An update of the mercury inventory and atmospheric mercury fluxes to and from Finland

Finland, the northern-most agricultural/industrial country in the world, has been for some time steadily improving environmental mercury (Hg) research. This paper focuses upon Hg recovery during zinc production, uses of Hg, updating of information on Hg emissions and atmospheric transport of Hg to and from Finland. The recovery of Hg as a by-product of zinc production began in 1970. The highest amount of recovered Hg was noted to be 160 t in 1989. Total uses of Hg in different sectors were about 7.4 t in 1992, which had decreased by 50% since the year 1987. In 1992, the estimated Hg emission to air was 2 t yr^?1, whereas to water and land the emission was about 0.20 and 3.67 t yr^?1, respectively. Natural Hg emission in Finland was estimated to be about 0.4 t yr^?1 (range: 0.3 to 0.5 t yr^?1). In addition, an initial attempt was made to estimate the atmospheric Hg flux to and from Finland; these values were noted to be 2.7 and 2.1 t yr^?1, respectively.     

Particle-stabilizing effects of flavonoids at the oil-water interface

It has been shown that some common food flavonoids can act as excellent stabilizers of oil-in-water emulsions through their adsorption as water-insoluble particles to the surface of the oil droplets, i.e., Pickering emulsions are formed. Flavonoids covering a wide range of octanol-water partition coefficients (P) were screened for emulsification behavior by low shear mixing of flavonoid+n-tetradecane in a vortex mixer. Most flavonoids with very high or very low P values were not good emulsifiers, although there were exceptions, such as tiliroside, which is very insoluble in water. When a high shear jet homogenizer was used with 20 vol% oil in the presence of 1 mM tiliroside, rutin, or naringin, much finer emulsions were produced: the average droplet sizes (d32) were 16, 6, and 5 μm, respectively. These results may be highly significant with respect to the delivery of such insoluble compounds to the gut, as well as their digestion and absorption.     

Wet deposition of mercury and ambient mercury concentrations at a site in the Lake Champlain basin

The “Great Waters” program, established in the 1990 Clean Air Act Amendments, mandated that atmospheric deposition of hazardous air pollutants to Lake Champlain (including Hg) be assessed. An assessment of the magnitude and seasonal variation of atmospheric Hg deposition in the Lake Champlain basin was initiated in December 1992 with one year of event precipitation collection, as well as collection of vapor and particle phase Hg in ambient air. Samples were collected at the Vermont Monitoring Cooperative air monitoring site at the Proctor Maple Research Center in Underhill Center, VT. The average volume-weighted concentration for Hg in precipitation was 8.3 ng/L for the sampling year and the average amount of Hg deposited with each precipitation event was 0.069 μg/m². The total amount of Hg deposited through precipitation during 1993 was 9.26 μg/m²/yr. A seasonal pattern for Hg in precipitation was evident, with increased concentrations and deposition during spring and summer months. Meteorological analysis indicated the highest levels of Hg in precipitation were associated with regional transport from the south regardless of season, and with transport from the west, southwest and northwest during spring and summer months. Concentrations of ambient vapor phase Hg were typical of rural locations and consistent across seasons. Ambient particulate Hg concentrations averaged 11 pg/m³ with highest concentrations during the winter months.     

Analysis of beta-casein-monopalmitin mixed films at the air-water interface

The surface pressure (pi)-area (A) isotherms and Brewster angle microscopy (BAM) images of monopalmitin and beta-casein mixed films spread on buffered water at pHs 5 and 7 and at 20 degrees C were determined as a function of the mass fraction of monopalmitin in the mixture (X). The structural characteristics and morphology of monopalmitin-beta-casein mixed films are dependent on surface pressure, pH, and monolayer composition. The prevalence of monopalmitin in the interface increases with the amount of monopalmitin in the mixture and at higher pi. At the monopalmitin monolayer collapse the mixed film is practically dominated by the presence of monopalmitin. However, some degree of interactions exist between monopalmitin and beta-casein in the mixed film, and these interactions are more pronounced as the monolayer is compressed at the highest surface pressures.     

