Controlling disinfection byproducts from treated wastewater using adsorption with granular activated carbon: Impact of pre-ozonation and pre-chlorination.

This study measured chlorine- and chloramine-reactive precursors using formation potential (FP) tests of nine U.S. Environmental Protection Agency (EPA) regulated and 57 unregulated disinfection byproducts (DBPs) in tertiary-filtered wastewater before and after pilot-scale granular activated carbon (GAC) adsorption. Using breakthrough of precursor concentration and of concentration associated calculated cytotoxicity and genotoxicity (by correlating known lethal concentrations reported elsewhere), the performance of three parallel GAC treatment trains were compared against tertiary-filtered wastewater: ozone/GAC, chlorine/GAC, and GAC alone. Results show GAC alone was the primary process, versus ozone or chlorine alone, to remove the largest fraction of total chlorine- and chloramine-reactive DBP precursors and calculated cytotoxicity and genotoxicity potencies. GAC with pre-ozonation removed the most chlorine- and chloramine-reactive DBP precursors followed by GAC with pre-chlorination and lastly GAC without pre-treatment. GAC with pre-ozonation produced an effluent with cytotoxicity and genotoxicity of DBPs from FP that generally matched that of GAC without pre-oxidation; meanwhile removal of toxicity was greater by GAC with pre-chlorination. The cytotoxicity and genotoxicity of DBPs from FP tests did not scale with DBP concentration; for example, more than 90% of the calculated cytotoxicity resulted from 20% of the DBPs, principally from haloacetaldehydes, haloacetamides, and haloacetonitriles. The calculated cytotoxicity and genotoxicity from DBPs associated with FP-chloramination were at times higher than with FP-chlorination though the concentration of DBPs was five times higher with FP-chlorination. The removal of DBP precursors using GAC based treatment was at least as effective as removal of DOC (except for halonitromethanes for GAC without pre-oxidation and with pre-chlorination), indicating DOC can be used as an indicator for DBP precursor adsorption efficacy. However, the DOC was not a good surrogate for total cytotoxicity and genotoxicity breakthrough behavior, therefore, unregulated DBPs could have negative health implications that are disconnected from general water quality parameters, such as DOC, and regulated classes of DBPs. Instead, cytotoxicity and genotoxicity correlate with the concentration of specific classes of unregulated DBPs.

Does Granular Activated Carbon with Chlorination Produce Safer Drinking Water? From Disinfection Byproducts and Total Organic Halogen to Calculated Toxicity.

Granular activated carbon (GAC) adsorption is well-established for controlling regulated disinfection byproducts (DBPs), but its effectiveness for unregulated DBPs and DBP-associated toxicity is unclear. In this study, GAC treatment was evaluated at three full-scale chlorination drinking water treatment plants over different GAC service lives for controlling 61 unregulated DBPs, 9 regulated DBPs, and speciated total organic halogen (total organic chlorine, bromine, and iodine). The plants represented a range of impacts, including algal, agricultural, and industrial wastewater. This study represents the most extensive full-scale study of its kind and seeks to address the question of whether GAC can make drinking water safer from a DBP perspective. Overall, GAC was effective for removing DBP precursors and reducing DBP formation and total organic halogen, even after >22 000 bed volumes of treated water. GAC also effectively removed preformed DBPs at plants using prechlorination, including highly toxic iodoacetic acids and haloacetonitriles. However, 7 DBPs (mostly brominated and nitrogenous) increased in formation after GAC treatment. In one plant, an increase in tribromonitromethane had significant impacts on calculated cytotoxicity, which only had 7-17% reduction following GAC. While these DBPs are highly toxic, the total calculated cytotoxicity and genotoxicity for the GAC treated waters for the other two plants was reduced 32-83% (across young-middle-old GAC). Overall, calculated toxicity was reduced post-GAC, with preoxidation allowing further reductions.

Varied influence of microcystin structural difference on ELISA cross-reactivity and chlorination efficiency of congener mixtures.

