Dynamics of mercury and methylmercury in forest floor and runoff of a forested watershed in Central Europe

Forested watersheds are an important part of the terrestrialmercury and methylmercury cycle, and a link between theatmospheric and aquatic environment. This study was conducted todetermine the contribution of the forest floor to the pools andfluxes of total Hg (Hg_total) and methylmercury (MeHg) in aforested catchment, and to identify factors influencing themobility of both compounds. Throughfall deposition, litterfall,runoff and fluxes with forest floor percolate of Hg_total and MeHgwere sampled during one year in a coniferous catchment inGermany. Total deposition of Hg_total was 552 mg ha_–1 a_–1 withlitterfall contributing one third. Nearly 60% of the total inputof Hg_total reached the mineral soil with the forest floorpercolate, but less than half of this fraction was found in therunoff of the catchment. Total deposition of MeHg was 2.6 mg ha_–1a_–1, with litterfall as the dominating pathway. Only 19% of theMeHg deposition was discharged from the forest floor, but theflux of MeHg with runoff was nearly twice as high. Only fewcorrelations with other solution parameters were found. Fluxes ofboth compounds with forest floor percolates depended mainly onwater fluxes, which was not true for the runoff. The forest floorof the upland soil is an effective sink for MeHg, but not forHg_total. Differences in the mobility of both compounds in theforest floor disappeared at the catchment scale, probably becauseother processes (i.e. Hg_total immobilization and MeHg formation)dominated.     

Biogeochemistry of trimethyllead and lead in a forested ecosystem in Germany

Lead compounds, especially ionic organolead compounds (OLC), are highly toxic and mobile pollutants strongly affecting many ecosystems. Soil pools and fluxes with precipitation, litterfall and runoff of trimethyllead (TML), one of the dominant ionic OLC in the environment, and Pb_total were investigated in a forested ecosystem in NE-Bavaria, Germany. In addition, ad/desorption of TML to soils was studied in batch experiments and its degradation in soils was investigated using long term incubations. Total soil storage in the catchment was 11.56 mg Pb ha^–1 for TML and 222 kg Pb ha^–1 for Pb_total. More than 90% of the soil storage of TML was found in the wetland soils of the catchment representing only 30% of the area. Most Pb_total (>90%) was found in the upland soils. In upland soils, TML was only detectable in the forest floor. The annual total deposition from the atmosphere, estimated as throughfall + litterfall fluxes, amounted to 3.7 mg Pb ha^–1 year^–1 for TML and 52 g Pb ha^–1 year^–1 for Pb_total. The contribution of litterfall was 1.5 and 32%, respectively. The concentrations of TML and Pb_total in wet precipitation were: fog > throughfall > bulk precipitation. The annual fluxes with runoff from the catchment was 0.5 mg Pb ha^–1 year^–1 for TML and 2.8 g Pb ha^–1 year^–1 for Pb_total. TML degraded rapidly in the forest floor (Oa horizon) with a half-life (t _1/2) of 33.5 days. The degradation of TML in Fen (t _1/2 = 421 days) and in the mineral soil (Bw-C horizon, t _1/2 = 612 days) was much slower. Emission of tetramethyllead from wetland soils was not observed during the 1 year incubation. The adsorption affinity of TML to different soils was Fen > Oa > A Bw-C. The ratio of total soil storages to the present annual input were 3.6 years for TML. TML and Pb_total are still deposited in remote areas even after the use of tetraalkyllead as additives has been terminated for years. The rates of deposition are, however, much lower than in the past. Forest soils act as a sink for deposited TML and Pbtotal. TML is accumulated mostly in wetland soils and seems to be stable under anoxic conditions for a long time. In upland soils, TML decomposes rapidly. Only small amounts of TML are transferred from soils into runoff.     

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.     

