Recent increase in atmospheric deposition of mercury to California aquatic systems inferred from a 300-year geochronological assessment of lake sediments

Age-dated sediment cores from 4 remote lakes across California were analyzed for total Hg (Hg_T) concentration as a function of pre- and post-industrialization. Particle size, magnetic susceptibility and organic C and N, were measured to determine if the Hg concentration in sediment cores could be related to atmospheric deposition and/or watershed processes. Results indicate that (a) for each lake modern (1970–2004) Hg_T lake sediment concentrations have increased by an average factor of 5 times more than historic (pre-1850) Hg_T concentrations; (b) the ratio of modern to pre-industrial lake sediment Hg_T for these lakes are higher than estimated for other locations where atmospheric deposition is presumed to be the main source of Hg; (c) 2 of the 4 studied lakes demonstrated significant relationships between Hg_T concentrations and percentage organic material (r² = 0.68 and p < 0.01; r² = 0.67 and p < 0.01) whereas the other two indicated no significant relationship (r² = 0.05 and p = 0.51; r² = 0.12 and p = 0.36).     

Atmospheric deposition of cadmium in the northeastern USA

Lake sediment cores, dated by ²¹⁰Pb, were collected from Spectacle Pond (SP), Massachusetts, and Side Pistol Lake (SPL) and Sargent Mountain Pond (SMP), Maine, USA. SP is a kettle seepage lake in granitic sand and gravel. SMP is a drainage pond on granite with little soil in the small watershed. SPL is a drainage lake in granitic till. The three cores were analyzed for total Cd. For SP and SMP, maximum concentrations of 1.7 and 3.9 mg/kg, four and eight times background concentrations, respectively, occur in the late 1960s. Accumulation rates reach maximum values concurrently with concentration and are 0.054 and 0.016 μg/cm²/a, more than 10 times background. Concentration and accumulation rate age relationships in SMP and SP are similar for background values, timing and magnitude of increase to peak values, and the decrease nearly to background values since about 1975. The chemical response to decreased atmospheric deposition lags in SPL sediment. Kettle-like lakes more clearly indicate changes in atmospheric deposition than drainage lakes.     

Mercury contamination chronologies from Connecticut wetlands and Long Island Sound sediments

Sediment cores were used to investigate the mercury deposition histories of Connecticut and Long Island Sound. Most cores show background (pre-1800s) concentrations (50-100 ppb Hg) below 30-50 cm depth, strong enrichments up to 500 ppb Hg in the core tops with lower Hg concentrations in the surface sediments (200-300 ppb Hg). A sediment core from the Housatonic River has peak levels of 1,500 ppb Hg, indicating the presence of a Hg point source in this watershed. The Hg records were translated into Hg contamination chronologies through ²¹⁰Pb dating. The onset of Hg contamination occurred in ~1840-1850 in eastern Connecticut, whereas in the Housatonic River the onset is dated at around 1820. The mercury accumulation profiles show periods of peak contamination at around 1900 and at 1950-1970. Peak Hg* (Hg*= Hg measured minus Hg background) accumulation rates in the salt marshes vary, dependent on the sediment character, between 8 and 44 ng Hg/cm² per year, whereas modern Hg* accumulation rates range from 4-17 ng Hg/cm² per year; time-averaged Hg* accumulation rates are 15 ng Hg/cm² per year. These Hg* accumulation rates in sediments are higher than the observed Hg atmospheric deposition rates (about 1-2 ng Hg/cm² per year), indicating that contaminant Hg from the watershed is focused into the coastal zone. The Long Island Sound cores show similar Hg profiles as the marsh cores, but time-averaged Hg* accumulation rates are higher than in the marshes (26 ng Hg/cm² a year) because of the different sediment characteristics. In-situ atmospheric deposition of Hg in the marshes and in Long Island Sound is only a minor component of the total Hg budget. The 1900 peak of Hg contamination is most likely related to climatic factors (the wet period of the early 1900s) and the 1950-1970 peak was caused by strong anthropogenic Hg emissions at that time. Spatial trends in total Hg burdens in cores are largely related to sedimentary parameters (amount of clay) except for the high inventories of the Housatonic River, which are related to Hg releases from hat-making in the town of Danbury. Much of the contaminated sediment transport in the Housatonic River Basin occurs during floods, creating distinct layers of Hg-contaminated sediment in western Long Island Sound. The drop of about 40% in Hg accumulation rates between the 1960s and 1990s seems largely the result of reduced Hg emissions and to a much lesser extent of climatic factors.     

