Applied Geochemistry (v.21, #11)

Mercury in coal and the impact of coal quality on mercury emissions from combustion systems by Allan Kolker; Constance L. Senior; Jeffrey C. Quick (1821-1836).
The proportion of Hg in coal feedstock that is emitted by stack gases of utility power stations is a complex function of coal chemistry and properties, combustion conditions, and the positioning and type of air pollution control devices employed. Mercury in bituminous coal is found primarily within Fe-sulfides, whereas lower rank coal tends to have a greater proportion of organic-bound Hg. Preparation of bituminous coal to reduce S generally reduces input Hg relative to in-ground concentrations, but the amount of this reduction varies according to the fraction of Hg in sulfides and the efficiency of sulfide removal. The mode of occurrence of Hg in coal does not directly affect the speciation of Hg in the combustion flue gas. However, other constituents in the coal, notably Cl and S, and the combustion characteristics of the coal, influence the species of Hg that are formed in the flue gas and enter air pollution control devices. The formation of gaseous oxidized Hg or particulate-bound Hg occurs post-combustion; these forms of Hg can be in part captured in the air pollution control devices that exist on coal-fired boilers, without modification. For a given coal type, the capture efficiency of Hg by pollution control systems varies according to type of device and the conditions of its deployment. For bituminous coal, on average, more than 60% of Hg in flue gas is captured by fabric filter (FF) and flue-gas desulfurization (FGD) systems. Key variables affecting performance for Hg control include Cl and S content of the coal, the positioning (hot side vs. cold side) of the system, and the amount of unburned C in coal ash. Knowledge of coal quality parameters and their effect on the performance of air pollution control devices allows optimization of Hg capture co-benefit.

Total dissolved and total particulate Hg mass balances were estimated during one hydrological period (July 2001–June 2002) in the Thur River basin, which is heavily polluted by chlor-alkali industrial activity. The seasonal variations of the Hg dynamics in the aquatic environment were assessed using total Hg concentrations in bottom sediment and suspended matter, and total and reactive dissolved Hg concentrations in the water. The impact of the chlor-alkali plant (CAP) remains the largest concern for Hg contamination of this river system. Upstream from the CAP, the Hg partitioning between dissolved and particulate phases was principally controlled by the dissolved fraction due to snow melting during spring high flow, while during low flow, Hg was primarily adsorbed onto particulates. Downstream from the CAP, the Hg partitioning is controlled by the concentration of dissolved organic and inorganic ligands and by the total suspended sediment (TSS) concentrations. Nevertheless, the particulate fluxes were five times higher than the dissolved ones. Most of the total annual flux of Hg supplied by the CAP to the river is transported to the outlet of the catchment (total Hg flux: 70 μg m−2  a−1). Downstream from the CAP, the bottom sediment, mainly composed of coarse sediment (>63 μm) and depleted in organic matter, has a weak capacity to trap Hg in the river channel and the stock of Hg is low (4 mg m−2) showing that the residence time of Hg in this river is short.

Mercury speciation in soils of the industrialised Thur River catchment (Alsace, France) by Sandrine Remy; Pascale Prudent; Jean-Luc Probst (1855-1867).
Methylmercury (MeHg) and total Hg (THg) concentrations in soil profiles were monitored in the Thur River basin (Alsace, France), where a chlor-alkali plant has been located in the city of Vieux-Thann since the 1930s. Three soil types were studied according to their characteristics and location in the catchment: industrial soil, grassland soil and alluvial soil. Contamination of MeHg and THg in soil was important in the vicinity of the plant, especially in industrial and alluvial soil. Concentrations of MeHg reached 27 ng g−1 and 29,000 ng g−1 for THg, exceeding the predictable no effect concentration. Significant ecotoxicological risk exists in this area and remedial actions on several soil types are suggested. In each type of soil, MeHg concentrations were highest in topsoil, which decreased with depth. Concentrations of MeHg were negatively correlated with soil organic matter and total S, particularly when MeHg concentrations exceeded 8 ng g−1. Under these conditions, MeHg concentrations in soil seemed to be influenced by THg, soil organic matter and total S concentrations. It was found that high MeHg/THg ratios (near 2%) in soil were mainly related to the combined soil environmental conditions such as low THg concentrations, low organic C/N ratios (<11) and relatively low pH (5–5.5). Nevertheless, even when the MeHg/THg ratio was low (∼0.04%), MeHg and THg concentrations were elevated, up to 13 ng g−1 and to 29,000 ng g−1, respectively. Thus, both THg and MeHg concentrations should be taken into account to assess potential environmental risks of Hg.

