Phase partitioning of mercury, arsenic, selenium, and cadmium in Chlamydomonas reinhardtii and Arthrospira maxima microcosms.

As the global human population increases, demand for protein will surpass our current production ability without an increase in land use or intensification. Microalgae cultivation offers a high yield of protein, and utilization of wastewater from municipal or agricultural sources in place of freshwater for microalgae aquaculture may increase the sustainability of this practice. However, wastewater from municipal and agricultural sources may contain contaminants, such as mercury (Hg), cadmium (Cd), selenium (Se), and arsenic (As). Association of these elements with algal biomass may present an exposure risk to product consumers, while volatilization may present an exposure hazard to industry workers. Thus, the partitioning of these elements should be evaluated before wastewater can be confidently used in an aquaculture setting. This study explored the potential for exposure associated with Arthrospira maxima and Chlamydomonas reinhardtii aquaculture in medium contaminated with 0.33 µg Hg L-1, 60 µg As L-1, 554 µg Se L-1, and 30 µg Cd L-1. Gaseous effluent from microalgae aquaculture was analyzed for Hg, As, Se, and Cd to quantify volatilization. A mass balance approach was used to describe the partitioning of elements between the biomass, medium, and gas phases at the end of exponential growth. Contaminants were recovered predominantly in medium and biomass, regardless of microalgae strain. In the case of Hg, 48 ± 2% was associated with A. maxima biomass and 55 ± 8% with C. reinhardtii when Hg was present as the only contaminant, but this increased to 85 ± 11% in C. reinhardtii biomass when As, Se, and Cd were also present. A small and highly variable abiotic volatilization of Hg was observed in the gas phase of both A. maxima and C. reinhardtii cultures. Evidence presented herein suggests that utilizing wastewater containing Hg, Cd, Se, and As for microalgae cultivation may present health hazards to consumers.

Atmospheric reactive mercury concentrations in coastal Australia and the Southern Ocean.

Mercury (Hg), especially reactive Hg (RM), data from the Southern Hemisphere (SH) are limited. In this study, long-term measurements of both gaseous elemental Hg (GEM) and RM were made at two ground-based monitoring locations in Australia, the Cape Grim Baseline Air Pollution Station (CGBAPS) in Tasmania, and the Macquarie University Automatic Weather Station (MQAWS) in Sydney, New South Wales. Measurements were also made on board the Australian RV Investigator (RVI) during an ocean research voyage to the East Antarctic coast. GEM was measured using the standard Tekran® 2537 series analytical platform, and RM was measured using cation exchange membranes (CEM) in a filter-based sampling method. Overall mean RM concentrations at CGBAPS and MQAWS were 15.9 ± 6.7 pg m-3 and 17.8 ± 6.6 pg m-3, respectively. For the 10-week austral summer period on RVI, mean RM was 23.5 ± 6.7 pg m-3. RM concentrations at CGBAPS were seasonally invariable, while those at MQAWS were significantly different between summer and winter due to seasonal changes in synoptic wind patterns. During the RVI voyage, RM concentrations were relatively enhanced along the Antarctic coast (up to 30 pg m-3) and GEM concentrations were variable (0.2 to 0.9 ng m-3), suggesting periods of enrichment and depletion. Both RM and GEM concentrations were relatively lower while transiting the Southern Ocean farther north of Antarctica. RM concentrations measured in this study were higher in comparison to most other reported measurements of RM in the global marine boundary layer (MBL), especially for remote SH locations. As observations of GEM and RM concentrations inform global ocean-atmosphere model simulations of the atmospheric Hg budget, our results have important implications for understanding of total atmospheric Hg (TAM).

An innovative approach to bioremediation of mercury contaminated soils from industrial mining operations.

