Publications

2018

The upper Columbia River and associated valley systems are highly contaminated with metal wastes from nearby smelting operations in Trail, British Columbia, Canada (Teck smelter), and to a lesser extent, Northport, Washington, USA (Le Roi smelter). Previous studies have investigated depositional patterns of airborne emissions from these smelters, and documented the Teck smelter as the primary metal contamination source. However, there is limited research directed at whether these contaminants are bioavailable to aquatic organisms. This study investigates whether smelter derived contaminants are bioavailable to freshwater zooplankton. Trace metal (Zn, Cd, As, Sb, Pb and Hg) concentrations and Pb isotope compositions of zooplankton and sediment were measured in lakes ranging from 17 to 144 km downwind of the Teck smelter. Pb isotopic compositions of historic ores used by both smelters are uniquely less radiogenic than local geologic formations, so when zooplankton assimilate substantial amounts of smelter derived metals their compositions deviate from local baseline compositions toward ore compositions. Sediment metal concentrations and Pb isotope compositions in sediment follow significant (p < 0.001) negative exponential and sigmoidal patterns, respectively, as distance from the Teck smelting operation increases. Zooplankton As, Cd, and Sb contents were related to distance from the Teck smelter (p < 0.05), and zooplankton Pb isotope compositions suggest As, Cd, Sb and Pb from historic and current smelter emissions are biologically available to zooplankton. Zooplankton from lakes within 86 km of the Teck facility display isotopic evidence that legacy ore pollution is biologically available for assimilation. However, without water column data our study is unable to determine if legacy contaminants are remobilized from lake sediments, or erosional pathways from the watershed.
Labaut Y, Betancourt C, iaz-Asencio MD \, Beutel M. Influence of dominant environmental processes in the tropical Cuban basin Hanabanilla and reservoir on sediment composition. Limnetica. 2018;37(2):297–309.
The Hanabanilla reservoir was built in 1960 in the center-south of Cuba and is used for human supply and power generation. This research was aimed at identifying the important processes affecting sediment composition, through the analysis of particle size, and organic carbon (OC), nutrients, and major trace elements concentrations in sediment samples taken at the outlet point of the reservoir. The documentary review allowed us to identify how the nature and management of the basin and the operation of the reservoir affected sediment quality. The application of principal components analysis (PCA), and the determination of ionic relationships and correlations between the sediment quality variables, allowed for the identification of influential processes on sediment quality. Anthropic activities in the period 1960-2012 produced residues rich in OC, total phosphorus (TP) and total nitrogen (TN) that were stored in reservoir sediments. During the first years of the reservoir (1964-1976) the highest concentrations of sediment TP were recorded and the sediments functioned as a sink. The OC and TN mean concentrations were higher in the last stage of the study (2006-2012). The main influential processes on sediment composition were the operation of the reservoir, the geochemical cycle of P, the mineralization of the substances in the water column, and the weathering of silicates and the contribution of organic matter from the basin. Sediment quality data indicate that OC and TN were of allochthonous origin and TP was of autochthonous origin. Levels of sediment OC and TN also corresponded with an increase in anthropic activities in the basin.
A warming climate is expected to lead to stronger thermal stratification, less frequent deep mixing, and greater potential for bottom water anoxia in deep, temperate oligotrophic lakes. As a result, there is growing interest in understanding nutrient cycling at the profundal sediment-water interface of these rare ecosystems. This paper assessed nutrient content and nutrient flux rates from profundal sediment at Lake Tahoe, California/Nevada, USA. Sediment is a large reservoir of nutrients, with the upper 5 cm containing reduced nitrogen (6,300 metric tons) and redox-sensitive phosphorus (710 metric tons) equivalent to 15 times the annual external load. Experimental results indicate that if deep water in Lake Tahoe goes anoxic, profundal sediment will release appreciable amounts of phosphate (0.13–0.29 mg P/ m2 d), ammonia (0.49 mg N/m2 d), and iron to overlaying water. Assuming a 10 year duration of bottom water anoxia followed by a deep-water mixing event, water column phosphate, and ammonia concentrations would increase by an estimated 1.6 mg P/L and 2.9 mg N/L, nearly doubling ambient concentrations. Based on historic nutrient enrichment assays this could lead to a 40% increase in algal growth. Iron release could have the dual effect of alleviating nitrate limitation on algal growth while promoting the formation of fine iron oxyhydroxide particles that degrade water clarity. If the depth and frequency of lake mixing decrease in the future as hydrodynamic models suggest, large-scale in-lake management strategies that impede internal nutrient loading in Lake Tahoe, such as bottom water oxygen addition or aluminum salt addition, may need to be considered.

