Staged Coagulation for Treatment of Refractory Organics

Seasonal periods of high rainfall have been shown to cause elevated natural organic matter (NOM) loadings at treatment works. These high levels lead to difficulties in removing sufficient NOM to meet trihalomethane standards, and hence better alternative treatments are required. Here the removal of NOM was investigated by conventional coagulation treatment using both bulk and fractionated NOM. Initial experiments showed that over 70% removal of the hydrophobic and hydrophilic acid fractions was achieved at the works, while only 16% of the hydrophilic nonacid fraction was being removed. Bench scale jar testing of the isolated NOM fractions demonstrated that high removals of the hydrophobic fractions were achieved and that optimized conditions increased removal of the hydrophilic fractions, indicating that staged coagulation could be of benefit in the removal of the recalcitrant fractions. Experiments using optimized staged coagulation indicated that a small increase in the removal of the total NOM of this water was possible when compared to conventional treatment.     

NOM Accumulation at NF Membrane Surface: Impact of Chemistry and Shear

The effects of solution chemistry, surface shear, and composition of natural organic matter (NOM) were investigated for their impact on accumulation of foulant material at the surface of charged polymeric nanofiltration membranes. The source of NOM was the Suwannee River. A bench-scale, batch recycle system was used with 20 hollow fiber, nanofiltration membranes. Membrane flux decline and foulant accumulation increased at low pH and high ionic strength as a result of neutralization of charge, electric double layer compression, and the apparent shift in conformation of charged NOM macromolecules. The rate of NOM accumulation decreased with operating time, suggestive of an eventual steady state between adsorption and desorption. The effect of NOM composition on membrane fouling could not be discerned by a standard technique to isolate hydrophobic and hydrophilic NOM fractions, quite possibly because of the fractionation methodology's failure to recover a small but important fouling fraction or because of NOM interactions that are lost when individual fractions are separately tested. However, a greater percentage of the hydrophilic than hydrophobic fraction permeated the membrane, in agreement with prior observations by others. Increasing the cross flow velocity from 85 to 255 cm∕s reduced the extent of flux decline, presumably due to hydrodynamic disruption of cake layer formation.     

Fluorescence Technique for Rapid Identification of DOM Fractions

The dissolved organic carbon parameter has typically been used as a measure of organic content in natural water. However, dissolved organic carbon is an aggregate parameter and does not provide information on the organic character of natural organic matter in water. Natural organic matter from New Jersey surface water sources was isolated and fractionated by resin adsorption into hydrophobic acid, hydrophobic neutral, hydrophobic base, hydrophilic acid, hydrophilic neutral, and hydrophilic base. The spectral fluorescent signature technique was developed for the identification of the six dissolved organic matter (DOM) fractions through a multiple linear regression model. High sensitivity, rapid identification, and quantification of DOM fractions are among the main advantages of this technique. The technique∕model has spatial and temporal potential use for the rapid qualitative and quantitative measurement of the problematic DOM fraction(s) for source water characterization∕assessment and water treatment process optimization.     

Modeling Uncoupled Solute Transport in Natural Organic Matter Size Fractionation by Ultrafiltration

Physicochemical separation of organic macrosolutes and colloidal particles is routinely required during the analysis of natural, waste, and process waters derived from aquatic and terrestrial environmental samples. This study was conducted to demonstrate the utility of a two-parameter nonlinear permeation coefficient model (PCM) in describing the uncoupled transport of solutes in dilute heterogeneous solutions subjected to batch ultrafiltration (UF). The PCM was used in conjunction with natural organic matter (NOM) permeate data for a natural water and six hydrophobic and hydrophilic subfractions to determine permeation coefficients p and NOM concentrations Cr0 with apparent molecular weight less than membrane specific cutoff values of moderately hydrophilic YC/YM series Amicon? UF membranes. Experimentally measured permeation coefficients p determined for the whole water were found to correlate well with composite permeation coefficients p? calculated using a mass-fraction weighted average of individual NOM subfraction permeation coefficient values. Correlation of experimentally measured and calculated permeation coefficient values (p and p?) indicated that the PCM can adequately describe uncoupled transport of chemically distinct solute fractions during batch UF of heterogeneous dilute solutions.     