Mercury in water and biomass of microbial communities in hot springs of Yellowstone National Park, USA by Susan A. King; Sabrina Behnke; Kim Slack; David P. Krabbenhoft; D. Kirk Nordstrom; Mark D. Burr; Robert G. Striegl (1868-1879).
Ultra-clean sampling methods and approaches typically used in pristine environments were applied to quantify concentrations of Hg species in water and microbial biomass from hot springs of Yellowstone National Park, features that are geologically enriched with Hg. Microbial populations of chemically-diverse hot springs were also characterized using modern methods in molecular biology as the initial step toward ongoing work linking Hg speciation with microbial processes. Molecular methods (amplification of environmental DNA using 16S rDNA primers, cloning, denatured gradient gel electrophoresis (DGGE) screening of clone libraries, and sequencing of representative clones) were used to examine the dominant members of microbial communities in hot springs. Total Hg (THg), monomethylated Hg (MeHg), pH, temperature, and other parameters influential to Hg speciation and microbial ecology are reported for hot springs water and associated microbial mats.Several hot springs indicate the presence of MeHg in microbial mats with concentrations ranging from 1 to 10 ng g−1 (dry weight). Concentrations of THg in mats ranged from 4.9 to 120,000 ng g−1 (dry weight). Combined data from surveys of geothermal water, lakes, and streams show that aqueous THg concentrations range from l to 600 ng L−1. Species and concentrations of THg in mats and water vary significantly between hot springs, as do the microorganisms found at each site.

Mercury geochemistry of the Scioto River, Ohio: Impact of agriculture and urbanization by W. Berry Lyons; Timothy O. Fitzgibbon; Kathleen A. Welch; Anne E. Carey (1880-1888).
The Scioto River is a major tributary to the Ohio River, which runs from its headwaters in row crop dominated agricultural lands in central Ohio, south through the city of Columbus, the 15th largest city in the USA. During a high flow event in April 2004, water was collected from seven locations along the river, and analyzed for a number of chemical constituents including total and dissolved Hg. Total Hg concentration increased continually downstream with the highest concentrations found at Commercial Point, just below two large sewage treatment plants that serve metropolitan Columbus. The highest Cl concentration was also found there. The highest NO 3 - concentrations were found in the agriculturally dominated portion of the river. The highest dissolved Hg concentration occurred in downtown Columbus. Using flow data from the day when the samples were collected, Hg yields were calculated at three locations within the basin: at Prospect in the northern, agriculture-dominated part of the basin; at Bellepoint located upstream of two reservoirs, just north of Columbus proper; and at downtown Columbus. The dissolved Hg yields in ng km−2  s−1 increased by a factor of 2 from Prospect to Bellepoint and then another 50% at Columbus. The particulate Hg yields increased only 10% from Prospect to Bellepoint, but 30% from Bellepoint to Columbus, with the particulate Hg yields about ∼2.5 to 4.5 times greater than the dissolved ones. These data suggest that yields of particulate Hg are affected more by urbanization than agricultural activities. The cause of the increasing yields of dissolved Hg as the river proceeded downstream is not clear at this time. It is assumed that the last increase is due to input from the urbanized portion of the watershed. As demonstrated previously, it appears that urbanized regions may retain a lower percentage of atmospherically deposited Hg than other landscape types.

There are seven stable isotopes of Hg that can be fractionated as a result of inorganic and organic interactions. Important inorganic reactions involve speciation changes resulting from variations in environmental redox conditions, and phase changes resulting from variations in temperature and/or atmospheric pressure. Important organic reactions include methylation and demethylation, reactions that are bacterially mediated, and complexing with organic anions in soils. The measurement of Hg isotopes by multi-collector-inductively coupled plasma-mass spectrometry (MC-ICP-MS) is now sufficiently precise and sensitive that it is potentially possible to develop the systematics of Hg isotopic fractionation. This provides an opportunity to evaluate the utility of Hg isotopes in identifying source processes, transport mechanisms, and sinks. New values are provided for, 201Hg/198Hg, 200Hg/198Hg, 199Hg/198Hg for three standard materials (IRMM-AE639, SRM 1641c, SRM 3133) that can be used to make inter-laboratory data comparisons, and these values are tabulated with published isotopic information. Overall, the isotopic data for these standards agree to approximately 0.2‰. The paper reviews Hg isotope studies that deal with hydrothermal ore deposits, sediments, coal and organic complexing.

