Liisa Ukonmaanaho

Enrichment of Cu, Ni, Zn, Pb and As in an ombrotrophic peat bog near a Cu-Ni smelter in southwest Finland.

The accumulation of selected trace elements (Cu, Ni, Zn, Pb, As) in the surface peat layer of an ombrotrophic bog 2.4 km from a Cu-Ni smelter at Harjavalta, Finland was studied using a peat core. A reference core was taken from an ombrotrophic bog at a background site, Hietajärvi, in eastern Finland. Element concentrations were analysed from 1-cm slices and enrichment factors (EF) were calculated. The enrichment factors of both Cu and Ni in the Harjavalta peat bog are extremely high compared to the Hietajärvi site. However, only the 6-cm surface peat Pb values are higher in Harjavalta compared to Hietajärvi. Precipitation was collected during 1992-1996, in the vicinity of the Harjavalta smelter, in order to estimate the current atmospheric deposition load. Comparison between the precipitation and peat data reveals that at Harjavalta the surface peat is relatively much more polluted than the current precipitation. The variation in EF of the Harjavalta peat core with respect to depth shows two patterns: Cu and Pb are similar, as are Ni, Zn and As. The vertical gradient in Harjavalta Cu EF suggests that Cu supplied to the peat by atmospheric deposition is very well preserved by the bog.

Heavy metal budgets for two headwater forested catchments in background areas of Finland

Mean annual (1994-1996) budgets for Cd, Cu, Ni, Pb and Zn at two background, forested catchments, VK and HJ, in Finland are presented. Budgets for plots (VK3, HJ1 and HJ4) included throughfall (TF), litterfall (LF) and soil leaching fluxes, and for catchments terrestrial retention and leaching and lake sedimentation fluxes. Total deposition (TD) loads were relatively low (Cd < 0.1, Cu < 2, Ni < 1, Pb < 3 and Zn < 5 mg m-2 year-1) and that even in these areas almost half of the TD was in the form of dry deposition. Retention of TD within catchments was > or = 77% for all metals, except for Ni at VK (54%). For Cu and Pb, the retention was 94-97%. Most of the retention (74-97%) took place in the terrestrial part of the catchment, lake sedimentation accounting for the remainder. Plot-scale soil leaching fluxes at 40 cm of Cd, Cu (VK3) and Ni (VK3) were greater (> or = 100%) than TD inputs. Most of the catchment retention must therefore have taken place either deeper in the soil or in the lowland peatland areas. The humus layer was particularly effective in retaining Cu and Cd (65-81% and 51-78% of total inputs to the forest floor (TF + LF)). The retention of Pb by the humus layer was less than expected (26-54% of TF + LF). Litterfall was a particularly important internal flux for Zn.

Heavy Metal and Arsenic Profiles in Ombrogenous Peat Cores from Four Differently Loaded Areas in Finland

The concentrations and vertical distribution of Cu, Ni, Zn, Pb and As were studied in four different ombrotrophic peat bogs with varying heavy metal loads at Hietajärvi, Outokumpu, Harjavalta and Alkkia in Finland. At each site a peat sample (15 cm × 15 cm × 100 cm) was taken using a Titanium Wardenaar corer, and the samples were cut into 5 cm slices. Dried and milled samples were determined by X-ray fluorescence (XRF). The mean concentrations of the elements were at their highest at Harjavalta (the most polluted area), apart from Cu which had the highest value at the Cu-treated site at Alkkia. Cu concentrations were above ‘the lowest effective limit’ (LOEL) on all the plots except for the background plot at Hietajärvi. The maximum Cu values were reached in the topmost 20 cm layer, indicating the effects of mining and smelting activities. The highest Zn and Ni concentrations occurred in the 0–40 cm layer. At all sites, the maximum Pb concentrations were located between 10 and 50 cm. However, the Pb concentrations were higher at Alkkia and Harjavalta than at Outokumpu and Hietajärvi, indicating anthropogenic sources of Pb at the former sites. The As concentration was also the highest in the uppermost peat layers. The mean concentrations were markedly lower in the deeper layers (40–80 cm) than in the upper layers.

Weathering release of heavy metals from soil in comparison to deposition, litterfall and leaching fluxes in a remote, boreal coniferous forest

Soil weathering release rates of Cd, Cu, Ni, Pb and Zn were determined at 4 plots in a forested catchment located in eastern Finland. The rates are compared with atmospheric deposition, litterfall and leaching fluxes at two of the plots. The soils were Haplic Podzols and developed in glaciofluvial deposits or glacial till having sandy loam to loamy sand fine-earth (<2 mm) textures. The bedrock in the area consists of granodiorites. Total concentrations of heavy metals in the <2 mm fraction of the parent material were determined from a mixed acid (HF and HClO4) digestion using ICP–MS. Weathering rates were calculated assuming that the molar ratio of heavy metal to base cation (Ca+Mg) weathering rates (previously determined by the Zr depletion method) equalled the molar ratio of heavy metal to base cation concentrations in the parent material. The mean weathering release rates were 8.3 μmol m−2 a−1 for Zn, 5.2 for Ni, 4.3 for Cu, 1.5 for Pb, and 0.011 for Cd. These rates were similar to the deposition, litterfall, and leaching fluxes for each metal. Weathering is therefore an important process in the heavy metal biogeochemistry of boreal, forest ecosystems.

