Methylmercury concentrations and production rates across a trophic gradient in the northern Everglades

Methylmercury (MeHg) concentrations and production rates were examined along with sulfur biogeochemistry in Everglades sediments in March, July and December, 1995, as part of a large, multi-investigator study, the Aquatic Cycling of Mercury in the Everglades (ACME) project. The sites examined constitute a trophic gradient, generated from agricultural runoff, across the Everglades Nutrient Removal (ENR) Area, which is a re-constructed wetland, and Water Conservation Areas (WCA) 2A, 2B and 3 in the northern Everglades. MeHg concentrations and %MeHg (MeHg as a percent of total Hg) were lowest in the more eutrophic areas and highest in the more pristine areas in the south. MeHg concentrations ranged from <0.1 ng gdw^-1 sediment in the ENR to 5 ng gdw^-1 in WCA3 sediments; and MeHg constituted <0.2% of total Hg (Hg_T) in ENR, but up to about 2% in two sites in WCA2B and WCA3. Methylation rates in surficial sediments, estimated using tracer-level injections of²⁰³ Hg(II) into intact sediment cores, ranged from 0 to 0.12 d^-1, or about 1 to 10 ng g^-1 d^-1when the per day values are multiplied by the ambient total Hg concentration. Methylation was generally maximal at or within centimeters of the sediment surface, and was never observed in water overlying cores. The spatial pattern of MeHg production generally matched that of MeHg concentration. The coincident distributions of MeHg and its production suggest that in situ production controls concentration, and that MeHg concentration can be used as an analog for MeHg production. In addition, the spatial pattern of MeHg in Everglades sediments matches that in biota, suggesting that MeHg bioaccumulation may be predominantly a function of the de novo methylation rate in surficial sediments.Sulfate concentrations in surficial pore waters (up to 400 µm), microbial sulfate-reduction rates (up to 800 nm cc^-1 d^-1) and resultant pore water sulfide concentrations (up to 300 µm) at the eutrophic northern sites were all high relative to most freshwater systems. All declined to the south, and sulfate concentrations in WCA2B and in central WCA3 resembled those in oligotrophic lakes (50–100 µm). MeHg concentration and production were inversely related to sulfate reduction rate and pore water sulfide. Control of MeHg production in the northern Everglades appears to mimic that in an estuary, where sulfate concentrations are high and where sulfide produced by microbial sulfate reduction inhibits MeHg production.     

A Michaelis–Menten type equation for describing methylmercury dependence on inorganic mercury in aquatic sediments

Methylation of mercury (Hg) is the crucial process that controls Hg biomagnification along the aquatic food chains. Aquatic sediments are of particular interest because they constitute an essential reservoir where inorganic divalent Hg (Hg^II) is methylated. Methylmercury (MeHg) concentrations in sediments mainly result from the balance between methylation and demethylation reactions, two opposite natural processes primarily mediated by aquatic microorganisms. Thus, Hg availability and the activity of methylating microbial communities control the MeHg abundance in sediments. Consistently, some studies have reported a significant positive correlation between MeHg and Hg^II or total Hg (Hg_T), taken as a proxy for Hg^II, in aquatic sediments using enzyme-catalyzed methylation/demethylation mechanisms. By compiling 1,442 published and unpublished Hg_T–MeHg couples from lacustrine, riverine, estuarine and marine sediments covering various environmental conditions, from deep pristine abyssal to heavily contaminated riverine sediments, we show that a Michaelis–Menten type relationship is an appropriate model to relate the two parameters: MeHg = aHg_T/(K _m  + Hg_T), with a = 0.277 ± 0.011 and K _m  = 188 ± 15 (R ² = 0.70, p < 0.001). From K _m variations, which depend on the various encountered environmental conditions, it appears that MeHg formation and accumulation are favoured in marine sediments compared to freshwater ones, and under oxic/suboxic conditions compared to anoxic ones, with redox potential and organic matter lability being the governing factors.     

