Christiane Hoppe-Jones

The role of organic matter in the removal of emerging trace organic chemicals during managed aquifer recharge.

This study explored the effect of different bulk organic carbon matrices on the fate of trace organic chemicals (TOrC) during managed aquifer recharge (MAR). Infiltration through porous media was simulated in biologically active column experiments under aerobic and anoxic recharge conditions. Wastewater effluent derived organic carbon types, differing in hydrophobicity and biodegradability (i. e., hydrophobic acids, hydrophilic carbon, organic colloids), were used as feed substrates in the column experiments. These carbon substrates while fed at the same concentration differed in their ability to support soil biomass growth during porous media infiltration. Removal of degradable TOrC (with the exception of diclofenac and propyphenazone) was equal or better under aerobic versus anoxic porous media infiltration conditions. During the initial phase of infiltration, the presence of biodegradable organic carbon (BDOC) enhanced the decay of degradable TOrC by promoting soil biomass growth, suggesting that BDOC served as a co-substrate in a co-metabolic transformation of these contaminants. However, unexpected high removal efficiencies were observed for all degradable TOrC in the presence of low BDOC concentrations under well adopted oligotrophic conditions. It is hypothesized that removal under these conditions is caused by a specialized microbial community growing on refractory carbon substrates such as hydrophobic acids. Findings of this study reveal that the concentration and character of bulk organic carbon present in effluents affect the degradation efficiency for TOrC during recharge operation. Specifically aerobic, oligotrophic microbiological soil environments present favorable conditions for the transformation of TOrC, including rather recalcitrant compounds such as chlorinated flame retardants.

Attenuation of total organic carbon and unregulated trace organic chemicals in U.S. riverbank filtration systems.

There is increasing concern regarding the presence of unregulated trace organic chemicals in drinking water supplies that receive discharge from municipal wastewater treatment plants. In comparison to conventional and advanced drinking water treatment, riverbank filtration represents a low-cost and low-energy alternative that can attenuate total organic carbon (TOC) as well as trace organic chemicals (TOrC). This study examined the role of predominant redox conditions, retention time, biodegradable organic carbon, and temperature to achieve attenuation of TOC and TOrC through monitoring efforts at three full-scale RBF facilities in different geographic areas of the United States. The RBF systems investigated in this study were able to act as a reliable barrier for TOC, nitrogen, and certain TOrC. Temperature (seasonal) variation played an important role for the make-up of the river water quality and performance of the RBF systems. Temperatures of less than 10 degrees C did not affect TOC removal but resulted in diminished attenuation of nitrate and select TOrC.

Dissolved Organic Carbon Influences Microbial Community Composition and Diversity in Managed Aquifer Recharge Systems

ABSTRACT This study explores microbial community structure in managed aquifer recharge (MAR) systems across both laboratory and field scales. Two field sites, the Taif River (Taif, Saudi Arabia) and South Platte River (Colorado), were selected as geographically distinct MAR systems. Samples derived from unsaturated riverbed, saturated-shallow-infiltration (depth, 1 to 2 cm), and intermediate-infiltration (depth, 10 to 50 cm) zones were collected. Complementary laboratory-scale sediment columns representing low (0.6 mg/liter) and moderate (5 mg/liter) dissolved organic carbon (DOC) concentrations were used to further query the influence of DOC and depth on microbial assemblages. Microbial density was positively correlated with the DOC concentration, while diversity was negatively correlated at both the laboratory and field scales. Microbial communities derived from analogous sampling zones in each river were not phylogenetically significantly different on phylum, class, genus, and species levels, as determined by 16S rRNA gene pyrosequencing, suggesting that geography and season exerted less sway than aqueous geochemical properties. When field-scale communities derived from the Taif and South Platte River sediments were grouped together, principal coordinate analysis revealed distinct clusters with regard to the three sample zones (unsaturated, shallow, and intermediate saturated) and, further, with respect to DOC concentration. An analogous trend as a function of depth and corresponding DOC loss was observed in column studies. Canonical correspondence analysis suggests that microbial classes Betaproteobacteria and Gammaproteobacteria are positively correlated with DOC concentration. Our combined analyses at both the laboratory and field scales suggest that DOC may exert a strong influence on microbial community composition and diversity in MAR saturated zones.

Start-up performance of a full-scale riverbank filtration site regarding removal of DOC, nutrients, and trace organic chemicals

The performance of a full-scale riverbank filtration facility in Colorado was evaluated from initial start-up over a period of seven years including the impact of seasonal variations to determine whether sustainable attenuation of various chemical constituents could be achieved. Both, annual and seasonal average concentrations were determined for several wastewater-derived constituents including dissolved organic carbon (DOC), ultraviolet absorbance at 254 nm, nitrate, phosphate for the years 2006, 2009, 2010, 2012, and trace organic chemicals (TOrC) for years 2009, 2010, and 2012. ANOVA analyses and Students t-tests were performed to evaluate the consistency of contaminant attenuation at the site. Findings revealed no significant statistical differences for any of the bulk parameters with the exception of phosphate suggesting a highly reliable attenuation of DOC and nitrate from start-up to full-scale performance. Phosphate attenuation, however, exhibited a steady decline, which was likely attributed to exhaustion of sorption sites in the subsurface porous media. The rivers flow regime influenced both occurrence levels and attenuation of TOrC during riverbank filtration, i.e. less river discharge resulted in higher TOrC concentrations and lower proportion of river water in the recovered groundwater. Differences in removal performance between annual data sets for caffeine, trimethoprim, sulfamethoxazole, and carbamazepine were caused by variations in the source; concentrations in riverbank filtrate remained similar over several years. The seasonal assessment for TOrC revealed steady or improving removal between winter and summer seasons based on the statistical analysis with atenolol being the only exception likely due to an increased microbial activity at elevated temperatures.