Design and initial tests of a dynamic enclosure chamber for measurements of vapor-phase mercury fluxes over soils

In an effort to establish reliable methodologies for measuring fluxes of mercury (Hg) across the soil-air interface, we have developed a field flux chamber built with FEP Teflon. To evaluate our field flux chamber system, a series of laboratory and field tests were performed. The observations of relatively low chamber blanks and low blank-to-sample ratios for the FEP Teflon chamber suggest its potential in Hg flux investigations. Despite its potential, Hg exchange rate measurements using the field flux chamber method must be made with great caution since it can be subject to contamination problems associated with the selection of chamber materials.     

Ambient levels and dry deposition fluxes of mercury to Lakes Huron,Erie and St. Clair

Ambient concentrations and dry deposition fluxes of Hg in the gas and particle phase to Lakes St. Clair, Erie and Huron were estimated with a hybrid receptor-deposition model (HRD). The ambient gas and particulate phase Hg concentrations were predicted to vary by a factor of 12 to 18 during the transport of air masses traversing the lakes. The ensemble average deposition fluxes of fine particle Hg ranged from 7 pg/m²-h to 15.3 pg/m²-h over Lake St. Clair, 0.5 to 4.2 pg/m²-h over Lake Huron and 5.1 to 20.6 pg/m²-h over Lake Erie. The deposition flux of coarse particle Hg was in the range of 50 to 84 pg/m²-h over Lake St. Clair, 4.7 to 24.2 pg/m²-h over Lake Huron and 5.1 to 20.6 pg/m²-h over Lake Erie. Gaseous Hg volatilized at a rate of 0.21 to 0.52 ng/m²-h from Lake Huron and 0.13 to 0.36 from Lake Erie. Gas phase Hg was deposited at a rate of 5.9 ng/m²-h and/or volatilized at a rate of 0.5 ng/m²-h from Lake St. Clair depending upon the location of the sampling site used in the HRD model. The effect of meteorological conditions, particle size distributions and type and location of the sampling sites played an important role in the transfer of atmospheric Hg to and/or from the lakes.     

Detection of food additives by voltammetry at the liquid-liquid interface

Electrochemistry at the liquid-liquid interface enables the detection of nonredoxactive species with electroanalytical techniques. In this work, the electrochemical behavior of two food additives, aspartame and acesulfame K, was investigated. Both ions were found to undergo ion-transfer voltammetry at the liquid-liquid interface. Differential pulse voltammetry was used for the preparation of calibration curves over the concentration range of 30-350 microM with a detection limit of 30 microM. The standard addition method was applied to the determination of their concentrations in food and beverage samples such as sweeteners and sugar-free beverages. Selective electrochemically modulated liquid-liquid extraction of these species in both laboratory solutions and in beverage samples was also demonstrated. These results indicate the suitability of liquid-liquid electrochemistry as an analytical approach in food analysis.     

Benthic fluxes of mercury during redox changes in pristine coastal marine sediments from the Gulf of Trieste (northern Adriatic Sea)

Purpose

The Gulf of Trieste (northern Adriatic Sea) is an example of a coastal environment contaminated with mercury (Hg). Contamination is a consequence of nearly 500?years of activity at the Idrija Mine (western Slovenia), which is the second largest Hg mine in the world. Oxygen depletion can be common in the Gulf of Trieste due to late summer stratification of the water column and accumulation of labile organic matter. Since changing redox conditions can have an impact on Hg transformations, we studied the effect of oxygen depletion, in parallel with sulphide, iron (Fe), manganese (Mn), fluorescent dissolved organic matter (FDOM) and nitrogen (N) and phosphorus (P) availability, on total Hg and methylmercury (MeHg) fluxes from sediments.

