Watershed influences on the transport, fate and bioavailability of mercury in Lake Superior: Field measurements and modelling approaches

The issuance of fish consumption advisories in US states bordering Lake Superior has heightened the need for understanding the biogeochemical cycling and transformations of mercury in this great lake. Major routes of mercury (Hg) transport to lakes include atmospheric deposition (wet and dry), direct discharges and riverine (watershed) inputs. The specific objectives of this ongoing study are to: (i) determine the speciation and bioavailability of Hg transported to Lake Superior (ii) determine the importance of watershed‐specific characteristics that control physical and chemical forms of Hg; (iii) identify key mechanisms controlling Hg bioavailability and speciation in near‐shore zones relative to open lake regions; and (iv) provide process‐level information to compliment concurrent development of Hg fate and transport models of the Lake Superior ecosystem. Three tributaries of Lake Superior were chosen for detailed field study based on previous results and particular watershed characteristics. Mixing zones represent a potentially important zone of Hg entry into the food chain, and were sampled for biota, water and sediment in transects between the tributary mouth and the lake end member. Sampling of open‐water sites was conducted during Environmental Protection Agency‐sponsored cruises on the research vessel Lake Guardian. Results from our work on Lake Superior tributaries demonstrate that dissolved organic carbon and methylmercury (MeHg) export was greatest from watersheds containing wetlands. In Lake Superior, concentrations of Hg species were small at pelagic stations (total mercury (HgT) averaged 0.49 ng/L, MeHg averaged 6.4 pg/L). In contrast, MeHg concentrations in tributaries ranged from 100 to 250 pg/L. Watershed sites dominated by wetlands exhibited the greatest MeHg concentrations, occasionally in excess of 12 ng/L. Samples of bulk zooplankton ranged from 20 to 130 ng/g dry weight HgT and from 15 to 45 ng/g dry weight MeHg, and demonstrated typical bioacculmulation of mercury as well as distinct seasonality in concentrations.     

Trophic structure and mercury transfer in the subarctic fish community of Great Slave Lake,Northwest Territories,Canada

In recent decades, mercury concentrations have increased in fish of Great Slave Lake (GSL), a subarctic great lake in northern Canada with important recreational, subsistence, and commercial fisheries. This study characterized habitat use and trophic position of common fish species in GSL near the City of Yellowknife (Northwest Territories, Canada), measured mercury concentrations in water and in taxa from lower trophic levels of the food web, and examined trophic and biological influences on mercury concentrations within and among fish species. Northern pike (Exos lucius) and lake whitefish (Coregonus clupeformis) fed predominantly nearshore, cisco (Coregonus artedi) and longnose sucker (Catostomus catostomus) fed predominantly offshore, and burbot (Lota lota) fed roughly equally in both habitats. Habitat-specific feeding did not influence mercury bioaccumulation in fish, in contrast with published studies of smaller lakes. Water concentrations of total mercury and methylmercury were low and showed little spatial variation among sites or depths. Zooplankton (>200 μm) had similarly low methylmercury concentrations as littoral and profundal amphipods, suggesting little habitat-variation of mercury exposure near the base of the food web. Age, size, and trophic position were significant explanatory variables for muscle total mercury concentrations within populations of fish species. Among fish species, size and trophic position explained 80% of the variation in muscle total mercury concentrations. This study generated the most comprehensive dataset to date on mercury bioaccumulation in the food web of GSL, which will serve as a baseline for future studies of this great lake.     

A comparison of mercury cycling in Lakes Michigan and Superior

Mercury cycling in Lake Superior and Lake Michigan was evaluated based on measurements of mercury levels, modeling of evasional fluxes, and development of first-order mass balance models. Total mercury, methylmercury, and dissolved gaseous mercury were measured on sampling cruises in Lake Michigan (2005) and Lake Superior (2006). Average total mercury concentrations in unfiltered surface water were higher in Lake Michigan (420 ± 40 pg/L) compared to Lake Superior (210 ± 20 pg/L). Methylmercury levels were below the detection limit in Lake Michigan. Larger sample volumes were collected to lower detection limits in Lake Superior in 2006 and methylmercury levels averaged 7 ± 6 pg/L. Dissolved gaseous mercury concentrations were also higher in Lake Michigan (27 ± 7 pg/L) compared to Lake Superior (14 ± 8 pg/L). Evasional fluxes were estimated using a two-film model for air–water exchange. The annual evasional flux in Lake Michigan was determined to be ~ 380 kg/yr from Lake Michigan and ~ 160 kg/yr from Lake Superior. Total mercury burdens in each lake were estimated to be ~ 2500 kg in Superior and ~ 2100 kg in Lake Michigan demonstrating that evasional fluxes play an important role in the mass balance of each lake, particularly Lake Michigan. A simple first-order mass balance model demonstrates the importance of air–water exchange and sedimentation as primary removal processes for Hg in each lake. Uncertainties in the mass balance model are highlighted due to lack of key data, particularly in Lake Superior.     

