The effect of induced anoxia and reoxygenation on benthic fluxes of organic carbon, phosphate, iron, and manganese

Eutrophication causes seasonally anoxic bottom waters in coastal environments, but we lack information on effects of onset of anoxia and subsequent reoxygenation on benthic fluxes of redox-sensitive minerals and associated organic carbon (OC). As the first study, we determined the effect of inducing anoxia and subsequently restoring oxic conditions in mesocosms with surface sediment and water from a coastal environment. These concentration changes were compared with those in an oxygenated control. We determined water column concentrations of dissolved organic carbon (DOC), particulate organic carbon (POC), iron, manganese, and phosphate.Benthic fluxes of DOC, POC, and iron increased at the onset of anoxia in oxygen-depleted treatments. DOC and iron concentrations increased concomitantly towards maxima, which may have indicated reductive dissolution of FeOOH and release of associated OC. The subsequent concomitant concentration decreases may have been the result of coprecipitation of OC with iron-containing minerals. In contrast, the phosphate-concentration increase occurred several days after the onset of anoxia and the manganese concentration was not affected by the onset of anoxia. Restoring oxic conditions resulted in a decrease in DOC, POC, and phosphate concentrations, which may indicate coprecipitation of OC with phosphate-containing minerals. The high DOC fluxes at the onset of anoxia indicate that redox oscillations may be important in OC degradation. Further, our results indicate a close coupling between OC cycling and dissolution/precipitation of iron-containing minerals in intermittently anoxic sediments.     

Influences of iron, manganese, and dissolved organic carbon on the hypolimnetic cycling of amended mercury

The biogeochemical cycling of iron, manganese, sulfide, and dissolved organic carbon were investigated to provide information on the transport and removal processes that control the bioavailability of isotopic mercury amended to a lake. Lake profiles showed a similar trend of hypolimnetic enrichment of Fe, Mn, DOC, sulfide, and the lake spike ((202)Hg, purity 90.8%) and ambient of pools of total mercury (HgT) and methylmercury (MeHg). Hypolimnetic enrichment of Fe and Mn indicated that reductive mobilization occurred primarily at the sediment-water interface and that Fe and Mn oxides were abundant within the sediments prior to the onset of anoxia. A strong relationship (r(2)=0.986, n=15, p<0.001) between filterable Fe and Mn indicated that reduction of Fe and Mn hydrous oxides in the sediments is a common in-lake source of Fe(II) and Mn(II) to the hypolimnion and that a consistent Mn:Fe mass ratio of 0.05 exists in the lake. A strong linear relationship of both the filterable [Fe] (r(2)=0.966, n=15, p<0.001) and [Mn] (r(2)=0.964, n=15, p<0.001) to [DOC] indicated a close linkage of the cycles of Fe and Mn to DOC. Persistence of iron oxides in anoxic environments suggested that DOC was being co-precipitated with Fe oxide and released into solution by the reductive dissolution of the oxide. The relationship between ambient and lake spike HgT (r(2)=0.920, n=27, p<0.001) and MeHg (r(2)=0.967, n=23, p<0.001) indicated that similar biogeochemical processes control the temporal and spatial distribution in the water column. The larger fraction of MeHg in the lake spike compared to the ambient pool in the hypolimnion suggests that lake spike may be more available for methylation. A linear relationship of DOC to both filterable ambient HgT (r(2)=0.406, n=27, p<0.001) and lake spike HgT (r(2)=0.314, n=15, p=0.002) suggest a role of organic matter in Hg transport and cycling. However, a weak relationship between the ambient and lake spike pools of MeHg to DOC indicated that other processes have a major role in controlling the abundance and distribution of MeHg. Our results suggest that Fe and Mn play important roles in the transport and cycling of ambient and spike HgT and MeHg in the hypolimnion, in part through processes linked to the formation and dissolution of organic matter-containing Fe and Mn hydrous oxides particles.     

Determination of mercury methylation potentials in the water column of lakes across Canada

A stable isotope technique was used to trace the formation of methylmercury in lake water incubation assays at in situ conditions in five lakes across Canada. Methylation activity was only detected in the anoxic hypolimnia of lakes. The stable isotope was methylated at varying rates between lakes and depths within lakes ranging from 0.56%/day to 14.8%/day. A peak in methylation potential was typically observed just below the oxycline, which decreased with increasing depth. The depth and rates of methylation potential changed seasonally with no methylation activity occurring after fall turnover. A decrease in the sulfate concentration was concomitant with the zone of mercury methylation potential indicating the likely involvement of sulfate reducing bacteria in the methylation process. A simple correlation test between DOC concentrations and methylation rates indicated a positive relationship (r2=0.62; p=0.006; n=27). The demethylation rate constant in the anoxic hypolimnia was less than 0.12 d(-1).     