Soils contaminated with mercury (Hg) have proved expensive and logistically difficult to remediate. Research continues into finding suitable environmentally-friendly and efficient ways of achieving this end. Bioremediation is an option, which employs the strategies microorganisms have evolved to deal with Hg. One microbial strategy involves uptake and intracellular volatilisation of mercuric ions, which passively diffuse from the cell and back into the atmosphere. In this work, Pseudomonas veronii cells grown to stationary phase were immobilised in a xanthan gum-based biopolymer via encapsulation. The P. veronii-biopolymer mix was then coated onto natural zeolite granules. Zeolite immobilised cells remained viable for at least 16 weeks stored under ambient room temperature. Furthermore, the immobilised cells were shown to retain both viability and Hg volatilisation functionality after transportation from Australia to the USA, where they were applied to Hg contaminated soil. Maximum flux rates exceeded 10 µg Hg m2 h-1 from mine tailings (≈7 mg kg-1 Hg with 50% v/v water). This was 4 orders of magnitude above background flux levels. It is envisioned that emitted gaseous elemental mercury (GEM) can be readily captured, and transformed back into metallic Hg, which can then be stored appropriately or recycled. This breaks the Hg cycle, as GEM is no longer translocated back to the atmospheric compartment. The immobilising excipients used in this research overcome many logistical issues with delivery of suitable microbial loads to locations of mercury contamination and presents a facile and inexpensive method of augmenting contaminated sites with selected microbial consortia for bioremediation.

Native fishes in the Truckee River: Are in-stream structures and patterns of population genetic structure related?

In-stream structures are recognized as significant impediments to movement for freshwater fishes. Apex predators such as salmonids have been the focus of much research on the impacts of such barriers to population dynamics and population viability however much less research has focused on native fishes, where in-stream structures may have a greater impact on long term population viability of these smaller, less mobile species. Patterns of genetic structure on a riverscape can provide information on which structures represent real barriers to movement for fish species and under what specific flow conditions. Here we characterize the impact of 41 dam and diversion structures on movement dynamics under varying flow conditions for a suite of six native fishes found in the Truckee River of California and Nevada. Microsatellite loci were used to estimate total allelic diversity, effective population size and assess genetic population structure. Although there is spatial overlap among species within the river there are clear differences in species distributions within the watershed. Observed population genetic structure was associated with in-stream structures, but only under low flow conditions. High total discharge in 2006 allowed fish to move over potential barriers resulting in no observed population genetic structure for any species in 2007. The efficacy of in-stream structures to impede movement and isolate fish emerged only after multiple years of low flow conditions. Our results suggest that restricted movement of fish species, as a result of in-stream barriers, can be mitigated by flow management. However, as flow dynamics are likely to be altered under global climate change, fragmentation due to barriers could isolate stream fishes into small subpopulations susceptible to both demographic losses and losses of genetic variation.

Interannual Variability in Baseline Ozone and Its Relationship to Surface Ozone in the Western U.S.

Baseline ozone refers to observed concentrations of tropospheric ozone at sites that have a negligible influence from local emissions. The Mount Bachelor Observatory (MBO) was established in 2004 to examine baseline air masses as they arrive to North America from the west. In May 2012, we observed an O3 increase of 2.0-8.5 ppbv in monthly average maximum daily 8-hour average O3 mixing ratio (MDA8 O3) at MBO and numerous other sites in the western U.S. compared to previous years. This shift in the O3 distribution had an impact on the number of exceedance days. We also observed a good correlation between daily MDA8 variations at MBO and at downwind sites. This suggests that under specific meteorological conditions, synoptic variation in O3 at MBO can be observed at other surface sites in the western U.S. At MBO, the elevated O3 concentrations in May 2012 are associated with low CO values and low water vapor values, consistent with transport from the upper troposphere/lower stratosphere (UT/LS). Furthermore, the Real-time Air Quality Modeling System (RAQMS) analyses indicate that a large flux of O3 from the UT/LS in May 2012 contributed to the observed enhanced O3 across the western U.S. Our results suggest that a network of mountaintop observations, LiDAR and satellite observations of O3 could provide key data on daily and interannual variations in baseline O3.

Trends in mercury wet deposition and mercury air concentrations across the U.S. and Canada.