This study addresses the physical geochemical aspects of the relationship between Hg and organic matter in recent sediment from eutrophic lakes in central Alberta, Canada. The types of organic matter in the sediment are classified based on their degree of thermal degradation and their petrographical characteristics. This study uniquely applies the methods conventionally used in petroleum geosciences (Rock-Eval® analyses and organic petrology) to investigate the relationship between various types of organic matter and the concentration of Hg in sediment.The results show that the total organic carbon (TOC) in sediment represents the sum of various organic compounds, which may play a completely different role in the distribution and accumulation of Hg. Strong correlations between TOC and the concentration of Hg in the studied sediment arise mainly from the thermally labile portion of organic matter released during pyrolysis under 300 °C. These compounds primarily consist of easily degradable algal-derived lipids and various pigments, which are petrographically described as soluble organic matter (SOM). The preserved SOM in sediment is commonly entrapped within the cell walls of phytoplankton and also appear as surface coating on sediment particles. The strong affinity between Hg and SOM is due not only to its chemical reactivity, but also to the physical characteristic of these labile compounds. The SOM may provide a substrate with enormous surface area by concentrating on the finer sediment size fractions and potentially acting as a “concentrator” for Hg and other organic-associated elements. Lastly, the quantity of the SOM has been calculated as an “elemental concentrator” portion of the TOC, which plays the most important role in the distribution of Hg in sediment.

Mercury exchange between the atmosphere and low mercury containing substrates by Mae Sexauer Gustin; Mark Engle; Jody Ericksen; Seth Lyman; Jelena Stamenkovic; Mei Xin (1913-1923).
Mercury is emitted to the air from Hg-enriched and low Hg-containing (natural background) substrates. Emitted Hg can be geogenic, or can be derived from the re-emission of Hg that was previously deposited to the soil from the atmosphere. Atmospheric Hg can be derived from natural and/or anthropogenic sources and can be deposited by wet or dry processes. It is important to understand the relative magnitude of emission, deposition, and re-emission of Hg associated with terrestrial ecosystems with natural background soil Hg concentrations because these landscapes cover large terrestrial surface areas. This information is also important for developing biogeochemical mass balances, assessing the impacts of atmospheric Hg sources, and predicting the effectiveness of regulatory controls at local, regional, and global scales.The major focus of this paper is to discuss air–substrate Hg exchange for low Hg-containing soils (<0.1 μg Hg g−1) from two areas in Nevada and one in Oklahoma, USA. Data collected with field and laboratory gas exchange systems are presented. Results indicate that in order to adequately characterize substrate–air Hg exchange, diel and seasonal data must be collected under a variety of environmental conditions. Field and laboratory data showed that dry deposition of gaseous Hg to substrates with low Hg concentrations is an important process. Environmental parameters important in influencing emissions include soil water content, incident light, temperature, atmospheric oxidants, and air Hg concentrations. There are synergistic and antagonistic effects between these parameters complicating prediction of flux.