The isotopic evolution of atmospheric Pb in central Ontario since AD 1800, and its impacts on the soils, waters, and sediments of a forested watershed, Kawagama Lake

A peat core from an ombrotrophic bog documents the isotopic evolution of atmospheric Pb in central Ontario since AD 1804 ± 53 (²¹⁰Pb dating). Despite the introduction of unleaded gasoline in the mid-1970’s, the ratio ²⁰⁶Pb/²⁰⁷Pb in atmospheric deposition has not increased as expected, but rather continues to decline. In fact, snowpack sampling (2005 and 2009) and rainwater samples (2008) show that the isotopic composition of atmospheric Pb today is often far less radiogenic than the gasoline lead that had been used in Canada in the past. The peat, snow, and rainwater data presented here are consistent with the Pb isotope data for aerosols collected in Dorset in 1984 and 1986 which were traced by Sturges and Barrie (1989) to emissions from the Noranda smelter in northern Quèbec, Canada’s largest single source of atmospheric Pb. Understanding atmospheric Pb deposition in central Ontario, therefore, requires not only consideration of natural sources and past contributions from leaded gasoline, but also emissions from metal smelting and refining.Lead in the streams which enter Kawagama Lake today (²⁰⁶Pb/²⁰⁷Pb = 1.16 − 1.19) represents a mixture between the natural values (1.191 − 1.201 estimated using pre-industrial lake sediments) and the values found in the humus layer of the surrounding forest soils (²⁰⁶Pb/²⁰⁷Pb = 1.15 − 1.19). In the lake itself, however, Pb is much less radiogenic (²⁰⁶Pb/²⁰⁷Pb as low as 1.09) than in the streams, with the dissolved fraction less radiogenic than particulate material. The evolution of Pb isotope ratios within the watershed apparently reflects preferential removal by sedimentation of comparatively dense, radiogenic, terrestrial particles (derived from the mineral fraction of soils) from the humus particles with lower ratios of ²⁰⁶Pb/²⁰⁷Pb (because of atmospheric Pb contamination). Despite the contemporary enrichments of Pb in rain and snow, concentrations of dissolved Pb in the lake are extremely low (sometimes below 10 ng/l), with Pb concentrations and Pb/Sc ratios approaching “natural” values because of efficient binding to particles, and their subsequent removal in the watershed.     

Toward a geochemical mass balance of major elements in Lake Qinghai,NE Tibetan Plateau: A significant role of atmospheric deposition

Sediments in Lake Qinghai archive important information about past environmental changes. In order to faithfully interpret the sediment records and constrain the elemental cycles, it is critical to trace various sources of sediments in the lake. The results show that the elemental input–output budgets are imbalanced for most major elements between riverine fluxes and mass accumulation rate (MAR) of Lake Qinghai sediments. A realistic model must include contributions of dry/wet atmospheric deposition that allow the major element mass balance for the lake to be defined. The budget estimation is based on mass balances of Si and Al, which are relatively immobile and carried to the lake via particulate forms. Estimated annual budget of dry atmospheric deposition is ∼1.3 ± 0.3 × 10³ kt/a (accounting for ∼65% of the total inputs) to the lake sediments, assuming local loess within the catchment as a candidate for dry atmospheric deposition to the lake. The resultant flux of 300 ± 45 g/m²/a falls within the flux average of the desert area (400 g/m²/a) and the loess plateau (250 g/m²/a), consistent with the geographical setting of Lake Qinghai. The role of atmospheric deposition would be more significant if wet deposition via rainfall and snow were taken into account. This highlights the potential importance of dust as a significant source for sediment preservation flux for other catchments worldwide. The results also indicate that nearly all Ca input was preserved in the lake sediments under modern conditions, consistent with Ca²⁺ supersaturation of the lake water.     

Whole-watershed mercury balance at Sagehen Creek, Sierra Nevada, CA

Few data are available on mercury (Hg) dynamics at high-elevation mountain sites. In this project, a whole-watershed approach was used to quantify major fluxes and pools of Hg in Sagehen basin, a closed basin in the Sierra Nevada mountains in California. Over a period spanning 9 months (January-September 2009), we estimated wet deposition inputs to the watershed at 3.8 μg m⁻². Dry deposition added additional Hg in the range of 0.30-2.45 μg m⁻² during this time period, and was the dominant deposition process during summer time. Seasonal snowpack accounted for only half of the Hg deposited by wet deposition. We suggest that photo-induced reduction of Hg(II) in snow and subsequent volatilization was responsible for this loss. Thus, snowpacks in the Sierra Nevada mountains likely reduce the effective atmospheric mercury flux via wet deposition due to significant emission fluxes prior to snowmelt. As such, wet Hg deposition could be of lesser importance as a Hg source in snow-dominated systems. Finally, stream runoff collected at the outlet of the watershed could account for only 4% of total Hg wet deposition suggesting that a large fraction of mercury deposition was sequestered in the ecosystem, specifically in the soils.     

