Sources and characteristics of dissolved organic carbon in the McKenzie River, Oregon, related to the formation of disinfection by-products in treated drinking water

Abstract

Executive Summary This study characterized the concentration and quality of dissolved organic carbon (DOC) in the McKenzie River, a relatively undeveloped watershed in western Oregon, and its link to forming disinfection by-products (DBPs) in treated drinking water. The study aimed to identify the primary source(s) of DOC in source water for the Eugene Water & Electric Board’s (EWEB) conventional treatment plant on the McKenzie River near river mile 11, upstream of Hayden Bridge. The two classes of regulated compounds examined—trihalomethanes (THMs) and haloacetic acids (HAAs)—form when organic carbon in raw source water reacts with chlorine and (or) bromine during water treatment. The objectives of the study were to: characterize the amount and quality of DOC in the McKenzie River and select tributaries during storms; identify the most common types of carbon using UV-vis spectroscopy and other methods; evaluate optical properties for predicting DBP precursors in surface water; and identify land cover classes or vegetation types that may be important sources of organic carbon and DBP precursors in EWEB’s source water. Eleven storms were sampled synoptically in upstream-to-downstream fashion to provide a “snapshot” of water quality conditions at four sites on the McKenzie River from Frissell Bridge (6 miles downstream from Trail Bridge Reservoir) to the EWEB water treatment plant at Hayden Bridge and nine contributing tributaries. Storms included late summer and early autumn “first flush” events and late autumn, winter, and spring storms spanning a range in streamflows from 3,000 to 26,000 cubic feet per second as measured in the main stem McKenzie River at the EWEB water intake. Water samples were analyzed for DOC concentrations and optical properties (fluorescence and ultraviolet absorbance [UVA]) across a range of wavelengths to characterize the quantity and quality of dissolved organic matter (DOM) in the McKenzie River at the drinking water intake and upstream locations. Paired sets of source and finished water samples were collected at the EWEB treatment plant to identify DOC quality parameters in raw source water that might predict DBP concentrations in finished drinking water. DOC concentrations were relatively low in the McKenzie River (0.4–3 milligrams per liter [mg/L]; average 1.5 mg/L) but much higher in the tributaries. The highest DOC concentrations occurred during “first flush” storms in October 2012 and September 2013; the highest value (16 mg/L) was measured at the 52nd Street stormwater outfall. The average DOC concentration in the lower basin-tributaries was 3.8 mg/L; three middle basin tributaries—Quartz, Gate, and Haagen Creeks, which drain private forestland with less coniferous forest compared with other higher elevation tributaries— had slightly lower average DOC concentrations (2.8 mg/L). These middle-basin watersheds may be important sources of DOC and DBP precursors to the McKenzie River, even more so than the lower basin tributaries, depending on their flows (and loads). This is particularly true after the September 2020 Holiday Farm fire, which burned much of this area. DOC concentrations increased 68 percent in the McKenzie River between the uppermost reference site at Frissell Bridge and Vida; this includes drainage from Quartz Creek, Blue River Lake and Cougar Reservoir, which all contributed DOC to the main stem. In contrast, the lowermost tributaries draining most of the agricultural and urban land did not have a large effect on DOC in the McKenzie River despite their higher DOC concentrations because of their presumed relatively low streamflows and, consequently, DOC loads. Apart from the continuous flow monitors in the McKenzie River and some tributaries (Blue River and South Fork McKenzie River, and streamflow at Hayden Bridge and Vida, Camp Creek and some other locations), streamflow was not assessed during sample collection for this study. This lack of streamflow data precludes a detailed analysis of loads, which is discussed in the future studies section. All DBP concentrations in finished drinking water were less than EPA maximum contaminant levels (MCLs) of 0.080 mg/L for the four trihalomethanes (THM4) and 0.060 mg/L for five haloacetic acids (HAA5). During the 11 storm sampling events the maximum summed concentrations were about 0.040 mg/L for both THM4 and HAA5. Compliance monitoring samples, collected separately by EWEB, yielded some higher concentrations—0.046 mg/L THM4 and 0.047 HAA5—during the December 2012 storm. The corresponding benchmark quotient (BQ) values, which indicate how close a measured DBP concentration is to the MCL, were 0.58 and 0.78, respectively, for THM4 and HAA5. Compared with a similar 2007–08 McKenzie River study that did not target storm events, concentrations of THM4 and HAA5 in finished water were 68 percent and 33 percent higher, respectively, during the current study. Due to the high dilution rates in the McKenzie River main stem, many of the individual fluorescence excitation-emission measurements were low (<0.1 Raman units) and approached analytical detection limits. Parallel factor analysis (PARAFAC) resulted in a five-component model (C1–C5) that represents five unique organic fluorophores. Components C1, C2, and C3 represent DOM associated with soil-derived, humic-like, more degraded organic matter. In contrast, components C4 and C5 represent “fresher” DOM, derived from terrestrial and aquatic plants, including algae and cyanobacteria