Stoichiometry of coagulation revisited

The roles of particles and natural organic matter (NOM) in determining coagulant (alum) doses in potable water treatment were investigated at two pH conditions (6 and 7). The concentrations of NOM and colloidal silica particles in raw water were systematically varied separately and in combination, and the impacts of these two classes of contaminants on the minimum effective alum doses were investigated using observations of turbidity and dissolved organic carbon (DOC) in laboratory jar tests. At both pHs, coagulant requirements for the removal of these contaminants by sedimentation and filtration were dominated by the DOC concentration in the raw water. The presence of low NOM concentrations (0.75-1.5 mg of C/L) decreased the minimum effective alum dose dramatically for waters low in silica particles, possibly by promoting the precipitation of aluminum hydroxide and/or Al-NOM solids, whose removal would otherwise be limited by low collision opportunities. Strong stoichiometric relationships were observed between DOC and coagulant demand at both pHs regardless of silica particle concentration. Silica contributed to coagulant demand only at very high particle concentrations.     

Optimization of method for detecting and characterizing NOM by HPLC-size exclusion chromatography with UV and on-line DOC detection

High-performance liquid chromatography (HPLC)-size exclusion chromatography (SEC) with ultraviolet absorbance (UVA) and on-line dissolved organic carbon (DOC) detectors has been adapted and optimized under various conditions. An enhanced HPSEC-UVA system employing a modified commercially available DOC detector provides a better understanding of the qualitative and quantitative natural organic matter (NOM) properties in water samples by detecting aromatic and nonaromatic fractions of NOM as a function of molecular weight (MW). The most critical merit of this system is that the DOC detector is readily available and widely used. With only a few modifications, a commercially available TOC analyzer served as a DOC detector, integrated with the HPSEC to measure DOC along with UVA, and provided a specific UVA (SUVA) chromatograph that is useful information for drinking water plant design and operation. Without preconcentration, samples can be analyzed with a small amount of sample, with a DOC detection limit as low as 0.1 mg/L (as DOC).     

Exploring how organic matter controls structural transformations in natural aquatic nanocolloidal dispersions

The response of the dispersion nanostructure of surface river bed sediment to the controlled removal and readdition of natural organic matter (NOM), in the absence and presence of background electrolyte, was examined using the technique of small-angle neutron scattering (SANS). Partial NOM removal induced aggregation of the mineral particles, but more extensive NOM removal restored colloidal stability. When peat humic acid (PHA) was added to a NOM-deficient sediment concentration-related structural transformations were observed: at 255 mg/L PHA aggregation of the nanocolloid was actually enhanced, but at 380 mg/L PHA disaggregation and colloidal stability were promoted. The addition of 2 mM CaCl(2) induced mild aggregation in the native sediment but not in sediments with added PHA, suggesting that the native NOM and the PHA respond differently to changes in ionic strength. A first attempt at using SANS to directly characterize the thickness and coverage of an adsorbed PHA layer in a natural nanocolloid is also presented. The results are discussed in the context of a hierarchical aquatic colloidal nanostructure, and the implications for contemporary studies of the role of dissolved organic carbon (DOC) in sustaining the transport of colloidal iron in upland catchments.     

Biodegradability, DBP formation, and membrane fouling potential of natural organic matter: characterization and controllability

Various natural organic matter (NOM) constituents were evaluated in terms of their biodegradability, disinfection byproduct (DBP) formation potentials, and membrane fouling. The biodegradability of NOM was evaluated with respect to biodegradable dissolved organic carbon (BDOC) and its inhibition control. NOM was divided into (i) colloidal and noncolloidal NOM, using a dialysis membrane with a molecular weight cutoff of 3500 Da and (ii) hydrophobic, transphilic, and hydrophilic NOM constituents, using XAD-8/4 resins. The colloidal, and noncolloidal hydrophilic, NOM were identified as being more problematic than the other components, exhibiting relatively higher biodegradability and reactivity toward DBP formation potential. A higher biodegradability especially can provide a high risk of membrane biofouling, if a membrane is fouled by highly biodegradable NOM. Colloidal, and noncolloidal hydrophilic, NOM constituents were also shown as major foulants of negatively charged membranes due to their high neutral fractions. Filter adsorber (F/A) types of activated carbons were evaluated in terms of removals of NOM, DBP formation potential, and BDOC and were compared to conventional processes and a nanofiltration membrane. The F/A process exhibited a comparatively good efficiency, especially in DBP and BDOC control, but was not so good at removing NOM. This suggests that F/A could potentially be combined with a membrane process to minimize the DBP formation potential and bio-/organic-fouling (i.e., F/A process as a pretreatment for a membrane process).     

