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1.
Liming to neutralize acidic surface waters involves a possible risk of toxicity to fish due to precipitation or changes in speciation of Al. We report the response of captive brown trout to the experimental liming of an acid stream rich in Al. Within 15 m of lime dosing 0.22 µm filterable Al fell from 580 to 230 µg L?1, and to 120 jig L?1, within 30 m, though total Al was unchanged. After 24 hr, fish mortality was 100% at untreated acidic sites, 80% up to 30 m downstream of liming, declining to zero within 100 m. Mortality was 70% at 15 m below the confluence of an acidic tributary with the limed stream, despite little change in pH or total Al concentration. Mortalities were significantly correlated with concentrations of Al and Fe in gill tissues, and with 0.22 µm filterable Al and Fe in the water, but not with particulate Al or Fe. AI(OH)4 ?, precipitating A1 or polymeric hydrolysis products are all possible causes of the observed toxicity. Iron may have also have contributed, but the stream concentrations of this metal were relatively low. The practical conclusion is that changes in Al chemistry, where waters of differing acidity mix, may be important in some circumstances where river systems are limed selectively.  相似文献   

2.
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.  相似文献   

3.
White precipitates collected from stream bottoms and well tubes in the Senne area consist of amorphous aluminium hydroxide, coprecipitated with minor amounts of sulfate, phosphate and silica. The precipitates have presumably formed by the interaction of slightly alkaline water from calcareous subsoil sediments, with acidic water draining off sandy soils affected by high inputs of acidic atmospheric deposition. From many hydrochemical studies, precipitation of aqueous aluminium is known to occur in subsurface horizons of acid soils affected by acid rain. On the basis of presumed equilibrium with soil solutions, jurbanite, AlOHSO4 · 5H2O, is often assumed to be the secondary mineral involved. However, direct evidence for jurbanite from solid phase analysis is lacking. This first analysis of such a secondary phase does not support the jurbanite hypothesis, and shows that amorphous Al hydroxide can be formed instead.  相似文献   

4.
Near-stream and upslope soil chemical properties were analyzed to infer linkages between soil and surface water chemistry atthe Bear Brook Watershed in Maine [BBWM]. Organic and mineral soil samples were collected along six 20 m transects perpendicular to the stream and one 200 m transect parallel tothe stream. O horizon soils immediately adjacent to the streamhad a significantly higher pH (4.20) and lower soil organic matter percentage (54%) than upslope O horizons (3.84 and 76%,respectively). Additionally, near-stream O horizon soils hadsignificantly higher concentrations of water-soluble Al (2.7 ×),exchangeable Al (2.3 ×), and organically-bound Al (3.9 ×) andsignificantly lower concentrations of exchangeable Ca (0.4 ×) than O horizons upslope. These results suggest that Al can accumulate in non-hydric near-stream zone soils at this site. Mobilization of labile Al from near-stream zone soils duringhydrologic events could play a key role in explaining controls on Al in stream water at BBWM.  相似文献   

5.
Results from surveys of low-ANC lakes (high elevation, and seepage lakes), and of surface waters in dystrophic, acidic bogs, indicate that acidic precipitation and organic acidity are each generally necessary, but not solely sufficient, for chronically acidic status in Maine lakes. Acidic, low DOC (ANC < 0; DOC < 5 mg L-1) lakes of all hydrologic types are acidic due largely to acidic deposition; high DOC (DOC > 30 mg L-1) acidic seepage lakes are acidic due largely to organic acidity, and high DOC drainage lakes are acidic due to a combination of both factors. No low DOC drainage lakes are known with pH less than about 5.0, suggesting that organic acidity is necessary to depress lake pH values to below 5 in Maine at current deposition loadings,The dominant anion of low DOC, acidic waters is sulfate. Acidic waters with intermediate concentrations of DOC (5 to 30 mg L-1), may be dominated by S04 and/or organic acidity. Seepage-input lakes were the only group to include both organically-dominated (37% of the acidic lakes) and S04-dominated members (63% of the acidic lakes). High DOC systems are typically low pH bogs, and are all organic acid-dominated.  相似文献   