Methylation of Hg downstream from the Bonanza Hg mine,Oregon

Speciation of Hg and conversion to methyl-Hg were evaluated in stream sediment, stream water, and aquatic snails collected downstream from the Bonanza Hg mine, Oregon. Total production from the Bonanza mine was >1360 t of Hg, during mining from the late 1800s to 1960, ranking it as an intermediate sized Hg mine on an international scale. The primary objective of this study was to evaluate the distribution, transport, and methylation of Hg downstream from a Hg mine in a coastal temperate climatic zone. Data shown here for methyl-Hg, a neurotoxin hazardous to humans, are the first reported for sediment and water from this area. Stream sediment collected from Foster Creek flowing downstream from the Bonanza mine contained elevated Hg concentrations that ranged from 590 to 71,000 ng/g, all of which (except the most distal sample) exceeded the probable effect concentration (PEC) of 1060 ng/g, the Hg concentration above which harmful effects are likely to be observed in sediment-dwelling organisms. Concentrations of methyl-Hg in stream sediment collected from Foster Creek varied from 11 to 62 ng/g and were highly elevated compared to regional baseline concentrations (0.11–0.82 ng/g) established in this study. Methyl-Hg concentrations in stream sediment collected in this study showed a significant correlation with total organic C (TOC, R² = 0.62), generally indicating increased methyl-Hg formation with increasing TOC in sediment. Isotopic-tracer methods indicated that several samples of Foster Creek sediment exhibited high rates of Hg-methylation. Concentrations of Hg in water collected downstream from the mine varied from 17 to 270 ng/L and were also elevated compared to baselines, but all were below the 770 ng/L Hg standard recommended by the USEPA to protect against chronic effects to aquatic wildlife. Concentrations of methyl-Hg in the water collected from Foster Creek ranged from 0.17 to 1.8 ng/L, which were elevated compared to regional baseline sites upstream and downstream from the mine that varied from <0.02 to 0.22 ng/L. Aquatic snails collected downstream from the mine were elevated in Hg indicating significant bioavailability and uptake of Hg by these snails. Results for sediment and water indicated significant methyl-Hg formation in the ecosystem downstream from the Bonanza mine, which is enhanced by the temperate climate, high precipitation in the area, and high organic matter.     

Pb chronology and trace metal geochemistry at Los Tuxtlas, Mexico, as evidenced by a sedimentary record from the Lago Verde crater lake

Lago Verde is a fresh-water maar found on the lower slopes of San Martin volcano, at the Sierra de Los Tuxtlas, Mexico, currently the northernmost remnant of the tropical rain forest in America. ²¹⁰Pb and ¹³⁷Cs analyzed in a sediment core were used to reconstruct the historical fluxes of Ag, Cd, Cu, Pb, Hg and Zn to the site during the last ∼ 150 yr. The ²¹⁰Pb_xs-derived sediment accumulation rates, the magnetic susceptibility, C/N ratios and δ¹³C data evidenced background conditions at the lake until 1960s, when enhanced erosion related to the clearing of large forested areas at Los Tuxtlas promoted higher accumulation rates of a heavier and more magnetic sedimentary material. Recent sediments from Lago Verde were found enriched by Pb (26-fold natural concentration level [NCLs]) and moderately enriched by Cd > Cu > Zn and Hg (6-, 5-, 4- and 4-fold corresponding NCLs, respectively). The fluxes of Cu, Hg, Pb and Zn have significantly increased since 1940s, with peak ratios of total modern to pre-industrial fluxes of 11, 11, 19 and 49, respectively. The lake occupies a relatively pristine, non-industrialized basin, and therefore the increased metal fluxes might be related to long-distance aeolian transport of trace metals.     

Anthropogenic contributions to atmospheric Hg, Pb and As accumulation recorded by peat cores from southern Greenland and Denmark dated using the C “bomb pulse curve”

