The impacts of atmospheric n inputs on throughfall,soil and stream water interactions for different aged forest and moorland catchments in Wales

A study of inorganic-N concentrations in streams, soil waters, throughfall and rainfall was conducted for one year in five moorland and 20 Sitka spruce plantation catchments in upland Wales. The forest ages ranged from 10 to 55 yr. Highly significant positive relationships with forest stand age existed for inorganic-N concentrations in streamwater, B and O horizon soil waters and throughfall. Inorganic-N in streams and B horizon waters was entirely NO₃ ^?. Inorganic-N fluxes in throughfall also showed a significant, positive relationship with stand age. Throughfall flux of inorganic-N in the oldest stand was 25.1 kgN ha^?1 yr^?1, double that in incident rainfall. The older forest stands appear unable to utilise the available N. Nitrification is very active in the soils of these older stands, resulting in significant soil acidification. The processes responsible for the observed NO₃ ^? leaching losses, and the implications for the debate on Nitrogen Critical Loads are discussed.     

Deposition of acidifying compounds in Sweden

The Swedish Environmental Research Institute (IVL) has monitored deposition of acidifying compounds in Sweden. The monitoring programmes were initiated by various air quality protection associations, and regional forest and environmental authorities. The purpose is to quantify sulphur (S) and nitrogen (N) deposition to forests, and to illustrate possible acidification of the soil. Actual deposition of S and N is compared with critical loads. Deposition is investigated by precipitation studies in open field areas and by throughfall studies in forest stands. Soilwater chemistry is examined in the forest stands and used as indication of soil conditions. For most of the study sites, data on needle loss, forest growth, and soil chemistry are available from the National Board of Forestry. All available data are combined in a computer database for evaluation. Evaluation of data during 1985–94 shows that regional deposition monitoring illustrates the size and distributional pattern of S and seasalts. Monitoring data can identify certain regions receiving heavy loads of N, which can be found mainly in southern Sweden. Soilwater analyses indicates that large areas in Sweden have heavily acidified forest soils, low pH-values, low levels of calcium (Ca²⁺), magnesium (Mg²⁺), and potassium (K⁺), and raised levels of inorganic aluminium (iAl). Forest sites in the coastal regions of southern and south-western Sweden also showed raised inorganic N levels in soilwater. The relationship between deposition load and effects on soil chemistry is recognised by a correlation between S deposition and iAl levels in soilwater. Another correlation was found between N deposition (throughfall) and N levels in soilwater.     

Changes in the concentrations and speciation of aluminum in response to an experimental addition of ammonium sulfate to the bear Brook Watershed,Maine, USA

An understanding of the biogeochemistry of aluminum (Al) in acid-sensitive terrestrial and aquatic ecosystems is critical to assessments of the effects of acidic deposition. Bear Brook Watershed, Maine, USA includes paired watersheds, East Bear and West Bear. Starting in November 1989, experimental additions of ammonium sulfate ((NH₄)₂SO₄; 900 mol/ha-yr) have been made to West Bear Brook Watershed. Chemical analysis of soil and stream waters were conducted to evaluate the speciation of Al prior to (1987–89) and following (1989–92) the experimental treatments. Before the treatments, soilwater Al occurred largely as inorganic monomeric Al (Ali). Concentrations of organic monomeric Al (Alo), Ali and dissolved organic C (DOC) were high in soil solutions draining the E horizon, and decreased in the lower mineral soilwater (Bs horizon) and streamwater. Streamwater concentrations of monomeric Al (Alm) were largely in the form of Alo. After the (NH₄)₂SO₄ treatments were initiated in the West Bear Brook Watershed, concentrations of Alm increased in soilwater and streamwater, largely as Ali. These increases in Al accompanied decreases in pH and increases in concentrations of SO₄ ^2? and NO₃ ^? in drainage waters. Increases in stream concentrations of Al were particularly evident during high flow events. This pattern, coupled with the increases in concentrations of Ali in upper soilwaters in response to the (NH₄)₂SO₄ addition, suggests that episodic increases in Ali were due to inputs of water entering the stream from shallow hydrologic flowpaths.     

Can forest-soil liming mitigate acidification of surface waters in Sweden?

