Laboratory and Field-Based Assessment of the Effects of Sediment Capping Materials on Zinc Flux, Bioavailability, and Toxicity.

A former mining site has been the subject of extensive remediation and restoration, with a significant focus on disconnecting mine spoils from groundwater and managing the quantity and quality of runoff. A remaining task is ensuring concentrations of zinc (Zn) in the stream outflow of a pit lake are reduced below water quality standards. The efficacy of multiple capping materials for decreasing Zn dissolution from sediments was conducted under natural and reasonable worst-case conditions (pH = 5.5). Capping materials included AquaBlok™, limestone, and limestone-bone char. Field exposures were conducted in limnocorrals that isolated overlying water columns above the sediment and capping treatments. Simultaneous in situ and ex situ toxicity tests were conducted using Daphnia magna, Hyalella azteca, and Chironomus dilutus. In situ caged organisms were protected from temperature shock (warm epilimnetic waters) by deploying within a Toxicity Assessment Container System (TACS). Organisms were exposed to surficial sediments, caps, and hypolimnetic overlying waters for 4 d. Ex situ testing was conducted in core tube mesocosms containing sediments and caps at similar temperatures (15-19 °C). Results demonstrated the usefulness of TACS deployment in stratified lake systems. There were no differences in responses between treatments involving sediment capping materials in both in situ and ex situ tests. The lack of differences was likely due to dissolved Zn in surface water being below the hardness-adjusted threshold effects levels (164 µg L-1 ). This field- and laboratory-based weight-of-evidence study provided site-specific data to support the selection of an effective remedy, with reduced uncertainty compared to laboratory and chemistry-only approaches. Environ Toxicol Chem 2019;39:240-249. © 2019 SETAC.

Biogeochemical controls on the speciation and aquatic toxicity of vanadium and other metals in sediments from a river reservoir.

Effects of hydrologic variability on reservoir biogeochemistry are relatively unknown, particularly for less studied metals like vanadium (V). Further, few studies have investigated the fate and effects of sediment-associated V to aquatic organisms in hydrologically variable systems. Our primary objective was to assess effects of hydrologic manipulation on speciation and toxicity of V (range: 635 to 1620mgkg-1) and other metals to Hyalella azteca and Daphnia magna. Sediments were collected from a reservoir located in a former mining area and microcosm experiments were conducted to emulate 7-day drying and inundation periods. Despite high sediment concentrations, V bioavailability remained low with no significant effects to organism survival, growth, or reproduction. The lack of V toxicity was attributed to reduced speciation (III, IV), non-labile complexation, and sorption to Al/Fe/Mn-oxyhydroxides. Zinc (Zn) increased in surface and porewater with inundation, for some sediments exceeding the U.S. EPA threshold for chronic toxicity. While no effects of Zn to organism survival or growth were observed, Zn body concentrations were negatively correlated with H. azteca growth. Results from this study indicate that V bioavailability and environmental risk is dependent on V-speciation, and V is less influenced by hydrologic variability than more labile metals such as Zn.

Sediment Zn-release during post-drought re-flooding: Assessing environmental risk to Hyalella azteca and Daphnia magna.

Hydrologic variability exacerbated by climate change affects biogeochemical cycling in sediments through changes in pH, redox, and microbial activity. These alterations affect the lability and speciation of metals, such that toxicity may be observed in otherwise non-toxic sediments. In this study, we investigate the effects of drought and reflooding on metal bioavailability in sediments with low to moderate concentrations of Zn (18-270 mg kg-1). Sediments were collected from coastal wetlands in Michigan, dried (36-days) and re-inundated in lab microcosms. We investigated the relationships between key parameters, for surface/porewater (dissolved and particulate metals, dissolved oxygen, redox (Eh), reduced iron, and temperature) and sediment (simultaneously extracted metals (SEM), acid volatile sulfide (AVS), Fe/Mn-oxyhydroxide, organic carbon, water content analyses, and diffusive gradient in thin films (DGTs) metal concentrations). Porewater Zn increased with inundation of dried sediments for all sediment types, exceeding United States Environmental Protection Agency (U.S. EPA) chronic criteria for freshwater organisms, and decreased as sediments became reduced. Effects on Hyalella azteca (7-day exposure) and Daphnia magna (10-day exposure) were quantified. Results show decreased growth of H. azteca for sites with elevated Zn and increased Zn-body concentration (BCZn) in the most contaminated sediment type. Further, BCZn was negatively correlated with H. azteca growth. D. magna survival, growth, and reproduction were not affected. DGT metal concentrations were more reflective of porewater than organism bioaccumulation. Outcomes of predictive toxicology methods are compared to toxicity test results and suggestions are provided for model improvements. This study demonstrates that post-drought re-flooding of sediments affects Zn biogeochemical cycling with potentially adverse effects on benthic organisms, even in sediments with only moderately elevated concentrations (>150 mg kg-1).

Indirect effects of climate change on zinc cycling in sediments: The role of changing water levels.

Increased variability in lake and river water levels associated with changing climate could impact the fate and effects of metals in redox-sensitive sediments through the alteration of microbial communities and of acid-base and redox chemistry. The objective of the present study was to determine the influence of water level fluctuation on metal speciation in porewater and predict environmental risk to high-carbonate systems. Using experimental microcosms with sediments collected from 4 metal-contaminated coastal freshwater wetlands in Michigan, USA, we conducted water level fluctuation experiments. Porewater and sediment metals (Ca, Cu, Fe, Mg, Mn, Ni, Zn) and important metal binding phases (iron-oxide speciation, acid-volatile sulfide) were quantified. In a short-term drying (seiche) experiment, there were decreases in all porewater metals after inundation of saturated sediments. During a drought experiment, re-inundation of oxidized sediments increased porewater Cu, Zn, Mg, Ca for most sites. Porewater Zn increased after inundation to levels exceeding the US Environmental Protection Agency threshold for chronic toxicity. These data show that the dissolution of metal carbonates and metal sulfates contributes to metal release after re-flooding and indicate that we might expect increased ecological risk to organisms present in drought-sensitive regions where altered hydroperiods are likely to increase metal bioavailability. Environ Toxicol Chem 2017;36:2456-2464. © 2017 SETAC.