Increased Mercury and Reduced Insect Diversity in Linked Stream-Riparian Food Webs Downstream of a Historical Mercury Mine.

Historical mining left a legacy of abandoned mines and waste rock in remote headwaters of major river systems in the western United States. Understanding the influence of these legacy mines on culturally and ecologically important downstream ecosystems is not always straightforward because of elevated natural levels of mineralization in mining-impacted watersheds. To test the ecological effects of historic mining in the headwaters of the upper Salmon River watershed in Idaho (USA), we measured multiple community and chemical endpoints in downstream linked aquatic-terrestrial food webs. Mining inputs impacted downstream food webs through increased mercury accumulation and decreased insect biodiversity. Total mercury (THg) in seston, aquatic insect larvae, adult aquatic insects, riparian spiders, and fish at sites up to 7.6 km downstream of mining was found at much higher concentrations (1.3-11.3-fold) and was isotopically distinct compared with sites immediately upstream of mining inputs. Methylmercury concentrations in bull trout and riparian spiders were sufficiently high (732-918 and 347-1140 ng MeHg g-1 dry wt, respectively) to affect humans, birds, and piscivorous fish. Furthermore, the alpha-diversity of benthic insects was locally depressed by 12%-20% within 4.3-5.7 km downstream from the mine. However, because total insect biomass was not affected by mine inputs, the mass of mercury in benthic insects at a site (i.e., ng Hg m-2 ) was extremely elevated downstream (10-1778-fold) compared with directly upstream of mining inputs. Downstream adult aquatic insect-mediated fluxes of THg were also high (~16 ng THg m-2 day-1 ). Abandoned mines can have ecologically important effects on downstream communities, including reduced biodiversity and increased mercury flux to higher order consumers, including fish, birds, and humans. Environ Toxicol Chem 2022;41:1696-1710. Published 2022. This article is a U.S. Government work and is in the public domain in the USA.

MiniSipper: a new in situ water sampler for high-resolution, long-duration acid mine drainage monitoring.

Abandoned hard-rock mines can be a significant source of acid mine drainage (AMD) and toxic metal pollution to watersheds. In Colorado, USA, abandoned mines are often located in remote, high elevation areas that are snowbound for 7-8 months of the year. The difficulty in accessing these remote sites, especially during winter, creates challenging water sampling problems and major hydrologic and toxic metal loading events are often under sampled. Currently available automated water samplers are not well suited for sampling remote snowbound areas so the U.S. Geological Survey (USGS) has developed a new water sampler, the MiniSipper, to provide long-duration, high-resolution water sampling in remote areas. The MiniSipper is a small, portable sampler that uses gas bubbles to separate up to 250 five milliliter acidified samples in a long tubing coil. The MiniSipper operates for over 8 months unattended in water under snow/ice, reduces field work costs, and greatly increases sampling resolution, especially during inaccessible times. MiniSippers were deployed in support of an U.S. Environmental Protection Agency (EPA) project evaluating acid mine drainage inputs from the Pennsylvania Mine to the Snake River watershed in Summit County, CO, USA. MiniSipper metal results agree within 10% of EPA-USGS hand collected grab sample results. Our high-resolution results reveal very strong correlations (R(2)>0.9) between potentially toxic metals (Cd, Cu, and Zn) and specific conductivity at the Pennsylvania Mine site. The large number of samples collected by the MiniSipper over the entire water year provides a detailed look at the effects of major hydrologic events such as snowmelt runoff and rainstorms on metal loading from the Pennsylvania Mine. MiniSipper results will help guide EPA sampling strategy and remediation efforts in the Snake River watershed.

Climate-change-driven deterioration of water quality in a mineralized watershed.

A unique 30-year streamwater chemistry data set from a mineralized alpine watershed with naturally acidic, metal-rich water displays dissolved concentrations of Zn and other metals of ecological concern increasing by 100-400% (400-2000 µg/L) during low-flow months, when metal concentrations are highest. SO(4) and other major ions show similar increases. A lack of natural or anthropogenic land disturbances in the watershed during the study period suggests that climate change is the underlying cause. Local mean annual and mean summer air temperatures have increased at a rate of 0.2-1.2 °C/decade since the 1980s. Other climatic and hydrologic indices, including stream discharge during low-flow months, do not display statistically significant trends. Consideration of potential specific causal mechanisms driven by rising temperatures suggests that melting of permafrost and falling water tables (from decreased recharge) are probable explanations for the increasing concentrations. The prospect of future widespread increases in dissolved solutes from mineralized watersheds is concerning given likely negative impacts on downstream ecosystems and water resources, and complications created for the establishment of attainable remediation objectives at mine sites.

Measurement of total Zn and Zn isotope ratios by quadrupole ICP-MS for evaluation of Zn uptake in gills of brown trout (Salmo trutta) and rainbow trout (Oncorhynchus mykiss).