Acidification of surface waters and forest soils is severe in large parts of southern Sweden. The shallow groundwaters are also affected. Large scale liming of surface waters and streams is in operation, often combined with wetland liming to limit the effects of acid episodes, e.g. at snow melt. Acid episodes are perhaps the most severe problem in limed surface waters and in many as yet well buffered waters, because of temperature-layered acid inflow, often superficial. As a result of some investigations, a large scale forest liming programme covering 6.500–10.000 km² was recently suggested. The main objectives of this forest liming programme are to retard cation depletion and to prevent nutrient imbalance and forest decline in acidified areas. This paper deals with the effects of forest soil liming on streams and surface waters. The response of water chemistry is very dependent on hydrological and soil properties. Although pH itself may be little affected by liming, the acidity (or negative ANC) decreases, inorganic Al-species decrease and the Al/BC-ratio increases in the runoff water. Especially interesting is that this is also true during acid episodes. This means that toxicity for acid sensitive biota decreases. These results indicate that large scale liming may have beneficial effects on surface water chemistry. Furthermore, as surface waters are expected to respond to smaller decreases in acid deposition than do forests soils, forest soil liming may allow less frequent liming of lakes. Consequently, forest soil liming in combination with the anticipated emission reductions may have very beneficial results on surface waters in certain areas of Sweden.     

Microbiological Properties in Acidic Forest Soils with Special Consideration of KCl Extractable Al

To determine the importance of Al-availability for soil micro-organisms 95 forest soils from Tyrol/Austria with comparable topography, vegetation, climatic conditions, soil type and with low soil pH (median = 3.9) were investigated for their physical (percentage of stable aggregates, water holding capacity), chemical (pH, electrical conductivity, contents of organic matter, concentrations of easily extractable aluminium, calcium, potassium, magnesium and phosphorus) and microbiological characteristics (microbial biomass and respiration, metabolic quotient, content of ATP, activities of protease and CM-cellulase, cfu-values of total and Al-tolerant bacteria and fungi). A highly significant negative correlation was detected between concentrations of KCl-extractable aluminium and soil pH. By the application of multivariate statistical methods, the effect of the concentration of KCl-extractable aluminium on abundance and activities of soil micro-organisms could be revealed. Al turned out to be of great importance for micro-organisms and often outmatched the significance of other well known soil properties like organic matter, pH or water holding capacity. However, due to very healthy trees at the sites under investigation no effect of Al or soil acidification on forest decline could be detected.     

Temporal Variations of Aluminium Fractions in Streams in the Delsbo Area, Central Sweden

Stream waters were sampled weekly during spring and monthly during summer and autumn in 1998. The streams are more or less acidified, and some have been treated with lime. The aluminium fractions (total monomeric Al, organic monomeric Al, inorganic monomeric Al) were determined colourimetrically with pyrocatechol violet combined with cation exchange using Continuous Flow Analysis (Autoanalyzer I). The levels of inorganic monomeric aluminium varied substantially, between <3 to 271 µg/l. The levels were higher in untreated than in limed waters and twice as high in the most humic waters as in less humic waters. The importance of aluminium mobilisation from the catchments was obvious, with higher aluminium concentrations in surface runoff (unbalanced stream waters) compared to lake outlets (balanced and precipitated lake water). The highest mean levels were measured at spring, whereas the highest single peaks occurred during summer. Inorganic monomeric and total monomeric aluminium was best correlated to ion ratio and pH whereas acid soluble aluminium and organic monomeric aluminium was best correlated to TOC, water colour and iron.     

Calcium concentration in leaf litter alters the community composition of soil invertebrates in warm-temperate forests

Many studies have shown the effects of aboveground plant species on soil organisms due to differences in litter quality. However, the calcium concentration in soil has received less attention as a controlling factor of soil invertebrate communities, even though it is an essential element for many animals, especially crustaceans. Litter of Japanese cedar (Cryptomeria japonica) plantations, which account for 19% of the forested area in Japan, has a higher calcium concentration compared to other taxa such as broad-leaved trees. We predicted that C. japonica plantations affect soil invertebrates by altering calcium availability. We compared soil properties including exchangeable calcium concentration and soil invertebrate communities between C. japonica plantations and natural broad-leaved forests. Exchangeable calcium was significantly higher in soil from cedar plantations than in that from broad-leaved forests. The invertebrate community composition differed between the two forest types and was best explained by the exchangeable calcium concentration. In particular, two major taxa of soil crustaceans (Talitridae and Ligidium japonicum) were found only in cedar plantations. Our results suggest that calcium concentrations in soil are altered in C. japonica plantations and that this affects soil invertebrate communities.     