武汉城市湖泊汞的迁移与富集

对武汉远郊、城乡结合部和市区3种环境中6个湖泊的水、界面水、沉积物和生物(鱼)进行调查采样,用离心机离心出沉积物中的孔隙水,用原子荧光光谱仪进行汞含量测定。以土壤—水—界面水—孔隙水—沉积物—生物为轴线,探讨了汞在研究区土壤—沉积物系统、湖水—沉积物系统和湖水—界面水—孔隙水系统中的分配以及湖泊鲢鱼肉中汞与沉积物和水中汞的关系。建立了武汉城市湖泊汞的迁移、富集理想模式:湖泊水汞经悬浮物吸附沉淀而富集于沉积物中,沉积物中汞经化学转化传输给孔隙水;存在于悬浮物中的界面水汞,经解吸附后向湖水扩散而产生二次污染。湖水汞被鱼吸收而产生生物富集。从而得出湖水—界面水—孔隙水—沉积物、湖水—鱼的两种富集机制。     

Sedimentation dynamics within a large shallow lake and its role in sediment transport in a continental-scale watershed

A comprehensive understanding of the sedimentation dynamics within Lake Winnipeg (surface area: 23,750 km²) and its role in sediment transport in the downstream river system was achieved by determining the properties of lake bottom sediment and patterns of sediment accumulation rates and by constructing a conceptual total (i.e., organic and inorganic) sediment budget. Net deposition was the governing process in the South and North Basins, whereas transportation dominated in the Narrows. The largest fluvial source of sediments to the lake, the Red River, supplies 35% of the total sediment load. Although accumulation rates in profundal zones progressively decreased northward from this source at the south end of the lake, high accumulation rates with low inventories of fallout radionuclides in the northern margin of the North Basin indicate a second sediment source, which was determined to be erosion of north shore banks, which accounts for up to 50% of the total sediment load to the lake. The nearshore-offshore gradient in bottom sediment properties in the North Basin confirmed that the signature of this source can reach at least 20 km southward into the lake. However, the properties of bottom sediments, sedimentation dynamics, and sediment budget suggested that some of the materials eroded from the north shore are exported without interaction with the lake bottom and this local sediment source is the dominant source for the downstream river system. It was concluded that Lake Winnipeg effectively disconnects the downstream Nelson River from sediment transport processes in its upstream watershed (953,250 km²).     

Content and Chemical Form of Mercury and Selenium in Lake Ontario Salmon and Trout

The content and chemical form of mercury and selenium were determined in the edible tissue of salmon (coho, chinook) and trout (lake, brown) taken offshore from Lake Ontario near Rochester, New York. For all fish species, total mercury content ranged from 0.3 to 0.8 μg/g (fresh-weight), which is similar to concentrations commonly found in canned tuna. Most of the total mercury (63 to 79 percent) was present as methylmercury, the remainder being divalent inorganic mercury. For all species, 6 to 45 percent of the total selenium content was present as selenate (SeVI), the remainder being selenite (SeIV) and selenide (Se-11). On a molar basis, total selenium content usually exceeded that of total mercury. Samples of smoked and unsmoked brown trout fillets were also examined. Based on the results of this study there is no immediate human health hazard from mercury and selenium. However, there is a need to report specific chemical forms of these metals in Lake Ontario salmonid fishes so that elevated concentrations can be better evaluated.     

