Metal speciation in rivers affected by enhanced soil erosion and acidity

Dissolved (<1 kDa), colloidal (1 kDa–0.45 μm) and particulate (>0.45 μm) size fractions of 30 elements were determined for four rivers (Sirppujoki, Laajoki, Mynäjoki and Paimionjoki), including 12 low-order inflow streams, largely affected by soil erosion and acidity in SW Finland. In addition, geochemical modelling was used to predict the formation of free ions and complexes in these rivers. Total metal concentrations were relatively high but most of the elements occurred mainly in a colloidal or particulate form and even elements expected to be very soluble occurred to a large extent in colloidal form. According to geochemical modelling these patterns could be explained by in-stream metal complexation/adsorption only to a limited extent. Instead there were strong indications that the high metal concentrations and dominant solid fractions were largely caused by erosion of metal bearing phyllosilicates. A strong influence of acid sulphate (AS) soils, known to exist in the catchment, could be clearly distinguished in Sirppujoki river as it had very high concentrations of dissolved metals, while in the two nearby rivers (Laajoki and Mynäjoki) the influence of AS soils was largely masked by eroded phyllosilicates. In Paimionjoki river the colloidal and particulate fractions dominated very strongly, indicating that total metal concentrations are almost solely controlled by erosion of phyllosilicates. Consequently, rivers draining clay plains sensitive to erosion, like those in SW Finland, have generally high “background” metal concentrations due to erosion of relatively non-toxic colloidal/particulate phyllosilicates. Thus, relying on only semi-dissolved (<0.45 μm) concentrations obtained in routine monitoring and/or speciation modelling can lead to a great overestimation of the water toxicity in this environment.     

Distribution and speciation of metals,phosphorus, sulfate and organic material in brackish estuary water affected by acid sulfate soils

Dissolved (<1 kDa) and colloidal (1 kDa-0.45 μm) size fractions of sulfate, organic carbon (OC), phosphate and 17 metals/metalloids were investigated in the acidic Vörå River and its estuary in Western Finland. In addition, geochemical modelling was used to predict the formation of free ions and complexes in these waters. The sampling was carried out during high-water flow in autumn and in spring when the abundantly occurring acid sulfate (AS) soils in the catchment area are extensively flushed. Based on the high concentrations of sulfate, acidity and several metals, it is clear that the Vörå River and its estuary is strongly affected by AS soils. The high dissolved form of metals limits also the existence of fish and other organisms in this estuary, and certainly also in other similar shallow brackish estuaries elsewhere in the Gulf of Bothnia. However, generally already <20% saline sea water reduces the concentration for OC and several elements (Al, Cu, Cr, Fe, Pb, PO₄ and U) by half and c. 20–30% saline sea water is needed to halve concentrations of Cd, Co, Mn, Ni and Zn. Consequently, these elements as well as organic matters were rapidly precipitated in the estuary, even after mixing with fairly small amounts of the alkaline brackish sea water. Aluminium, Cu, Fe and U most likely precipitate together with organic matter closest to the river mouth. Manganese is relatively persistent in solution and, thus, precipitates further down the estuary as Mn oxides, which concomitantly capture Ba, Cd, Co, Cu, Ni and Zn. In the inner estuary, the high contents of Al is as important than Fe in removing PO₄ and, thus, also reducing the risk of algae blooms in near coastal areas influenced by AS soils in the Gulf of Bothnia. Moreover, the dispersion of metals far out in the estuary is dependent on hydrological conditions, i.e. with high flows the plume of metal-rich water will spread further out in the estuary. Furthermore, the extensive drainage of the catchment and subsequent artificial enlargement of the river channel during recent decades has not only enabled oxidation of sulfidic sediments, but strongly increased flow peaks that reach further out in the estuary.     