Character of Organic Matter in Soil-Aquifer Treatment Systems

The objective of this study was to investigate the character and fate of bulk organics in reclaimed water used for groundwater recharge via soil-aquifer treatment (SAT). The study design followed a watershed guided approach considering hydraulically corresponding samples of drinking water sources, SAT-applied wastewater effluents, and subsequent post-SAT samples representing a series of different travel times in the subsurface. Water samples were fractionated into hydrophobic acids, transphilic acids, and hydrophilic carbon using a XAD resin-based protocol. Extensive characterization of organic carbon in the different samples was performed using state-of-the-art analytical techniques including excitation–emission matrix fluorescence spectroscopy, size exclusion chromatography, carbon-13 nuclear magnetic resonance spectroscopy (13C-NMR), Fourier transform infrared spectroscopy (FTIR), and elemental analysis. During SAT, transphilic and hydrophilic organic matter were preferentially removed. The results generally demonstrated that naturally derived (NOM) and effluent-derived organic matter after SAT overlap extensively in molecular weight distribution, amount and distribution of hydrophobic and hydrophilic carbon fractions, and chemical characteristics based on elemental analysis and 13C-NMR and FTIR spectroscopy. However, the residual portion of the dissolved organic carbon contained both effluent-derived organic matter and NOM.     

Dissolved Component Recovery Following Resin Exchange Based DOM Fractionation

Organic and inorganic components in natural waters are intimately interrelated and constitute a dissolved material matrix (DMM). The objective of this study was to systematically investigate the distribution and recovery of both organic and inorganic components in chemically fractionated natural waters. Untreated and previously coagulated natural waters were fractionated into hydrophobic and hydrophilic acid, base, and neutral DMM fractions using a resin exchange based protocol. Mass balances on nonpurgable dissolved organic carbon, aluminum, iron, and manganese were used to evaluate DMM component recovery. Quantitative recovery of dissolved organic matter was achieved, whereas, aluminum, iron, and manganese recoveries were largely incomplete (30–92%). Coagulation increased the recovery of all metals examined. Incomplete metals recovery was attributed to imperfect elution from MSC-1 cation exchange resin and appeared related to the distribution coefficient Kd of each metal with this resin. DMM component distribution among chemical fractions was altered by coagulation, with dissolved organic matter preferentially removed in the hydrophobic acid fraction. Unrecovered metals appeared to consist primarily of colloidal mineral (hydr)oxides solubilized by acidic pH conditions imposed during fractionation.     

Application of Fluorescence Technique for Rapid Identification of DOM Fractions in Source Waters

Dissolved organic carbon has been typically used as a measure of organic content in source waters. However, dissolved organic carbon is an aggregate parameter and does not provide information on the organic character of natural organic matter in water. The spectral fluorescent signatures technique coupled with a multiple linear regression model was applied for the rapid identification of six dissolved organic matter (DOM) fractions (hydrophobic acid, hydrophobic neutral, hydrophobic base, hydrophilic acid, hydrophilic neutral, and hydrophilic base) along a major river in a New Jersey watershed. The technique∕model enabled rapid spatial and temporal determination for the rapid qualitative and quantitative measurement of the DOM fraction(s) in the river. The analysis of DOM fractions also enables screening of the watershed for variations in humic and nonhumic substances input/output along the reaches.     