Food web structure and mercury trophodynamics in two contrasting embayments in northern Lake Victoria

Nearshore regions of lakes are important sources of fish, and can be strongly influenced by anthropogenic inputs of nutrients as well as contaminants. This study characterizes food web structure, mercury concentrations, and biomagnification of mercury in two embayments in northern Lake Victoria that differ in their connectivity to the open lake, trophic status, and the influence of local anthropogenic pollution. Murchison Bay is a semi-confined hypereutrophic bay in a densely populated region, while Napoleon Gulf is mesotrophic and is well flushed with water from the open lake. Based on stable carbon and nitrogen isotope analysis, food web structure was similar at both sites, with short food chains and conspecific fish occupying similar trophic positions. However, there were strong differences in net phytoplankton δ¹⁵N and δ¹³C between sites; net phytoplankton δ¹³C was largely related to trophic status, while δ¹⁵N values appeared to be influenced by inputs of human waste and the prevalence of biological nitrogen fixation. Total mercury (THg) concentrations in fish were consistently below 200 ng/g wet weight, and despite elevated THg concentrations in water in Murchison Bay, THg concentrations in net phytoplankton and fish from both embayments did not differ, highlighting that THg in water is not always a good predictor of concentrations in fish. We also observed that biomagnification of mercury was occurring at a lower rate in Murchison Bay than in Napoleon Gulf, and we propose that the hypereutrophic state of Murchison Bay may be acting to reduce potential Hg exposure for higher trophic level fish.     

Algal-Available Particulate Phosphorus in the Great Lakes Basin

For the purpose of comparing the relative availability of particulate phosphorus (P) from various sources to the Great Lakes, algal-available P was determined on suspended solids and bottom sediments from tributaries, wastewater suspended solids, lake bottom sediments, and eroding bluff solids from the region. Physicochemical and bioassay methods were used to estimate the rate and extent of available P release from particulates. Considering all types of particulates examined, ultimately available P ranged from nil to approximately 70 percent of total phosphorus (Total-P) content. During algal bioassays, changes in levels of base-extractable inorganic P (R-NaOH-P) in tributary suspended solids were nearly equivalent to the amounts of P used by algae during bioassays. For the tributary solids, ultimately available P averaged approximately 90 percent of R-NAOH-P. Consistent differences were found in amounts of available P among particles from different sources. Sources of particle-bound P ranked in order of decreasing availability were: wastewater solids, lake bottom sediments, tributary solids, and eroding bluff solids. Differences in available P release rates also existed among the different types of particles. Wastewater solids displayed the largest first-order release rates, eroding bluff samples and tributary-suspended solid samples that were high in apatite showed essentially no available P release, while other tributary suspended solids displayed intermediate release rates.     

Do wood fibers from a pulp mill affect the distribution of total and methyl mercury in river sediments?

The St. Lawrence River near Cornwall Ontario is affected by industrial mercury contamination of sediments and biota. It has been suggested that pulp and paper mill effluents may stimulate bacterial mercury methylation in these sediments, leading to contamination of aquatic biota. To test this hypothesis, we examined sediment–porewater dynamics of total mercury (THg) and methyl mercury (MeHg) at a site with high concentrations of wood fibers from a pulp and paper mill effluent and a nearby reference site with low wood fiber content. Dissolved phase THg (THg_diss) and MeHg (MeHg_diss) in porewater profiles showed that 38 ± 30.9% (SD) of THg in porewaters was in the methylated form regardless of wood fiber content. MeHg_diss and THg_diss concentrations were homogeneous between porewater and overlying water, indicating (a) that there is minimal net diffusion of MeHg_diss and THg_diss and (b) that redox-dependent processes such as sulfate reduction and Fe reduction were not associated with MeHg_diss distribution in these sediment profiles. MeHg and THg in solid phase showed coincident subsurface peaks at depths > 40 cm suggesting either that historical deposits of MeHg on particles (MeHg_(p)) are preserved in deep sediments, or that Hg methylation is active in deep sediments.     

Suspended solids transport in the regulated River Blithe,Staffordshire, U.K.

Suspended solids concentrations and turbidity were monitored on the regulated River Blithe at two sites downstream of the reservoir for a period of 18 months. Changes in the suspended solids loads transported and the nature of the material in suspension are related to dam overspill and tributary flood events. A hysteretic relationship between suspended solids concentrations and discharge is characteristic of both sites, sediment supply being limited within the regulated river. Downstream of the dam, rapid bank erosion occurred on meander bends but the suspended solids loads transported by the regulated river relate more to the resuspension and transport of tributary injected sediments and scouring of a dense periphyton. Close to the dam, fine biogenic matter dominated the seston, which scanning electron microscopy revealed to contain algal fragments and inorganic diatom frustules, but downstream, tributary-derived minerogenic particles were dominant.     

