Long-term changes in the acidity of forest soils in North-East Scotland

Abstract. Fifteen soil profiles in the Alltcailleach Forest in NE Scotland have been resampled after almost 40 years. The pH, in 0.01 M CaCl₂, of the soil has decreased by 0.07 to 1.28 units in 80% of the surface organic horizons and by 0.16 to 0.54 units in 73% of the mineral horizons below 40 cm. The key factors governing increases and decreases in soil pH are changes in ground vegetation and tree canopy, although some effects of acid deposition cannot be ruled out.     

Long-term changes in the Cu,Pb, and Zn content of forest soil organic horizons from North-East Scotland

Forest soil organic horizons from old and young plantations in the Alltcailleach Forest, N.E. Scotland were first sampled in 1949/50 and resampled in 1987. Copper, Pb and Zn in the soils were determined simultaneously on the original (stored) and the resampled soils. Overall mean Cu and Pb concentrations increased from 12.7 to 15.3 and 49.5 to 60.8 mg kg^?1 between 1949/50 and 1987. Zinc concentrations decreased from 76.4 to 60.7 mg kg^?1. Amounts of all 3 heavy metals increased because of increases in the thickness of organic horizons. Mean accumulation rates for Cu, Pb and Zn were 39.1, 186 and 114 g ha^?1 yr^?1, respectively. The rate of accumulation of Pb was significantly related to the rate of accumulation of organic matter. Copper and Zn concentrations were directly correlated with pH and inversely correlated with C/N ratio, whereas Pb was inversely correlated with pH and directly correlated with % C and C/N ratio. The more acidic soil organic horizons therefore contained higher concentrations of Pb and lower concentrations of Cu and Zn.     

Long-term trends in NADP/NTN precipitation chemistry data: Results of different statistical analyses

This paper summarizes the results of four statistical approaches for the estimation of long-term trends (1983–92) in sulfate concentration data from 90 monitoring sites across the United States. Least squares regression models and nonparametric techniques were applied to these data. Sulfate concentrations were found to be generally decreasing on the order of 0–4% at most sites. There was general agreement that trends were significant in the Great Lakes, Pacific northwest, and southwest regions. Although strengths and weaknesses are described for each approach, all of these approaches are useful for long-term trend estimation. Visualization techniques are recommended for displaying trend patterns and associated levels of statistical significance.     

Long-term recovery of stream habitat structure and benthic invertebrate communities from in-stream restoration

Headwater streams channelized for water transport of timber in Finland are being restored to their pre-channelization state. The primary motivation is the enhancement of sport fisheries, but restoration probably has profound impacts also on other stream organisms. We assessed how such “single-goal” restorations affect benthic macroinvertebrate communities. We revisited the streams sampled by Laasonen et al. [Aquatic Conservation: Marine and Freshwater Ecosystems 8 (1998)] in the early 1990s when the streams had been recently restored. In 1997, the recovery period of these streams ranged from 4 to 8 years. Habitat structure among the stream types represented a distinct recovery gradient, with streams restored 1 month before sampling and natural streams being the endpoints of a gradient in moss cover (highest in natural, lowest in recently restored streams). Channelized streams supported a characteristic set of indicator species, whereas shifts in species composition between restored and natural streams were more gradual. Macroinvertebrate communities in unmodified streams changed little between the two surveys, whereas communities in restored streams had undergone considerable changes. In-stream restoration is an unpredictable disturbance, to which stream biota cannot have any evolved responses. Therefore, the relatively rapid recovery of habitat structure and macroinvertebrate communities in restored streams is encouraging. However, long-term monitoring of benthic communities in both restored and natural streams is needed to assess whether restoring rivers by these techniques will enhance the recovery of benthic biodiversity in boreal streams.     