2017

Beutel M, Duvil R, Cubas F, Grizzard T. Effects of nitrate addition on water column methylmercury in Occoquan Reservoir, Virginia, USA. Water Research. 2017;110:288–296.
Mercury bioaccumulation in aquatic biota poses a widespread threat to human and environmental health. Methylmercury (MeHg), the toxic form of mercury, tends to build up under anaerobic conditions in the profundal zones of lakes. In this study we performed a two-year assessment of spatial and temporal patterns of dissolved oxygen, nitrate, MeHg, manganese (Mn) and iron (Fe) in Occoquan Reservoir, a large run-of-the-river drinking water reservoir in Virginia, USA. A tributary to the reservoir receives input of nitrate-rich tertiary-treated wastewater that enhances the oxidant capacity of bottom water. Multiple lines of evidence supported the hypothesis that the presences of nitrate and/or oxygen in bottom water correlated with low MeHg in bottom water. Bottom water MeHg was significantly lower in a nitrate-rich tributary (annual mean of 0.05 ng/L in both 2012 and 2013) compared to a nitrate-poor tributary (annual mean of 0.58 ng/L in 2012 and 0.21 ng/L in 2013). The presence of nitrate and oxygen in bottom water corresponded with significantly lower bottom water MeHg at an upstream station in the main reservoir (0.05 versus 0.11 ng/L in 2013). In 2012 the reservoir exhibited a longitudinal gradient with nitrate and oxygen decreasing and MeHg and Mn increasing downstream. In both study years, there was a clear threshold of oxygen equivalent (3e5 mg/L), a metric that combines the oxidant capacity of nitrate and oxygen, above which MeHg (<0.05 ng/L), Mn (<0.3 mg/L) and Fe (<0.5 mg/L) were low. Results indicated that the addition of nitrate-rich tertiary-treated wastewater to the bottom of anaerobic reservoirs can reduce MeHg concentrations, and potentially decrease mercury bioaccumulation, while increasing the safe water yield for potable use.
Williams J, Chung S, Johansen A, Lamb B, Vaughan J, Beutel M. Evaluation of atmospheric nitrogen deposition model performance in the context of US critical load assessments. Atmospheric Environment. 2017;150:244–255.
Air quality models are widely used to estimate pollutant deposition rates and thereby calculate critical loads and critical load exceedances (model deposition > critical load). However, model operational performance is not always quantified specifically to inform these applications. We developed a performance assessment approach designed to inform critical load and exceedance calculations, and applied it to the Pacific Northwest region of the U.S. We quantified wet inorganic N deposition performance of several widely-used air quality models, including five different Community Multiscale Air Quality Model (CMAQ) simulations, the Tdep model, and ‘PRISM x NTN’ model. Modeled wet inorganic N deposition estimates were compared to wet inorganic N deposition measurements at 16 National Trends Network (NTN) monitoring sites, and to annual bulk inorganic N deposition measurements at Mount Rainier National Park. Model bias (model e observed) and error (jmodel e observedj) were expressed as a percentage of regional critical load values for diatoms and lichens. This novel approach demonstrated that wet inorganic N deposition bias in the Pacific Northwest approached or exceeded 100% of regional diatom and lichen critical load values at several individual monitoring sites, and approached or exceeded 50% of critical loads when averaged regionally. Even models that adjusted deposition estimates based on deposition measurements to reduce bias or that spatially-interpolated measurement data, had bias that approached or exceeded critical loads at some locations. While wet inorganic N deposition model bias is only one source of uncertainty that can affect critical load and exceedance calculations, results demonstrate expressing bias as a percentage of critical loads at a spatial scale consistent with calculations may be a useful exercise for those performing calculations. It may help decide if model performance is adequate for a particular calculation, help assess confidence in calculation results, and highlight cases where a non-deterministic approach may be needed.