Materials and methods

Pore water concentrations and benthic fluxes of total dissolved Hg and MeHg were studied in situ and in microcosm laboratory experiments using flux chambers encompassing three different stages: oxic, anoxic and reoxidation.

Results and discussion

Our experiments showed that in the oxic stage there were small effluxes of MeHg to the water column, which increased in the anoxic stage and dropped rapidly in a subsequent reoxic stage, showing influx. Our results support the hypothesis that MeHg desorption from reduced metal hydroxides under anoxic conditions, and co-precipitation with Fe-oxides and MeHg demethylation in the reoxidation stage, may play a major role in determining MeHg benthic fluxes. For Hg and MeHg, it appears that there is little relationship between their pore water distribution and flux and that of FDOM, i.e. humics.

Conclusions

The results indicate that there was no significant difference in Hg and MeHg pore water levels and their benthic fluxes between the contaminated northern and central parts of the Gulf of Trieste and the pristine southern part. This suggests that shallow and stratified coastal marine environments, in general, represent areas with a risk of high benthic release of toxic MeHg.     

Rheology of mixed beta-casein/beta-lactoglobulin films at the air-water interface

The adsorption of dilute mixtures of beta-casein/beta-lactoglobulin to the air-water interface was investigated using surface dilatation and surface shear rheology. The data were fitted to simple rheological models to try to gain further information regarding the composition and nature of the interface. The dilatational measurements suggested that the composition of the interface could be determined using these models and that the surface concentration was dominated by the beta-casein in the early stages of adsorption but that high levels of beta-lactoglobulin were present in the final stages. Surface shear rheological measurements showed a similar trend. However, the shear measurements appeared to be more sensitive to the strength of the network than to the composition of the interface. Fluorescence microscopy supported the findings and demonstrated that any "phase separation" capable of affecting the surface rheological measurements occurred at the sub-micrometer scale. The results also demonstrated that the heterogeneity of the interface, once formed, is kinetically trapped, and no further phase separation occurs over the time span of the experiments.     

Regulation of bacterial and fungal MCPA degradation at the soil-litter interface

Much is known about mechanisms and regulation of phenoxy acid herbicide degradation at the organism level, whereas the effects of environmental factors on the performance of the phenoxy acid degrading communities in soils are much less clear. In a microcosm experiment we investigated the small-scale effect of litter addition on the functioning of the MCPA degrading communities. ¹⁴C labelled MCPA was applied and the functional genes tfdA and tfdAα were quantified to characterise bacterial MCPA degradation. We identify the transport of litter compounds as an important process that probably regulates the activity of the MCPA degrading community at the soil-litter interface. Two possible mechanisms can explain the increased tfdA abundance and MCPA degradation below the litter layer: 1) transport of α-ketoglutarate or its metabolic precursors reduces the costs for regenerating this co-substrate and thereby improves growth conditions for the MCPA degrading community; 2) external supply of energy and nutrients changes the internal resource allocation towards enzyme production and/or improves the activity of bacterial consortia involved in MCPA degradation. In addition, the presence of litter compounds might have induced fungal production of litter-decaying enzymes that are able to degrade MCPA as well.     

Endogeic earthworms alter carbon translocation by fungi at the soil-litter interface