Major nutrients and acidity: budgets and trends at four remote boreal stands in Finland during the 1990s.

Major nutrients and acidity were studied at six plots in four Integrated Monitoring catchments in Finland, located along a south-north deposition gradient. The quality and quantity of bulk precipitation, throughfall, soil water, and litterfall were monitored during the period 1989-1997. The results showed a marked decline in SO4 and H+ concentrations overall. Trends in throughfall ANC values were positive, while those in soil water were mostly negative. The increase in throughfall ANC values indicates recovery from acid deposition. The adsorption of base cations and release of organic acids was implicated in the decrease in soil water ANC trends. For all variables, the changes tended to be the greatest in the most southerly catchment, which received the most deposition loads. Mass balance budgets showed that total deposition inputs were greater than soil leaching outputs (at 40 cm) for NO3, NH4 and SO4, and were attributed to nutrient uptake and cycling processes. In contrast, for Ca, Mg, K and Na, and S (Valkea-Kotinen3 and Vuoskojärvi2 plots only), inputs were less than outputs, indicating net leaching. Throughfall + litterfall inputs to the forest floor showed that the organic layer is particularly important in the retention of Ca, Mg and N. Sulfur was retained in the lower soil layers, and attributed to Al and Fe hydroxide adsorption in the B horizon.

Trends in Sulfate, Base Cations and H+ Concentrations in Bulk Precipitation and Throughfall at Integrated Monitoring Sites in Finland 1989-1995

Temporal trends in sulfate, base cation (Ca2+ + Mg2+ + K+), and H+ ion concentrations in bulk precipitation and throughfall samples collected over a seven year period (1989-95) in four forested catchments in Finland are presented. The catchments are in remote locations and span the boreal zone (61-69 °N). The stands represent old, undisturbed forests, and are composed of varying proportions of Scots pine, Norway spruce and deciduous species (mainly Betula spp.). Monthly SO42- and H+ ion concentrations in bulk precipitation averaged over the study period and catchments were: 18.7 µmol L-1 and 32.3 µmol L-1. The corresponding values for throughfall were: 37.4 µmol L-1 and 32.4 µmol L-1. Sulfate and H+ ion concentrations in bulk precipitation and throughfall both showed negative linear trends, which were significant (p < 0.05) for the three southernmost catchments. Concentrations and trend slope decreased northwards (e.g., bulk precipitation SO42- slope estimates: -1.6 to -1.0 µmol L-1 yr-1). The decline was greater for throughfall than for bulk precipitation, indicating a proportionally greater reduction in dry deposition than wet. The sum of base cation concentrations averaged 12.1 µmol(+) L-1 in bulk precipitation and 83.1 µmol(+) L-1 in throughfall. There were no significant trends in the sum of base cations (p > 0.05). It is concluded that the reported reduction in S emissions over the study period has resulted in a significant reduction in the acidity and SO42- concentration of bulk precipitation, and this reduction has has been reflected in throughfall concentrations. The greatest reduction has taken place in the southern part of the country.

The importance of leaching from litter collected in litterfall traps

Litterfall (LF) is usually collected by means of opentraps. However, this litter will be subject toleaching by the throughfall which passes through theaccumulated litter in the traps. The nutrients lostduring this leaching are not taken into account in thecalculation of LF nutrient fluxes. We report theresults from a 2-month (August–September) studycarried out in 8 northern coniferous forest stands toassess the possible importance of leaching from litterin LF traps. Compared to throughfall (TF), thelitterfall leachate (LFLgross), which includes athroughfall component, had significantly (p < 0.05)higher concentrations and fluxes of Ca, Mg, Na and S.The average net LFL (i.e., LFLnet = LFLgross-TF) fluxes were 21 (Ca), 7 (Mg), 57 (K), 10 (Na), 10 (N), and 19 (S) mg m-2 mo-1. LFLnet accounted for 42%, 37% and 50% of the LFLgross flux, and for 91%, 51% and 49% of the total litterfall flux (i.e.,LF + LFLnet) of Na, S and K, respectively. ForCa, Mg and N, the LFLnet flux accounted for 64%,58% and 29% of the LFLgross flux, and for< 14% of the total litterfall flux. Compared to TF,LF was the dominant return pathway for Ca, Mg and N tothe forest floor regardless of whether LFLnet wasincluded or not. However, for K and S, takingLFLnet into account determined whether TF or LFwas the dominant pathway. TF remained the dominantpathway for Na even when LFLnet was included.