This study examined the spatial and temporal trends of mercury (Hg) in wet deposition and air concentrations in the United States (U.S.) and Canada between 1997 and 2013. Data were obtained from the National Atmospheric Deposition Program (NADP) and Environment Canada monitoring networks, and other sources. Of the 19 sites with data records from 1997-2013, 53% had significant negative trends in Hg concentration in wet deposition, while no sites had significant positive trends, which is in general agreement with earlier studies that considered NADP data up until about 2010. However, for the time period 2007-2013 (71 sites), 17% and 13% of the sites had significant positive and negative trends, respectively, and for the time period 2008-2013 (81 sites) 30% and 6% of the sites had significant positive and negative trends, respectively. Non-significant positive tendencies were also widespread. Regional trend analyses revealed significant positive trends in Hg concentration in the Rocky Mountains, Plains, and Upper Midwest regions for the recent time periods in addition to significant positive trends in Hg deposition for the continent as a whole. Sulfate concentration trends in wet deposition were negative in all regions, suggesting a lower importance of local Hg sources. The trend in gaseous elemental Hg from short-term datasets merged as one continuous record was broadly consistent with trends in Hg concentration in wet deposition, with the early time period (1998-2007) producing a significantly negative trend (-1.5±0.2%year(-1)) and the recent time period (2008-2013) displaying a flat slope (-0.3±0.1%year(-1), not significant). The observed shift to more positive or less negative trends in Hg wet deposition primarily seen in the Central-Western regions is consistent with the effects of rising Hg emissions from regions outside the U.S. and Canada and the influence of long-range transport in the free troposphere.

Identifying sources of ozone to three rural locations in Nevada, USA, using ancillary gas pollutants, aerosol chemistry, and mercury.

Ozone (O3) is a secondary air pollutant of long standing and increasing concern for environmental and human health, and as such, the US Environmental Protection Agency will revise the National Ambient Air Quality Standard of 75 ppbv to ≤ 70 ppbv. Long term measurements at the Great Basin National Park (GBNP) indicate that O3 in remote areas of Nevada will exceed a revised standard. As part of the Nevada Rural Ozone Initiative, measurements of O3 and other air pollutants were made at 3 remote sites between February 2012 and March 2014, GBNP, Paradise Valley (PAVA), and Echo Peak (ECHO). Exceptionally high concentrations of each air pollutant were defined relative to each site as mixing ratios that exceeded the 90th percentile of all hourly data. Case studies were analyzed for all periods during which mean daily O3 exceeded the 90th percentile concurrently with a maximum 8-h average (MDA8) O3 that was "exceptionally high" for the site (65 ppbv at PAVA, 70 ppbv at ECHO and GBNP), and of potential regulatory significance. An MDA8 ≥ 65 ppbv occurred only five times at PAVA, whereas this occurred on 49 and 65 days at GBNP and ECHO, respectively. The overall correlation between O3 and other pollutants was poor, consistent with the large distance from significant primary emission sources. Mean CO at these locations exceeded concentrations reported for background sites in 2000. Trajectory residence time calculations and air pollutant concentrations indicate that exceedances at GBNP and ECHO were promoted by air masses originating from multiple sources, including wildfires, transport of pollution from southern California and the marine boundary layer, and transport of Asian pollution plumes. Results indicate that the State of Nevada will exceed a revised O3 standard due to sources that are beyond their control.

Testing and modeling the influence of reclamation and control methods for reducing nonpoint mercury emissions associated with industrial open pit gold mines.

Industrial gold mining is a significant source of mercury (Hg) emission to the atmosphere. To investigate ways to reduce these emissions, reclamation and dust and mercury control methods used at open pit gold mining operations in Nevada were studied in a laboratory setting. Using this information along with field data, and building off previous work, total annual Hg emissions were estimated for two active gold mines in northern Nevada. Results showed that capping mining waste materials with a low-Hg substrate can reduce Hg emissions from 50 to nearly 100%. The spraying of typical dust control solutions often results in higher Hg emissions, especially as materials dry after application. The concentrated application of a dithiocarbamate Hg control reagent appears to reduce Hg emissions, but further testing mimicking the actual distribution of this chemical within an active leach solution is needed to make a more definitive assessment.

Fast time resolution oxidized mercury measurements during the Reno Atmospheric Mercury Intercomparison Experiment (RAMIX).

