Long-term rates of acidification of UK upland acidic soils

Abstract. The approximate time-scales for serious lowering of the base status of acidic upland soils in northeast Scotland have been based on assessments of geochemical weathering rates in two upland catchments. Periods of 1100 and 12000 years are obtained for soils evolved primarily from granite and quartz-biotite-norite respectively. Factors regulating the rate of removal of base cations in drainage water are discussed, to elucidate those which significantly influence long-term rates of soil acidification. The relationship between base cation leaching and river water acidity is briefly considered.     

Weathering rates in catchments calculated by different methods and their relationship to acidic inputs

The sensitivity of catchments to acidification is often assessed by calculation of weathering rates for comparison of the rates of release of base cations with the measured acidic inputs. Methods of calculation of weathering rates include (1) long-term rates from elemental depletion in soil profiles; (2) current rates from input-output budgets; (3) strontium isotope ratios to modify current rates for calcium; (4) modelling using PROFILE or MAGIC; (5) laboratory experimental methods. Not all these methods can be applied in any one situation and when more than one method can be used, there are often discrepancies in the resulting figures. Comparison of long-term and current rates with acidic inputs are often consistent with the known acidification status of some Scottish catchments, but in others it is often difficult to establish a relationship. In some catchments where acidification only occurs under high-flow conditions, for example, long-term rates (12–24 meq m^?2a^?1) are an order of magnitude lower than current rates (185–340 meq m^?2a^?1). In seven Scottish catchments on four rock types, weathering rates calculated by PROFILE are of the same order of magnitude as long-term rates calculated for the same soil profiles. Current rates, on the other hand, are always higher than the long-term rates, sometimes by a factor as high as 22, and although this could indicate that release of base cations from these soils has increased in recent times, possibly due to anthropogenic inputs, the comparisons may not be valid.     

土壤风化速率研究及其应用

土壤矿物风化是土壤、也是整个生态系统中无机矿质养分的最重要来源,不仅为植物长期提供养分和保持土壤的化学平衡稳定性,并缓冲土壤和地表水的酸化,还影响全球气候变化。风化速率在全球碳循环、酸临界负荷和土壤侵蚀等研究中都是非常重要的参数。土壤化学风化是一个不断进行的自然释放过程,气候是最主要的驱动力,而矿物本身的稳定性也影响了风化速率的快慢。由于人为影响下的大气酸沉降和农业活动已经非常普遍,目前的土壤风化速率也因此而改变。本文从风化速率的研究方法、风化速率的影响因素以及风化速率在全球变化中的应用3个方面介绍了近年来在风化速率方面的研究进展,并探讨了相关研究未来的发展趋势。     

Long-Term Evaluation of Acidic Atmospheric Deposition on Soils and Soil Solution Chemistry in the Daniel Boone National Forest,USA

Combustion of fossil fuels has contributed to many environmental problems including acid deposition. The Clean Air Act (CAA) was created to reduce ecological problems by cutting emissions of sulfur and nitrogen. Reduced emissions and rainfall concentrations of acidic ions have been observed since the enactment of the CAA, but soils continue to receive some acid inputs. Many soils sensitive to acid deposition are found to have low pH, a loss of base cations, and a shift in the mineral phase controlling the activity of Al³⁺ and/or SO₄ ^2?. If inputs continue, soil may be depleted of base cations and saturated with Al and could cause low forest productivity. Soil samples and soil solutions from pan lysimeters were taken on ridge-tops in the Daniel Boone National Forest to evaluate potential impacts of acid deposition recently and in the future. Sample results were compared to historical data from identical locations. Physicochemical characteristics of the soils revealed that sites were very low in base saturation and pH and high in exchangeable acidity, illustrating change since previously sampled. Soil solution data indicated that sites periodically received high acid inputs leading to saturation of Al in soils and the formation of Al-hydroxy-sulfate minerals. Given these conditions, long-term changes in soil chemistry from acid deposition are acknowledged.     