Partitioning of fluorotelomer alcohols to octanol and different sources of dissolved organic carbon

Interest in the environmental fate of fluorotelomer alcohols (FTOHs) has spurred efforts to understand their equilibrium partitioning behavior. Experimentally determined partition coefficients for FTOHs between soil/water and air/water have been reported, but direct measurements of partition coefficients for dissolved organic carbon (DOC)/water (K(doc)) and octanol/ water(K(ow)) have been lacking. Here we measured the partitioning of 8:2 and 6:2 FTOH between one or more types of DOC and water using enhanced solubility or dialysis bag techniques, and also quantified K(ow) values for 4:2 to 8:2 FTOH using a batch equilibration method. The range in measured log K(doc) values for 8:2 FTOH using the enhanced solubility technique with DOC derived from two soils, two biosolids, and three reference humic acids is 2.00-3.97 with the lowest values obtained for the biosolids and an average across all other DOC sources (biosolid DOC excluded) of 3.54 +/- 0.29. For 6:2 FTOH and Aldrich humic acid, a log K(doc) value of 1.96 +/- 0.45 was measured using the dialysis technique. These average values are approximately 1 to 2 log units lower than previously indirectly estimated K(doc) values. Overall, the affinity for DOC tends to be slightly lower than that for particulate soil organic carbon. Measured log K(ow) values for 4:2 (3.30 +/- 0.04), 6:2 (4.54 +/- 0.01), and 8:2 FTOH (5.58 +/- 0.06) were in good agreement with previously reported estimates. Using relationships between experimentally measured partition coefficients and C-atom chain length, we estimated K(doc) and K(ow) values for shorter and longer chain FTOHs, respectively, that we were unable to measure experimentally.     

Biogenic nanoscale colloids in wastewater effluents

The size, surface area, metal complexation capacity, organic pollutant sorption potential, reactivity with disinfectants, and elevated nitrogen content of biogenic organic nanoscale material (BONM) can potentially affect aquatic environments. BONM in effluents from 11 full-scale wastewater treatment plants (WWTPs), which use a range of biological processes, were characterized in two ways. First, BONM was measured by hydrodynamic size-exclusion chromatography coupled with an online organic carbon and UV detector. Second, BONM was isolated from the wastewater using rotary evaporation and dialysis and then characterized by elemental analysis, transmission electron microscopy, and Fourier transform infrared spectroscopy. The wastewaters contained 6-10 mg/L of dissolved organic carbon (DOC). BONM accounted for 5%-50% of the DOC in wastewater effluent organic matter, and the largest size fraction (>10 kDa) of organic carbon correlated with the organic carbon content determined after rotary evaporation and dialysis. Membrane bioreactor WWTPs had the lowest fraction of BONM (<10% of the DOC), followed by conventional activated sludge (10% to 30% of the DOC), with other processes (e.g., trickling filters, aerated lagoons) containing larger BONM percentages. BONM had a lower carbon to nitrogen ratio (6.2 ± 1.7) compared with the literature values for humic or fulvic acids, exhibited chemical bonds that were indicative of amides and polysaccharides, and contained fibril entangled networks. This work has important implications for operations efficiency of WWTPs, including controlling membrane fouling and release of organic nitrogen into sensitive environments.     

Formation of N-nitrosodimethylamine (NDMA) from humic substances in natural water