6.
A 10-month study of surface waters in Canadian Creek (Ballarat, Victoria, Australia) showed the significant influence of historic gold mining waste material. The investigation focussed on the hydrogeochemistry of the surface waters and soils in order to: (1) document the levels and seasonal trends in major, minor and trace elements in the creek, (2) identify the process by which As is released from the soil/waste mining material to surface waters. For most dissolved major and trace elements (Na, Ca, Mg, K, and As) in surface waters, the concentrations decreased with the increasing rainfall and flow conditions except for Al and Fe. Two sites selected along the creek (< 1 km apart) allowed evaluation of the possibility that mining waste material is contributing to the elevated As concentrations (up to 145 μg/l) in downstream surface water. Arsenic concentration varied more than 28 fold seasonally and was highest in autumn and lowest in spring. Elevated concentrations of As (up to 1946 mg/kg) at the downstream site indicated the presence of a source of As concentration in both surface and subsurface soils. Oxidation of arsenic sulphides under aerobic conditions with redox fluctuations (7 to 201 mV) could cause elevated As levels in the creek. Significant statistical correlations among the major cations (Ca, Na and Mg) point to a common source(s) resulting in neutral to slightly alkaline (pH ~ 6.5 to 7.8) surface water. Fe and Al secondary phases under oxidising conditions are a significant controlling mechanism for the mobilization of As in highly contaminated soils (> 1500 mg/kg) in the study area. The large As adsorption capacity of Fe and Al could be limiting extreme mobilization into the water. Rainfall with relatively low pH is possibly causing mobilisation of Al, Fe and As from highly alkaline soils (pH ≈ 9.0) into the nearby creek.  相似文献   

7.
Abstract

Pedogenetic acidification processes in forest soils derived from sedimentary rocks under mesic and thermic soil temperature regimes (MSTR and TSTR; corresponding to mean annual soil temperatures of 8–15°C and 15–22°C, respectively) in the Kinki District were investigated based on titratable alkalinity and acidity characteristics and soil solution composition. According to statistical analyses of the soil properties, the titratable alkalinity required to acidify soils to pH 3.0 was considered to be derived from reactions occurring at the surface of amorphous Al oxides, while titratable acidity at a pH ranging from 5.5 to 8.3 results from dissociation of acidic functional groups of soil humus and/or deprotonation of oxide surfaces. These reactions were generally more prevalent in MSTR soils. Based on the soil solution composition and titratable alkalinity and acidity in the soil profiles, two processes were postulated for pedogenetic acidification, that is, eluvi-illuviation of inorganic Al followed by subsequent adsorption of dissolved organic carbon (DOC) onto the precipitates of Al hydroxides and comigration of Al and DOC in the form of organo-mineral complexes. Both processes were conspicuous in MSTR soils and significantly contributed to soil organic matter storage in the subsoil layers. Pedogenetic acidification in forest soils with MSTR was characterized by an accumulation of acidity in the form of amorphous compounds and/or organo-mineral complexes in the B horizon. It seems, to some extent, similar to podzol formation, at least in terms of Al translocation. Amorphous Al hydroxides protect against further acidification through protonation and/or partial monomerization and can, thus, be regarded as a temporary storage of acid neutralizing capacity of the soil, which would be otherwise leached out directly from the soil profile. In contrast, the acid-buffering reactions of TSTR soils seemed to occur, if at all, mostly at or near the soil surface and the contribution of the B-horizon soils was limited.  相似文献   

8.
Agricultural peat soils in the Sacramento-San Joaquin Delta, California have been identified as an important source of dissolved organic carbon (DOC) and trihalomethane precursors in waters exported for drinking. The objectives of this study were to examine the primary sources of DOC from soil profiles (surface vs. subsurface), factors (temperature, soil water content and wet-dry cycles) controlling DOC production, and the relationship between C mineralization and DOC concentration in cultivated peat soils. Surface and subsurface peat soils were incubated for 60 d under a range of temperature (10, 20, and 30 °C) and soil water contents (0.3-10.0 g-water g-soil−1). Both CO2-C and DOC were monitored during the incubation period. Results showed that significant amount of DOC was produced only in the surface soil under constantly flooded conditions or flooding/non-flooding cycles. The DOC production was independent of temperature and soil water content under non-flooded condition, although CO2 evolution was highly correlated with these parameters. Aromatic carbon and hydrophobic acid contents in surface DOC were increased with wetter incubation treatments. In addition, positive linear correlations (r2=0.87) between CO2-C mineralization rate and DOC concentration were observed in the surface soil, but negative linear correlations (r2=0.70) were observed in the subsurface soil. Results imply that mineralization of soil organic carbon by microbes prevailed in the subsurface soil. A conceptual model using a kinetic approach is proposed to describe the relationships between CO2-C mineralization rate and DOC concentration in these soils.  相似文献   