亚热带花岗岩地区土壤矿物风化过程中盐基离子的释放特征

矿物风化过程中盐基离子释放遵从一定的化学计量关系,这种化学计量关系一般只能通过模拟实验来获取。本研究采用pH 7.0的EDTA-乙酸铵溶液将土壤中的交换性盐基离子完全洗脱出来,然后用Batch方法模拟不同pH溶液淋溶洗脱盐基和未洗脱盐基土壤,旨在消除土壤中交换性盐基离子的影响后更为准确地判断土壤矿物风化的盐基离子释放特征。结果表明:未洗脱盐基土壤的淋出液pH由3.73±0.14逐渐上升到4.23±0.06,主要原因是淋溶液中有高浓度的NH_4~+;洗脱盐基土壤矿物风化后淋出液pH从7.39±0.02逐渐下降到5.39±0.17,主要是由于土壤中可风化矿物减少。土壤交换性盐基离子会改变盐基离子释放特征、释放总量:未洗脱盐基土壤经酸雨淋溶后,各盐基离子释放均呈现急速下降后逐渐平缓的趋势,洗脱盐基土壤矿物风化后,K~+及盐基离子释放总量呈波动上升趋势,且盐基离子释放总量比未洗脱盐基土壤低。土壤交换性盐基离子的存在还会改变淋出液中的盐基离子化学计量关系:未洗脱盐基土壤的K~+︰Ca~(2+)︰Mg~(2+)︰Na+化学计量关系为11︰13︰4︰1(当量比),而洗脱盐基土壤为7︰2︰2︰1。K~+是盐基离子中风化释放量最多的,大部分K~+来自于土壤中云母的风化。因此,只有利用洗脱盐基土壤的盐基离子释放量才能准确计算矿物风化速率并获得准确的化学计量关系。土壤矿物风化作用随着淋溶液酸度增大而增强,但模拟一年降雨量的情况下,p H 3.5、4.5和5.5三种不同p H溶液对矿物风化后盐基离子的释放在实验期间没有显著性影响,较长时间后的差异性有待观察。本研究表明,可以通过预洗脱盐基土壤然后模拟酸雨淋溶的方法,观察矿物风化特征,特别是盐基离子释放的化学计量特征。     

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.     

Chemical and mineralogical weathering rates and processes in an upland granitic till catchment in Scotland

Weathering in an upland granitic till catchment receiving an intermediate level of acidic deposition has been studied by chemical and mineralogical analyses of soil profiles and chemical analysis of precipitation and streamwater. Long-term weathering rates for base cations calculated from analyses of soil profile horizons using Zr as an internal, immobile, index element are similar for alpine podzols and peaty podzols and are 2–3 meq.m^–2.a^–1 for Ca and Mg, and 10–11 meq.m^–2.a^–1 for K and Na. The high loss of Na is associated with the weathering of oligoclase, particularly in the coarse sand fraction. Loss of K is related to weathering of K-feldspar and micas. Current weathering rates for base cations calculated from input-output budgets are higher than long-term rates by factors of 12, 8 and 3 for Ca, Mg and Na, but lower by a factor of 7 for K probably due to biomass uptake. The higher current overall loss of base cations may be due to increased rates of weathering in recent times but this is not conclusive as there are large uncertainties inherent in both methods of estimation.     

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.     

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.     

Are ion exchange processes important in controlling the cation chemistry of soil- and runoff waters ?

Soil- and stream water elemental concentrations from a subcatchment in the Lake Gårdsjön area have been used to evaluate the importance of ion exchange processes on the transport of cations to aquatic ecosystems. The importance of cation exchange processes in the upper organic and upper B soil horizons was demonstrated using lysimeter water data from a recharge area and soil water flow simulated with SOIL model during winter rain events with high sea-salt concentration. The importance of the hydrological conditions, such as water flow and water pathway, silicate weathering and the ion exchange of Al with H⁺ on the streambed materials in controlling cation concentrations in soil and stream waters are also discussed. With the SAFE model, the contribution of cations from ion exchange by depletion of base cations from the exchange matrixes compared to from weathering was also assessed. SAFE calculations indicate that the release rate of base cation by ion exchange to runoff water has decreased since 1945 and is very low, approx. 0.1 keq/ha per year, at present time as a result of soil acidification due to S and N inputs.     