Enzyme-linked immunosorbent assay (ELISA) is an antibody-based analytical method that has been widely applied in water treatment utilities for the screening of toxic cyanobacteria metabolites such as microcystins (MCs). However, it is unknown how the minor structural difference of MCs may impact their chlorination kinetics and measurement via ELISA method. It was found in this study that, regardless of the experimental conditions (n = 21), there was no MC-YR or MC-LY residual, while different removal rates of other MCs were observed (MC-RR > MC-LR > MC-LA âˆ¼ MC-LF) as measured by liquid chromatography tandem mass spectrometry (LC-MS/MS), which was consistent with the relative reactivity of the amino acid variables with free chlorine. The removal of total MCs was generally lower as measured by ELISA than by LC-MS/MS. By incorporating both analytical results, existence of ADDA-containing byproducts or byproducts that had a higher sensitivity toward the ELISA kit was demonstrated, after excluding the contribution of the cross-reactivity of the parent MCs. It should be noted, however, that the cross-reactivities of MCs could be influenced not only by MC congeners, but also by other conditions such as mixtures and the applied ELISA kit.

Evaluating Evidence for Association of Human Bladder Cancer with Drinking-Water Chlorination Disinfection By-Products.

Exposure to chlorination disinfection by-products (CxDBPs) is prevalent in populations using chlorination-based methods to disinfect public water supplies. Multifaceted research has been directed for decades to identify, characterize, and understand the toxicology of these compounds, control and minimize their formation, and conduct epidemiologic studies related to exposure. Urinary bladder cancer has been the health risk most consistently associated with CxDBPs in epidemiologic studies. An international workshop was held to (1) discuss the qualitative strengths and limitations that inform the association between bladder cancer and CxDBPs in the context of possible causation, (2) identify knowledge gaps for this topic in relation to chlorine/chloramine-based disinfection practice(s) in the United States, and (3) assess the evidence for informing risk management. Epidemiological evidence linking exposures to CxDBPs in drinking water to human bladder cancer risk provides insight into causality. However, because of imprecise, inaccurate, or incomplete estimation of CxDBPs levels in epidemiologic studies, translation from hazard identification directly to risk management and regulatory policy for CxDBPs can be challenging. Quantitative risk estimates derived from toxicological risk assessment for CxDBPs currently cannot be reconciled with those from epidemiologic studies, notwithstanding the complexities involved, making regulatory interpretation difficult. Evidence presented here has both strengths and limitations that require additional studies to resolve and improve the understanding of exposure response relationships. Replication of epidemiologic findings in independent populations with further elaboration of exposure assessment is needed to strengthen the knowledge base needed to better inform effective regulatory approaches.

Effects of ozone and ozone/peroxide on trace organic contaminants and NDMA in drinking water and water reuse applications.

An ozone and ozone/peroxide oxidation process was evaluated at pilot scale for trace organic contaminant (TOrC) mitigation and NDMA formation in both drinking water and water reuse applications. A reverse osmosis (RO) pilot was also evaluated as part of the water reuse treatment train. Ozone/peroxide showed lower electrical energy per order of removal (EEO) values for TOrCs in surface water treatment, but the addition of hydrogen peroxide increased EEO values during wastewater treatment. TOrC oxidation was correlated to changes in UV(254) absorbance and fluorescence offering a surrogate model for predicting contaminant removal. A decrease in N-nitrosodimethylamine (NDMA) formation potential (after chloramination) was observed after treatment with ozone and ozone/peroxide. However, during spiking experiments with surface water, ozone/peroxide achieved limited destruction of NDMA, while in wastewaters net direct formation of NDMA of 6-33 ng/L was observed after either ozone or ozone/peroxide treatment. Once formed during ozonation, NDMA passed through the subsequent RO membranes, which highlights the significance of the potential for direct NDMA formation during oxidation in reuse applications.

Impact of drought on wastewater contaminants in an urban water supply.

The concentrations of selected wastewater contaminants, including conductivity, nitrate, and pharmaceuticals and endocrine disrupting compounds (EDCs), were monitored from 2003 to 2007 in Lake Mead, the raw (untreated) drinking water for southern Nevada. Monitoring was also conducted in two inflows to Lake Mead: the Colorado River and the wastewater-dominated Las Vegas Wash. There was a statistically significant increase in source water conductivity, nitrate, and pharmaceutical and EDC concentrations over this time period, concomitant with a statistically significant decline in the volume of Lake Mead. There was no statistically significant increase in conductivity and nitrate in the Colorado River or the Las Vegas Wash over this period, nor was there an increase in flow of the Las Vegas Wash or Colorado River. Thus, the deterioration of source drinking water quality is due to the decrease in the volume of Lake Mead which has been attributed to drought. This phenomenon may also be a harbinger of how water quality may be adversely affected by climate change as patterns of surface water flow shift and treated wastewater becomes a larger fraction of surface water flow in some areas.