9.
Although the increased mobilization of aluminum from soils to surface waters is widely recognized as one of the most important ecological effects of acidic deposition, lumped-parameter mathematical models of acidification response typically overestimate the change in Al concentration under changing deposition by a considerable margin. The assumption of equilibrium with gibbsite (Al(OH)3) in the MAGIC model and other models of acid-base chemistry is shown to be inconsistent with measured values for a large variety of lake and stream databases. A modified algorithm for predicting Al concentration, based on empirical relationships evident in field data, provided superior estimates of changes in Al concentration in three long-term monitoring data sets and under experimental conditions at two experimental watershed manipulation sites.  相似文献   

10.
Dissolved organic carbon (DOC) in acid‐sensitive upland waters is dominated by allochthonous inputs from organic‐rich soils, yet inter‐site variability in soil DOC release to changes in acidity has received scant attention in spite of the reported differences between locations in surface water DOC trends over the last few decades. In a previous paper, we demonstrated that pH‐related retention of DOC in O horizon soils was influenced by acid‐base status, particularly the exchangeable Al content. In the present paper, we investigate the effect of sulphate additions (0–437 µeq l?1) on DOC release in the mineral B horizon soils from the same locations. Dissolved organic carbon release decreased with declining pH in all soils, although the shape of the pH‐DOC relationships differed between locations, reflecting the multiple factors controlling DOC mobility. The release of DOC decreased by 32–91% in the treatment with the largest acid input (437 µeq l?1), with the greatest decreases occurring in soils with very small % base saturation (BS, < 3%) and/or large capacity for sulphate (SO42?) retention (up to 35% of added SO42?). The greatest DOC release occurred in the soil with the largest initial base status (12% BS). These results support our earlier conclusions that differences in acid‐base status between soils alter the sensitivity of DOC release to similar sulphur deposition declines. However, superimposed on this is the capacity of mineral soils to sorb DOC and SO42?, and more work is needed to determine the fate of sorbed DOC under conditions of increasing pH and decreasing SO42?.  相似文献   

11.
Automated stream dosers that deliver a wet slurry of calcite were installed in 1987 on two Maryland Coastal Plain streams subject to acidic pulses during rainstorms to evaluate the use of stream liming technology to maintain suitable water quality for early life stages of anadromous fish. Results of water quality sampling during baseflow conditions and hydrologic events indicated that significant changes in water chemistry occurred at the upstream (untreated) site during elevated flows on each stream. Observed responses in stream chemistry during the events included declines in pH, acid neutralizing capacity (ANC), and Ca, and increases in monomeric Al concentrations. With the addition of calcite, stream chemistry conditions at the downstream (treated) sites during each event were similar to those observed during baseflow. In situ bioassay experiments indicated that survival of yellow perch eggs and newly-hatched larvae may be enhanced by stream liming.  相似文献   

12.
A study was undertaken to examine whether ‘acid pulses’ from snowmelt created permanent changes in a pond's chemistry. Water samples were collected from clearwater acidic Cone Pond in the White Mountain National Forest, New Hampshire. The pond, inlet, and outlet were intensively sampled throughout winter and early spring 1983–84. Thaws brought more H+ into upper waters of the pond, but most was gone within a week. In contrast, SO4 2? and Al showed dilution with increased streamflow into the pond, and NO3 ? was only detected in ice, slush, and surface waters. Bottom waters were anoxic throughout the winter and had pH 6.0 compared to 4.7 for most of the water column. Alkalinity at the bottom rose from 0 in November 1983 to 190 μeq L?1 in April 1984. Between November and April the pond gained Al but lost SO4 2? and H+. Most of the Al gain came after ice-out when loading through the inlet increased, but during the final snowmelt a temporary increase in Al concentration was also seen throughout the water column.  相似文献   