Towards a new method of setting a critical load of acidity for ombrotrophic peat

Critical loads of acidity for mineral soils can be set according to the capacity of the underlying bedrock to replenish the base cations leached by acid deposition. Unfortunately, this relatively simple approach cannot be applied to peat, one of the most widely occurring soil types in the wetter, western areas of Europe. These organic soils depend on atmospheric deposition for their supply of base cations rather than mineral weathering. We aim to develop a critical load methodology for ombrotrophic peat, using a combination of field observations and laboratory experiments. Simulated rain has been applied to intact cores of peat to determine the key chemical processes governing the response of these soils to both increases and decreases in acid deposition. It is evident that peat does not behave as a simple ion exchanger; the complex reactions of decomposition, sulphate reduction, nitrate uptake and organic acid production also control the response to acid inputs. This paper looks at some of the results from these experiments and considers the implications for setting critical loads.     

Evaluation of the Impacts of Marine Salts and Asian Dust on the Forested Yakushima Island Ecosystem, a World Natural Heritage Site in Japan

To elucidate the influence of airborne materials on the ecosystem of Japan??s Yakushima Island, we determined the elemental compositions and Sr and Nd isotope ratios in streamwater, soils, vegetation, and rocks. Streamwater had high Na and Cl contents, low Ca and HCO₃ contents, and Na/Cl and Mg/Cl ratios close to those of seawater, but it had low pH (5.4 to 7.1), a higher Ca/Cl ratio than seawater, and distinct ⁸⁷Sr/⁸⁶Sr ratios that depended on the bedrock type. The proportions of rain-derived cations in streamwater, estimated by assuming that Cl was derived from sea salt aerosols, averaged 81?% for Na, 83?% for Mg, 36?% for K, 32?% for Ca, and 33?% for Sr. The Sr value was comparable to the 28?% estimated by comparing Sr isotope ratios between rain and granite bedrock. The soils are depleted in Ca, Na, P, and Sr compared with the parent materials. At Yotsuse in the northwestern side, plants and the soil pool have ⁸⁷Sr/⁸⁶Sr ratios similar to that of rainwater with a high sea salt component. In contrast, the Sr and Nd isotope ratios of soil minerals in the A and B horizons approach those of silicate minerals in northern China??s loess soils. The soil Ca and P depletion results largely from chemical weathering of plagioclase and of small amounts of apatite and calcite in granitic rocks. This suggests that Yakushima??s ecosystem is affected by large amounts of acidic precipitation with a high sea salt component, which leaches Ca and its proxy (Sr) from bedrock into streams, and by Asian dust-derived apatite, which is an important source of P in base cation-depleted soils.     

Effects of acid deposition on acidity and exchangeable cations in podzols of the Kola Peninsula

Response of soil and soil water of podzols in the Kola Peninsula to acid deposition was estimated under both field and laboratory conditions. A significant increasing trend of exchangeable acidity in organic (O) horizons and exchangeable Al in podzolic (E) horizons of podzols with distance from the nickel smelter was observed. The simulated rain at pH 4.5 did not alter chemical properties of soils and soil solutions. As much as 95–99% of the applied H⁺ ions were retained by soils and appeared in the percolates after a treatment period that depended on acid load and soil thickness. Ca and Mg in soil solutions were highly sensitive to acid loading. Simulated acid rain enhanced the leaching of exchangeable base cations out of root zone. Acid inputs resulted in decreased pH, amount of exchangeable base cations and base saturation, in elevated exchangeable acidity and it's Al fraction in soil solid phase. The most significant changes occurred in O and E horizons. Substantial amounts of both Ca and Mg can be lost from the root zone of podzols in the north-western Kola, subjected to acid deposition, thus leading to forest productivity damage.     

热带亚热带酸性土壤硝化作用与氮淋溶特征

通过室内好气培养和土柱模拟淋洗培养试验,研究了氨基氮肥加入对热带亚热带4种不同性质和利用方式酸性土壤硝化、氮及盐基离子淋溶、土壤及淋出液酸化的影响。4种土壤分别为采自花岗岩发育的海南林地砖红壤(HR)、玄武岩发育的云南林地砖红壤(YR)、第四纪红黏土发育的江西旱地红壤(RU)和第四纪下蜀黄土发育的江苏旱地黄棕壤(YU)。结果表明:4种土壤硝化作用大小表现为YURUYRHR。HR主要以可溶性有机氮(DON)和NH_4~+-N形态淋失,YU土壤的氮淋溶形态以NO_3~–-N为主,YR和RU土壤的氮淋溶形态NO_3~–-N、NH_4~+-N和DON兼而有之。盐基离子总淋失量与NO_3~–-N淋失量显著正相关,但各盐基离子淋失由于离子本性和土壤性质差异并不完全一致。Ca~(2+)在缓冲外源NH_4~+-N硝化致酸和平衡NO_3~–-N淋失所带负电荷过程中起重要作用。在阳离子交换量小、盐基饱和度低的土壤(如RU土壤),外源NH_4~+-N的硝化和淋失不仅导致盐基离子淋失,而且引发NH_4~+-N、甚至是H~+淋失。综上,热带亚热带地区土壤上外源氮输入的增加可能会在更短的时间内导致氮素向系统外的流失,引发环境问题。     