Metal species in a Boreal river system affected by acid sulfate soils

The bioavailability of metals and their potential for environmental pollution depends not simply on total concentrations but on their chemical form. Consequently, knowledge of aqueous metal speciation is essential in investigating potential metal toxicity and mobility. Dissolved (<1 kDa), colloidal (1 kDa–0.45 μm) and particulate (>0.45 μm) size fractions of sulfate, organic C (OC) and 18 metals/metalloids were investigated in the extremely acidic Vörå River system in Western Finland, which is strongly affected by acid sulfate (AS) soils. In addition, geochemical modelling was used to predict the formation of free ions and complexes in these acidic waters. The most important finding of this study is that the very large amounts of elements known to be released from AS soils (including Al, Ca, Cd, Co, Cu, Mg, Mn, Na, Ni, Si and U) occur and can prevail mainly in toxic forms throughout acidic river systems; as free ions and/or sulfate-complexes. This has serious effects on the biota and particularly dissolved Al can be expected to have acute effects on fish and other organisms. In the study area, only the relatively forested upstream area (higher pH and contents of OC) had significant amounts of a few bioavailable elements (including Al, Cu, Ni and U) due to complexation with the more abundantly occurring colloidal OC in the upstream area. It is, however, notable that some of the colloidal/particulate metals were most likely associated with metal bearing phyllosilicates eroded from clay soils. Moreover, the mobilisation of Fe and As was small and As was predicted to be associated with Fe oxides, indicating a considerable influence of Fe oxides on the mobilisation/immobilisation processes of As. Elements will ultimately be precipitated in the recipient estuary, where the acidic metal-rich river water will gradually be diluted/neutralised with brackish seawater in the Gulf of Bothnia. According to speciation modelling, such a pH rise may first cause precipitation of Al, Cu and U together with organic matters closest to the river mouth, in line with previous sediment studies from the estuary.     

Lanthanoid behaviour in an acidic landscape

Lanthanoids were studied in a boreal landscape where an abundance of acid sulfate soils and Histosols provide a unique opportunity to increase the understanding of how these metals behave in acidic soils and waters and interact with soil and aqueous organic matter. In the acid sulfate soils lanthanoids are mobile as reflected in high to very high concentrations in soil water and runoff (typically a few mg l⁻¹ but up to 12 mg l⁻¹) and abundant release by several relatively weak extractants (ammonium acetate EDTA, sodium pyrophosphate, hydroxylamine hydrochloride) applied on bulk soil. Normalisation with the lanthanoid pool in the underlying parent materials (sulphide-bearing sediments deposited in brackish-water) and soil water showed that the extensive release/retention in the acidic soil was accompanied by large, and variable, fractionation trends across the lanthanoid series. In low-order streams draining these soils, the lanthanoid concentrations were high and, as indicated by frontal ultrafiltration and geochemical modelling, largely dissolved (<1 kDa) in the form of the species LnSO₄⁺ and Ln³⁺. In other moderately acidic stream waters (pH 4.3-4.6), organic complexation was predicted to be important in the <1 kDa fraction (especially for the heavy lanthanoids) and strongly dominating in the colloidal phase (1 kDa-0.45 μm). Along the main stem of a stream in focus (catchment area of 223 km²), lanthanoid concentrations increased downstream, in particular during high flows, caused by a downstream increase in the proportion of acid sulfate soils which are extensively flushed during wet periods. The geochemical models applied to the colloidal Ln-organic phase were not successful in predicting the measured fractionation patterns.     

Spatial trends and losses of major and trace elements in agricultural acid sulphate soils distributed in the artificially drained Rintala area,W. Finland

Acid sulphate soils, common in the coastal areas of Finland, contribute strongly to high acid, S and metal loadings on adjacent surface waters. This, in turn, is causing significant harm to the aquatic ecology. There is, however, limited knowledge on the total amounts of acidity and chemical elements leached from these soils. The overall objective of this study was to determine geochemical patterns in acid sulphate soils and their parent sediments and, based on the identified patterns assess the extent, mechanisms and present state of leaching of major and trace elements from these soils. The distribution of pH, aqua regia extractable concentrations of P and metals (Al, Ba, Ca, Co, Cr, Cu, Fe, K, La, Mg, Mn, Na, Ni, Sr, Th, Ti, V, Zn) and total concentrations of S and C were determined in 30 vertical profiles collected in the 23 km² large Rintala agricultural area (mid-western Finland) underlain largely with S-rich sediments. It was found that approximately 70% of the area consists of acid sulphate soils with a minimum pH<4.0, an average depth of 1.8 m, and S concentrations in the parent sediments varying from 0.24 to 1.04%. Acid sulphate soils have not developed where the S concentrations in the sediments are ⩽0.10% or where the concentrations of organic C in the soil zones are >4%. Four different methods were used to estimate the losses of chemical elements from the acid sulphate soils: (1) the concentrations in the soil were compared with those in the parent sediments, (2) due to indicated heterogeneities in several profiles, the vertical changes of the immobile Ti was used to re-calculate element losses, (3) element depletions in the acid sulphate soils (as compared to those in the parent sediments) were compared to the corresponding depletions in the non acid sulphate soils, (4) element concentrations in drainage waters were compared with those in the parent sediments. Based on these calculations, it was assessed that the percentual leaching of the aqua regia extractable fraction (total for S) has been as follows: S (40–50%), Na (30–50%), Mn (25–35%), Sr (15–20%), Ca–Ni–Co (approximately 10%), Mg–K–Zn (5–10%), Th–La–Cu–Al–P–Ti–Fe (<5%), and Ba–Cr–V (<1%). While it was possible to quite accurately estimate the percentages and thus the amounts of elements lost, it was not possible to estimate the rate of leaching as there is no available detailed information on dates when ditching activities and thus oxidation-acidification processes started. Other calculations indicated that the mobile S reservoir is still some 15 ton/hectare, which is huge but still smaller than the losses that have occurred since the area was drained (23–28 ton/hectare).     