Responses of lake macrophyte beds dominated by Eurasian watermilfoil (Myriophyllum spicatum) to best management practices in agricultural sub-watersheds: Declines in biomass but not species dominance

Long-term studies of macrophyte beds growing near streams in Conesus Lake, New York, have revealed a high biomass and continuing dominance of the invasive rooted species Eurasian watermilfoil (Myriophyllum spicatum). We tested whether agricultural best management practices (BMPs) designed to reduce tributary nutrient and soil loss from the watershed could reduce populations of Eurasian watermilfoil downstream in the lake littoral. Six macrophyte beds were monitored during a 3-year baseline period (2001–2003) prior to the implementation of BMPs and for a 4-year experimental period after a variety of agricultural BMPs were implemented in three sub-watersheds. For three macrophyte beds downstream from sub-watersheds managed as part of our project, quadrat biomass decreased by 30–50% and was statistically lower than Pre-BMP baseline values in 7 of 11 experimental sample years. Biomass loss primarily in the form of the dominant Eurasian watermilfoil ranged from 6.2 to 10 t wet weight for each bed. The declines in biomass coincided with significant annual and January–August decreases in the concentrations and fluxes of dissolved nutrients, total phosphorus, and total suspended solids in nearby streams. For three macrophyte beds downstream from watersheds in which landowners applied less extensive or no new agricultural management, biomass was statistically indistinguishable from Pre-BMP baseline values in all 12 experimental sample years. Milfoil remained the overwhelmingly dominant species at all sites during the entire study period. These results provide impetus for the use of watershed nutrient management to control the nuisance growth of Eurasian watermilfoil on a local scale in the lake littoral.     

Wave Climate and Potential Longshore Sediment Transport Patterns,Nottawasaga Bay,Ontario

A storm wave climate for Nottawasaga Bay, Ontario, is hindcast, using the SMB technique, from wind records at Cove Island for the period 1966-1970. Thirteen wave classes, defined on the basis of significant wave height, period, and direction, are identified and these are used as inputs into a computer model of wave refraction within the bay. The total and longshore component of wave energy flux are determined for each wave class. The total annual energy flux P₁ and the net longshore component P₁ are determined for 55 points spaced at one kilometre intervals by multiplying the value of energy flux at each point by the mean annual frequency for that wave class and summing the values for all relevant waves. A simple model of potential erosion, transport, and deposition patterns within the bay is then developed from the variation in the net P₁ values. The predicted model is compared with geomorphological evidence of sediment transport patterns visible in vertical aerial photographs and with measurements of erosion and accretion at selected points. It is concluded that the continued eastward growth of the Wasaga spit results primarily from deposition of sediments from the Nottawasaga River rather than littoral transport.     

小浪底水库支流倒灌与淤积形态模型试验

利用小浪底水库实体模型开展水库拦沙后期运用方式长系列年试验,对争议较大的库区支流倒灌及其淤积形态问题进行重点分析。结果表明:库区最大支流畛水河口门狭窄且库容较大,拦门沙问题最为突出,其纵坡面形态与设计有一定的差别;支流年淤积量与当年大于2600 m3/s流量时段的总水量有较好的相关性;通过优化水库运用方式可较长时期保持动态三角洲淤积形态,有利于支流库容的有效利用;水库干流河床处于动平衡状态时,支流河床仍然会逐渐淤积抬升而使得干支流淤积面高差趋于减少。     

Total and methyl mercury accumulation in 1994–1995 Lake Michigan lake trout and forage fish