The role of microbial adaptation and biodegradable dissolved organic carbon on the attenuation of trace organic chemicals during groundwater recharge.

It is widely recognized that efficient biological attenuation of bulk organic matter and trace organic chemicals (TOrC) can occur in managed aquifer recharge (MAR) systems receiving reclaimed water. The heterotrophic microbial activity in these subsurface systems is a function of the availability of biodegradable dissolved organic carbon (BDOC) present in reclaimed water. This study examined the influence of environmental factors, such as BDOC-rich (>1.6 mg/L) and BDOC-starving (<1mg/L) conditions and microbial adaptation, on the attenuation of TOrC, including clofibric acid, dichlorprop, gemfibrozil, ibuprofen, ketoprofen, mecoprop, and naproxen, within soil-columns mimicking groundwater recharge. Under conditions that were characterized by a lack of BDOC and a biocommunity that was not yet adapted to these conditions, attenuation of biodegradable TOrC was less than 15%. After a three-month adaptation period, biotransformation increased to more than 80% for the biodegradable TOrC. This suggests that adaptation likely initiates enzyme expressions that eventually results in TOrC transformations even under seemingly less favorable conditions (i.e., lack of biodegradable carbon). For both non-adapted (stressed) and adapted conditions in the presence of higher concentrations of BDOC and travel times of 7 days, the degree of biotransformation was variable across compounds but generally exceeded 25%. This suggests that BDOC above a minimum level (>1.6 mg/L) can provide favorable microbial conditions resulting in TOrC removal, even for non-adapted systems. However, it is noteworthy that adapted MAR systems that were fed with low BDOC levels performed similarly or better with respect to TOrC biotransformation than systems that received BDOC levels above 1.6 mg/L. These findings are important for field-scale applications. They suggest that MAR facilities that are microbiologically active and are fed with highly treated water with effluent concentrations of less than 1 mg/L (i.e., nanofiltration permeate) can still attenuate biodegradable TOrC.

Results of an interlaboratory comparison of analytical methods for contaminants of emerging concern in water.

An evaluation of existing analytical methods used to measure contaminants of emerging concern (CECs) was performed through an interlaboratory comparison involving 25 research and commercial laboratories. In total, 52 methods were used in the single-blind study to determine method accuracy and comparability for 22 target compounds, including pharmaceuticals, personal care products, and steroid hormones, all at ng/L levels in surface and drinking water. Method biases ranged from <10% to well over 100% in both matrixes, suggesting that while some methods are accurate, others can be considerably inaccurate. In addition, the number and degree of outliers identified suggest a high degree of variability may be present between methods currently in use. Three compounds, ciprofloxacin, 4-nonylphenol (NP), and 4-tert-octylphenol (OP), were especially difficult to measure accurately. While most compounds had overall false positive rates of ≤5%, bisphenol A, caffeine, NP, OP, and triclosan had false positive rates >15%. In addition, some methods reported false positives for 17β-estradiol and 17α-ethynylestradiol in unspiked drinking water and deionized water, respectively, at levels higher than published predicted no-effect concentrations for these compounds in the environment. False negative rates were also generally <5%; however, rates were higher for the steroid hormones and some of the more challenging compounds, such as ciprofloxacin. The elevated false positive/negative rates of some analytes emphasize the susceptibility of many current methods to blank contamination, misinterpretation of background interferences, and/or inappropriate setting of detection/quantification levels for analysis at low ng/L levels. The results of both comparisons were collectively assessed to identify parameters that resulted in the best overall method performance. Liquid chromatography-tandem mass spectrometry coupled with the calibration technique of isotope dilution were able to accurately quantify most compounds with an average bias of <10% for both matrixes. These findings suggest that this method of analysis is suitable at environmentally relevant levels for most of the compounds studied. This work underscores the need for robust, standardized analytical methods for CECs to improve data quality, increase comparability between studies, and help reduce false positive and false negative rates.

Sonochemical degradation of perfluorinated chemicals in aqueous film-forming foams

Aqueous film-forming foams (AFFFs) are complex mixtures containing 1-5% w/w fluorocarbons (FCs). Here, we have investigated degradation of two commercial AFFF formulations, 3M and Ansul, using sound field at 500kHz and 1MHz, with varying initial concentrations ranging from 200 to 930× dilution. The foams were readily degraded by 1MHz, with percentage of defluorination ranging from 11.1±1.4% (200× dilution of 3M) to 47.1±5.8% (500× dilution of Ansul). Removal of total organic carbon (TOC) ranged from 16.0±1.4% (200× dilution Ansul) to 39.0±7.2% (500× dilution Ansul). Degradation of AFFF was affected by sound frequency with rates of defluorination 10-fold greater when the frequency was 1MHz than when it was 500kHz. Mineralization of TOC was 1.5- to 3.0-fold greater under 1MHz than 500kHz. Rate of fluoride release was 60% greater for the greatest initial concentration of FC in Ansul compared to the least initial concentration. While the rate of mineralization of AFFF was directly proportional to the initial concentration of Ansul, that was not the case for 3M, where the rates of mineralization were approximately the same for all three initial concentrations. Results of the study demonstrate that sonolysis is a promising technology to effectively treat AFFFs.