N-nitrosodimethylamine (NDMA)formation in chloraminated Iowa River water (IRW) is primarily attributed to reactions with natural organic matter (NOM) generally classified as humic substances. Experiments were conducted to determine the contribution of various NOM humic fractions to the NDMA formation potential (NDMA FP) in this drinking water source. NOM was concentrated by reverse osmosis (RO) and humic fractions were obtained by a series of resin elution procedures. Mass balances showed that nearly 90% of the NDMA formation potential could be recovered in the NOM concentrate and in water reconstituted using additions of the various humic fractions. Generally, the hydrophilic fractions tended to form more NDMA than hydrophobic fractions, and basic fractions tend to form more NDMA than acid fractions when normalized to a carbon basis. Overall, the hydrophobic acid fraction was the dominant source of NDMA when both formation efficiency and water composition were considered. The amount of NDMA formed in a sample was found to correlate linearly with an oxidation-induced decrease in specific UV absorbance (SUVA) value at 272 nm. This is consistent with a mechanism in which precursors are formed as the direct consequence of the oxidation of NOM. The NDMA FP estimated using the slope of this relationship and the initial SUVA value compared closely to the value obtained by measuring the NDMA formed in solutions dosed with excess concentrations of monochloramine that presumably exhaust all potential precursor sources. However, the NOMA FP could not be correlated to the SUVA value of the individual humic fractions indicating that the relationship of the NDMA FP to SUVA value is probably a water-specific parameter dependent on the exact composition of humic fractions. It is hypothesized that either specific NDMA precursors are distributed among the various humic fractions or that the humic material itself represents a "generic" nonspecific precursor source that requires some degree of oxidation to eventually produce NDMA. The nonmonotonic behavior of NOM fluorescence spectra during chloramination and lack of correlation between NOM fluorescence characteristics and NDMA formation limited the usage of fluorescence spectra into probing NDMA formation.     

Nature and abundance of organic radicals in natural organic matter: effect of pH and irradiation

Dissolved natural organic matter (NOM) plays an essential role in freshwater geochemical and biochemical processes. A major property, its redox behavior, can be attributed to the chinone building blocks, which can form stable radicals. However, electron paramagnetic resonance (EPR) data indicating free radicals on solid NOM are sparse. Here we present EPR spectra of 23 NOM from European surface waters isolated by reverse osmosis. The organic radical concentrations of NOM ranged from 5 x 10(15) to 1.84 x 10(17) spins g(-1), and g values ranged from 2.0031 to 2.0045. Number and type of organic radicals in solid NOM are significantly influenced by the pH of raw water. EPR experiments indicate the presence of semiquinone-type radicals in coexistence with carbon-centered "aromatic" radicals, with the semiquinone-type radicals dominating at alkaline pH. Basically these processes are reversible. Organic radical concentrations in NOM adjusted to pH 6.5 before freeze-drying correlate with iron and aluminum contents. UV- and VIS-irradiation of solid NOM can lead to more than a 10-fold increase of the concentration of organic radicals. These radicals were long-lived and had the same g value as the original radical. Similar effects were not observed with isolated humic and fulvic acids, demonstrating the limited reflection of environmental properties of organic carbon by the classical isolation procedure.     

Model assessment of biogeochemical controls on dissolved organic carbon partitioning in an acid organic soil

A chemical model (constructed in the ORCHESTRA modeling framework) of an organic soil horizon was used to describe soil solution data (10 cm depth) and assess if seasonal variations in soil solution dissolved organic carbon (DOC) could be explained by purely abiotic (geochemical controls) mechanisms or whether factors related to biological activity are needed. The NICA-Donnan equation is used to describe the competitive binding of protons and cations and the charge on soil organic matter. Controls on organic matter solubility are surface charge and a parameter, gamma, that accounts for the distribution of humic molecules between hydrophobic and hydrophilic fractions. Calculations show that the variations in solute chemistry alone are not sufficient to account for the observed variations of DOC, but factors that alter gamma, such as biological activity, are. Assuming that DOC in organic soils is derived from soluble humic material and that gamma is modified seasonally due to biological activity (with monthly soil temperature used as a surrogate for biological activity) we are able to model the observed seasonality of soil solution DOC over a 10-year period. Furthermore, with modeled DOC coupled to other geochemical processes we also model soil solution pH and Al concentrations.     

UV photolysis of nitrate: effects of natural organic matter and dissolved inorganic carbon and implications for UV water disinfection

