Hydrochemical budgets of a small forested granitic catchment exposed to acid deposition: The strengbach catchment case study (Vosges massif,France)

Hydrochemical budgets have been obtained for the 3-yr period 1986–89 at Strengbach, a small granitic basin in the Vosges mountains (north-eastern France). Here, the spruce forest shows both yellowing and crown thinning, symptoms of forest decline. Water amount and surface water chemistry were monitored in each ecosystem compartment. Bulk precipitation is acidic. Some pollution episodes occur in winter and early spring, but the annual bulk deposition acidity is rather low. Throughfall however, is much more concentrated, particularly for H⁺ and associated strong acid anions. These inputs come as occult deposits which comprise major ecosystem inputs, as confirmed by the chloride balance for the catchment. Input-output budgets for the catchment indicate a net deficit of base cations, especially calcium. Sulfate also shows a net loss while N budget is well balanced. As the soil exchange capacity is nearly exhausted for base cations, and dominated by H⁺ and Al, the neutralization of incident acid inputs occurs mainly in the weathered bedrock. Silicate weathering processes lead to high losses of cations and of silica. Aluminium hydroxide is precipitated; however, bicarbonate remains very low indicating poorly-buffered surface water.     

Factors affecting streamwater chemistry in The Great Smoky Mountains,USA

The Great Smoky Mountains in the southeastern U.S. receive high total atmospheric deposition of sulphur and nitrogen (N) and contain large areas of shallow, poorly buffered soils. Results from extensive surveys conducted in October 1993 and March 1994 showed mat stream pH values were near or below 5.5 and Acid Neutralizing Capacity (ANC) was below SO μeq·L^?1 at high elevations. Mechanisms of acidification varies among stream systems in the study. We classified each study catchment into one of five water quality districts based upon within-basin elevational gradients of streamwater quality. Geologic factors, cf. the presence of calcareous or pyritic bedrock types exhibited a major influence on water quality and within-basin elevational gradients. Atmospheric deposition is an important factor affecting water quality at high elevations in all districts. Nitrate was the dominant strong acid anion in streamwater in many catchments, particularly at high elevation and especially in basins draining old growth forests. Most high elevation catchments appear to be N saturated. Continued high atmospheric loadings of N will likely spread N saturation of catchments downslope into areas where second growth forests are now maturing. Stream sulphate concentrations were lower than expected at higher elevations and may be related to the N saturation status of fliese systems.     

Base Cation Supply in Spruce and Beech Ecosystems of the Strengbach Catchment (Vosges Mountains, N-E France)

In spruce and beech stands, mineral budgets for a rotation period were calculated from measured element fluxes. The release of base cations by mineral weathering was calculated with the steady state soil chemistry model PROFILE. The calcium release rate by weathering of the mineral fine earth was extremely low. For the period of one rotation, mineral weathering cannot provide enough Ca to compensate timber harvesting and leaching. Forest sustainability depends strongly on the amounts of Ca gained from deposition and lost by biomass removal. Magnesium was supplied by atmospheric deposition and mineral weathering. Calculated weathering rates were close to present soil losses. However, as the model assumes that all dissolution reactions are congruent, the computed release rate of Mg from illite might be too high. Main inputs of K to the soil solutions were primarily attributed to canopy leaching and litterfall in upper horizons and to mineral weathering in deeper horizons. The cation budget of the beech stand was much more equilibrated than that of the spruce stand. Given possible changes in silviculture and deposition chemistry, the sustainability of the present stands is rather improbable with respect to their mineral supply.     

Evidence of Current Soil Acidification in Spruce Stands in the Vosges Mountains,North-Eastern France

To demonstrate directly soil acidification under spruce stands in the Strengbach catchment, soils from two adjacent stands aged 40 and 90 years were sampled intensively in 1990 and resampled in 1996. Soils already were very acid in 1990. Between 1990 and 1996, soils had experienced a significant decrease in exchangeable Ca2+ and Mg2+ at all depths at the two sites except in the 0-10 cm layer, for which base saturation remained constant. Losses of Ca2+ calculated from a budget study at the same sites and from the comparison of exchangeable stores were similar. In contrast, the loss of Mg2+ from the exchange complex was higher than that computed from the field budget. Various reasons, including most probably uncertainties linked to the extremely low levels of Mg in the ecosystem, may explain this discrepancy. Since 1987, a general decrease of the (Ca2+ + Mg2+)/Al3+ ratio in soil solution was observed at both sites. These results are consistent with present day acidification of soils poor in weatherable minerals under spruce stands in the Vosges Mountains.     