Effect of widespread severely acidic soils on spatial features and abundance of trace elements in streams

In the coastal area of western Finland, a large number of streams are strongly acidic and contaminated with metals. The reason for this is not historical and present industrial, mining and urban activities, but a current high rate of weathering and leaching of widespread acid sulphate soils (pH 2.5–4.0) developed in artificially drained Holocene marine and lacustrine sulphide-bearing sediments. Evaluation of existing hydro- and geochemical field and experimental data revealed that: (1) cobalt, Ni and Zn are extensively leached from the acid sulphate soils and thus exist abundantly in streams affected by such soils, (2) copper and Tl are also leached abundantly from the acid sulphate soils, although not to the same extent as are Co, Ni and Zn, (3) vanadium is in general depleted and Cr only weakly enriched in streams draining ‘the average acid sulphate soil’, but they increase substantially in severely acidic streams in catchments underlain with particularly acidic soil, (4) arsenic and Pb are not leached more abundantly from the acid sulphate soils than from the common types of soils and sediments (till, glaciofluvial deposits, peat) resulting in aquatic abundance and distribution patterns unrelated to the acid sulphate soil occurrences.     

Atmospheric sulfur deposition and streamwater quality in Finland

The correlation between sulfate concentrations in Finnish headwater streams and atmospheric sulfate deposition has been studied by using data from the streamwater chemistry in August–September 1990 and computed S deposition from the anthropogenic emissions. The sulfate concentrations and acidity in water are interpolated and smoothed into a deposition model grid. These data are compared with geological and pedogeochemical (glacial till) background information. The areas where the streamwater SO₄ concentrations are mainly controlled by either anthropogenic S deposition or sulfur in till is estimated by applying the fuzzy Gustafsson-Kessel algorithm, which provides a soft clustering suitable for overlapping control factors. Residual areas can be well explained by the SO₄-rich Littorina clay deposits. The higher overall background SO₄ concentrations in streams in south Finland compared with central and northern Finland are an indisputable consequence of the heavier S deposition load in the south. However, anthropogenic sulfur deposition has a clear correlation with the sulfates in streamwaters only in northeastern Lapland impacted by the large industrial emissions in the Kola Peninsula. The secondary sulfide and sulfate minerals of marine Littorina sediments are dominating sources in the broad coastal belts, as are the primary sulfide minerals locally in the Pori-Vammala area, at the eastern end of the main sulfide ore belt between Lake Ladoga and the Gulf of Bothnia, in the Outokumpu area, and in the Peräpohja and central Lapland schist belts. Consequently, in addition to the anthropogenic deposition, there are natural sources of sulfur which cause acidity of streamwaters.     