Nitrite (NO2-) formation during ultraviolet (UV) photolysis of nitrate was studied as a function of pH and natural organic matter (NOM) concentration to determine water-quality effects on quantum yields and overall formation potential during UV disinfection of drinking water with polychromatic, medium-pressure (MP) Hg lamps. Quantum yields measured at 228 nm are approximately 2 times higher than at 254 nm under all conditions studied. In the absence of NOM, NO2- quantum yields decrease with time. With addition of NOM, initial quantum yields increase, and the time-dependent decrease is eliminated. At 15 ppm dissolved organic carbon (DOC) as NOM, the quantum yield increases with time. Dissolved inorganic carbon significantly decreases NO2- yields at pH 8 but not pH 6, presumably by reaction of CO2(aq) with peroxynitrite, a major intermediate in NO2- formation. The results indicate important and previously unrecognized roles for NOM and CO2(aq) in nitrate photolysis. When photolysis was carried out using the full spectrum MPUV lamp and germicidally relevant UV doses, NO2- concentrations remained well below the U.S. maximum contaminant level of 1 ppm N, even with nitrate initially present at 10 ppm N. Under current U.S. regulations, NO2- formation should not pose a significant problem for water utilities during UV disinfection of drinking water with MP Hg lamps.     

Applications of fluorescence spectroscopy for predicting percent wastewater in an urban stream

Dissolved organic carbon (DOC) is a significant organic carbon reservoir in many ecosystems, and its characteristics and sources determine many aspects of ecosystem health and water quality. Fluorescence spectroscopy methods can quantify and characterize the subset of the DOC pool that can absorb and re-emit electromagnetic energy as fluorescence and thus provide a rapid technique for environmental monitoring of DOC in lakes and rivers. Using high resolution fluorescence techniques, we characterized DOC in the Tualatin River watershed near Portland, Oregon, and identified fluorescence parameters associated with effluent from two wastewater treatment plants and samples from sites within and outside the urban region. Using a variety of statistical approaches, we developed and validated a multivariate linear regression model to predict the amount of wastewater in the river as a function of the relative abundance of specific fluorescence excitation/emission pairs. The model was tested with independent data and predicts the percentage of wastewater in a sample within 80% confidence. Model results can be used to develop in situ instrumentation, inform monitoring programs, and develop additional water quality indicators for aquatic systems.     

Solid phase dosing and sampling technique to determine partition coefficients of hydrophobic chemicals in complex matrixes

Determination of polymer-water and dissolved organic carbon (DOC)-water distribution coefficients of very hydrophobic chemicals (log K0w > 6) is not straightforward. Poor water solubility of the test compounds complicates the spiking and analysis of actual freely dissolved concentrations. By dosing a system via a PDMS-fiber and monitoring the depletion in the polymer, spiking and analysis of concentrations in the aqueous phase are avoided, and sorption to the polymer and other hydrophobic phases can be determined easily and accurate. In this publication we report the determination of poly(dimethyl-siloxane) (PDMS)-water, and Aldrich humic acid-water distribution coefficients for six PAHs with log K0w values varying from 4.56 to 6.85. The distribution coefficients to a PDMS fiber llog Kf) and the DOC (log KDOC) range from 3.86 to 5.39 and 4.78 to 7.43, respectively. Even for the most hydrophobic compounds, the distribution coefficients show small standard errors (< or = 0.05 log units). Therefore, this method might be applied to determine sorption coefficients of numerous, even more hydrophobic compounds, to humic acids as well as other dissolved hydrophobic matrixes.     

Varations of molecular weight estimation by HP-size exclusion chromatography with UVA versus online DOC detection

High performance size exclusion chromatography (HPSEC) with ultraviolet absorbance (UVA) detection has been widely utilized to estimate the molecular weight (MW) and MW distribution of natural organic matter (NOM). However, the estimation of MW with UVA detection is inherently inaccurate because UVA at 254 nm only detects limited components (mostly pi bonded molecules) of NOM, and the molar absorptivity of these different NOM constituents is not equal. In comparison, a SEC chromatogram obtained with a DOC detector showed significant differences compared to a corresponding UVA chromatogram, resulting in different MW values as well as different estimates of polydispersivity. The MWs of Suwannee River humic acid (SRHA), Suwannee River fulvic acid (SRFA), and various mixtures thereof were estimated with HPSEC coupled with UVA and DOC detectors. The results show that UVA is not an adequate detector for quantitative analysis of MW estimation but rather can be used only for limited qualitative analysis. The NOM in several natural waters (Irvine Ranch, California groundwater, and Barr Lake, Colorado surface water) were also characterized to demonstrate the different MWs obtained with the two detectors. The results of the SEC-DOC chromatograms revealed NOM constituent peaks that went undetected by UVA. Utilizing online DOC detection, a better representation of NOM MWs was suggested, with NOM displaying higher weight-averaged MW (Mw) and lower number-averaged MW (Mn) as well as higher polydispersivity. A method for estimation of the MWs of NOM fractional components and polydispersivities is presented.     

