The existence of trihalomethanes (THMs) in a drinking water plant of Nicaragua has been investigated in order to see whether the concentration exceeded the maximum contaminant level recommended by the environmental protection agency of the United States (USEPA) and the Nicaragua guidelines. The influence of pH, temperature, chlorine dose and contact time on the formation of THMs were studied. The contents of organic matter measured by surrogate parameters such as total organic carbon, dissolved organic carbon, ultraviolet absorbance and specific ultraviolet absorbance were also determined in order to show which type of organic matter is most reactive with chlorine to form THMs. Models developed by other researchers to predict the formation of trihalomethanes were tested to see whether they can be used to estimate the trihalomethane concentration. In addition, empirical models were development to predict the THM concentration of the drinking water plant analysed. The raw water was treated by conventional and enhanced coagulation and these processes were compared with regard to the removal of natural organic matter (NOM). The significance of the results was assessed using statistic procedures. The average concentration of THMs found at the facility is below the USEPA and Nicaragua guideline values. Nevertheless the maximum contaminant level set by USEPA is sometimes exceeded in the rainy season when the raw water is rich in humic substances. Comparison between the water treated by conventional and enhanced coagulation shows that enhanced coagulation considerably diminished the trihalomethane formation and the value after enhanced coagulation never exceeded the guidelines. This is because enhanced coagulation considerably decreases the organic matter due to the high coagulant dose applied. The study of the trihalomethane formation when varying pH, time, temperature and chlorine dose using water treated by conventional and enhanced coagulation showed that higher doses of chlorine, higher pH, higher temperature and a longer time increases the formation of THMs. However, combinations of two and three factors are the opposite. The predicted THM formation equations cannot be used for the water at this facility, since the results shown that the measured THM differs significantly from the THM concentration predicted. Two empirical models were developed from the data for enhanced coagulation, using linear and non-linear regression. These models were tested using the database obtained with conventional coagulation. The non-linear model was shown to be able to predict the formation of THMs in the Boaco drinking water plant. / QC 20101129

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yes / NOM deteriorates water quality by forming taste, clarification, colour, and odour problems. It also increases coagulant and chlorine consumption which can initiate disinfection by-products harmful to human health. The coagulation-flocculation (CF) technique is an established method commonly employed to remove NOM in water treatment. Plant-based coagulant products (PCPs) derived from plants like the Moringa oleifera (MO) Strychnos potatorum Linn and Opuntia ficus indica, have been studied and proposed as sustainable alternatives to chemical coagulant, like, aluminium sulphate due to their abundant availability, low cost, low sludge volume and disposal cost, and biodegradability. This review paper provides an overview of the most widely studied plant-based coagulants and discusses their NOM and turbidity removal. It investigates recent analytical tools applied in their characterisation and floc morphological studies. The paper also investigates the effects of operating parameters such as coagulant dose, temperature, and pH, on NOM and turbidity removal. It also reviews up-to-date PCPs biophysical properties and CF mechanism and examines the efficiency of their extraction methods in reducing NOM. Finally, it discusses and suggests ways to overcome commercialisation draw-back caused by nutrient addition.

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Effective coagulation is critical to the production of safe, potable drinking water, but variations in the chemical composition of source water can present challenges in achieving targeted contaminant removal and predicting coagulation outcomes. A critical literature review describes factors affecting the hydrolysis reactions of metal salt coagulants and the resulting precipitates. Properties of two key contaminants, turbidity and natural organic matter (NOM), are explored in the context of removal during coagulation, and the influence of co-occurring ions is described. While it is apparent that NOM character determines the minimum achievable organic carbon residual, the effects of water quality—including pH, NOM character and concentration, and concentrations of synergistic and competitive ions—on overall coagulation efficacy and NOM removal may be underestimated. An experimental research plan was devised to investigate the influence of water quality in coagulation and provide data to support the development of a predictive coagulation model. NOM is capable of interfering with ferric iron hydrolysis and influencing the size, morphology, and identity of precipitates. Conversely, calcium is known to increase the size and aggregation of Fe3+ precipitates and increase surface potential, leading to more effective coagulation and widening the pH range of treatment. Experiments and modeling were conducted to investigate the significance of the Fe/NOM ratio and the presence of calcium in coagulation. At the high Fe/NOM ratio, sufficient or excess ferric hydroxide was available for NOM removal, and coagulation proceeded according to expectations based upon the literature. At the low Fe/NOM ratio, however, NOM inhibited Fe3+ hydrolysis, reduced zeta potential, and suppressed the formation of filterable Fe flocs, leading to interference with effective NOM removal. In these dose-limited systems, equilibrating NOM with 1 mM Ca2+ prior to dosing with ferric chloride coagulant increased the extent of Fe3+ hydrolysis, increased zeta potential, decreased the fraction of colloidal Fe, and improved NOM removal. In dose-limited systems without calcium, complexation of Fe species by NOM appears to be the mechanism by which coagulation is disrupted. In systems with calcium, data and modeling indicate that calcium complexation by NOM neutralizes some of the negative organic charge and minimizes Fe complexation, making Fe hydrolysis species available for growth and effective coagulation. Experiments were conducted to investigate the influence of aqueous silica and pH on the removal of natural organic matter (NOM) by coagulation with ferric chloride. Samples with preformed ferric hydroxide were also compared to samples coagulated in situ to assess the role of coprecipitation. The moderate (10 mg/L) and high (50 mg/L) SiO2 concentrations both demonstrated interference with NOM removal at pH 6.5-7.5. In turn, NOM at 2 mg/L as DOC interfered with silica sorption at the moderate silica level and in samples with preformed ferric hydroxide at the high silica level. The combination of NOM and high silica led to decreases in DOC sorption and unexpected increases in silica sorption in the coprecipitated samples. The fraction of colloidal Fe passing a 0.45-μm filter also increased in the coprecipitated samples with both NOM and high silica. It is hypothesized that the combination of NOM and high silica synergistically interfered with Fe precipitation and particle growth processes, with NOM having the greater effect at lower pH and shorter reaction times, and silica exerting greater influence at higher pH and longer reaction time. Direct competition for surface sites and electrostatic repulsion were also influential. An overall goal for this research was the development of a quantitative coagulation model. Previous attempts to model coagulation have been limited by the inherent complexities of simultaneously predicting ligand sorption, metal complexation, floc surface charge, and particle removal. A diffuse layer (DLM) surface complexation model was formulated to simultaneously predict sorption of NOM and other key species, including silica, calcium, and carbonate alkalinity. Predictions of surface potential were used to estimate zeta potential and resulting regimes of effective aggregation and turbidity removal. The model provided good predictive ability for data from bench-scale experiments with synthetic water and jar tests of nine U.S. source waters. Under most conditions, the model provides excellent capability for predicting NOM sorption, calcium sorption, and particle destabilization and adequate capability for predicting silica sorption. Model simulations of hypothetical scenarios and experimental results help to explain practical observations from the literature. The DLM can be optimized to site-specific conditions and expanded to include sorption of additional species, such as arsenic. / Ph. D.