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.     

Aluminium chemistry in two contrasted acid forest soils and headwater streams impacted by acid deposition,Vosges mountains,N.E. France

Al chemistry was studied in two acidic watersheds, one with a podzol, the other with an acid brown soil, in the Vosges mountains (N.E. France), by analysing both leaching and centrifugation soil solutions and spring waters over 3 yr. In the podzol, Al was mobilized in the eluvial horizons under the predominant influence of organic acidity, then leached down the profile as organic and F-bound Al. Strong undersaturation with respect to proto-imogolite and imogolite showed that the proto-imogolite theory of podzolization could not apply. Al was transferred from the soil to spring water mostly as Al³⁺ and Al-F. Al³⁺, as well as additional minor species (AlOH²⁺, AlSO₄ ⁺), originated from the redissolution of the top of the spodic horizons under the influence of both soil solution acidity and the occurrence of mobile anions derived from atmospheric deposition. Conversely, in the acid brown soil, Al mobilization was regulated by nitrate and occurred mainly as Al³⁺. Most of Al was retained in the deep soil and only traces of monomeric Al reached spring water. In the podzol eluvial horizons, soil solutions were undersaturated with respect to all relevant mineral phases and their chemical composition agree with the concept of a mobilization of Al from the solid soil organic Al and a control of Al³⁺ activity by complexation reaction with the solid and soluble soil organic matter and F. In the acid brown soil, soil solutions were found to be in equilibrium with natural alunite, and the formation of this mineral, if confirmed, would account for the occurrence of 'open' vermiculites instead of the expected hydroxy-Al interlayered vermiculites. Al solubility control in surface water of both watersheds remains unclear. The Al-F species in both watersheds and the likely control of Al solubility by alunite in the acid brown soil emphasize the influence of acid deposition on Al chemistry in acid watersheds.     

Factors affecting snowmelt streamwater chemistry in the black forest (West Germany)

Site conditions such as parent material, soils, but also vegetation cover and elevation explain the varying snowmelt streamwater chemistry in the Black Forest. The results are derived from multiple statistical analysis of a regional survey of 104 small mountain streams in the first phase of snowmelt in spring 1984. Cluster analysis classifies the snowmelt streams into three groups which are clearly linked to bedrock geology. Factor analysis finds podsolization, weathering and mineralization processes in the soils of the catchments to have most impact even under snowmelt conditions. There is no evidence that acidic atmospheric deposition directly affects the acidity of the investigated streams. However, the deposition rates are low compared to certain other regions in Central Europe. In areas with podsolic soils the organic soil layer plays a key role in the acidity and mobilization of Al and heavy metals. This is shown in the high correlations between pH, DOC, UV-extinction, color and metal concentrations. Because the concentrations of DOC are low (<10 mg.L^?1) and an anion deficit cannot be found, it is assumed that water acidity is not caused by dissolved humic acids, but by cations exchanged in the organic layer of acidic soils. Streamwater chemistry in areas with brown earth soil types is mainly affected by leaching of basic cations in the mineral soil horizons and mineral weathering.     

Critical loads of acidity to surface waters in the Vosges massif (north-east of France)

Acid clearwater fishless streams have been identified in the Vosges mountains. In order to evaluate the relatipnships between acidifying factors (such as atmospheric deposition), buffering factors (such as bedrock and soil type), and surface water acidity, an exhaustive survey of streamwater acidity in the Vosges mountains (N-E France) was performed. A network of 11 measurement stations of atmospheric deposition was used to estimate and map deposition over the whole massif (total area 5000 km²). Data on bedrock, soil, superficial deposits, and vegetation were collected from published studies. Sensitive areas as well as acidifying environment factors were derived from the corresponding maps. Over the whole massif, 19% of streams showed baseflow alkalinity below 30 eq.r¹ and 7.5 % were identified as acid (pH < 5.4).=" acid=" streams=" occur=" on=" the=" north-western=" side=" of=" the=" massif=" on=" quartzrich=" sandstone=" and=" acid=" granites.=" in=" each=" of=" these=" areas,=" we=" could=" clearly=" point=" out=" on=" one=" hand,=" the=" negative=" influence=" of=" conifer=" vegetation=" and=" glacial=" soil=" abrasion=" or=" induration,=" and=" on=" the=" other=" hand=" the=" buffering=" effect=" of=" moraine=" deposits.=" a=" corresponding=" range=" of=" critical=" loads=">< 0.2=" to=" 2.0=" keq.=">¹ yr¹) for surface water was calculated using the Steady State Water, Chemistry method (SSWC).     

