Abstract:The O levels in various catchment waters provided a ®rst approximation of mean residence times in the major hydrological stores. Preliminary estimates are 0 . 2±0 . 8 years for near-surface soil water that contributes to storm runo and 2 and 45 years for shallow and deeper groundwater, respectively. These 18 O data sets provide further evidence that the in¯uence of groundwater on the hydrology and hydrochemistry of upland catchments has been underestimated.

The chemical composition and invertebrate communities found in four streams in the Cairngorms, Scotland, were monitored between [1985][1986][1987][1988][1989][1990][1991][1992][1993][1994][1995][1996][1997]. Stream waters were mildly acidic (mean pH ca. 6.5), with low alkalinity (mean acid neutralising capacity varying from 35-117 meq l -1 ) and low ionic strength. Subtle differences in the chemistry of each stream were reflected in their invertebrate faunas. Strong seasonality in water chemistry occurred, with the most acid, low alkalinity waters observed during the winter and early spring. This was particularly marked during snowmelt between January and April. In contrast, summer flows were usually groundwater dominated and characterised by higher alkalinity and higher concentrations of most other weathering-derived solutes. Seasonality was also clear in the invertebrate data, with Canonical Correspondence Analysis (CCA) separating seasonal samples along axes related to water temperature and discharge characteristics. Inter-annual hydrological and chemical differences were marked, particularly with respect to the winter period. Invertebrate communities found in each of the streams also varied from year to year, with spring communities significantly more variable (P<0.01) than other seasons (quantified using Euclidean distance on CCA ordinations). Hydrochemical trends over the study period were analysed using a seasonal Kendall test, LOcally WEighted Scatterplot Smoothing (LOWESS) and graphical techniques. These indicated that a reduction in sulphate concentrations in stream water is occurring, consistent with declining levels of atmospheric deposition. This may be matched by increases in pH and declining calcium concentrations, though available evidence is inconclusive. Other parameters, such as chloride, total organic carbon and zinc, reveal somewhat random patterns, probably reflecting irregular variations in climatic factors and/or atmospheric deposition. Previous studies have shown that the stream invertebrate communities have remained stable over this period (i.e. no significant linear trends) and show no evidence of acid-related impoverishment. Thus, over longer timescales invertebrates in these streams appear robust to the short-term (seasonal and inter-annual) environmental variability and long-term (decadal) chemical changes identified.

Abstract. Springs are important groundwater discharge points on the high altitude (>800m) plateaux of the Cairngorm mountains, Scotland and form important wetland habitats within what is often a dry, sub-arctic landscape. The hydrogeochemistry of a typical spring in the Allt a'Mharcaidh catchment was examined between 1995-98 in order to characterise its chemical composition, identify the dominant controls on its chemical evolution and estimate groundwater residence time using 18O isotopes. Spring water, sustained by groundwater flow in shallow drift deposits and fractured bedrock, was moderately acidic (mean pH 5.89), with a very low alkalinity (mean 18 μeq l-1) and the ionic composition was dominated by sea-salts derived from atmospheric sources. Geochemical modelling using NETPATH, predicted that the dissolution of plagioclase mainly controls the release of Si, non-marine Na, Ca, K and Al into spring water. Hydrological conditions influenced seasonal variations in spring chemistry, with snowmelt associated with more rapid groundwater flows and lower weathering rates than summer discharges. Downstream of the spring, the chemistry of surface water was fundamentally different as a result of drainage from larger catchment areas, with increased soil and drift cover, and higher evaporation rates. Thus, the hydrogeochemical influence of springs on surface waters appears to be localized. Mean δ18O values in spring water were lower and more damped than those in precipitation. Nevertheless, a sinusoidal seasonal pattern was observed and used to estimate mean residence times of groundwater of around 2 years. Thus, in the high altitude plateau of the Cairngorms, shallow, coarse drift deposits from significant aquifers. At lower altitudes, deeper drift deposits, combined with larger catchment areas, increase mean groundwater residence times to >5 years. At high altitudes, the shallow, permeable nature of the drifts dictates that groundwater is vulnerable to impacts of environmental changes that could be usefully monitored at spring sites.

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The hydrological and ecological significance of groundwater has generally been under-estimated in headwater catchment studies within the Celtic regions. The paper presents data from headwater catchments in both upland and lowland settings in northern Scotland to address this gap in our understanding. Research in the 10 km2 Allt a’ Mharcaidh catchment in the western Cairngorms has demonstrated that a range of groundwater sources in various drift deposits can account for c. 50% of annual runoff, even in a high altitude headwater stream. Despite the traditional assumption that upland catchments have limited aquifer storage, oxygen isotope studies of groundwater imply mean water residence times of up to five years which indicate a range of groundwater sources in montane environments. Moreover, hydrogeochemical reactions in the saturated zone appear to regulate stream water chemistry at moderate and low flows. In such montane environments, groundwater discharges at springs create unique wetland habitats which often form the source of headwater streams and affect riparian areas. In lowland catchments the hydrological significance of groundwater is equally important. In addition, recent studies in a salmon spawning stream in the Newmills Burn, Aberdeenshire has shown that aquifer-stream interactions in hyporheic zones are crucial in maintaining habitat conditions conducive to the survival of salmonid eggs, and the subsequent population of salmon streams. It is concluded that interdisciplinary studies incorporating hydrogeological investigations are fundamental to a proper understanding of the hydrology and functional ecology of catchment systems in the Celtic regions.