Seasonal changes in phytoplankton community structure in relation to physico-chemical factors in Loch Lomond,Scotland

Surface waters, sediments and the polychaete Nereis diversicolor were sampled in the ScheldtEstuary between 1990 and 1994. In surface watersparticulate Hg (Hg_P) concentrations ranged from350–1610 ng g^-1. They are essentiallycontrolled by physical mixing of polluted fluvialparticulates with relatively unpolluted marineparticulates, but unaffected by seasonal changes.Dissolved Hg species, on the other hand, show largeseasonal variations essentially controlled by theredox conditions in the estuary, as well as bybacterial and phytoplankton activity. Total dissolvedHg (Hg_TD) concentrations ranged from 0.5 to 3.0 ngl^-1 with 10 to 90% as reactive Hg. Highconcentrations of Hg_TD are found in the upperestuary in the winter and decrease rapidly withincreasing salinity. In summer Hg_TDconcentrations are low in the anoxic upper estuary andincrease as oxygen is restored in the estuary.Significant variations were observed in dissolvedMonomethyl Hg (MMHg) concentrations withconcentrations ranging from 0.01 to 0.120 ng l^-1 in the winter and 0.08 to 0.6 ng l^-1 in summerand autumn. Particulate MMHg ranged from 2 to 6 ngg^-1 in winter and from 4 to 10 ng g^-1 insummer and accounted for 20 to 80% of the total MMHg.Hg° concentrations ranged from 0.02 to 0.130 ngl^-1 and are higher in summer than in winter. Inthe lower estuary a positive correlation betweenHg° and phytoplankton pigments was observed. Sediments and the polychaete N. diversicolorwere sampled on the intertidal flat GrootBuitenschoor. Hg_{_T} concentrations in surfacesediments ranged from 144 to 1890 ng g^-1 and MMHgfrom 0.8 to 6 ng g^-1 accounting for 0.4 to 0.8%of the total mercury present. Both total Hg (Hg_T)and MMHg concentrations increased with increasedorganic matter content and anoxic conditions. On theother hand, accumulation of Hg_T and MMHg washigher in N. diversicolor living in coarse grainsandy sediments than in muddy sediments. MMHgconcentrations in N. diversicolor ranged from2.2 to 20.9 ng g^-1 accounting for an average of18% of the Hg_T. Seasonal variationssignificantly affected Hg speciation in sediments andN. diversicolor. Higher Hg_T concentrationswere found in the sediments in autumn and winter,whereas MMHg concentrations increased in spring andsummer. Likewise, higher MMHg concentrations were alsoobserved in N. diversicolor in spring andsummer. This revised version was published online in July 2006 with corrections to the Cover Date.     

Mercury dynamics in Tivoli South Bay, a freshwater tidal mudflat wetland in the Hudson River

The accumulation of total mercury (Hg_T) andmethylmercury (MeHg) was evaluated in sediments ofTivoli South Bay, a freshwater tidal mudflat wetlandin the Hudson River National Estuarine ResearchReserve system. Hg_T concentrations in sedimentcores were measured to evaluate the spatialvariability of Hg_T deposition, and to establisha chronology of Hg_T accumulation. Cores takenfrom the northern, middle, and southern sections ofthe bay had similar distribution patterns andconcentrations of Hg_T, suggesting a common sourceof Hg_T throughout the bay. Sedimentconcentrations ranged from 190 to 1040 ng Hg g^–1,2 to 10 times greater than concentrations expected insediments from non-anthropogenic sources. Hg_Tdeposition rates were similar in different regions ofthe bay, and increased from 200 ng Hg cm^–2yr^–1in the 1930s to a maximum of 300 ngHg cm^–2 yr^–1 in the 1960s. Deposition rateshave steadily declined since the 1970s and arecurrently at 80 ng Hg cm^–2 yr^–1. Transportof Hg_T by tidal waters from the Hudson River islikely the main source of Hg_T in the bay.Distribution patterns and absolute concentrations ofMeHg in sediment cores were similar throughout thebay, with concentrations ranging from 0.43 to 2.95ng g^–1. Maxima in MeHg concentration profilesoccurred just below the sediment-water interface andat a depth of 30 cm. The maximum at 30 cm wascoincident with maximum Hg_T concentrations. MeHgconcentrations in suspended particulate matter (SPM)from the Hudson River suggest that MeHg in the baycould be derived from riverine SPM rather than formedin situ.     