Mercury-selenium interactions in relation to histochemical staining of mercury in the rat liver

Summary Selenium has been suggested to enhance the histochemical staining of mercury when sections of tissue are subjected to the silver-enhancement method. In the present study, histochemical staining patterns of mercury in tissue sections of rat livers were compared with the actual content of organic and inorganic Hg in the livers, in both the presence and the absence of Se. Rats were injected intravenously with 5g of Hgg^–1 body weight as methyl [²⁰³Hg] mercury chloride (MeHg) or as [²⁰³Hg]mercuric chloride (Hg²⁺). After 2h, half the rats received an additional intraperitoneal injection of 2g of Se g^–1 body weight as sodium [⁷⁵Se]selenite. All the rats were killed 1h later. Homogenized liver samples were prepared for mercury analysis by two different methods: alkaline digestion and ultrasonic disintegration. Quantitative chemical analysis based on benzene extrction of the radioactively labelled Hg compounds showed that the chemical form of mercury, either organic or inorganic, was preserved from its administration to its deposition in the liver. Light and electron microscopy demonstrated that no silver enhancement of Hg occurred when MeHg alone was present in the sections of tissue, whereas MeHg accompanied by Se induced a moderate deposition of silver grains. In contrast, sections containing Hg²⁺ alone yielded some staining, and the addition of Se increased the staining dramatically. The results of the present study show that acute selenite pretreatment is a prerequisite for the histochemical demonstration of methyl mercury, and greatly increases the staining of inorganic mercury when applying the silver-enhancement method.     

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.     

Biogeochemistry of trimethyllead and lead in a forested ecosystem in Germany

Lead compounds, especially ionic organolead compounds (OLC), are highly toxic and mobile pollutants strongly affecting many ecosystems. Soil pools and fluxes with precipitation, litterfall and runoff of trimethyllead (TML), one of the dominant ionic OLC in the environment, and Pb_total were investigated in a forested ecosystem in NE-Bavaria, Germany. In addition, ad/desorption of TML to soils was studied in batch experiments and its degradation in soils was investigated using long term incubations. Total soil storage in the catchment was 11.56?mg Pb?ha^?1 for TML and 222?kg Pb?ha^?1 for Pb_total. More than 90% of the soil storage of TML was found in the wetland soils of the catchment representing only 30% of the area. Most Pb_total (>90%) was found in the upland soils. In upland soils, TML was only detectable in the forest floor. The annual total deposition from the atmosphere, estimated as throughfall?+?litterfall fluxes, amounted to 3.7?mg Pb?ha^?1 year^?1 for TML and 52?g Pb?ha^?1 year^?1 for Pb_total. The contribution of litterfall was 1.5 and 32%, respectively. The concentrations of TML and Pb_total in wet precipitation were: fog?>?throughfall?>?bulk precipitation. The annual fluxes with runoff from the catchment was 0.5?mg Pb?ha^?1 year^?1 for TML and 2.8?g Pb?ha^?1 year^?1 for Pb_total. TML degraded rapidly in the forest floor (Oa horizon) with a half-life (t) of 33.5 days. The degradation of TML in Fen (t?=?421 days) and in the mineral soil (Bw-C horizon, t?=?612 days) was much slower. Emission of tetramethyllead from wetland soils was not observed during the 1 year incubation. The adsorption affinity of TML to different soils was Fen?>?Oa?>?A?≥?Bw-C. The ratio of total soil storages to the present annual input were 3.6 years for TML. TML and Pb_total are still deposited in remote areas even after the use of tetraalkyllead as additives has been terminated for years. The rates of deposition are, however, much lower than in the past. Forest soils act as a sink for deposited TML and Pb_total. TML is accumulated mostly in wetland soils and seems to be stable under anoxic conditions for a long time. In upland soils, TML decomposes rapidly. Only small amounts of TML are transferred from soils into runoff.     

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.     