Photoreduction and evolution of mercury from seawater

The photoreduction of mercury (Hg2+ to Hg0) in natural seawater was investigated by means of a radiotracer (203Hg2+) solution exposed to natural and simulated sunlight. Different light regimes (dark, natural daylight, and a solar simulator), and dissolved organic carbon (DOC) levels from commercially available humic acids concentrations, were tested in the laboratory to evaluate the possibility of occurrence of the reaction in the environment. The natural seawater prepared accordingly to each experimental condition was continuously purged of the Hg0 formed, which was then re-oxidised in an acid trap and determined. The use of a solar simulator permitted the test of light intensity and wavelength dependence of the process under investigation. The reaction is dependent on the concentration of DOC in the experimental solution, increasing light intensity and decreasing wavelength. Reduction rates were in the range of 0.04-2.2% h(-1) for the DOC concentrations and light regimes tested. The process might have geochemical implications for the cycling of mercury around the air-sea interface.     

Nitrate suppresses internal phosphorus loading in an eutrophic lake

The presence of nitrate in the hypolimnion of the eutrophic, dimictic Upper Mystic Lake has been previously shown to suppress the release of arsenic from lake sediments during seasonal anoxia, in large part by oxidizing iron (II) and producing iron oxyhydroxides that sorb inorganic arsenic. Because of the importance of internal phosphorus loading in the phosphorus budget of many eutrophic lakes, the chemical similarities between phosphate and arsenate, and the need to account for internal phosphorus loading as part of many lake restoration strategies, we carried out measurements to determine if the presence of nitrate also suppressed the release of phosphorus from the sediments of this lake during anoxia. Observations showed that this was the case. Arsenic, phosphorus, and iron (II) concentrations were strongly correlated in the water column, as expected, and the depths below which phosphorus and iron concentrations increased relative to epilimnetic values was predicted by the depth at which nitrate concentration approached zero. The results suggest that knowledge of a lake’s nitrogen budget may be a useful tool in the design of lake remediation efforts, even though phosphorus is typically the limiting nutrient.     

Climate induced thermocline change has an effect on the methyl mercury cycle in small boreal lakes

We conducted a whole-lake experiment by manipulating the stratification pattern (thermocline depth) of a small polyhumic, boreal lake (Halsjärvi) in southern Finland and studying the impacts on lake mercury chemistry. The experimental lake was compared to a nearby reference site (Valkea-Kotinen Lake). During the first phase of the experiment the thermocline of Halsjärvi was lowered in order to simulate the estimated increase in wind speed and in total lake heat content (high-change climate scenario). The rate of methyl mercury (MeHg) production during summer stagnation (May-August) was calculated from water profiles before the treatment (2004), during treatment (2005, 2006) and after treatment (2007). We also calculated fluxes of MeHg from the epilimnion and from the hypolimnion to the sediments using sediment traps. Experimental mixing with a submerged propeller caused a 1.5-2 m deepening of the thermocline and oxycline. Methyl mercury production occurred mostly in the oxygen free layers in both lakes. In the experimental lake there was no net increase in MeHg during the experiment and following year; whereas the reference lake showed net production for all years. We conclude that the new exposed epilimnetic sediments caused by a lowering of the thermocline were a major sink for MeHg in the epilimnion. The results demonstrate that in-lake MeHg production can be manipulated in small lakes with anoxic hypolimnia during summer. The climate change induced changes in small boreal lakes most probably affect methyl mercury production and depend on the lake characteristics and stratification pattern. The results support the hypothesis that possible oxygen related changes caused by climate change are more important than possible temperature changes in small polyhumic lakes with regularly occurring oxygen deficiency in the hypolimnion.     

