Dissolved arsenic concentrations in surface waters within the upper portions of the Klamath River Basin, Oregon and California

Abstract

Arsenic toxicity is an environmental health problem. Levels of arsenic in surface waters at some locations in the Klamath River Basin in southern Oregon and northern California can exceed the U.S. Environmental Protection Agency (EPA) standard for drinking water. There are both anthropogenic and natural sources of arsenic. The Klamath River Basin consists primarily of volcanic deposits and contains an underground geothermal system with hot springs and warm water wells, all known natural sources of arsenic. Anthropogenic sources of arsenic are related to the agricultural use of herbicides, fungicides, and insecticides. Surface water arsenic levels can also be affected by fertilizer amendments, evaporative concentration, oxygen-level depletion, and various geochemical transformations that can increase arsenic mobilization. In this study by the U.S. Geological Survey and the Bureau of Reclamation, dissolved concentrations of arsenic, copper, and lead were measured in surface waters at 39 unique sites within the upper portions of the Klamath River Basin between 2018 and 2022. In every year, except 2022, sites were sampled four times between April and November. Surface-water arsenic concentrations varied up to four-orders of magnitude among sites. Median arsenic concentration was lowest at Cherry Creek (0.03 micrograms per liter [μg/L]) and highest at Wood Kimball Spring (36.7 μg/L), two sites located north of Upper Klamath Lake. The highest arsenic concentrations (17.4±4.9 μg/L, n =3) were found in drain sites (defined here as a waterbody returning used irrigation water) while the lowest arsenic concentrations were found in an artesian well (0.8 μg/L, n =1). The elevated arsenic concentrations of the drain sites suggest that arsenic might be concentrated or mobilized by agricultural activities, water re-use practices, and (or) by geochemical processes occurring around water stored in drains (that is, in the water column and across sediment water boundaries). A source of arsenic in drain water in the Klamath Strait Drain area includes water used for irrigation originating from Ady Canal. Other potential sources include groundwater, geothermal water, and local soils and sediments. Seasonal differences in surface-water arsenic concentrations were detected at 13 sites, 10 of which had higher arsenic concentrations in summer than in either spring or fall. The sites sampled around Upper Klamath Lake, the impounded rivers, one of the two canal sites, and 5 of the 14 river sites had higher surface-water arsenic concentrations in the summer than in either spring or fall. Surface-water arsenic concentrations from groundwater sources (that is, springs and in the artesian well) did not vary significantly among seasons (p-values greater than 0.1). Median surface-water concentrations of copper and lead ranged from 0.03 to 3.7 μg/L, and from 0.013 to 0.175 μg/L ( n =2–18), respectively. Dissolved concentrations of both metals were below acute toxicity endpoints reported by the EPA for freshwater animals. Surface-water arsenic concentrations varied independently from corresponding changes in surface-water lead or copper concentrations. However, arsenic concentrations measured in bed-sediment samples collected from a subset of sites located north of Upper Klamath Lake correlated strongly and significantly with the corresponding sedimentary lead concentrations ( p =0.015). Aqueous arsenic speciation measured in a subset of sites in 2019 and 2022 showed that all the arsenic existed as arsenic (V), the most oxidized arsenic species, and presumably, the least toxic. The highest proportions of arsenite (As(III)), the presumably most toxic arsenic species, relative to total arsenic concentrations were found at drain sites. Our assessment of dissolved arsenic concentrations in various surface-water bodies in the Upper Klamath River Basin reveals geographical areas of consistently low (below 2.1 μg/L), moderate (below 10 μg/L) and high (above 10 μg/L) surface-water arsenic concentrations. South of Upper Klamath Lake, surface-water arsenic concentrations were consistently higher than 20 μg/L at two drain sites located in an area of predominant agricultural land use with extensive water re-use practices. North of Upper Klamath Lake, surface-water arsenic concentrations greater than 20 μg/L were consistently measured at sites with limited nearby agricultural activities, suggesting a geogenic source. The consistently high arsenic levels from the Wood River at Jackson F. Kimball State Park, Fort Creek, and Crooked Creek, which are sites located at or near headwater spring sources, suggest a natural background source of arsenic. Water flowing downstream from this area could be a potential source of arsenic to Upper Klamath Lake and the Upper Klamath River.