The Reno Atmospheric Mercury Intercomparison Experiment (RAMIX) was carried out from 22 August to 16 September, 2011 in Reno, NV to evaluate the performance of new and existing methods to measure atmospheric mercury (Hg). Measurements were made using a common sampling manifold to which controlled concentrations of Hg species, including gaseous elemental mercury (GEM) and HgBr2 (a surrogate gaseous oxidized mercury (GOM) compound), and potential interferents were added. We present an analysis of Hg measurements made using the University of Washington's Detector for Oxidized Hg Species (DOHGS), focusing on tests of GEM and HgBr2 spike recovery, the potential for interference from ozone (O3) and water vapor (WV), and temporal variability of ambient reactive mercury (RM). The mean GEM and HgBr2 spike recoveries measured with the DOHGS were 95% and 66%, respectively. The DOHGS responded linearly to HgBr2. We found no evidence that elevated O3 interfered in the DOHGS RM measurements. A reduction in RM collection and retention efficiencies at very high ambient WV mixing ratios is possible. Comparisons between the DOHGS and participating Hg instruments demonstrate good agreement for GEM and large discrepancies for RM. The results suggest that existing GOM measurements are biased low.

Measurement and scaling of air-surface mercury exchange from substrates in the vicinity of two Nevada gold mines.

The state of Nevada has extensive mineral resources, and is the largest producer of gold in the USA as well as fourth in world gold production. Mercury (Hg) is often present in the hydrothermal systems that produce gold deposits, and can be found in elevated concentrations in gold ore. As a result, mining of gold ore in Nevada has been shown to release Hg to the atmosphere from point and non-point sources. This project focused on measurement of air-soil Hg exchange associated with undisturbed soils and bedrock outcrops in the vicinity of two large gold mines. Field and laboratory data collected were used to identify the important variables controlling Hg flux from these surfaces, and to estimate a net flux from the areas adjacent to the active mines as well as that occurring from the mined area pre-disturbance. Mean daily flux by substrate type ranged from 9 ng m(-2) day(-1) to 140 ng m(-2) day(-1). Periods of net deposition of elemental Hg were observed when air masses originating from a mine site moved over sampling locations. Based on these observations and measured soil Hg concentrations we suggest that emissions from point and non-point sources at the mines are a source of Hg to the surrounding substrates with the amount deposited not being of an environmental concern but of interest mainly with respect to the cycling of atmospheric elemental Hg. Observations indicate that while some component of the deposited Hg is sequestered in the soil, this Hg is gradually released back to the atmosphere over time. Estimated pre-disturbance emissions from the current mine footprints based on field data were 0.1 and 1.7 kg yr(-1), compared to that estimated for the current non-point mining sources of 19 and 109 kg yr(-1), respectively.

New technique for quantification of elemental Hg in mine wastes and its implications for mercury evasion into the atmosphere.

Mercury in the environment is of prime concern to both ecosystem and human health. Determination of the molecular-level speciation of Hg in soils and mine wastes is important for understanding its sequestration, mobility, and availability for methylation. Extended X-ray absorption fine structure (EXAFS) spectroscopy carried out under ambient P-T conditions has been used in a number of past studies to determine Hg speciation in complex mine wastes and associated soils. However, this approach cannot detect elemental (liquid) mercury in Hg-polluted soils and sediments due to the significant structural disorder of liquid Hg at ambient-temperature. A new sample preparation protocol involving slow cooling through the crystallization temperature of Hg(0) (234 K) results in its transformation to crystalline α-Hg(0). The presence and proportion of Hg(0), relative to other crystalline Hg-bearing phases, in samples prepared in this way can be quantified by low-temperature (77 K) EXAFS spectroscopy. Using this approach, we have determined the relative concentrations of liquid Hg(0) in Hg mine wastes from several sites in the California Coast Range and have found that they correlate well with measured fluxes of gaseous Hg released during light and dark exposure of the same samples, with higher evasion ratios from samples containing higher concentrations of liquid Hg(0). Two different linear relationships are observed in plots of the ratio of Hg emission under light and dark conditions vs % Hg(0), corresponding to silica-carbonate- and hot springs-type Hg deposits, with the hot springs-type samples exhibiting higher evasion fluxes than silica-carbonate type samples at similar Hg(0) concentrations. Our findings help explain significant differences in Hg evasion data for different mine sites in the California Coast Range.

Empirical models for estimating mercury flux from soils.