Variation in iron,aluminum and dissolved organic carbon mass transfer coefficients in lakes

Steady-state mass balance models have been successfully used to predict annual loads and concentrations of numerous substances in lakes. A major limitation of the model is that the value of the mass transfer coefficient, nu(X), for some substance, X, is assumed constant and is taken as a mean value of a set of calibration lakes. The range in mean values between lakes for nu(X) is typically two- to three-fold. Thus, there is some potential for error in model predictions if the true but unknown value for a given lake differs from the mean, calibration value. Moreover, the use of a region-specific value for nu(X) for all lakes in a region means that when environmental conditions change, the model will have to be re-calibrated requiring many more years of monitoring. In this study, mass balances for two substances, total iron and aluminum, are presented along with simple empirical relationships that predict mass transfer coefficients for iron as a function of dissolved organic carbon (DOC) concentration and aluminum as a function of DOC and pH. The relationships, which are consistent with current understanding of iron and aluminum behavior, account for >90% of the variation in nu(X). Improvements in mass balance model predictions are expected when these coefficients are used in place of constant values.     

Measurement of biodegradable dissolved organic carbon (BDOC) in lake water with a bioreactor

Once-through, plug-flow bioreactors were colonised and maintained with a microbial community from a mesotrophic lake and used to measure the concentration of biodegradable dissolved organic carbon (BDOC). A BDOC measurement can be done within 3-4h by this method. Glucose was used to test whether oxygen consumption (BOD) could substitute for measurements of dissolved organic carbon (DOC). All added glucose was utilised, however, without a concomitant increase in oxygen demand. Oxygen consumption should not be used in bioreactor measurements. The site-specificity was tested by comparing DOC utilisation in bioreactors with batch cultures inoculated with indigenous bacteria and incubated for 28 days. The bioreactors were not site-specific and required no acclimation to measure BDOC from three different systems. However, humic substances were adsorbed in the reactors and about two days were needed to equilibrate the reactors. The BDOC concentrations in two lakes varied 2-fold over diurnal cycles and 3-fold during the period February-June. No significant relations to the light, dark cycle, chlorophyll, and DOC were found. The absolute BDOC concentrations ranged from 20 to almost 200 microM and averaged 13% of the DOC in the lakes. It is concluded that BDOC in lakes and other fresh waters can be measured quickly and reliably with a bioreactor.     

Photo-induced formation of dissolved gaseous mercury in coastal and offshore seawater of the Mediterranean basin

The first measurements on the daily trend of dissolved gaseous mercury (DGM) concentration determined in coastal and offshore waters of the Mediterranean basin are reported. Marked daily behaviour tracking solar radiation has been observed at the coastal sampling station with DGM values ranging from 11.0 to 38.9 pg/l. Contrary to these observations the DGM values in offshore water samples (11.9-20.0 pg/l) were independent of the sampling time, thus identifying the absence of higher levels during the hours of maximum insolation. The availability of Hg2+ substrate necessary for the photo-reaction processes of DGM formation has been evaluated by measuring the reactive mercury concentration. In offshore waters the lower DGM concentrations are attributable to the substrate as a limiting factor. The highest concentration of DOC measured in coastal seawater with respect to the offshore one could moreover enhance the reaction rates of DGM production through the formation of inorganic mercury complexes and weaker organic associations.     

Dissolved organic matter fluorescence as a water-flow tracer in the tropical wetland of Pantanal of Nhecolândia, Brazil

The Nhecolandia is a sub-region of the Brazilian Pantanal wetland, where saline and freshwater lakes coexist in close proximity. Measurements of dissolved organic carbon (DOC) content and analysis of fluorescence excitation-emission matrices (EEM) were conducted in an effort to characterize spatial variability in concentration and source of dissolved organic matter (DOM) and to further understand the hydrochemical functioning of this complex environment. Increasing pH under the influence of evaporation resulted in an increasing DOC solubility ranging from 50 to over 300 mgC L(-1) in surface water. Spectrofluorescence characterisation indicates the presence of several families of dissolved organic matter (fulvic and humic-type and proteinaceous materials), which are related to the type of lake and its hydro-bio-geochemical functioning. Moreover, the fluorescence signatures from lake water DOM and from surrounding soil-water-extracted organic matter (WEOM) show strong similarities although some labile proteinaceous compounds disappeared during humification. Results from the characterisation of DOM and WEOM not only suggest that spectrofluorescence is a reliable technique for the tracing of water flows, but also for the marking of the origin of organic horizons in this environment.     