The effect of endogeic earthworms (Octolasion tyrtaeum (Savigny)) on the translocation of litter-derived carbon into the upper layer of a mineral soil by fungi was investigated in a microcosm experiment. Arable soil with and without O. tyrtaeum was incubated with ¹³C/¹⁵N-labelled rye leaves placed on plastic rings with gaze (64 μm mesh size) to avoid incorporation of leaves by earthworms. The plastic rings were positioned either on or 3 cm above the soil surface, to distinguish between biotic and chemical/physical translocation of nutrients by fungi and leaching.Contact of leaves to the soil increased ¹³C translocation, whereas presence of O. tyrtaeum reduced the incorporation of ¹³C into the mineral soil in all treatments. Although biomass of O. tyrtaeum decreased during the experiment, more ¹³C and ¹⁵N was incorporated into earthworm tissue in treatments with contact of leaves to the soil. Contact of leaves to the soil and the presence of O. tyrtaeum increased cumulative ¹³CO₂-C production by 18.2% and 14.1%, respectively.The concentration of the fungal bio-indicator ergosterol in the soil tended to be increased and that of the fungal-specific phospholipid fatty acid 18:2ω6 was significantly increased in treatments with contact of leaves to the soil. Earthworms reduced the concentration of ergosterol and 18:2ω6 in the soil by 14.0% and 43.2%, respectively. Total bacterial PLFAs in soil were also reduced in presence of O. tyrtaeum, but did not respond to the addition of the rye leaves. In addition, the bacterial community in treatments with O. tyrtaeum differed from that without earthworms and shifted towards an increased dominance of Gram-negative bacteria.The results indicate that litter-decomposing fungi translocate litter-derived carbon via their mycelial network in to the upper mineral soil. Endogeic earthworms decrease fungal biomass by grazing and disruption of fungal hyphae thereby counteracting the fungal-mediated translocation of carbon in soils.     

Field-measured redox potentials in soils at the groundwater–surface-water interface

At the groundwater–surface-water interface the last modification of discharging groundwater takes place. In this study the redox potential was measured in situ in four groundwater discharge areas with a size of 3–4 m². Three of them were the upper reaches of streams in coniferous forests and one was an alder fen. Measurements were made at different seasons, with 50 and 100 platinum micro-electrodes respectively, in each area. Readings were taken in the upper 30 cm of the soil, at two depths. A method study showed that the electrodes needed a longer equilibrium time than is usually reported. The main finding of this study was the large spatial variation within soils in the discharge zone; regions as small as 10 cm in diameter could have redox potentials covering several hundred mV. It was not possible to identify a seasonal variation due to the large spatial variation. Differences in the distribution of the redox potential with depth may be explained by the structure of the peat affecting flow patterns and the residence time of water.     

Subcatchment output of mercury and methylmercury at Svartberget in northern Sweden

The subcatchments of two tributaries and the headwater mire of the 50 ha Swartberget catchment were studied. Monthly sampling was conducted during 1993 on the two tributaries and at the outlet of a mire. This was complemented by more intensive sampling during spring flood and a rain-driven episode at the end of July. Samples were analyzed for total methylmercury (MeHg), total mercury (Hg-tot) and TOC. The MeHg and TOC content of water were also fractionated into humic and non-humic components. Outputs budgets based on continuous flow monitoring and monthly volume weighted average concentrations of MeHg/ Hg were calculated for the subcatchments of the two tributaries and the mire. There was a pronounced decline in MeHg concentrations at all sampling locations during the spring flood. A clear pattern of the seasonal variation in the MeHg outputs was evident at all three sampling locations. Minimum MeHg concentrations occurred during spring flood and increased during the summer to peak levels in the autumn before tapering off during the winter (except for at the mire). The mire had larger increases in MeHg concentrations during the summer and did not decline during the winter. The warmth and increased soil humidity may promote the biogeochemical processes, including methylation, demethylation which make MeHg available for export by runoff from the soil. Variations in Hg-tot concentrations were differed from MeHg in streams that there were increases in Hg-tot concentrations with flow during both spring flood and the July rain event in runoff from the forested tributaries. The highest outputs of both humic and non-humic MeHg occurred during summer from all subcatchments. Those high outputs extended into the autumn at the mire. The largest monthly output of Hg-tot was during the spring flood period and the next largest was during the period of summer rainfall. Despite the similarity in mineralogy and atmospheric deposition on the two tributary subcatchments, there was ca 30% larger ouput of MeHg per unit area from the tributary which had deeper riparian peats. The output of Hg-tot, however, was higher on the catchment with the shallower riparian peats. The difference in the geometry of the riparian zone may contribute to these differences in output. The annual output concentrations at the mire outlet of MeHg was 0.65 ng /L and of Hg-tot was 4.04 ng/L. In the main tributary MeHg was 0.42 ng/L and Hg-tot was 3.64 ng/L. In the Västrabäcken tributary, the mean MeHg concerntration was 0.25 ng/L and the Hg-tot concerntration was 4.02 ng/L. Among the three subcatchments the largest annual output fluxes of MeHg were from the mire, 0.16 g/km2^*yr, the next from Kallkällbäcken below the mire, 0.12 g/km2^*yr, and the lowest from Västrabäcken, 0.08 g/km2^*yr.     