Aspects of Bioavailability of Mercury for Methylation in Pure Cultures of Desulfobulbus propionicus (1pr3)

We have previously hypothesized that sulfide inhibits Hg methylation by decreasing its bioavailability to sulfate-reducing bacteria (SRB), the important methylators of Hg in natural sediments. With a view to designing a bioassay to test this hypothesis, we investigated a number of aspects of Hg methylation by the SRB Desulfobulbus propionicus, including (i) the relationship between cell density and methylmercury (MeHg) production, (ii) the time course of Hg methylation relative to growth stage, (iii) changes in the bioavailability of an added inorganic Hg (Hg_I) spike over time, and (iv) the dependence of methylation on the concentration of dissolved Hg_I present in the culture. We then tested the effect of sulfide on MeHg production by this microorganism. These experiments demonstrated that under conditions of equal bioavailability, per-cell MeHg production was constant through log-phase culture growth. However, the methylation rate of a new Hg spike dramatically decreased after the first 5 h. This result was seen whether methylation rate was expressed as a fraction of the total added Hg or the filtered Hg_I concentration, which suggests that Hg bioavailability decreased through both changes in Hg complexation and formation of solid phases. At low sulfide concentration, MeHg production was linearly related to the concentration of filtered Hg_I. The methylation of filtered Hg_I decreased about fourfold as sulfide concentration was increased from 10⁻⁶ to 10⁻³ M. This decline is consistent with a decrease in the bioavailability of Hg_I, possibly due to a decline in the dissolved neutral complex, HgS⁰.     

Factors Affecting Methylmercury Levels in Surficial Tailings from Historical Nova Scotia Gold Mines

Large quantities of Hg remain in tailings dumps from historical Nova Scotian gold mines. Depth profiles of total Hg (Hg_T) and methylmercury (MeHg) were compared with geochemical and microbiological variables, to identify factors influencing MeHg levels in tailings. Hg_T and MeHg were highly variable in tailings (0.2–73.5 μ mol kg^{? 1} and < dl-56.4 nmol kg^{? 1}, respectively), and were influenced by a complex set of in situ factors. Elevated MeHg was linked with > 5 μ mol kg^?1 Hg_T, organic matter, hydrology, abundance and activity of sulfate reducing bacteria, and demethylation processes. Methylmercury levels in tailings from a wet, bog-like site appeared to undergo seasonal fluctuations, with higher concentrations measured in September and October, and lower concentrations in May. Evaluations of amalgamation tailings should examine MeHg and Hg_T transport out of low-lying, saturated tailings dumps after snowmelt and major rainfall events, and should take into account the possibility of seasonal variation in MeHg levels in northern regions.     

The Influence of Sulphate Deposition on the Seasonal Variation of Peat Pore Water Methyl Hg in a Boreal Mire

In this paper we investigate the hypothesis that long-term sulphate (SO₄ ²⁻) deposition has made peatlands a larger source of methyl mercury (MeHg) to remote boreal lakes. This was done on experimental plots at a boreal, low sedge mire where the effect of long-term addition of SO₄ ²⁻ on peat pore water MeHg concentrations was observed weekly throughout the snow-free portion of 1999. The additions of SO₄ ²⁻ started in 1995. The seasonal mean of the pore water MeHg concentrations on the plots with 17 kg ha⁻¹ yr⁻¹ of sulphur (S) addition (1.3±0.08 ng L⁻¹, SE; n = 44) was significantly (p<0.0001) higher than the mean MeHg concentration on the plots with 3 kg ha⁻¹ yr⁻¹ of ambient S deposition (0.6±0.02 ng L⁻¹, SE; n = 44). The temporal variation in pore water MeHg concentrations during the snow free season was larger in the S-addition plots, with an amplitude of >2 ng L⁻¹ compared to +/−0.5 ng L⁻¹ in the ambient S deposition plots. The concentrations of pore water MeHg in the S-addition plots were positively correlated (r² = 0.21; p = 0.001) to the groundwater level, with the lowest concentrations of MeHg during the period with the lowest groundwater levels. The pore water MeHg concentrations were not correlated to total Hg, DOC concentration or pH. The results from this study indicate that the persistently higher pore water concentrations of MeHg in the S-addition plots are caused by the long-term additions of SO₄ ²⁻ to the mire surface. Since these waters are an important source of runoff, the results support the hypothesis that SO₄ ²⁻ deposition has increased the contribution of peatlands to MeHg in downstream aquatic systems. This would mean that the increased deposition of SO₄ ²⁻ in acid rain has contributed to the modern increase in the MeHg burdens of remote lakes hydrologically connected to peatlands.     