This study evaluates the potential use of stable zinc isotopes in toxicity studies measuring zinc uptake by the gills of brown trout (Salmo trutta) and rainbow trout (Oncorhynchus mykiss). The use of stable isotopes in such studies has several advantages over the use of radioisotopes, including cost, ease of handling, elimination of permit requirements, and waste disposal. A pilot study using brown trout was performed to evaluate sample preparation methods and the ability of a quadrupole inductively coupled plasma mass spectrometer (ICP-MS) system to successfully measure changes in the (67)Zn/(66)Zn ratios for planned exposure levels and duration. After completion of the pilot study, a full-scale zinc exposure study using rainbow trout was performed. The results of these studies indicate that there are several factors that affect the precision of the measured (67)Zn/(66)Zn ratios in the sample digests, including variations in sample size, endogenous zinc levels, and zinc uptake rates by individual fish. However, since these factors were incorporated in the calculation of the total zinc accumulated by the gills during the exposures, the data obtained were adequate for their intended use in calculating zinc binding and evaluating the influences of differences in water quality parameters.

An enriched stable-isotope approach to determine the gill-zinc binding properties of juvenile rainbow trout (Oncorhynchus mykiss) during acute zinc exposures in hard and soft waters.

The objective of the present study was to employ an enriched stable-isotope approach to characterize Zn uptake in the gills of rainbow trout (Oncorhynchus mykiss) during acute Zn exposures in hard water (approximately 140 mg/L as CaCO3) and soft water (approximately 30 mg/L as CaCO3). Juvenile rainbow trout were acclimated to the test hardnesses and then exposed for up to 72 h in static exposures to a range of Zn concentrations in hard water (0-1000 microg/L) and soft water (0-250 microg/L). To facilitate detection of new gill Zn from endogenous gill Zn, the exposure media was significantly enriched with 67Zn stable isotope (89.60% vs. 4.1% natural abundance). Additionally, acute Zn toxicity thresholds (96-h median lethal concentration [LC50]) were determined experimentally through traditional, flow-through toxicity tests in hard water (580 microg/L) and soft water (110 microg/L). Following short-term (< or =3 h) exposures, significant differences in gill accumulation of Zn between hard and soft water treatments were observed at the three common concentrations (75, 150, and 250 microg/L), with soft water gills accumulating more Zn than hard water gills. Short-term gill Zn accumulation at hard and soft water LCS0s (45-min median lethal accumulation) was similar (0.27 and 0.20 microg/g wet wt, respectively). Finally, comparison of experimental gill Zn accumulation, with accumulation predicted by the biotic ligand model, demonstrated that model output reflected short-term (<1 h) experimental gill Zn accumulation and predicted observed differences in accumulation between hard and soft water rainbow trout gills. Our results indicate that measurable differences exist in short-term gill Zn accumulation following acclimation and exposure in different water hardnesses and that short-term Zn accumulation appears to be predictive of Zn acute toxicity thresholds (96-h LC50s).

Effects of acid rock drainage on stocked rainbow trout (Oncorhynchus mykiss): an in-situ, caged fish experiment.

In-situ caged rainbow trout (Oncorhynchus mykiss) studies reveal significant fish toxicity and fish stress in a river impacted by headwater acid rock drainage (ARD). Stocked trout survival and aqueous water chemistry were monitored for 10 days at 3 study sites in the Snake River watershed, Colorado, U.S.A. Trout mortality was positively correlated with concentrations of metals calculated to be approaching or exceeding conservative toxicity thresholds (Zn, Mn, Cu, Cd). Significant metal accumulation on the gills of fish stocked at ARD impacted study sites support an association between elevated metals and fish mortality. Observations of feeding behavior and significant differences in fish relative weights between study site and feeding treatment indicate feeding and metals-related fish stress. Together, these results demonstrate the utility of in-situ exposure studies for stream stakeholders in quantifying the relative role of aqueous contaminant exposures in limiting stocked fish survival.

Actinides in deer tissues at the rocky flats environmental technology site.

Limited hunting of deer at the future Rocky Flats National Wildlife Refuge has been proposed in U.S. Fish and Wildlife planning documents as a compatible wildlife-dependent public use. Historically, Rocky Flats site activities resulted in the contamination of surface environmental media with actinides, including isotopes of americium, plutonium, and uranium. In this study, measurements of actinides [Americium-241 (241Am); Plutonium-238 (238Pu); Plutonium-239,240 (239,240Pu); uranium-233,244 (233,234U); uranium-235,236 (235,236U); and uranium-238 (238U)] were completed on select liver, muscle, lung, bone, and kidney tissue samples harvested from resident Rocky Flats deer (N = 26) and control deer (N = 1). In total, only 17 of the more than 450 individual isotopic analyses conducted on Rocky Flats deer tissue samples measured actinide concentrations above method detection limits. Of these 17 detects, only 2 analyses, with analytical uncertainty values added, exceeded threshold values calculated around a 1 x 10(-6) risk level (isotopic americium, 0.01 pCi/g; isotopic plutonium, 0.02 pCi/g; isotopic uranium, 0.2 pCi/g). Subsequent, conservative risk calculations suggest minimal human risk associated with ingestion of these edible deer tissues. The maximum calculated risk level in this study (4.73 x 10(-6)) is at the low end of the U.S. Environmental Protection Agency's acceptable risk range.