Long-term trends in chemistry of precipitation after longscale transport-effects of atmospheric rehabilitation in East-Germany

Components in precipitation are dominantly dependent on structure and quantity of emissions on the course of the rainy air masses. It can be proved after meso-and long-range transport. Starting in 1982, precipitation is collected in 4-hour-periods at sites far from industry in East-Germany. For regions with specific geographical or uniform emission features arrival sectors are established, e. g. former GDR, Scandinavia, Poland, or Czech. The classification of the samples is done by back-trajectories. From the former GDR the anthropogenical components were most significantly raised before the political change, but acidity remained on an average level. After the change, the most emission products decline considerably —except NO_X. Consequently, those lead to essential changes of pollutants in precipitation. The reduction is not uniformly. The report represents long-term data and discusses clear differences between components in deposition from sectors of the former GDR and West-Germany. The effects of atmospheric rehabilitation are analysed. Specially starting in 1993 the acidity of rain from the former GDR increases very strikingly up to now threefold more than from West-Germany (average ≤pH 4 at some sites). An explanation in terms of emission components only is devious, a complex consideration of change of dust composition as neutralizing factors and of processes of cloud formation and dispersal is necessary. It must be mentioned, that the acidity of precipitation from West-Germany and Scandinavia declines slightly in recent period. Therefore only sector-classified data show the real range of acidity.     

Long-term trends in the abundance of Mediterranean wetland vertebrates: From global recovery to localized declines

Biodiversity loss is unevenly distributed in space and time. Species have reached critically low population sizes in some areas, and remain abundant in others. Similarly, some species may benefit from successful conservation plans, while others still experience severe population depletions driven by negative impacts of human activities. Although several indicators have been proposed to measure the fate of biodiversity, they are generally only implemented globally so their relevance for regional assessment is still unclear. Here, we calculated the first regional trend in the Living Planet Index for the Mediterranean wetlands (Med LPI), an indicator that summarizes the fate of global biological diversity based on the temporal trends in abundance of vertebrate populations. The Med LPI was based on 1641 vertebrate populations of 311 species recorded in Mediterranean wetlands from 1970–2008, in 27 different countries. We investigated whether trends in the Med LPI differed between eastern and western Mediterranean countries, which have different socio-economic contexts. Finally, we assessed whether and how the trend in the Med LPI was robust to changes in the number and identity of species considered. We found that, at the Mediterranean scale, the Med LPI increased steeply, which could be taken at first sight, as a general recovery of wetland biodiversity in this biogeographical region. However, we found highly contrasting spatial trends within the Mediterranean region: the average trend was positive for western and negative for eastern countries. Moreover, we showed that depending on the method used to estimate the trend in Med LPI, it can be sensitive to the number and identity of the species considered. We suggest that understanding the regional discrepancies of the trend in biodiversity indicators as well as their robustness to the species represented in the index will enhance progress assessment towards global and regional conservation strategies.     

Upland afforestation: influences on stream hydrology and chemistry

Abstract. Afforestation in the British uplands can lead to changes in the hydrology, sediment load and chemistry of streams. These changes may affect water resource management costs, stream biota and the health of fisheries. Some of the changes can be related to specific phases of the forest management cycle, e.g. site preparation, fertilization, felling; modifications in management practice can limit their impact. Other changes in water yield and chemistry seem to have complex origins in forest-atmosphere and forest-soil interactions; these are more difficult to counteract.     

Long-term trends in the chemistry of precipitation and lake water in the Adirondack Region of New York,USA

Long-term changes in the chemistry of precipitation (1978–94) and 16 lakes (1982–94) were investigated in the Adirondack region of New York, USA. Time-series analysis showed that concentrations of SO₄ ^2–, NO₃ ^–, NH₄ ⁺ and basic cations have decreased in precipitation, resulting in increases in pH. A relatively uniform rate of decline in SO₄ ^2– concentrations in lakes across the region (1.81±0.35 eq L^–1 yr^–1) suggests that this change was due to decreases in atmospheric deposition. The decrease in lake SO₄ ^2– was considerably less than the rate of decline anticipated from atmospheric deposition. This discrepancy may be due to release of previously deposited SO₄ ^2– from soil, thereby delaying the recovery of lake water acidity. Despite the marked declines in concentrations of SO₄ ^2– in Adirondack lakes, there has been no systematic increase in pH and ANC. The decline in SO₄ ^2– has corresponded with a near stoichiometric decrease in concentrations of basic cations in low ANC lakes. A pattern of increasing NO₃ ^– concentrations that was evident in lakes across the region during the 1980's has been followed by a period of lower concentrations. Currently there are no significant trends in NO₃ ^– concentrations in Adirondack lakes.     

