TOTAL MERCURY AND METHYLMERCURY RESPONSE IN WATER

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TOTAL MERCURY AND METHYLMERCURY RESPONSE IN WATER, SEDIMENT, AND BIOTA TO DESTRATIFICATION OF THE GREAT SALT LAKE, UTAH, USA Carla Valdes, Frank J Black, Blair Stringham, Jeffrey N. Collins, James R Goodman, Heidi J. Saxton, Christopher R. Mansfield, Joshua N. Schmidt, Shu Yang, and William P. Johnson Environ. Sci. Technol., Just Accepted Manuscript • DOI: 10.1021/acs.est.6b05790 • Publication Date (Web): 12 Apr 2017 Downloaded from http://pubs.acs.org on April 13, 2017

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Environmental Science & Technology

Photo credit: NASA ISS040-E-043230 (6 July 2014) 82x49mm (300 x 300 DPI)

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Draft 2016-03-25

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TOTAL MERCURY AND METHYLMERCURY RESPONSE IN WATER, SEDIMENT, AND

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BIOTA TO DESTRATIFICATION OF THE GREAT SALT LAKE, UTAH, USA

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Carla Valdes‡, Frank J Black §, Blair Stringham †, Jeffrey N Collins §, James R Goodman §,

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Heidi J Saxton §, Christopher R Mansfield §, Joshua N Schmidt §,

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Shu Yang‡, and William P Johnson *,‡

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§

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Department of Geology & Geophysics, University of Utah, Salt Lake City, UT 84112

†

Department of Chemistry, Westminster College, Salt Lake City UT 84105

Division of Wildlife Resources, Utah Department of Natural Resources, Salt Lake City, UT 84114

19 20 21 22 23

*

Corresponding author, [email protected] (801)-664-8289

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Abstract:

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Measurements of chemical and physical parameters made before and after sealing of culverts in

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the railroad causeway spanning Great Salt Lake in late 2013 documented dramatic alterations in

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the system in response to the elimination of flow between the Great Salt Lake’s north and south

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arms. The flow of denser, more saline water through the culverts from the north arm (Gunnison

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Bay) to the south arm (Gilbert Bay) previously drove the perennial stratification of the south arm

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and the existence of oxic shallow brine and anoxic deep brine layers. Closure of the causeway

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culverts occurred concurrently with a multiyear drought that resulted in a decrease in the lake

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elevation and a concomitant increase in top-down erosion of the upper surface of the deep brine

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layer by wind-forced mixing. The combination of these events resulted in replacement of the

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formerly stratified water column in the south arm with one that is vertically homogeneous and

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oxic. Total mercury concentrations in the deep waters of the south arm decreased by

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approximately 81%, and methylmercury concentrations in deep waters decreased by roughly

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86%, due to destratification. Methylmercury concentrations decreased by 77% in underlying

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surficial sediment whereas there was no change was observed in total mercury. The dramatic

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mercury loss from deep waters and methylmercury loss from underlying sediment in response to

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causeway sealing provides new understanding of the potential role of the deep brine layer in the

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accumulation and persistence of methylmercury in the Great Salt Lake. Additional mercury

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measurements in biota appear to contradict the previously implied connection between elevated

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methylmercury concentrations in the deep brine layer and elevated mercury in avian species

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reported prior to causeway sealing.