Mercury concentrations are clearly elevated in the surface and sub-surface layers of peat cores collected from a minerotrophic (“groundwater-fed”) fen in southern Greenland (GL) and an ombrotrophic (“rainwater-fed”) bog in Denmark (DK). Using ¹⁴C to precisely date samples since ca. AD 1950 using the “atmospheric bomb pulse,” the chronology of Hg accumulation in GL is remarkably similar to the bog in DK where Hg was supplied only by atmospheric deposition: this suggests not only that Hg has been supplied to the surface layers of the minerotrophic core (GL) primarily by atmospheric inputs, but also that the peat cores have preserved a consistent record of the changing rates of atmospheric Hg accumulation. The lowest Hg fluxes in the GL core (0.3 to 0.5 μg/m²/yr) were found in peats dating from AD 550 to AD 975, compared to the maximum of 164 μg/m²/yr in AD 1953. Atmospheric Hg accumulation rates have since declined, with the value for 1995 (14 μg/m²/yr) comparable to the value for 1995 obtained by published studies of atmospheric transport modelling (12 μg/m²/yr).The greatest rates of atmospheric Hg accumulation in the DK core are also found in the sample dating from AD 1953 and are comparable in magnitude (184 μg/m²/yr) to the GL core; again, the fluxes have since gone into strong decline. The accumulation rates recorded by the peat core for AD 1994 (14 μg/m²/yr) are also comparable to the value for 1995 obtained by atmospheric transport modelling (18 μg/m²/yr). Comparing the Pb/Ti and As/Ti ratios of the DK samples with the corresponding crustal ratios (or “natural background values” for preanthropogenic peat) shows that the samples dating from 1953 also contain the maximum concentration of “excess” Pb and As. The synchroneity of the enrichments of all three elements (Hg, Pb, and As) suggests a common source, with coal-burning the most likely candidate. Independent support for this interpretation was obtained from the Pb isotope data (²⁰⁶Pb/²⁰⁷Pb = 1.1481 ± 0.0002 in the leached fraction and 1.1505 ± 0.0002 in the residual fraction) which is too radiogenic to be explained in terms of gasoline lead alone, but compares well with values for U.K. coals. In contrast, the lowest values for ²⁰⁶Pb/²⁰⁷Pb in the DK profile (1.1370 ± 0.0003 in the leached fraction and 1.1408 ± 0.0003 in the residual fraction) are found in the sample dating from AD 1979: this shows that the maximum contribution of leaded gasoline occurred approximately 25 yr after the zenith in total anthropogenic Pb deposition.     

A comparison of winter mercury accumulation at forested and no-canopy sites measured with different snow sampling techniques

Atmospheric mercury (Hg) is delivered to ecosystems via rain, snow, cloud/fog, and dry deposition. The importance of snow, especially snow that has passed through the forest canopy (throughfall), in delivering Hg to terrestrial ecosystems has received little attention in the literature. The snowpack is a dynamic system that links atmospheric deposition and ecosystem cycling through deposition and emission of deposited Hg. To examine the magnitude of Hg delivery via snowfall, and to illuminate processes affecting Hg flux to catchments during winter (cold season), Hg in snow in no-canopy areas and under forest canopies measured with four collection methods were compared: (1) Hg in wet precipitation as measured by the Mercury Deposition Network (MDN) for the site in Acadia National Park, Maine, USA, (2) event throughfall (collected after snowfall cessation for accumulations of >8 cm), (3) season-long throughfall collected using the same apparatus for event sampling but deployed for the entire cold season, and (4) snowpack sampling. Estimates (mean ± SE) of Hg deposition using these methods during the 91-day cold season in 2004–2005 at conifer sites showed that season-long throughfall Hg flux (1.80 μg/m²) < snowpack Hg (2.38 ± 0.68 μg/m²) < event throughfall flux (5.63 ± 0.38 μg/m²). Mercury deposition at the MDN site (0.91 μg/m²) was similar to that measured at other no-canopy sites in the area using the other methods, but was 3.4 times less than was measured under conifer canopies using the event sampling regime. This indicates that snow accumulated under the forest canopy received Hg from the overstory or exhibited less re-emission of Hg deposited in snow relative to open areas. The soil surface of field-scale plots were sprayed with a natural rain water sample that contained an Hg tracer (²⁰²Hg) just prior to the first snowfall to explore whether some snowpack Hg might be explained from soil emissions. The appearance of the ²⁰²Hg tracer in the snowpack (0–64% of the total Hg mass in the snowpack) suggests that movement of Hg from the soil into the snowpack is possible. However, as with any tracer study the ²⁰²Hg tracer may not precisely represent the reactivity and mobility of natural Hg in soils.     

Accumulation rates and predominant atmospheric sources of natural and anthropogenic Hg and Pb on the Faroe Islands