Inorganic mercury (Hg2+) transport through lipid bilayer membranes

Summary Diffusion of inorganic mercury (Hg²⁺) through planar lipid bilayer membranes was studied as a function of chloride concentration and pH. Membranes were made from egg lecithin plus cholesterol in tetradecane. Tracer (²⁰³Hg) flux and conductance measurements were used to estimate the permeabilities to ionic and nonionic forms of Hg. At pH 7.0 and [Cl^–] ranging from 10–1000mm, only the dichloride complex of mercury (HgCl₂) crosses the membrane at a significant rate. However, several other Hg complexes (HgOHCl, HgCl ₃ ^– and HgCl ₄ ^2– ) contribute to diffusion through the aqueous unstirred layer adjacent to the membrane. The relation between the total mercury flux (J _Hg), Hg concentrations, and permeabilities is: 1/J _Hg=1/P ^ul[Hg ^t ]+1/P ^m [HgCl₂], where [Hg ^t ] is the total concentration of all forms of Hg,P ^ul is the unstirred layer permeability, andP ^m is the membrane permeability to HgCl₂. By fitting this equation to the data we find thatP ^m =1.3×10^–2 cm sec^–1. At Cl^– concentrations ranging from 1–100mm, diffusion of Hg ^t through the unstirred layer is rate limiting. At Cl^– concentrations ranging from 500–1000mm, the membrane permeability to HgCl₂ becomes rate limiting because HgCl₂ comprises only about 1% of the total Hg. Under all conditions, chemical reactions among Hg²⁺, Cl^– and/or OH^– near the membrane surface play an important role in the transport process. Other important metals, e.g., Zn²⁺, Cd²⁺, Ag⁺ and CH₃Hg⁺, form neutral chloride complexes under physiological conditions. Thus, it is likely that chloride can facilitate the diffusion of a variety of metals through lipid bilayer and biological membranes.     

Biogeochemical consequences of the transformation of native Cerrado into Pinus caribaea plantations in Brazil

Under the same climatic and edaphic conditions, native savanna vegetation in Brazil, the Cerrado, shows a lower stature and canopy cover than planted Pinus caribaea Morelet forests. To assess the differences in biogeochemical element cycling we compared the nutrient economy of Cerrado and Pinus on three replicate plots of each forest type. The mean nutrient storage in the soil organic layer under Pinus (N: 2630; P: 141; K: 103; Ca: 131; Mg: 20 kg ha^–1) was substantially higher than under Cerrado (N: 23; P: 1.2; K: 0.83; Ca: 5.8; Mg: 1.0 kg ha^–1) probably because the Pinus roots explored a larger soil volume. The Pinus trees had a higher nutrient-use efficiency as indicated by higher mean litter mass per unit nutrient in litter (N: 108; P: 2290; K: 729; Ca: 1360; Mg: 5420; S: 1190; Fe: 2960; Mn: 9990, Zn: 145000) than the Cerrado trees (N: 94; P: 1810; K: 619; Ca: 302; Mg: 938, S: 746; Fe: 1800; Mn: 7880; Zn: 63700). Mean annual small litterfall collected in 0.25-m² samplers between May 1997 and April 1999 was 2.1 Mg ha^–1 in Cerrado and 7.8 in Pinus. The litterfall rates of the 1–3 week collection intervals correlated negatively with the soil matric potential indicating that litterfall was partly related to water stress. The fluxes of N (73 kg ha^–1 year^–1), P (3.7), K (11), S (7.0), and Mn (0.83) to the soil with litterfall under Pinus were greater than the litterfall+turnover of the grass/herbs layer under Cerrado (N: 39, P: 2.8, K: 8.6, S: 5.4, Mn: 0.79 kg ha^–1 year^–1), those of Zn (0.06–0.07) were similar, and those of Ca (Pinus: 5.9/Cerrado: 10), Mg (1.5/4.4), and Fe (2.9/4.0) were smaller. Mean residence times of the organic matter and of all elements were longer in the soil organic layer under Pinus (3.7–26 years in the Oi horizon, 8.1–907 years in the whole organic layer) than under Cerrado (0.22–3.6 years in the Oi horizon, the only organic horizon under Cerrado). Our results demonstrate that the main differences in biogeochemical element cycling between the Pinus forest and the Cerrado consisted of a larger nutrient storage in the organic layer, a higher nutrient-use efficiency, and slower nutrient release rates from the organic layer in the Pinus forest than in the Cerrado. Nutrient cycling as assessed by the nutrient fluxes with litterfall was only partly faster in the Pinus forest than in the Cerrado.     