As part of the Lake Michigan Mass Balance Project, total and methyl mercury were determined for lake trout (Salvelinus namaycush) and five forage fish species collected from Lake Michigan near Saugatuck, Michigan, and Port Washington, Sheboygan Reef, and Sturgeon Bay, Wisconsin, between 1994 and 1995. With a mean concentration of 179 ng/g wet wt., whole lake trout total mercury (Hg_T) concentrations ranged between 27.6 and 348 ng/g wet wt. For combined sites, 1–4 yrs, 5–6 yrs, 7–11 yrs, and 12–15 yrs lake trout mean Hg_T concentrations were 73.7, 130, 212, and 280 ng/g, respectively. Forage fish species alewife (Alosa pseudoharengus), bloater (Coregonus hoyi), slimy sculpin (Cottus cognatus), deepwater sculpin (Myoxocephalus thompsoni), and rainbow smelt (Osmerus mordax) had mean Hg_T concentrations of 63.8, 55.3, 36.7, 51.4, and 35.2 ng/g wet wt., respectively. With the exception of alewife, bloater, and slimy sculpin, all fish species contained approximately 100% methyl mercury (MeHg). Field bioaccumulation factors (BAF) were consistent with a Lake Michigan food chain that is more efficient at transferring MeHg to higher trophic levels than some inland lakes. This and other studies of lake trout from Lake Michigan document decreasing Hg_T concentrations in lake trout from 1971 to 1985 and constant or increasing concentrations between 1985 and 2000. These observations were supported by a similar trend in Lake Michigan Hg sediment fluxes. To our knowledge, this is the most intense two year study of mercury in fish for any Great Lake or other large fresh water system and is one of the most complete studies of mercury cycling in the Lake Michigan food chain.     

Mercury and Zinc in the Sediments of Seneca Lake,Seneca River,and Keuka Outlet,New York

Levels of total mercury and total zinc in the sediments of Seneca Lake, New York, and of its principal tributary and outflow, show a pattern of industrial and municipal pollution in a predominantly rural environment. An interpolation technique based on the relationship of heavy metal concentration to overlying water depth is used to estimate the total mercury content of the upper 2 cm of Seneca Lake sediments, and the increment of mercury above an assumed unperturbed distribution. An approximate mass balance suggests that defunct industry and a 200 megawatt coal-burning power plant represent comparable pollution sources, and that most of the emitted mercury leaves the watershed in aqueous solution or as vapor. The distribution of zinc parallels that of mercury, with a relatively constant Zn/Hg ratio in the lake sediments.     

Record of mercury pollution in sediments of lakes Nakaumi and Shinji in Japan

Two sediment core profiles from lakes Shinji and Nakaumi were studied in order to understand the level of mercury (Hg) pollution in lakes in northwestern Japan. The sedimentation rates were established on the basis of the activity of [²¹⁰Pb] and [¹³¹Cs] in the sediments. In Lake Shinji, the highest level of Hg (130 ng g^–1) in the sediment was found at a depth of 20–22 cm, while 195 ng g^–1 was found at a depth of 10–12 cm in the core profiles from Lake Nakaumi. The relative increase in Hg concentration in lake sediments started after 1960 and significant contamination events occurred in the early 1960s. Mercury profiles in lake sediments from lakes Shinji and Nakaumi are found to reflect the anthropogenic Hg released into the environment in the 1950s and 1960s. A pronounced maximun concentration of Hg is found in both lakes, where sediment accumulation rates differ.     

Physico-Chemical Model of Toxic Substances in the Great Lakes

A physico-chemical model of the fate of toxic substances in the Great Lakes is constructed from mass balance principles, incorporating principal mechanisms of paniculate sorption-desorption, sediment-water and atmosphere-water interactions, and chemical and biochemical decay. The steady state mass balance model of the suspended solids in the open lake water yields net solids loss rates from 0.02 mjdfor Saginaw Bay to 1.22 m/dfor Lake Ontario. Calibration of the toxic model is through comparison to plutonium-239 data collected in the 1970s using a 23-year time variable calculation. The results indicate that, in general, the sediments are interactive with the water column in the Great Lakes through resuspension and horizontal transport. Fifty percent response times of ²³⁹Pu following a cessation of load extend beyond 10 years with sediment resuspension. The calibrated model was also applied to polychlorinated biphenyl (PCB) using a high and low estimate of contemporary external load and with and without volatilization. The lower load level (lake range 640 to 1,390 kg/yr) with volatilization (at an exchange rate of 0.1 m/d) appears to be more representative of observed surface sediment data for the open lake waters. Calculated water column concentrations for the lower load level with and without volatilization ranged from 0.25 to 0.90 ng/Lfor open lake waters. Fifty percent response times for PCB following cessation of load varied from less than 5 years when volatilization was included to 10 to 20 years without volatilization. Comparison of these response times to decline of concentrations of PCB in Lake Michigan bloaters indicates that, at least for that lake, volatilization is occurring at an exchange rate of about 0.1 m/d.     