A monolith representing 5420 ¹⁴C yr of peat accumulation was collected from a blanket bog at Myrarnar, Faroe Islands. The maximum Hg concentration (498 ng/g at a depth of 4.5 cm) coincides with the maximum concentration of anthropogenic Pb (111 μg/g). Age dating of recent peat accumulation using ²¹⁰Pb (CRS model) shows that the maxima in Hg and Pb concentrations occur at AD 1954 ± 2. These results, combined with the isotopic composition of Pb in that sample (²⁰⁶Pb/²⁰⁷Pb = 1.1720 ± 0.0017), suggest that coal burning was the dominant source of both elements. From the onset of peat accumulation (ca. 4286 BC) until AD 1385, the ratios Hg/Br and Hg/Se were constant (2.2 ± 0.5 × 10^-4 and 8.5 ± 1.8 × 10^-3, respectively). Since then, Hg/Br and Hg/Se values have increased, also reaching their maxima in AD 1954. The age date of the maximum concentrations of anthropogenic Hg and Pb in the Faroe Islands is consistent with a previous study of peat cores from Greenland and Denmark (dated using the atmospheric bomb pulse curve of ¹⁴C), which showed maximum concentrations in AD 1953.The average rate of atmospheric Hg accumulation from 1520 BC to AD 1385 was 1.27 ± 0.38 μg/m²/yr. The Br and Se concentrations and the background Hg/Br and Hg/Se ratios were used to calculate the average rate of natural Hg accumulation for the same period, 1.32 ± 0.36 μg/m²/yr and 1.34 ± 0.29 μg/m²/yr, respectively. These fluxes are similar to the preanthropogenic rates obtained using peat cores from Switzerland, southern Greenland, southern Ontario, Canada, and the northeastern United States. Episodic volcanic emissions and the continual supply of marine aerosols to the Faroe Islands, therefore, have not contributed significantly to the Hg inventory or the Hg accumulation rates, relative to these other areas. The maximum rate of Hg accumulation was 34 μg/m²/yr. The greatest fluxes of anthropogenic Hg accumulation calculated using Br and Se, respectively, were 26 and 31 μg/m²/yr. The rate of atmospheric Hg accumulation in 1998 (16 μg/m²/yr) is comparable to the values recently obtained by atmospheric transport modeling for Denmark, the Faroe Islands, and Greenland.     

Methylmercury cycling in sediments on the continental shelf of southern New England

Exposure of humans to monomethylmercury (MMHg) occurs primarily through consumption of marine fish, yet there is limited understanding concerning the bioaccumulation and biogeochemistry of MMHg in the biologically productive coastal ocean. We examined the cycling of MMHg in sediments at three locations on the continental shelf of southern New England in September 2003. MMHg in surface sediments is related positively to inorganic Hg (Hg(II) = total Hg − MMHg), the geographical distribution of which is influenced by organic material. Organic matter also largely controls the sediment-water partitioning of Hg species and governs the availability of dissolved Hg(II) for methylation. Potential gross rates of MMHg production, assayed by experimental addition of ²⁰⁰Hg to intact sediment cores, are correlated inversely with the distribution coefficient (K_D) of Hg(II) and positively with the concentration of Hg(II), most probably as HgS⁰, in 0.2-μm filtered pore water of these low-sulfide deposits. Moreover, the efflux of dissolved MMHg to overlying water (i.e., net production at steady state) is correlated with the gross potential rate of MMHg production in surface sediments. These results suggest that the production and efflux of MMHg from coastal marine sediments is limited by Hg(II), loadings of which presumably are principally from atmospheric deposition to this region of the continental shelf. The estimated diffusive flux of MMHg from the shelf sediments averages 9 pmol m⁻² d⁻¹. This flux is comparable to that required to sustain the current rate of MMHg accumulation by marine fish, and may be enhanced by the efflux of MMHg from near-shore deposits contaminated more substantially with anthropogenic Hg. Hence, production and subsequent mobilization of MMHg from sediments in the coastal zone may be a major source of MMHg to the ocean and marine biota, including fishes consumed by humans.     

Estimating selenium removal by sedimentation from the Great Salt Lake,Utah

The mass of Se deposited annually to sediment in the Great Salt Lake (GSL) was estimated to determine the significance of sedimentation as a permanent Se removal mechanism. Lake sediment cores were used to qualitatively delineate sedimentation regions (very high to very low), estimate mass accumulation rates (MARs) and determine sediment Se concentrations. Sedimentation regions were defined by comparison of isopach contours of Holocene sediment thicknesses to linear sedimentation rates determined via analysis of ²¹⁰Pb, ²²⁶Ra, ⁷Be and ¹³⁷Cs activity in 20 short cores (<5 cm), yielding quantifiable results in 13 cores. MARs were developed via analysis of the same radioisotopes in eight long cores (>10 cm). These MARs in the upper 1–2 cm of each long core ranged from 0.019 to 0.105 g_sed/cm²/a. Surface sediment Se concentrations in the upper 1 or 2 cm of each long core ranged from 0.79 to 2.47 mg/kg. Representative MARs and Se concentrations were used to develop mean annual Se removal by sedimentation in the corresponding sedimentation region. The spatially integrated Se sedimentation rate was estimated to be 624 kg/a within a range of uncertainty between 285 and 960 kg/a. Comparison to annual Se loading and other potential removal processes suggests burial by sedimentation is not the primary removal process for Se from the GSL.     