Evaluation of on-site wastewater treatment technology to remove estrogens, nonylphenols, and estrogenic activity from wastewater.

A series of five on-site wastewater treatment systems were monitored for the removal of steroid estrogens, nonylphenols, and total estrogenic activity through several stages of pretreatment including aerobic and anaerobic sand filters. The objectives of this study were (1) to examine the ability of traditional septic systems and different types of pretreatment add-ons to remove nonylphenols (NPs) and the steroid estrogens estrone (E1), 17beta- estradiol (E2), estriol (E3), and 17alpha- ethinylestradiol (EE2) from the final effluent prior to discharge into the environment and (2) to examine the ability of each system and each stage of treatment within the system to remove total estrogenic activity as measured by a yeast estrogen screen (YES) assay. YES data and instrumental data are compared in the context of analyte recovery and estradiol equivalents. Results indicate excellent removal of NPs and total estrogenic activity to near or below detection limits when multiple stages of pretreatment including aerobic sand filters are used. However, only moderate removal of the steroid estrogens was observed through the anaerobic sand filters.

Rapid analysis of perchlorate, chlorate and bromate ions in concentrated sodium hypochlorite solutions.

A sensitive, rapid, and rugged liquid chromatography with tandem mass spectrometry (LC-MS/MS) method for measuring concentrations of perchlorate, chlorate, and bromate ions in concentrated sodium hypochlorite solutions is presented. The LC-MS/MS method offers a practical quantitation limit (PQL) of 0.05 microg L(-1) for ClO(4)(-), 0.2 microg L(-1) for BrO(3)(-), and 0.7 microg L(-1) for ClO(3)(-) and a sample analysis time of only 10 min. Additionally, an iodometric titration technique was compared with the LC-MS/MS method for measurement of chlorate ion at high concentration. The LC-MS/MS method was the most reproducible for chlorate concentrations below 0.025 M while the iodometric titration method employed was the most reproducible above 0.025 M. By using both methods, concentrations of chlorate can be measured over a wide range, from 0.7 microg L(-1) to 210 g L(-1) in hypochlorite ion solutions. Seven quenching agents were also evaluated for their ability to neutralize hypochlorite ion, thereby stopping formation of perchlorate ion in solution, without adversely impacting the other oxyhalide ions. Malonic acid was chosen as the quenching agent of choice, meeting all evaluation criteria outlined in this manuscript.

The impact of co-contaminants and septic system effluent quality on the transport of estrogens and nonylphenols through soil.

The impact that varying qualities of wastewater may have on the movement of steroid estrogens through soils into groundwater is little understood. In this study, the steroid estrogens 17beta-estradiol (E2) and estrone (E1) were followed through batch and column studies to examine the impact that organic wastewater constituents from on-site wastewater treatment systems (i.e., septic systems or decentralized systems) may have on influencing the rate of transport of estrogens through soils. Total organic carbon (TOC) content (as a surrogate indicator of overall wastewater quality) and the presence of nonyl-phenol polyethoxylate surfactants (NPEO) at concentrations well below the critical micelle concentration were independently shown to be indicative of earlier breakthrough and less partitioning to soil in batch and column experiments. Both NPEO and wastewater with increasing TOC concentrations led to shifts in the equilibrium of E1 and E2 towards the aqueous phase and caused the analytes to have an earlier breakthrough than in control experiments. The presence of nonylphenols, on the other hand, did not appreciably impact partitioning of E1 or E2. Biodegradation of the steroids in soil was also lower in the presence of septic tank effluents than in an organic-free control water. Furthermore, the data indicate that the rate of movement of E1 and E2 present in septic tank effluent through soils and into groundwater can be decreased by removing the NPEOs and TOC through wastewater treatment prior to sub-surface disposal. This study offers some insights into mechanisms which impact degradation, transformation, and retardation, and shows that TOC and NPEO surfactants play a role in estrogen transport.

An evaluation of a pilot-scale nonthermal plasma advanced oxidation process for trace organic compound degradation.