Diurnal variation of dissolved gaseous mercury (DGM) levels in a southern reservoir lake (Tennessee, USA) in relation to solar radiation

Variations of dissolved gaseous mercury (DGM) concentrations in a southern reservoir lake (Cane Creek Lake, Cookeville, TN, USA) in relation to solar radiation were investigated consecutively from June 2003 to May 2004. The daytime DGM levels in the lake exhibited a two-phase diurnal trend; the DGM concentrations rose in the morning, peaked around noontime and then fell in the afternoon through the evening; these trends followed the general pattern of diurnal solar radiation variations. The morning and afternoon phases appeared to be asymmetrical with the former relatively steep and the latter gradual. A variety of daytime DGM level variations other than the typical two-phase diurnal patterns were also observed. For the time spans studied, the daytime mean DGM concentrations of the lake ranged from 12 to 68 pg L(-1) (60-340 fM). The daytime mean DGM levels in the summertime (June, July, August) showed values above 30 pg L(-1) (150 fM) in most cases and a large number of peak DGM concentrations above 50 pg L(-1) (250 fM). The summer DGM levels in the lake appear to be comparable to those observed in the large northern lakes for the summertime. The daytime DGM levels in the lake were found to correlate with solar radiation to various degrees (cases of r values above 0.8: approximately 12% and approximately 18% of the total sampling days for correlation with global solar radiation and UVA radiation, respectively). Correlating trends are recognizable between the daytime mean DGM concentration and the corresponding mean global solar radiation (r = 0.66, p < 0.0005) and between the daytime mean DGM concentration and the corresponding mean UVA radiation (r = 0.62, p < 0.0005).     

Speciation of Al, Fe, and P in recent sediment from three lakes in Maine, USA

Sequential extraction of sediments [Psenner R, Pucsko R. Die Fraktionierung organischer und anorganischer Phosphorverbindungen von Sedimenten. Arch Hydrobiol/Suppl 1988. 70(1): 111-155.] from short, (210)Pb-dated cores from three lakes in Maine USA demonstrates that sediment P is dominantly associated with the NaOH-extractable fraction (P-NaOH(25)) and less with the bicarbonate-dithionite extractable fraction (P-BD). The ratios (Al-NaOH(25))/(Fe-BD) and (Al-NaOH(25))/(P-NH(4)Cl+P-BD) for upper sediment for two oligo-mesotrophic lakes exceeded 3 and 25, the thresholds for preventing substantial release of P from sediments during hypolimnetic anoxia [Kopácek J, Borovec J, Hejzlar J, Ulrich K-U, Norton SA, Amirbahman A. Aluminum control of phosphorus sorption by lake sediments. Environ Sci Technol 2005a;39:8784-8789.]. Hypolimnetic water chemistry verifies this effect. The third lake, currently eutrophic, has values for the ratios that are below the thresholds and this lake has substantial release of P from recent sediment. The sediment characteristics remain relatively constant over the last 150+ years, indicating that the processes responsible for P retention have operated long before atmospheric acidification of watersheds might have influenced the flux of Al and Fe to the lake. In 2002, the pH of inlets and the lakes was generally between 6 and 8. Input to the lakes had high concentrations of acid-soluble particulate and dissolved Al, Fe, and P, and dissolved Al and Fe complexed with dissolved organic carbon (DOC). Lake water column and outlet Al, Fe, and P were typically 90-95% lower than inlet concentrations over a 12 month period. Photo-oxidation of Al-DOC and Fe-DOC in the lake, liberation of inorganic Al and Fe, precipitation of Al(OH)(3) and Fe(OH)(3), adsorption of P by the hydroxides, and sedimentation are responsible for the changes in water quality and long-term sediment characteristics.     

The influence of forestry activity on the structure of dissolved organic matter in lakes: implications for mercury photoreactions

It is well known that dissolved organic matter (DOM) increases in lakes associated with forestry activity but characterization of the DOM structure is incomplete. Twenty-three lakes with a wide range of forestry activities located in central Quebec, Canada were sampled and analyzed for dissolved organic carbon (DOC) concentration, DOC fluorescence, and ultra violet-visible (UV-VIS) absorption spectra. The results show that DOC increases (as does the associated DOC fluorescence) with increased logging (slope=0.122, r2=0.581, p<0.001; and slope=0.283, r2=0.308, p<0.01, respectively) in the 23 lakes sampled however, the aromaticity of the DOM does not change with changes in logging (as found by UV-VIS ratios, absorbance slope in the UV region, and DOC normalized fluorescence (slope=1.42x10(-2), r2=0.331, p<0.01). The DOM from four of these lakes was concentrated using reverse osmosis (RO) followed by freeze-drying. The structures of the concentrated dissolved organic matter (DOM) samples were analyzed using X-ray analysis of near edge structures (XANES), X-ray diffraction (XRD), and 13C solid-state nuclear magnetic resonance (13C NMR) analysis. XANES analysis of functional groups in the four concentrated samples shows that there are significant differences in reduced sulphur between the samples, however there was no clear relationship with forestry activity in the associated catchment. XRD data showed the presence of amorphous sulphide minerals associated with the DOM concentrate that may be important sites for mercury binding. The 13C NMR spectra of these samples show that the percentage of carbon present in carboxylic functional groups increases with increasing logging. Such structures are important for binding photo-reducible mercury and their presence may limit mercury photo-reduction and volatilization. We propose a mechanism by which increased logging leads to increased carboxylic groups in DOM and thereby increased weak binding of photo-reducible mercury. These results, in part, explain the decrease in dissolved gaseous mercury (DGM) production rates with increased logging found in our previous work.     