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.     

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.     

Precipitation and streamwater chemistry from undisturbed watersheds in the cascade mountains of Oregon

Long-term records of precipitation and streamwater chemistry are rare; such records from forested watersheds relatively free of acidic deposition are even rarer. Precipitation and streamwater chemistry have been measured on two undisturbed forested watersheds at the H. J. Andrews Experimental Forest located on the western slopes of the Cascade Mountains of Oregon. Data from one watershed spans the period 1973–1985, the other 1969–1985. The mean annual pH of precipitation was 5.5 with a range of 4.7 to 6.0. HCO₃ ^? was the dominant anion; Ca²⁺ and Na⁺ were the dominant cations. The mean annual pH of streamwater was 7.3, and was dominated by HCO₃ ^? and Ca²⁺. These data contrast sharply with data from other calibrated watersheds in the north Cascade Mountains of Washington and British Columbia, and with data from New Hampshire and North Carolina where pH of precipitation averages 4.14 and 4.43, respectively, with SO₄ ^2? the dominant anion.     

Interfacing hydrological and hydrogeochemical models for simulating streamwater chemistry in the Turkey Lakes Watershed,Canada

The results obtained by interfacing a hydrological model with a hydrogeochemical model are presented and compared to the observed data collected from the Turkey Lakes Watershed. The most prominent feature shown in the data is the progressive increase of pH, alkalinity and Ca⁺⁺ + Mg⁺⁺ in the downstream direction. Analysis of the model results indicates that the proportion of groundwater input to total runoff in the headwater and downstream areas plays an important role in creating these spatial gradients. The model also reproduces many of the episodic events, both temporal and spatial, shown in the observed data.     

Relationships between Collembola,soil chemistry and humus types in forest stands (France)

Soil samples were taken under four tree species in various forest sites located in southern France. For each sampled A horizon of the soil profile, pH, organic matter content, C:N ratio and amounts of exchangeable cations (K, Ca, Mg) were measured, and collembolan fauna was extracted using Berlese-Tullgren funnels. A total of 78 species representing 11 families and 47 genera were identified. The relationships between Collembola and soil parameters were determined by co-inertia analysis which corresponds to the simultaneous Correspondence Analysis of the collembolan data table and the Multiple Correspondence Analysis of the environmental data table. The analysis revealed that the distribution of 10 species was related to pH, organic matter content via C and N and to base cations (K, Ca, Mg). Samples, linking these collembolan species and chemical parameters, were clustered according to humus forms. Collembola seem to be linked closer to the physical structure of humus than to its chemical parameters. Their specific contribution to pedogenetic processes as yet remains to be clarified.     

近58年天山降雪/降水量比率变化特征及未来趋势

降雪/降水量比率(S/P)能够反映不同形态降水特征,对气候变化十分敏感。该文基于天山及周边49个气象台站观测数据和IPCC-CMIP5气候情景数据,分析了近58 a来中国天山山区冷季(10-4月)降雪量、降水量和S/P时空变化特征,并预估在RCP4.5排放情景下各指标的未来变化趋势。结果表明:天山山区冷季S/P受地形影响,呈山区大于盆地,北坡大于南坡的分布格局,与海拔显著正相关。1961—2018年天山山区平均冷季降雪量、降水量均显著增加,S/P变化不大,在0.35~0.67之间波动,以-0.016%/10a的速率呈微弱减少趋势;平均气温变化是引起S/P变化的重要因素。在RCP4.5气候情景下,天山山区未来冷季降雪量缓慢减少,降水量显著增加,S/P显著减少。相比基准期(1986—2005年),到2050s冷季降雪量平均减少8.9%,降水量增加10.1%,S/P减少14.7%。该研究对科学认识全球变暖背景下天山地区水文响应以及区域水资源调控具有重要意义。     

