Coagulation behavior and floc characteristics of a novel composite poly-ferric aluminum chloride-polydimethyl diallylammonium chloride coagulant with different OH/(Fe3+ + Al3+) molar ratios.

In this paper, flocculating performance and mechanisms of a new composite coagulant, poly-ferric aluminum chloride-polydimethyl diallylammonium chloride (PFAC-PD) with different OH-/(Fe3+ + Al3+) molar ratios, were investigated for humic acid (HA)-kaolin synthetic wastewater treatment. The impact of OH-/(Fe3+ + Al3+) molar ratios on the removal efficiencies of turbidity and dissolved organic carbon, specific UV absorbance, coagulation mechanisms and dynamics was explored during the coagulation process using composite coagulants. The coagulation experimental results revealed that the composite coagulants with lower OH-/(Fe3+ + Al3+) molar ratio exhibited better coagulation efficiency. When OH-/(Fe3+ + Al3+) molar ratio of the composite coagulant was 1.5, adsorption-bridging played a dominant role in coagulating HA-kaolin synthetic wastewater. The floc growth rate and floc size, increased with increasing OH-/(Fe3+ + Al3+) molar ratio and the highest peak height of the size distribution was obtained by PFAC-PD with OH-/(Fe3+ + Al3+) = 1.5. Also, the composite coagulants with higher OH-/(Fe3+ + Al3+) molar ratio formed more compact flocs, as reflected by the higher fractal dimension value. The flocs coagulated by PFAC-PD with basicity value of 1.0 gave strong strength and good recoverability.

Principal component regression model applied to dimensionally reduced spectral fluorescent signature for the determination of organic character and THM formation potential of source water.

The characterization of dissolved organic matter (DOM) in source water not only is central to the study of precursors to disinfection by-products (DBPs), but can also aid in controlling the discharge of potentially harmful organic chemicals in water bodies. Rapid determination of six DOM fraction concentrations provides an added advantage in understanding the organic character of water in comparison to the measure of dissolved organic carbon (DOC), which is an aggregate parameter typically used by water purveyors. The experimental procedure for DOM isolation and fractionation by ionic resins is lengthy and tedious. Many attempts have been made towards the development of faster and reliable techniques including statistical analysis applied to spectral fluorescent signature (SFS). Fluorescence is a very sensitive technique and works best only at certain wavelengths that are different for different materials. It is therefore difficult to quantify a material using fluorescence technique, especially when the entire fluorescence matrix is considered. To address this difficulty, an innovative two-stage processing technique is developed in this research in order to build an enhanced, more robust empirical model. At stage I, the dimensionality of the input data is reduced by focusing on specific portion of the entire matrix obtained by applying scatter removal, peak analysis, and coefficient of variation (CV) analysis. Then statistical analysis in the form of principal component regression (PCR) follows as stage II. In addition, the same technique is applied to predict trihalomethanes formation potential (THMFP). This model provides better sensitivity and accuracy, while maintaining the advantages of the SFS technique for rapid identification and quantification of DOM fractions.

Interaction between organic species in the formation of haloacetic acids following disinfection.

The formation of haloacetic acids (HAAs) from the chlorination of individual and binary mixtures of organic fractions obtained from the intake of Bangkhen Water Treatment Plant in Bangkok, Thailand was investigated. Experimental results revealed that, as an individual fraction, hydrophobic base (HPOB) was the most active in forming HAAs (approx. 200 microg/mg) whereas hydrophilic acid (HPIA) was the least (approx. 40 microg/mg). In binary mixtures, acid fractions exhibited stronger inhibitory effect in forming HAAs than base fractions. With the set of experimental data obtained from this work, no relationships between specific HAA formation potential and various organic fractions concentrations in binary mixtures could be formulated. Among the various individual HAA species obtained from the chlorination of each individual organic fraction, dichloroacetic acid (DCAA) was found to be predominant. On the other hand, the chlorination of binary organic fraction mixtures often led to the formation of monochloroacetic acid (MCAA) as the predominant HAA species.

FTIR evaluation of functional groups involved in the formation of haloacetic acids during the chlorination of raw water.