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Introduction: Mercury is a global pollutant that migrates through natural systems by complex

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transformation and transport processes that are in large part governed by redox conditions in the

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environment.1 Mercury exists in nature as elemental mercury Hg(0), divalent mercury Hg(II),

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and organomercury compounds such as monomethylmercury (MeHg), the bioaccumulative form

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of mercury. Biomagnification of MeHg can result in potentially toxic levels of MeHg exposure

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to humans and wildlife through consumption of prey, causing detrimental neurological,

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behavioral, and reproductive effects.2

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The methylation of inorganic mercury in the environment is predominantly biologically

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mediated, occurs in anoxic environments, and is carried out largely by sulfate-reducing

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bacteria.3-5 Methylation by iron-reducing bacteria and methanogens can also be important, and

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many other microbes have been shown to contain the hgcAB gene cluster responsible for

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mercury methylation.6-9 Abiotic parameters, such as dissolved organic matter (DOM), have also

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been shown to increase mercury methylation under sulfidic conditions in lab experiments,5,10 and

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MeHg concentrations in aquatic sediments are often positively correlated with concentrations of

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dissolved organic carbon (DOC), although this is not always the case due to the complex effects

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of DOM on mercury’s biogeochemical cycling via its role as a substrate for microbial respiration

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and its role in inorganic mercury complexation and chemical speciation.11-13

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The Great Salt Lake (GSL) is the largest terminal lake in the Western Hemisphere, and

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the Western Hemisphere Shorebird Reserve Network recognizes it as a habitat of hemispheric

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importance for millions of migratory birds (Figure 1). Over 1.4 million shorebirds use the GSL

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for breeding and staging areas, and over 7 million waterfowl utilize the GSL and its adjacent

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1,900 km2 of freshwater and brackish wetlands during some portion of their biannual migration.


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The GSL avian community feeds on aquatic organisms adapted to highly saline conditions,

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which includes brine shrimp (Artemia fransicana), brine fly (Ephydra spp.), water boatman

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(corixid) and numerous algal species.14 In 2007, human consumption advisories were placed on

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three duck species (Cinnamon Teal, Northern Shoveler, and Common Goldeneye) at the GSL

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based on elevated mercury levels in breast muscle tissue exceeding the EPA screening value (0.3

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µg/kg, ww).15-17

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The construction of a railroad causeway in 1959 restricted water flow between the north

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arm (Gunnision Bay), and the south arm (Gilbert Bay).15 Because the south arm receives nearly

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all surface water inflows of freshwater to the GSL, the north arm is evaporatively concentrated to

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a greater extent than the south arm, yielding brine in the north arm (250-280 g/L) that is 1.4 to

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1.6 times more saline than the south arm (110-180 g/L), the latter being 3–5 times more saline

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than seawater (33-36 g/L).18-19 Culverts in the causeway allowed bidirectional flow, with

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shallow water flowing from the south arm to the north arm, and deeper denser water flowing

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from the north to south arm. This flow of dense brine from the north arm, along with limited

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wind-driven mixing, resulted in saline based density-driven stratification and the formation of a

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monimolimnion, herein referred to as the deep brine layer (DBL), in the south arm that persisted

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6-7 m below the surface of the lake, and that was not subject to annual turnover.15,18,19,20 The

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DBL was anoxic with elevated DOC (59 – 88 mg/L) and sulfide (7 –29 mg/L)18,22,23, high

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activities of sulfate-reducing bacteria, 24 and elevated MeHg (20 to 32 ng/L) and total mercury

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(HgT) (38-80 ng/L) with a high percentage of HgT existing as MeHg.22 Several studies20,25-27

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have implicated the elevated MeHg in the DBL as a potential source of elevated mercury in

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biota, possibly via mixing into the oxic upper brine layer where uptake into the food chain could

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subsequently occur. However, a previous laboratory study23 reported no difference in the HgT



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concentration of brine shrimp grown for 14 days in a water column where a DBL was absent

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compared to a stratified water column where an anoxic DBL was present. And they reported that

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brine shrimp grown in water created by mixing different ratios of the upper brine layer and DBL

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accumulated Hg in proportion to the Hg:POC (particulate organic carbon) ratio, such that at least

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the short term effect of mixing in water from the DBL was a decrease in the HgT concentration

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in the brine shrimp.