Applying combinatorial chemistry and biology to food research

In the past decade combinatorial chemistry has become a major focus of research activity in the pharmaceutical industry for accelerating the development of novel therapeutic compounds. The same combinatorial strategies could be applied to a broad spectrum of areas in agricultural and food research, including food safety and nutrition, development of product ingredients, and processing and conversion of natural products. In contrast to "rational design", the combinatorial approach relies on molecular diversity and high-throughput screening. The capability of exploring the structural and functional limits of a vast population of diverse chemical and biochemical molecules makes it possible to expedite the creation and isolation of compounds of desirable and useful properties. Several studies in recent years have demonstrated the utility of combinatorial methods for food research. These include the discovery of synthetic antimicrobial, antioxidative, and aflatoxin-binding peptides, the identification and analysis of unique flavor compounds, the generation of new enzyme inhibitors, the development of therapeutic antibodies for botulinum neurotoxins, the synthesis of unnatural polyketides and carotenoids, and the modification of food enzymes with novel properties. The results of such activities could open a large area of applications with potential benefits to the food industry. This review describes the current techniques of combinatorial chemistry and their applications, with emphasis on examples in food science research.     

Influence of wetlands and coal mining on stream water chemistry

Comparisons of stream water chemistry over a 2 yr period in East Fork, which drains an entirely forested watershed, and Big Run, which drains a forested watershed 8 % of which is occupied by Big Run Bog, indicated that Big Run Bog had no effect on stream water H⁺ or Cl^? concentrations, but with increasing stream discharge the wetland was a source of Ca⁺⁺ Mg⁺⁺, K⁺, Na⁺, NO₃ ^?, and SO₄ ^?, and a sink for Fe^{+ +}. Further comparisons with Tub Run, which drains a forested watershed, 13 and 12% of which is occupied by Tub Run Bog and an abandoned, unreclaimed coal surface mine, respectively, suggested that Tub Run Bog removes H⁺, Ca ++, Mg⁺⁺, Fe⁺⁺, and 50₄ ^? from inputs of acid mine drainage. Wetland areas on the landscape contribute to the regulation of stream water chemistry in ways that are different from upland areas, and wetlands may have considerable applied potential for minimizing the impact of the mine drainage on stream water quality.     

Long-term chemical and biological trends in Scottish streams and lochs

Between 1975 and 1985 several catchments in Scotland were established as reference sites to determine short-term (hours, days, weeks) and long-term (years, decades) changes in major physical, chemical and biological variables. The initial selection criteria included catchment size, land-use and deposition loading. Changes in fish status of lochs were determined by systematic netting while quantitative estimates of fish populations were made at stream sites. Egg survival and year class distribution assisted interpretation. Historical changes in pH based on stratigraphical changes in diatom assemblages are compared with recent measured changes which have occurred during the past 20 years when SO₂ emissions declined. Significant chemical and biological trends due to changes in pollutant loading are best detected in sensitive lochs which are unmanaged and with low organic content and acid neutralising capacity (ANC) close to zero. Significant trends are less apparent in lochs with managed (forested) catchments. Many stream sites also reveal long-term improvements in pH, sulphate (SO₄) Alkalinity (Alk) etc, but the significance of these trends is much less because of the greater inherent chemical variability. Stream sites close to ANC=0 provide the most wide-ranging evidence of ecological change, ie, increase in Alk, decrease in SO₄ and increase in numbers of juvenile salmonids. Measured chemical changes are compared with predicted estimates, based on critical load calculations and problems in interpretation are discussed.     