The Idrija Mine, the second largest Hg mine in the world, ceased operation in 1995, but still delivers large quantities of Hg downstream including into the northern Adriatic Sea, 100 km away. Transformation of Hg species in sediment in sites over 60 km from the mine, including marine sites in the Adriatic Sea, was measured to determine the ability of the system to transform and mobilize Hg and to produce methylmercury (MeHg). Cores from a freshwater impoundment, a brackish estuarine site, and three marine sites in the Gulf of Trieste were sectioned anaerobically, and Hg methylation and MeHg demethylation activities determined using radio-techniques (203Hg for methylation and 14C-MeHg for demethylation). Total and dissolved Hg and MeHg were determined as were other geochemical parameters. In addition, rates of SO4 reduction were determined in marine sediment using a 35S technique. Mercury was readily methylated and demethylated at all sites. Marine sediment was investigated in winter and summer with rates of Hg transformation and SO4 reduction corresponding only in winter. Methylation of Hg in summer displayed subsurface peaks that may have been influenced by bioturbation. Total Hg and MeHg were most abundant in the freshwater, estuarine, and near-shore marine sites, but dissolved pore water Hg and MeHg were highest in the estuarine region where S cycling appeared ideal for the mobilization of Hg. The impoundment sediment also seemed to be a ‘hotspot’ of Hg transformations. MeHg demethylation occurred via the oxidative demethylation pathway (CO2 produced from MeHg), except in surficial sediment offshore in the Gulf during winter, where sediment was more oxidizing and significant amounts of CH4 were liberated during MeHg degradation via reductive demethylation. The CH4 formation was likely due to an increased influence from the expression of MeHg degradative enzymes encoded by the mer detoxification bacterial genetic system. The freshwater site also liberated CH4 from MeHg, but it appeared to be due to oxidative demethylation by methanogenic bacteria.

Speciation and microbial transformation of Hg was studied in mine waste from abandoned Hg mines in SW Texas to evaluate the potential for methyl-Hg production and degradation in mine wastes. In mine waste samples, total Hg, ionic Hg2+, Hg0, methyl-Hg, organic C, and total S concentrations were measured, various Hg compounds were identified using thermal desorption pyrolysis, and potential rates of Hg methylation and methyl-Hg demethylation were determined using isotopic-tracer methods. These data are the first reported for Hg mines in this region. Total Hg and methyl-Hg concentrations were also determined in stream sediment collected downstream from two of the mines to evaluate transport of Hg and methylation in surrounding ecosystems. Mine waste contains total Hg and methyl-Hg concentrations as high as 19,000 μg/g and 1500 ng/g, respectively, which are among the highest concentrations reported at Hg mines worldwide. Pyrolysis analyses show that mine waste contains variable amounts of cinnabar, metacinnabar, Hg0, and Hg sorbed onto particles. Methyl-Hg concentrations in mine waste correlate positively with ionic Hg2+, organic C, and total S, which are geochemical parameters that influence processes of Hg cycling and methylation. Net methylation rates were as high as 11,000 ng/g/day, indicating significant microbial Hg methylation at some sites, especially in samples collected inside retorts. Microbially-mediated methyl-Hg demethylation was also observed in many samples, but where both methylation and demethylation were found, the potential rate of methylation was faster. Total Hg concentrations in stream sediment samples were generally below the probable effect concentration of 1.06 μg/g, the Hg concentration above which harmful effects are likely to be observed in sediment dwelling organisms; whereas total Hg concentrations in mine waste samples were found to exceed this concentration, although this is a sediment quality guideline and is not directly applicable to mine waste. Although total Hg and methyl-Hg concentrations are locally high in some mine waste samples, little Hg appears to be exported from these Hg mines in stream sediment primarily due to the arid climate and lack of precipitation and mine runoff in this region.

Gold mining related mercury contamination in Tongguan, Shaanxi Province, PR China by Xinbin Feng; Qianqin Dai; Guangle Qiu; Guanghui Li; Lei He; Dingyong Wang (1955-1968).
Elemental Hg–Au amalgamation mining practices are used widely in many developing countries resulting in significant Hg contamination of surrounding ecosystems. The authors examined for the first time Hg contamination in air, water, sediment, soil and crops in the Tongguan Au mining area, China, where elemental Hg has been used to extract Au for many years. Total gaseous Hg (TGM) concentrations in ambient air in the Tongguan area were significantly elevated compared to regional background concentrations. The average TGM concentrations in ambient air in a Au mill reached 18,000 ng m−3, which exceeds the maximum allowable occupational standard for TGM of 10,000 ng m−3 in China. Both total and methyl-Hg concentrations in stream water, stream sediment, and soil samples collected in the Tongguan area were elevated compared to methyl-Hg reported in artisanal Au mining areas in Suriname and the Amazon River basin. Total Hg concentrations in vegetable and wheat samples ranged from 42 to 640 μg kg−1, all of which significantly exceed the Chinese guidance limit for vegetables (10 μg kg−1) and foodstuffs other than fish (20 μg kg−1). Fortunately, methyl-Hg was not significantly accumulated in the crops sampled in this study, where concentrations varied from 0.2 to 7.7 μg kg−1.