Mercury Concentration in Sediment Cores from Sundarban Mangrove Wetland,India

The work presents an extended database (n = 123) of total mercury (T_Hg) in fine-grained sediment fraction (<63 μm) of core samples in 10 sampling stations of the Sundarban mangrove wetland, India, formed at the estuarine realm of the Hugli (Ganga) River. Results revealed a wide range of spatial, seasonal, and intertidal flat variations of T_Hg (7.3 to 93.3 ng/g) with a definite enhancement level at the lower stretch of the estuary, which has extreme mangrove vegetation. An overall enrichment of T_Hg in surface/subsurface layers of the core is tentatively explained by remobilization and resuspension of the metal from deeper sediments (36–40 cm). A strong positive correlation was observed between the Hg and clay fraction content of the sediments, while correlations of Hg with organic carbon was poor. Based on the index of geoaccumulation (I_geo), enrichment factor (EF), and anthropogenic factor (AF) values, it is suggested that the sediments of Sundarban were found to be less polluted with respect to total mercury. The data reported are a useful baseline for T_Hg in Sundarban and would be of importance in future sediment quality studies.     

Mercury inputs and outputs at a small lake in northern Minnesota

Storages and cycling of total mercury (Hg_T), methylmercury (MeHg), and Hg⁰ are described for Spring Lake, a small bog lake in the Marcell Experimental Forest in north-central Minnesota. We quantified photoredox transformations, MeHg photolysis, burial to the sediments, and internal and external loadings of Hg_T and MeHg. Atmospheric deposition was the main input of Hg_T; MeHg was supplied by a combination of atmospheric, near-shore wetland, and biotic (methylation) sources. Hg_T outputs were dominated by burial (67%), and Hg⁰ evasion accounted for 26% of Hg_T outputs. The watershed of Spring Lake is small (3.7× lake surface area), and accordingly, bog and upland runoff were minor contributors to both Hg_T and MeHg inputs. Wet deposition was ∼9% of total MeHg input, and other external inputs (runoff, sediment porewater) provided only an additional 7%, indicating that internal production of MeHg was occurring in the lake. Photolysis of MeHg, measured in the field and laboratory, removed ∼3× the lake mass of MeHg (20 mg) annually, and was the dominant sink for MeHg. Residence times of MeHg and Hg_T in the lake were 48 and 61 days, respectively, during the open-water season, compared with only 8 days for the residence time of MeHg on settling particles (seston). Photoreduction of Hg²⁺ to Hg⁰ was greater than the reverse reaction (Hg⁰ photooxidation), and the residence time of Hg⁰ in the photic zone was short (hours). Data from this study show active cycling of all the measured species of mercury (Hg_T, MeHg, and Hg⁰) and the importance of MeHg photolysis and photo-redox processes.     

Effect of Electron Donor to Sulfate Ratio on Mercury Methylation in Floodplain Sediments under Saturated Flow Conditions

A column transport experiment was conducted to examine the release and methylation of Hg using Hg contaminated sediment from the floodplain of the South River near Waynesboro, Virginia. Three input solutions were sequentially introduced into the column. Input 1 was unamended South River water, Input 2 was river water amended with 100 mg L^?1 SO₄ and 3600 mg L^?1 lactate, and Input 3 was river water amended with 500 mg L^?1 SO₄ and 340 mg L^?1 lactate. During the first stage of the experiment (Input 1) the effluent Hg concentration was initially 4 µg L^?1 and peaked at 21 µg L^?1 and after 21 pore volumes stabilized at 13 µg L^?1. During the second stage, at high lactate to SO₄ ratios, elevated concentrations of acetic and propionic acids were detected, indicating that fermentative bacteria were dominant. During the third stage, at high SO₄ to lactate ratios, a decrease in SO₄ and an increase in H₂S concentrations were detected in the column effluent indicating that SO₄ reduction was occurring. Concentrations of methyl Hg (MeHg) in the effluent were variable over the duration of the experiment. During the first phase, concentrations of MeHg remained <3.3 ng L^?1. During the fermentative stage, concentrations of MeHg increased to a maximum value of 32 ng L^?1, and during the sulfate-reducing stage to a maximum value of 266 ng L^?1. When the column was deconstructed both molecular and cultural techniques indicated that sulfate reducing bacteria were most dominant near the influent port. These results indicate that the formation of MeHg in the sediment is not limited by the availability of Hg and that the bacterial community that contributes to mercury methylation can respond quickly to changes in the abundances of electron donors and acceptors.     