Historical deposition and fluxes of mercury in Narraguinnep Reservoir,southwestern Colorado,USA

Narraguinnep Reservoir has been identified as containing fish with elevated Hg concentrations and has been posted with an advisory recommending against consumption of fish. There are presently no point sources of significant Hg contamination to this reservoir or its supply waters. To evaluate potential historical Hg sources and deposition of Hg to Narraguinnep Reservoir, the authors measured Hg concentrations in sediment cores collected from this reservoir. The cores were dated by the ¹³⁷Cs method and these dates were further refined by relating water supply basin hydrological records with core sedimentology. Rates of historical Hg flux were calculated (ng/cm²/a) based on the Hg concentrations in the cores, sediment bulk densities, and sedimentation rates. The flux of Hg found in Narraguinnep Reservoir increased by approximately a factor of 2 after about 1970. The 3 most likely sources of Hg to Narraguinnep Reservoir are surrounding bedrocks, upstream inactive Au–Ag mines, and several coal-fired electric power plants in the Four Corners region. Patterns of Hg flux do not support dominant Hg derivation from surrounding bedrocks or upstream mining sources. There are 14 coal-fired power plants within 320 km of Narraguinnep Reservoir that produce over 80 × 10⁶ MWH of power and about 1640 kg-Hg/a are released through stack emissions, contributing significant Hg to the surrounding environment. Two of the largest power plants, located within 80 km of the reservoir, emit about 950 kg-Hg/a. Spatial and temporal patterns of Hg fluxes for sediment cores collected from Narraguinnep Reservoir suggest that the most likely source of Hg to this reservoir is from atmospheric emissions from the coal-fired electric power plants, the largest of which began operation in this region in the late-1960s and early 1970s.     

Assessing the natural recovery of a lake contaminated with Hg using estimated recovery rates determined by sediment chronologies

Deer Lake is an impoundment located near Ishpeming, Michigan, USA. Iron mining assay laboratories located in Ishpeming disposed of Hg salts to the city sewer whose outfall was located along an inlet to Deer Lake. An effort to remediate the system in the mid 1980s which consisted of drawing down water in the impoundment in order to volatize Hg from the sediments did not result in recovery of the system. Since the mid 1990s, the remediation strategy has been to allow the continual burial of the contaminated sediments, i.e., natural recovery. The goal of this study was to assess the effectiveness of this strategy. This was accomplished by investigating the state of the system in terms of its recovery and estimating the time frame for recovery. Sediment cores were collected in 2000 to determine historical trends in accumulation rates and concentrations of Hg and other metals. Sedimentation rates and sediment ages were estimated using ²¹⁰Pb. Event-based dating (e.g., peak of ¹³⁷Cs in 1963) was used to supplement ²¹⁰Pb data due to non-monotonic features in the ²¹⁰Pb profile and activities that were not at supported levels at the base of the core. Selected results are that: (1) drawdown significantly influenced sedimentation patterns causing slopes for ²¹⁰Pb profiles that reflected the influx of older sediment, (2) periods of Fe production correlate to Hg loading indicating the point source for contamination, a relationship not previously identified, (3) Hg:Al ratios indicate a recent change to a watershed pathway for Hg loading and (4) Hg concentrations had decreased from their peak, remain elevated, and were increasing after 1997. The cause of the recent Hg concentrations may be related to influx of contaminated watershed soils or sediments. Estimating the time frame for recovery is challenging in this system because the process of natural recovery seems to have been arrested and deeper, uncontaminated sediments, were not recovered as a basis for reference. However, a recovery to background conditions is likely not achievable since rates of Hg loading to nearby lakes and the current rate of atmospheric deposition are greater than an estimate of background conditions for Deer Lake. Assuming recovery continued after 2000, estimates of the time required for recovery varied based on the system state used to define it (e.g., recent rates of wet Hg deposition or Hg surface concentrations/fluxes from similar systems), but were less than 12 a. However, the recent increasing values of recovery indicators (e.g., Hg concentrations) suggests that these estimates are conservative and will be longer if recovery remains arrested, which may in part be due to the legacy of Hg contamination on the landscape. This study shows that estimates of recovery of highly disturbed lake systems can be made in the absence of within lake reference conditions by using comparisons to reference systems and challenges of estimating ages from atypical ²¹⁰Pb activity profiles can be overcome in part using event-based dating techniques.     