Removal of 17β Estradiol and Fluoranthene by Nanofiltration and Ultrafiltration

With the recent emergence of endocrine disrupting compounds as an important potable drinking water and reclaimed wastewater quality issue, the removal of two estrogenic compounds (17β-estradiol and fluoranthene) by nanofiltration and ultrafiltration membranes was investigated. A less hydrophobic organic compound model species [parachlorobenzoic acid (PCBA)] was tested. 17β-estradiol (E2), fluoranthene, and PCBA were applied to the membrane in the presence and absence of natural organic matter (NOM). Both batch adsorption and dead-end stirred-cell filtration experiments indicated that adsorption is an important mechanism for transport/removal of relatively hydrophobic compounds, and is related to the octanol-water partition coefficient (KOW) values. All filtration measurements were performed approximately the same permeate flow rate in order to minimize artifacts from concentration polarization varied with different hydrodynamic operating conditions at the membrane interface. The percent removal by dead-end stirred-cell filtration ranged from 10 to >95% depending upon membrane pore size/hydrophobicity and presence/absence of NOM at an initial concentration ranging from 0.1 to 0.5 μM. Additional batch adsorption experiments with radio-label (3H) E2 at lower concentrations ranging 0.025 to 5 nM showed that E2 removal due to adsorption was independent of its initial concentration. Adsorption occurs both on the membrane surface and interior membrane pore surfaces. However, adsorption was insignificant for PCBA (log?KOW = 2.7), but removal presumably occurred due to electrostatic exclusion. Partition coefficients (log?K) of 0.44 to 4.86 measured in this study increased with log?KOW and membrane pore size.     

Effects of Bromide Ion and Natural Organic Matter Fractions on the Formation and Speciation of Chlorination By-Products

The impacts of bromide concentration and natural organic matter (NOM) characteristics on the formation and speciation of disinfection by-products (DBPs) in chlorinated NOM fractions were investigated. A total of 20 bulk water NOM fractions with a wide range of specific ultraviolet (UV) absorbance (SUVA254) values were obtained from a source water employing XAD-8 or XAD-4 resin adsorption in completely mixed batch reactors. SUVA was not a good predictor of DBP [trihalomethanes (THMs), haloacetic acids (HAAs), and adsorbable organic halogens (AOX)] formation and speciation. The destruction in the UV254 absorbance from chlorination did not correlate with DBP formation at any bromide level. NOM moieties which do not absorb UV light at 254?nm significantly contributed to DBP formation. Mass balance calculations on halogens using THMs, HAAs, and AOX data indicated that significant amounts of DBPs (>54% of AOX) other than THMs and HAAs were formed in NOM fractions with 60–110?μg/L bromide concentration. The relative occurrence of such other halogenated by-products decreased with increasing bromide concentrations up to 500?μg/L level. NOM in the studied water was more susceptible to the formation of brominated THM species as opposed to brominated HAAs. At constant dissolved organic carbon concentration, chlorine dose and pH, increasing bromide concentrations in NOM fractions increased the total concentrations of DBPs and resulted in a shift toward the formation of brominated species. Further, increasing bromide concentrations increased the spectrum of detected species (i.e., occurrence of all nine HAAs) and provided a competitive advantage to THM and HAA precursors in NOM over precursors of other DBPs.     

Use of Dubinin–Astakhov Equation to Describe Preloading Effect of Natural Organic Matter

This note presents a simple model to quantify the preloading effect of naturally occurring organic matter (NOM) in water on the adsorption capacity of activated carbon for a trace synthetic organic chemical (SOC). The model was developed from the Dubinin–Astakhov (DA) equation based on the assumption that the NOM preloading irreversibly reduced the limiting adsorption pore volume for the target SOC. Given that the DA-n value equal to one, the model reduces to a form similar to the one obtained by modifying the Freundlich equation directly. By assuming that the reduction of the limiting adsorption pore volume was proportional to the volume of NOM adsorbed, the NOM preloading effect was correlated directly to the amount of total organic carbon preloaded on the carbon. The resulting model was then compared with the experimental data in the literature. This simple model may be useful for certain practical applications that require only the estimation of the NOM preloading effect on the adsorption capacity of a target SOC from natural water.     