Predicting soil classes with parameters derived from relief and geologic materials in a sandstone region of the Vosges mountains (Northeastern France)

The present study involves the possibility of using geology and relief to map soil classes. We initially focused on two small catchments considered as representative of a 6000-ha forested area overlying a sandstone bed. The catchments differed in the stratigraphic sequence of sandstones, i.e., rich or poor in weatherable minerals. In one, the depleted bedrock was downstream and the rich was upstream, and the converse obtained for the second. Relationships between soil classes and environmental factors were modeled using two discriminant functions corresponding to the two types of stratigraphic sequences found in the catchments. More than 70% of the soil class distribution in small catchments can be explained by the nature of the substratum and attributes derived from a digital elevation model (DEM). These relationships were then applied to a larger region. An automatic catchment delineation was first carried out with the DEM and was then combined with geologic maps. The choice between the two discriminant functions was based on the stratigraphic sequences in each catchment. Predicted soil classes were compared to soil classes conventionally mapped in 1978 at the scale of 1:100,000. The results show that the model reproduced the soil map over 55% of the area studied. Disagreements were due primarily to the existence of superficial deposits not mentioned on the geologic maps and to an altitude effect that is not sufficiently considered in the study of small catchments.     

Soil solution chemistry and element budgets of three Scots pine ecosystems along a deposition gradient in north-eastern Germany

Since 1993 we are studying three Scots pine ecosystems along a deposition gradient in north-eastern Germany (formerly GDR). Dramatic reductions of pollutant emissions are reported for the period since 1989/90. S-deposition is high at the sites Roesa and Taura (25 kg S ha^?1yr^?1) compared to Neuglobsow. Inputs of basic cations, especially Ca, by alkaline dust immissions decrease in the order Roesa > Taura > Neuglobsow. The soil solution data show high concentrations of Ca and SO₄ at Roesa decreasing drastically along the deposition gradient. The elevated pH values reflect the impact of alkaline dust deposition particularly in the organic surface layer at Roesa. The site Taura received less base cation deposition and is marked by the lowest pH values throughout the soil profile combined with increased Al concentrations in the solution of the mineral soil. Thus, the composition of the soil solutions clearly reflects the different deposition regimes of the past. The element budgets show that large amounts of base cations, sulfur, and, at Taura, also aluminum are actually released from the soils that were previously stored.     

Seasonal cycle of polychlorinated biphenyls in the waters of the catchment basin of the river seine (France)

In an attempt to explain the origin of Polychlorinated biphenyl (PCB) pollution peaks exceeding 1000 ng L^?1 in the River Seine, their concentrations have been studied in relation to the flow rate and the solid load. Longitudinal profiles of the River Seine and two of its tributaries, the Marne and the Orge, show that the PCB concentration in these rivers follows a seasonal rhythm, depending on how much leaching occurs. Indeed leaching is the main cause of the concentrations above 200 ng L^?1 observed at high water, both in rural and urban zones. When investigating floods in the sewerage network and the rivers, the PCB concentrations are usually seen to follow the flow rate. PCB and suspended matter concentrations vary in the same way during flood time, though when comparing the distribution of PCBs in the aqueous phase and the solid load, scarcely any connection is seen between PCB transport and the solid load. Thus during flood time in the Seine at Paris, PCB transport remains under the control of the soluble phase (75%). We have been unable to establish a link between the hydric conditions and the PCB spectrum in the river waters.     

Water flow paths and the spatial distribution of soils as a key to understanding differences in streamwater chemistry between three catchments (Norway)

Here results are presented of a hydrochemical study at a pristine and two acid rain-impacted catchments in Norway. An analysis of streamwater chemical data interpreted as mixtures of observed soil solutions, is combined with data on the spatial distribution of soils. The analysis reveals that at all three sites low flow streamwater is dominated by groundwater, relatively rich in base cations, originating from the peat bogs adjacent to the brook. By contrast, high flow largely originates in catchment-specific acidic soil horizons on the hill slopes. Results indicate that short-term and long-term hydrochemical responses to acid deposition may differ between catchments which at first glance have a ‘similar’ make up of acidic soils. This illustrates the difficulty in selecting appropriate sites for comparative studies of the effect of acid atmospheric deposition on the chemistry of streamwater.