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Mixing between the DBL and upper brine layer in the south arm of the GSL is believed

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to be relatively limited, with previous research28 indicating that the pools of dissolved inorganic

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nitrogen (DIN) and total dissolved phosphorous (TDP) in the shallow brine layer are only weakly

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coupled to those in the deep brine layer. But despite persistent stratification in the GSL, Beisner

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et al.29 reported evidence that limited mixing between the DBL and shallow brine layer occurred

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during conveyance of the DBL from the northern to southern areas of the south arm, and Jones

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and Wurtsbaugh23 estimated that 40% of the DBL was entrained into the shallow brine layer

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annually. Such mixing would allow for the transfer of MeHg from the DBL to the overlying

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shallow brine layer, and by extension, into the base of the food chain, and eventually to brine fly

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larvae and brine shrimp that serve as diet for many avian species.23,27,28,30,31 Such an indirect

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connection was inferred by Johnson et al.22 based on elevated Hg concentrations previously

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reported in birds (eared grebes)32 and brine flies26 on the southwestern side of Gilbert Bay

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(where the DBL existed at depth in the most proximal water body), as well as due to the

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temporal correspondence of reduced Hg(II)-methylation rates in the DBL and reduced Hg

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burdens among aquatic invertebrates (brine shrimp30,33 and brine flies26).

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In November 2012 and December 2013, two railway causeway culverts that allowed limited water flow between the north and south arms of the GSL were closed due to deteriorating


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structural integrity. These closures provided the opportunity to determine the geochemical

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response of the system to elimination of flow between the north and south arms and

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destratification and disappearance of the DBL in the south arm (described below). This event

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also allowed us to quantify how HgT and MeHg concentrations in the water column, surficial

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sediment, and biota responded to the disappearance of the DBL, thus providing insight into the

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role of the DBL in the biogeochemical cycling of mercury in the GSL.

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Methods

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Water and Sediment Sampling and Analysis

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Periodically from October 2015 to December 2016, water column chemical and physical

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conditions were characterized at seven locations across the south arm of GSL (Figure 1). Water

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samples were collected at five stations (2267, 2565, 2767, N1018, 2820, 3510, and 4069) at 0.2

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m below lake surface and 0.5 m above lake bottom, referred to as shallow and deep samples,

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respectively. The data from these samples collected after the disappearance of the DBL were

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compared to previous data collected from the shallow and deep brine layers from May 2007 to

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December 2012, prior to causeway closure when the DBL was present22,34 (Figure 1). Water

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column temperature, specific conductance, pH, and dissolved oxygen (DO) were measured in the

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field using a YSI Professional Series Quatro probe that was calibrated within 12 hours prior to

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sampling.22 The YSI probe corrects for temperature but not salinity. Thus, the DO values

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presented have a positive bias and are qualitative, but are still useful for accurately denoting oxic

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versus anoxic conditions. Sulfide was measured in filtered water samples in the field

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immediately after collection using a photometric method (V-2000 Multi-analyte LED

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Photometer and Vacu-vials®, CHEMetrics).22



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Clean hands - dirty hands protocol was followed during sample collection and analysis.35

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Unfiltered Hg water samples were collected by peristaltic pump using acid-washed PTFE tubing

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into pre-cleaned FLPE bottles. Bottles used to collect anoxic water samples were filled to

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overflowing in order to minimize headspace. Filtered water samples were passed through a 0.45-

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micron pore size, pre-acid rinsed capsule filters in the field (Geotech Environmental). After

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collection, water samples for HgT and MeHg analyses (unfiltered) were stored on ice in the field

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and acidified to 0.5% using trace-metal grade sulfuric acid for preservation the same day as

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sampling. All samples were then refrigerated and analyzed within two weeks of collection.

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HgT samples were oxidized by amendment to 5% BrCl at least 24 hours prior to analysis.