Reciprocal transfer of carbon and nitrogen by decomposer fungi at the soil-litter interface

We have investigated whether decomposer fungi translocate litter-derived C into the underlying soil while simultaneously translocating soil-derived inorganic N up into the litter layer. We also located and quantified where the translocated C is deposited within the soil aggregate structure. When ¹³C-labeled wheat straw was decomposed on the surface of soil amended with ¹⁵N-labeled inorganic N, we found that C and N were reciprocally transferred by fungi, with a significant quantity (121-151 μg C g⁻¹ whole soil) of litter-derived C being deposited into newly formed macroaggregates (>250 μm sized aggregates). Fungal inhibition reduced fungal biomass and the bidirectional C and N flux by approximately 50%. The amount of litter-derived C found in macroaggregates was positively correlated with litter-associated fungal biomass. This fungal-mediated litter-to-soil C transfer, which to our knowledge has not been demonstrated before for saprophytic fungi, may represent an important mechanism by which litter C enters the soil and becomes stabilized as soil organic matter within the macroaggregate structure.     

Agricultural zinc fluxes into soils and crops of central Iran at regional scale

Mass flux assessment can provide information that is essential for a sustainable management of elements in agricultural soils. In this article, we present an assessment of regional-scale averages of zinc (Zn) fluxes into agricultural soils and crops of central Iran for the period 1997–2011, using available databases such as regional agricultural statistics. The basic units of the balances were 15 townships of the provinces Qom, Isfahan and Fars. Averaged over the entire study region, the net Zn input into arable soil resulting from all fertilizer inputs – Zn removal with harvested crops was 1515 g ha^?1 yr^?1 across the entire region, with a range of 438–3009 g ha^?1 yr^?1 among townships. Estimated average Zn inputs with manure, mineral fertilizers, sewage sludge and compost were 1254, 531, 19 and 7 g ha^?1 yr^?1, respectively. The input-to-output ratio of these fluxes ranged from 1.8 to 12.9 among townships and averaged 6.1 for the entire study area. Considering that outputs other than with crop harvests are minor, Zn stocks are rapidly building up in the soils of the study region. Uncertainties in the manure and crop removal data were the main sources of estimation uncertainty in this study.     

Lateral phase separation in adsorbed binary protein films at the air-water interface.

Lateral phase separation in two-dimensional mixed films of soy 11S/beta-casein, acidic subunits of soy 11 (AS11S)/beta-casein, and alpha-lactalbumin/beta-casein adsorbed at the air-water interface has been studied using an epifluorescence microscopy method. No distinct lateral phase separation was observed in the mixed protein films when they were examined after 24 h of adsorption from the bulk phase. However, when the soy 11S/beta-casein and AS11S/beta-casein films were aged at the air-water interface for 96 h, phase-separated regions of the constituent proteins were evident, indicating that the phase separation process was kinetically limited by a viscosity barrier against lateral diffusion. In these films, beta-casein always formed the continuous phase and the other globular protein the dispersed phase. The morphology of the dispersed patches was affected by the protein composition in the film. In contrast with soy 11S/beta-casein and AS11S/beta-casein films, no lateral phase separation was observed in the alpha-lactalbumin/beta-casein film at both low and high concentration ratios in the film. The results of these studies proved that proteins in adsorbed binary films exhibit limited miscibility, and the deviation of competitive adsorption behavior of proteins at the air-water interface from that predicted by the ideal Langmuir model (Razumovsky, L.; Damodaran, S. J. Agric. Food Chem. 2001, 49, 3080-3086) is in fact due to thermodynamic incompatibility of mixing of the proteins in the binary film. It is hypothesized that phase separation in adsorbed mixed protein films at the air-water and possibly oil-water interfaces of foams and emulsions might be a source of instability in these dispersed systems.     