Sr isotopes as a tracer of weathering processes and dust inputs in a tropical granitoid watershed, Luquillo Mountains, Puerto Rico

Sr isotope data from soils, water, and atmospheric inputs in a small tropical granitoid watershed in the Luquillo Mountains of Puerto Rico constrain soil mineral development, weathering fluxes, and atmospheric deposition. This study provides new information on pedogenic processes and geochemical fluxes that is not apparent in watershed mass balances based on major elements alone. ⁸⁷Sr/⁸⁶Sr data reveal that Saharan mineral aerosol dust contributes significantly to atmospheric inputs. Watershed-scale Sr isotope mass balance calculations indicate that the dust deposition flux for the watershed is 2100 ± 700 mg cm⁻² ka⁻¹. Nd isotope analyses of soil and saprolite samples provide independent evidence for the presence of Saharan dust in the regolith. Watershed-scale Sr isotope mass balance calculations are used to calculate the overall short-term chemical denudation velocity for the watershed, which agrees well with previous denudation rate estimates based on major element chemistry and cosmogenic nuclides. The dissolved streamwater Sr flux is dominated by weathering of plagioclase and hornblende and partial weathering of biotite in the saprock zone. A steep gradient in regolith porewater ⁸⁷Sr/⁸⁶Sr ratio with depth, from 0.70635 to as high as 0.71395, reflects the transition from primary mineral-derived Sr to a combination of residual biotite-derived Sr and atmospherically-derived Sr near the surface, and allows multiple origins of kaolinite to be identified.     

Coupling between Pbex and organic matter in sediments of a nutrient-enriched lake: An example from Lake Chenghai, China

Sediment cores were collected from deep-water areas of Lake Chenghai, China in June 1997. The vertical profile of ¹³⁷Cs activity gives reliable geochronological results. The results also indicate that sediment accumulation rates in deep-water areas of Lake Chenghai were relatively constant in recent decades, averaging 0.43 g cm^− 2 y^− 1, despite a variable organic carbon influx. ²¹⁰Pb_eq (= ²²⁶Ra) activity was relatively constant also, with an average value of 54.3 ± 3.2 Bq kg^− 1. Vertical profiles of ²¹⁰Pb_ex (= ²¹⁰Pb_total − ²²⁶Ra) decreased exponentially, resulting in somewhat lower sediment accumulation rates (0.3 g cm^− 2 y^− 1). These lower rates are likely less reliable, as the relatively large fluctuations in ²¹⁰Pb_ex activities correlate closely to the organic carbon (C_org) content of the sediments. For example, the vertical profile of ²¹⁰Pb_ex activity displays peaks at mass depths of 3.7-4.7 g cm^− 2 (10-12 cm) and 10-11 g cm^− 2(25-28 cm), similar to the maxima in the vertical profile of C_org. This phenomenon must be related to the delivery of particulate organic matter (POM) from the water to the sediments, or to watershed soil erosion. Since the mean atomic ratios of H_org / C_org and C_org / N_org in Lake Chenghai sediments are 5.5 and 7.0, respectively, indicating that POM was predominantly derived from the remains of authigenic algae, this eliminates watershed erosion rates as a primary control on lake sedimentation rates as resolved by ²¹⁰Pb_ex. Sedimentation fluxes (F(C_org)) of particulate organic carbon since 1970 varied between 60 to 160 g m^− 2 y^− 1, and appeared to closely influence variations in ²¹⁰Pb_ex concentrations. For example, sedimentation fluxes of ²¹⁰Pb_ex (F(²¹⁰Pb_ex)) showed maxima in the years 1972-1974 and 1986-1989, likely reflecting historical variations of lake biological productivity or carbon preservation.     

Lake sediment cores as indicators of historical metal(loid) accumulation – A case study in Mexico

To examine and compare historical accumulation of metal(loid)s in Mexican lakes and reservoirs, ²¹⁰Pb and ¹³⁷Cs dated sediment cores were evaluated: two from the remote Zempoala and Miramar Lagoons and three from Lake Pátzcuaro, and the Intermedia and Silva dams that are affected by human activities. Sediment ecotoxicology was assessed using consensus-based sediment quality guidelines for freshwater ecosystems. The +100 a sediment core from the remote Miramar Lagoon had the highest concentrations of Cr and Ni these being higher than the Probable Effect Levels (PELs). Zinc concentrations were also higher in the Miramar Lagoon compared to the other lakes and reservoirs, with concentrations higher than the Threshold Effect Level (TEL). Mercury concentrations from this lagoon were comparable to those for the Intermedia dam that receives water from urban, industrial and agricultural areas. The higher metal concentrations in the core from the Miramar Lagoon suggest that metal concentrations in the rocks of the watershed are high. Another explanation for the higher metal concentrations is the slow sediment accumulation that causes metals to be accumulated over longer time-periods at the sediment–water interface. A decrease in the concentration of As in the Intermedia dam was observed in sediments corresponding to the last decades. This may be due to an increase in sediment accumulation rate or to the reduction in sources of this metalloid in the watershed. In the Miramar Lagoon, an increase was observed in concentrations of As and Cr in more recent sediments, probably related to increased deforestation in the area or the eruption of El Chichonal volcano in 1982. Concentrations of Pb showed a decreasing tendency over the past decades in the Lake Pátzcuaro, Miramar and Zempoala Lagoons sediment cores while such behavior was not be observed for the Intermedia dam. This reduction in concentrations of Pb was attributed to the decrease in use of leaded gasoline.     