Effects of whole lake mixing on water quality and phytoplankton

This paper describes the effect of artificial mixing of two Oklahoma lakes with a downflow pump on water quality and algal biomass. Artificial pumping in Arbuckle Lake (951 ha), advanced autumnal turnover, but never destratified the lake completely. Ammonia decreased in the epilimnion, while sulfide (H₂S) declined and dissolved oxygen (DO) increased in the hypolimnion. Other water quality parameters did not change. Near-bottom concentrations of manganese (Mn²⁺) increased, indicating pumping did not affect water chemistry near deep sediments (> 16 m). Pumping did not change significantly the depth of the Secchi disc or algal biomass as measured by chlorophyll a. The algal flora was dominated by diatoms at all times, and the density of blue-green algae was always low. Pumping kept Ham's Lake (41 ha) destratified, but seldom produced completely isothermal conditions or isochemical concentrations of DO. There was no drastic change in other water quality parameters. However, artificial mixing decreased water clarity and increased algal biomass by a factor of about 2.5, probably by reducing sinking rates of the phytoplankton. Artificial mixing apparently eliminated a fall pulse of Microcystis.     

Decreased DOC concentrations in soil water in forested areas in southern Sweden during 1987-2008

During the last two decades, there is a common trend of increasing concentrations of dissolved organic carbon (DOC) in streams and lakes in Europe, Canada and the US. Different processes have been proposed to explain this trend and recently a unifying hypothesis was presented, concluding that declining sulphur deposition and recovery from acidification, is the single most important factor for the long-term DOC concentration trends in surface waters. If this recovery hypothesis is correct, the soil water DOC concentrations should increase as well. However, long-term soil water data from Sweden and Norway indicate that there are either decreasing or indifferent DOC concentrations, while positive DOC trends have been found in the Czech Republic. Based on the soil water data from two Swedish integrated monitoring sites and geochemical modelling, it has been shown that depending on changes in pH, ionic strength and soil Al pools, the DOC solubility might be positive, negative or indifferent. In this study, we test the acidification recovery hypothesis on long-term soil water data (25 and 50 cm soil depth) from 68 forest covered sites in southern Sweden, showing clear signs of recovery from acidification. The main aim was to identify potential drivers for the DOC solubility in soil solution by comparing trends in DOC concentrations with observed changes in pH, ionic strength and concentrations of Alⁿ⁺. As in earlier Swedish and Norwegian studies, the DOC concentrations in soil water decreased or showed no trend. The generally small increases in pH (median < 0.3 pH units) during the investigation period seem to be counterbalanced by the reduced ionic strength and diminished Al concentrations, increasing the organic matter coagulation. Hence, opposite to the conclusion for surface waters, the solubility of organic matter seems to decrease in uphill soils, as a result of the acidification recovery.     

Effects of aerobic and anaerobic conditions on P, N, Fe, Mn, and Hg accumulation in waters overlaying profundal sediments of an oligo-mesotrophic lake

Concentrations of key nutrients and metals in water overlaying profundal sediments were evaluated in replicate experimental chambers containing undisturbed sediment-water interface samples from Deer Lake, an oligo-mesotrophic lake in eastern Washington. Chambers were incubated under three sequential phases: aerobic (21d), anaerobic (27d), and second aerobic (14d). In general, nutrients and metals in chamber water were lower under aerobic versus anaerobic conditions. However, in some cases compounds anticipated to appear only under anaerobic conditions, including ammonia, phosphate, and manganese, were observed during aerobic conditions. Correlation analysis elucidated a number of interactions between compounds. Phosphate correlated significantly (p<0.05) with iron during all incubation phases, suggesting that phosphorus cycling was controlled by iron. Cycling of nitrate and ammonia was tightly and significantly coupled under aerobic conditions. During both aerobic phases, nitrate increased while ammonia decreased, likely as a result of biological nitrification. Finally, mercury appeared during mildly reducing conditions and showed a significant correlation with manganese during the anaerobic phase, suggesting that Mn oxide reduction was the source of Hg in chamber water.     