Quantification of spatial and temporal variations in trace element fluxes originating from urban areas at the catchment scale

Journal of Soils and Sediments - The release of trace elements (TE) associated with the development of human activities has accelerated since the nineteenth century, leading to the pollution of...     

Incompatibility of mixing of proteins in adsorbed binary protein films at the air-water interface.

Competitive adsorption of proteins from several binary protein solutions to the air-water interface has been studied. With a few exceptions, the equilibrium composition of the saturated monolayer of mixed protein films at various bulk concentration ratios did not follow a Langmuir-type competitive adsorption model. The deviation from ideal behavior results from incompatibility of mixing of proteins in the film at the air-water interface. This immiscibility alters the ratio of the binding affinity of the proteins in a protein 1/protein 2/water ternary film compared to that in a protein 1/water and protein 2/water binary film. A method to determine the extent of incompatibility between two proteins in a mixed protein film has been developed. It is shown that the incompatibility index derived for 19 protein 1/water and protein 2/water systems studied show a linear relationship with the absolute difference between Flory-Huggins protein-solvent interaction parameters, that is, /chi(1s) - chi(2)/, of the constituent proteins. On the basis of the evidence, it is theorized that, because of incompatibility, proteins in a mixed protein film at interfaces may undergo two-dimensional phase separation.     

Carbon dioxide fluxes in coastal Douglas-fir stands at different stages of development after clearcut harvesting

Forests play a significant role in the global carbon (C) cycle. Variability in weather, species, stand age, and current and past disturbances are some of the factors that control stand-level C dynamics. This study examines the relative roles of stand age and associated structural characteristics and weather variability on the exchange of carbon dioxide between the atmosphere and three different coastal Douglas-fir stands at different stages of development after clearcut harvesting. The eddy covariance technique was used to measure carbon dioxide fluxes and a portable soil chamber system was used to measure soil respiration in the three stands located within 50 km of each other on the east coast of Vancouver Island, British Columbia, Canada. In 2002, the recently clearcut harvested stand (HDF00) was a large C source, the pole/sapling aged stand (HDF88) was a moderate C source, and the rotation-aged stand (DF49) was a moderate C sink (net ecosystem production of −606, −133, and 254 g C m⁻² year⁻¹, respectively). Annual gross ecosystem production and ecosystem respiration also increased with increasing stand age. Differences in stand structural characteristics such as species composition and phenology were important in determining the timing and magnitude of maximum gross ecosystem production and net ecosystem production through the year. Both soil and ecosystem respiration were exponentially related to soil temperature in each stand with total ecosystem respiration differing more among stands than soil respiration. Between 1998 and 2003, annual net ecosystem production ranged from 254 to 424 g C m⁻² year⁻¹ over 6 years for DF49, from −623 to −564 g C m⁻² year⁻¹ over 3 years for HDF00, and from −154 to −133 g C m⁻² year⁻¹ over 2 years for HDF88. Interannual variations in C exchange of the oldest, most structurally stable stand (DF49) were related to variations in spring weather while the rapid growth of understory and pioneer species influenced variations in HDF00. The differences in net ecosystem production among stands (maximum of 1000 g C m⁻² year⁻¹ between the oldest and youngest stands) were an order of magnitude greater than the differences among years within a stand and emphasized the importance of age-related differences in stand structure on C exchange processes.