Characteristics of dissolved organic matter in Baltic coastal sea ice: allochthonous or autochthonous origins?

The origin of dissolved organic matter (DOM) within sea ice in coastal waters of the Baltic Sea was investigated using parallel factor (PARAFAC) analysis of DOM fluorescence. Sea ice DOM had distinctly different fluorescence characteristics than that of the underlying humic-rich waters and was dominated by protein-like fluorescence signals. PARAFAC analysis identified five fluorescent components, all of which were present in both sea ice and water. Three humic components were negatively correlated to salinity and concluded to be terrestrially derived material. Baltic Sea ice DOM was found to be a mixture of humic material from the underlying water column incorporated during ice formation and autochthonous material produced by organisms within the ice. Dissolved organic carbon (DOC) and nitrogen (DON) concentrations were correlated to the humic fluorescence, indicating that the majority of the organic carbon and nitrogen in Baltic Sea ice is bound in terrestrial humic material trapped within the ice. This has implications for our understanding of sea ice carbon cycling in regions influenced by riverine input (e.g., Baltic and Arctic coastal waters), as the susceptibility of DOM to degradation and remineralization is largely determined by its source.     

Winter-time climatic control on dissolved organic carbon export and surface water chemistry in an Adirondack forested watershed

Although most of forested watersheds in temperate and boreal regions are snow-covered for a substantial portion of the year, responses of biogeochemical processes under the snow pack to climatic fluctuations are poorly understood. We investigated responses of dissolved organic carbon (DOC) and surface water chemistry in stream and lake discharge waters draining the Arbutus Lake Watershed in the Adirondacks of New York State to climatic fluctuations during the snow-covered months from December through April. Interannual variability in stream discharge corresponded to changes in air temperature and snow pack depth across the winter months. Concentrations of DOC in stream water draining a subcatchment showed immediate positive responses to rising temperatures and subsequent increases in runoff during most snowmelt events. Increases in DOC concentrations usually coincided with decreases in pH and increases in total aluminum (Al) concentrations, while the correlations between concentrations of DOC and SO4(2-) or base cations were negative. Although changes in air temperature, snow pack depth, and runoff were all significantly correlated with stream water concentrations of major solutes, stepwise linear regression found that runoff was the best predictor of solute concentrations. Results of stepwise linear regression with long-term monthly monitoring data collected at the lake outlet showed weaker but still consistent climatic effects on interannual variations in concentrations of DOC and other solutes. Over the 17 winter periods from December 1983 through April 2000, changes in seasonal average concentrations of DOC, H+, and Al in lake discharge generally corresponded to interannual variations in temperature, precipitation, and runoff, while SO4(2-) and base cations displayed an opposite trend. The results suggest that snowmelt-mediated DOC responses to temperature fluctuations during the winter months might offset increases in the surface water pH caused by decreasing acidic deposition and pose a potential hazard of Al toxicity in surface waters.     

Oxidation of the cyanobacterial hepatotoxin microcystin-LR by chlorine dioxide: influence of natural organic matter

Cyanobacteria (blue-green algae) are known producers of cytotoxic, hepatotoxic, and neurotoxic compounds with severe acute and chronic effects on vertebrates. Successful removal of these toxins in drinking water treatment is therefore of importance for public health. In the present work the oxidation of the cyanobacterial hepatotoxin microcystin-LR (MC-LR) by chlorine dioxide (ClO2) was studied at natural microcystin concentrations (10 microg L(-1)) and normal ClO2 dosages (1 mg L(-1)) in the absence and presence of natural organic matter (NOM). ClO2 was found to be rapidly consumed by fulvic and humic acids, leaving less residual ClO2 to oxidize MC-LR. Predicted decrease rates in MC-LR concentration correlated highly with experimental data both in pure water and in the presence of NOM. Rate constants determined at high ClO2 and MC-LR concentrations in pure water could be used to predict the oxidation of MC-LR at natural concentrations. Toxicity tests with a protein phosphatase inhibition assay on reaction solutions and high-performance liquid chromatography fractions revealed that PP1 enzyme inhibition emerged only from intact MC-LR, while the oxidation products, dihydroxy isomers of MC-LR, were nontoxic even at unnaturally high concentrations.     