This work investigated the formation potential of haloacetic acid (HAA) compounds in the raw water for the Bangkhen water treatment plant (Bangkok, Thailand). The resin adsorption technique (with three different types of resins, i.e. DAX-8, AG-MP-50 and WA-10) was employed to characterize the organic content in the raw water into six fractions, i.e. hydrophobic neutral (HPON), hydrophobic acid (HPOA), hydrophobic base (HPOB), hydrophilic neutral (HPIN), hydrophilic acid (HPIA) and hydrophilic base (HPIB). Hydrophilic species appeared to be the predominant organic species in this water source (approximately 60%) with the neutral fraction being the most abundant (approximately 40%). Hydrophobic species, on the other hand, played the most important role in the formation of haloacetic acids as they contributed to as much as approximately 56% of total HAA formation potential. Among the three hydrophobic species, the hydrophobic base exhibited the highest specific HAA formation with 208mugHAAs/mg of dissolved organic carbon (DOC). Each organic fraction was examined for its associated functional groups by Fourier transform infrared (FTIR). The investigation of the formation of HAAs was achieved by tracking the changes in the FTIR results of the same water sample before and after the chlorination reaction. Based on the results obtained from this study, carboxylic acids, ketone, amide, amino acids and aromatic characteristic organics seemed to be the main precursors to HAA formation.

Trihalomethanes formation potential of shrimp farm effluents.

Shrimp farm effluents along the Bangpakong River in the Chachoengsao Province of Thailand were evaluated for their trihalomethane formation potential (THMFP) and related parameters. The dissolved organic carbon (DOC), salinity and bromide ion concentrations of shrimp farm effluents were in the ranges of 12-14 mg/L, 0.1-14.5 ppt, and 0-14 mg/L, respectively. The dissolved organic matter was fractionated into hydrophobic and hydrophilic fractions having a range concentration of 3-5 and 8-10mg/L, respectively. The THMFP for all shrimp farm effluents analyzed was in the range of 810-3100 microg/L. The hydrophilic organic fraction was found to be a more active precursor of trihalomethanes (THMs) with 700-966 microg/L THMFP obtained from this fraction, while only 111-363 microg/L THMFP was derived from the hydrophobic fraction. The experimental results showed that salinity and bromide played crucial roles in the formation of THMs. At low salinity and bromide levels, chloroform was the dominant THM species, whereas at high salinity and bromide levels, bromoform became the dominant species. A Fourier Transform Infrared (FTIR) spectrum analysis of the samples before and after chlorination illustrated that the functional groups involved in the THM formation reaction were phenolic compounds, amines, aromatic hydrocarbons, aliphatic bromo-compounds, and aliphatic chloro-compounds.

Characterization of haloacetic acid precursors in source water.

Raw water from the Bangkok (Thailand) main municipal water supply canal was examined for its natural organic composition by fractionation with adsorption resins. DAX-8 resin was the first resin employed to fractionate the hydrophobic fractions. Fractionation at neutral pH resulted in the separation of the hydrophobic neutral components; at a high pH level (approx. 10) separation of the hydrophobic base components occurred; and at a low pH level (approx. 2) the hydrophobic acid components were separated. AG-MP-50 cationic resin was then used to separate the hydrophilic base components, and WA-10, a weak anionic resin, was applied finally to fractionate the hydrophilic acid and neutral components. Subsequently, each fraction was tested for its chlorine disinfection by-product (DBP) formation potential. The HAA formation tests demonstrated that the various organic fractions had different reactivity levels for the formation of haloacetic acids (HAAs). For this source water, the hydrophilic neutral fraction dominated over the other five fractions in being the main organic component and the most significant precursor of HAAs formation. On the other hand, in terms of specific HAA formation potential (FP), the hydrophobic and hydrophilic base fractions were the most reactive precursors to the formation of HAAs. In all cases, the quantity of HAAs formed depended linearly upon the amount of organic constituents in the water sample.

Biosorption of Cu2+, Cd2+, Pb2+, and Zn2+ using dried marine green macroalga Caulerpa lentillifera.

The sorption of Cu2+, Cd2+, Pb2+, and Zn2+ by a dried green macroalga Caulerpa lentillifera was investigated. The removal efficiency increased with pH. The analysis with FT-IR indicated that possible functional groups involved in metal sorption by this alga were O-H bending, N-H bending, N-H stretching, C-N stretching, C-O, SO stretching, and S-O stretching. The sorption of all metal ions rapidly reached equilibrium within 20min. The sorption kinetics of these metals were governed by external mass transfer and intraparticle diffusion processes. The sorption isotherm followed the Langmuir isotherm where the maximum sorption capacities was Pb2+>Cu2+>Cd2+>Zn2+.

Reduction of organic matter and trihalomethane formation potential in reclaimed water from treated industrial estate wastewater by coagulation.