Controls on surface water chemistry in the southern Blue Ridge and Piedmont provinces

Using lake and stream data collected during the National Surface Water Survey (NSWS), and corrected for regional wet deposition and local cultural contamination, the role of weathering in supplying base cations C_B, silica, and alkalinity is evaluated for the southern Blue Ridge (SBR) and southern Piedmont (SPM) Provinces of the United States. Silicate weathering can account for virtually all of the non-cultural (Na+K) leaving the catchments, consistent with the weathering of feldspars to kaolinite, and in some dilute montane catchments, gibbsite. The net export of divalent C_B (Ca+Mg) represents 62 to 66% (median values) of total C_B export for the regional NSWS index sample populations; the alkalis account for the remainder. The median percentage (Ca+Mg) is significantly lower (53%) for SBR special sites, consistent with their unusual vulnerability to acid deposition. Exchange-leaching currently accounts for < 17% of the divalent C_B mobilized in these SBR and SPM catchments, possibly because of the high regional retention rates for both nitrate and sulfate.     

盐阳离子类型及浓度对土壤持水及干缩开裂的作用效果

为探索阳性盐离子对土壤持水性能的影响,同时定量分析失水过程所致的土体收缩及裂缝特征,选取陕西粉黏壤土作为供试土壤,分别采用含有K+、Na+、Ca2+和Mg2+4种离子的盐溶液(浓度均为5、30和100 g/L)对土样进行饱和处理,采用离心机法测定土-水曲线,进一步对土壤持水能力进行评价;同时测定土体沉降高度,采用数字图像处理技术获取面积密度和长度密度等裂隙度量指标,对土体收缩和开裂水平进行定量分析。结果发现:1)van Genuchten模型适用于盐溶液浸泡土壤的土-水曲线拟合;2)4种盐离子均基本导致土壤持水能力降低(5 g/L Na+除外),且持水性与离子浓度呈负相关关系;同时使得土壤饱和含水率、残余含水率和进气吸力降低,其中土壤饱和含水率与离子浓度呈负相关关系;3)K+和高浓度Na+有利于减轻土壤轴向收缩度,且土体轴向收缩应变与K+(P0.01)和Na+(P0.05)浓度呈负相关关系;在收缩过程中,不同离子对土壤容重的影响程度表现为Mg2+Ca2+Na+K+;4)4种离子均可减轻土壤开裂程度,且裂缝面积密度和长度密度与K+(P0.01)、Na+(P0.01)和Ca2+(P0.05)浓度呈负相关关系,与Mg2+浓度呈正相关关系(P0.01)。研究可为盐碱土壤持水能力评价、制定灌溉制度提供参考。     

Transport of metal cations through a nutrient-poor forest ecosystem

Metal cations were analyzed in bulk precipitation, soil water, and stream flow in a southeastern U.S. lower Coastal Plain pine flatwoods for 6 yr. Extractable ions in mineral soil and total amounts in herbaceous vegetation were also determined. Concentrations for all ions were higher in soil water than in bulk precipitation, but especially Na⁺ and Mg⁺⁺. There were smaller concentration differences between soil water and stream flow, except for three-fold higher Ca⁺⁺ in stream flow. Base saturation in the mineral soil was less than 10%, with Al dominating cation exchange sites. Of all cations, only K showed a significant relationship between exchangeable amounts in the soil and total amounts in herb layer vegetation. Soils in the watershed-ecosystem are experiencing minimal mineral weathering, although this can be spatially quite variable. We conclude that the chemistry of such soils is susceptible to change over several forest harvest rotations and continued acid deposition.