Assessment of Sulfate Concentrations in Water Used During Chemical Stabilization and Its Potential Impact on Sulfate Induced Heave

The occurrence of sulfate-induced heave of roadways that were chemically stabilized with either lime or cement can require expensive road repairs. Previous research attributed the heave to the formation of an expansive mineral named ettringite. However, not all chemically stabilized soils will exhibit heave. The overall goal of this research was to determine if the sulfate concentration in water can contribute to, or even cause, sulfate induced heave. Two soils, one with a soluble sulfate level below 3000 mg/kg and one with >8000 mg/kg sulfate, were stabilized with either lime or cement and subjected to a capillary soak with distilled water or saturated sulfate water. The low sulfate soils did not swell above the accepted limit of 1.5 %. The high sulfate soils swelled significantly (p < 0.05) above accepted level regardless of the stabilizer used. Overall, stabilized soils subjected to a capillary soak with saturated sulfate water swelled more than soils soaked with distilled water. The results found in this study demonstrated that cement will increase the axial load capacity of the soil, but the soil will still have the potential to heave excessively if sulfate and aluminum are present above the stoichiometric requirements to from ettringite.     

A quantitative estimation of the factors affecting pH changes using simple geochemical data from acid mine drainage

The behavior of heavy metals in acid mine drainage (AMD) is mainly controlled by pH values. Therefore, a quantitative estimation of factors affecting pH values in AMD is very important in predicting the behavior of those metals. Many different factors cause pH changes in streams affected by AMD and we quantitatively estimated those factors by making simple equations from geochemical data collected from the Dalsung mine. In a stream from that mine, the pH values decrease as the stream flows downstream from the AMD source, which is different from normal streams affected by AMD. The stream shows low pH ranges (4.04–5.96), high electrical conductivity (1,407–1,664 μS/cm), and sulfate concentration (680–854 ppm). Most ion concentrations decrease or do not show noticeable changes mainly due to dilution. The change of the iron content is most significant, even though the concentration of iron is relatively low compared with other ions. The iron concentration (13.4 ppm) becomes almost 0 ppm due to precipitation. Schwertmannite is the dominant precipitated phase downstream and whitish basaluminite is observed in the upstream. From our pH estimation, precipitation is the most important process lowering pH values from 5.96 to 4.04. The dilution factor was calculated by the concentration changes in sulfate ions. Dilution increases pH values, but compared with the precipitation factor, the contribution of the dilution factor to pH is relatively small. Alkalinity is the main factor that buffers hydrogen, which is released by precipitation. The redox changes, which were calculated from the pH and Eh values, also affect pH at each sampling site. The trend of estimated pH changes is almost identical to the observed ones, but the values are slightly different. Some errors are expected mainly due to the uncertainty in the observed Eh values and the chemistry of the added water for dilution.     

Isotopic variations of dissolved copper and zinc in stream waters affected by historical mining

Zinc and Cu play important roles in the biogeochemistry of natural systems, and it is likely that these interactions result in mass-dependent fractionations of their stable isotopes. In this study, we examine the relative abundances of dissolved Zn and Cu isotopes in a variety of stream waters draining six historical mining districts located in the United States and Europe. Our goals were to (1) determine whether streams from different geologic settings have unique or similar Zn and Cu isotopic signatures and (2) to determine whether Zn and Cu isotopic signatures change in response to changes in dissolved metal concentrations over well-defined diel (24-h) cycles.Average δ⁶⁶Zn and δ⁶⁵Cu values for streams varied from +0.02‰ to +0.46‰ and −0.7‰ to +1.4‰, respectively, demonstrating that Zn and Cu isotopes are heterogeneous among the measured streams. Zinc or Cu isotopic changes were not detected within the resolution of our measurements over diel cycles for most streams. However, diel changes in Zn isotopes were recorded in one stream where the fluctuations of dissolved Zn were the largest. We calculate an apparent separation factor of ∼0.3‰ (^66/64Zn) between the dissolved and solid Zn reservoirs in this stream with the solid taking up the lighter Zn isotope. The preference of the lighter isotope in the solid reservoir may reflect metabolic uptake of Zn by microorganisms. Additional field investigations must evaluate the contributions of soils, rocks, minerals, and anthropogenic components to Cu and Zn isotopic fluxes in natural waters. Moreover, rigorous experimental work is necessary to quantify fractionation factors for the biogeochemical reactions that are likely to impact Cu and Zn isotopes in hydrologic systems. This initial investigation of Cu and Zn isotopes in stream waters suggests that these isotopes may be powerful tools for probing biogeochemical processes in surface waters on a variety of temporal and spatial scales.     

Characterization of acid sulfate soils and assessing their impact on a humic boreal lake

Due to acidity and metals from acid sulfate soils (a.s. soils), many watercourses in midwestern Finland have since 1960s regularly experienced short but intensive periods of poor water quality during high water flow. This has led to occasional massive fish kills and a significant decline in fish populations.     