Temporal variations in dissolved organic carbon concentrations in upland and lowland lakes in North Wales

Over a period of 18 months, the dissolved organic carbon (DOC) concentration of a series of four lakes in North Wales was measured monthly. The lake catchment profiles consisted of an upland thin peat/soil (Llyn Cwellyn), an upland thin peat/soil associated with an adjacent area of small bog (Llyn Teyrn), an upland blanket bog (Llyn Conwy), and large lowland fen and fertile agricultural area (Llyn Cefni). The results examine the indirect effect of temperature and precipitation on the DOC concentrations found in the lakes fed by the catchments. The lowest DOC of the four sites was observed for Llyn Teyrn, varying from 1.2 to 3.30 mg/L, and with the highest being recorded for Llyn Cefni (5.45–10.83 mg/L). Temperature and rainfall data were both collected. Correlations with the DOC exhibited significant relationships with temperature for three of the sampled lakes Cwellyn (r 0.490), Teyrn (r 0.640) and Cefni (r 0.472). Recomputation versus 30‐ and 60‐day temperature lag times improved the correlation coefficients. The data showed weak and insignificant correlations for DOC versus rainfall for the three lakes, but the upland lake, Llyn Conwy, with its blanket bog catchment, did not demonstrate any statistical correlation with temperature, although it did show a significant correlation for DOC versus rainfall (r 0.553, P < 0.05). Over the sampling period, although tentative relationships were found among temperature, rainfall and DOC levels, an indirect association tempered by site hydrology is suggested.     

Long-term lake water quality predictors

Daily water temperature and dissolved oxygen profiles in 3002 Minnesota lakes have been simulated by deterministic process-based water quality models with daily meteorological conditions from 1955 to 1979 as input. From the simulated results, indicators of lake water quality and fish habitat characteristics have been extracted and correlated selectively with normal air temperature, lake mean depth, wind-related densimetric Froude number and Lake number. A seasonal maximum Lake number was found to be a good predictor for volume averaged water temperatures, maximum water temperatures near lake bottom, seasonal stratification characteristics, volume averaged dissolved oxygen concentrations, anoxia characteristics and fish good-growth habitat. Lakes with a maximum daily Lake number bigger than 1.0, are seasonally stratified, have low hypolimnetic dissolved oxygen concentration, and only a fraction of lake depth available for good-growth of fish. Lakes with maximum daily Lake number less than 1.0 are polymictic, with high dissolved oxygen concentration, and with maximum depth available for good fish growth. Empirical formulas for lake water quality and stratification indicators derived from the simulation results give good predictions of temperature and dissolved oxygen characteristics estimated from measurements in seven Minnesota lakes.     

Application of ultrafiltration and stable isotopic amendments to field studies of mercury partitioning to filterable carbon in lake water and overland runoff

Results from pilot studies on colloidal phase transport of newly deposited mercury in lake water and overland runoff demonstrate that the combination of ultrafiltration, and stable isotope amendment techniques is a viable tool for the study of mercury partitioning to filterable carbon. Ultrafiltration mass balance calculations were generally excellent, averaging 97.3, 96.1 and 99.8% for dissolved organic carbon (DOC), total mercury (Hg(T)), and methylmercury (MeHg), respectively. Sub nanogram per liter quantities of isotope were measurable, and the observed phase distribution from replicate ultrafiltration separations on lake water agreed within 20%. We believe the data presented here are the first published colloidal phase mercury data on lake water and overland runoff from uncontaminated sites. Initial results from pilot-scale lake amendment experiments indicate that the choice of matrix used to dissolve the isotope did not affect the initial phase distribution of the added mercury in the lake. In addition there was anecdotal evidence that native MeHg was either recently produced in the system, or at a minimum, that this 'old' MeHg partitions to the same subset of DOC that binds the amended mercury. Initial results from pilot-scale overland runoff experiments indicate that less than 20% of newly deposited mercury was transported in the filterable fraction (<0.7 microm). There is some indication of colloidal phase enrichment of mercury in runoff compared to the phase distribution of organic carbon, but the mechanism of this enrichment is unclear. The phase distribution of newly deposited mercury can differ from that of organic carbon and native mercury, suggesting that the quality of the carbon (available ligands), not the quantity of carbon, regulates partitioning. Further characterization of DOC is needed to clarify the underlying mechanisms.