Determination of low methylmercury concentrations in peat soil samples by isotope dilution GC-ICP-MS using distillation and solvent extraction methods

Most often, only total mercury concentrations in soil samples are determined in environmental studies. However, the determination of extremely toxic methylmercury (MeHg) in addition to the total mercury is critical to understand the biogeochemistry of mercury in the environment. In this study, N2-assisted distillation and acidic KBr/CuSO4 solvent extraction methods were applied to isolate MeHg from wet peat soil samples collected from boreal forest catchments. Determination of MeHg was performed using a purge and trap GC-ICP-MS technique with a species-specific isotope dilution quantification. Distillation is known to be more prone to artificial MeHg formation compared to solvent extraction which may result in the erroneous MeHg results, especially with samples containing high amounts of inorganic mercury. However, methylation of inorganic mercury during the distillation step had no effect on the reliability of the final MeHg results when natural peat soil samples were distilled. MeHg concentrations determined in peat soil samples after distillation were compared to those determined after the solvent extraction method. MeHg concentrations in peat soil samples varied from 0.8 to 18 μg kg(-1) (dry weight) and the results obtained with the two different methods did not differ significantly (p=0.05). The distillation method with an isotope dilution GC-ICP-MS was shown to be a reliable method for the determination of low MeHg concentrations in unpolluted soil samples. Furthermore, the distillation method is solvent-free and less time-consuming and labor-intensive when compared to the solvent extraction method.

Levels and Characteristics of TOC in Throughfall, Forest Floor Leachate and Soil Solution in Undisturbed Boreal Forest Ecosystems

Total organic carbon (TOC) concentrations and fluxes in throughfall, forest floor leachate, soil solution (15 and 35 cm depths), and groundwater for coniferous forest sites in the boreal zone throughout Finland are described. Eight upland forest stands and one peatland forest stand are included in the study and the samples were collected during 1991–1997. Carbon (C) pools in the living tree biomass and soil compartments are presented, and the hydrophobic/hydrophilic and acidic components of dissolved organic carbon (DOC) in samples collected in autumn 1999 and spring 2000 from two of the sites are compared. Biomass (aboveground and belowground) pools of C averaged 88 Mg ha−1 and soil (humus layer + 20 cm soil layer) averaged 55 Mg ha−1. Stand throughfall TOC monthly mean concentrations ranged from 4.0 to 18.6 mg L−1 and annual fluxes averaged 4.0 g m−2 yr−1. TOC concentrations in the water passing through the forest floor and soil decreased with depth. Plot mean concentrations at 35 cm depth values ranged from 4.1 to 21.2 mg L−1 and fluxes averaged 3.7 g m−2 yr−1. Throughfall TOC concentrations were lowest during the winter, snowfall period and highest during the growing season. No monotonic trends in throughfall TOC concentrations over the 1991–1997 period were found. Soil solution TOC concentrations varied considerably, both within and between years. DOC in throughfall, forest floor, and soil solutions and in both autumn and spring seasons was dominated by hydrophobic fractions, particularly acids. Spruce canopies and litter appear to be important sources of soluble organic carbon, particularly acidic and hydrophobic compounds. Further studies on the nature and dynamics of organic carbon fluxing through coniferous, boreal forest ecosystems are needed.

Leaching of Dissolved Organic Carbon and Trace Elements After Stem-Only and Whole-Tree Clear-cut on Boreal Peatland

The aim of this work was to study the short-term effect of clear-cut harvest on concentrations of dissolved organic carbon (DOC), B, Al, Zn, Cu, Ni, Cr, Cd and Pb in drainage water from northern peatland catchments in Finland underlain by granitic or black shale bedrock, the latter having higher concentrations of several trace elements, such as Ni and Zn. Stem-only harvest (SOH) or whole-tree harvest (WTH) with stump removal were carried out at coniferous sites. Controls were left unharvested. DOC and trace element concentrations were monitored during one pre-treatment and two post-treatment years. There was no constant increase in the element concentrations. However, there were signs that both SOH and WTH clear-cut harvest on northern peatland catchments increases the concentrations of DOC, B, Al, Zn and Ni in ditchwater in some sites irrespective of the bedrock type. The greatest increases were observed in WTH sites but the study does not allow us to assess the statistical significance of the magnitude of the difference between SOH and WTH. We conclude that the element concentrations in ditchwater depend largely on site characteristics masking the possible effect of harvest.