Raw water from treated industrial estate wastewater in northern Thailand was used in jar-test coagulation experiments with variations of separate alum and ferric chloride dosages from 10 to 80 mg/L at pH conditions ranging from 5 to 6.5. Natural organic matter (NOM) surrogates and trihalomethane formation potential (THMFP) were determined to study their reduction. The obtained results showed that total organic carbon (TOC) were gradually reduced from the average value of about 6.1 mg/L to a level of about 4.0 mg/L by alum and ferric chloride dosages of approximately 40 mg/L. Moreover, dissolved organic carbon (DOC) were reduced from an average value of 5.1 mg/L to a level of about 4.0 mg/L by alum and ferric chloride dosages of approximately 40 mg/L. Specific ultraviolet absorption (SUVA) were decreased from an average value of approximately 4.7 L/mg-m to a level of about 2 L/mg-m by alum and ferric chloride dosages of approximately 20 mg/L. In addition, chlorine demands at 1-day reaction were the same as those of 7-day demands with a correlation coefficient of 0.98 (n = 10, correlation significant at the 0.01 level). Interestingly, chloroform of approximately 65 and 60% of total THMFP was found as the predominant THMFP species in treated industrial estate wastewater and reclaimed water, respectively, in comparison with other THM species. Maximum THMFP percentage removal of 25 and 28 by using alum and ferric chloride dosages of about 80 mg/L at pH 5.5 and 5 were obtained, respectively, at the examined conditions.

Reduction of organic matter and trihalomethane formation potential in reclaimed water from treated industrial estate wastewater by coagulation.

Raw water from treated industrial estate wastewater in northern Thailand was used in jar-test coagulation experiments with variations of separate alum and ferric chloride dosages from 10 to 80 mg/L at pH conditions ranging from 5 to 6.5. Natural organic matter (NOM) surrogates and trihalomethane formation potential (THMFP) were determined to study their reduction. The obtained results showed that total organic carbon (TOC) were gradually reduced from the average value of about 6.1 mg/L to a level of about 4.0 mg/L by alum and ferric chloride dosages of approximately 40 mg/L. Moreover, dissolved organic carbon (DOC) were reduced from an average value of 5.1 mg/L to a level of about 4.0 mg/L by alum and ferric chloride dosages of approximately 40 mg/L. Specific ultraviolet absorption (SUVA) were decreased from an average value of approximately 4.7 L/mgm to a level of about 2 L/mgm by alum and ferric chloride dosages of approximately 20 mg/L. In addition, chlorine demands at 1 day reaction were the same as those of 7-day demands with a correlation coefficient of 0.98 (n = 10, correlation significant at the 0.01 level). Interestingly, chloroform of approximately 65 and 60% of total THMFP was found as the predominant THMFP species in treated industrial estate wastewater and reclaimed water, respectively, in comparison with other THM species. Maximum THMFP percentage removal of 25 and 28 by using alum and ferric chloride dosages of about 80 mg/L at pH 5.5 and 5 were obtained, respectively, at the examined conditions.

Kinetics of trihalomethane formation from organic contaminants in raw water from the Bangkhen water treatment plant.

The fractionation of raw water from Bangkhen water treatment plant, Bangkok, Thailand revealed that the mass distribution sequence of the six organic fractions from high to low was hydrophilic neutral (HPIN), hydrophobic acid (HPOA), hydrophilic acid, hydrophobic neutral, hydrophilic base, and hydrophobic base. The main organic matter components in raw water were HPIN and HPOA, which were also the two most important contributors of trihalomethane formation potential (THMFP). Linear dependencies between the level of each organic fraction and the formation potential of THM species were observed, which suggested the reactions between the organic fraction and chlorine during the chlorination were first order. The fractionation led to a deviation of bromide concentration in each organic fraction from the original concentration, and this affected the formation of brominated THM species. However, this effect was demonstrated to be within an acceptable range. The chlorination of an individual organic fraction resulted in a higher level of THMFP than that of the raw water and mixed fractions, indicating an inhibitory effect between the organic species.

Characterization of precursors to trihalomethanes formation in Bangkok source water.

Resin adsorption techniques using three types of resin (DAX-8, AG-MP-50, and WA-10) were employed to characterize the raw water (RW) from the major 3 million m3/day (793 million gal/day) drinking water treatment plant in Bangkok, Thailand. The dissolved organic carbon (DOC) mass distribution sequences of the six organic fractions in raw water, from high to low, were hydrophilic neutral (HPIN), hydrophobic acid (HPOA), hydrophilic acid (HPIA), hydrophobic neutral (HPON), hydrophilic base (HPIB), and hydrophobic base (HPOB). HPIN and HPOA were the two main precursors for trihalomethanes formation (THMFP) in this water source following chlorination. The chlorination of HPON and HPIN fractions only led to the formation of mostly chloroform, while other organic fractions formed both chloroform and bromodichloromethane. The linear dependency between each organic fraction concentration and THMFP indicated that the reactions of each organic fraction with chlorine were first-order.