This study evaluated a pilot-scale nonthermal plasma (NTP) advanced oxidation process (AOP) for the degradation of trace organic compounds such as pharmaceuticals and potential endocrine disrupting compounds (EDCs). The degradation of seven indicator compounds was monitored in tertiary-treated wastewater and spiked surface water to evaluate the effects of differing water qualities on process efficiency. The tests were also conducted in batch and single-pass modes to examine contaminant degradation rates and the remediation capabilities of the technology, respectively. Values for electrical energy per order (EEO) of magnitude degradation ranged from <0.3 kWh/m(3)-log for easily degraded compounds (e.g., carbamazepine) in surface water to 14 kWh/m(3)-log for more recalcitrant compounds (e.g., meprobamate) in wastewater. Changes in the bulk organic matter based on UV(254) absorbance and excitation-emission matrices (EEM) were also monitored and correlated to contaminant degradation. These results indicate that NTP may be a viable alternative to more common AOPs due to its comparable energy requirements for contaminant degradation and its ability to operate without any additional feed chemicals.

Evaluation of a photocatalytic reactor membrane pilot system for the removal of pharmaceuticals and endocrine disrupting compounds from water.

A photocatalytic reactor membrane pilot system, employing UV/TiO(2) photocatalysis, was evaluated for its ability to remove thirty-two pharmaceuticals, endocrine disrupting compounds, and estrogenic activity from water. Concentrations of all compounds decreased following treatment, and removal followed pseudo-first-order kinetics as a function of the amount of treatment. Twenty-nine of the targeted compounds in addition to total estrogenic activity were greater than 70% removed while only three compounds were less than 50% removed following the highest level of treatment (4.24 kW h/m(3)). No estrogenically active transformation products were formed during treatment. Additionally, the unit was operated in photolytic mode (UV only) and photolytic plus H(2)O(2) mode (UV/H(2)O(2)) to determine the relative amount of energy required. Based on the electrical energy per order (EEO), the unit achieved the greatest efficiency when operated in photolytic plus H(2)O(2) mode for the conditions tested.

Pharmaceuticals and endocrine disrupting compounds in U.S. drinking water.

The drinking water for more than 28 million people was screened for a diverse group of pharmaceuticals, potential endocrine disrupting compounds (EDCs), and other unregulated organic contaminants. Source water, finished drinking water, and distribution system (tap) water from 19 U.S. water utilities was analyzed for 51 compounds between 2006 and 2007. The 11 most frequently detected compounds were atenolol, atrazine, carbamazepine, estrone, gemfibrozil, meprobamate, naproxen, phenytoin, sulfamethoxazole, TCEP, and trimethoprim. Median concentrations of these compounds were less than 10 ng/L, except for sulfamethoxazole in source water (12 ng/L), TCEP in source water (120 ng/L), and atrazine in source, finished, and distribution system water (32, 49, and 49 ng/L). Atrazine was detected in source waters far removed from agricultural application where wastewater was the only known source of organic contaminants. The occurrence of compounds in finished drinking water was controlled by the type of chemical oxidation (ozone or chlorine) used at each plant. At one drinking water treatment plant, summed monthly concentrations of the detected analytes in source and finished water are reported. Atenolol, atrazine, DEET, estrone, meprobamate, and trimethoprim can serve as indicator compounds representing potential contamination from other pharmaceuticals and EDCs and can gauge the efficacy of treatment processes.

Isotope dilution for quantitation of steroid estrogens and nonylphenols by gas chromatography with tandem mass spectrometry in septic, soil, and groundwater matrices.

A simplified, in-line solid-phase extraction and clean-up process is presented for rapid extraction and analysis of steroid estrogens and nonylphenols by gas chromatography with tandem mass spectrometry. Isotope dilution with multiple deuterated standards has been developed, evaluated, and verified using this method against standard addition for the analysis of estrone, estradiol, estriol, ethinylestradiol, and 4-nonylphenols in septic, soil, and groundwater matrices. The accuracy and precision of isotope dilution was comparable to standard addition yet was able to quantify analytes with the use of fewer samples by including [(2)H(4)]estradiol, [(2)H(4)]ethinylestradiol, [(2)H(4)]nonylphenol, and estradiol-17-acetate as internal standards. Specific details and validation of the method are presented as are data showing the occurrence of estrogens and nonylphenols in an on-site wastewater treatment (septic) system with advanced stages of pretreatment and recirculation to an office building for non-potable reuse.