Multiple parameters have been suggested to influence the exchange of mercury (Hg) between the atmosphere and soils. However, models applied for estimating soil Hg flux are simple and do not consider the potential synergistic and antagonist relationships between factors controlling the exchange. This study applied a two-level factorial experimental design in a gas exchange chamber (GEC) to investigate the individual and combined effects of three environmental factors (temperature, light, and soil moisture) on soil Hg flux. It was shown that individually irradiation, soil moisture, and air temperature all significantly enhance Hg evasive flux (by 90-140%). Synergistic effects (20-30% of additional flux enhancement) were observed for all two-factor interactions, with air temperature/soil moisture and air temperature/irradiation being the most significant. Results from the factorial experiments suggest that a model incorporating the second-order interactions can appropriately explain the flux response to the changes of the studied factors. Based on the factorial experiment results and using the flux data for twelve soil materials measured with a dynamic flux chamber (DFC) at various temperatures, soil moisture contents, solar radiation exposures, and soil Hg contents, two empirical models for estimating Hg flux from soils were developed. Model verification with ambient flux data not used to develop the models suggested that the models were capable of estimating dry soil Hg flux with a high degree of predictability (r ∼ 0.9).

Testing and application of surrogate surfaces for understanding potential gaseous oxidized mercury dry deposition.

Currently there is no standard method for measurement of atmospheric mercury dry deposition. While all operationally defined forms of atmospheric mercury (elemental, oxidized, and particulate) can be dry deposited, oxidized forms are of concern due to high deposition velocities, water solubility, and reactivity. This paper describes the development of a surrogate surface for characterizing potential dry deposition of gaseous oxidized mercury (GOM). Laboratory tests showed that the surface collected HgCl2, HgBr2, and HgO with equal efficiency, and deposition was not significantly influenced by temperature, humidity, or ozone concentrations. Deposition of mercury to surfaces in field deployments was correlated with GOM concentrations (r2 = 0.84, p < 0.01, n = 326. Weekly mean GOM deposition velocities from surface deployments (1.1 +/- 0.6 cm s(-1)) were higher than modeled values (0.4 +/- 0.2 cm s(-1)) at four field sites, but were within the range reported for direct measurements. Although the surfaces do not simulate the heterogeneity of natural surfaces and need to be validated by direct measurements, they do provide a physical means for estimating temporal trends and spatial variability of dry deposition of GOM.

Application of a rule-based model to estimate mercury exchange for three background biomes in the continental United States.

Ecosystems that have low mercury (Hg) concentrations (i.e., not enriched or impacted by geologic or anthropogenic processes) cover most of the terrestrial surface area of the earth yet their role as a net source or sink for atmospheric Hg is uncertain. Here we use empirical data to develop a rule-based model implemented within a geographic information system framework to estimate the spatial and temporal patterns of Hg flux for semiarid deserts, grasslands, and deciduous forests representing 45% of the continental United States. This exercise provides an indication of whether these ecosystems are a net source or sink for atmospheric Hg as well as a basis for recommendation of data to collect in future field sampling campaigns. Results indicated that soil alone was a small net source of atmospheric Hg and that emitted Hg could be accounted for based on Hg input by wet deposition. When foliar assimilation and wet deposition are added to the area estimate of soil Hg flux these biomes are a sink for atmospheric Hg.

Nonstomatal versus stomatal uptake of atmospheric mercury.

Atmospheric constituents may be deposited to and incorporated into plant leaves, with gases entering via stomata, and gas and particles being sorbed at the surface and in some cases traversing the cuticle, possibly reaching the epidermis. Plants are known to be a sink for atmospheric mercury (Hg), and the current paradigm is that uptake of gaseous elemental Hg occurs by way of the stomata. Four plant species, Rudbeckia hirta, Sorghastrum nutans, Andropogon gerardii, and Populus tremuloides, were exposed to air from different sources and with different Hg and CO2 concentrations in light and dark within a gas exchange chamber at approximately 25% relative humidity. Data showed that Hg concentration and air source had a significant effect (p < 0.001) on leaf-atmosphere Hg flux, with more deposition to the leaf occurring in elevated-Hg air, and in scrubbed air compared to ambient air. Deposition also occurred during dark and elevated CO2 exposures, when stomatal conductance was reduced. These observations and the fact that limited or no Hg emission occurred after deposition of atmospheric Hg suggests that the nonstomatal pathway may be an important route of foliar accumulation of atmospheric Hg.