Role of Organic Carbon Sources and Sulfate in Controlling Net Methylmercury Production in Riverbank Sediments of the South River,VA (USA)

Mercury (Hg) transport and methylmercury (MeHg) production in riverbank sediments are complex processes influenced by site-specific physical and biogeochemical conditions. The South River watershed in VA, USA, contains elevated concentrations of Hg in riverbank and floodplain sediments, which has the potential to methylate. The role of specific organic carbon sources in promoting methylation reactions in natural sediments under dynamic flow conditions is not well understood. Four saturated column experiments were conducted, including a control column, which received South River water as an influent solution, and three columns that received South River water amended with: acetate (5.8 mM); lactate (5.7 mM); and lactate (5.7 mM) with SO₄^2? (10.1 mM). The amendments were selected to promote growth of different microorganisms to gain an understanding of the microbial processes, controlling rates of methylation. The column receiving lactate and SO₄^2? had the highest MeHg concentrations in the effluent and in the pore water near the effluent at 1.8 and 4.9 μg L^?1, respectively. At the cessation of the column experiments, the lactate–sulfate column sediments contained the highest populations of enumerable sulfur-reducing bacteria and the highest solid-phase MeHg at 530 ± 100 ng g^?1 dry wt. from the interval closest to the influent. The results suggest that the form and availability of electron donors and acceptors are primary factors controlling rates of methylation in the South River sediment.     

Inorganic sulfur turnover in oligohaline estuarine sediments

Inorganic sulfur turnover was examined in oligohaline (salinity < 2 g kg^-1) Chesapeake Bay sediments during the summer. Cores incubated for < 3 hr exhibited higher sulfate reduction (SR) rates (13–58 mmol m^-2 d^-1) than those incubated for 3–8 hr (3–8 mmol m^-2 d^-1). SR rates (determined with³⁵SO ₄ ^2- ) increased with depth over the top few cm to a maximum at 5 cm, just beneath the boundary between brown and black sediment. SR rates decreased below 5 cm, probably due to sulfate limitation (sulfate < 25 μM). Kinetic experiments yielded an apparent half-saturating sulfate concentration (K_s) of 34 μM, ≈ 20-fold lower than that determined for sediments from the mesohaline region of the estuary. Sulfate loss from water overlying intact cores, predicted on the basis of measured SR rates, was not observed over a 28-hr incubation period. Reduction of³⁵SO ₄ ^2- during diffusion experiments with intact core segments from 0–4 and 5–9 cm horizons was less than predicted by non-steady state diagenetic models based on³⁵SO ₄ ^2- reduction in whole core injection experiments. The results indicate that net sulfate flux into sediments was an order of magnitude lower than the gross sulfur turnover rate. Solid phase reduced inorganic sulfur concentrations were only 2–3 times less than those in sediments from the mesohaline region of the Bay, despite the fact that oligohaline bottom water sulfate concentrations were 10-fold lower. Our results demonstrate the potential for rapid SR in low salinity estuarine sediments, which are inhabited by sulfate-reducing bacteria with a high affinity for sulfate, and in which sulfide oxidation processes replenish the pore water sulfate pool on a time scale of hours.     

Shifts in the relative availability of phosphorus and nitrogen along estuarine salinity gradients

Phosphorus (P) availability in estuaries may increase with increasing salinity because sulfate from sea salt supports production of sulfide in sediments, which combines with iron (Fe) making it less available to sequester P. Increased P availability with increased salinity may promote the generally observed switch from P limitation of primary production in freshwater ecosystems to nitrogen (N) limitation in coastal marine waters. To investigate this hypothesis, we analyzed pore water from sediment cores collected along the salinity gradients of four Chesapeake Bay estuaries (the Patuxent, Potomac, Choptank, and Bush Rivers) with watersheds differing in land cover and physiography. At salinities of 1–4 in each estuary, abrupt decreases in pore water Fe²⁺ concentrations coincided with increases in sulfate depletion and PO₄ ^3? concentrations. Peaks in water column PO₄ ^3? concentrations also occur at about the same position along the salinity gradient of each estuary. Increases in pore water PO₄ ^3? concentration with increasing salinity led to distinct shifts in molar NH₄ ⁺:PO₄ ^3? ratios from >16 (the Redfield ratio characteristic of phytoplankton N:P) in the freshwater cores to <16 in the cores with salinities >1 to 4, suggesting that release of PO₄ ^3? from Fe where sediments are first deposited in sulfate-rich waters could promote the commonly observed switch from P limitation in freshwater to N limitation in mesohaline waters. Finding this pattern at similar salinities in four estuaries with such different watersheds suggests that it may be a fundamental characteristic of estuaries generally.     