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This higher BrCl concentration relative to established protocols that call for 1% BrCl was

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necessary36 to fully oxidize the high levels of dissolved organic matter (75.4 ± 11.1 mg/L) in

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these water samples (as described below). HgT concentrations in water were determined via

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reduction with SnCl2, purge and trap onto gold traps, thermal desorption, with quantification by

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cold vapor atomic fluorescence spectroscopy (CVAFS) using a MERX-T automated system

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(Brooks Rand) using established techniques.36 Mean laboratory blank concentrations were 0.07 ±

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0.008 ng/L HgT. HgT matrix spike recovery averaged 98.3 ± 3.2% (n=3). MeHg concentration

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in water was measured after distillation with ammonium pyrrolidine dithiocarbamate (APDC),

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followed by aqueous phase ethylation, purge and trap onto tenax traps, thermal desorption,

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pyrolitic decomposition, and CVAFS detection using a MERX-M automated system (Brooks

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Rand) using established techniques.37 MeHg blanks averaged 0.15 ± 0.10 ng/L. Because no

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certified reference material exists for MeHg in water, MeHg matrix spikes were included in each

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distillation; MeHg spike recoveries (n=2) averaged 93 ± 29%. Water samples for dissolved

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organic carbon (DOC) analysis were placed on ice in the field then placed in a refrigerator upon


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return tio the laboratory. DOC was measured in water samples (TOC-5000a, Shimadzu) within

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one week of sample collection using EPA Method 1684.38

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Surficial sediment was sampled at eleven sites (A1, A2, B1, B2, C1, C2, CB, 2565, 3510,

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4069, and N1018) in the GSL (Figure 1), and were collected by peristaltic pump using acid-

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washed PTFE tubing into pre-cleaned 500 mL FLPE bottles filled to overflowing to minimize

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headspace, and stored on ice in the field. The preferred method for examining vertical variations

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involves collecting a sediment core that is subsequently sectioned. However, because our focus

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was geographic variations in surficial sediment, we employed a faster method to collect

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sediment. The method composites surficial sediment across depths of a few cm. Naftz et al.39

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reported 40% variation of HgT concentration within the top 2 cm of GSL sediment. Previous

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studies22 using this method showed relatively low variability in HgT and MeHg in surficial

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sediment, indicating that collected sediment was representative.

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Subsamples were oven dried at 105°C for 12 hours and re-weighed to determine water

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content and allow conversion between wet and dry weight concentrations (without salt

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correction). HgT was extracted from sediment by digestion in a 7:3 mixture of HNO3:H2SO4

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(trace metal grade) at 80°C for 6 hours, followed by amendment to 5% BrCl.36 MeHg was

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leached from sediment with a mixture of potassium bromide, sulfuric acid, and copper sulfate,

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extracted into methylene chloride, back extracted into water, followed by aqueous phase

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ethylation, purge and trap, thermal desorption, pyrolitic decomposition, and CVAFS detection

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according to established techniques.36,37,41 Certified reference materials (CRMs) for HgT

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(MESS-3) and MeHg (CC-580) in sediment were also analyzed, with recoveries averaging 99%

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and 119%, respectively.

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Biota Collection and Analyses Adult brine flies (Ephydra spp.) were collected from Lady Finger Point on Antelope

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Island of the GSL (Figure 1) from spring to fall of 2012 to 2015. Flies were collected with nets,

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transferred into polypropelene tubes, placed on ice in the field, and frozen back in the lab the

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same day. Seventy-six waterfowl were harvested in mid-September of 2014 and ninety-nine

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were harvested in late August and early September of 2015 from the GSL and surrounding

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wetlands by the Utah Division of Wildlife Resources. The waterfowl were harvested from the

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Farmington Bay, Ogden Bay, Howard Slough, and Harold Crane Waterfowl Management Areas

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(Figure 1). Ducks were harvested with shotguns using non-lead shot then frozen. The age of each

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bird was determined by physical characteristics; examining rectrices, wing and body plumage,

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and cloacal characters. The species sampled were Northern Shovelers (Anas clypeata) (DBL