Increased Levels of Aluminium in Forest Soils: Effects on the Stores of Soil Organic Carbon

Acid atmospheric deposition results in increased levels of mobile aluminium (Al) in forest soils. Laboratory studies suggest that increased binding of Al to soil organic matter (SOM) in the forest floor results in decreased mobility of organic matter in soil water, viz. lower concentrations of dissolved organic carbon (DOC). Other laboratory studies indicate decreased decomposition rates of SOM as a result of Al binding. So far, little field evidence supporting these effects of Al on the lability of SOM have been reported. Here we present a field manipulation experiment in mature Norway spruce forest in Norway, where the content of Al in soil and soil water was increased. Increased Al in the forest floor caused a pronounced decrease in the leaching of DOC. Simultaneously, the decomposition rate of SOM decreased by 30% to 40%. This suggests that elevated Al in the forest floor stimulates accumulation of SOM. In a companion paper we present the effect of increased Al on forest vitality.     

Uncertainty in predicting weathering rate and environmental stress factors with the profile model

The PROFILE model is a steady state soil chemistry model which is used to calculate soil weathering rate. The model has also been used to calculate critical loads of acidity and N to forest soils, using the ratio of Ca+Mg+K to total inorganic aluminium in the soil solution as criterion, and to surface waters, using the ANC leached from the soil column as criterion. An uncertainty analysis of the PROFILE model was performed by Monte Carlo analysis, varying input parameter errors individually and simultaneously in ranges of ±10–100%, depending on parameter. The uncretainty in calculation of weathering rate, ANC leaching and ratio of Ca+Mg+K to inorganic Al in the soil solution was studied for three Nordic sites. Furthermore, the effect of uncertainty in estimates of critical load for forest soils was assessed. The analysis shows that the weathering rate can be calculated with high precision, provided that the errors of input parameter are within the range that has been reported in the literature. The model tend to be less sensitive to errors in input parameters for the range of conditions where forest damage is most likely to occur. Critical loads of acid deposition for one site calculated on the basis of the model varies within a largest range of ±40%. A study of one geographical grid included in the Swedish critical loads assessment shows that with the number of calculation points in the grid, the distribution of critical loads will stay stable independently of stochastic errors.     

Plant community composition and surface water chemistry of fen peatlands in West Virginia's Appalachian Plateau

I analyzed plant community composition, surface water chemistry, soil saturation, landscape position, and disturbance history in 4 small peatlands in WV's Allegheny Plateau, to determine vegetational differences among communities and identify environmental variables associated with community patterning. Thirty-four plant communites were identified, representing 5 physiognomic types: forest, tall and low shrub, herbaceous, and bryophyte. Of 138 species, only 34 were common to all sites; 56 were unique to single sites. Principal components analysis identified a major physiognomic separation between forest and tall shrub communities with less acid surface waters (pH 4.6–5.0) dominated by base cations (Ca⁺⁺, Mg⁺⁺, Na⁺, K⁺), vs. low shrub and bryophyte communities with more acidic surface waters (pH 4.0–4.4). Much of the variation in community composition resulted from changes in the distributions of Hypericum densiflorum, Rubus hispidus, Polytrichum commune, and Sphagnum fallax, with changes in soil saturation. Community distribution reflected an underlying pattern of basin geomorphology modified by beaver disturbance.     

Do stream invertebrates accumulate aluminium at low pH conditions?

Acidified surface waters often show elevated aluminium (Al) levels, detrimental to fish and some invertebrates. Whether Al can accumulate in benthic invertebrates, with time and/or along the food chain, is not clear. To test this, benthic invertebrates, representing different functional feeding groups, were collected in spring from streams, with different acidity and Al concentrations. Weight-specific Al content was determined with an AAS. At localities with pH ≈ 4, high Al contents (≈ 1 mg inorg-Al g^?1 af dw) were found in shredders and/or deposit feeders (Asellus aquaticus, Nemoura sp., and limnephilids), while the predator Isoperla grammatica contained only ≈ 0.3 mg Al g^?1, and the “filtering predator” Plectrocnemia conspersa almost no Al. Also at pH ≈ 6 Nemoura sp. and limnephilids showed significantly higher Al contents than did the predators Isoperla grammatica and Rhyacophila nubila, Al concentrations of the animals were often higher at pH 4 than at pH 6. Thus, no evidence of any food chain accumulation (or biomagnification) of Al could be validated. Accordingly, this study gives no support that the high concentrations of Al in fish and birds are due to their feeding on benthic invertebrates at low pH conditions. It was also found that animals that inhabit and/or consume benthic detritus as food contain highest Al levels.     