Step-wise analysis of precipitation and river chemistry trends in Atlantic Canada

Monotonic trends in hydrogen (H⁺), sulfate (SO₄ ^–2)and nitrate (NO₃ ^–) were calculated using non-parametric techniques at four Canadian Air and Precipitation Monitoring Network (CAPMoN) sites and six nearby river systems in Atlantic Canada for the period 1983–1991. Over the whole interval, there were increasing nitrate concentrations and deposition trends at three of the four monitoring sites and no trends in SO₄ ^–2 or H⁺ concentrations and deposition. We found that SO₄ ^–2 concentrations increased at three of our six river sites, NO₃ ^– increased at one site and H⁺ decreased at one site. River exports showed no trends in the entire study interval. The series were also analyzed in five year time windows, incremented by six months, to see if changes in trend presence or direction would occur, compared to trend analysis over the entire interval. We show that while trends in river chemistry do not contradict deposition patterns, the changes that occurred were not necessarily in step. We also found that the trends which we measured were the result of short-term changes as opposed to long-term continuous monotonic trends. The time lag between precipitation and chemistry trend changes seemed longer in basins dominated by softwoods than by hardwoods.     

Atmospheric deposition effects on the chemistry of a stream in Northeastern Georgia

A modeling study of the Allt a Mharcaidh catchment in the Cairngorm region of Scotland has been undertaken to investigate long term trends in acidification and model sensitivity to soil physical and chemical characteristics. The MAGIC model (Model of Acidification of Groundwater In Catchments) is used to demonstrate that the sulphate adsorption ability of the soil and quality and quantity of rainfall inputs have significant effects on model output. Optimal weathering rates and predicted present day ion concentrations in streamwater compare well with measured and observed values. The analysis shows that the catchment has become progressively acidified since pre-industrial times but major changes in stream acidity have yet to occur.     

recent lake acidification and recovery trends in southern quebec,canada

A total of 51 lakes in southern Quebec, Canada, were sampled between 1985 and 1993 to study changes in water chemistry following reductions in SO₂ emissions (main precursor of acid precipitation). Time series analysis of precipitation chemistry revealed significant reductions in concentrations and deposition of SO₄ ^2- from 1981 to 1992 in southern Quebec as well as reductions in concentrations and deposition of base cations (Ca²⁺, Mg²⁺), NO₃ ^- and H⁺ in the western section of the study area. Reductions in atmospheric inputs of SO₄ ^2- have resulted in decreased lakewater SO₄ ^2- concentrations in the majority of the lakes in our study, although only a small fraction (9 of 37 lakes used in the temporal analysis) have improved significantly in terms of acidity status (pH, acid neutralizing capacity – ANC). The main response of the lakes to decreased SO₄ ^2- is a decrease in base cations (Ca²⁺+Mg²⁺), which was observed in 17 of 37 lakes. Seventeen lakes also showed significant increases in dissolved organic carbon (DOC) over the period of study. The resulting increases in organic acidity as well as the decrease in base cations could both play a role in delaying the recovery of our lakes.     

Evidence of Springwater Acidification in the Vosges Mountains (North-East of France): Influence of Bedrock Buffering Capacity