13.
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.  相似文献   

14.
Although there have been recent significant gains in our understanding of mercury (Hg) cycling in aquatic environments, few studies have addressed Hg cycling on a watershed scale. In particular, attention to Hg species transfer between watershed components (upland soils, groundwater, wetlands, streams, and lakes) has been lacking. This study describes spatial and temporal distributions of total Hg and MeHg among watershed components of the Allequash Creek watershed (northern Wisconsin, USA). Substantial increases in total Hg and MeHg were observed as groundwater discharged through peat to form springs that flow into the stream, or rivulets that drain across the surface of the wetland. This increase was concomitant with increases in DOC. During fall, when the Allequash Creek wetland released a substantial amount of DOC to the stream, a 2–3 fold increase in total Hg concentrations was observed along the entire length of the stream. Methylmercury, however, did not show a similar response. Substantial variability was observed in total Hg (0.9 to 6.3) and MeHg (<0.02 to 0.33) concentrations during synoptic surveys of the entire creek. For the Allequash Creek watershed, the contributing groundwater basin is about 50% larger than the topographic drainage basin. Total Hg concentrations in groundwater, the area of the groundwater basin, and annual stream flow data give a watershed-yield rate of 1.2 mg/km2/d, which equates to a retention rate of 96%. The calculated MeHg yield rate for the wetland area is 0.6 to 1.5 mg/km2/d, a value that is 3–6 fold greater than the atmospheric deposition rate.  相似文献   

15.
We have examined the roles of dissolved organic carbon (DOC) and pH in determining patterns of Pb fractionation in surface water from Sphagnum-dominated peatlands in undisturbed and urbanized watersheds of the Pinelands of New Jersey. In undisturbed wetlands, the water is highly acidic (pH 3.5) and has high concentrations of DOC; wetlands receiving urban runoff are less acidic and have lower concentrations of DOC. The effects of PH were separated from the effects of DOC by experimentally raising the pH of water from the undisturbed site to 6.0. A separation procedure was compiled from the literature to separate the soluble Pb fraction into labile (exchangeable on ion-exchange resin) and non-labile fractions, and the latter fraction was further separated into photo-oxidation-sensitive and insensitive fractions. In low pH, high DOC waters, 95% of added PbCl2 remained soluble, and 56 to 80% of this Pb was labile (varying with contact time with the resin). In high-pH swamp waters, a smaller fraction (64 to 71%) remained soluble; the distribution of the soluble Pb among non-labile forms varied with the source of the water. Pb fractionation in runoff was quite different from that in runoff-impacted swamp water at the same pH, and may reflect differences in DOC and/or higher levels of Fe in the runoff.  相似文献   

16.
Contaminated soils and surface waters, from copper mining in Galicia, are acidic, high in sulphate and increase appreciably in the concentration of elements such as Al, Fe, Ca, Mg, K, Mn, Cu and Zn by contact with soils and fragments of rock of an amphibolic composition. Application of activity data to mineral equilibrium diagrams illustrates the instability of Al-hydroxides and aluminosilicates compared to Al-sulphates of the alunite and jurbanite type, in the waters which are most acid and display sulphate activities close to 10?2 M. The solution extracted from soils around the spoil heaps reflects the strong influence of the most heavily contaminated run-off waters, with little or no buffering by the solid phase. This aspect may be accounted for by both a brief time of residence and a real decrease of the acid buffering power of these soils, whose primary minerals undergo strong acidolysis. Neoformation of Al-sulphate (and Fe-sulphate) is observed both in soils and in the channels of the contaminated streams, above all the points of contact with non-acid or slightly acid waters.  相似文献   

17.
Long‐term monitoring data from eastern North America and Europe indicate a link between increased dissolved organic carbon (DOC) concentrations in surface waters over the last two decades and decreased atmospheric pollutant and marine sulphur (S) deposition. The hypothesis is that decreased acidity and ionic strength associated with declining S deposition has increased the solubility of DOC. However, the sign and magnitude of DOC trends have varied between sites, and in some cases at sites where S deposition has declined, no significant increase in DOC has been observed, creating uncertainty about the causal mechanisms driving the observed trends. In this paper, we demonstrate chemical regulation of DOC release from organic soils in batch experiments caused by changes in acidity and conductivity (measured as a proxy for ionic strength) associated with controlled SO42? additions. DOC release from the top 10 cm of the O‐horizon of organo‐mineral soils and peats decreased by 21–60% in response to additions of 0–437 µeq SO42? l?1 sulphuric acid (H2SO4) and neutral sea‐salt solutions (containing Na+, Mg2+, Cl?, SO42?) over a 20‐hour extraction period. A significant decrease in the proportion of the acid‐sensitive coloured aromatic humic acids (measured by specific ultra‐violet absorbance (SUVA) at 254 nm) was also found with increasing acidity (P < 0.05) in most, but not all, soils, confirming that DOC quality, as well as quantity, changed with SO42? additions. DOC release appeared to be more sensitive to increased acidity than to increased conductivity. By comparing the change in DOC release with bulk soil properties, we found that DOC release from the O‐horizon of organo‐mineral soils and semi‐confined peats, which contained greater exchangeable aluminium (Al) and had lower base saturation (BS), were more sensitive to SO42? additions than DOC release from blanket peats with low concentrations of exchangeable Al and greater BS. Therefore, variation in soil type and acid/base status between sites may partly explain the difference in the magnitude of DOC changes seen at different sites where declines in S deposition have been similar.  相似文献   