Nanosilver inhibits nitrification and reduces ammonia‐oxidising bacterial but not archaeal amoA gene abundance in estuarine sediments

Silver nanoparticles (AgNPs) enter estuaries via wastewater treatment effluents, where they can inhibit microorganisms, because of their antimicrobial properties. Ammonia‐oxidising bacteria (AOB) and archaea (AOA) are involved in the first step of nitrification and are important to ecosystem function, especially where effluent discharge results in high nitrogen inputs. Here, we investigated the effect of a pulse addition of AgNPs on AOB and AOA ammonia monooxygenase (amoA) gene abundances and benthic nitrification potential rates (NPR) in low‐salinity and mesohaline estuarine sediments. Whilst exposure to 0.5 mg L^?1 AgNPs had no significant effect on amoA gene abundances or NPR, 50 mg L^?1 AgNPs significantly decreased AOB amoA gene abundance (up to 76% over 14 days), and significantly decreased NPR by 20‐fold in low‐salinity sediments and by twofold in mesohaline sediments, after one day. AgNP behaviour differed between sites, whereby greater aggregation occurred in mesohaline waters (possibly due to higher salinity), which may have reduced toxicity. In conclusion, AgNPs have the potential to reduce ammonia oxidation in estuarine sediments, particularly where AgNPs accumulate over time and reach high concentrations. This could lead to long‐term risks to nitrification, especially in polyhaline estuaries where ammonia‐oxidation is largely driven by AOB.     

The chemistry and transport of mercury in a small wetland in the Adirondack region of New York, USA

The biogeochemistry of Hg was evaluated in a small wetland in the Adirondack region of New York. Concentrations of total Hg (Hg_T) in streamwater draining the wetland showed little temporal variation. The annual areal watershed flux of Hg_T (2.2 µg/m²-yr) was considerably smaller than regional inputs of atmospheric deposition of Hg_T, indicating that the terrestrial environment is a net sink for atmospheric deposition of Hg_T. Drainage inputs of Hg_T were conservatively transported through the beaver impoundment. The annual flux of total methyl mercury (CH₃Hg⁺ _T was greater than literature values of atmospheric deposition suggesting that the watershed is a net source of CH₃Hg⁺ _T . Stream concentrations of CH₃Hg⁺ _T increased during low-flow summer conditions in a riparian wetland, and particularly at the outlet of the beaver impoundment. Net production of CH₃Hg⁺ _T occurred in the beaver impoundment (0.45 µg/m²-yr). Rates of net methylation for the beaver impoundment were comparable to values reported in the literature for wetlands.     

Dissolved and suspended mercury. species in the Wabigoon River (Ontario,Canada): seasonal and regional variations