Investigations on springwater acidity were carried out in the Vosges mountains (north-eastern France). Acid or poorly buffered spring and streamwaters were detected in the same area. The proportion of acid springwaters (pH < 5.6) is about 20% among 220 springs. The springwater pH on granite are equally spread between 5.0 and 6.8 whereas on sandstone a majority of springs is in the range 5.6 to 6.2. As a whole, but mainly on sandstone, from the 1960's to 1990's, the shape of the pH distributions shifts toward greater acidity. In the sandstone area, trends in pH, alkalinity, total hardness (corresponding to divalent cations), sulfate and nitrate were considered over the 30 yr period (1963-1996) in relation to the bedrock chemical composition. Kendall seasonal tau coefficients indicate that decreasing trends were significant for the first three parameters. Linear regression on the smoothed mean value revealed 18 and 90% decrease for pH and alkalinity respectively, for springwaters draining poor-base cation sandstone whereas only 8 and 30% decrease respectively, was observed on clay-enriched sandstone. On silica-enriched sandstone, alkalinity began to decrease in the early 70's as well as pH. Loss of alkalinity only occurred in the early 80's for springs draining clay enriched sandstone. This can be interpreted as a titration process by acid atmospheric inputs of the buffering capacity of weathering and exchange processes in the soils and the catchment bedrock. The nitrate presents an increasing step in the early seventies but possibly as a result of change in analytical technics and/or increase in atmospheric inputs mainly resulting from increase in fertiliser inputs in agricultural areas or in car traffic. Surprisingly no change in sulfate was noticed in any groups of springs probably as a result of the adsorption/mobilisation in the soils. These long-term trends in spring waters (1963-1996) confirmed the soil and streamwater acidification trends already mentioned in this region, in relation to acid atmospheric inputs since no climate nor forestry practice changes have been detected over the period. Moreover, in spite of acid atmospheric input reductions, no recovery can presently be detected.     

The relationship between salmonid fish densities and critical ANC at exceeded and non-exceeded stream sites in Scotland

The critical load concept is now accepted throughout Europe as a means of estimating the sensitivity of key components of aquatic and terrestrial ecosystems to atmospheric inputs of sulphur (S) and nitrogen (N). Current UK freshwater maps, based on steady-state water chemistry, are derived using a critical acid neutralising capacity (ANC_LIM) value of zero eql^–1, which is based on the probability of occurrence of salmonid fish in lakes. In practice most acidification damage to salmonid fish occurs in nursery streams at the emergence and first feeding stages. In general a clear relationship exists between salmon (Salmo salar L.) and trout (S. trutta L.) densities in Scottish streams and ANC values. However, differences between sites depend on which ANC value is used (eg maximum, minimum or mean). By contrast, when the exceedance of critical loads is compared with salmonid densities the relationship is less clear because many exceeded sites have good salmonid densities. Many of these latter sites are found in north-west Scotland where sea-salt inputs are high and ANC is usually greater than zero eql^–1, although diatom-based studies indicated slight acidification of these waters, with a point of change in diatom flora close to ANC=20 eql^–1. These false exceedances are probably due to preferential adsorption of acidic SO₄ deposition which results in an overestimate of exceedance values. All sites with a mean ANC 0 are fishless but some sites with negative minimum ANC values had normal salmonid densities. Consequently a mean ANC_LIM value of zero in the critical load equations for UK freshwaters appears to be too low to protect salmonid stocks. Values between 20–50 eql^–1 represent a more realistic range if prevention of long term damage to salmonid stocks is to be achieved.     

Long-term changes in fish populations of acid streams and lochs in galloway South West Scotland

During 1978–79, and again in 1984, fish populations were surveyed in 22 lochs and 27 streams in Galloway, southwest Scotland. Chemical analyses of these waters and of bulk precipitation were made over the same period. The study area includes moorland catchments and catchments with young or semi-mature coniferous forest. Trout were not caught in nets set in 5 lochs which were known to contain fish in the past. Angling records also indicated a decline in catches and increased average weight of trout in two other lochs. Evidence for the decline in fish populations suggests that this process has occurred over a period of at least 50 yr. In fishless lochs and streams the levels of acidity and Al were in the range known to be toxic to fish. Stream acidity and sulphate concentrations were significantly higher in catchments with semi-mature coniferous forests. The available evidence for long-term acidification of Galloway lochs and streams is discussed and it is concluded that acid depositions are likely to be the major cause of changes in the status of fisheries in this region.     

Evidence for transport of bedload in waves: Analysis of fluvial sediment samples in a small upland stream channel

Data pertaining to the transport of fluvial sediment sampled in detail during a five hour long event in a small upland stream channel in the extremely arid Southern Negev are presented. Considerations based on comparative evaluations of water discharge, stream power, total and fractional sediment concentration, and total and fractional sediment discharge suggest that bedload transport in channels of even very small upland catchments practically devoid of continuous alluvial cover takes place in waves, which are not a priori related to any water discharge characteristic, but rather reflect some intrinsic feature of watershed dynamics, such as slope-channel topographic contrasts or fluvial bifurcation. The regular spacing of pools and riffles and of gravel bars in the more alluvial reaches downstream may therefore be initiated from upstream.     