that are common in the McKenzie River and its tributaries and reservoirs. The fluorescence data and PARAFAC modeling suggest that most of the DOC in the McKenzie River originated from terrestrial sources (primarily components C1 and C2). The largest increases in DOC in the main stem occurred in the reach upstream of Vida, from inflows by Quartz Creek, Blue River, South Fork McKenzie River, and other tributaries. Concentrations of DBPs in EWEB’s finished drinking water were positively correlated with DOC concentrations in raw source water (THM4, p <0.05; HAA5, p <0.01) for paired samples collected 12−24 hours apart. DOC concentrations were significantly positively correlated ( p <0.001) with laboratory-based fluorescent dissolved organic matter (fDOM) measurements, suggesting fDOM as a useful parameter for monitoring and predicting DOC concentration in surface water and DBP concentrations in finished water. Of all the PARAFAC components in surface water, C5 had the highest correlations with DBPs in finished water (rho = 0.77–0.84, p <0.01), followed by components C1 and C2 (rho = 0.75 and 0.71, respectively, p <0.01). This C5 carbon is associated with recently produced DOM, possibly from decomposed terrestrial and aquatic vegetation. Model loadings of these three components were considerably higher in the sampled tributaries relative to the main stem McKenzie River, with most of the observed increases in the main stem apparent at Vida. This points to Quartz Creek or other tributaries in the reach between Frissell Bridge and the sampling site near Vida (South Fork McKenzie and Blue Rivers) as potentially key contributors of DOM source material that leads to the production of DBPs in treated drinking water. A limited load analysis showed that the reservoirs contributed 8–37 percent of the instantaneous DOC loads observed at Vida at the time of sampling, which suggests other sources such as Quartz Creek and other streams in the reach between Frissell Bridge and Vida are more important. Random forest analyses identified PARAFAC components C1 and C5 and fluorescence peaks A, C, M, T and N as the best predictors for HAA5 concentrations in finished drinking water, explaining 62.5 percent of the variation. The best predictors for THM4 were C1, C4 + C5, and peaks T, A, and N, which explained 33 percent of the variation. Several land cover and vegetation classes were correlated with DOC concentration and other optical measurements. The percentage of evergreen forest in each of the subwatersheds sampled was negatively correlated ( p <0.001) with DOC concentration and many optical indicators of DOM quantity: UVA 254 , fDOM, and all of the fluorescence peaks. In contrast, mixed (deciduous) forest was positively correlated ( p <0.001) with DOC, fDOM, UVA 254 , and several fluorescence peaks, demonstrating the importance of deciduous leaf fall in generating DOC and DBP precursors. The high level of human activities in the middle and lower portion of the basin—including timber harvesting and road construction on private forestland, agricultural, rural, industrial, and urban development—have resulted in the greatest loss in native coniferous and mixed deciduous forests in the basin. DOC loading from these tributaries and reservoir releases, which contain DOC from terrestrial and aquatic productivity, both enrich the McKenzie River. Concentrations of DOC increased an average of 71 percent (range 30–120 percent) in the McKenzie River between Frissell Bridge, the upstream reference site, and Vida. PARAFAC components C1, C2, and C5—which were correlated with DBPs in finished water—increased, on average, 109–136 percent (range 20–250 percent) in this same Frissell-to-Vida reach. These increases occur from input of tributaries in the middle basin such as Quartz Creek and others, as noted above. Future monitoring, field, and lab studies can improve our understanding of seasonal and spatial sources of organic carbon contributing DBP precursors to the McKenzie River and allow detection of long-term trends resulting from the recent Holiday Farm Fire, which burned 173,393 acres of forestland, including riparian areas along the main stem, and numerous structures, homes, and outbuildings in September 2020. Future studies could examine DOC fluxes and flushing of carbon from the watershed, investigate the role of precipitation amount and intensity in mobilizing carbon and sediment, and evaluate impacts to aquatic communities and human health as part of a post-fire assessment. Other areas ripe for study include evaluating the impacts of potential temperature increases on carbon sequestration and decomposition in the burned and unburned forests and identifying practices that foster sequestration of carbon in forest soils. The use of fluorescence sensors such as fDOM to monitor the concentration and composition of raw water supplies may be improved for detection of specific DBP precursors, to provide continuous and real-time information to treatment plant operators. Future studies that monitor DOM amount and quality, and DBP Formation Potential (FP), particularly during storm events, paired with streamflow measurements, as suggested above, could help identify areas that contribute high DOC loads and thus help managers identify the key areas to focus restoration activities. Other studies could examine treatment options for currently regulated DBPs and potentially unregulated compounds, including advanced biological treatments for their removal. This study was a collaboration between the U.S. Geological Survey (USGS) and EWEB in Eugene, Oregon, with additional funding provided from USGS Cooperative Matching Funds Program.