Meteorological impacts on the water quality in the Pajuluoma acid sulphate area,W. Finland

Water samples (n = 354) from a small catchment (7.4 km²) covered by acid sulphate soils (pH < 4) were collected during all seasons and all types of hydrological conditions in 1990–2001. The electric conductivity (EC) and pH, i.e. the key indicators of acid sulphate soil impact in the current setting, were determined. Representative daily runoff and precipitation data was available for the whole study period. The 10th and 90th percentiles for EC and pH were 29–140 mS/m and 3.8–4.6, respectively. While the water quality varied remarkably from year to year, and even within seasons, some regularity was found. The water quality was generally worst in late autumn (water temperature < 5 °C) and in spring. Of all seasons the variations were clearly smallest in spring, indicating that most representative samples can be obtained in this season. There were significant correlations between autumn, early winter and spring water quality within hydrological years. Thus acid and metal surges in spring are somewhat predictable. At base flow conditions (runoff about 1 L/s km² or less), the water quality was relatively good in all seasons. Above base flow conditions, the impact of acid sulphate soils tended to slightly increase with increasing runoff and precipitation, especially in early summer, but not in late summer. No significant signs of dilution during flood conditions (up to 100 L/s km²) were found and neither were there any correlations to rising or falling limbs. The severity of individual summer droughts, which in theory should increase the oxidation of S and acidity in the soils, had little or no impact on the water quality in subsequent autumn and spring. On the other hand, there was a remarkable long-term increase in EC and a corresponding decrease in pH (starting in 1995) after a suite of several very dry summers. After that the water quality did not improve even if the dry summers were followed by some wet summers. This indicates that the temporary pool of readily leachable acidity in the soils is fairly large. Moreover, it indicates that the potential shift towards more extreme global weather conditions (with more severe dry spells) may have significant impacts on the water quality in midwestern Finland, a region that is heavily affected by acidity and metals from acid sulphate soils.     

Origin and Formation of Sulfate in Soils from Three Ohio Counties

Sulfate induced heave has been attributed to ettringite, which can form when there is an elevated pH as well as sufficient amounts of aluminum, sulfate, calcium and water present. The primary objective of this project was to study the origin and formation of sulfate in Ohio soils in order to assist with selecting appropriate soil stabilization strategies for future roadway construction. Three roadway construction project areas were evaluated: State Route 2 in Lake (LAK) County, US Highway 24 in Paulding and Defiance Counties and Interstate-71 in Morrow (MRW) County. Defiance County had the most soil samples with sulfate concentrations above acceptable risk level (3000 mg/kg SO₄). Morrow County had the next highest number of unacceptable sulfate levels. Of the 42 Lake County soils analyzed, 11 contained sulfate above acceptable risk level. The soils surrounding the road construction activities along State Route 2 and US-24 had similar geological characteristics. A potential source of sulfate in Paulding and Defiance Counties was attributed to the direct deposition of gypsum as a soil amendment for farmlands. The most likely sources of soil sulfate in Morrow County were deposition of gypsum for farmland activities and the oxidative weathering of pyrite.     

Is groundwater in the Tarkwa gold mining district of Ghana potable?

Hand-pump wells in the Tarkwa gold mining district and the geologically similar Bui area were chemically analysed and compared in an effort to determine whether groundwaters in the Tarkwa area have been affected by mining. Significant chemical differences attributed to mine water discharges have been observed in streams in the Tarkwa area. Groundwater chemistry from hand-pump wells in Tarkwa and Bui areas reveal similar hydrochemical facies, predominantly Ca–Na–Mg–HCO₃–Cl. However, except for SO₄^2–, ionic concentrations of groundwaters from Bui are greater than those from Tarkwa probably due to differences in (1) water availability during sedimentation (2) water-rock interactions and/or residence times for water. No demonstrable impact of mining on groundwaters from hand-pumped wells in the Tarkwa area has been noted. Hydrogeological inference suggests that the main streams which receive mine water discharges are both gaining and are groundwater divides. The overwhelming majority of population centres and mining operations are located on opposite sides of these groundwater divides, therefore, it is unlikely aquifers tapped for drinking by these communities would be affected by mining.     