Relationships between afforestation,water chemistry and fish stocks in an upland catchment in south west Scotland

The soils and waters in the Galloway hills of south-west Scotland have undergone considerable acidification during the present century. The aims of this study were to examine the extent to which afforestation can influence water chemistry, and the occurrence of fish stocks within an individual catchment in this area. Studies were carried out at 45 sites in the Bladnoch catchment during 1994. River water samples were collected at all sites and determinations made of pH, total organic carbon, calcium and monomeric aluminium concentrations. In order to quantify the size and abundance of fish populations, electrofishing was carried out at 21 of the sites. Estimates of afforestation were made by a combination of field surveys and the use of 1∶:10 000 scale ordnance survey maps. The presence of coniferous trees had a substantial affect on water chemistry. In areas where the whole catchment was afforested, the water pH was 0.7 units lower than in unafforested areas (p<0.001). Afforestation was also correlated with low concentrations of calcium, and increases in the concentrations of monomeric aluminium and total organic carbon. There was a clear relationship between fish populations and water chemistry. Numbers of trout were positively correlated with pH (r ²=0.69; p<0.001), and with concentrations of calcium (r ²=0.55; p<0.001). The study has shown that salmonid fish populations are sensitive to acidity and the associated changes in river water chemistry; these problems were exacerbated by afforestation.     

Organo‐mineral associations in temperate soils: Integrating biology,mineralogy, and organic matter chemistry

We summarize progress with respect to (1) different approaches to isolate, extract, and quantify organo‐mineral compounds from soils, (2) types of mineral surfaces and associated interactions, (3) the distribution and function of soil biota at organo‐mineral surfaces, (4) the distribution and content of organo‐mineral associations, and (5) the factors controlling the turnover of organic matter (OM) in organo‐mineral associations from temperate soils. Physical fractionation achieves a rough separation between plant residues and mineral‐associated OM, which makes density or particle‐size fractionation a useful pretreatment for further differentiation of functional fractions. A part of the OM in organo‐mineral associations resists different chemical treatments, but the data obtained cannot readily be compared among each other, and more research is necessary on the processes underlying resistance to treatments for certain OM components. Studies using physical‐fractionation procedures followed by soil‐microbiological analyses revealed that organo‐mineral associations spatially isolate C sources from soil biota, making quantity and quality of OM in microhabitats an important factor controlling community composition. The distribution and activity of soil microorganisms at organo‐mineral surfaces can additionally be modified by faunal activities. Composition of OM in organo‐mineral associations is highly variable, with loamy soils having generally a higher contribution of polysaccharides, whereas mineral‐associated OM in sandy soils is often more aliphatic. Though highly reactive towards Fe oxide surfaces, lignin and phenolic components are usually depleted in organo‐mineral associations. Charred OM associated with the mineral surface contributes to a higher aromaticity in heavy fractions. The relative proportion of OC bound in organo‐mineral fractions increases with soil depth. Likewise does the strength of the bonding. Organic molecules sorbed to the mineral surfaces or precipitated by Al are effectively stabilized, indicated by reduced susceptibility towards oxidative attack, higher thermal stability, and lower bioavailability. At higher surface loading, organic C is much better bioavailable, also indicated by little ¹⁴C age. In the subsurface horizons of the soils investigated in this study, Fe oxides seem to be the most important sorbents, whereas phyllosilicate surfaces may be comparatively more important in topsoils. Specific surface area of soil minerals is not always a good predictor for C‐stabilization potentials because surface coverage is discontinuous. Recalcitrance and accessibility/aggregation seem to determine the turnover dynamics in fast and intermediate cycling OM pools, but for long‐term OC preservation the interactions with mineral surfaces, and especially with Fe oxide surfaces, are a major control in all soils investigated here.