Behavior of mercury in the Patuxent River estuary

An overview of a comprehensive study of the behavior and fate of mercury in the estuarine Patuxent River is presented. Total Hg (Hg_T) and methylmercury (MeHg) exhibited weakly non-conservative behavior in the estuary. Total Hg concentrations ranged from 6 ng L^-1 in the upper reaches of the sub-urbanized tidal freshwater river to <0.5 ng L^-1 in the mesohaline lower estuary. Filterable (0.2 µm) Hg_T ranged from 0.2 to 1.5 ng L^-1. On average, MeHg accounted for <5% of unfiltered Hg_T and <2% of filterable Hg_T. Dissolved gaseous section Hg (DGHg) concentrations were highest (up to 150 pg L^-1) in the summer in the mesohaline, but were not well correlated with primary production or chlorophyll a, demonstrating the complex nature of Hg⁰ formation and cycling in an estuarine environment. Organic matter content appeared to control the Hg_T content of sediments, while MeHg in sediments was positively correlated with Hg_T and organic matter, and negatively correlated with sulfide. MeHg in sediments was low (0.1 to 0.5% of Hg_T). Preliminary findings suggest that net MeHg production within sediments exceeds net accumulation. Although Hg_T in pore waters increased with increasing sulfide, bulk MeHg concentrations decreased. The concentration of MeHg in sediments was not related to the concentration of Hg_T in pore waters. These observations support the hypothesis that sulfide affects the speciation and therefore bioavailability of dissolved and/or solid-phase Hg for methylation. Comparison with other ecosystems, and the negative correlation between pore water sulfide and sediment MeHg, suggest that sulfide limits production and accumulation of MeHg in this system.     

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.     

中亚热带常绿阔叶林凋落物分解过程中汞的动态变化及迁移机理

森林凋落物对于汞在林地土壤的生物地球化学循环中起到重要作用,为研究森林凋落物分解过程中汞的迁移转化特征,以重庆四面山风景名胜区典型林分(常绿阔叶林)作为研究对象。于2014年3月—2015年3月连续监测典型林分凋落物中各形态汞浓度和有机质变化量,同时监测周围土壤中汞浓度变化。结果表明:四面山典型林分凋落物分解过程中汞浓度整体上升,总汞浓度(初始浓度:78 ng/g)的增幅最高达53%,甲基汞浓度(初始浓度:0.32 ng/g)最高增幅达138%;在春季和夏季,水溶态和酸溶态两种活性态汞含量分别增加了851%和96%,在分解前期和末期,凋落物汞的中惰性汞比例最高,占比达75%。土壤腐殖质层中总汞和甲基汞浓度比较稳定。凋落物中活性态汞通过雨水淋洗进入土壤与有机质络合并发生甲基化/去甲基化过程,通过地表径流、地下径流进入水体。凋落物中C含量减少了22%,N含量增加了15%,总汞浓度与C/N比呈负相关,与N含量呈正相关。凋落物中微生物C、N含量整体增加,与汞浓度峰值同步,且夏季含量显著高于冬季含量(P0.05),说明微生物与凋落物固定汞和汞的甲基化过程密切相关。     

Development of an automated micrometeorological method for measuring the emission of mercury vapor from wetland vegetation

The ability of green plants to act as conduits to enhance the transport ofHg from soils to the atmosphere is now established, but the data base isseverely limited. The potential role of this process in mobilizing Hg inglobal and regional cycles makes it imperative that automated methods bedeveloped to increase our capability to measure and understand the processin a variety of ecosystems. We previously published a tower-basedmicrometeorological gradient method for measuring gas-phase Hg^°fluxes in terrestrial systems based on the Modified Bowen ratio (MBR)approach. The method relied on demanding and time-consuming manualsampling of Hg gradients. Automated Hg sampling methods now exist, andwe describe here applications of the Tekran Hg analyzer to automatednear-real-time measurements of Hg gradients over wetland vegetation. Weuse these data with MBR to compute fluxes of Hg from those of othertrace gases. From 1996 to 1998 we sampled Hg fluxes over emergentmacrophytes in the Florida Everglades, beginning with manual methods, butlater deploying automated methods for most of the study to collect morethan 500 30-min fluxes over 2 y. The limitations of the manual methodresulted in considerable uncertainly in our earlier observations, even to theextent that we initially doubted that vegetation emissions were real. However, the automated method allowed us to quantify the actualdevelopment of Hg emission gradients over wetland vegetation. Followingsunrise Hg fluxes show diel patterns similar to those of CO₂ andH₂O, providing information on the possible mechanisms of Hgemission. Our data suggest mean daytime emission rates of Hg over thesewetlands on the order of 30 ng m^-2 h^-1. Fluxes wereinfluenced by temperature, solar radiation, and atmospheric turbulence. There exists a significant biotic re-emission of Hg^° from the oceans,and our data provide the first direct evidence of a similar process insubtropical wetlands.     