A hydrodynamic approach to modeling phosphorus distribution in Lake Erie

The purpose of this paper is to show how a high-resolution numerical circulation model of Lake Erie can be used to gain insight into the spatial and temporal variability of phosphorus (and by inference, other components of the lower food web) in the lake. The computer model simulates the detailed spatial and temporal distribution of total phosphorus in Lake Erie during 1994 based on tributary and atmospheric loading, hydrodynamic transport, and basin-dependent net apparent settling. Phosphorus loads to the lake in 1994 were relatively low, about 30% lower than the average loads for the past 30 years. Results of the model simulations are presented in terms of maps of 1) annually averaged phosphorus concentration, 2) temporal variability of phosphorus concentration, and 3) relative contribution of annual phosphorus load from specific tributaries. Model results illustrate that significant nearshore to offshore gradients occur in the vicinity of tributary mouths and their along-shore plumes. For instance, the annually averaged phosphorus concentration can vary by a factor of 10 from one end of the lake to the other. Phosphorus levels at some points in the lake can change by a factor of 10 in a matter of hours. Variance in phosphorus levels is up to 100 times higher near major tributary mouths than it is in offshore waters. The model is also used to estimate the spatial distribution of phosphorus variability and to produce maps of the relative contribution of individual tributaries to the annual average concentration at each point in the lake.     

Phosphorus fractionation in soil and sediments along a continuum from agricultural fields to nearshore lake sediments: Potential ecological impacts

The movement of phosphorus (P) from agricultural fields to streams and deposition in the nearshore of the lake presents a continuum of related physical and chemical properties that act to partition P into different physico-chemical fractions. We investigated changes in soil and sediment P fractionation as material was eroded from predominantly agricultural fields, transported via stream sediments, and deposited in a nearshore lake environment. Total phosphorus content of the soils and sediment decreased from field soils with an average concentration of 553.81 mg P kg^? 1 to 202.28 mg P kg^? 1 in stream sediments to 67.47 mg P kg^? 1 in lake sediments. Significant changes in P fractionation occurred during erosion, transport, and deposition of the particulate or sediment phase. The fractionation of P within the soils and sediments changed significantly from aluminum and organic matter associated P dominant in field soils to calcium associated P dominant in nearshore lake sediments. Various physical and chemical processes appear to be responsible for these transformations which impact the mobility and bioavailability of P. A significant amount of P was lost from field soils as they were transported and deposited. This P has either become available to biota or deposited in deeper portions of the lake system. Ultimately, the impact of P export on the nearshore lake environment may be influenced by the changes in P fractionation that occurred during transport and deposition and by the influence of macrophytes on the biogeochemical cycling of P in the sediment.     

The Vertical Distribution of Runoff and its Suspended Load in Lake Malawi

Lake Malawi, in south-eastern Africa, is subject to increasing loading of suspended solids caused by land use pressure in its watershed. Whether this load is transported into the lake as overflow, interflow or deep underflow determines to a large extent its effect on the lake ecosystem. In this paper, vertical distributions of suspended solids in the Linthipe River delta region of the lake are described from multiple surveys during two rainy seasons. These data are supplemented by data from a single survey near four northern rivers also tributary to the lake. Profiles of temperature, conductance, and suspended solids concentrations (SSC, estimated from optical backscatter and beam transmission) are used to identify fluvial intrusions into the water column. Most inflow plunged to the seasonal metalimnion where it spread along high density gradients as interflow. While SSC in surface plumes rarely exceeded 10 g m⁻³, and in intrusions in the lower metalimnion was rarely greater than 1 g m⁻³, concentrations up to 420 g m⁻³ were recorded in interflow near the thermocline. Although storm runoff density often exceeded 100 m depth-equivalence in the lake, underflow density was reduced to metalimnion-equivalence (30–50 m depth) within a few 100s of meters of the river mouth. We attribute bottom-attached turbid layers, and the few unattached turbid layers in the lower metalimnion, all with positive conductance anomalies, to sediment resuspension and not to runoff. We conclude that the upper metalimnion is the prevailing pathway carrying watershed runoff horizontally throughout Lake Malawi.