July, August, and September. An average of 76.4% of the nitrate intersected with cells of the pollution vulnerability index over 100.

Stream water‐quality monitoring conducted in support of the Iowa Nutrient Reduction Strategy (2016)

Monitoring of nitrogen and phosphorus in streams and rivers throughout Iowa is an essential element of the Iowa Nutrient Reduction Strategy (INRS). Sampling and analysis of surface water is necessary to develop periodic estimates of the amounts of nitrogen and phosphorus transported from Iowa. Surface and groundwater monitoring provides the scientific evidence needed to document the effectiveness of nutrient reduction practices and the impact they have on water quality. Lastly, monitoring data informs decisions about where and how best to implement nutrient reduction practices, by both point sources and nonpoint sources, to provide the greatest benefit at the least cost. The impetus for this report comes from the Water Resources Coordination Council (WRCC) which states in its 2014‐15 Annual Report “Efforts are underway to improve understanding of the multiple nutrient monitoring efforts that may be available and can be compared to the nutrient WQ monitoring framework to identify opportunities and potential data gaps to better coordinate and prioritize future nutrient monitoring efforts.” This report is the culmination of those efforts.

Iowa Nutrient Reduction Strategy stream water quality monitoring in Iowa : measuring progress (2016)

The Iowa Nutrient Reduction Strategy (NRS) is a research- and technology-based approach to assess and reduce nutrients—nitrogen and phosphorus—delivered to Iowa waterways and the Gulf of Mexico by 45 percent. To measure progress, researchers track many different factors, from inputs (e.g. funding) and the human domain (e.g. farmer perspectives) to land management (e.g. on-farm practices) and water quality. Monitoring Iowa streams provides valuable insight into measuring water quality progress and the reduction of surface water nutrient loss. The Iowa Nutrient Reduction Strategy (NRS) aims to reduce the load, or total amount (e.g. tons), of nutrients lost annually. Researchers calculate the load from water monitoring results, which measure concentration combined with stream flow.

Animal Control - What constitutes a reliable cue to stop animal movement ?

Controlling free-ranging livestock requires low-stress cues to alter animal behaviour. Recently modulated sound and electric shock were demonstrated to be effective in controlling free-ranging cattle. In this study the behaviour of 60, 300 kg Belmont Red heifers were observed for behavioural changes when presented cues designed to impede their movement through an alley. The heifers were given an overnight drylot shrink off feed but not drinking water prior to being tested. Individual cattle were allowed to move down a 6.5 m wide alley towards a pen of peers and feed located 71 m from their point of release. Each animal was allowed to move through the alley unimpeded five times to establish a basal behavioural pattern. Animals were then randomly assigned to treatments consisting of sound plus shock, vibration plus shock, a visual cue plus shock, shock by itself and a control. The time each animal required to reach the pen of peers and feed was recorded. If the animal was prevented from reaching the pen of peers and feed by not penetrating through the cue barrier at set points along the alley for at least 60 sec the test was stopped and the animal was returned to peers located behind the release pen. Cues and shock were manually applied from a laptop while animals were observed from a 3.5 m tower located outside the alley. Electric shock, sound, vibration and Global Position System (GPS) hardware were housed in a neck collar. Results and implications will be discussed.

Removal of toxic arsenic and antimony from groundwater Spiro Tunnel Bulkhead in Park City Utah using colloidal iron hydroxide : comparison with reverse ssmosis

Verification testing of two model technologies in pilot scale to remove arsenic and antimony based on reverse osmosis and chemical coagulation/filtration systems was conducted in Spiro Tunnel Water Filtration Plant located in Park City, Utah, US. The source water was groundwater in abandoned silver mine, naturally contaminated by 60-80 ppb of arsenic and antimony below 10 ppb. This water represents one of the sources of drinking water for Park City and constitutes about 44% of the water supply. The failure to remove antimony efficiently by coagulation/filtration (only 4.4% removal rate) under design conditions is discussed in terms of the chemistry differences between Sb (III, V) and As (III, V). Removal of Sb(V) at pH > 7, using coagulation/filtration technology, requires much higher (50 to 80 times) concentration of iron (III) than As. The stronger adsorption of arsenate over a wider pH range can be explained by the fact that arsenic acid is tri-protic, whereas antimonic acid is monoprotic. This difference in properties of As(V) and Sb(V) makes antimony (V) more difficult to be efficiently removed in low concentrations of iron hydroxide and alkaline pH waters, especially in concentration of Sb < 10 ppb.