Seasonal and regional variations in the speciation, sediment-water partitioning, and dynamics of mercury (Hg) were studied at selected sites along the Hg-polluted Wabigoon River, and at unpolluted headwater and tributary sites, during April–September, 1979. ‘Dissolved’ and ‘particulate’ forms of Hg in the water were separated by continuous-flow centrifugation in the field. The Hg and other pollutants such as wood chips and salt had been discharged from a chlor-alkali plant and paper mill at Dryden, Ontario. Concentrations and loadings of particulate methyl mercury (CH₃Hg⁺) and total particulate Hg (and loadings of total ‘dissolved’ Hg) were greatest during the spring flood (April-May) owing to accelerated resuspension and transport of sediments. Concentrations of ‘dissolved’ CH₃Hg⁺, however, were highest in the summer (July–September), probably reflecting stimulation of microbial methylating activity by elevated temperatures, together with factors such as reduced levels of metal-scavenging particulates and minimal dilution by runoff. Total dissolved Hg concentrations were relatively high in September at polluted sites only, possibly because of desorption from sediments due to elevated concentrations of Cl⁻ ions. Loadings of dissolved CH₃Hg⁺ tended to be high in the summer but were generally depressed (suggesting sorption by suspended particles) during the major spring-flood episode in May. During July–August dissolved CH₃Hg⁺ was a function of total dissolved Hg, suggesting rapid biomethylation of desorbed inorganic Hg; but in general dissolved and suspended CH₃Hg⁺ levels depended on environmental variables and were unrelated to total Hg concentrations. In the summer only, total dissolved Hg was a function of dissolved Cl⁻. Hg species in particulates were associated with sulfides, hydrated Fe and Mn oxides, organic matter (notably high molecular weight humic and humic-Fe components), and selenium (Se); but CH₃Hg⁺ and total Hg differed in their specific preferences for binding agents, implying that binding sites discriminate between CH₃Hg⁺ and Hg²⁺ ions. CH₃Hg⁺ was associated with sulfide and (in the spring only) with Fe oxides, whereas total Hg was associated with organic matter and Se and with DTPA- and NaOH-extractable Fe in the spring but with Mn oxide and NaOH-extractable organics in the summer. Sulfides were most abundant in May, indicating that they were eroded from bottom sediments, but Fe and Mn oxides were most abundant in the summer, probably owing to activities of filamentous iron bacteria and other micro-organisms. Particulate Hg was 98–100% nonextractable by mild solvents such as Ca acetate, CaCl₂, dilute acetic acid, and (at polluted sites only) DTPA solutions, suggesting that the particulate Hg mobilized in the spring may not be readily available to organisms; association with Se and high molecular weight humic matter also supports this hypothesis. Hg probably becomes more bio-available in the summer, as suggested by the upsurge in dissolved CH₃Hg⁺ and total dissolved Hg levels, and by increases in the solubility of particulate Hg in acetic acid, DTPA, H₂O₂, and NaOH solutions, as well as an increase in the relative importance of lower molecular weight fractions of NaOH-extractable Hg (in September). Regional variations in Hg speciation and partitioning reflected a gradient in sediment composition from wood chips near Dryden to silt-clay mud further downstream. Hg in silt-clay mud relatively far (> 35 km) downstream from the source of pollution or in unpolluted areas appeared to be more readily solubilized by Cl⁻ ions or chelators such as DTPA, more readily methylated (as indicated by downstream increases in dissolved CH₃Hg⁺ levels and CH₃Hg⁺/total Hg ratios), and was to a greater degree organically bound (H₂O₂-extractable), and thus was probably more bio-available, than Hg in wood-chip deposits. Possible explanations include weaker binding of Hg by the mud, the more finely divided state of the mud, and improved microbial growth at lower concentrations of toxic pollutants. Owing to enrichment in sulfides and Fe oxides, resuspended wood-chip sediments were especially efficient scavengers of CH₃Hg⁺. The results indicate that in any pollution abatement plan aimed at lowering the Hg levels in the biota of lakes fed by the Wabigoon River, immobilization, removal, or detoxification of dissolved as well as particulate forms of Hg in the river would probably have to be considered. Possibly, Hg species could be ‘scrubbed’ from the river water by increasing the suspended load and by sedimentation and treatment with Hg-binding agents in special receiving basins.     

Xylem sap as a pathway for total mercury and methylmercury transport from soils to tree canopy in the boreal forest

Conifer needles are an important link in the cycling of Total Mercury (THg) and Methylmercury (MeHg) in the boreal ecosystem due to the high THg and MeHg concentrations in litterfall. Translocation within the tree of Hg from soils to the crown canopy has been assumed to be a minor source of the Hg in litterfall. This paper, however, is the first to present direct observations of THg/MeHg transport from the soil via xylem sap. Xylem sap concentrations of THg and MeHg were measured in sap drained from different levels along the boles of freshly cut 100 year old Norway spruce (Picea abies) and Scots pine (Pinus sylvestris). The trees came from a mixed stand growing on podzolized till soils at the Svartberget Forest Research Station in N. Sweden. Soil solution concentrations of THg and MeHg at different levels in the soil profile were measured for comparison.Concentrations of THg in xylem sap ranged from 10–15 ng L^-1 in both the Scots pine and Norway spruce. Concentrations of MeHg varied from 0.03 ng L^-1to 0.16 ng L^-1, with higher values in Scots pine than Norway spruce. If these concentrations are representative of the transport from soils to needles in xylem sap at this site, then only 3% of the MeHg in litterfall (0.12 mg ha^-1 yr^-1) and 11% of the THg (26 mg ha^-1 yr^-1) can originate via this pathway. The upward transport via xylem sap is larger relative to the open field inputs (84% of THg and 17% of MeHg). Comparison of soil solution and xylem sap THg/MeHg suggested some degree of THg exclusion during water uptake in Scots pine and Norway spruce, but MeHg exclusion only in Norway spruce.     