Effects of acid-sulfate weathering and cyanide-containing gold tailings on the transport and fate of mercury and other metals in Gossan Creek: Murray Brook mine, New Brunswick, Canada by Tom A. Al; Matthew I. Leybourne; Antu C. Maprani; Kerry T. MacQuarrie; John A. Dalziel; Don Fox; Phillip A. Yeats (1969-1985).
Gossan Creek, a headwater stream in the SE Upsalquitch River watershed in New Brunswick, Canada, contains elevated concentrations of total Hg (HgT up to 60 μg/L). Aqueous geochemical investigations of the shallow groundwater at the headwaters of the creek confirm that the source of Hg is a contaminated groundwater plume (neutral pH with Hg and Cl concentrations up to 150 μg/L and 20 mg/L, respectively), originating from the Murray Brook mine tailings, that discharges at the headwaters of the creek. The discharge area of the contaminant plume was partially delineated based on elevated pH and Cl concentrations in the groundwater. The local groundwater outside of the plume contains much lower concentrations of Hg and Cl (<0.1 μg/L and 3.8 mg/L, respectively) and displays the chemical characteristics of an acid-sulfate weathering system, with low pH (4.1–5.5) and elevated concentrations of Cu, Zn, Pb and SO4 (up to 5400 μg Cu/L, 8700 μg Zn/L, 70 μg Pb/L and 330 mg SO4/L), derived from oxidation of sulfide minerals in the Murray Brook volcanogenic massive sulfide deposit and surrounding bedrock. The HgT mass loads measured at various hydrologic control points along the stream system indicate that 95–99% of the dissolved HgT is attenuated in the first 3–4 km from the source. Analyses of creek bed sediments for Au, Ag, Cu, Zn, Pb and Hg indicate that these metals have partitioned strongly to the sediments. Mineralogical investigations of the contaminated sediments using analytical scanning electron microscopy (SEM), transmission electron microscopy (TEM) and scanning transmission electron microscopy (STEM), reveal discrete particles (<1–2 μm) of metacinnabar (HgS), mixed Au–Ag–Hg amalgam, Cu sulfide and Ag sulfide.

Mercury mobility in unsaturated gold mine tailings, Murray Brook mine, New Brunswick, Canada by Sean A. Shaw; Tom A. Al; Kerry T.B. MacQuarrie (1986-1998).
Elevated concentrations of Hg are present (averaging 36 μg/g), mainly as cinnabar, in the Murray Brook Au deposit, located in northern New Brunswick, Canada. After the mined ore was subjected to CN leaching, the tailings were deposited in an unsaturated pile, and 10 a after mine closure an estimated 4.7 × 103  kg of CN and 1.1 × 104  kg of Hg remain in the pile. Elevated Hg concentrations have been measured in the groundwater (up to 11,500 μg/L) and surface water (up to 32 μg/L) down-gradient of the tailings. To investigate the controls on Hg mobility and leaching persistence, laboratory experiments were conducted using unsaturated columns filled with tailings. Within the first 0.2 pore volumes (PV) eluted, the concentrations of Hg and CN increased to peak concentrations of 12,900 μg Hg/L and 16 mg CN/L, respectively. In the subsequent 0.9 PV, concentrations decreased to approximately 1300 μg Hg/L and 2.8 mg CN/L. Thermodynamic calculations demonstrate that >99.8% of the mobilized Hg in the tailings pore water is in the form of Hg–CN complexes, indicating that Hg mobility to the surrounding aquatic environment is directly dependent on the rate of CN leaching. One-dimensional transport simulations suggest that leached CN can be partitioned into conservative (24%) and non-conservative (76%) fractions. Extrapolation of simulation results to the field scale suggests that CN, and by extension Hg, will continue to elute from the tailings for at least an additional 130 a.