Pyrolysis-GC∕FID Test for Biogenic Interference in Contaminated Soil

“Biogenic interference” is that portion of natural organic matter in soil that cannot be distinguished from petroleum in a standard test for contamination. Biogenic interference is normally a small fraction of total natural organic matter. In organic soils, however, biogenic interference alone can exceed “petroleum” limits set by regulatory agencies. A test using a pyrolysis-gas chromatograph∕flame ionization detector (GC∕FID) was developed to quantify biogenic interference in soil samples from northern Alaska. The samples had no known history of contamination, so all measured “petroleum” was derived from biogenic interference. The pyrolysis test was found to predict biogenic interference in soil samples more accurately than any combination of standard soil tests, including C:N ratio, pH, percent organic carbon, extractable carbon, humic acids, fulvic acids, low molecular weight acids, hydrophobic neutrals, and hydrophilic neutrals. Analysis of samples contaminated in the laboratory confirmed that the pyrolysis test could quantify biogenic interference in soils recently contaminated by petroleum.     

Natural Organic Matter Removal by Adsorption onto Carbonaceous Nanoparticles and Coagulation

Nanoparticles have emerged as promising adsorbents for water purification. In this study, nanoscale carbon black was employed to remove natural organic matter (NOM) from water in the presence and absence of coagulation. Standard Suwannee River NOM was employed as the targeted pollutant. In the absence of coagulation, more than 60% NOM removal was achieved by carbon black adsorption. A higher hydrogen ion concentration (pH) (3–5) was favorable for NOM removal. More than 35% NOM was removed by carbon black adsorption in the first 20 min, and the adsorption of NOM onto carbon black occurred within about 2 h. Proper stirring was essential for the mixture of NOM and carbon black, while insufficient stirring or overstirring decreased NOM removal efficiency. When low dosages of coagulants were used in combination with carbon black at pH 6–7, the removal efficiency of NOM increased significantly. Depending on the coagulant, the sequencing of adsorption and coagulation can be important. Almost 90% NOM was removed in 15 min by carbon black adsorption and alum coagulation, which is a higher removal than for conventional treatment. This study indicated that carbon black might be an important adsorbent for NOM removal in water treatment in combination with low doses of alum.     

Iron Oxide Enhanced Chlorine Decay and Disinfection By-Product Formation

This study investigates the interaction of natural organic matter with iron oxide (goethite) on chlorine decay, disinfection by-product (DBP) formation, and DBP compound speciation [total trihalomethanes (TTHM4) and haloacetic acids (HAA5)]. Batch experiments were conducted with goethite, multiple finished drinking waters, variable chlorine dose, and fixed pH 8. The overall objective was to assess natural organic matter (NOM) adsorption onto goethite and its effect on chlorine decay and DBP formation. Chlorine consumption always increased in the presence of goethite and is attributed to an increase in the reactivity and/or modification of adsorbed NOM. Adsorbed NOM also led to an overall increase in TTHM4, however, HAA5 formation was suppressed during the first 2?h. Chloroform was identified as the increasing species and dichloracetic acid was identified as the suppressed species. This study clearly shows that goethite, which is the predominant iron oxide of pipe deposits, alters both chlorine decay and DBP formation and should be considered when assessing water treatment plant operations and DBP monitoring site selection.     

Predicting Minimum Carbon Usage for PAC Adsorption of Trace Organic Contaminants from Natural Water

Powdered activated carbon (PAC) is an excellent adsorbent for drinking water treatment of many trace organic contaminants. To evaluate and design a PAC adsorption process for a particular application, it is necessary to know the minimum (lowest economical) carbon (adsorbent) usage (MCU) defined thermodynamically. In this work, an explicit relationship is developed for predicting the MCU required for a desirable level of treatment of a target trace organic compound (TC). The adsorption processes considered are PAC slurry contactors idealized either as batch reactors, plug flow reactors, or continuous-flow stirred tank reactors. Comparing with the ones previously available in the literature, this newly developed relationship, as a predictive tool for practical uses as well, is more accurate because it does not need to assume that the MCU required for target TC removal can always reduce the competing background natural organic matter (NOM) to a level much less than the NOM initial/influent concentration. Applications of the relationship developed herein to PAC adsorption of typical trace organic contaminants in natural water are demonstrated with isotherm data from multiple literature sources.     

