Biological Assessment of Existing TMDL Stream (Contract 2005-TMDL4) Status Report

Transcription

1 Biological Assessment of Existing TMDL Stream (Contract 2005-TMDL4) Status Report Covering activities from July to November 2005 Prepared by Donald G. Huggins Niang C. Lim Central Plains Center for BioAssessment Kansas Biological Survey University of Kansas for Kansas Department of Health and Environment November 2005

2 Introduction Selenium was the only trace constituent associated with irrigation drainage that was observed to be at elevated levels in water, bottom sediment, and biota within the Upper Arkansas River basin (Mueller et al. 1991). Selenium is usually associated with the clay content in rocks and so high concentration of selenium is often found in shales. Cretaceous marine shales and limestone are exposed extensively in that region. Thus, the main natural selenium source is runoff from the shales. Selenium becomes concentrated along the Arkansas River due to evapotranspiration and leaching of selenium by irrigation (Whitmer 2000). The main goal of this project is to determine the degree of selenium impairment in the Upper Arkansas River. The study area extends from Garden City, Kansas, to the Colorado state line. The selenium levels in water, bottom sediment, and biota along the Arkansas River within Finney, Kearny, and Hamilton counties are to be assessed. This report aims to summarize field activities of the Arkansas River conducted in late summer Water-quality data and preliminary correlations of selenium levels among the three media at three selected sampling locations along the Arkansas River were presented. Raw data were attached to this report as a separate spreadsheet. Study Approach It has been known that much of the water that enters Kansas from Colorado is lost due to infiltration through the streambed, diversion for irrigation, and evapotranspiration. During our first visit to the Arkansas River on September 6 and 7, Arkansas River near Garden City and Deerfield were observed to be dry. Thus, no water samples could be collected from the Arkansas River within the Finney County. Arkansas River near Lakin was the first site observed to have water flow as we traveled westward and upstream from Garden City to the Colorado state line, i.e., from sites near Lakin, Kendall, Syracuse, and to Coolidge. Water samples were collected at Arkansas River near Lakin, Kendall, and Coolidge (Figure 1). Water sample was not collected at Syracuse site to avoid data redundancy (Kendall, Syracuse, and Coolidge are all in Hamilton County). Dissolved oxygen (DO), temperature, specific conductance, salinity, ph, and turbidity were measured in situ using a Horiba U-10 Water Quality Checker. Two 1-liter grab samples were taken at each site. One bottle was preserved with 5 ml of nitric acid for selenium analysis and the other one was for nutrient and chlorophyll a analyses. Five periphyton samples were taken at each site. All periphyton samples were taken from sand, the dominant substrate of the Arkansas River. Sediment samples were randomly collected from four to five spots within 50 m upstream and downstream from the bridge at each of the sites. The sediment samples were mixed with a spoon in a baking pan and were stored in 8 oz glass jars. Fish were collected using the electrofishing technique. We electroshocked approximate 100 m upstream and downstream from the bridge. Collected fish were put in a bucket and fish of less than 2 inches were released to the river. Fish samples were identified and were then individually wrapped in aluminum foil and stored in Ziploc bags. Water, sediment, and fish samples were transported on ice in coolers to Kansas Biological Survey (KBS) Ecotoxicology Laboratory for analyses. Sample handling procedures and analytical methods of water-quality parameters measured in this study were summarized in Table 1. 1