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present: n = 16; DBL absent: n= 16), Mallard (Anas platyrhynchos) (DBL present: n= 16; DBL

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absent: n= 21), Gadwall (Anas strepera) (DBL present: n = 15; DBL absent: n =22), and

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Cinnamon Teal (Anas cyanoptera) (DBL present: n = 23; DBL absent: n = 31). Tissue samples

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were thawed, then a scalpel was used to remove the skin, and breast muscle tissue was harvested

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and stored in a Whirl-Pak (NASCO) polyethylene bag and frozen. Breast muscle was analyzed

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because it is the most likely tissue to be consumed by duck hunters.

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Both brine fly and waterfowl samples were freeze-dried and homogenized prior to

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analysis, and thus all HgT concentrations in biota are reported on a dry weight basis. Brine flies

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were digested in Teflon vials with 10 mL of a 2:1 mixture of trace metal grade nitric and sulfuric

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acids. Samples were allowed to predigest at room temperature for 1 hour, then heated to 100 °C

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for 4 hours. Following the digestion, samples were amended to 1% BrCl. All digestions included

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at least 2 digestion blanks and 2 certified reference materials (TORT-2 and DORM-3, National


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Research Council Canada), each digested in duplicate. Aliquots of the digested samples were

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measured by oxidation with BrCl, reduction with SnCl2, purge and trap using dual-stage gold

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trap amalgamation and quantification by CVAFS.36 The average daily HgT detection limit,

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based on 3 times the standard deviation of digestion blanks, was 2.3 ng g-1, assuming a 100-mg

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sample. Recoveries for HgT in the biota certified reference materials averaged 101.4% ± 7.8%, n

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= 88. The duck muscle tissue was analyzed using thermal decomposition, amalgamation, and

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atomic absorption spectrophotometry using a DMA-80 (Milestone) following established

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protocols.42 Muscle tissue samples were only analyzed for HgT because previous studies have

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shown that >95% of Hg in most bird muscle is MeHg43. Each analysis run included each of the

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two certified reference materials (TORT-2 and DORM-3) analyzed in duplicate, with recoveries

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of HgT ranging from 88% to 123%. Analytical precision of the HgT measurements was

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assessed by analyzing eight samples in triplicate, and the average percent relative standard

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deviation was 5.2%.

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The HgT concentrations in the waterfowl were log transformed prior to statistical

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analysis in order to meet the assumptions of parametric statistics. The data were analyzed using

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multifactor ANOVA using a crossed design. While we did not anticipate a priori that the sex of

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the waterfowl would have any effect on their HgT concentrations, we initially included sex in the

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statistical model, which included the following five variables as fixed factors: duck species, age,

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year, site, and sex. The fully crossed model could not be run due to missing cells because not all

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sites were sampled both years. We therefore used a reduced model made by removing the five-

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way and four-way interactions.44 In this model none of the interactions involving sex, nor sex as

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a main factor, were significant (p>0.49 in all cases). Given this result along with our a priori

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assumption regarding the importance of sex, this factor was removed from the model. The



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multifactor ANOVA using a crossed design with the fixed factors duck species, age, year, and

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site was then reduced by removing the four-way interaction and the three-way interaction Age ×

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Site × Year due to the missing cells, as described above.

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Results

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Water Quality Parameters

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Before 2013, prior to closure of the causeway culverts, shallow waters in the south arm

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were oxic (DO = 9.48 ± 0.70 mg/L), whereas deep waters in areas where the DBL exists were

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anoxic (DO = 0.05 ± 0.02 mg/L) (Figure 2). After causeway closure, mean DO was 9.1 ± 3.4

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mg/L in shallow waters and 7.2 ± 5.2 mg/L in all deep waters. Prior to culvert closure DO

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concentrations were significantly higher in surface waters than in the DBL (t-test, p

TOTAL MERCURY AND METHYLMERCURY RESPONSE IN WATER

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