Both Na+-K+ ATPase and Na +-H+ exchanger are immediately active upon post-ischemic reperfusion in isolated rat hearts

Lipases contained in commercial samples of lipase extracts from Rhizopus niveus (RNL) and Candida rugosa (CRL) have been selectively adsorbed on hydrophobic supports at very low ionic strength. Under these conditions, adsorption of other proteins (including some esterases) is almost negligible. More interestingly, these lipases could be separated in several active fractions as a function of a different rate or a different intensity of adsorption on supports activated with different hydrophobic groups (butyl-, phenyl- and octyl-agarose). Thus, although RNL seemed to be a homogeneous sample by SDS-PAGE, it could be separated, via sequential adsorption on the different supports, into three different fractions with very different thermal stability and substrate specificity. For example, one fraction hydrolyzed more rapidly ethyl acetate than ethyl butyrate, while another hydrolyzed the acetate ester 7-fold slower than the butyrate. Similar results were obtained with samples of CRL. Again, we could obtain three different fractions showing very different properties. For example, enantioselectivity for the hydrolysis of (R,S) 2-hydroxy-4-phenylbutanoic acid ethyl ester ranged from 1.2 to 12 for different CRL fractions. It seems that very slight structural differences may promote a quite different interfacial adsorption of lipases on hydrophobic supports as well as a quite different catalytic behavior. In this way, this new 'interfacial affinity chromatography' seems to be very suitable for an easy separation of such slightly different lipase forms.     

Characterization of the Flocculation Process from the Evolution of Particle Size Distributions

A flocculator-imaging system was developed to characterize the dynamics of particle size distribution (PSD) during flocculation. The system consisted of a flocculator coupled with an external flow-through cell for observation and photography, a microscopic charge-coupled device video recorder with backlighting, and an image analyzer. This nonintrusive side-stream setup was used to record the evolution of the PSD to determine the flocculation dynamics of three types of particle systems: Clean kaolin, kaolin coated with natural organic matter (NOM), and the kaolin/NOM system after ozonation. In addition to the PSD measurement, the ζ potential, NOM reduction, and turbidity removal after the jar test of flocculation and sedimentation were determined for the particle systems at various alum dosages. The results of the ζ-potential analysis and the PSD measurement indicated that flocculation takes place rapidly to form highly porous aggregates when the particle surface charge is fully neutralized. The adsorption of NOM on the particle surface stabilized the particles considerably, and thus hindered the flocculation process. Sweep flocculation using a much higher alum dosage was an effective means of process enhancement for the removal of particulates and associated organic matter. Ozonation of the kaolin/NOM solution, however, did not appear to have any positive effect on particle destabilization and flocculation. It is argued that ozonation produced more acidic functional groups in the NOM on kaolin, which increased the surface charge density and hence the stability of the particles in softer water.     

Zeta Potential, Dissolved Organic Carbon, and Removal of Cryptosporidium Oocysts by Coagulation and Sedimentation

This study evaluated the removal of viable Cryptosporidium parvum oocysts and changes in zeta potential during alum coagulation and sedimentation. Experiments were designed to evaluate oocyst removal and oocyst zeta potential at three initial dissolved organic carbon (DOC) concentrations and a wide range of alum doses and coagulation pH values. The study showed that changes in the initial DOC concentration affected the zeta potential of Cryptosporidium parvum oocysts and the removal of oocysts. Oocysts did not appear to be removed by a charge neutralization mechanism under the conditions used in this research. Sweep flocculation appeared to be the primary removal mechanism at the lowest DOC concentration tested in this study. For the highest DOC concentration tested, optimal coagulation conditions for oocyst removal coincided with optimal coagulation conditions for natural organic matter (NOM) removal, suggesting that NOM played a key role in the interaction between oocysts and the aluminum hydroxide precipitate.     