The Carson River flows in a closed basin system and the total flow of the river water decreases downstream due to both evaporation and consumptive uses. This river system is fed primarily by snow pack in the Sierra Nevada during the winter, which flows down gradient following melting in spring and summer. Water loss through evaporation in the Carson River results in a downstream buildup of conservative elements such as Cl and certain oxyanion forming elements including Se, Mo and W, which are known to interfere with the transformation of Hg within the S cycle. In addition to these naturally occurring hydrologic processes and the resulting affects on water chemistry, the Carson River Basin has been historically impacted by Au and Ag mining that used Hg amalgamation techniques. Contamination of Hg in the Carson River system is now well documented and published Hg concentrations in different environmental compartments are extremely high. In this study, hydrologically driven changes in water chemistry of the river system and the resulting effects on Hg cycling were examined. Results show that periods of low water flow correspond to high water pH (up to 8.3), relatively high concentrations of oxyanion forming elements (e.g., As, Se, Mo and W), and low Hg methylation potential in sediment. In contrast, periods of high flow bring about dilution, which results in lower pH (∼7), lower concentrations of oxyanion forming elements, but higher Hg methylation potential. Overall, changes in flow regimes likely affect rates of methyl-Hg (MeHg) production through a combination of factors such as high pH, which favors MeHg demethylation, and the occurrence of relatively high concentrations of Group VI oxyanions that could interfere with microbial SO4 reduction and MeHg production.

Weathering versus atmospheric contributions to mercury concentrations in French Guiana soils by Stephane Guedron; Catherine Grimaldi; Catherine Chauvel; Lorenzo Spadini; Michel Grimaldi (2010-2022).
This work focuses on two possible sources of Hg in tropical soils, (i) lithogenic Hg from in situ weathering of soil parental material, and (ii) exogenic Hg from natural long-term atmospheric inputs and anthropogenic input from past and present industrial activities. The concentration of lithogenic Hg [Hg]lithogenic was based on comparison of measured Hg concentration with those of elements resistant to weathering such as Nb, U, Zn, Fe. Exogenic Hg was quantified by subtracting [Hg]lithogenic from total Hg concentrations. This calculation was applied to 4 French Guiana soil profiles, 3 profiles on the same toposequence (ferralsol, acrisol, hydromorphic soil) and one acrisol close to a Au mine, where elemental Hg is used. In all profiles, [Hg]lithogenic varied slightly and was always below 40 μg kg−1, whereas [Hg]exogenic varied considerably and reached 500 μg kg−1. The highest [Hg]exogenic was calculated for the upper horizon of the acrisol close to Au mining activity, but also in the ferralsol. Concentrations of Hg were insignificant in the compact alterite in acrisols. It was concluded that pedogenesis processes that affect the natural Hg supply, combined with anthropogenic sources, explain the Hg concentrations in these tropical soils.

Use of constructed wetlands with four different experimental designs to assess the potential for methyl and total Hg outputs by Mae Sexauer Gustin; Prithviraj V. Chavan; Keith E. Dennett; Susan Donaldson; Eric Marchand; George Fernanadez (2023-2035).
This study used 10 parallel, smallscale constructed wetlands to investigate the potential for methylmercury (MeHg) production and water quality improvement using water and sediment from a creek that is a significant source of non-point nutrient, sediment and Hg pollution to a pristine river. The 4 replicated experimental designs utilized: (1) creek or Hg-contaminated water (25–320 ng Hg L−1) and creek or Hg-contaminated sediment (0.86 ± 0.52 μg Hg g−1) (MW-MS), (2) Hg contaminated water and clean sediment (0.09 ± 0.03 μg Hg g−1) (MW-CS), (3) clean water (effluent from a wastewater treatment plant; 4–16 ng Hg L−1) and Hg contaminated sediment (CW-MS), and (4) clean water and clean sediment (CW-CS). All designs functioned as sinks for N, P, sediment, and total Hg (THg). However, designs receiving clean water as the influent exhibited the least removal.Seasonal variations in net MeHg output were observed for designs with MW-MS and CW-MS, with concentrations peaking during warmer months. Designs with CS did not exhibit clear seasonal trends. Wetlands with CW and MS were the greatest MeHg sources. This was probably due to the fact that the treated wastewater had greater SO 4 2 - and total organic C (TOC) concentrations, lower pH, and, in general, higher temperatures than the creek water, and to the greater pool of Hg available in the Hg contaminated sediment, all of which could lead to enhanced Hg methylation. Temperature and SO 4 2 - correlated best with MeHg output in all designs. Although data from these small systems cannot be scaled up to predict the response in larger wetlands, results indicated that the benefits of a wetland, such as nutrient, suspended solids and THg removal, should be considered together with the risk of MeHg production.