3 Results and Discussion Selenium in water, fish, and sediment Freshwater usually has background selenium concentration of µg/l (DOI 1998). Nevertheless, selenium levels in Arkansas River near Lakin, Kendall, and Coolidge were approximately 5 µg/l, the chronic selenium aquatic life criterion that is currently revised by the Environmental Protection Agency (EPA). Due to the bioaccumulative properties of selenium, the proposed draft chronic criterion is expressed as selenium concentration in fish tissue rather than concentration in water because fish tissue samples provide a better indicator of the presence of selenium in a particular waterbody. Fish move throughout a waterbody and contaminants such as selenium can be absorbed into their tissue. Thus, fish tissue effectively reflects the level and duration of a particular contaminant in a waterbody over time. Most fish species have whole-body selenium concentrations of less than 4 µg/g (DOI 1998). The revised draft proposes that if selenium in whole-body fish tissue samples exceed 5.85 µg/g dry weight (dw) during summer or fall, fish should be monitored during winter to determine if selenium exceeds 7.91 µg/g dw. Twenty-three fish were collected during the late-summer sampling trip. Collected fish species included carp, catfish, stoneroller, plains killifish, gizzard shad, green sunfish, and mosquitofish. Carp was the only common species captured at all three sites. EPA Method (EPA 1991) was used to determine the selenium concentration in fish tissue. A maximum of 5 g of frozen tissue sample was used in the acid and hydrogen peroxide digestion process. Fish that were too small (< 2 g) could not be dissected properly and thus the whole-body digestion was performed. Dry weight determination could not be performed for these small fish as there was not enough aliquot of fish tissue sample to properly perform this analysis. A plains killifish (weight 2.5 g and length 2.5 in) that was captured at Lakin site had the highest selenium level (9.0 µg/g dw) whereas a carp (weight 25.7 g and length 4.5 in) that was found at Coolidge site had the lowest selenium level (1.2 µg/g dw). Three out of fourteen fish (that had dry weight basis) exceeded 5.85 µg/g dw. Those three fish species were plains killifish (9.0 µg/g dw; Lakin site), stoneroller (7.7 µg/g dw; Kendall site), and carp (7.8 µg/g dw; Coolidge site). The selenium levels in carp at all three sites ranged from 1.2 to 7.8 µg/g dw with a median of 3.2 µg/g dw. However, both the highest (7.8 µg/g dw) and the lowest (1.2 µg/g dw) selenium concentration in carp were observed at the Coolidge site. Figure 2 shows the distribution of selenium levels in tissue of all collected fish species at the three sites. Since selenium levels in water at all three sites were similar, a plot of fish weight (all fish species) vs. total selenium in fish tissue was created (Figure 3) and its relationship is significant (R 2 = , p < 0.05). In other words, the larger the fish, the larger amount of total selenium in fish tissue (Note: The relationship remains significant (R 2 = , p < 0.05) when the single outlying highend data point is ignored). Soil rarely has selenium concentration exceeds 2 mg/kg dw. Selenium concentration in sediment greater than 4 mg/kg dw is a concern because there is a potential for bioaccumulation in fish and wildlife (Lemly and Smith 1987). The baseline selenium concentration in soil of the western United States is 0.23 mg/kg (Whitmer 2000). Lakin, Kendall, and Coolidge sites had sediment selenium concentrations of 0.27, 2

4 0.33, and 0.61 mg/kg dw, respectively, indicating that the accumulation of selenium in sediment is not significant within the study area. The potential reason is that sand is the main substrate of the bottom sediment of Arkansas River and yet selenium is usually associated with the clay content in sediment. Thus, the selenium level in sediment within the study area is not likely to impose potential significant risk to aquatic life. Salinity and nitrate The Arkansas River is one of the most saline rivers in the United States. The main concern is the contamination of ground water in the alluvial and High Plains aquifers by saline water of the Arkansas River that enters Kansas from Colorado. Based upon the United States Geological Survey (USGS) data, for the period, the specific conductance of the Arkansas River near Coolidge ranged from 1.54 to 6.01 ms/cm (Whittemore 2000). During our field sampling, the measured specific conductance of the Arkansas River near Coolidge, Kendall, and Lakin were 4.23, 3.62, and 3.87 ms/cm, respectively. In addition to the salinity problem, another ground water problem within the study area is the increasing nitrate (NO 3 ) concentrations. Nevertheless, according to the study conducted by Whittemore (2000) from 1995 to 2000, the increasing nitrate concentrations in the alluvial aquifer do not appear to be mainly from infiltration of Arkansas River water because the river nitrate concentrations were generally lower than the ground-water concentrations. Nitrate concentrations in the Arkansas River usually ranged from 1-3 mg/l (Whittemore 2000). In this study, Kendall site had 1.6 mg/l NO 3 -N whereas Lakin and Coolidge sites had 0.8 and 0.7 mg/l NO 3 -N, respectively. Other Physical and Chemical Properties The Arkansas River was under low-flow conditions during our site visit as September 2005 had the lowest monthly discharge since October 2004 based upon USGS data (Table 2). On September 7, 2005, the average discharge at Coolidge and Kendall sites were 14 and 26 cfs, respectively (There is no USGS gaging station at Arkansas River near Lakin). The river water was clear and the average turbidity of the three sites was 14 ± 3 NTU. DO concentrations were 9.52, 8.59, and 8.22 mg/l at Coolidge, Kendall, and Lakin sites, respectively. Total phosphorus concentrations ranged from 5.6 to 17.4 µg/l at all three sites. The average chlorophyll a concentration of the three sites was 6.6 ± 0.4 µg/l. Conclusions The Arkansas River water remains saline. Based upon the past selenium chronic criteria for aquatic life, the selenium level in water is a concern. Selenium concentrations in water were similar at Coolidge, Kendall, and Lakin sites. Despite fish species, the larger the fish, the larger the total amount of selenium in fish tissue. At this point, there is no trend as to whether selenium level in fish tends to be higher in upstream than in downstream of the Arkansas River. Perhaps a better correlation can be established when more fish data are gathered in early winter (December 2005) and in mid-spring (April 2006). The selenium concentration in sediment was relatively insignificant compared to selenium levels in water and fish tissue. 3