Binding of phosphate in sediment accumulation areas of the eastern Gulf of Finland,Baltic Sea

The relationships between P and components binding P were studied by analysing the concentrations of N, P, Fe, Mn, Ca and Al in sediments and pore water along the estuarine transect of the River Neva in August 1995. The high sediment organic matter concentration resulted in low surface redox potential and high pore-water o-P concentration, whereas the abundance of amphipods resulted in high surface redox potentials and low pore-water o-P concentration. However, despite the variation in sediment organic matter and the abundance of amphipods, very reduced conditions and slightly variable concentrations of Tot-P (0.7–1.1 mg g^–1 DW) were observed in the 10–15 cm sediment depth along the estuarine gradient, indicating that the pools of mobile P were largely depleted within the depth of 0–15 cm. Multiple regression analysis demonstrated that organic matter and Tot-Fe concentration of the sediment were closely related to the variation in Tot-P concentration of the sediments (r ² = 0.817, n=32). In addition, the high total Fe:P ratio suggested that there is enough Fe to bind P in sediments along the estuarine gradient. However, low Fe_diss concentrations in the pore water of reduced sediment (redox-potential <–50 mV) indicated efficient precipitation of FeS (FeS and FeS₂), incapable to efficiently bind P. Consequently, the low Fe_diss:o-P ratio (< 1) recorded in pore water in late summer implied that Fe³⁺ oxides formed by diffusing Fe_diss in the oxic zone of the sediments were insufficient to bind the diffusing o-P completely. The measured high o-P concentrations in the near-bottom water are consistent with this conclusion. However, there was enough Fe_diss in pore water to form Fe³⁺ oxides to bind upwards diffusing P in the oxic sediment layer of the innermost Neva estuary and the areas bioturbated by abundant amphipods.     

Interaction between migration behaviour and estuarine mortality in cultivated Atlantic salmon Salmo salar smolts

Migration behaviour and estuarine mortality of cultivated Atlantic salmon Salmo salar smolts in a 16 km long estuary were studied using two methods: (1) acoustic telemetry and (2) group tagging in combination with trap nets. Progression rates of surviving individuals through the estuary were relatively slow using both methods [0·38 L_T (total length) s^?1 v. 0·25 L_T s^?1]. In 2012, the progression rate was slow from the river to the estuary (0·55 L_T s^?1) and the first part of the estuary (0·31 L_T s^?1), but increased thereafter (1·45–2·21 L_T s^?1). In 2013, the progression rate was fast from the river to the estuary (4·31 L_T s^?1) but was slower thereafter (0·18–0·91 L_T s^?1). Survival to the fjord was higher in 2012 (47%) compared to 2013 (6%). Fast moving individuals were more likely to migrate successfully through the estuary compared to slower moving individuals. Adult recapture of coded‐wire‐tagged S. salar was generally low (0·00–0·04%). Mortality hot spots were related to topographically distinct areas such as the river outlet (in 2012) or the sill separating the estuary and the fjord (in 2013). At the sill, an aggregation of cod Gadus morhua predating on cultivated smolts was identified. The results indicate that slow progression rates through the estuary decreases the likelihood of smolts being detected outside the estuary. The highly stochastic and site‐specific mortality patterns observed in this study highlight the complexity in extrapolating mortality patterns of single release groups to the entire smolt run of wild S. salar.     

System controls on the aqueous distribution of mercury in the northern Florida Everglades

The forms and partitioning of aqueous mercury species in the canals and marshes of the Northern Florida Everglades exhibit strong spatial and temporal variability. In canals feeding Water Conservation Area (WCA) 2A, unfiltered total Hg (HgT_U) is less than 3 ng L^-1 and relatively constant. In contrast, methyl mercury (MeHg) exhibited a strong seasonal pattern, with highest levels entering WCA-2A marshes during July. Stagnation and reduced flows also lead to particle enrichment of MeHg. In the marshes of WCA-2A, 2B and 3A, HgT_U is usually <5 ng L^-1 with no consistent north–south patterns. However, for individual dates, aqueous unfiltered MeHg (MeHg_U) levels increase from north to south with generally lowest levels in the eutrophied regions of northern WCA-2A. A strong relationship between filtered Hg species and dissolved organic carbon (DOC), evident for rivers draining wetlands in Wisconsin, was not apparent in the Everglades, suggesting either differences in the binding sites of DOC between the two regions, or non-organic Hg complexation in the Everglades.