2016

Chiarantini L, , Benvenuti M, Beutel M, Costagliola P. Black pine (Pinus nigra) barks as biomonitors of airborne mercury pollution. Science of the Total Environment. 2016;569:105–113.
Tree barks are relevant interfaces between plants and the external environment, and can effectively retain airborne particles and elements at their surface. In this paper we have studied the distribution of mercury (Hg) in soils and in black pine (Pinus nigra) barks from the Mt. Amiata Hg district in southern Tuscany (Italy), where past Hg mining and present-day geothermal power plants affect local atmospheric Hg concentration, posing serious environmental concerns. Barks collected in heavily Hg-polluted areas of the district display the highest Hg concentration ever reported in literature (8.6 mg/kg). In comparison, barks of the same species collected in local reference areas and near geothermal power plants show much lower (range 19–803 μg/kg) concentrations; even lower concentrations are observed at a “blank” site near the city of Florence (5–98 μg/kg). Results show a general decrease of Hg concentration from bark surface inwards, in accordance with a deposition of airborne Hg, with minor contribution from systemic uptake from soils. Preliminary results indicate that bark Hg concentrations are comparable with values reported for lichens in the same areas, suggesting that tree barks may represent an additional useful tool for biomonitoring of airborne Hg.
Chiarantini L, Benvenuti M, Beutel M, Costagliola P, Covelli S, Gabbani G. Mercury and arsenic in stream sediments and surface waters of the Orcia River Basin, southern Tuscany, Italy. Water, Air & Soil Pollution. 2016;227(11):408.
The Orcia River basin lies north of the Mt. Amiata mining district and may receive potentially harmful/toxic elements such as mercury (Hg) and arsenic (As) therefrom. The Orcia River eventually flows to the Ombrone River, which in turn flows to the Tyrrhenian Sea. The analysis of stream sediments collected in the Orcia River and its main tributaries, as well as in the Ombrone River, indicates moderate concentrations of both Hg and As (median values, Hg 118 μg/kg and As 5.25 mg/kg), rarely exceeding Italian environmental quality standards. Exceptionally high values for both elements are observed only in close proximity to the former Pietrineri Hg mine (Hg 195 mg/kg and As 35 mg/kg). Travertine and unconsolidated deposits associated with thermal springs in the area generally exhibit low Hg concentrations (4–320 μg/kg), with a significant exception of 23 mg/kg at Bagni San Filippo. Arsenic concentration in the same deposits is more variable with a peak level of 358 mg/kg. Surface waters collected at the same sites as stream sediments show Hg and As concentrations below the Italian mandatory limits for drinking waters (1 μg/L for Hg and 10 μg/L for As). Likewise, in thermal springs, Hg concentrations are low, whereas As concentrations are relatively high (up to 23.4 μg/L), which is in agreement with previous studies. At present, the input of toxic elements from the mining district into the Orcia and Ombrone watersheds is lower than inputs documented in the Paglia and Tiber catchments south of Mt. Amiata and does not pose an immediate environmental threat. However, the possible remobilization of Hg-contaminated sediments during flash flood events cannot be dismissed.
Beutel M, Duvil R, Cubas F, Matthews D, Wilhelm F, Grizzard T. A review of managed nitrate addition to enhance surface water quality. Critical Reviews in Environmental Science and Technology. 2016;46(7):673–700.