Modeling and Mapping of Atmospheric Mercury Deposition in Adirondack Park,New York

The Adirondacks of New York State, USA is a region that is sensitive to atmospheric mercury (Hg) deposition. In this study, we estimated atmospheric Hg deposition to the Adirondacks using a new scheme that combined numerical modeling and limited experimental data. The majority of the land cover in the Adirondacks is forested with 47% of the total area deciduous, 20% coniferous and 10% mixed. We used litterfall plus throughfall deposition as the total atmospheric Hg deposition to coniferous and deciduous forests during the leaf-on period, and wet Hg deposition plus modeled atmospheric dry Hg deposition as the total Hg deposition to the deciduous forest during the leaf-off period and for the non-forested areas year-around. To estimate atmospheric dry Hg deposition we used the Big Leaf model. The average atmospheric Hg deposition to the Adirondacks was estimated as 17.4 g m yr with a range of −3.7–46.0 g m yr. Atmospheric Hg dry deposition (370 kg yr) was found to be more important than wet deposition (210 kg yr) to the entire Adirondacks (2.4 million ha). The spatial pattern showed a large variation in atmospheric Hg deposition with scattered areas in the eastern Adirondacks having total Hg deposition greater than 30 μg m⁻² yr⁻¹, while the southwestern and the northern areas received Hg deposition ranging from 25–30 μg m⁻² yr⁻¹.     

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.     

Deposition of ammonia to the forest floor under spruce and beech at the Höglwald site

Laboratory and field measurements of the flux of ammonia to forest floor canopies of spruce and beech stands at the Höglwald site in southern Bavaria are reported. Measurements were performed with an open chamber method. A linearity between ammonia concentration and ammonia flux from the atmosphere to the ground floor canopy was detected. Deposition of ammonia showed no saturation even at air concentrations up to 50 g NH₃ m^–3 air. Temperature, water content and the moss layer of the ground floor canopy had a minor influence on the deposition velocity in laboratory experiments. Deposition velocity of ammonia was higher to the spruce (1.3 cm s^–1), and limed spruce ground floor canopy (1.17 cm s^–1) compared to the beech stand (0.79 cm s^–1). In field studies, a diurnal course of the deposition velocity was detected with highest velocities in midday and minor during night times, but not in the climatic chamber. The flux of ammonia to the ground floor canopy was estimated of app. 10 kg N ha^–1 yr^–1 for the soil under spruce, 9 kg N ha^–1 yr^–1 for the limed spruce and 6 kg N ha^–1yr^–1 for the soil under beech. The fluxes are interpreted as fluxes from the atmosphere to the ground canopies of the stands.     

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.     

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.     

Nutrient pools and fluxes of the ground vegetation in coniferous forests due to fertilizing,liming and amelioration

The effects of fertilization and amelioration treatments on some nutrient pools and fluxes of ground vegetation in mature pine and spruce stands on acid soils in South Germany are described. In N-limited pine forests with moderate canopy density and with Deschampsia flexuosa an additional N-accumulation in biomass of 20–40 kg ha^-1 occurred 3 years after pure N-fertilization. The N, P, K-cycling through ground vegetation was stimulated more than 10 years by a combined N + CaCO₃ + P treatment leading toa shift in dominance from cryptogams and Ericaceae towards Deschampsia flexuosa and ruderal species like Epilobium angustifolium. The effect of a lupine treatment (combined with initial soil preparation, liming and P supply) was far stronger than the effect of the other experimental procedures. But the fertilizer and amelioration effects on the herb layer of pine forests tended to decline after two decades for different reasons.The shade-tolerant ground vegetation in a nitrogen-saturated spruce forest was not able to prevent heavy additional nitrate losses from upper mineral soil after dolomitic liming. But the Ca, Mg and K fluxes through ground vegetation were strongly elevated in the third year after treatment.