18.
The results of the seasonal analysis of the chemistry of rain, fog and surface water of central India for the two years: June 1996 to May 1998 are presented. A total of 636 rain water samples, 146 fog water samples and 226 surface water samples of 8 locations: namely, Ambikapur, Baikunthpur, Korba, Bilaspur, Raipur, Bhilai, Dallirajhara and Kanker, from different sites were collected for the present study. This paper documents the occurrence of acidic rain and fog events and their effect on surface water pH and aquatic life in central India. Most of the rain and fog water samples collected from Baikunthpur and Korba sites were found to be acidic in nature (i.e. pH < 5). The volume weighted mean pH of rain and fog water samples of these sites was 4.8 and 4.4 with lowest pH 4.4 and 4.0, respectively. However, samples from Ambikapur, Bilaspur, Raipur and Bhilai were slightly acidic and their pH values were always around 5.8. One reservoir (mean pH 5.8) and two stop dams (mean pH 4.4 and 4.2) in Baikunthpur area were found to be acidic. The effect of acidification of water on metal-accumulation in muscles of fishes was studied. Concentrations of Al, Hg, Mn, Cd and Pb were higher in fish from acid, than from less acid waters. Causes of acidification of the atmospheric water and surface water are critically discussed.  相似文献   

19.
The modified Tessier’s sequential extraction procedure and rhizobox cultivation were employed to investigate the distribution of aluminum (Al) fractions in the acidic rhizosphere soil of Masson pine (Pinus massoniana lamb) seedlings. The results showed that the Al in soils was fractionated into five operationally defined fractions. Three sets of soil samples used in the rhizoboxes were collected from the three forest sites in the southeast of China: Sichuan, Zhejian, and Jiangsu. At the end of 100-day cultivation, the rhizosphere Al fractions for the original or bulk soils were in the order of residual > iron-manganese (Fe-Mn) oxides > organic > carbonate > exchangeable. However, in rhizosphere soil, the Al fraction follows the order of residual > organic > Fe-Mn oxides > carbonate > exchangeable. On average, the rhizosphere experienced significant increase in organically bound Al and slight decrease in exchangeable Al contents, but had decreases in contents for the other three Al fractions compared to the nonrhizosphere. The correlation analysis indicated that the Al contents accumulated in roots were significantly and positively correlated with exchangeable Al contents in the rhizosphere, and also characterized by the major portion of organically bound Al, which exhibited a bioavailable transformation of Al fractions. Results indicated that decreases in both redox potential and soil pH, as well as increase in dissolved organic carbon (DOC), were observed in the rhizosphere. Exchangeable Al and organic Al fractions were dependent mainly on soil pH (hydrogen ion concentration) and DOC, accordingly. Decreasing rhizosphere pH from 5.93 to 3.42 accelerated the secretion of organic carbon. These data are helpful for understanding the mobility and bioavailability of Al fractions in the acidic rhizosphere soils of Masson pine.  相似文献   

20.
To determine the geological distribution of acid buffering capacity and exchangeable Al of forest soils in Japan, surface soils under forest vegetation were collected nationwide from a total of 1,034 sites. Generally, surface soils in Japanese forests are mostly acidic and low in both exchangeable cation content and exchangeable Al. The median of soil pH(H2O), total exchangeable cations, and exchangeable Al are 5.1, 76 mmol(+)Kg?1, and 19.6 mmol(+)kg?1, respectively. Acid buffering capacities of selected soils were determined using a soil column, which was comparable to the capacity that resulted from cation exchanges with protons. Soils with high buffering capacity and low exchangeable Al are widely distributed in Japan, and overlap with the areas of Andisol distribution. Volcanogenic materials seem to mask soil characteristics derived from underlying geology even though they are not Andisols. However, central to western Honshu Island, Shikoku Island, and northern Kyushu Island showed weak acid buffering capacities with high exchangeable Al potential in surface soils.  相似文献   

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