Aluminium speciation; effects of sample storage

Effects of storage on surface waters fractionated for labile and non-labile aluminium (Al) were investigated. Water samples were collected from streams at two occasions; low and high flow respectively representing in varying concentrations of Al, organic substances and pH. Aluminium was measured as total monomeric Al and non-labile monomeric Al by the colourimetric reaction of pyrocatechol violet (PCV) combined with cation exchange using continuous flow analysis. The potentially toxic fraction, labile Al, can be calculated as the difference between total monomeric and non-labile monomeric Al.The samples were stored at 4 ± 2°C and the Al-fractions and pH were determined at several times during one to two months. The results indicate that the effects of sample storage were fairly small in stable low-flow waters with pH 6–8, but larger in unbalanced high-flow waters with pH 4–7, especially for the distribution of non-labile and labile monomeric Al.     

Mobilization of aluminium, iron and silicon by Picea abies and ectomycorrhizas in a forest soil

Weathering of soil minerals is a key determinant of ground and surface water quality and is also important in pedogenic and rhizosphere processes. The relative importance of biotic and abiotic studies in mineral weathering, however, is poorly understood. We investigated the impact of Picea abies seedlings, an ectomycorrhizal fungus and humic acid on the solubilization of aluminium (Al), iron (Fe) and silicon (Si) in an E horizon forest soil over 10 months. Elemental budgets were constructed based upon losses in drainage water, accumulation in plants and changes in the pools of exchangeable ions. Plants and mycorrhizas or both had a significant effect on the total amounts of Al, Fe and Si mobilized from the soil. Significantly larger amounts of Al and Fe were recovered in plants than those lost in drainage water, whereas the opposite trend was true for Si. The continual addition of dissolved organic matter to the soil in the form of humic acid had an effect only on mobilization of Fe, which increased due to larger plant uptake and an increase in the exchangeable pool. The mobilization of Fe and Si were positively correlated with hyphal length, soil respiration and concentrations of oxalate in the soil solution, and mobilization of Al was strongly correlated with plant weight. Scanning electron microscopy revealed that most fungal hyphae were associated with mineral surfaces with little occupation of cracks and micropores within mineral grains. Evidently ectomycorrhizas have important impacts on mineral dissolution and the chemistry of forest soils.     

Effects of Afforestation on Acidity and Invertebrates in Danish Streams and Implications for Freshwater Communities in Denmark

The relationship between acidity and benthic invertebrate communities was investigated in two small streams in coniferous forests in central Jutland, Denmark, during 1992 and 1993. Stream pH was acid (mean pH 4.8 and 5.4) and alkalinity fluctuated greatly with mean values around zero. During rain events, water from springfed reaches upstream were mixed downstream with brown humic acid water with high aluminium content, and pH declined from circumneutral near the springs down to pH below 4 over a very short distance (0.5–1.5 km). The benthic invertebrate communities in the most acidic downstream reaches of both streams were dominated by filipalpian stoneflies, mainly Leuctra nigra (Olv.). Community composition remained very similar throughout the sampling period despite variations in pH. In the upper (neutral) reaches invertebrates intolerant of low pH such as Gammarus pulex L. were found. The concentrations of chloride and sulphate in the streams were more than double the concentrations in a nearby moorland stream indicating a strong impact of acidifying atmospheric deposition on the two forest streams. Results of this study indicate that afforestation with conifers on sandy Danish soils with low buffering capacity (about 25% of the total Danish land area) may lead to an increased acidification of surface waters and thereby also to an impoverished aquatic fauna.     