In order to better predict the aggregation state of nanomaterials, the factors that influence aggregation must be understood. The combined effects of natural and engineered coatings have been shown to factor into nanoparticle aggregation behavior in preliminary research. In this study, aggregation behaviors of gold nanoparticles with two different engineered coatings were investigated in the presence of the monovalent electrolyte KCl and the divalent electrolyte CaCl���. Aggregation studies were conducted using dynamic light scattering to determine the relative stability of the NMs in environments of varying ionic strength in the absence and presence of Suwannee River Natural Organic Matter (SRNOM). Coatings which provided primarily electrostatic stabilization were found to adhere closely to DLVO theory, while coatings which provided steric stability inhibited aggregation over a wide range of ionic strengths for both electrolytes. The presence of SRNOM was found to provide some electrostatic stability in the presence of KCl, but appeared to form agglomerates with calcium ions, especially at higher SRNOM concentrations. / Graduation date: 2013

An investigation was conducted focusing on how NOM affects coagulation in a United States south eastern coastal surface water. Current water treatment practice at Savannah Water I and D was investigated to determine the efficacy of NOM removal using existing coagulation methods. A robust assessment of alum and ferric sulfate for use as coagulants in the removal of disinfection byproduct (DBP) precursor material was conducted using composite water created from sample sites within the SWID watershed. Both coagulants were optimized for the removal of NOM. Pragmatic methods of NOM size analysis and its reactivity with chlorine was investigated. UF membranes were used in conjunction with a permeation coefficient model (PCM) to determine an apparent molecular weight distribution of NOM present in the watershed. Individual size classes were assessed for their potential to form trihalomethanes (THMs) upon chlorination. Coagulation using alum and ferric sulfate was assessed to determine removal efficiency of individual NOM size classes under various coagulation scenarios. Finally, UV254 absorbance (UVA) was assessed to determine its potential use as an indicator of DOC concentration in raw and treated water at SWID. Additionally, an investigation into the relationship between specific UVA (SUVA) and THM formation potential (THM-FP) was conducted.

Climate change is predicted to be the most pronounced in high latitude ecosystems, however very little is known about their vulnerability to the projected warmer temperatures. In particular, natural organic matter (NOM) in the high latitude cryosphere which includes dissolved organic matter (DOM) and cryoconite organic matter (COM) from glaciers and soil organic matter (SOM) in permafrost, is highly susceptible to climate change which may lead to severe consequences on both local and global carbon biogeochemical cycles. Examination of DOM in glacier ice by a novel 1H nuclear magnetic resonance (NMR) water suppression pulse sequence at its natural abundance revealed and quantified the composition and the organic constituents in ice samples from Antarctica. 1H NMR spectra of samples from several glaciers were acquired and compared to the dominant fluorescent DOM fraction. This comprehensive approach showed that glacier ice DOM was mainly composed of small, labile biomolecules associated with microbes. Examination of the organic debris found on glacier surfaces (COM) from both Arctic and Antarctic glaciers were determined to be derived from microbes. Samples from Arctic glaciers were more chemically heterogeneous with small inputs of plant-derived material detected after targeted extractions. Therefore the COM carbon composition was determined to be dependent on the local glacier environment, suggesting a site specific contribution to the carbon cycle. Finally, the distribution of extracted branched glycerol dialkyl glycerol tetraether (GDGT)microbial membrane lipids and the deuterium incorporation of plant-wax n-alkane biomarkers extracted from dated permafrost SOM (paleosols) were independently applied for Canadian Arctic climate reconstruction during the last glacial maximum. Overall, the branched GDGT based temperature reconstructions from the Arctic paleosols reconstruct higher temperatures, likely when bacterial activity was optimal. The deuterium composition of the C29 n-alkane plant lipids appears to integrate an average annual signal. Further analysis by both non-selective NMR spectroscopic and targeted biomarker techniques on these paleosol samples revealed that the major vegetative sources from this paleoecosystem originated from woody and non-woody angiosperms. This thesis demonstrates several novel analytical characterization techniques, along with the major sources and composition of NOM in the cryosphere while demonstrating its use in paleoclimate applications.