Sources of mercury to San Francisco Bay surface sediment as revealed by mercury stable isotopes

Mercury (Hg) concentrations and isotopic compositions were examined in shallow-water surface sediment (0-2 cm) from San Francisco (SF) Bay to determine the extent to which historic Hg mining contributes to current Hg contamination in SF Bay, and to assess the use of Hg isotopes to trace sources of contamination in estuaries. Inter-tidal and wetland sediment had total Hg (Hg_T) concentrations ranging from 161 to 1529 ng/g with no simple gradients of spatial variation. In contrast, inter-tidal and wetland sediment displayed a geographic gradient of δ²⁰²Hg values, ranging from −0.30‰ in the southern-most part of SF Bay (draining the New Almaden Hg District) to −0.99‰ in the northern-most part of SF Bay near the Sacramento-San Joaquin River Delta. Similar to SF Bay inter-tidal sediment, surface sediment from the Alviso Slough channel draining into South SF Bay had a δ²⁰²Hg value of −0.29‰, while surface sediment from the Cosumnes River and Sacramento-San Joaquin River Delta draining into north SF Bay had lower average δ²⁰²Hg values of −0.90‰ and −0.75‰, respectively. This isotopic trend suggests that Hg-contaminated sediment from the New Almaden Hg District mixes with Hg-contaminated sediment from a low δ²⁰²Hg source north of SF Bay. Tailings and thermally decomposed ore (calcine) from the New Idria Hg mine in the California Coast Range had average δ²⁰²Hg values of −0.37 and +0.03‰, respectively, showing that Hg calcination fractionates Hg isotopes resulting in Hg contamination from Hg(II) mine waste products with higher δ²⁰²Hg values than metallic Hg(0) produced from Hg mines. Thus, there is evidence for at least two distinct isotopic signals for Hg contamination in SF Bay: Hg associated with calcine waste materials at Hg mines in the Coast Range, such as New Almaden and New Idria; and Hg(0) produced from these mines and used in placer gold mines and/or in other industrial processes in the Sierra Nevada region and SF Bay area.     

Geochemical and anthropogenic enrichments of Mo in sediments from perennially oxic and seasonally anoxic lakes in Eastern Canada

We measured the vertical distributions of Mo, Fe, Mn, sulfide, sulfate, organic carbon, major ions, and pH in sediment porewater from one perennially oxic and three seasonally anoxic lacustrine basins in Eastern Canada, as well as those of Mo, acid volatile sulfide, Fe, Mn, Al, organic C, ²¹⁰Pb and ¹³⁷Cs in sediment cores from the same sites. The only input of anthropogenic Mo to these lakes comes from atmospheric deposition.The relatively monotonous distribution of Mo in the porewater of three seasonally anoxic basins suggests that Mo is not redistributed in the sedimentary column during periods of anoxia. In contrast, porewater Mo profiles obtained at three sampling dates in a perennially oxic basin display sharp Mo peaks below the sediment-water interface, indicating redistribution subsequent to deposition. Modeling of these latter porewater Mo profiles with a diagenetic reaction-transport equation coupled to comparisons among the various porewater and solid phase profiles reveal that Mo is released at 1-2 cm depth as a consequence of the reductive dissolution of Fe oxyhydroxides and scavenged both at the vicinity of the sediment-water interface, by re-adsorption onto authigenic Fe oxyhydroxides, and deeper in the sediments where dissolved sulfide concentrations are higher. The estimated rate constant for the adsorption of Mo onto Fe oxyhydroxides is 36 ± 45 cm³ mol⁻¹ s⁻¹.Diagenetic modeling indicates that authigenic Mo in sediments of the perennially oxic basin represents about one-third of the total solid phase Mo in the first cm below the sediment-water interface and only one tenth below this horizon. If we assume that no authigenic Mo is accumulated in the seasonally anoxic lake sediments we conclude that the sediment Mo concentrations, which are up to 3-16 times higher than the average lithogenic composition, depending on the lake, are mainly due to atmospheric deposition of anthropogenic Mo and not to the formation of authigenic Mo phases. Reconstructed historical records of the atmospheric Mo deposition indicate maximum values in the 1970s and 1980s and significant decreases since then. Emissions to the atmosphere associated with the smelting of non-ferrous ores and coal combustion appear to be the most important sources of anthropogenic Mo.