Involvement of humic substances in regrowth

There appear to be interactions in the distribution system that complicate the ability to use AOC/BDOC as an independent assessment of regrowth potential. Two such complications are the limitation of the assays themselves and the potential interaction between the organic carbon concentration with the presence of disinfectants and pipe materials. To address these interactions, a series of experiments spanning several years have been conducted in model distribution systems at the Center for Biofilm Engineering (CBE) using soil-derived humics. When compared to easily utilized organics, humic substances supported the same order of magnitude of biofilm organisms. As carbon concentration was increased from 500 to 1000 to 2000 ppb, there was no increase in growth rate of the organisms, suggesting zero-order kinetics. If the system was chlorinated, there was less biomass, but growth rates were higher. In the presence of corrosion products, humic-fed systems supported more organisms than a control system fed biologically treated water. When free chlorine was maintained at a residual of about 0.2 mg/l, biofilm numbers on the surfaces were reduced. Phosphate alone did not result in fewer bacteria, while a combination of chorine and phosphate had the best results (lowest biofilm numbers). Adjustment to pH 9 was not effective. Recently completed work compared increasing levels of humic substances in the presence of free chlorine and monochloramine on biofilm growth on a number of surfaces (PVC, epoxy, cement, ductile iron). As the concentration of humic substances was increased from 0, 0.5 to 2 mg/l, there was an increase in biofilm numbers on all surfaces. This effect was the most pronounced on iron surfaces. These results illustrate that carbon compounds not measured by the BDOC or AOC tests may profoundly influence biofilm numbers. In addition, iron surfaces are at much higher risk for elevated biofilm counts in the presence of humic substances, even if disinfection is practiced. However, corrosion control may mitigate this interaction.     

Dissolved organic carbon enhances the mass transfer of hydrophobic organic compounds from nonaqueous phase liquids (NAPLs) into the aqueous phase

The hypothesis that dissolved organic carbon (DOC) enhances the mass transfer of hydrophobic organic compounds from nonaqueous phase liquids (NAPLs) into the aqueous phase above that attributable to dissolved molecular diffusion alone was tested. In controlled experiments, mass transfer rates of five NAPL-phase PAHs (log K(OW) 4.15-5.39) into the aqueous phase containing different concentrations of DOC were measured. Mass transfer rates were increased by up to a factor of 4 in the presence of DOC, with the greatest enhancement being observed for more hydrophobic compounds and highest DOC concentrations. These increases could not be explained by dissolved molecular diffusion alone, and point to a parallel DOC-mediated diffusive pathway. The nature of the DOC-mediated diffusion pathway as a function of the DOC concentration and PAH sorption behavior to the DOC was investigated using diffusion-based models. The DOC-enhanced mass transfer of NAPL-phase hydrophobic compounds into the aqueous phase has important implications for their bioremediation as well as bioconcentration and toxicity.     

Disinfection byproduct relationships and speciation in chlorinated nanofiltered waters

The formation and speciation of disinfection byproducts (DBPs) resulting from chlorination of nanofilter permeates obtained from various source water locations and membrane types are examined. Specific ultraviolet absorbance and bromide utilization are shown to decrease following nanofiltration. Both dissolved organic carbon (DOC) concentration and ultraviolet absorbance at 254 nm were found to correlate strongly with trihalomethane (THM), haloacetic acid (HAA), and total organic halide (TOX) concentrations in chlorinated nanofilter permeates, suggesting that they can be employed as surrogates for DBPs in nanofiltered waters. Because smooth curves were obtained for individual THM and HAA species as well as bromine and chlorine incorporation into THMs and HAAs as a function of Br-/DOC molar ratio, it is likely that mole fractions of these DBPs are more strongly influenced by chlorination conditions, Br-, and DOC concentrations than NOM source and membrane type. Mole fractions of mono-, di-, and trihalogenated HAAs were found to be independent of Br-/DOC. Even at a very low Br-/DOC of 2.9microM/mM, the mixed bromochloro- and tribromoacetic acids constituted 20% of total HAAs on a molar basis. This increased to approximately 50% as Br-/DOC increased to approximately 25microM/mM or more, proving that a large fraction of HAAs may not be covered under existing federal regulations. Total THM and HAA9 concentrations decreased in permeate waters with increasing Br-/DOC suggesting that nanofilter permeates are limited with respect to DBP precursors.