A SEM and X-ray study for investigation of solidified/stabilized arsenic-iron hydroxide sludge.

Despite the fact that the solidification/stabilization of arsenic containing wastes with Portland cement and lime has an extensively documented history of use, the physical and chemical phenomena as a result of the interaction between arsenic and cement components have not been fully characterized. The study investigates the behavior of synthesized arsenic-iron hydroxide sludge, the by-product of arsenic removal by coagulation with ferric chloride, in solidified/stabilized matrices as well as its binding mechanisms by exploring the cementitious matrices in the micro-scale by scanning electron microscopy equipped with energy dispersive X-ray spectrometer (SEM-EDS). It was revealed that arsenic can be chemically fixed into cementitious environment of the solidified/stabilized matrices by three important immobilization mechanisms; sorption onto C-S-H surface, replacing SO4(2-) of ettringite, and reaction with cement components to form calcium-arsenic compounds, the solubility limiting phases.

Predicting organic loading in natural water using spectral fluorescent signatures.

Spectral fluorescent signature (SFS) is a rapid, reagent free and inexpensive technique, which has great potential for environmental monitoring of aqueous systems, especially for predicting dissolved organic carbon (DOC) along natural waters. This technical note aimed to examine the possibility to use SFS associated with partial least squares regression (PLS) to assess the organic loading in natural water. A model was built using samples of water collected between October 1999 and February 2002 on the Passaic River at Little Falls, NJ, USA. A correlation was established between measured DOC, SFS, and the corresponding daily registered flow from United States Geological Survey (USGS) New Jersey's streamflow database. The methodology presented herein looks promising in making use of the significant organic characteristics information contained in a SFS for application and use in spatial and temporal water quality management and treatment.

Modified dissolved organic matter fractionation technique for natural water.

A technique to fractionate dissolved organic materials (DOMs) from low DOM water (<5mg/l) was developed by using triple columns of DAX-8 adsorption resin, one column of AG-MP-50 cationic resin, and another column of WA 10 weak anionic resin in sequence. The procedure was then applied to fractionate water samples obtained at various sampling locations throughout two surface water treatment plants (WTPs) in central New Jersey to study its effectiveness, DOM occurrence, and variation along treatment units. The treatment plants utilize different treatment methods, hence producing variability in DOM fractions suitable for examining the procedure's effectiveness. This procedure was compared with current fractionation protocols and proved to be accurate in fractionation of low DOM water.

Comparison of spectral fluorescent signatures-based models to characterize DOM in treated water samples.

Statistical procedures enable a multivariate analysis of the measurements to identify specific characteristics of the dissolved organic matter (DOM) fractions in raw natural water, including the concentrations. In this work, three already established models were used to predict the concentrations of fractions of DOM from spectral fluorescent signatures (SFSs): a general linear regression (GLR), loadings and scores of a principal components analysis (PCA), and a partial least squares regression (PLS). Details about the method undertaken to prepare the fractions were given. Water samples from surface water treatment plants in New Jersey were used for the testing. In all cases, PLS have shown much better biases and accuracies than GLR and PCA models. Hydrophilic neutral, however, showed poor performances (bias 33%) due to the isolation technique used. Recommendations were provided in order to improve the DOM characterization through SFS, which linked to PLS make a powerful and cost-effective surrogate parameter to characterize DOM.

Using principal component analysis to monitor spatial and temporal changes in water quality.

Chemical, biological and physical data monitored at 12 locations along the Passaic River, New Jersey, during the year 1998 are analyzed. Principal component analysis (PCA) was used: (i) to extract the factors associated with the hydrochemistry variability; (ii) to obtain the spatial and temporal changes in the water quality. Solute content, temperature, nutrients and organics were the main patterns extracted. The spatial analysis isolated two stations showing a possible point or non-point source of pollution. This study shows the importance of environmental monitoring associated with simple but powerful statistics to better understand a complex water system.

Spectral fluorescence signatures and partial least squares regression: model to predict dissolved organic carbon in water.

Spectro-fluorescence signature (SFS) of water samples contains information that may be used to quantify dissolved organic carbon (DOC) if combined with multivariate analyses. A model was built through SFS and partial least squared (PLS) regression. The SFSs of 219 samples of natural water along the Raritan River and Millstone River watersheds located in central New Jersey, and their corresponding DOC concentrations were used to build the model. Calibration, full cross-validation, and prediction performances of various models were statistically compared before optimal model selection. The final selected model, tested on the Passaic River watershed in northern New Jersey, provided a bias of 0.028 mg/l and a root mean squared error of prediction (RMSEP) of 0.35 mg/l. Linked to PLS, SFS can be a quality and cost effective method to perform on-line rapid DOC measurements.