5 Literature Cited Clesceri, L. S., A. E. Greenberg and A. D. Eaton Standard methods for the examination of water and wastewater, 20 th Ed. American Public Health Association, American Water Works Association, and Water Environment Federation. Washington, D.C. Ebina, J. T., Tsuyoshi and T. Shirai Simultaneous determination of total nitrogen and total phosphorus in water using peroxodisulfate oxidation. Water Research 17: EPA Methods for the determination of metals in environmental samples. EPA- 600/ Office of research and development. Washington D.C. 293 pp. Lemly, A. D. and G. J. Smith Aquatic cycling of selenium: implications for fish and wildlife. Fish and Wildlife Service, United States Department of the Interior. Fish and Wildlife Leaflet pp. Mueller, D. K., L. R. DeWeese, A. J. Garner and T. B. Spruill Reconnaissance investigation of water quality, bottom sediment, and biota associated with irrigation drainage in the middle Arkansas River basin, Colorado and Kansas, USGS Water Resources Investigation Report pp. United States Department of the Interior (DOI) Guidelines for interpretation of the biological effects of selected constituents in biota, water, and sediment: selenium. National Irrigation Water Quality Program Information Report No pp. Whitmer, J. M Fate and transport of selenium and uranium in the upper Arkansas River valley of southwestern Kansas. Thesis. University of Kansas. 218 pp. Whittemore, D. O Water quality of the Arkansas River in Southwest Kansas. A report to the Kansas Water Office. Kansas Geological Survey Open-File Report

6 Figure 1 Sampling sites of Arkansas River in this study. 5

7 10.0 Selenium in Fish Tissue (µg/g dw) Coolidge Kendall Lakin Figure 2 Box plot of selenium levels in fish tissue samples for all collected fish species at Coolidge (n = 3), Kendall (n = 5), and Lakin (n = 6) sites. Figure 3 Fish weight vs. total selenium in tissue of all collected fish species in this study. 6

8 Table 1 Sample handling procedures and analytical methods of water-quality parameters measured in this study Parameter Container Instrument/Method Method Citation Detection Limit Laboratory Analyses Total Phosphorus 1L Amber Glass 250 o F and 15 psi, Lachat QuikChem 8500* Ebina et al µg/l Orthophosphate-P 1L Amber Glass Lachat QuikChem 8500* 4500-P 1 µg/l Total Nitrogen 1L Amber Glass 250 o F and 15 psi, Lachat QuikChem 8500* Holding Time Preservation 5 days 4 o C 48 hrs 4 o C Ebina et al mg/l 5 days 4 o C Ammonia-N 1L Amber Glass Lachat QuikChem 8500* 4500NH 3 1 µg/l 24 hrs 4 o C Nitrate-N 1L Amber Glass Lachat QuikChem 8500* 4500NO mg/l 48 hrs 4 o C Nitrite-N 1L Amber Glass Lachat QuikChem 8500* 4500NO mg/l 48 hrs 4 o C Chlorophyll a 1L Amber Glass Optical Tech. Devices, Ratio-2 System Filter Fluorometer H 1.0 µg/l 30 days 4 o C Selenium in Water 1L Amber Glass Perkin-Elmer Atomic Absorption (AA) ph < 2 with EPA Method µg/l 180 days Spectrophotometer Model 5100 HNO 3,4 o C Selenium in Perkin-Elmer Atomic Absorption (AA) 8 oz Glass Jar EPA Method 3050B Sediment Spectrophotometer Model days 4 o C Selenium in Fish Perkin-Elmer Atomic Absorption (AA) Aluminum foil EPA Method Tissue Spectrophotometer Model < 0 o C In situ Measurements ph NA Horiba U-10 Water Quality Checker 4500-H NA NA Conductivity NA Horiba U-10 Water Quality Checker DO NA Horiba U-10 Water Quality Checker Turbidity NA Horiba U-10 Water Quality Checker Water/Air Temp. NA Horiba U-10 Water Quality Checker * Flow injection analyzer NA = not applicable 2510 A-B 4500-O G 2130-B 2550-B 0.01 ms/cm NA NA 0.1 mg/l NA NA 1 NTU NA NA 0.1 o C NA NA 7

9 Table 2 Monthly discharge of Arkansas River near Coolidge and Kendall during water year 2005 (USGS data) Month Arkansas River near Coolidge Discharge (cfs) Arkansas River near Kendall October November December January February March April May June July August September