Nitrate is a significant water pollutant with potential environmental impacts ranging from eutrophication to health risks to infants. But under certain circumstances nitrate may enhance water quality through a number of mechanisms, including enhancing oxidant capacity, regulation of redox potential, and suppression of nitrogen-fixing cyanobacteria. In this review the authors explore a range of case studies in which nitrate addition enhanced surface water quality including: purposeful addition of nitrate salts to lakes to repress internal phosphorus (P) loading, enhance organic matter oxidation, or impede bottom-water accumulation of methylmercury; purposeful and incidental addition of nitrate from point and nonpoint discharges to reservoirs and lakes; nitrogen (N) addition to lakes to affect phytoplankton and zooplankton composition; and nitrate addition to estuary sediment to repress hydrogen sulfide production. Nitrate addition decreased internal P and methylmercury loading, repressed sulfide production, and enhanced surface water quality by lowering total P, chlorophyll content, and phytoplankton dominance by cyanobacteria. No case study reported a worsening of eutrophic conditions due to nitrate addition, and a number of studies reported near complete loss of nitrate from the systems to which it was added. When purposely adding nitrate to anoxic surface waters, protocols should be used to maximize nitrate loss via biological denitrification but minimize enhancement of phytoplankton productivity. These protocols should include adding nitrate close to the sediment-water interface to promote nitrate loss via denitrification, managing the timing and magnitude of nitrate addition so that nitrate is depleted prior lake overturn in the fall, and not adding nitrate to N-limited systems. Elimination of existing N discharges to receiving waters should be implemented on a case-by-case basis with the awareness that nitrate in discharges may enhance surface water quality, particularly by suppressing internal P loading and associated phytoplankton productivity. In addition, managers and regulators should look to couple existing nitrate discharges with hypoxic water bodies in an effort to sustainably enhance water quality while removing nitrate from aquatic ecosystems via biological denitrification.
Williams J, Beutel M, Nurse A, Moore B, Hampton S, Saros J. Phytoplankton responses to nitrogen enrichment in Pacific Northwest, USA Mountain Lakes. Hydrobiologia. 2016;776(1):261–276.
Limited information is available about threshold lake nitrogen concentrations necessary to stimulate phytoplankton species and biomass responses in remote nitrogen-limited mountain lakes. We conducted in situ enrichment bioassays in mountain lakes within Mount Rainier, North Cascades, and Olympic National Parks in Washington State, USA to characterize phytoplankton species and biomass responses to nitrogen enrichment, and associated dissolved inorganic nitrogen (DIN) concentration thresholds. Based on biomass and growth measurements, phytoplankton were nitrogen-limited or colimited by nitrogen and phosphorus in the nine bioassay lakes. We identified 20 taxa that responded to nitrogen enrichment, and estimated response thresholds using nitrogen Monod half-saturation constants (Ks) for 18 of these taxa. DIN thresholds in nitrogen-limited lakes were 13 lgNl-1 for any increase in chlorophyll a, and 25 lgNl-1 , for an increase beyond typical inter-annual chlorophyll a variation. Ks values ranged from 0.02 to 77 lg N l -1 across most N-responsive taxa, and diatom Ks values were higher than those previously quantified in U.S. Rocky Mountain lakes. Approximately, 75% of sampled mountain lakes in the parks have summer dissolved inorganic nitrogen concentrations below biomass response thresholds. This finding suggests that phytoplankton in park mountain lakes are likely sensitive to future deposition-induced lake nitrogen enrichment.
Surface water reservoirs trap inorganic mercury delivered from their watersheds, create conditions that convert inorganic mercury to highly toxic methylmercury (MeHg), and host sportfish in which MeHg bioaccumulates. The Santa Clara Valley Water District (District) actively manages and monitors four mercury-impaired reservoirs that help to serve communities in South San Francisco Bay, California. The Guadalupe River watershed, which contains three of those reservoirs, also includes the New Almaden mercury-mining district, the largest historic mercury producer in North America. Monthly vertical profiles of field measurements and grab samples in years 2011–2013 portray annual cycling of density stratification, dissolved oxygen (DO), and MeHg. Monitoring results highlight the role that hypolimnetic hypoxia plays in MeHg distribution in the water column, as well as the consistent, tight coupling between MeHg in ecological compartments (water, zooplankton, and bass) across the four reservoirs. Following the 2011–2013 monitoring period, the District designed and installed hypolimnetic oxygenation systems (HOS) in the four reservoirs in an effort to repress MeHg buildup in bottom waters and attain regulatory targets for MeHg in water and fish tissue. Initial HOS operation in Calero Reservoir in 2014 enhanced bottom water DO and depressed hypolimnetic buildup of MeHg, but did not substantially decrease mercury levels in zooplankton or small fish.