     

Pedogenesis and weathering rates of a Histic Andosol in Iceland: Field and experimental soil solution study

It is important to study the rate determining processes of chemical weathering and soil formation in volcanic islands since a significant part of the carbon fixed by chemical weathering of silicates on Earth is fixed at the surface of volcanic islands. These soils are fertile and much of the river suspended matter delivered to the ocean stems from these islands. This study determines the factors that drive the pedogenesis of a Histic Andosol in Western Iceland. Soil solutions were extracted from the profile in the field, from undisturbed ex situ mesocosms and from repacked laboratory microcosms. Concentrations of measured and calculated inorganic species in the field and experimental soil solutions were used for thermodynamic and kinetic interpretation, and to calculate the weathering rates.

The main primary rock constituent of the 205 cm thick soil profile was basaltic glass, allophane content ranged from 2 to 22% and the soil carbon content ranged from 11 to 42%. Mean soil solution pH value ranged from 4 to 6 with the lowest value at 80 cm depth and highest between 150 to 205 cm. The high solute concentrations in soil solutions in the beginning of the microcosm weathering experiment declined faster for anions than cations. Under field conditions inorganic anions were supplied by marine and anthropogenic rather than pedogenic sources and hence these anions were subsequently leached out during the experimental duration when there was a limited input of anions through experimental precipitation. The factor, which defined the rate at which each ion was depleted from the exchange complex of the soil, decreased down the soil profile. The release sequence at 50 cm depth was Cl > Na > SO₄ > F > Si. The Si and base cations experimental weathering rate when normalized to geographical surface area are similar to or lower than those measured from river catchments in Southwestern Iceland. The dissolved Al flux was much higher from the soil when compared to the river catchments.

Field and experimental soil solutions were all highly undersaturated with respect to basaltic glass. Field and mesocosm samples were supersaturated with respect to secondary allophane and imogolite, while samples from the microcosms were often undersaturated with respect to allophane and imogolite. Predicted dissolution rate was dictated by the soil solution aH+3/aAl3+ activity ratio but slowed down by up to 20% and 30% by decreasing undersaturation in field and mesocosms respectively. Predicted dissolution rates according to the aH+3/aAl3+ activity ratio increased up to factor of 7, 30 and 37 by speciating Al3+ with oxalate in field, mesocosms and microcosms respectively. Speciation with oxalate, which represents the maximum effect of the dissolved organic carbon (DOC) on dissolution rates, generally had more effect near the surface than at deep levels in the soil profile. This study shows that at fixed temperature, reactive surface area, and composition of the volcanic glass in the soil, the chemical weathering rates of Andosols are dictated by: 1) aeolian deposition rates and drainage, which affect the saturation state and the aH+3/aAl3+ activity ratio, 2) the production of organic anions within the soil, and 3) external supply of anions capable of complexing Al3+.     

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.     

Extreme acidification in small catchments in southwestern Norway associated with a sea salt episode

During heavy storm events in January 1993 in the coastal areas of south-western Norway, a sea salt episode created extreme acidification in the afforested Svela catchment. Stream-water chloride increased sharply to eight times the normal concentration and the non-marine Na concentration was calculated to ?208 μeq L^?1. Negative values indicate that Na was retained in the soil profile. By ion-exchange processes this was largely compensated by an increase in stream-concentrations of Al and H⁺. Concentrations of inorganic monomeric Al increased from about 20 to 200 μeq L^?1 and pH decreased from 4.90 to 4.45. Due to the low pH and the dramatic increase in inorganic monomeric Al the water toxicity for aquatic organisms increased. Acidification associated with the storm was also observed in a forested and a non-forested catchment, but never reached the levels of the afforested catchment. The extra vulnerability of afforested catchments may be due to their ability to intercept larger amounts of sea salts than areas less dominated by dense tree stands. Although both pH and Al went back to normal levels for the area after 3–4 months the Na/Cl-relationship in cumulated transport values indicated a longlasting effect (> 2 years) on the soil profile. Reloading the soil profile with Al and H⁺ back to prestorm values will affect the catchments ability to mobilize these ions during future sea salt episodes. More frequent episodes will probably result in less acid and Al-rich stream-water during the episodes than documented here due to incomplete reacidification of the soils.