Estimating the Removal of Anthropogenic Organic Chemicals from Raw Drinking Water by Coagulation Flocculation

A mathematical model was developed to estimate the efficacy of coagulation–flocculation treatment for removing neutral hydrophobic organic chemicals from raw drinking water. The model assumed that the only significant removal mechanism was the destabilization and settling of organic matter containing sorbed anthropogenic organic compounds. The model was validated with standard jar tests using compounds with a range of hydrophobicities (log?Kow = 1.89?to?5.48), including contaminant candidate list chemicals, pesticides, pharmaceuticals, and endocrine disrupting chemicals. Final concentrations of test compounds after coagulation and flocculation were in good agreement with model estimations for synthetic waters composed of Aldrich (Milwaukee, WI) humic acid solutions. The final compound concentrations in coagulated natural waters from two drinking water reservoirs were about 80% lower than those estimated with the model. Overestimations of treated water concentrations by the model were attributed to an increase in sorption by natural organic matter when coiled in aluminum hydroxide flocs, compared to sorption to dispersed natural organic matter in untreated water.     

Load Dampening System for Vapor Phase Bioreactors

Vapor phase bioreactors are receiving increasing attention as a cost-effective treatment method for air contaminated with volatile organic compounds (VOCs). In this study, a novel absorption and humidification system was evaluated for its ability to dampen transient VOC loads, and to reduce their detrimental effects on a downstream bioreactor. A model based on the mass transfer characteristics of two target compounds (acetone and toluene) was developed and takes into account a closed water recirculation loop that minimizes fugitive emissions and simultaneously humidifies the inlet gas stream. When water is used as the scrubbing liquid, model and experimental results indicate that the system effectively dampens hydrophilic compounds and segregates them from the hydrophobic compounds in the waste gas stream. The response of a vapor phase bioreactor to the pretreated stream has also been assessed, and results indicate that the load dampening system works effectively for hydrophilic, but not hydrophobic, VOCs. However, when an organic cosolvent is used in conjunction with water, hydrophobic VOCs can also be dampened efficiently.     

The effect of hypothermia on the expression of neurotrophin mRNA in the hippocampus following transient cerebral ischemia in the rat

Acetylcholinesterase (AChE, EC 3.1.1.7) was extracted from sheep platelets by successive homogenizations, yielding low-salt soluble (LSS), high-salt soluble (HSS) and detergent-soluble (DS) fractions. These accounted, respectively, for about 30%, 7% and 60% of total AChE activity. Applications of hydrophobic chromatography on phenyl-agarose to three solubilized fractions revealed that hydrophilic forms were almost exclusively located in the LSS fraction ( approximately 27% of total AChE), whereas most amphiphilic forms were present in DS extracts ( approximately 59% of total AChE), the remaining forms being distributed among aqueous soluble fractions. Enzyme molecular forms in the solubilized extracts were identified by centrifugation in 5-20% sucrose gradients containing Triton X-100 or Brij 97 to differentiate between hydrophilic or amphiphilic species. A predominance of hydrophilic dimeric forms ( approximately 22%), with small amounts of hydrophilic monomers (5%) and amphiphilic dimers and monomers (3%), was found in soluble AChE (LSS fraction). Amphiphilic AChE forms extracted in the HSS and DS fractions had a single peak in the sedimentation profiles with sedimentation coefficients of about 6S in gradients with Triton X-100; these were slightly shifted in the presence of Brij 97. After treatment with dithiothreitol, this molecular form solubilized in DS was converted to another molecular form with a lower sedimentation coefficient. Our results show that amphiphilic globular dimers are the dominant molecular form in sheep platelet AChE, suggesting a partial conversion of this membrane-bound form into soluble dimers and monomers, mainly with a hydrophilic character, through the action of either endogenous proteases and phospholipases or residual endogenous reducing agents.