Eucalyptus camaldulensis and Pinus caribaea growth in relation to soil physico-chemical properties in plantation forests in Northern Nigeria

The present study described the relationship between growth and soil physico-chemical properties in Eucalyptus camaldulensis (Myrtaceae) and Pinus caribaea (Pinaceae), two important species in Nigerian forest recovery programs. The study sites were located in a 17-year-old plantation in a Northern Nigeria forest reserve. The soils at the study sites were nutrient poor compared with other plantations. Growth of E. camaldulensis was positively correlated with exchangeable K content in soils 0–20 cm deep, and negatively correlated with total N and exchangeable Na in soils 20–150 cm deep. Growth of P. caribaea was positively correlated with available P in soils 0–20 cm deep, and volumetric water content in soils 20–150 cm deep. Soils in the top layers were very hard and plinthite layers were well developed at shallow soil depths at most sites. E. camaldulensis exhibited a comparatively high survival rate, and its growth was comparable to that in other plantations. However, the survival rates of P. caribaea were low and its growth was lower than that in other plantations. The survival rate of E. camaldulensis was lower at sites where plinthite layers were found within 50.8 cm of the surface. These results indicated that E. camaldulensis is suitable for afforestation in Northern Nigeria. However, it is not recommended for sites where the plinthite layer occurs at shallow soil depths.     

Changes in soil N status and N supply rates in agricultural land afforested with eucalypts in south-western Australia

In south-western Australia, plantations of Eucalyptus globulus are being established on land that has previously been used for conventional agriculture. Sustaining the productivity of these tree plantations in second and subsequent rotations will depend partly on maintenance of soil fertility, especially soil nitrogen (N) supply rates. We compared soil N status and supply rates between adjacent pasture and 6-11 year old first-rotation eucalypt plantations at 31 paired sites in south-western Australia. Total soil N varied widely among sites (0.07-0.68% in the fraction <2 mm of the 0-10 cm soil layer), but concentrations averaged over all sites did not differ between land-use types. However, measurements of the indices of mineralization (mineral N produced during incubation of intact cores), potentially available N (from short-term anaerobic incubation) and model-predicted mineralization rates during 28-day aerobic incubations were generally lower in afforested soils than in pasture soils. This finding was supported by in situ field estimates of N mineralization over a full year at two contrasting paired pasture-plantation sites. At each site there was a marked reduction (2-3-fold) in net annual mineral N flux rates in soils under eucalypt plantations. Reduced N mineralization associated with tree plantations was due to both changes in soil organic matter quality and the generally lower soil moisture content under trees in comparison with pasture. These results suggest that N supply rates of pasture soils are likely to decline when the land is planted to successive crops of eucalypts. Eucalypt plantation managers will need to take account of this and implement management strategies to maintain adequate N nutrition to sustain tree growth in future rotations.     

Magnesium deficiency in Douglas-fir and Grand fir growing on a sandy outwash soil amended with sewage sludge

Soil and plant samples were collected from chlorotic plantations of Grand fir (Abies grandis) and Douglas-fir (Pseudotsuga menziesii) in Winter, 1989. The soils had been amended in 1981 with an average of 300 dry Mg ha^?1 of municipal sewage sludge. The sludge amendment resulted in an N application rate of approximately 8000 kg ha^?1. Foliage analysis indicated a severe Mg deficiency (0.25 g kg^?1 in sludge-treated vs. 0.93 g kg^?1 in untreated area) might be the cause of chlorosis. No other nutrient showed concentrations in the deficient or toxic ranges. Trace metal levels in foliage were elevated significantly for Ni, Cd and Cr in sludge-treated sites, but not toxic levels. Soil samples taken to a depth of 1.4 m indicated the potential for soil acidification (up to 0.9 pH unit) in soil surface horizons. In addition, exchangeable Ca, Mg and K may have been depleted in surface horizons. Exchangeable Al and Fe were greater in the surface of sludge-treated sites. These observations and the loss of much of the nitrogen added during the sludge amendment indicated that nitrification and cation leaching was likely the mechanism for acidification and depletion of exchangeable cations. Fertilization of the plantation with MgSO₄ or dolomitic limestone was carried out in Spring 1990. New foliage collected in June, 1990 was non-chlorotic and significantly higher in Mg concentration than unfertilized foliage (1.1. vs. 0.7 g kg^?1, respectively). Results of this study indicate that it is important to assess the potential for initiating a nutrient deficiency due to secondary effects of sludge application in forest systems.     