Atmospheric mercury exchange with a tallgrass prairie ecosystem housed in mesocosms.

This study focused on characterizing air-surface mercury Hg exchange for individual surfaces (soil, litter-covered soil and plant shoots) and ecosystem-level flux associated with tallgrass prairie ecosystems housed inside large mesocosms over three years. The major objectives of this project were to determine if individual surface fluxes could be combined to predict ecosystem-level exchange and if this low-Hg containing ecosystem was a net source or sink for atmospheric Hg. Data collected in the field were used to validate fluxes obtained in the mesocosm setting. Because of the controlled experimental design and ease of access to the mesocosms, data collected allowed for assessment of factors controlling flux and comparison of models developed for soil Hg flux versus environmental conditions at different temporal resolution (hourly, daily and monthly). Evaluation of hourly data showed that relationships between soil Hg flux and environmental conditions changed over time, and that there were interactions between parameters controlling exchange. Data analyses demonstrated that to estimate soil flux over broad temporal scales (e.g. annual flux) coarse-resolution data (monthly averages) are needed. Plant foliage was a sink for atmospheric Hg with uptake influenced by plant functional type and age. Individual system component fluxes (bare soil and plant) could not be directly combined to predict the measured whole system flux (soil, litter and plant). Emissions of Hg from vegetated and litter-covered soil were lower than fluxes from adjacent bare soil and the difference between the two was seasonally dependent and greatest when canopy coverage was greatest. Thus, an index of plant canopy development (canopy greenness) was used to model Hg flux from vegetated soil. Accounting for ecosystem Hg inputs (precipitation, direct plant uptake of atmospheric Hg) and modeled net exchange between litter-and-plant covered soils, the tallgrass prairie was found to be a net annual sink of atmospheric Hg.

Foliar mercury accumulation and exchange for three tree species.

The goals of this study were to (1) investigate plant mercury (Hg) uptake using different air and soil Hg concentrations near natural background values for three tree species, and (2) test if measured foliar Hg fluxes could explain observed foliar Hg concentrations. Plants were exposed to three soil treatments (<0.01, 0.09 +/- 0.02, and 0.92 +/- 0.27 microg Hg g(-1)), and to three atmospheric exposure concentrations (5.9 +/- 2.3, 14.3 +/- 2.7, and 30.1 +/- 3.5 ng Hg m(-3)). Foliar Hg concentrations were found to be influenced primarily by atmospheric Hg concentrations and to a lesser extent by soil Hg exposures. Data indicated that deciduous species might play a more active role in ecosystem Hg cycling than evergreen trees. Foliar mercury fluxes quantified using a dynamic single-plant gas-exchange chamber for two species were variable and accumulation rates were lower than those predicted based on foliar Hg concentrations. A hypothesis to explain this discrepancy is that the plant gas-exchange chamber measures net flux which includes emission, deposition, adsorption, and reemission of Hg at the leaf surface, while total foliar accumulation represents only deposition and assimilation.

Air-substrate mercury exchange associated with landfill disposal of coal combustion products.

Previous laboratory studies have shown that lignite-derived fly ash emitted mercury (Hg) to the atmosphere, whereas bituminous- and subbituminous-derived fly ash samples adsorbed Hg from the air. In addition, wet flue gas desulfurization (FGD) materials were found to have higher Hg emission rates than fly ash. This study investigated in situ Hg emissions at a blended bituminous-subbituminous ash landfill in the Great Lakes area and a lignite-derived ash and FGD solids landfill in the Midwestern United States using a dynamic field chamber. Fly ash and saturated FGD materials emitted Hg to atmosphere at low rates (-0.1 to 1.2 ng/ m2hr), whereas FGD material mixed with fly ash and pyrite exhibited higher emission rates (approximately 10 ng/m2hr) but were still comparable with natural background soils (-0.3 to 13 ng/ m2hr). Air temperature, solar radiation, and relative humidity were important factors correlated with measured Hg fluxes. Field study results were not consistent with corresponding laboratory observations in that fluxes measured in the latter were higher and more variable. This is hypothesized to be partially an artifact of the flux measurement methods.