The use of oxygen isotopic ratios to identify natural and anthropogenic mercury concentrations in the Lower Brazilian Pantanal

Previous studies in the Amazon Basin and the Upper Pantanal show widespread mercury contamination of fish and water as a result of gold mining, and subsequent volatilization of mercury during the recovery process. A study was initiated to assess whether atmospheric transport of mercury to the south has resulted in elevated levels in water and fish in the Lower Pantanal. Water samples were collected from streams and rivers from the Pantanal (Mato Grosso do Sul) down into the southernmost state of Brazil (Rio Grande do Sul) for total Hg concentration and oxygen isotopic analyses. Based on oxygen isotopes and conductivity, surface water samples can be considered as mixtures of three endmembers: groundwater, rain and “aged” surface water. Lowest concentrations (<2 ng/L) of total Hg were observed in the northernmost samples, especially those associated with the groundwater sources. Further south, Hg concentrations tended to increase, but higher concentrations (>2 ng/L) likely reflect direct input from more localized watershed sources. Fish collected from streams in the Pantanal had extremely low concentrations of total Hg regardless of their size or feeding habit, although one large carnivorous fish (>2 kg) had concentrations approaching 400 ng/g wet wt. All concentrations, however, were considerably lower than those observed in similar species from the region of the Amazon Basin affected by gold mining.     

Origin and influence of coal mine drainage on streams of the United States

Degradation of water quality related to oxidation of iron disulfide minerals associated with coal is a naturally occurring process that has been observed since the late seventeenth century, many years before commencement of commercial coal mining in the United States. Disturbing coal strata during mining operations accelerates this natural deterioration of water quality by exposing greater surface areas of reactive minerals to the weathering effects of the atmosphere, hydrosphere, and biosphere. Degraded water quality in the temperate eastern half of the United States is readily detected because of the low mineralization of natural water. Maps are presented showing areas in the eastern United States where concentrations of chemical constituents in water affected by coal mining (pH, dissolved sulfate, total iron, total manganese) exceed background values and indicate effects of coal mining. Areas in the East most affected by mine drainage are in western Pennsylvania, southern Ohio, western Maryland, West Virginia, southern Illinois, western Kentucky, northern Missouri, and southern Iowa. Effects of coal mining on water quality in the more arid western half of the United States are more difficult to detect because of the high degree of mineralization of natural water. Normal background concentrations of constituents are not useful in evaluating effects of coal mine drainage on streams in the more arid West. Three approaches to reduce the effects of coal mining on water quality are: (1) exclusion of oxygenated water from reactive minerals, (2) neutralization of the acid produced, (3) retardation of acid-producing bacteria population in spoil material, by application of detergents that do not produce byproducts requiring disposal. These approaches can be used to help prevent further degradation of water quality in streams by future mining.     

Geochemistry of stream water in a catchment in Finland affected by sulphidic fine sediments

The impact of sediment type on stream water geochemistry was studied in a catchment in Finland affected by sulphidic fine-grained sediments. Stream water samples for general characterisation of water quality (pH, electrical conductivity) were taken at the basin outlet during various hydrological conditions, while samples for detailed geochemical analysis were collected at 119 sites in the catchment on one single occasion during high-water flow in autumn. The occurrence of sulphidic fine sediments was estimated based on data from an airborne electromagnetic survey carried out by the Geological Survey of Finland.Growing-symbol maps, which were prepared for each of the studied variables in water, and statistical calculations including factor analysis and Spearman correlations show that the concentrations of Al, Ga, U and Tl, all the lanthanides and several alkali and alkaline earth metals (K, Mg, Na, Li, Ca, Rb, Sr), transition metals (Cd, Co, Cu, Zn, Sc, Mn, Ni, Y, Hf) and non-metals (S, Br, I, Si) increase in water when the proportion of the catchment cover of sulphidic fine sediments increases. It is therefore argued that these elements are released and mobilised in considerable amounts by the oxidation and subsequent acidification and weathering of this type of sediment. Other elements are either slightly depleted in streams in areas of sulphidic fine sediments (V, Nb, Pb, Zr), have a distribution unrelated to sediment type (Fe, Cr, Cs, Mo), or are only weakly impacted by the occurrence of sulphidic sediments in the catchment (As, Ti, Ba). It is argued that these elements are not leached extensively from the oxidising sulphidic sediments, and that their distributions at least partly may be controlled by the contents of dissolved humic material and/or suspended organic and inorganic phases in the water.     