Aluminiumformen in Pseudogleyen unter Laub- und Nadelwald

Forms of aluminium in pseudogley soils under deciduous and coniferous forests In pseudogleys under a near-natural oak-hornbeam forest and under three spruce stands of different age (5, 15 and about 70 years) several fractions of aluminium were extracted by a concentrated HCl/HNO₃-mixture, 0,2 M NH₄-oxalate/oxalic acid (pH 3,0), M NH₄Cl and water resp. The selected sites are situated close to each other and allow the assumption of an originally uniform state of the soils. The pH-values of the soils tend to be the lower the older the spruce stands are. The pH-values are correlated positively with acid soluble Al, negatively with oxalate soluble Al and NH₄Cl-exchangeable Al. The highest contents of water soluble Al were found in the soil of the oldest spruce stand. Compared with the soil under deciduous forest the acidification of the soils under spruce is connected with accelerated weathering of clay minerals, reduction of exchange capacity, displacement of exchangeable Ca by Al ions and finally with Al-toxicity. The high interception of acids by the spruce stands being situated at the lee side of the industrial district of Nordrhein-Westfalen, is discussed as a cause of the accelerated soil degradation.     

Aluminum compounds in soil solutions and their migration in podzolic soils on two-layered deposits

The fractional composition of aluminum compounds was studied in soil solutions obtained using vacuum lysimeters from loamy podzolic soils on two-layered deposits. The concentration of aluminum was estimated in brooks and a river draining the area with a predominance of these soils. In soil solutions, the concentration of aluminum was experimentally determined in the following compounds: (1) organic and inorganic monomers, (2) stable complexes with HAs and FAs together with polymers, and (3) the most stable complexes with HAs and FAs together with fine-crystalline and colloidal compounds. The total Al concentration in soil solutions from forest litter was 0.111–0.175 mmol/l and decreased with depth to 0.05 mmol/l and lower in solutions from the IIBD horizons. More than 90% of the Al in the solutions was bound into complexes with organic ligands. Some amount of Al in solution could occur in aluminosilicate sols. The translocation of Al complexes from the litter through the AE horizon to the podzolic horizon was accompanied by an increase in the ratio between the Al concentration in fraction 2 and the C concentration in the solution. The concentrations of Al_tot in the surface waters varied in the range from 0.015 to 0.030 mmol/l. Most of the Al came to the surface waters from the litter and AE horizons and partially from the podzolic horizon due to the lateral runoff along the waterproof IIBD horizon. Approximate calculations showed that the recent annual removal of Al from the AE and E horizons with the lateral runoff was 7 to 560 mg (3–21 mmol) from 1 m².     

The influence of vegetation and soil type on the speciation of iron in soil water

Soluble organic matter derived from exotic Pinus species has been shown to form stronger complexes with iron (Fe) than that derived from most native Australian species. It has also been proposed that the establishment of exotic Pinus plantations in coastal southeast Queensland may have enhanced the solubility of Fe in soils by increasing the amount of organically complexed Fe, but this remains inconclusive. In this study we test whether the concentration and speciation of Fe in soil water from Pinus plantations differs significantly from soil water from native vegetation areas. Both Fe redox speciation and the interaction between Fe and dissolved organic matter (DOM) were considered; Fe – DOM interaction was assessed using the Stockholm Humic Model. Iron concentrations (mainly Fe²⁺) were greatest in the soil waters with the greatest DOM content collected from sandy podosols (Podzols), where they are largely controlled by redox potential. Iron concentrations were small in soil waters from clay and iron oxide‐rich soils, in spite of similar redox potentials. This condition is related to stronger sorption on to the reactive clay and iron oxide mineral surfaces in these soils, which reduces the amount of DOM available for electron shuttling and microbial metabolism, restricting reductive dissolution of Fe. Vegetation type had no significant influence on the concentration and speciation of iron in soil waters, although DOM from Pinus sites had greater acidic functional group site densities than DOM from native vegetation sites. This is because Fe is mainly in the ferrous form, even in samples from the relatively well‐drained podosols. However, modelling suggests that Pinus DOM can significantly increase the amount of truly dissolved ferric iron remaining in solution in oxic conditions. Therefore, the input of ferrous iron together with Pinus DOM to surface waters may reduce precipitation of hydrous ferric oxides (ferrihydrite) and increase the flux of dissolved Fe out of the catchment. Such inputs of iron are most probably derived from podosols planted with Pinus.