Impact of historical metalworks on the concentrations of major and trace elements in sediments: a case study in Finland

The concentrations of major and trace elements were determined (aqua regia leach and ICP-AES analyses) in stream, lake and dredged sediments downstream of the historical Antskog iron- and copperworks, S.Finland. The levels of Ag, Cd, Cu, Pb and Zn are highly elevated in all studied sediment types: roughly half of the studied lake-sediment samples contain >5 ppm Ag, >15 ppm Cd, >0.1% Cu, >0.1% Pb and >0.3% Zn. In the dredged sediment material located onshore, the concentrations of Ag, Cu and Pb are comparable to those in the polluted lake-sediment samples, while in stream sediments elevated metal concentrations are found especially in samples characterised by high concentrations of organic material. The source of the elevated metal concentrations is the historical metalworks at Antskog, mainly the copperworks of the 19th century. Compared to the limit values for contaminated soils in Finland, the concentrations of Cu, Pb and Zn are on average elevated by factors >10 in the polluted horizons of lake sediments, >5 in the dredged sediment located onshore and >2 at the most heavily contaminated site in the stream. Since the surface waters in the area are used for agricultural purposes and for various leisure activities, it is necessary to make further detailed investigations into the extent of the metal pollution and to determine species, mobility and bioavailability of the metals.     

Schwertmannite stability in acidified coastal environments

A combination of analytical and field measurements has been used to probe the speciation and cycling of iron in coastal lowland acid sulfate soils. Iron K-edge EXAFS spectroscopy demonstrated that schwertmannite dominated (43-77%) secondary iron mineralization throughout the oxidized and acidified soil profile, while pyrite and illite were the major iron-bearing minerals in the reduced potential acid sulfate soil layers. Analyses of contemporary precipitates from shallow acid sulfate soil groundwaters indicated that 2-line ferrihydrite, in addition to schwertmannite, is presently controlling secondary Fe(III) mineralization. Although aqueous pH values and concentrations of Fe(II) were seasonally high, no evidence was obtained for the Fe(II)-catalyzed crystallization of either mineral to goethite. The results of this study indicate that: (a) schwertmannite is likely to persist in coastal lowland acid sulfate soils on a much longer time-scale than predicted by laboratory experiments; (b) this mineral is less reactive in these types of soils due to surface-site coverage by components such as silicate and possibly, to a lesser extent, natural organic matter and phosphate and; (c) active water table management to promote oxic/anoxic cycles around the Fe(II)-Fe(III) redox couple, or reflooding of these soils, will be ineffective in promoting the Fe(II)-catalyzed transformation of either schwertmannite or 2-line ferrihydrite to crystalline iron oxyhydroxides.     

Estimation of weathering rates for critical load calculations in Finland

 The formation of base cations through mineral weathering in forest soils is one of the key parameters in calculating critical loads. Weathering rates in Finland have been estimated using a variety of methods. In the first approach, three weathering rate categories were assigned to soils according to the bedrock type. The second approach was based on an empirical relationship obtained from Swedish field studies. Changes in zirconium content through the soil profile were used to estimate element losses in soil after deglaciation. These calculated losses correlated well with the total calcium and magnesium concentrations in till C-horizons and the effective temperature sum (ETS). Comprehensive geochemical data for the parent till fine fraction (<0.06 mm) was available through the reconnaissance scale till geochemical mapping program of the Geological Survey of Finland (GSF). The equations obtained from Swedish studies were based on the use of the coarse (<2.0 mm) till fraction, and the differences in element concentrations between the fine and coarse size fractions remained a potential source of uncertainty estimating overall weathering rates. In the third approach, new geochemical data from the <2.0 mm till fraction from southern Finland were used to make new weathering rate estimates. The use of soil geochemistry instead of bedrock map classification clearly led to an improvement in the estimates of soil weathering rates in glacied terrains. The use of the fine till fraction (<0.06 mm) in the zirconium approach generally resulted in overestimations of the weathering rate. The new geochemical data for the coarse till fraction (<2 mm) are now consistent with the input requirements of the zirconium method, although the results still require further evaluation. Finnish soil profiles have a shorter weathering history than most of the Swedish ones and the uppermost layer in Finnish podsols has in some cases developed in a different till layer than the C-horizon. Received: 15 October 1995 · Accepted: 8 March 1996